SUPPORTING INFORMATIONSynthesis and Crystal Structures of Ni(II)/(III) and Zn(II) Complexes with Schiff Base Ligands

Printed in the Republic of Korea

http://dx.doi.org/10.5012/jkcs.2013.57.6.1 단신

(Notes)

SUPPORTING INFORMATION

Synthesis and Crystal Structures of Ni(II)/(III) and Zn(II) Complexes with Schiff Base Ligands

Bon Kweon Koo*

Department of Chemistry, Catholic University of Daegu, Gyeongbuk 712-702, Korea.

*E-mail: [email protected]

(Received September 27, 2013; Accepted October 26, 2013)

Complex 1 Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Computing Details

Data collection: Bruker SMART; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: Bruker SHELXTL; molecular graphics: Bruker SHELXTL; software used to prepare material for publica- tion: Bruker SHELXTL.

(kbkno6-m) Crystal Data

C

H

N

O

Zn M

= 666.03 Triclinic, P1 a = 10.6428 (6) Å b = 12.5122 (7) Å c = 12.9696 (7) Å α = 66.234 (1)°

β = 83.802 (1)°

γ = 83.602 (1)°

V = 1567.01 (15) Å

Z = 2

F(000) = 688 D

= 1.412 Mg m

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2961 reflections θ = 2.5–24.6°

µ = 0.83 mm

T = 200 K Block, yellow

0.24 × 0.15 × 0.10 mm Data Collection

CCD area detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator

phi and ω scans

11790 measured reflections 7684 independent reflections 3588 reflections with I > 2σ(I) R

= 0.046

θ

= 28.3°, θ

= 1.7°

h = −14→14 k = −16→16 l = −10→17 Refinement

Refinement on F

Least-squares matrix: full R[F

> 2σ(F

)] = 0.052 wR(F

) = 0.101

S = 0.89

Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained

7684 reflections 424 parameters 0 restraints

Primary atom site location: structure-invariant direct methods w = 1/[σ

(Fo

) + (0.0105P)

]

where P = (F

+ 2F

)/3 ( ∆/σ)

= 0.001

∆ρ

= 0.84 e Å

∆ρ

= −1.38 e Å

Special Details

Geometry: All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full cova- riance matrix. The cell esds are taken into account indi- vidually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry.

An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement: Refinement of F

against ALL reflections.

The weighted R-factor wR and goodness of fit S are based on F

, conventional R-factors R are based on F, with F set to zero for negative F

. The threshold expression of F

> 2sigma (F

) is used only for calculating R-factors (gt) etc. and is not relevant to the choice of reflections for refinement. R-fac- tors based on F

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å

)

x y z Uiso*/Ueq

Zn1 0.71278 (4) 0.70527 (4) 0.66587 (4) 0.03047 (14)

N1 0.6530 (3) 0.5242 (3) 0.7429 (3) 0.0311 (8)

C1 0.6009 (4) 0.4674 (4) 0.8468 (4) 0.0418 (11)

H1 0.5823 0.5090 0.8945 0.050*

C2 0.5725 (4) 0.3518 (4) 0.8892 (4) 0.0483 (12)

H2 0.5344 0.3149 0.9633 0.058*

C3 0.6012 (4) 0.2928 (4) 0.8205 (4) 0.0559 (14)

H3 0.5831 0.2130 0.8471 0.067*

C4 0.6562 (4) 0.3471 (3) 0.7127 (4) 0.0448 (12)

H4 0.6766 0.3058 0.6649 0.054*

C5 0.6811 (3) 0.4647 (3) 0.6759 (3) 0.0305 (10)

C6 0.7431 (3) 0.5289 (3) 0.5628 (3) 0.0295 (10)

C7 0.7616 (3) 0.4785 (3) 0.4766 (3) 0.0312 (10)

C8 0.6639 (4) 0.4862 (4) 0.4112 (4) 0.0470 (12)

H8 0.5851 0.5261 0.4207 0.056*

C9 0.6788 (4) 0.4371 (4) 0.3327 (4) 0.0548 (14)

H9 0.6101 0.4429 0.2892 0.066*

C10 0.7916 (4) 0.3798 (3) 0.3165 (4) 0.0483 (12)

H10 0.8015 0.3463 0.2618 0.058*

C11 0.8905 (4) 0.3712 (4) 0.3803 (4) 0.0499 (13)

H11 0.9694 0.3319 0.3698 0.060*

C12 0.8745 (4) 0.4199 (3) 0.4596 (4) 0.0436 (12)

H12 0.9430 0.4130 0.5037 0.052*

N2 0.7770 (3) 0.6306 (3) 0.5507 (3) 0.0310 (8)

N3 0.8412 (3) 0.6967 (3) 0.4531 (3) 0.0320 (8)

O1 0.8223 (2) 0.8313 (2) 0.5403 (2) 0.0350 (7)

C13 0.8642 (4) 0.7981 (3) 0.4616 (3) 0.0301 (10)

C14 0.9515 (3) 0.8728 (3) 0.3702 (3) 0.0263 (9)

C15 1.0141 (4) 0.8356 (3) 0.2902 (4) 0.0402 (11)

H15 0.9973 0.7624 0.2906 0.048*

C16 1.1004 (4) 0.9028 (3) 0.2098 (4) 0.0440 (12)

H16 1.1428 0.8759 0.1554 0.053*

C17 1.1252 (4) 1.0093 (3) 0.2087 (4) 0.0435 (12)

H17 1.1850 1.0557 0.1536 0.052*

C18 1.0635 (4) 1.0482 (3) 0.2869 (3) 0.0391 (11)

H18 1.0804 1.1216 0.2857 0.047*

C19 0.9770 (3) 0.9807 (3) 0.3673 (3) 0.0332 (10)

H19 0.9344 1.0082 0.4212 0.040*

N4 0.5358 (3) 0.7855 (2) 0.5818 (3) 0.0290 (8)

Atomic displacement parameters (Å

)

C20 0.5088 (4) 0.7963 (3) 0.4795 (3) 0.0357 (10)

H20 0.5632 0.7547 0.4430 0.043*

C21 0.4058 (4) 0.8650 (3) 0.4238 (3) 0.0356 (10)

H21 0.3881 0.8688 0.3521 0.043*

C22 0.3301 (4) 0.9274 (3) 0.4763 (3) 0.0367 (11)

H22 0.2593 0.9763 0.4404 0.044*

C23 0.3569 (4) 0.9191 (3) 0.5809 (3) 0.0339 (10)

H23 0.3056 0.9625 0.6175 0.041*

C24 0.4610 (3) 0.8456 (3) 0.6324 (3) 0.0245 (9)

C25 0.4976 (4) 0.8320 (3) 0.7458 (3) 0.0279 (9)

C26 0.4122 (4) 0.8834 (3) 0.8146 (3) 0.0285 (9)

C27 0.2853 (4) 0.8597 (3) 0.8386 (3) 0.0387 (11)

H27 0.2546 0.8047 0.8158 0.046*

C28 0.2037 (4) 0.9145 (4) 0.8947 (3) 0.0445 (12)

H28 0.1176 0.8964 0.9111 0.053*

C29 0.2457 (4) 0.9953 (4) 0.9272 (4) 0.0455 (12)

H29 0.1882 1.0362 0.9624 0.055*

C30 0.3726 (4) 1.0166 (3) 0.9083 (4) 0.0432 (12)

H30 0.4030 1.0701 0.9332 0.052*

C31 0.4551 (4) 0.9604 (3) 0.8535 (3) 0.0369 (10)

H31 0.5424 0.9745 0.8422 0.044*

N5 0.6082 (3) 0.7778 (2) 0.7696 (3) 0.0267 (8)

N6 0.6577 (3) 0.7586 (2) 0.8704 (3) 0.0286 (8)

O2 0.8275 (2) 0.6716 (2) 0.7948 (2) 0.0349 (7)

C32 0.7746 (3) 0.7037 (3) 0.8708 (3) 0.0266 (9)

C33 0.8471 (4) 0.6820 (3) 0.9705 (3) 0.0293 (10)

C34 0.7931 (4) 0.6979 (3) 1.0655 (3) 0.0405 (11)

H34 0.7062 0.7245 1.0687 0.049*

C35 0.8648 (4) 0.6753 (4) 1.1568 (4) 0.0520 (13)

H35 0.8273 0.6864 1.2220 0.062*

C36 0.9905 (4) 0.6369 (3) 1.1513 (4) 0.0513 (14)

H36 1.0396 0.6207 1.2136 0.062*

C37 1.0459 (4) 0.6217 (4) 1.0576 (4) 0.0549 (14)

H37 1.1331 0.5960 1.0547 0.066*

C38 0.9748 (4) 0.6438 (3) 0.9669 (4) 0.0424 (11)

H38 1.0133 0.6328 0.9020 0.051*

U¹¹ U²² U³³ U¹² U¹³ U²³

Zn1 0.0308 (3) 0.0324 (3) 0.0281 (3) 0.0007 (2) −0.0024 (2) −0.0125 (2)

N1 0.0269 (19) 0.0344 (19) 0.029 (2) −0.0041 (15) −0.0022 (17) −0.0090 (18)

C1 0.039 (3) 0.043 (3) 0.040 (3) −0.003 (2) −0.006 (2) −0.013 (2)

C2 0.047 (3) 0.044 (3) 0.039 (3) −0.009 (2) −0.002 (2) −0.001 (3)

C3 0.057 (3) 0.039 (3) 0.058 (4) −0.011 (2) −0.001 (3) −0.004 (3)

C4 0.043 (3) 0.035 (3) 0.057 (3) −0.004 (2) −0.006 (3) −0.018 (3)

C5 0.025 (2) 0.026 (2) 0.033 (3) −0.0014 (17) −0.003 (2) −0.004 (2)

C6 0.023 (2) 0.024 (2) 0.042 (3) 0.0045 (17) −0.008 (2) −0.013 (2)

C7 0.023 (2) 0.027 (2) 0.041 (3) −0.0009 (17) −0.003 (2) −0.012 (2)

C8 0.028 (2) 0.059 (3) 0.053 (3) 0.001 (2) −0.009 (2) −0.021 (3)

C9 0.042 (3) 0.079 (4) 0.052 (3) −0.009 (3) −0.014 (3) −0.031 (3)

C10 0.056 (3) 0.052 (3) 0.046 (3) −0.012 (2) −0.005 (3) −0.027 (3)

C11 0.041 (3) 0.057 (3) 0.061 (4) 0.009 (2) −0.005 (3) −0.036 (3)

Geometric parameters (Å, º) for (kbkno6-m)

C12 0.037 (3) 0.046 (3) 0.055 (3) 0.004 (2) −0.009 (2) −0.027 (3)

N2 0.0270 (19) 0.0343 (19) 0.026 (2) 0.0000 (15) 0.0005 (16) −0.0071 (17)

N3 0.0307 (19) 0.0333 (19) 0.029 (2) −0.0006 (15) −0.0013 (17) −0.0102 (17)

O1 0.0376 (17) 0.0336 (15) 0.0318 (18) −0.0013 (12) −0.0012 (14) −0.0117 (14)

C13 0.032 (2) 0.027 (2) 0.030 (3) 0.0066 (18) −0.009 (2) −0.011 (2)

C14 0.029 (2) 0.024 (2) 0.024 (2) −0.0012 (17) −0.0027 (19) −0.0074 (19)

C15 0.048 (3) 0.032 (2) 0.040 (3) −0.002 (2) 0.000 (2) −0.015 (2)

C16 0.050 (3) 0.043 (3) 0.034 (3) −0.004 (2) 0.009 (2) −0.013 (2)

C17 0.039 (3) 0.042 (3) 0.040 (3) −0.007 (2) 0.004 (2) −0.007 (2)

C18 0.038 (3) 0.039 (3) 0.037 (3) −0.008 (2) −0.002 (2) −0.010 (2)

C19 0.037 (2) 0.035 (2) 0.030 (3) 0.0005 (19) −0.007 (2) −0.015 (2)

N4 0.0305 (19) 0.0302 (18) 0.024 (2) 0.0078 (15) −0.0107 (16) −0.0087 (17)

C20 0.041 (3) 0.032 (2) 0.033 (3) 0.0044 (19) −0.007 (2) −0.013 (2)

C21 0.047 (3) 0.036 (2) 0.026 (2) −0.004 (2) −0.009 (2) −0.012 (2)

C22 0.034 (2) 0.039 (3) 0.037 (3) 0.0040 (19) −0.012 (2) −0.014 (2)

C23 0.032 (2) 0.035 (2) 0.038 (3) 0.0018 (18) −0.006 (2) −0.018 (2)

C24 0.019 (2) 0.027 (2) 0.028 (2) 0.0013 (16) −0.0004 (18) −0.0120 (19)

C25 0.032 (2) 0.023 (2) 0.027 (2) −0.0021 (17) −0.004 (2) −0.0082 (19)

C26 0.031 (2) 0.028 (2) 0.026 (2) 0.0013 (18) −0.007 (2) −0.0091 (19)

C27 0.035 (3) 0.044 (3) 0.038 (3) −0.003 (2) −0.002 (2) −0.018 (2)

C28 0.030 (2) 0.062 (3) 0.040 (3) 0.004 (2) 0.004 (2) −0.021 (3)

C29 0.051 (3) 0.051 (3) 0.036 (3) 0.013 (2) 0.000 (2) −0.024 (2)

C30 0.050 (3) 0.042 (3) 0.045 (3) 0.002 (2) 0.001 (3) −0.029 (2)

C31 0.039 (3) 0.042 (2) 0.033 (3) −0.006 (2) −0.001 (2) −0.018 (2)

N5 0.0305 (19) 0.0270 (18) 0.0199 (19) 0.0028 (14) −0.0053 (16) −0.0071 (16) N6 0.0301 (19) 0.0316 (18) 0.0240 (19) 0.0004 (15) −0.0047 (16) −0.0109 (16) O2 0.0307 (16) 0.0435 (16) 0.0363 (18) 0.0044 (13) −0.0043 (14) −0.0231 (15)

C32 0.030 (2) 0.021 (2) 0.024 (2) −0.0035 (17) −0.0032 (19) −0.0042 (19)

C33 0.030 (2) 0.026 (2) 0.031 (3) −0.0024 (17) −0.005 (2) −0.010 (2)

C34 0.038 (3) 0.048 (3) 0.035 (3) −0.004 (2) −0.003 (2) −0.015 (2)

C35 0.063 (3) 0.063 (3) 0.038 (3) −0.006 (3) −0.014 (3) −0.024 (3)

C36 0.060 (3) 0.051 (3) 0.047 (3) 0.007 (2) −0.034 (3) −0.020 (3)

C37 0.043 (3) 0.069 (3) 0.061 (4) 0.015 (2) −0.030 (3) −0.032 (3)

C38 0.038 (3) 0.051 (3) 0.042 (3) 0.007 (2) −0.009 (2) −0.024 (2)

Zn1—O2 2.056 (2) C16—C17 1.381 (5)

Zn1—N5 2.076 (3) C17—C18 1.371 (5)

Zn1—N2 2.082 (3) C18—C19 1.380 (5)

Zn1—O1 2.104 (3) N4—C24 1.335 (4)

Zn1—N4 2.210 (3) N4—C20 1.337 (4)

Zn1—N1 2.213 (3) C20—C21 1.387 (5)

N1—C1 1.336 (5) C21—C22 1.376 (5)

N1—C5 1.347 (5) C22—C23 1.377 (5)

C1—C2 1.380 (5) C23—C24 1.399 (4)

C2—C3 1.362 (6) C24—C25 1.500 (5)

C3—C4 1.380 (6) C25—N5 1.293 (4)

C4—C5 1.398 (5) C25—C26 1.481 (5)

C5—C6 1.481 (5) C26—C31 1.390 (5)

C6—N2 1.304 (4) C26—C27 1.390 (5)

C6—C7 1.477 (5) C27—C28 1.374 (5)

C7—C12 1.380 (5) C28—C29 1.374 (5)

C7—C8 1.383 (5) C29—C30 1.381 (5)

C8—C9 1.374 (6) C30—C31 1.379 (5)

C9—C10 1.369 (6) N5—N6 1.383 (4)

C10—C11 1.377 (5) N6—C32 1.352 (4)

C11—C12 1.380 (5) O2—C32 1.264 (4)

N2—N3 1.359 (4) C32—C33 1.493 (5)

N3—C13 1.367 (4) C33—C34 1.381 (5)

O1—C13 1.271 (4) C33—C38 1.391 (5)

C13—C14 1.485 (5) C34—C35 1.393 (5)

C14—C15 1.381 (5) C35—C36 1.374 (6)

C14—C19 1.392 (4) C36—C37 1.366 (6)

C15—C16 1.377 (5) C37—C38 1.384 (5)

O2—Zn1—N2 116.05 (11) C19—C14—C13 119.9 (4)

N5—Zn1—N2 166.85 (12) C16—C15—C14 121.1 (4)

O2—Zn1—O1 96.25 (10) C15—C16—C17 119.7 (4)

N5—Zn1—O1 110.24 (11) C18—C17—C16 120.1 (4)

N2—Zn1—O1 75.31 (11) C17—C18—C19 120.1 (4)

O2—Zn1—N4 150.25 (11) C18—C19—C14 120.6 (4)

N5—Zn1—N4 74.49 (11) C24—N4—C20 118.4 (3)

N2—Zn1—N4 93.66 (11) C24—N4—Zn1 113.7 (2)

O1—Zn1—N4 92.40 (10) C20—N4—Zn1 126.8 (3)

O2—Zn1—N1 91.39 (10) N4—C20—C21 123.6 (4)

N5—Zn1—N1 100.82 (12) C22—C21—C20 117.5 (4)

N2—Zn1—N1 74.28 (13) C21—C22—C23 120.0 (4)

O1—Zn1—N1 148.93 (11) C22—C23—C24 118.8 (4)

N4—Zn1—N1 95.73 (11) N4—C24—C23 121.7 (3)

C1—N1—C5 118.0 (3) N4—C24—C25 116.0 (3)

C1—N1—Zn1 128.3 (3) C23—C24—C25 122.4 (3)

C5—N1—Zn1 113.6 (3) N5—C25—C26 127.1 (4)

N1—C1—C2 123.9 (4) N5—C25—C24 112.9 (4)

C3—C2—C1 117.4 (4) C26—C25—C24 119.9 (3)

C2—C3—C4 120.9 (4) C31—C26—C27 117.8 (4)

C3—C4—C5 118.1 (4) C31—C26—C25 121.1 (4)

N1—C5—C4 121.6 (4) C27—C26—C25 121.0 (4)

N1—C5—C6 116.6 (3) C28—C27—C26 121.1 (4)

C4—C5—C6 121.7 (4) C27—C28—C29 120.5 (4)

N2—C6—C7 126.1 (4) C28—C29—C30 119.3 (4)

N2—C6—C5 112.7 (4) C31—C30—C29 120.3 (4)

C7—C6—C5 121.2 (3) C30—C31—C26 120.9 (4)

C12—C7—C8 117.4 (4) C25—N5—N6 120.7 (3)

C12—C7—C6 122.0 (4) C25—N5—Zn1 122.1 (3)

C8—C7—C6 120.5 (3) N6—N5—Zn1 117.1 (2)

C9—C8—C7 121.1 (4) C32—N6—N5 107.6 (3)

C10—C9—C8 120.8 (4) C32—O2—Zn1 112.7 (2)

C9—C10—C11 119.2 (4) O2—C32—N6 126.4 (3)

C10—C11—C12 119.7 (4) O2—C32—C33 118.0 (3)

C7—C12—C11 121.8 (4) N6—C32—C33 115.6 (4)

C6—N2—N3 119.2 (3) C34—C33—C38 118.9 (4)

C6—N2—Zn1 121.6 (3) C34—C33—C32 123.0 (4)

N3—N2—Zn1 118.5 (2) C38—C33—C32 118.1 (4)

N2—N3—C13 107.6 (3) C33—C34—C35 120.7 (4)

C13—O1—Zn1 111.2 (2) C36—C35—C34 119.1 (5)

O1—C13—N3 126.7 (4) C37—C36—C35 121.0 (4)

O1—C13—C14 118.3 (3) C36—C37—C38 119.9 (4)

N3—C13—C14 114.9 (4) C37—C38—C33 120.3 (4)

C15—C14—C19 118.4 (4)

Complex 2 Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Computing Details

Data collection: Bruker SMART; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: Bruker SHELXTL; molecular graphics: Bruker SHELXTL; software used to prepare material for publica- tion: Bruker SHELXTL.

(kbkno7-m) Crystal Data

C

H

N

NiO

M

= 659.37 Triclinic, P1 a = 10.7854 (5) Å b = 12.3971 (5) Å c = 12.6910 (6) Å α = 66.726 (1)°

β = 83.472 (1)°

γ = 82.652 (1)°

V = 1542.28 (12) Å

Z = 2

F(000) = 684 D

= 1.420 Mg m

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3510 reflections θ = 2.5–27.2

µ = 0.68 mm

T = 200 K Rod, brown

0.47 × 0.17 × 0.09 mm Data Collection

CCD area detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator

phi and ω scans

11603 measured reflections 7545 independent reflections 4017 reflections with I > 2σ(I)

R

= 0.046

θ

= 28.3

, θ

= 1.8

h = −14→14

k = −16→16 l = −16→10 Refinement

Refinement on F

Least-squares matrix: full R[F

> 2 σ(F

)] = 0.069 wR(F2) = 0.171 S = 1.09

Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained

7545 reflections 424 parameters 0 restraints

Primary atom site location: structure-invariant direct methods w = 1/[σ

(F

) + (0.P)

+ 4.3547P]

where P = (F

+ 2F

)/3 (∆/σ)

< 0.001

∆ρ

= 1.27 e Å

∆ρ

= −2.11 e Å

Special Details

Geometry: All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full cova- riance matrix. The cell esds are taken into account indi- vidually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry.

An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement: Refinement of F

against ALL reflections.

The weighted R-factor wR and goodness of fit S are based on F

, conventional R-factors R are based on F, with F set to zero for negative F

. The threshold expression of F

>

2sigma (F

) is used only for calculating R-factors (gt) etc.

and is not relevant to the choice of reflections for refine-

ment. R-factors based on F

are statistically about twice as

large as those based on F, and R-factors based on ALL data

will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å

)

x y z Uiso*/Ueq

Ni1 0.70489 (6) 0.70530 (6) 0.66286 (6) 0.02691 (18)

N1 0.6442 (4) 0.5334 (4) 0.7460 (4) 0.0300 (10)

C1 0.5896 (5) 0.4842 (5) 0.8503 (5) 0.0370 (14)

H1 0.5680 0.5303 0.8954 0.044*

C2 0.5627 (5) 0.3671 (5) 0.8962 (5) 0.0424 (15)

H2 0.5222 0.3339 0.9709 0.051*

C3 0.5961 (6) 0.3005 (5) 0.8310 (5) 0.0473 (16)

H3 0.5795 0.2200 0.8608 0.057*

C4 0.6540 (5) 0.3511 (5) 0.7217 (5) 0.0400 (15)

H4 0.6769 0.3060 0.6758 0.048*

C5 0.6778 (4) 0.4685 (4) 0.6805 (5) 0.0261 (11)

C6 0.7422 (5) 0.5290 (4) 0.5674 (5) 0.0303 (12)

C7 0.7633 (5) 0.4756 (4) 0.4804 (5) 0.0308 (13)

C8 0.8781 (5) 0.4189 (5) 0.4615 (5) 0.0392 (14)

H8 0.9462 0.4149 0.5045 0.047*

C9 0.8946 (6) 0.3682 (5) 0.3814 (5) 0.0461 (16)

H9 0.9741 0.3305 0.3692 0.055*

C10 0.7969 (6) 0.3718 (5) 0.3187 (5) 0.0447 (16)

H10 0.8082 0.3365 0.2637 0.054*

C11 0.6829 (6) 0.4272 (6) 0.3372 (6) 0.0474 (17)

H11 0.6148 0.4296 0.2947 0.057*

C12 0.6653 (5) 0.4791 (5) 0.4162 (5) 0.0419 (15)

H12 0.5858 0.5177 0.4271 0.050*

N2 0.7770 (4) 0.6305 (3) 0.5527 (4) 0.0262 (10)

N3 0.8416 (4) 0.6977 (4) 0.4544 (4) 0.0285 (10)

O1 0.8102 (3) 0.8339 (3) 0.5412 (3) 0.0293 (8)

C13 0.8593 (5) 0.8001 (5) 0.4617 (5) 0.0307 (12)

C14 0.9459 (5) 0.8751 (4) 0.3723 (5) 0.0287 (12)

C15 1.0128 (5) 0.8371 (5) 0.2912 (5) 0.0360 (14)

H15 0.9986 0.7633 0.2904 0.043*

C16 1.0998 (5) 0.9045 (5) 0.2115 (5) 0.0428 (15)

H16 1.1441 0.8776 0.1560 0.051*

C17 1.1215 (5) 1.0110 (5) 0.2134 (5) 0.0393 (14)

H17 1.1826 1.0568 0.1602 0.047*

C18 1.0552 (5) 1.0514 (5) 0.2922 (5) 0.0356 (13)

H18 1.0693 1.1255 0.2921 0.043*

C19 0.9679 (5) 0.9837 (4) 0.3713 (5) 0.0313 (12)

H19 0.9226 1.0118 0.4254 0.038*

N4 0.5420 (4) 0.7836 (3) 0.5761 (4) 0.0266 (10)

C20 0.5176 (5) 0.7909 (5) 0.4729 (5) 0.0310 (12)

H20 0.5725 0.7475 0.4367 0.037*

C21 0.4145 (5) 0.8598 (5) 0.4161 (5) 0.0358 (13)

H21 0.3980 0.8624 0.3431 0.043*

C22 0.3368 (5) 0.9242 (5) 0.4687 (5) 0.0337 (13)

H22 0.2656 0.9720 0.4323 0.040*

C23 0.3634 (5) 0.9186 (4) 0.5740 (5) 0.0302 (12)

H23 0.3125 0.9651 0.6094 0.036*

C24 0.4639 (4) 0.8456 (4) 0.6286 (4) 0.0235 (11)

C25 0.5003 (4) 0.8330 (4) 0.7430 (5) 0.0262 (12)

Atomic displacement parameters (Å

)

C26 0.4166 (5) 0.8851 (4) 0.8135 (4) 0.0281 (12)

C27 0.2900 (5) 0.8629 (5) 0.8355 (5) 0.0353 (13)

H27 0.2606 0.8085 0.8106 0.042*

C28 0.2077 (5) 0.9193 (5) 0.8929 (5) 0.0420 (15)

H28 0.1227 0.9019 0.9087 0.050*

C29 0.2478 (6) 1.0003 (5) 0.9273 (5) 0.0422 (15)

H29 0.1899 1.0423 0.9628 0.051*

C30 0.3732 (5) 1.0202 (5) 0.9098 (5) 0.0389 (14)

H30 0.4018 1.0741 0.9358 0.047*

C31 0.4572 (5) 0.9623 (4) 0.8548 (5) 0.0317 (12)

H31 0.5434 0.9753 0.8450 0.038*

N5 0.6113 (4) 0.7791 (3) 0.7668 (4) 0.0267 (10)

N6 0.6636 (4) 0.7602 (4) 0.8675 (3) 0.0253 (9)

O2 0.8278 (3) 0.6693 (3) 0.7882 (3) 0.0296 (8)

C32 0.7781 (5) 0.7032 (4) 0.8672 (5) 0.0260 (11)

C33 0.8531 (5) 0.6795 (4) 0.9662 (5) 0.0289 (12)

C34 0.8005 (5) 0.6908 (5) 1.0669 (5) 0.0357 (13)

H34 0.7137 0.7148 1.0732 0.043*

C35 0.8729 (6) 0.6675 (5) 1.1578 (5) 0.0446 (15)

H35 0.8359 0.6746 1.2266 0.054*

C36 0.9993 (6) 0.6337 (5) 1.1482 (6) 0.0486 (17)

H36 1.0494 0.6175 1.2106 0.058*

C37 1.0530 (6) 0.6236 (5) 1.0485 (6) 0.0479 (17)

H37 1.1402 0.6010 1.0420 0.058*

C38 0.9801 (5) 0.6464 (5) 0.9578 (5) 0.0400 (14)

H38 1.0176 0.6392 0.8891 0.048*

U¹¹ U²² U³³ U¹² U¹³ U²³

Ni1 0.0265 (4) 0.0265 (4) 0.0275 (4) −0.0013 (3) −0.0007 (3) −0.0108 (3)

N1 0.026 (2) 0.032 (2) 0.033 (3) −0.0042 (19) 0.001 (2) −0.015 (2)

C1 0.036 (3) 0.038 (3) 0.031 (3) −0.012 (3) 0.010 (3) −0.007 (3)

C2 0.045 (4) 0.039 (3) 0.036 (4) −0.004 (3) −0.003 (3) −0.008 (3)

C3 0.056 (4) 0.033 (3) 0.044 (4) −0.013 (3) 0.002 (3) −0.004 (3)

C4 0.048 (4) 0.028 (3) 0.042 (4) −0.006 (3) 0.002 (3) −0.012 (3)

C5 0.023 (3) 0.025 (3) 0.030 (3) −0.005 (2) −0.004 (2) 0.008 (2)

C6 0.019 (3) 0.029 (3) 0.041 (3) −0.003 (2) −0.002 (2) 0.011 (3)

C7 0.027 (3) 0.026 (3) 0.038 (3) −0.004 (2) 0.003 (3) 0.011 (3)

C8 0.034 (3) 0.039 (3) 0.048 (4) 0.002 (3) −0.009 (3) 0.020 (3)

C9 0.052 (4) 0.044 (4) 0.048 (4) 0.010 (3) −0.009 (3) 0.026 (3)

C10 0.054 (4) 0.049 (4) 0.040 (4) −0.014 (3) 0.005 (3) 0.026 (3)

C11 0.037 (4) 0.070 (5) 0.053 (4) −0.021 (3) 0.003 (3) 0.040 (4)

C12 0.023 (3) 0.055 (4) 0.054 (4) −0.003 (3) −0.002 (3) 0.028 (3)

N2 0.026 (2) 0.021 (2) 0.033 (3) −0.0023 (18) 0.003 (2) 0.013 (2)

N3 0.031 (2) 0.028 (2) 0.022 (2) −0.0091 (19) 0.006 (2) 0.0042 (19)

O1 0.040 (2) 0.0188 (18) 0.024 (2) −0.0086 (15) 0.0087 (17) 0.0043 (16)

C13 0.028 (3) 0.033 (3) 0.036 (3) −0.003 (2) 0.001 (3) 0.020 (3)

C14 0.027 (3) 0.030 (3) 0.028 (3) −0.002 (2) 0.002 (2) 0.012 (2)

C15 0.044 (3) 0.030 (3) 0.033 (3) −0.009 (3) 0.010 (3) 0.013 (3)

C16 0.043 (4) 0.042 (4) 0.041 (4) −0.007 (3) 0.014 (3) 0.018 (3)

C17 0.033 (3) 0.041 (3) 0.042 (4) −0.008 (3) 0.003 (3) 0.014 (3)

C18 0.038 (3) 0.032 (3) 0.041 (4) −0.012 (3) −0.001 (3) 0.016 (3)

Geometric parameters (Å, º) for (kbkno7-m)

C19 0.032 (3) 0.033 (3) 0.032 (3) −0.009 (2) −0.001 (3) −0.014 (3)

N4 0.027 (2) 0.024 (2) 0.029 (2) 0.0004 (18) −0.004 (2) −0.011 (2)

C20 0.036 (3) 0.036 (3) 0.028 (3) 0.001 (2) −0.012 (2) −0.018 (3)

C21 0.038 (3) 0.038 (3) 0.033 (3) −0.005 (3) −0.002 (3) −0.015 (3)

C22 0.032 (3) 0.038 (3) 0.029 (3) 0.000 (2) −0.013 (3) −0.009 (3)

C23 0.030 (3) 0.027 (3) 0.035 (3) 0.002 (2) −0.009 (2) −0.013 (3)

C24 0.021 (3) 0.022 (3) 0.023 (3) −0.002 (2) 0.003 (2) −0.005 (2)

C25 0.018 (2) 0.028 (3) 0.034 (3) 0.006 (2) 0.003 (2) −0.018 (2)

C26 0.032 (3) 0.027 (3) 0.025 (3) 0.002 (2) −0.009 (2) −0.009 (2)

C27 0.028 (3) 0.043 (3) 0.036 (3) −0.002 (3) −0.001 (3) −0.017 (3)

C28 0.029 (3) 0.053 (4) 0.042 (4) 0.003 (3) 0.003 (3) −0.020 (3)

C29 0.048 (4) 0.044 (4) 0.034 (3) 0.009 (3) 0.001 (3) −0.019 (3)

C30 0.044 (4) 0.038 (3) 0.041 (4) −0.001 (3) 0.004 (3) −0.025 (3)

C31 0.032 (3) 0.031 (3) 0.031 (3) −0.005 (2) −0.001 (2) −0.010 (3)

N5 0.026 (2) 0.028 (2) 0.032 (3) −0.0011 (18) −0.001 (2) −0.020 (2)

N6 0.027 (2) 0.032 (2) 0.022 (2) −0.0006 (19) −0.0063 (19) −0.016 (2)

O2 0.0259 (19) 0.034 (2) 0.029 (2) 0.0034 (16) −0.0105 (16) −0.0122 (17)

C32 0.025 (3) 0.023 (3) 0.030 (3) −0.003 (2) 0.005 (2) −0.011 (2)

C33 0.034 (3) 0.021 (3) 0.031 (3) −0.002 (2) −0.004 (2) −0.008 (2)

C34 0.033 (3) 0.041 (3) 0.033 (3) −0.005 (3) −0.002 (3) −0.014 (3)

C35 0.053 (4) 0.054 (4) 0.031 (3) −0.003 (3) −0.012 (3) −0.019 (3)

C36 0.056 (4) 0.042 (4) 0.051 (4) 0.004 (3) −0.026 (3) −0.018 (3)

C37 0.038 (4) 0.056 (4) 0.059 (4) 0.008 (3) −0.021 (3) −0.031 (4)

C38 0.036 (3) 0.048 (4) 0.035 (3) 0.006 (3) −0.011 (3) −0.015 (3)

Ni1—N2 2.002 (4) C16—C17 1.381 (8)

Ni1—N5 2.003 (4) C17—C18 1.379 (7)

Ni1—O2 2.063 (3) C18—C19 1.385 (7)

Ni1—O1 2.082 (3) N4—C20 1.332 (6)

Ni1—N4 2.098 (4) N4—C24 1.362 (6)

Ni1—N1 2.122 (4) C20—C21 1.392 (7)

N1—C1 1.322 (6) C21—C22 1.382 (7)

N1—C5 1.364 (6) C22—C23 1.372 (7)

C1—C2 1.389 (7) C23—C24 1.377 (7)

C2—C3 1.376 (8) C24—C25 1.490 (7)

C3—C4 1.387 (8) C25—N5 1.299 (6)

C4—C5 1.386 (7) C25—C26 1.468 (7)

C5—C6 1.470 (7) C26—C31 1.392 (7)

C6—N2 1.296 (6) C26—C27 1.402 (7)

C6—C7 1.480 (7) C27—C28 1.379 (7)

C7—C8 1.388 (7) C28—C29 1.374 (8)

C7—C12 1.392 (7) C29—C30 1.383 (8)

C8—C9 1.376 (8) C30—C31 1.382 (7)

C9—C10 1.377 (8) N5—N6 1.378 (5)

C10—C11 1.373 (8) N6—C32 1.343 (6)

C11—C12 1.375 (8) O2—C32 1.273 (6)

N2—N3 1.366 (5) C32—C33 1.482 (7)

N3—C13 1.348 (6) C33—C38 1.383 (7)

O1—C13 1.277 (6) C33—C34 1.389 (7)

C13—C14 1.475 (7) C34—C35 1.382 (7)

C14—C15 1.390 (7) C35—C36 1.380 (8)

C14—C19 1.391 (7) C36—C37 1.375 (8)

C15—C16 1.385 (7) C37—C38 1.385 (8)

N2—Ni1—N5 172.66 (18) C15—C14—C13 121.2 (5)

N2—Ni1—O2 109.62 (16) C19—C14—C13 120.4 (5)

N5—Ni1—O2 77.08 (16) C16—C15—C14 121.3 (5)

N2—Ni1—O1 76.76 (15) C17—C16—C15 119.3 (5)

N5—Ni1—O1 106.40 (15) C18—C17—C16 120.4 (5)

O2—Ni1—O1 92.81 (14) C17—C18—C19 119.9 (5)

N2—Ni1—N4 95.11 (17) C18—C19—C14 120.8 (5)

N5—Ni1—N4 78.33 (17) C20—N4—C24 119.3 (4)

O2—Ni1—N4 155.20 (15) C20—N4—Ni1 127.3 (4)

O1—Ni1—N4 91.10 (15) C24—N4—Ni1 112.8 (3)

N2—Ni1—N1 78.55 (17) N4—C20—C21 122.3 (5)

N5—Ni1—N1 98.72 (17) C22—C21—C20 118.2 (5)

O2—Ni1—N1 90.59 (15) C23—C22—C21 119.4 (5)

O1—Ni1—N1 154.77 (15) C22—C23—C24 120.1 (5)

N4—Ni1—N1 96.21 (16) N4—C24—C23 120.6 (5)

C1—N1—C5 120.0 (5) N4—C24—C25 115.2 (4)

C1—N1—Ni1 128.8 (4) C23—C24—C25 124.2 (5)

C5—N1—Ni1 111.0 (3) N5—C25—C26 126.5 (5)

N1—C1—C2 122.2 (6) N5—C25—C24 113.2 (4)

C3—C2—C1 118.5 (6) C26—C25—C24 120.2 (4)

C2—C3—C4 119.8 (5) C31—C26—C27 118.0 (5)

C5—C4—C3 119.0 (6) C31—C26—C25 121.9 (5)

N1—C5—C4 120.5 (5) C27—C26—C25 120.0 (5)

N1—C5—C6 116.4 (4) C28—C27—C26 120.8 (5)

C4—C5—C6 123.1 (5) C29—C28—C27 120.5 (6)

N2—C6—C5 114.0 (5) C28—C29—C30 119.4 (5)

N2—C6—C7 124.6 (5) C31—C30—C29 120.6 (5)

C5—C6—C7 121.4 (4) C30—C31—C26 120.6 (5)

C8—C7—C12 118.0 (5) C25—N5—N6 122.5 (4)

C8—C7—C6 122.2 (5) C25—N5—Ni1 119.7 (4)

C12—C7—C6 119.8 (5) N6—N5—Ni1 117.5 (3)

C9—C8—C7 121.0 (6) C32—N6—N5 108.7 (4)

C8—C9—C10 120.6 (6) C32—O2—Ni1 111.0 (3)

C11—C10—C9 118.8 (6) O2—C32—N6 125.3 (5)

C10—C11—C12 121.2 (6) O2—C32—C33 117.6 (4)

C11—C12—C7 120.4 (5) N6—C32—C33 117.1 (4)

C6—N2—N3 122.2 (4) C38—C33—C34 118.7 (5)

C6—N2—Ni1 118.5 (4) C38—C33—C32 119.0 (5)

N3—N2—Ni1 118.2 (3) C34—C33—C32 122.2 (5)

C13—N3—N2 108.7 (4) C35—C34—C33 120.8 (5)

C13—O1—Ni1 110.6 (3) C36—C35—C34 119.7 (6)

O1—C13—N3 125.0 (5) C37—C36—C35 120.2 (6)

O1—C13—C14 118.7 (4) C36—C37—C38 120.0 (6)

N3—C13—C14 116.3 (5) C33—C38—C37 120.6 (6)

C15—C14—C19 118.2 (5)

Complex 3 Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Computing Details

Data collection: Bruker SMART; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: Bruker SHELXTL; molecular graphics: Bruker SHELXTL; software used to prepare material for publica- tion: Bruker SHELXTL.

(kbkno2-ma) Crystal Data

C

H

N

NiO

·CH

O·ClO

M

= 666.73

Monoclinic, P2

/n a = 8.6475 (16) Å b = 10.625 (2) Å c = 33.376 (6) Å β = 96.438 (4)

V = 3047.3 (10) Å

Z = 4

F(000) = 1380 D

= 1.453 Mg m

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4723 reflections θ = 2.3–23.9

µ = 0.78 mm

T = 296 K Block, orange

0.26 × 0.25 × 0.13 mm Data Collection

CCD area detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator

phi and ω scans

Absorption correction: multi-scan Bruker SADABS T

= 0.814, T

= 0.901

22130 measured reflections 7523 independent reflections

4094 reflections with I > 2σ(I) R

= 0.064

θ

= 28.3

, θmin = 1.2

h = −10→11

k = −14→13 l = −44→39 Refinement

Refinement on F

Least-squares matrix: full R[F

> 2 σ(F

)] = 0.052 wR(F

) = 0.162

S = 1.10

Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained

7523 reflections 401 parameters 0 restraints

Primary atom site location: structure-invariant direct methods w = 1/[σ

(F

) + (0.0638P)

]

where P = (F

+ 2F

)/3 ( ∆/σ)

= 0.001

∆ρ

= 0.65 e Å

∆ρ

= −0.62 e Å

Special Details

Geometry: All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full cova- riance matrix. The cell esds are taken into account indi- vidually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry.

An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement: Refinement of F

against ALL reflections.

The weighted R-factor wR and goodness of fit S are based on F

, conventional R-factors R are based on F, with F set to zero for negative F

. The threshold expression of F

>

2sigma (F

) is used only for calculating R-factors (gt) etc.

and is not relevant to the choice of reflections for refine-

ment. R-factors based on F

are statistically about twice as

large as those based on F, and R-factors based on ALL data

will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å

)

x y z Uiso*/Ueq

Ni1 0.76581 (5) 0.85448 (4) 0.851529 (13) 0.03297 (16)

N1 0.9876 (3) 0.7819 (3) 0.84685 (9) 0.0349 (7)

C1 1.1149 (4) 0.7895 (3) 0.87332 (11) 0.0425 (9)

H1 1.1085 0.8312 0.8976 0.051*

C2 1.2563 (4) 0.7377 (4) 0.86608 (12) 0.0444 (10)

H2 1.3432 0.7445 0.8851 0.053*

C3 1.2652 (4) 0.6764 (3) 0.83040 (12) 0.0449 (10)

H3 1.3586 0.6405 0.8249 0.054*

C4 1.1341 (4) 0.6680 (3) 0.80237 (11) 0.0381 (9)

H4 1.1387 0.6261 0.7781 0.046*

C5 0.9971 (4) 0.7226 (3) 0.81107 (10) 0.0318 (8)

C6 0.8529 (4) 0.7248 (3) 0.78254 (10) 0.0333 (8)

C7 0.8386 (5) 0.6560 (4) 0.74323 (12) 0.0519 (11)

H7A 0.7366 0.6693 0.7293 0.078*

H7B 0.8548 0.5677 0.7481 0.078*

H7C 0.9153 0.6870 0.7270 0.078*

N2 0.7427 (3) 0.7903 (3) 0.79538 (8) 0.0341 (7)

N3 0.6006 (3) 0.8060 (3) 0.77228 (9) 0.0368 (7)

O1 0.5466 (3) 0.9179 (2) 0.82902 (7) 0.0379 (6)

C8 0.5094 (4) 0.8750 (3) 0.79318 (11) 0.0327 (8)

C9 0.3527 (4) 0.9040 (3) 0.77223 (11) 0.0346 (8)

C10 0.3000 (4) 0.8515 (3) 0.73488 (11) 0.0415 (9)

H10 0.3662 0.7999 0.7221 0.050*

C11 0.1519 (5) 0.8744 (4) 0.71651 (12) 0.0514 (11)

H11 0.1196 0.8398 0.6914 0.062*

C12 0.0515 (5) 0.9489 (4) 0.73557 (13) 0.0523 (11)

H12 0.0497 0.9621 0.7237 0.063*

C13 0.1009 (5) 1.0036 (4) 0.77217 (13) 0.0506 (11)

H13 0.0343 1.0560 0.7845 0.061*

C14 0.2498 (4) 0.9807 (3) 0.79056 (12) 0.0426 (9)

H14 0.2818 1.0169 0.8155 0.051*

N4 0.6933 (3) 0.6932 (3) 0.88117 (9) 0.0362 (7)

C15 0.6612 (5) 0.5795 (3) 0.86543 (12) 0.0469 (10)

H15 0.6649 0.5682 0.8379 0.056*

C16 0.6227 (5) 0.4778 (4) 0.88812 (15) 0.0612 (13)

H16 0.6018 0.3997 0.8762 0.073*

C17 0.6160 (6) 0.4945 (4) 0.92853 (15) 0.0678 (13)

H17 0.5891 0.4279 0.9444 0.081*

C18 0.6495 (5) 0.6113 (4) 0.94539 (13) 0.0566 (12)

H18 0.6460 0.6241 0.9728 0.068*

C19 0.6882 (4) 0.7091 (3) 0.92117 (11) 0.0369 (9)

C20 0.7311 (4) 0.8364 (3) 0.93698 (10) 0.0382 (9)

C21 0.7284 (5) 0.8715 (4) 0.98005 (12) 0.0576 (12)

H21A 0.8117 0.9292 0.9880 0.086*

H21B 0.7409 0.7973 0.9965 0.086*

H21C 0.6308 0.9108 0.9835 0.086*

N5 0.7716 (3) 0.9106 (3) 0.90938 (8) 0.0348 (7)

N6 0.8223 (3) 1.0323 (3) 0.91769 (8) 0.0373 (7)

O2 0.8600 (3) 1.0421 (2) 0.85147 (7) 0.0400 (6)

Atomic displacement parameters (Å

)

C22 0.8695 (4) 1.0934 (3) 0.88519 (11) 0.0352 (8)

C23 0.9375 (5) 1.2196 (3) 0.89226 (12) 0.0412 (9)

C24 0.9850 (5) 1.2659 (4) 0.93047 (14) 0.0611 (12)

H24 0.9714 1.2167 0.9529 0.073*

C25 1.0517 (6) 1.3831 (5) 0.93602 (16) 0.0776 (16)

H25 1.0794 1.4137 0.9619 0.093*

C26 1.0767 (7) 1.4539 (4) 0.90360 (19) 0.0878 (18)

H26 1.1249 1.5319 0.9071 0.105*

C27 1.0304 (7) 1.4093 (5) 0.86533 (18) 0.0879 (18)

H27 1.0461 1.4585 0.8431 0.105*

C28 0.9610 (6) 1.2927 (4) 0.85955 (14) 0.0644 (13)

H28 0.9302 1.2638 0.8336 0.077*

Cl1 0.26125 (15) 0.78206 (12) 0.98304 (3) 0.0666 (4)

O3 0.3493 (5) 0.8458 (4) 0.95587 (11) 0.1065 (14)

O4 0.2682 (7) 0.6541 (4) 0.97618 (14) 0.154 (2)

O5 0.1085 (5) 0.8255 (5) 0.97684 (13) 0.145 (2)

O6 0.3214 (4) 0.8091 (3) 1.02382 (9) 0.0823 (11)

C29 0.4041 (7) 0.1405 (6) 0.89468 (19) 0.107 (2)

H29A 0.4636 0.1340 0.9207 0.160*

H29B 0.3473 0.0639 0.8888 0.160*

H29C 0.3326 0.2096 0.8947 0.160*

O7 0.5067 (5) 0.1615 (3) 0.86465 (13) 0.0890 (11)

H7 0.5193 0.0954 0.8527 0.133*

U¹¹ U²² U³³ U¹² U¹³ U²³

Ni1 0.0366 (3) 0.0323 (3) 0.0298 (3) 0.0009 (2) 0.00291 (19) −0.0016 (2)

N1 0.0352 (17) 0.0362 (16) 0.0334 (17) 0.0040 (14) 0.0040 (13) 0.0009 (13)

C1 0.043 (2) 0.049 (2) 0.034 (2) −0.0001 (19) −0.0005 (17) 0.0014 (18)

C2 0.038 (2) 0.050 (2) 0.044 (2) 0.0024 (19) 0.0004 (18) 0.003 (2)

C3 0.035 (2) 0.042 (2) 0.059 (3) 0.0088 (17) 0.0078 (19) 0.006 (2)

C4 0.040 (2) 0.0332 (19) 0.042 (2) −0.0004 (17) 0.0105 (17) −0.0002 (16)

C5 0.036 (2) 0.0255 (17) 0.035 (2) −0.0002 (15) 0.0074 (16) −0.0003 (15)

C6 0.034 (2) 0.0285 (18) 0.038 (2) 0.0014 (16) 0.0059 (16) −0.0042 (15)

C7 0.050 (3) 0.060 (3) 0.045 (2) −0.004 (2) 0.0049 (19) −0.025 (2)

N2 0.0363 (17) 0.0335 (16) 0.0317 (17) −0.0012 (14) 0.0005 (13) 0.0003 (13) N3 0.0340 (17) 0.0401 (16) 0.0350 (17) 0.0025 (14) −0.0022 (14) −0.0039 (14)

O1 0.0401 (15) 0.0399 (14) 0.0333 (14) 0.0020 (12) 0.0027 (11) −0.0034 (11)

C8 0.033 (2) 0.0278 (18) 0.036 (2) 0.0030 (15) −0.0003 (16) 0.0032 (15)

C9 0.038 (2) 0.0311 (18) 0.036 (2) 0.0000 (16) 0.0082 (16) 0.0069 (16)

C10 0.044 (2) 0.045 (2) 0.035 (2) 0.0036 (19) −0.0005 (17) 0.0038 (18)

C11 0.056 (3) 0.058 (3) 0.039 (2) −0.005 (2) −0.002 (2) 0.004 (2)

C12 0.038 (2) 0.059 (3) 0.058 (3) 0.001 (2) −0.005 (2) 0.017 (2)

C13 0.045 (2) 0.046 (2) 0.061 (3) 0.007 (2) 0.005 (2) 0.009 (2)

C14 0.042 (2) 0.037 (2) 0.048 (2) 0.0017 (18) 0.0016 (18) 0.0053 (18)

N4 0.0359 (17) 0.0337 (15) 0.0388 (18) 0.0000 (14) 0.0034 (14) 0.0025 (14)

C15 0.051 (3) 0.035 (2) 0.054 (3) −0.0055 (19) 0.000 (2) −0.0050 (19)

C16 0.067 (3) 0.036 (2) 0.079 (4) −0.009 (2) 0.003 (3) −0.001 (2)

C17 0.086 (4) 0.046 (3) 0.072 (4) −0.012 (3) 0.010 (3) 0.018 (2)

C18 0.070 (3) 0.049 (3) 0.052 (3) −0.008 (2) 0.007 (2) 0.008 (2)

C19 0.034 (2) 0.034 (2) 0.043 (2) −0.0038 (16) 0.0047 (17) 0.0058 (17)

Geometric parameters (Å, º) for (kbkno2-ma)

C20 0.041 (2) 0.047 (2) 0.0268 (19) −0.0012 (18) 0.0046 (16) 0.0033 (17)

C21 0.078 (3) 0.057 (3) 0.039 (2) −0.007 (2) 0.011 (2) −0.001 (2)

N5 0.0401 (18) 0.0337 (16) 0.0306 (16) −0.0018 (14) 0.0033 (13) −0.0012 (13) N6 0.0456 (19) 0.0320 (16) 0.0341 (18) −0.0094 (14) 0.0038 (14) −0.0013 (13) O2 0.0536 (16) 0.0334 (13) 0.0336 (15) −0.0067 (12) 0.0076 (12) 0.0018 (11)

C22 0.034 (2) 0.0342 (19) 0.037 (2) −0.0034 (17) 0.0032 (16) −0.0011 (17)

C23 0.047 (2) 0.032 (2) 0.044 (2) −0.0028 (17) 0.0073 (18) −0.0007 (17)

C24 0.076 (3) 0.047 (2) 0.059 (3) −0.022 (2) 0.005 (2) 0.000 (2)

C25 0.098 (4) 0.065 (3) 0.069 (4) −0.036 (3) 0.004 (3) −0.017 (3)

C26 0.121 (5) 0.043 (3) 0.103 (5) −0.030 (3) 0.027 (4) −0.012 (3)

C27 0.123 (5) 0.053 (3) 0.093 (4) −0.029 (3) 0.037 (4) 0.016 (3)

C28 0.094 (4) 0.042 (2) 0.062 (3) −0.010 (2) 0.025 (3) 0.006 (2)

Cl1 0.0720 (8) 0.0836 (9) 0.0438 (7) 0.0007 (7) 0.0043 (6) −0.0169 (6)

O3 0.101 (3) 0.163 (4) 0.057 (2) −0.030 (3) 0.015 (2) 0.001 (2)

O4 0.259 (7) 0.086 (3) 0.116 (4) −0.019 (3) 0.010 (4) −0.055 (3)

O5 0.068 (3) 0.287 (7) 0.081 (3) 0.046 (4) 0.012 (2) 0.014 (3)

O6 0.109 (3) 0.088 (2) 0.046 (2) 0.003 (2) −0.0088 (18) −0.0150 (17)

C29 0.094 (5) 0.127 (6) 0.100 (5) 0.002 (4) 0.009 (4) −0.032 (4)

O7 0.104 (3) 0.060 (2) 0.102 (3) 0.004 (2) 0.008 (2) −0.017 (2)

Ni1—N2 1.983 (3) N4—C15 1.334 (4)

Ni1—N5 2.016 (3) N4—C19 1.352 (4)

Ni1—O1 2.072 (2) C15—C16 1.381 (6)

Ni1—N1 2.090 (3) C16—C17 1.368 (6)

Ni1—N4 2.109 (3) C17—C18 1.381 (6)

Ni1—O2 2.153 (2) C18—C19 1.380 (5)

N1—C1 1.334 (4) C19—C20 1.484 (5)

N1—C5 1.361 (4) C20—N5 1.291 (4)

C1—C2 1.386 (5) C20—C21 1.488 (5)

C2—C3 1.367 (5) N5—N6 1.383 (4)

C3—C4 1.389 (5) N6—C22 1.365 (4)

C4—C5 1.379 (5) O2—C22 1.245 (4)

C5—C6 1.482 (5) C22—C23 1.473 (5)

C6—N2 1.292 (4) C23—C28 1.373 (5)

C6—C7 1.494 (5) C23—C24 1.386 (5)

N2—N3 1.385 (4) C24—C25 1.376 (6)

N3—C8 1.331 (4) C25—C26 1.355 (7)

O1—C8 1.287 (4) C26—C27 1.379 (7)

C8—C9 1.486 (5) C27—C28 1.381 (6)

C9—C10 1.395 (5) Cl1—O4 1.382 (4)

C9—C14 1.397 (5) Cl1—O5 1.393 (4)

C10—C11 1.378 (5) Cl1—O3 1.420 (4)

C11—C12 1.382 (6) Cl1—O6 1.431 (3)

C12—C13 1.377 (5) C29—O7 1.428 (7)

C13—C14 1.384 (5)

N2—Ni1—N5 174.73 (12) C10—C11—C12 119.8 (4)

N2—Ni1—O1 77.17 (11) C13—C12—C11 120.1 (4)

N5—Ni1—O1 100.05 (11) C12—C13—C14 120.0 (4)

N2—Ni1—N1 78.39 (12) C13—C14—C9 121.0 (4)

N5—Ni1—N1 104.86 (11) C15—N4—C19 118.3 (3)

O1—Ni1—N1 154.59 (10) C15—N4—Ni1 127.7 (3)

N2—Ni1—N4 99.22 (12) C19—N4—Ni1 114.0 (2)

N5—Ni1—N4 76.58 (12) N4—C15—C16 123.0 (4)

O1—Ni1—N4 97.24 (11) C17—C16—C15 118.6 (4)

N1—Ni1—N4 93.38 (11) C16—C17—C18 119.2 (4)

N2—Ni1—O2 108.39 (10) C19—C18—C17 119.4 (4)

N5—Ni1—O2 76.00 (11) N4—C19—C18 121.5 (3)

O1—Ni1—O2 91.69 (10) N4—C19—C20 115.5 (3)

N1—Ni1—O2 89.50 (11) C18—C19—C20 123.0 (4)

N4—Ni1—O2 152.25 (11) N5—C20—C19 112.4 (3)

C1—N1—C5 118.9 (3) N5—C20—C21 124.8 (3)

C1—N1—Ni1 128.6 (3) C19—C20—C21 122.8 (3)

C5—N1—Ni1 112.5 (2) C20—N5—N6 122.2 (3)

N1—C1—C2 122.6 (4) C20—N5—Ni1 121.5 (2)

C3—C2—C1 118.5 (4) N6—N5—Ni1 116.2 (2)

C2—C3—C4 119.7 (4) C22—N6—N5 113.6 (3)

C5—C4—C3 119.1 (3) C22—O2—Ni1 113.0 (2)

N1—C5—C4 121.2 (3) O2—C22—N6 121.0 (3)

N1—C5—C6 115.3 (3) O2—C22—C23 121.9 (3)

C4—C5—C6 123.5 (3) N6—C22—C23 117.1 (3)

N2—C6—C5 113.2 (3) C28—C23—C24 118.4 (4)

N2—C6—C7 124.3 (3) C28—C23—C22 118.7 (4)

C5—C6—C7 122.5 (3) C24—C23—C22 122.9 (3)

C6—N2—N3 121.4 (3) C25—C24—C23 121.4 (4)

C6—N2—Ni1 119.9 (2) C26—C25—C24 119.8 (5)

N3—N2—Ni1 118.3 (2) C25—C26—C27 119.6 (5)

C8—N3—N2 108.4 (3) C26—C27—C28 120.9 (5)

C8—O1—Ni1 110.2 (2) C23—C28—C27 119.8 (5)

O1—C8—N3 125.6 (3) O4—Cl1—O5 111.1 (4)

O1—C8—C9 118.9 (3) O4—Cl1—O3 109.1 (3)

N3—C8—C9 115.5 (3) O5—Cl1—O3 108.3 (3)

C10—C9—C14 117.7 (3) O4—Cl1—O6 109.7 (3)

C10—C9—C8 121.8 (3) O5—Cl1—O6 108.2 (2)

C14—C9—C8 120.4 (3) O3—Cl1—O6 110.4 (2)

C11—C10—C9 121.4 (4)