The Crystal and Molecular Structure of Salicylaldehyde-4-morpholinothiosemicarbazone

DAEHAN HWAHAK HWOEJEE

(Journal of the Korean Chemical Society) Vol. 21, No. 1, 1977

Printed in Republic of Korea

결정 및 분자구조 具廷會 •金勳燮• 安里泰

서울대학교 자연과학대학 화학과

(1976.

10.

26

접수)

The Crystal and Molecular Structure of Salicylaldehyde-4-morpholinothiosemicarbazone

C. H. Koo, H. S. Kim and C. T. Ahn

Department of Chemistry^ College of Natural Sciences^

Seoul National University, Seoul, Korea

(Received

Oct.

26, 1976)

요 흐

E Salicylaldehyde-4-morpholinothiosemicarbazone, G2H15O2N3S,

결 정 은 직 각비 등축정 계 에 속 하며 공간군은

P

混

21

이다. 단위세포에는

4

개의 분자가 포함되며 세포 길이는

tz=LL85(5), 3=15.45 (5), 0=7.18(3) A

이 다. 농도는

multiple-film equi-inclination Weissenberg

사진으로 부터

3

차원적 농도 데 이 타를 얻 어 목측법 에 의 하여 측정 하였다. 결 정 구조는

Patterson

및

Fourier

법 으로 해 명 하였 으며 구조의 정 밀화는

block-diagonal

최 소자승법 으로 하였으며 & 값은

10M

개 의 반사에 대 하여

0.1L

이었다. 몰포린 고리는 의자형이며

1

분자내의 몰포린 고리와 황원자를제외한 원자들은 대략 한 평

면을 이룬다. 수산화기의 산소원자는 질소원자와

2.67A

의 거 리로

0—H…N

형 수소결합을 하고 있 고 분자간에는

van der Waals

접촉으로 연결되 어 있다.

ABSTRACT. Crystals of salicylaldehyde-4-morpholinothiosemicarbazone, C12H15O2N3S, are orthor­

hombic with space group Pna2i. Unit-cell dimensions are a=ll. 85(5), 3=15.45(5) c~7.18(3) A with z=4.

Three-dimensional intensity data were collected from the multiple-film equi-inclination Weissen­

berg photographs taken with CuKa radiation. The intensities were estimated visually. The structure was solved by Patterson and Fourier methods and refined by the block-diagonal least-squares me­

thods until the final R value becomes 0.11 for the 1064 observed independent reflections.

The morpholine ring has a chair form. The rest atoms of salicylaldehyde-4-morpholinothiosemi- carbazone molecule excluding morpholine ring and sulfur atom approximately lie on a plane. The hydroxyl group of the salicylaldehyde and the nitrogen atom of the thiosemicarbazone form an in­

tramolecular hydrogen bond, O—H…N, of 2. 67A. The short intermolecular distances all appear to be normal van der Waals contacts.

—3 —

4

_{具廷會,金} 勲 燮•安重泰

INTRODUCTION

A large number of a-(N) heterocyclic thio­

semicarbazones with definite carcinostatic activity were reported by French and Blanz1. Their hypothesis was that a thiosemicarbazone which could function as a tridentate

사

relate capable of forming octahedral complexes with metal ions would possess antitumor activity. The assump­

tion of French and Blanz regarding the

산

relating ability of thiosemicarbazone was confirmed by results of crystal structure analysis of

bis (iso-

quinoline-l-carboxaldehyde thiosemicarbazana- to) nickel (II) monohydrate by Mathew and Palenik2.

A comparison of the results of Palenik and coworker1 s3 structural studies on antitumor active 5-hydroxy~2-formylpyridine thiosemicarbazone sesquihydrate and inactive acetone thiosemicarba­

zone with the available structural data on other thiosemicarbazones suggested some generaliza­

tions regarding the electronic structures, com­

plexing abilities and biological activities of thio- semicarbazones.

Apparently a knowledge of conformation and bond lengths and angles which result from structure analysis could be much meaningful for the study of biological activity. Therefore, a crystal structure analysis of salicylaldehyde-4- morpholinothiosemicarbazone was undertaken as part of a program devoted to explain the rela­

tionship between three dimensional structure of thiosemicarbazone and its biological activities.

EXPERIMENTAL

A sample of salicylaldehyde-4-morpholinothio- semicarbazone was kindly provided by Y. S.

Chough at the College of Pharmacy, Seoul National University.

Crystals suitable for the determination of the unit-cell dimensions and for the measurement of

"一

NH-N=c"

/

\

the intensities were obtained by recrystallizing the dissolved crystals in a concentrated aqueous solution of

N,

JV^dimethylformamide. The density of single crystals was measured by the flotation method in a mixture of carbontetrachloride and benzene.

Cell dimensions were determined by least-' squares calibration from zero-layer Weissenberg photographs around

〔

010

〕

and C001J, calibration being made with superposed Al line.

Crystal data

Salicylaldehyde-4-morpholiothiosemicarbazone;

OH H I

丨

CT c=c/

! I H H Formula weight; 265. 34

Crystal system; orthorhombic

a=U.

85(5),

》=

15. 45(5),

c=7.

18(3) A 2 = 4

V=1314.6A3 ,

Dx~l.

34 g • cm-3

Dm = L

32 g-cm-3 Space group;

Pna2i

Systematic absences;

Okl

with

为

+Z=2

筮

+1 and

hOl

with

兀

=2

龙

+1.

Weissenberg photographs, using the multiple­

film technique, were taken with

CuKa

radiation, where the layers were from Oth to 6th about c-axis. Two layers, Oth and 1st, were taken about a-axis for scaling purposes. A total of 1064 independent reflections were recorded.

Intensties were estimated visually with a stan­

dard film strips and corrections were applied to the data for Lorentz and polarization effects as well as for spot shape, and reduced to the structure factors. No corrections were made for absorption. The structure factors of the various layers were put on a single scale by hand. An

Journal of the Korean Chemical Society

SalicylaIdehyde-4-morphelinothiosemicarbazones] 결정 및 분자구조 5 Table 1. Atomic positional parameters

and

anisotropic temperature factors

for

the non-hydrogen atoms

in salicylaldehyde-4-morpHolinothiosemicarbazone.

The

e.s.d?s are

given in

parentheses

in

units of the last decimal place.

(a) Positional

parameters

X y z

c(

1)

0. 016(3) -0.112(2)

0.448(2)

C(

2) -0. 073(3)

-0.163(2)

0. 347(3)

C(

3) 0.059(1)

-0. 253

⑴ 0.193(2)

C(

4) 0.157(3) -0.210(2)

0.302(2)

C( 5)

0. 202(1) -0.049(1) 0.

353(2)

C(

6) 0.499(1) -0. 025(1)

0.357(2)

C(

7)

0.

581(1) 0.045(1)

0. 336(2)

C(

8) 0.696(1) 0.

026(1) 0.367(3)

C( 9)

0.

784(3) 0.089(3)

0.

353(3)

C(10)

0.751(2)

0.176(2) 0.313(2)

C(ll)

0.

634(2) 0.201(2)

0. 274(2)

C(12)

0.553(1)

0.130(1) 0.290⑵

N( 1) 0.130(1) -o. 121(1) 0.362(2)

N(

2)

0.

316(1)

-0.075(1)

0. 342(2)

N(

3) 0. 394(1)

-0.008(1) 0.

322(2)

0(

1)

-0.041(1) -0.

2502(4)

0. 303 ⑴

0(

2)

0.442(1) 0.158(1) 0. 253(1)

s

0.1621(3)

0. 0554(2) 0.371(1)

(b) Anisotropic

temperature factors

The

anisotropic

temperature

factors

are

expressed in the form:

exp{

—(B11&2+B22

注+B3 丿

2

+ 2B12膈+2&3砂+

2

场 成/)}.

Values are

X10

5

and standard

deviations in parentheses refer

to

the least

significant

digits.

Bn b

2

^33 ■B12 ■®13 -B23

C

^⑴

1075(233)

652(176)

3300(432) -15(98) 141(230) 14(181)

c⑵ 1071(217)

637(169)

2874(391) -62(95)

21(217) -32(167)

c

⑶

975(112)

528(61)

2745(354) -87(76)

-138(170)

0(126)

c

⑷

1035(196) 709(151) 2419(413) -201 (88)

133(234)

22(130)

c

⑸

673(82) 511(50)

2465(290)

-5(53) -24(177) -158(129)

c

^{⑹ 596(70) 399(40)}

1868(241)

17(45) -125(144) -44(110)

c

⑺ 603(68) 422(42)

1830(287) -3(42)

34(115) 15(95)

c⑻

782(89) 494(49)

2166(287) 43(53) 239(197) 136(144)

c⑼ 967(208) 565(161) 3126(457)

32(88) -97(246) -136(160)

C(10)

1079(229) 591(167) 3570(459) -78(84)

-195(201)

18(159)

C(ll) 989(204)

450(155) 2442(417) 0(80) -202(251)

-30(145>

C(12) 696(89) 421(50),

2646(305) -13(56)

217(133) -86(106)

N

⑴ 733(61) 357(33)

1934(203)

2(38) -23(131)

11(95>

22) 580(63) 419(36)

1983(230) -1(36)

-16(107)

一

35 (82

〉

N

^{⑶ 851(74)} .

439( 驻 ) 2471(289) 7(49) -159(117)

107

(94>

O⑴ 563(48) 308(26)

1789(172)

-3(31)

-35( 72) -34(55)

0(2)

818(69) 499(39)

2565(221) 27(45)

-75(106) 35(80)

S 851(21)

503(12)

2595(71)

17(16)

0( 48) -17(36)

Vol. 21, No. 1,1977

Tabls 2. Observed ;and calcmlated structure factors.

H K L Fo Fc H K L Fo Fc H K L Fo Pc

0 2 54.4b 53.86 5 7 12.92 11

a

7.54 5.45

0 4 28.47 25.31 5 8 9.72 8.15 11

12

.1.87 2.83

0 6 19.45 16.00 5 12 5.09 6.91

1 고

0 2.41 2.10

0 8 4.65 5 14 i2・* 10.90

12 2

10.06

고

。

,

88

0 10 35.41 3*.b0 5 15 2.16 2・69

12

4 5.90 2.20

0 12 1.64 1.77 5 16 6.05 6・"

12

5 l.Tfl 1.46

0 16 9.03 11.17 5 17 3.69 4.45 12 8 11.27 11.16

0 18 0 1.93 0.94 5 16 0・65 0.65 12 10 1.62 2.31

1 1 0 29.32 29.93 6 0 21.85 22.14 13 1 4.64 4.93

1 2 0 74.85 74.45 6 2 0 30.50 32.98 13 4 女・65 5. 00

X

3 0 31.47 30.18 4 Q 11.56 10. 14 0 0 0.49 1.26

1

4 0 0.94 0,-66 6 0 3G.61 28.81 14 3 0 5.56 5.^4

1

5 0 51.02 49,93 7 g 21.29 13.20 14 5 0 3,27 3.8?

1

6 0 13.97 11.75 8 0 16.53 lb.77 14 B 0 1.73 1.44

2

7

0 29.77 28.17 9 0 13.84 12.11 15 ] 0 r・33 3.70

1 8 0 20.13 17.80 11 0 1.42 2.30 1 19.33 ie.9t

10 0 13.26 12.50 12 0 [4 . 12.66 3 ] _庭.36 62.22

1 11 0 5.45 3.94 6 14 o 4.63 3.37 0 5 1 e9“8 48.01

1 12 0 16.49 19.00 6 16 0 i.>7 2.43 0 7 1 61.36 60.91

1 13 0 6.96 7.19 b 17 0 5.86 6.2C 0 9 i 18« 65 19.C8

1 16 0 6.93 7.27 7 1 0 23.66 23.71 0 11 ] 10.66 9»94

1 17 0 6.42 6.99 7

2

0 7.11 6,48 0 13 1 17.84 19,42

1 19 0 4.01 3.96 7 5 0 11.30 1U.56 0 15 1 6.10 3.8 7

2 0 0 20・69 21.60 7 6 0 9.T1 10.47 0 17 1 7.31 9.12

2 1 0 14.74 14.57 7 8 0 12.7b 11.56 0 19 1 2.29 1.99

2

2

0 56.60 60.03 7 9 0 3.01 4,01 1

1

1 53.47

2 3 0 45.91 44.19 7 10 0 4.73 5.46 1 2 1 72.83 72.54

2 5 0 61.49 63.76 7 11 0 13.10 13.38 1 3 1 40-97 39.17

2 6 0 15.53 15.95 7 13 0 1.61 3.14 1 4 1 61.88 b 2.2 U

2 7 0 43.84 41.50 7 14 0 A.37 4.21 1 5 1 19.98 22,45

2

8 0 58.?fl

58.66

7 15 0 2.20 2.91 1

6

1 36.24 36.15

2 10 0 11.79 12,75 7 16 0 4M2 4,39 1 7 1 24 » Ob 23.27

2

11 0 10.95 10.3fl 7 17 0 0.6 7 5.k 1 a 1 9.24 10.4 0

2

12 0 -7・46 7.9

야

6 0 0 2^.11 25,07 1 g 1 9.06 12,36

2 13 0 8.50 7.4b 6 1 0 7.07 9"

。

1 10 1 10. uo 9.57

2 14 0 7.38 8.82 8 3 0 10.11 10.43 1 11 1 16.77 17.19

2 15 0 5.62 3.87 6 5 0 21,62 22.97 1 13 1 5« W % 34

2

17 0 4.35 3.30 8 & 0 13.74 13.72 1 15 1 11.77 10.21

2 18 0 3.74 e 8 0 6.bl 6.56 1 17 1 8.22 <1.99

3 1 0 55.x2 55.37 8 10 0 21.20 21.92 1 ia 1 3.97 3 .紬

3 2 0 26.81 25,48 e 11 0 15.05 12.89 1 19 1 4.67 4,68

3 4 0 16.64 14.66 8 12 0 5.46 6.01 2 0 1 73.63 73.06

3

5 0 7.27 7.44 8 13 0 4.77 4.58

2

1 1 43.00 42.96

3 6 0 11.37 9.63 8 14 0 1.41 1.11

2 2

1 33.81 33.03

3 7 0 12・68 11.07 8 15 0 fe.60 6.12

2

3 1 33.78 33.93

3 8 0 14.56 13.85 9 1 0 8.37 2G

2

4 1 13.74 11.25

3

9 0 20.25 22.34 9 2 0 3.09 2.78 2 5 1 39.06 39.27

3

10 0 29.17 26.68 9 3 0 22.15 23.00

2

6 1 26.71 24.85

3 11 0 27.96 25.91

느

4 0 28.76 28.18 2 7 1 7.66 5.07

3 12 0 4,94 5.lb 9 5 0 18.07 17.60 2 8 1 21.09 23.27

3 14 0 13.21 13.37 9 6 0 15・25 15.23 2 9 1 11.91 12.15

3 17 0 7.15 5・96 9 7 0 8.20 8.19

2

10 1 12.60 13.34

4 0 0 16.63 16,64 9 8 0 5.88 6.27 2 11 1 4.87

유.

38

4 1 0 7.31 5.54 9 9 0 4.15 5.11

2

12 1 40.08

4

2

0 17.59 10.63 9 11 0 4,17 2.50

2

13 1 lb.34 18.82

4 3 0 28.61 26,89 9 12 0 3.92 3.94

2 14

1 3.29 3.72

4 4 0 5.93 5.66 9 15 0 1.35 1.36

2

15 1 5.16 5.14

4 5 0 10.90 12.37 10 0 0 11.66 10.95

2

16 1 4.90 6.6?

4 6 0 3.29 4.72 10 X 0 2.09 3.98

2

18 1 5.41 4.63

4 7 0 19.55 17.96 10 2 0 24.48 24.61 3 1 1 18.14 19.09

4 8 0 12.74 13.60 10 3 0 29.62 2S. 8a 3

2

1 36.90 38.29

4 9 0 9.79 9.64 10 4 0 3.79 5.20 3 4 1 47.96 47,15

4 11 0 10.64 10.55 10 7 0 4.15 4.67 3 5 1 6.8 8 9.75

4 12 0 13.65 14.28 10 8 0 0.29 0.84 3 1 12M8 11.76

4 14 0 11.34 10.73 10 10- 0 10.47 9.37 3 1 20.40 20.65

4 16 0 4.77 5.84 10 13 0 5,82 5.21 3 1 9.30 8.75

4 18 0 a. 35 6.10 11 1 .0 8.60 8.80 3 1 14.04 13.87

5 1 0 23.75 22.31 11 2 0 13.02 13.69 3 10 1 29.18 2 7.90

5 3 0 3.68 fe.28 11 3 0 14.06 11.06 3 11 1 13.03 15-25

5 4 0 50.13 5O.fel 11 4 0 13.27 13.71 3 12 1 19.01 L9.61

5 6 0 13.24 13.22 Tl 6 0 5.54 b.42 3 13 1 6.4

。

5.53

Journal of the Korean Chemical Society

SaIicyIaldehyde-4-morpholinothiosemicarbazone^

결

정

및 분자구조

7 H

3 3 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 6 6 6 6 6 6 6 6 6 6 6 6 6 7 7 7 7 7 7 7 7 7 7 7 7 8 8 8 8 8 8 8 8 8 6 6 8 8 8 9

4 6 0 1 2 3 4 5 6 7 8 9 0 1 3 5 8 1 2 3 4 5 6 7 9 1 1

1 1 - 1 1 1

0 1 2 3 5 7 0 1 2 3 4 5 6 7 8 1 2 3 5 1 2 3 4 5 6 7 8 9 M

^

^

^ O 1 2 3 4 5 8 - 9 0

^ 2 3 4 6 1 1 1 1 1 1 1

1 1 1 1

n 1

1 1 1 1 i 1

Vol. 21,

L Fo 1 5.13 1 4.07 1 62.86 1 3.81 1 5.25 1 15.*7 1 40.02 1 48.90 1 24.06 1 12.38 1 9.86 1 7.18 1 20.65 1 5.68 1 6.75 1 7.27 1 4.79 1 60.26 i 35.84 1 5・23 1 15.68 1 15.61 1 4.63 1 18.21 1 12.66 1 8

.아

丄 1 12.33 1 7.00 1 2.91 1 6.36 1 9.06 1 25.54 1 16.73 1 31.94 1 4. !)6 1 14.33 1 11.93 1 16.85 1 10.55 1 6.40 1 9.88 1 6.21 丄 6.60 1 6.82 1 21.03 1 11.7^

1 8.79 1 20.57 1 5.61 1 23.19 1 29.01 1 33.02 1 22,16 1 7.00 1 7.54 1 4.00 1 22.2«

1 5.90 1 13.52 1 25.16 1 9.53 1 9.74 1 6.14 1 15.99 1 5.27 1 9.71 1 5.29 1 2.07 1 6.88 1 0.96 1 8.10 No. 1, 1977

i

) ) r

><

j

?

?

>

* + 7 5 2 3 6 2 9 3 2 6 2 4 6 9 5 9 1 o 6 q

2 6 1 0

* 1 02 6, 09 90 74 15 28 12 86 50 83 41

<,9 36 21 44 06 97 70 08 96 36 19 87 33 61 81 02 10 26 97 31 90 12 - 19 - 51

皿

• a5 - 83 - 02 '36 '50 - 12 - fe, - 40 - 2<, - 6i, - 4 ' 9 - 3 - 1 - 7 - 4 - 3 - 0 - 0 - 9 - 9 - 0 - 9 - 8 - 8 - 7 - 4 - 5 - 2 - 4 - 8 - 8 - 5

F

」

b 6 4 8 5 3 2 4 7 0 1 5 4 5 7 7 5 5 4 3 9 6 9 7 b 4 8 6 5 . / 4 4 9 7 6 4 2 , 0 1 . 8 6

1 3 4 2 1 2

5 3 1 1

n i l

2 1 3

i l l

V -

2 1 2 2 2

H 9 9 9

9 9 9 9. 9 0 0 0 0 0 0 0 0 0 0 0 0 1 1 1 1 1 2 2 2 2 2 2 3 3 3 3 3 3 4 4 4 0 0 0 0 0 0 0 0 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

K 2 4 6 7 8 0 1 2 3 4 5 0 1 2 3 4 5 6 7 8 0 1 3 2 3 7 9 1 0 3 4 5 6 1 1 4 6 7 8 9 0 5 6 0 2 4 6 0 0 2 6 8 1 2 3 4 5 6 7 8 9 0 1 2 4 6 7 0 1 2 3 1 1 1 1 1 1

i l l

1

1

1 1 1 1

1 1 1 1 1 1

K 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 B 9 0 1 2 3 4 5 6 7 0 1 2 3 4 5 7 8 9 0 1 2 3 4 5 6 8 1 2 3 4 5 6 7 8 9 0 2 4 - s 6 7 0 1 2 3

* - 5 6 2 1

上

고

1 1 1 1 1

1 1 1 1 1 1 1 1

1 1 1 1 1 1 1 1

1 1 1 1 1 1 H 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 e 4 4 4 4 4 ' 4 4 4 4 4 4 4 4 4 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 6 6 6 6 6 6 6 Fo

8.14

Fc 7.63 19.50 18.75 9.28 9.12 5.60 4.61 5.6Q 5.03 6.01 6.18 7.58 5,72 7.13 6・

^인>

3.92 4・77 8.33 9.03 3.05 2.91 6・66 6.30 5.60 4.33 6.94 8.15 19.22 19.94 15.98 15.02 7.00 6.06 6.97 7,58 16.57 14,22 6.05 4.56 S.02 7,60 1.34 1.62 6.03 5,38 B.12 9.45 4.18 4.39 9.76 7.66 3.72 4,46 2.36 2.16 5.67 6,52

A.30 «9

3.90 3.01 9.86 10.88 4.63 4.60 5.86 6.21 5.01 5.20 5.05 5.38 2.16 3.17 4.02 3

•야

3 2.94 3.70 2.08 1.72 6.03 3.49 4.70 3.45 4.61 3.43 295.50 288.67 103.99 99,30 25.72 26.58 18・ 14 14.70 19.73 19.40 25.74 22.65 11.25 12.55 7.74 7.99 4.31 4.46 48.27 4b. 69 32・64 51,12 44.17 44.18 3.70 4.71 27.78 27.15 19.30 18.68 21.02 20.62 12.51 11.76 9.62 B.79 10.77 9.69 6.10 6.55 15.08 13.99 6.73 7.2

q

4.84 5.37 6.40 5.70 36.12 36.29 2S.30 26.43 30-18 31.17 24 ・ 51 25,27

L Fo Fc

2 15.58 15.88 2 51.44 52.3fe 2 2 0.94 [알. 74 2 30.75 29.18 2 36・45 36.07 2 6.68 8.27

2

]8.37 18.85 2 10.43 18.16 2 5.32 6.74 2 2.26 2.95 2 5.36 *.89 2 5.16 3.80 2 2.67 2.4, 2 6.03 4.23 2 4.60 3.55 2 44.21 43.43 2 10-00 17.09 2 20.85 19.72 2 13.65 12.73 2 10.99 11.01 2 10.68 11.22 2 17.07 17,40 2 5.34 6.06 2 16.25 15.24 2 21.68 20.62 2 21.64 20・45 2 2.34 2,99 2 5.10 8.50

2

8.88 9.51 2 4.78 3.55 2 2.33 3.29 2 6.49 5.27 2 20.73 20,68 2 26.08 24・43 2 13.43 14.73 2 32.65 31.56 2 3.48 3.06 2 15.95 16.02 2 16.55 16.25 2 5.58 6.53 2 14.62 14,09 2 11.46 12.36 2 7.71 6.78

2

11.5A 11.62 2 7.54 7,98 2 7.47 7.67 2 5.70 4.96 2 5.03 5.99 2 5.80 5.73 2 10.60 11.41 2 16.93 16.78 2 1고. 82 10.06 2 31.60 31.82 2 15.94 13.17 2 20.77 19.46 2 12.89 11.77 2 9.68 9.10 2 5.62 5.65 2 6.C8 5.59 2 8. t>6 8,46 2 7.47 7.38 2 2.22 2.92 2 5.13 5.51 2 3.30 3.77 2 34.68 34.15 2 16.35 16.52 2 20.57 21.07

2

10.09 9.34 2 15.83 13.45 2 4.BO 5.54

2 23.19