Crystal structure of (E)-N'-(4-chloro-benzyl-idene)-4-methyl-benzene-sulfono-hydrazide: a hexa-gonal polymorph.

The title compound, C14H13ClN2O2S, crystallized in the enanti-omorphic defining hexa-gonal space group P61 [Flack parameter = -0.02 (7)]. The partially hydrated form of the same compound, crystallizing in the triclinic space group P-1, has been reported previously [Kia et al. (2009b). Acta Cryst. E65, o1119], as has the crystal structure of the bromo derivative, also crystallizing in the space group P-1 [Kia et al. (2009a). Acta Cryst. E65, o821]. The title mol-ecule is non-planar with the planes of the benzene rings being inclined to one another by 76.62 (13)°, and has an E conformation about the C=N bond. In the crystal, mol-ecules are linked via N-H⋯O hydrogen bonds forming 61 helical chains running along [001]. The chains are linked via C-H⋯O hydrogen bonds, C-H⋯π inter-actions and short Cl⋯O [3.015 (3) Å] inter-actions, forming a three-dimensional structure.

Related literature

For the biological activities of hydrazones, see: Ajani et al. (2010 ▶). For the crystal structure of the triclinic polymorph, which crystallized with two independent mol­ecules in the asymmetric unit, one of which was n class="Disease">disordered, and with 0.15 of a water mol­ecule, see: Kia et al. (2009b ▶). For the crystal structure of the bromo derivative, also crystallizing in space group P , see: Kia et al. (2009a ▶).

Experimental

Crystal data

C14H13ClN2O2S

M = 308.77

Hexagonal,

a = 10.8907 (3) Å

c = 21.4542 (7) Å

V = 2203.71 (11) Å3

Z = 6

Mo Kα radiation

μ = 0.40 mm−1

T = 293 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.871, T max = 0.910

22095 measured reflections

2586 independent reflections

2345 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.072

S = 1.04

2586 reflections

186 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.12 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 1257 Friedel pairs

Absolute structure parameter: −0.02 (7)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: n class="Gene">APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814023721/su2800sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023721/su2800Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814023721/su2800Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814023721/su2800fig1.tif

The mol­ecular structure of the title compound, with atom labelling. The displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

c . DOI: 10.1107/S1600536814023721/su2800fig2.tif

A view along the c axis of the crystal packing of the title compound. The N—H⋯O and C—H⋯O hydrogen bonds are indicated by dashed lines (see Table 1 for details; n class="Disease">H atoms not involved in these inter­actions have been omitted for clarity).

CCDC reference: 1031289

Additional supporting information: crystallographic information; 3D view; checkCIF report

C14H13ClN2O2S	Dx = 1.396 Mg m−3
Mr = 308.77	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P61	Cell parameters from 9375 reflections
Hall symbol: P 61	θ = 2.4–25.8°
a = 10.8907 (3) Å	µ = 0.40 mm−1
c = 21.4542 (7) Å	T = 293 K
V = 2203.71 (11) Å3	Block, yellow
Z = 6	0.35 × 0.30 × 0.25 mm
F(000) = 960

Bruker Kappa APEXII CCD diffractometer	2586 independent reflections
Radiation source: fine-focus sealed tube	2345 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω and φ scan	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.871, Tmax = 0.910	k = −12→12
22095 measured reflections	l = −25→25

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0306P)2 + 0.7106P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.072	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.12 e Å−3
2586 reflections	Δρmin = −0.16 e Å−3
186 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.0026 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1257 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (7)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	−0.1026 (3)	−0.5080 (4)	0.94696 (15)	0.0727 (9)
H1A	−0.2001	−0.5364	0.9392	0.109*
H1B	−0.0699	−0.4482	0.9831	0.109*
H1C	−0.0942	−0.5906	0.9539	0.109*
C2	−0.0151 (3)	−0.4286 (3)	0.89196 (13)	0.0480 (6)
C3	−0.0778 (3)	−0.4059 (3)	0.84061 (13)	0.0507 (6)
H3	−0.1751	−0.4410	0.8405	0.061*
C4	0.0019 (3)	−0.3321 (3)	0.78968 (12)	0.0496 (6)
H4	−0.0415	−0.3180	0.7553	0.060*
C5	0.1458 (2)	−0.2795 (2)	0.79003 (11)	0.0419 (5)
C6	0.2103 (3)	−0.3013 (3)	0.84070 (12)	0.0483 (6)
H6	0.3077	−0.2657	0.8408	0.058*
C7	0.1296 (3)	−0.3758 (3)	0.89098 (13)	0.0514 (6)
H7	0.1730	−0.3911	0.9250	0.062*
C8	0.1633 (3)	0.1027 (3)	0.74279 (11)	0.0426 (5)
H8	0.2543	0.1797	0.7474	0.051*
C9	0.0430 (3)	0.1244 (3)	0.74794 (10)	0.0415 (5)
C10	−0.0947 (3)	0.0146 (3)	0.74508 (13)	0.0520 (6)
H10	−0.1127	−0.0766	0.7367	0.062*
C11	−0.2070 (3)	0.0381 (3)	0.75456 (13)	0.0579 (7)
H11	−0.3000	−0.0366	0.7526	0.069*
C12	−0.1789 (3)	0.1731 (3)	0.76682 (12)	0.0522 (6)
C13	−0.0439 (3)	0.2844 (3)	0.76863 (13)	0.0574 (7)
H13	−0.0266	0.3758	0.7763	0.069*
C14	0.0664 (3)	0.2595 (3)	0.75898 (12)	0.0516 (6)
H14	0.1589	0.3353	0.7599	0.062*
O1	0.3852 (2)	−0.1677 (2)	0.73010 (9)	0.0597 (5)
O2	0.1652 (2)	−0.2455 (2)	0.67125 (8)	0.0605 (5)
S1	0.24764 (7)	−0.18427 (7)	0.72562 (3)	0.04549 (16)
Cl1	−0.31836 (9)	0.20068 (10)	0.78326 (4)	0.0779 (3)
N1	0.2735 (2)	−0.0230 (2)	0.73014 (10)	0.0445 (5)
N2	0.1474 (2)	−0.0187 (2)	0.73212 (9)	0.0424 (5)
H1	0.337 (2)	0.033 (2)	0.7573 (10)	0.050 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0601 (19)	0.084 (2)	0.0681 (19)	0.0315 (17)	0.0065 (15)	0.0170 (17)
C2	0.0489 (14)	0.0454 (14)	0.0498 (13)	0.0237 (12)	−0.0031 (13)	−0.0033 (12)
C3	0.0402 (14)	0.0510 (15)	0.0621 (16)	0.0238 (12)	−0.0056 (12)	−0.0032 (13)
C4	0.0518 (15)	0.0533 (15)	0.0512 (14)	0.0319 (13)	−0.0149 (12)	−0.0028 (13)
C5	0.0472 (14)	0.0423 (13)	0.0434 (13)	0.0278 (12)	−0.0050 (11)	−0.0061 (11)
C6	0.0403 (14)	0.0609 (16)	0.0473 (14)	0.0280 (13)	−0.0056 (11)	−0.0017 (12)
C7	0.0511 (15)	0.0625 (16)	0.0432 (12)	0.0304 (13)	−0.0069 (12)	0.0017 (13)
C8	0.0491 (15)	0.0436 (14)	0.0383 (12)	0.0255 (12)	−0.0016 (10)	−0.0019 (10)
C9	0.0537 (15)	0.0440 (13)	0.0353 (11)	0.0309 (12)	−0.0025 (10)	0.0000 (10)
C10	0.0600 (17)	0.0442 (15)	0.0621 (16)	0.0338 (14)	−0.0055 (13)	−0.0075 (12)
C11	0.0540 (16)	0.0562 (17)	0.0695 (18)	0.0321 (14)	−0.0018 (13)	−0.0022 (14)
C12	0.0623 (17)	0.0643 (18)	0.0480 (14)	0.0452 (15)	−0.0021 (12)	−0.0023 (13)
C13	0.0733 (19)	0.0496 (16)	0.0658 (17)	0.0430 (16)	−0.0017 (14)	−0.0071 (13)
C14	0.0529 (16)	0.0444 (15)	0.0627 (17)	0.0282 (13)	−0.0049 (12)	−0.0057 (12)
O1	0.0637 (12)	0.0735 (13)	0.0631 (11)	0.0502 (11)	0.0132 (9)	0.0121 (10)
O2	0.0933 (15)	0.0647 (12)	0.0418 (9)	0.0533 (12)	−0.0108 (10)	−0.0124 (9)
S1	0.0604 (4)	0.0513 (4)	0.0401 (3)	0.0394 (3)	0.0020 (3)	−0.0015 (3)
Cl1	0.0746 (5)	0.0945 (6)	0.0928 (6)	0.0635 (5)	−0.0005 (5)	−0.0118 (5)
N1	0.0498 (13)	0.0489 (12)	0.0446 (11)	0.0320 (11)	−0.0005 (10)	−0.0030 (10)
N2	0.0511 (12)	0.0469 (12)	0.0400 (11)	0.0327 (10)	−0.0022 (9)	−0.0032 (9)

C1—C2	1.491 (4)	C8—H8	0.9300
C1—H1A	0.9600	C9—C10	1.374 (3)
C1—H1B	0.9600	C9—C14	1.383 (3)
C1—H1C	0.9600	C10—C11	1.384 (4)
C2—C7	1.381 (3)	C10—H10	0.9300
C2—C3	1.382 (4)	C11—C12	1.369 (4)
C3—C4	1.376 (4)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.360 (4)
C4—C5	1.374 (3)	C12—Cl1	1.726 (3)
C4—H4	0.9300	C13—C14	1.373 (4)
C5—C6	1.378 (3)	C13—H13	0.9300
C5—S1	1.751 (3)	C14—H14	0.9300
C6—C7	1.372 (4)	O1—S1	1.4197 (18)
C6—H6	0.9300	O2—S1	1.4189 (19)
C7—H7	0.9300	S1—N1	1.637 (2)
C8—N2	1.265 (3)	N1—N2	1.399 (3)
C8—C9	1.447 (3)	N1—H1	0.875 (17)
C2—C1—H1A	109.5	C10—C9—C8	122.5 (2)
C2—C1—H1B	109.5	C14—C9—C8	119.1 (2)
H1A—C1—H1B	109.5	C9—C10—C11	120.9 (2)
C2—C1—H1C	109.5	C9—C10—H10	119.6
H1A—C1—H1C	109.5	C11—C10—H10	119.6
H1B—C1—H1C	109.5	C12—C11—C10	118.8 (3)
C7—C2—C3	118.4 (2)	C12—C11—H11	120.6
C7—C2—C1	121.2 (3)	C10—C11—H11	120.6
C3—C2—C1	120.3 (2)	C13—C12—C11	121.6 (2)
C4—C3—C2	120.9 (2)	C13—C12—Cl1	119.5 (2)
C4—C3—H3	119.5	C11—C12—Cl1	118.8 (2)
C2—C3—H3	119.5	C12—C13—C14	118.8 (2)
C5—C4—C3	119.6 (2)	C12—C13—H13	120.6
C5—C4—H4	120.2	C14—C13—H13	120.6
C3—C4—H4	120.2	C13—C14—C9	121.5 (3)
C4—C5—C6	120.4 (2)	C13—C14—H14	119.3
C4—C5—S1	119.71 (18)	C9—C14—H14	119.3
C6—C5—S1	119.89 (19)	O2—S1—O1	119.65 (12)
C7—C6—C5	119.4 (2)	O2—S1—N1	106.40 (11)
C7—C6—H6	120.3	O1—S1—N1	104.78 (11)
C5—C6—H6	120.3	O2—S1—C5	107.80 (12)
C6—C7—C2	121.2 (2)	O1—S1—C5	109.72 (11)
C6—C7—H7	119.4	N1—S1—C5	107.91 (11)
C2—C7—H7	119.4	N2—N1—S1	113.13 (16)
N2—C8—C9	121.5 (2)	N2—N1—H1	113.4 (17)
N2—C8—H8	119.3	S1—N1—H1	116.2 (17)
C9—C8—H8	119.3	C8—N2—N1	114.7 (2)
C10—C9—C14	118.3 (2)
C7—C2—C3—C4	−0.2 (4)	C11—C12—C13—C14	−1.2 (4)
C1—C2—C3—C4	179.7 (3)	Cl1—C12—C13—C14	176.3 (2)
C2—C3—C4—C5	−0.4 (4)	C12—C13—C14—C9	−0.4 (4)
C3—C4—C5—C6	0.6 (4)	C10—C9—C14—C13	1.8 (4)
C3—C4—C5—S1	−179.42 (19)	C8—C9—C14—C13	−175.3 (2)
C4—C5—C6—C7	−0.1 (4)	C4—C5—S1—O2	−35.4 (2)
S1—C5—C6—C7	179.9 (2)	C6—C5—S1—O2	144.6 (2)
C5—C6—C7—C2	−0.5 (4)	C4—C5—S1—O1	−167.3 (2)
C3—C2—C7—C6	0.7 (4)	C6—C5—S1—O1	12.8 (2)
C1—C2—C7—C6	−179.2 (3)	C4—C5—S1—N1	79.1 (2)
N2—C8—C9—C10	3.7 (4)	C6—C5—S1—N1	−100.9 (2)
N2—C8—C9—C14	−179.3 (2)	O2—S1—N1—N2	57.70 (19)
C14—C9—C10—C11	−1.6 (4)	O1—S1—N1—N2	−174.64 (16)
C8—C9—C10—C11	175.4 (2)	C5—S1—N1—N2	−57.77 (18)
C9—C10—C11—C12	0.1 (4)	C9—C8—N2—N1	−178.3 (2)
C10—C11—C12—C13	1.3 (4)	S1—N1—N2—C8	172.28 (18)
C10—C11—C12—Cl1	−176.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.88 (2)	2.13 (2)	2.952 (3)	156 (2)
C1—H1A···O1ii	0.96	2.55	3.496 (5)	169
C13—H13···Cgiii	0.93	2.94	3.823 (3)	160

Table 1

Hydrogen-bond geometry (, )

Cg is the centroid of the C2C7 ring.

DHA	DH	HA	D A	DHA
N1H1O2i	0.88(2)	2.13(2)	2.952(3)	156(2)
C1H1AO1ii	0.96	2.55	3.496(5)	169
C13H13Cg iii	0.93	2.94	3.823(3)	160

Symmetry codes: (i) ; (ii) ; (iii) .