(1Z,2E)-N'-{1-[2-(4-Bromo-phen-yl)hydrazin-1-yl-idene]-1-chloro-propan-2-yl-idene}thio-phene-2-carbohydrazide.

In the title compound, C(14)H(12)BrClN(4)OS, the thienyl ring is disordered over two orientations with a site-occupancy ratio of 0.853 (2):0.147 (2). The mol-ecule is roughly planar, with the dihedral angles between the thienyl and benzene rings being 6.24 (16) and 9.7 (11)° for the major and minor components, respectively. The central fragment is almost planar [r.m.s. deviation = 0.0275 (2) Å for the ten non-H atoms]. The mean plane through this middle unit makes a dihedral angle of 2.71 (7)° with the benzene ring, whereas these values are 4.46 (15) and 7.7 (11)° for the major and minor components of the thienyl ring, respectively. In the crystal, mol-ecules are linked into dimers by pairs of N-H⋯O hydrogen bonds, forming R(2) (2)(8) ring motifs. These dimers are arranged into sheets parallel to the ac plane.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to and the biological activity of (1Z,2E)-N-(ar­yl)propane­hydrazonoyl chlorides, see: Abdel-Aziz & Mekawey (2009 ▶); Abdel-Aziz et al. (2010 ▶). For a related structure, see: Abdel-Aziz et al. (2012 ▶). For the stability of the temperature controller, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C14H12BrClN4OS

M = 399.79

Monoclinic,

a = 13.5502 (14) Å

b = 3.8932 (4) Å

c = 29.816 (3) Å

β = 103.075 (2)°

V = 1532.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 3.00 mm−1

T = 100 K

0.38 × 0.10 × 0.06 mm

Data collection

Bruker APEX Duo CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.399, T max = 0.848

14314 measured reflections

4458 independent reflections

3378 reflections with I > 2σ(I)’

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.075

S = 1.05

4458 reflections

223 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017114/bq2351sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017114/bq2351Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812017114/bq2351Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H12BrClN4OS	F(000) = 800
Mr = 399.79	Dx = 1.733 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4458 reflections
a = 13.5502 (14) Å	θ = 1.4–30.0°
b = 3.8932 (4) Å	µ = 3.00 mm−1
c = 29.816 (3) Å	T = 100 K
β = 103.075 (2)°	Needle, yellow
V = 1532.1 (3) Å3	0.38 × 0.10 × 0.06 mm
Z = 4

Bruker APEX Duo CCD area detector diffractometer	4458 independent reflections
Radiation source: sealed tube	3378 reflections with I > 2σ(I)'
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 30.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
Tmin = 0.399, Tmax = 0.848	k = −2→5
14314 measured reflections	l = −41→41

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0313P)2 + 0.3052P] where P = (Fo2 + 2Fc2)/3
4458 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.54 e Å−3
6 restraints	Δρmin = −0.36 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually 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 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 > 2sigma(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	Occ. (<1)
Cl1	0.46435 (3)	0.69142 (13)	0.184855 (16)	0.01888 (11)
Br1	1.077635 (15)	0.50439 (6)	0.376036 (7)	0.02669 (7)
O1	0.38556 (10)	0.1793 (4)	−0.02052 (4)	0.0194 (3)
N1	0.66736 (13)	0.5947 (5)	0.24295 (6)	0.0197 (4)
N2	0.65558 (12)	0.4813 (4)	0.19957 (5)	0.0174 (3)
N3	0.47407 (12)	0.3945 (4)	0.09546 (5)	0.0158 (3)
N4	0.46842 (12)	0.2636 (5)	0.05229 (5)	0.0162 (3)
C1	0.84509 (14)	0.4225 (5)	0.25890 (7)	0.0176 (4)
H1A	0.8369	0.3350	0.2293	0.021*
C2	0.93831 (15)	0.4030 (5)	0.28961 (7)	0.0180 (4)
H2A	0.9929	0.3003	0.2808	0.022*
C3	0.95018 (14)	0.5373 (5)	0.33370 (7)	0.0171 (4)
C4	0.86974 (14)	0.6913 (5)	0.34736 (7)	0.0182 (4)
H4A	0.8786	0.7839	0.3768	0.022*
C5	0.77589 (14)	0.7069 (5)	0.31702 (7)	0.0174 (4)
H5A	0.7212	0.8057	0.3263	0.021*
C6	0.76335 (14)	0.5748 (5)	0.27276 (7)	0.0158 (4)
C7	0.57143 (14)	0.5059 (5)	0.17035 (6)	0.0165 (4)
C8	0.56220 (14)	0.3761 (5)	0.12343 (6)	0.0160 (4)
C9	0.65679 (14)	0.2370 (6)	0.11173 (7)	0.0204 (4)
H9A	0.6666	0.3445	0.0841	0.031*
H9B	0.6502	−0.0067	0.1071	0.031*
H9C	0.7139	0.2844	0.1365	0.031*
C10	0.38400 (13)	0.2968 (5)	0.01792 (6)	0.0151 (4)
C11	0.29185 (14)	0.4686 (5)	0.02516 (6)	0.0149 (4)
S1	0.26973 (5)	0.6374 (2)	0.07517 (3)	0.01674 (17)	0.854 (2)
C12	0.2069 (3)	0.5033 (13)	−0.01037 (15)	0.0204 (8)	0.854 (2)
H12A	0.2047	0.4293	−0.0402	0.024*	0.854 (2)
C13	0.1241 (3)	0.6605 (15)	0.00274 (13)	0.0175 (7)	0.854 (2)
H13B	0.0616	0.7008	−0.0171	0.021*	0.854 (2)
C14	0.1476 (2)	0.7459 (12)	0.04819 (11)	0.0174 (7)	0.854 (2)
H14B	0.1024	0.8517	0.0631	0.021*	0.854 (2)
S1X	0.2004 (5)	0.498 (2)	−0.02227 (19)	0.0144 (13)*	0.146 (2)
C12X	0.2653 (17)	0.592 (8)	0.0633 (8)	0.039 (8)*	0.146 (2)
H12B	0.3082	0.5916	0.0924	0.047*	0.146 (2)
C13X	0.1671 (17)	0.721 (8)	0.0541 (8)	0.0144 (13)*	0.15
H13A	0.1352	0.8097	0.0760	0.017*	0.146 (2)
C14X	0.125 (2)	0.698 (13)	0.0090 (9)	0.039 (8)*	0.15
H14A	0.0607	0.7818	−0.0042	0.047*	0.146 (2)
H1N4	0.5211 (19)	0.138 (7)	0.0459 (8)	0.035 (7)*
H1N1	0.6170 (15)	0.722 (6)	0.2508 (7)	0.013 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0152 (2)	0.0249 (3)	0.0170 (2)	0.00090 (19)	0.00470 (17)	−0.0032 (2)
Br1	0.01893 (10)	0.03023 (13)	0.02601 (12)	0.00166 (9)	−0.00517 (8)	−0.00167 (10)
O1	0.0184 (6)	0.0270 (8)	0.0133 (7)	0.0001 (6)	0.0047 (5)	−0.0034 (6)
N1	0.0163 (8)	0.0294 (10)	0.0135 (8)	0.0020 (7)	0.0039 (6)	−0.0054 (7)
N2	0.0177 (8)	0.0221 (9)	0.0122 (7)	−0.0014 (7)	0.0033 (6)	−0.0019 (7)
N3	0.0172 (8)	0.0185 (8)	0.0119 (7)	−0.0016 (6)	0.0039 (6)	−0.0006 (7)
N4	0.0139 (7)	0.0230 (9)	0.0116 (7)	0.0012 (7)	0.0028 (6)	−0.0022 (7)
C1	0.0182 (9)	0.0219 (10)	0.0137 (9)	−0.0002 (7)	0.0060 (7)	−0.0019 (8)
C2	0.0159 (9)	0.0188 (10)	0.0200 (10)	−0.0006 (7)	0.0056 (8)	−0.0007 (8)
C3	0.0145 (8)	0.0174 (10)	0.0176 (9)	−0.0019 (7)	−0.0003 (7)	0.0021 (8)
C4	0.0220 (9)	0.0182 (10)	0.0138 (9)	−0.0004 (8)	0.0030 (7)	−0.0003 (8)
C5	0.0185 (9)	0.0195 (10)	0.0147 (9)	0.0016 (8)	0.0051 (7)	0.0003 (8)
C6	0.0150 (8)	0.0181 (10)	0.0142 (9)	−0.0011 (7)	0.0029 (7)	0.0011 (8)
C7	0.0150 (8)	0.0212 (10)	0.0146 (9)	−0.0018 (8)	0.0057 (7)	−0.0002 (8)
C8	0.0162 (9)	0.0182 (9)	0.0137 (9)	−0.0009 (7)	0.0039 (7)	0.0002 (8)
C9	0.0153 (8)	0.0298 (12)	0.0156 (9)	0.0026 (8)	0.0026 (7)	−0.0037 (9)
C10	0.0146 (8)	0.0174 (9)	0.0140 (9)	−0.0031 (7)	0.0043 (7)	0.0019 (8)
C11	0.0150 (8)	0.0169 (9)	0.0138 (9)	−0.0025 (7)	0.0051 (7)	0.0005 (8)
S1	0.0170 (3)	0.0194 (3)	0.0146 (4)	0.0011 (2)	0.0052 (2)	−0.0011 (3)
C12	0.0187 (14)	0.0260 (16)	0.0185 (19)	−0.0034 (11)	0.0082 (15)	−0.0041 (19)
C13	0.0126 (12)	0.0226 (19)	0.0167 (14)	−0.0015 (10)	0.0020 (9)	0.0031 (14)
C14	0.0143 (16)	0.0217 (15)	0.0170 (15)	0.0056 (13)	0.0048 (12)	0.0032 (12)

Cl1—C7	1.7601 (19)	C8—C9	1.503 (3)
Br1—C3	1.8990 (19)	C9—H9A	0.9600
O1—C10	1.239 (2)	C9—H9B	0.9600
N1—N2	1.342 (2)	C9—H9C	0.9600
N1—C6	1.402 (2)	C10—C11	1.475 (3)
N1—H1N1	0.92 (2)	C11—C12X	1.36 (2)
N2—C7	1.272 (2)	C11—C12	1.383 (5)
N3—C8	1.295 (2)	C11—S1X	1.660 (6)
N3—N4	1.370 (2)	C11—S1	1.717 (2)
N4—C10	1.358 (2)	S1—C14	1.721 (2)
N4—H1N4	0.92 (3)	C12—C13	1.409 (5)
C1—C2	1.384 (3)	C12—H12A	0.9300
C1—C6	1.399 (3)	C13—C14	1.361 (4)
C1—H1A	0.9300	C13—H13B	0.9300
C2—C3	1.390 (3)	C14—H14B	0.9300
C2—H2A	0.9300	S1X—C14X	1.717 (19)
C3—C4	1.384 (3)	C12X—C13X	1.389 (18)
C4—C5	1.385 (3)	C12X—H12B	0.9300
C4—H4A	0.9300	C13X—C14X	1.339 (17)
C5—C6	1.391 (3)	C13X—H13A	0.9300
C5—H5A	0.9300	C14X—H14A	0.9300
C7—C8	1.466 (3)
N2—N1—C6	118.94 (16)	C8—C9—H9C	109.5
N2—N1—H1N1	119.5 (13)	H9A—C9—H9C	109.5
C6—N1—H1N1	120.4 (13)	H9B—C9—H9C	109.5
C7—N2—N1	121.87 (17)	O1—C10—N4	118.37 (17)
C8—N3—N4	115.57 (16)	O1—C10—C11	119.68 (17)
C10—N4—N3	122.12 (16)	N4—C10—C11	121.95 (17)
C10—N4—H1N4	117.1 (16)	C12X—C11—C12	105.9 (9)
N3—N4—H1N4	120.7 (16)	C12X—C11—C10	132.7 (9)
C2—C1—C6	119.53 (18)	C12—C11—C10	121.2 (2)
C2—C1—H1A	120.2	C12X—C11—S1X	113.6 (9)
C6—C1—H1A	120.2	C10—C11—S1X	113.6 (3)
C1—C2—C3	119.87 (18)	C12—C11—S1	110.5 (2)
C1—C2—H2A	120.1	C10—C11—S1	128.37 (14)
C3—C2—H2A	120.1	S1X—C11—S1	118.0 (3)
C4—C3—C2	120.75 (18)	C11—S1—C14	91.51 (15)
C4—C3—Br1	119.47 (15)	C11—C12—C13	114.0 (3)
C2—C3—Br1	119.78 (14)	C11—C12—H12A	123.0
C3—C4—C5	119.64 (18)	C13—C12—H12A	123.0
C3—C4—H4A	120.2	C14—C13—C12	111.2 (3)
C5—C4—H4A	120.2	C14—C13—H13B	124.4
C4—C5—C6	120.05 (17)	C12—C13—H13B	124.4
C4—C5—H5A	120.0	C13—C14—S1	112.9 (3)
C6—C5—H5A	120.0	C13—C14—H14B	123.6
C5—C6—C1	120.15 (18)	S1—C14—H14B	123.6
C5—C6—N1	118.55 (17)	C11—S1X—C14X	89.5 (9)
C1—C6—N1	121.30 (17)	C11—C12X—C13X	112.7 (16)
N2—C7—C8	119.82 (17)	C11—C12X—H12B	123.6
N2—C7—Cl1	121.57 (15)	C13X—C12X—H12B	123.6
C8—C7—Cl1	118.61 (14)	C14X—C13X—C12X	110 (2)
N3—C8—C7	117.55 (17)	C14X—C13X—H13A	124.9
N3—C8—C9	125.54 (17)	C12X—C13X—H13A	124.9
C7—C8—C9	116.89 (16)	C13X—C14X—S1X	113.8 (19)
C8—C9—H9A	109.5	C13X—C14X—H14A	123.1
C8—C9—H9B	109.5	S1X—C14X—H14A	123.1
H9A—C9—H9B	109.5
C6—N1—N2—C7	−176.96 (19)	N4—C10—C11—C12	179.3 (3)
C8—N3—N4—C10	−173.07 (18)	O1—C10—C11—S1X	−2.8 (4)
C6—C1—C2—C3	−0.6 (3)	N4—C10—C11—S1X	176.9 (3)
C1—C2—C3—C4	−0.1 (3)	O1—C10—C11—S1	177.55 (15)
C1—C2—C3—Br1	179.12 (15)	N4—C10—C11—S1	−2.7 (3)
C2—C3—C4—C5	1.1 (3)	C12X—C11—S1—C14	−32 (13)
Br1—C3—C4—C5	−178.13 (15)	C12—C11—S1—C14	0.7 (3)
C3—C4—C5—C6	−1.4 (3)	C10—C11—S1—C14	−177.4 (2)
C4—C5—C6—C1	0.7 (3)	S1X—C11—S1—C14	3.0 (4)
C4—C5—C6—N1	179.99 (19)	C12X—C11—C12—C13	2.2 (14)
C2—C1—C6—C5	0.3 (3)	C10—C11—C12—C13	177.5 (4)
C2—C1—C6—N1	−178.97 (19)	S1X—C11—C12—C13	−166 (4)
N2—N1—C6—C5	177.19 (18)	S1—C11—C12—C13	−0.8 (5)
N2—N1—C6—C1	−3.5 (3)	C11—C12—C13—C14	0.4 (7)
N1—N2—C7—C8	−179.62 (18)	C12—C13—C14—S1	0.1 (6)
N1—N2—C7—Cl1	0.1 (3)	C11—S1—C14—C13	−0.5 (4)
N4—N3—C8—C7	−178.66 (17)	C12X—C11—S1X—C14X	2 (2)
N4—N3—C8—C9	2.3 (3)	C12—C11—S1X—C14X	15 (4)
N2—C7—C8—N3	177.33 (19)	C10—C11—S1X—C14X	179.2 (19)
Cl1—C7—C8—N3	−2.4 (3)	S1—C11—S1X—C14X	−1.1 (19)
N2—C7—C8—C9	−3.5 (3)	C12—C11—C12X—C13X	−2 (3)
Cl1—C7—C8—C9	176.79 (15)	C10—C11—C12X—C13X	−176.9 (17)
N3—N4—C10—O1	178.17 (17)	S1X—C11—C12X—C13X	−1 (3)
N3—N4—C10—C11	−1.6 (3)	S1—C11—C12X—C13X	146 (15)
O1—C10—C11—C12X	173.4 (18)	C11—C12X—C13X—C14X	−2 (4)
N4—C10—C11—C12X	−6.8 (18)	C12X—C13X—C14X—S1X	4 (5)
O1—C10—C11—C12	−0.4 (4)	C11—S1X—C14X—C13X	−3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O1i	0.92 (3)	2.03 (3)	2.938 (2)	168 (2)
N1—H1N1···Cl1	0.92 (2)	2.51 (2)	2.9246 (19)	107.7 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯O1i	0.92 (3)	2.03 (3)	2.938 (2)	168 (2)
N1—H1N1⋯Cl1	0.92 (2)	2.51 (2)	2.9246 (19)	107.7 (15)

Symmetry code: (i) .