(Z)-1-(2,5-Dichloro-3-thien-yl)ethanone semicarbazone.

The title mol-ecule, C(7)H(7)Cl(2)N(3)OS, is approximately planar [maximum deviation = 0.062 (1) Å]. Short inter-molecular distances between the centroids of the five-membered rings [3.5340 (8) Å] indicate the existence of π-π inter-actions. An inter-esting feature of the crystal structure is the presence of short intra-molecular Cl⋯N inter-actions [3.0015 (11) Å]. Mol-ecules are linked via pairs of inter-molecular N-H⋯O hydrogen bonds, generating R(2) (2)(8) ring motifs. Furthermore, N-H⋯O hydrogen bonds form R(2) (1)(7) ring motifs with C-H⋯O contacts, further consolidating the crystal structure. In the crystal, mol-ecules are linked by these inter-molecular inter-actions, forming chains along [001].

Related literature

For the synthetic utility and applications of semicarbazone derivatives, see: Warren et al. (1977 ▶); Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Yogeeswari et al. (2004 ▶). For related structures, see: Fun et al. (2009a ▶,b ▶). For the preparation, see: Furniss et al. (1978 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C7H7Cl2N3OS

M = 252.12

Monoclinic,

a = 13.0796 (2) Å

b = 10.4316 (2) Å

c = 14.4352 (2) Å

β = 94.599 (1)°

V = 1963.21 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.84 mm−1

T = 100 K

0.49 × 0.22 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.683, T max = 0.934

16375 measured reflections

3742 independent reflections

3060 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.100

S = 1.13

3742 reflections

140 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.35 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809026567/tk2498sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026567/tk2498Isup2.hkl

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

C7H7Cl2N3OS	F(000) = 1024
Mr = 252.12	Dx = 1.706 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6313 reflections
a = 13.0796 (2) Å	θ = 2.5–33.2°
b = 10.4316 (2) Å	µ = 0.84 mm−1
c = 14.4352 (2) Å	T = 100 K
β = 94.599 (1)°	Plate, colourless
V = 1963.21 (6) Å3	0.49 × 0.22 × 0.08 mm
Z = 8

Bruker SMART APEXII CCD area-detector diffractometer	3742 independent reflections
Radiation source: fine-focus sealed tube	3060 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 33.2°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −20→19
Tmin = 0.683, Tmax = 0.934	k = −16→15
16375 measured reflections	l = −22→22

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0516P)2 + 0.6332P] where P = (Fo2 + 2Fc2)/3
3742 reflections	(Δ/σ)max = 0.002
140 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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

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
Cl1	1.17736 (3)	0.23231 (4)	0.62567 (3)	0.02794 (10)
Cl2	0.88955 (3)	0.12728 (4)	0.31571 (2)	0.02421 (10)
S1	1.06944 (2)	0.19596 (3)	0.43833 (3)	0.01940 (9)
O1	0.48318 (7)	−0.00827 (9)	0.37962 (6)	0.01622 (18)
N1	0.62401 (10)	0.02718 (15)	0.30045 (8)	0.0247 (3)
N2	0.63508 (8)	0.03704 (11)	0.46052 (7)	0.0150 (2)
N3	0.73470 (8)	0.07286 (10)	0.45321 (7)	0.0146 (2)
C1	0.57608 (9)	0.01731 (12)	0.37865 (8)	0.0147 (2)
C2	0.79348 (9)	0.09889 (12)	0.52643 (9)	0.0141 (2)
C3	0.89959 (10)	0.13686 (12)	0.51073 (9)	0.0150 (2)
C4	0.97547 (10)	0.16495 (13)	0.58619 (9)	0.0183 (2)
H4A	0.9621	0.1617	0.6485	0.022*
C5	1.06803 (10)	0.19643 (13)	0.55714 (10)	0.0194 (3)
C6	0.94260 (10)	0.15031 (13)	0.42725 (9)	0.0167 (2)
C7	0.76299 (11)	0.09363 (16)	0.62397 (9)	0.0232 (3)
H7A	0.6913	0.0734	0.6234	0.035*
H7B	0.7757	0.1753	0.6533	0.035*
H7C	0.8024	0.0288	0.6579	0.035*
H1N1	0.5931 (16)	0.0142 (19)	0.2466 (16)	0.036 (5)*
H2N1	0.6797 (17)	0.0442 (19)	0.3063 (14)	0.030 (5)*
H1N2	0.6027 (14)	0.0324 (17)	0.5102 (13)	0.022 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.01347 (16)	0.0327 (2)	0.0365 (2)	−0.00378 (13)	−0.00478 (14)	−0.00720 (15)
Cl2	0.01543 (15)	0.0411 (2)	0.01659 (15)	−0.00354 (13)	0.00432 (11)	0.00003 (12)
S1	0.01115 (15)	0.02034 (16)	0.02707 (17)	−0.00210 (11)	0.00391 (12)	0.00104 (12)
O1	0.0101 (4)	0.0251 (5)	0.0135 (4)	−0.0015 (4)	0.0005 (3)	0.0007 (3)
N1	0.0116 (5)	0.0502 (8)	0.0124 (5)	−0.0061 (5)	0.0008 (4)	−0.0013 (5)
N2	0.0102 (4)	0.0224 (5)	0.0122 (4)	−0.0034 (4)	0.0008 (4)	−0.0002 (4)
N3	0.0095 (4)	0.0199 (5)	0.0148 (4)	−0.0027 (4)	0.0018 (4)	−0.0003 (4)
C1	0.0121 (5)	0.0185 (6)	0.0136 (5)	−0.0006 (4)	0.0020 (4)	−0.0001 (4)
C2	0.0113 (5)	0.0156 (5)	0.0152 (5)	−0.0010 (4)	0.0010 (4)	−0.0004 (4)
C3	0.0113 (5)	0.0154 (5)	0.0182 (5)	−0.0006 (4)	0.0006 (4)	−0.0008 (4)
C4	0.0137 (6)	0.0199 (6)	0.0208 (6)	−0.0011 (5)	−0.0010 (5)	−0.0029 (5)
C5	0.0121 (5)	0.0195 (6)	0.0261 (6)	−0.0011 (5)	−0.0020 (5)	−0.0041 (5)
C6	0.0117 (5)	0.0192 (6)	0.0192 (6)	−0.0010 (5)	0.0016 (4)	0.0000 (4)
C7	0.0164 (6)	0.0390 (8)	0.0140 (5)	−0.0029 (6)	0.0005 (5)	−0.0002 (5)

Cl1—C5	1.7137 (14)	N3—C2	1.2851 (16)
Cl2—C6	1.7182 (13)	C2—C3	1.4782 (18)
S1—C5	1.7167 (15)	C2—C7	1.4949 (18)
S1—C6	1.7211 (13)	C3—C6	1.3773 (19)
O1—C1	1.2452 (15)	C3—C4	1.4436 (18)
N1—C1	1.3384 (17)	C4—C5	1.3530 (19)
N1—H1N1	0.86 (2)	C4—H4A	0.9300
N1—H2N1	0.75 (2)	C7—H7A	0.9600
N2—N3	1.3677 (15)	C7—H7B	0.9600
N2—C1	1.3741 (16)	C7—H7C	0.9600
N2—H1N2	0.863 (19)
Cg1···Cg1i	3.7188 (6)	Cl2···N3	3.0015 (11)
C5—S1—C6	90.35 (6)	C4—C3—C2	122.41 (12)
C1—N1—H1N1	122.3 (14)	C5—C4—C3	113.17 (13)
C1—N1—H2N1	116.2 (16)	C5—C4—H4A	123.4
H1N1—N1—H2N1	122 (2)	C3—C4—H4A	123.4
N3—N2—C1	116.57 (10)	C4—C5—Cl1	126.87 (12)
N3—N2—H1N2	127.8 (12)	C4—C5—S1	112.98 (10)
C1—N2—H1N2	115.3 (12)	Cl1—C5—S1	120.14 (8)
C2—N3—N2	120.34 (11)	C3—C6—Cl2	130.02 (10)
O1—C1—N1	123.33 (12)	C3—C6—S1	113.90 (10)
O1—C1—N2	120.24 (11)	Cl2—C6—S1	116.08 (8)
N1—C1—N2	116.44 (11)	C2—C7—H7A	109.5
N3—C2—C3	115.96 (11)	C2—C7—H7B	109.5
N3—C2—C7	125.43 (11)	H7A—C7—H7B	109.5
C3—C2—C7	118.61 (11)	C2—C7—H7C	109.5
C6—C3—C4	109.59 (11)	H7A—C7—H7C	109.5
C6—C3—C2	128.00 (12)	H7B—C7—H7C	109.5
C1—N2—N3—C2	176.77 (12)	C3—C4—C5—Cl1	−178.46 (10)
N3—N2—C1—O1	−175.87 (11)	C3—C4—C5—S1	0.65 (16)
N3—N2—C1—N1	4.15 (18)	C6—S1—C5—C4	−0.70 (11)
N2—N3—C2—C3	−179.86 (11)	C6—S1—C5—Cl1	178.47 (9)
N2—N3—C2—C7	0.1 (2)	C4—C3—C6—Cl2	179.02 (11)
N3—C2—C3—C6	1.5 (2)	C2—C3—C6—Cl2	−0.5 (2)
C7—C2—C3—C6	−178.55 (13)	C4—C3—C6—S1	−0.35 (15)
N3—C2—C3—C4	−177.95 (12)	C2—C3—C6—S1	−179.82 (10)
C7—C2—C3—C4	2.03 (19)	C5—S1—C6—C3	0.60 (11)
C6—C3—C4—C5	−0.19 (17)	C5—S1—C6—Cl2	−178.86 (9)
C2—C3—C4—C5	179.32 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ii	0.86 (2)	2.02 (2)	2.8766 (15)	177.3 (19)
N2—H1N2···O1iii	0.863 (19)	2.035 (19)	2.8949 (14)	174.2 (17)
C7—H7A···O1iii	0.96	2.38	3.3370 (17)	176

Table 1

Selected interatomic distance (Å)

Cg1⋯Cg1i

3.7188 (6)

Symmetry code: (i) . Cg1 is the centroid of the S1/C3–C6 five-membered ring.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ii	0.86 (2)	2.02 (2)	2.8766 (15)	177.3 (19)
N2—H1N2⋯O1iii	0.863 (19)	2.035 (19)	2.8949 (14)	174.2 (17)
C7—H7A⋯O1iii	0.96	2.38	3.3370 (17)	176

Symmetry codes: (ii) ; (iii) .