(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3-yl)ethyl-idene]thio-semicarbazide.

The title compound, C(12)H(10)BrN(3)O(2)S, exists in an E configuration with respect to the C=N bond. The approximately planar 2H-chromene ring system [maximum deviation = 0.059 (1) Å] is inclined at a dihedral angle of 17.50 (5)° with respect to the mean plane through the thio-semicarbazide unit and an intra-molecular N-H⋯N hydrogen bond generates an S(5) ring. In the crystal structure, adjacent mol-ecules are linked by N-H⋯S hydrogen bonds, forming [010] chains built up from R(2) (2)(8) loops, such that each S atom accepts two such bonds. These chains are further inter-connected into sheets parallel to the ab plane via short Br⋯O inter-actions [3.0732 (13) Å] and a π-π aromatic stacking inter-action [3.7870 (8) Å] is also observed.

Related literature

For general background to and applications of the title thio­semicarbazide compound, see: Anderson et al. (2002 ▶); Chulian et al. (2009 ▶); Desai et al. (1984 ▶); Finn et al. (2004 ▶); Hofmanová et al. (1998 ▶); Hoult & Payá (1996 ▶); Kimura et al. (1985 ▶); Laffitte et al. (2002 ▶); Mitscher (2002 ▶); Moffett (1964 ▶); Pillai et al. (1999 ▶); Shukla et al. (1984 ▶); Tassies et al. (2002 ▶); Weber et al. (1998 ▶). For the preparation, see: Moamen et al. (2009 ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For a related structure, see: Arshad et al. (2010 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C12H10BrN3O2S

M = 340.20

Triclinic,

a = 6.3796 (6) Å

b = 8.1260 (7) Å

c = 13.3756 (12) Å

α = 106.697 (2)°

β = 95.095 (2)°

γ = 98.925 (2)°

V = 649.57 (10) Å3

Z = 2

Mo Kα radiation

μ = 3.33 mm−1

T = 100 K

0.73 × 0.20 × 0.15 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.196, T max = 0.637

19355 measured reflections

5036 independent reflections

4733 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.084

S = 1.17

5036 reflections

185 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.73 e Å−3

Δρmin = −0.56 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 datablocks global, I. DOI: 10.1107/S1600536810019240/hb5461sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019240/hb5461Isup2.hkl

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

C12H10BrN3O2S	Z = 2
Mr = 340.20	F(000) = 340
Triclinic, P1	Dx = 1.739 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3796 (6) Å	Cell parameters from 9969 reflections
b = 8.1260 (7) Å	θ = 2.7–35.1°
c = 13.3756 (12) Å	µ = 3.33 mm−1
α = 106.697 (2)°	T = 100 K
β = 95.095 (2)°	Needle, yellow
γ = 98.925 (2)°	0.73 × 0.20 × 0.15 mm
V = 649.57 (10) Å3

Bruker APEXII DUO CCD diffractometer	5036 independent reflections
Radiation source: fine-focus sealed tube	4733 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 33.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.196, Tmax = 0.637	k = −12→12
19355 measured reflections	l = −20→20

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ2(Fo2) + (0.0569P)2 + 0.0443P] where P = (Fo2 + 2Fc2)/3
5036 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.56 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
Br1	0.831903 (19)	−0.130575 (15)	0.134917 (9)	0.01986 (5)
S1	−0.52737 (6)	0.26734 (4)	0.52668 (3)	0.02208 (7)
O1	0.39540 (15)	0.46915 (12)	0.12143 (7)	0.01830 (16)
O2	0.14155 (19)	0.62282 (15)	0.15561 (9)	0.0270 (2)
N1	−0.08889 (17)	0.33908 (13)	0.34997 (8)	0.01559 (17)
N2	−0.24110 (18)	0.37175 (14)	0.41584 (8)	0.01611 (17)
N3	−0.2610 (2)	0.08895 (15)	0.41915 (9)	0.0204 (2)
C1	0.2259 (2)	0.50976 (16)	0.17462 (10)	0.0177 (2)
C2	0.48940 (19)	0.32942 (15)	0.12434 (9)	0.01509 (18)
C3	0.6564 (2)	0.29964 (17)	0.06532 (10)	0.0179 (2)
H3A	0.7011	0.3720	0.0255	0.022*
C4	0.75479 (19)	0.15951 (17)	0.06722 (9)	0.0178 (2)
H4A	0.8675	0.1375	0.0288	0.021*
C5	0.68424 (19)	0.05161 (16)	0.12688 (9)	0.01630 (19)
C6	0.51529 (19)	0.07869 (15)	0.18374 (9)	0.01632 (19)
H6A	0.4670	0.0031	0.2210	0.020*
C7	0.41777 (18)	0.22285 (15)	0.18420 (9)	0.01446 (18)
C8	0.25545 (18)	0.27089 (15)	0.24813 (9)	0.01512 (18)
H8A	0.2113	0.2048	0.2915	0.018*
C9	0.16407 (18)	0.41112 (15)	0.24698 (9)	0.01454 (18)
C10	−0.00056 (18)	0.46198 (15)	0.31560 (9)	0.01494 (18)
C11	−0.33190 (19)	0.23856 (15)	0.44883 (9)	0.01633 (19)
C12	−0.0508 (2)	0.64307 (16)	0.34349 (10)	0.0196 (2)
H12A	−0.0674	0.6814	0.4167	0.029*
H12B	−0.1814	0.6417	0.3013	0.029*
H12C	0.0641	0.7218	0.3302	0.029*
H1N2	−0.308 (5)	0.438 (4)	0.420 (3)	0.060 (9)*
H1N3	−0.317 (3)	0.005 (3)	0.4346 (16)	0.019 (4)*
H2N3	−0.164 (5)	0.094 (4)	0.383 (3)	0.057 (9)*

	U11	U22	U33	U12	U13	U23
Br1	0.02111 (7)	0.01997 (7)	0.02278 (7)	0.01169 (5)	0.00823 (5)	0.00757 (5)
S1	0.02734 (16)	0.01628 (13)	0.03123 (16)	0.01088 (11)	0.02016 (13)	0.01232 (11)
O1	0.0205 (4)	0.0197 (4)	0.0223 (4)	0.0104 (3)	0.0121 (3)	0.0121 (3)
O2	0.0334 (5)	0.0302 (5)	0.0330 (5)	0.0205 (4)	0.0192 (4)	0.0220 (4)
N1	0.0174 (4)	0.0165 (4)	0.0162 (4)	0.0071 (3)	0.0086 (3)	0.0062 (3)
N2	0.0191 (4)	0.0145 (4)	0.0197 (4)	0.0078 (3)	0.0116 (3)	0.0078 (3)
N3	0.0264 (5)	0.0157 (4)	0.0259 (5)	0.0104 (4)	0.0158 (4)	0.0099 (4)
C1	0.0197 (5)	0.0189 (5)	0.0199 (5)	0.0086 (4)	0.0097 (4)	0.0096 (4)
C2	0.0157 (4)	0.0162 (4)	0.0162 (4)	0.0063 (4)	0.0057 (3)	0.0066 (4)
C3	0.0181 (5)	0.0216 (5)	0.0186 (5)	0.0077 (4)	0.0089 (4)	0.0092 (4)
C4	0.0166 (5)	0.0219 (5)	0.0176 (5)	0.0078 (4)	0.0075 (4)	0.0063 (4)
C5	0.0164 (4)	0.0176 (5)	0.0172 (4)	0.0084 (4)	0.0054 (4)	0.0053 (4)
C6	0.0173 (5)	0.0163 (4)	0.0186 (5)	0.0071 (4)	0.0068 (4)	0.0069 (4)
C7	0.0154 (4)	0.0149 (4)	0.0154 (4)	0.0055 (3)	0.0058 (3)	0.0058 (3)
C8	0.0158 (4)	0.0155 (4)	0.0171 (4)	0.0060 (4)	0.0068 (4)	0.0069 (4)
C9	0.0158 (4)	0.0152 (4)	0.0156 (4)	0.0059 (3)	0.0068 (3)	0.0064 (3)
C10	0.0155 (4)	0.0155 (4)	0.0167 (4)	0.0061 (4)	0.0065 (4)	0.0065 (3)
C11	0.0198 (5)	0.0146 (4)	0.0184 (5)	0.0068 (4)	0.0090 (4)	0.0072 (4)
C12	0.0234 (5)	0.0159 (5)	0.0248 (5)	0.0092 (4)	0.0121 (4)	0.0090 (4)

Br1—C5	1.8965 (11)	C3—C4	1.3879 (17)
S1—C11	1.6957 (12)	C3—H3A	0.9300
O1—C2	1.3722 (14)	C4—C5	1.3969 (17)
O1—C1	1.3770 (14)	C4—H4A	0.9300
O2—C1	1.2091 (15)	C5—C6	1.3827 (16)
N1—C10	1.2890 (15)	C6—C7	1.4079 (15)
N1—N2	1.3738 (14)	C6—H6A	0.9300
N2—C11	1.3516 (15)	C7—C8	1.4307 (16)
N2—H1N2	0.73 (3)	C8—C9	1.3613 (15)
N3—C11	1.3288 (15)	C8—H8A	0.9300
N3—H1N3	0.81 (2)	C9—C10	1.4846 (16)
N3—H2N3	0.82 (3)	C10—C12	1.5033 (16)
C1—C9	1.4665 (16)	C12—H12A	0.9600
C2—C3	1.3917 (16)	C12—H12B	0.9600
C2—C7	1.3930 (15)	C12—H12C	0.9600
C2—O1—C1	122.75 (9)	C5—C6—H6A	120.6
C10—N1—N2	119.10 (10)	C7—C6—H6A	120.6
C11—N2—N1	117.19 (10)	C2—C7—C6	118.95 (10)
C11—N2—H1N2	111 (3)	C2—C7—C8	118.13 (10)
N1—N2—H1N2	128 (3)	C6—C7—C8	122.83 (10)
C11—N3—H1N3	119.9 (15)	C9—C8—C7	121.52 (10)
C11—N3—H2N3	112 (2)	C9—C8—H8A	119.2
H1N3—N3—H2N3	128 (3)	C7—C8—H8A	119.2
O2—C1—O1	116.08 (11)	C8—C9—C1	119.13 (10)
O2—C1—C9	126.61 (11)	C8—C9—C10	120.96 (10)
O1—C1—C9	117.31 (10)	C1—C9—C10	119.90 (10)
O1—C2—C3	117.34 (10)	N1—C10—C9	113.79 (10)
O1—C2—C7	120.50 (10)	N1—C10—C12	124.38 (10)
C3—C2—C7	122.16 (10)	C9—C10—C12	121.81 (10)
C4—C3—C2	118.48 (11)	N3—C11—N2	117.80 (11)
C4—C3—H3A	120.8	N3—C11—S1	122.45 (9)
C2—C3—H3A	120.8	N2—C11—S1	119.74 (9)
C3—C4—C5	119.89 (10)	C10—C12—H12A	109.5
C3—C4—H4A	120.1	C10—C12—H12B	109.5
C5—C4—H4A	120.1	H12A—C12—H12B	109.5
C6—C5—C4	121.73 (10)	C10—C12—H12C	109.5
C6—C5—Br1	119.11 (9)	H12A—C12—H12C	109.5
C4—C5—Br1	119.11 (9)	H12B—C12—H12C	109.5
C5—C6—C7	118.75 (10)
C10—N1—N2—C11	179.07 (11)	C5—C6—C7—C8	−174.14 (11)
C2—O1—C1—O2	−171.47 (12)	C2—C7—C8—C9	3.45 (17)
C2—O1—C1—C9	7.73 (18)	C6—C7—C8—C9	179.96 (12)
C1—O1—C2—C3	178.59 (11)	C7—C8—C9—C1	3.09 (18)
C1—O1—C2—C7	−1.23 (18)	C7—C8—C9—C10	−178.55 (11)
O1—C2—C3—C4	179.76 (11)	O2—C1—C9—C8	170.56 (14)
C7—C2—C3—C4	−0.43 (19)	O1—C1—C9—C8	−8.54 (18)
C2—C3—C4—C5	0.48 (19)	O2—C1—C9—C10	−7.8 (2)
C3—C4—C5—C6	0.93 (19)	O1—C1—C9—C10	173.08 (11)
C3—C4—C5—Br1	−176.32 (9)	N2—N1—C10—C9	178.83 (10)
C4—C5—C6—C7	−2.35 (18)	N2—N1—C10—C12	0.63 (18)
Br1—C5—C6—C7	174.90 (9)	C8—C9—C10—N1	−18.82 (16)
O1—C2—C7—C6	178.81 (11)	C1—C9—C10—N1	159.52 (11)
C3—C2—C7—C6	−0.99 (18)	C8—C9—C10—C12	159.43 (12)
O1—C2—C7—C8	−4.54 (17)	C1—C9—C10—C12	−22.22 (17)
C3—C2—C7—C8	175.65 (11)	N1—N2—C11—N3	2.93 (17)
C5—C6—C7—C2	2.34 (18)	N1—N2—C11—S1	−177.80 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2···S1i	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3···S1ii	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2⋯S1i	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3⋯S1ii	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)

Symmetry codes: (i) ; (ii) .