1-(5-Bromo-2-oxoindolin-3-yl-idene)thio-semicarbazide acetonitrile monosolvate.

In the crystal structure of the title compound, C(9)H(7)BrN(4)OS·C(2)H(3)N, the mol-ecules are connected via N-H⋯O and N-H⋯S inter-actions into zigzag chains perpendicular to [001]. The mol-ecules in these chains are additionally linked to acetonitrile solvent mol-ecules through N-H⋯N hydrogen bonding. The mol-ecules are arranged in layers and are stacked in the direction of the c axis indicative of π-π inter-actions, with distance = 3.381 (7) Å for the C⋯C interaction parallel to [001]. An intra-molecular N-H⋯O hydrogen bond is also observed in the main mol-ecule.

Related literature

For the pharmacological properties of isatin-thio­semicarbazone derivatives against cruzain, falcipain-2 and rhodesain, see: Chiyanzu et al. (2003 ▶). For the synthesis of 5-bromo­isatin-3-thio­semicarbazone, see: Campaigne & Archer (1952 ▶).

Experimental

Crystal data

C9H7BrN4OS·C2H3N

M = 340.21

Monoclinic,

a = 20.017 (4) Å

b = 13.352 (2) Å

c = 13.190 (5) Å

β = 129.258 (2)°

V = 2729.6 (12) Å3

Z = 8

Mo Kα radiation

μ = 3.16 mm−1

T = 293 K

0.22 × 0.20 × 0.16 mm

Data collection

Bruker CCD X8 APEXII diffractometer

10884 measured reflections

3377 independent reflections

2754 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.105

S = 1.09

3377 reflections

173 parameters

H-atom parameters constrained

Δρmax = 1.03 e Å−3

Δρmin = −0.86 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023786/nc2233sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023786/nc2233Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811023786/nc2233Isup3.cml

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

C9H7BrN4OS·C2H3N	F(000) = 1360
Mr = 340.21	Dx = 1.656 Mg m−3
Monoclinic, C2/c	Melting point: 544.15 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.017 (4) Å	Cell parameters from 3718 reflections
b = 13.352 (2) Å	θ = 2.6–27.6°
c = 13.190 (5) Å	µ = 3.16 mm−1
β = 129.258 (2)°	T = 293 K
V = 2729.6 (12) Å3	Block, yellow
Z = 8	0.22 × 0.20 × 0.16 mm

Bruker CCD X8 APEXII diffractometer	2754 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, Bruker CCD X8 APEXII	Rint = 0.030
graphite	θmax = 28.3°, θmin = 2.0°
φ and ω scans	h = −26→14
10884 measured reflections	k = −16→17
3377 independent reflections	l = −7→17

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0396P)2 + 12.0809P] where P = (Fo2 + 2Fc2)/3
3377 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 1.03 e Å−3
0 restraints	Δρmin = −0.86 e Å−3

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
C9	0.3611 (2)	−0.2695 (2)	0.4897 (3)	0.0175 (6)
C10	0.0960 (2)	−0.0277 (3)	0.2196 (3)	0.0297 (8)
H8	0.0967	−0.0995	0.2159	0.045*
H9	0.0735	−0.0003	0.1361	0.045*
H10	0.0602	−0.0075	0.2410	0.045*
C11	0.1832 (2)	0.0088 (3)	0.3192 (4)	0.0296 (8)
C6	0.52345 (19)	0.0354 (2)	0.6478 (3)	0.0166 (6)
C5	0.4655 (2)	0.1144 (2)	0.5889 (3)	0.0169 (6)
H3	0.4062	0.1038	0.5301	0.020*
C4	0.5007 (2)	0.2109 (2)	0.6225 (3)	0.0205 (6)
C3	0.5890 (2)	0.2282 (2)	0.7097 (3)	0.0214 (7)
H2	0.6101	0.2934	0.7300	0.026*
C2	0.6469 (2)	0.1459 (3)	0.7675 (3)	0.0224 (7)
H1	0.7063	0.1558	0.8254	0.027*
C1	0.6126 (2)	0.0514 (2)	0.7353 (3)	0.0181 (6)
C8	0.5995 (2)	−0.1188 (3)	0.7243 (3)	0.0191 (6)
C7	0.51065 (19)	−0.0725 (2)	0.6367 (3)	0.0152 (6)
Br	0.42473 (2)	0.32205 (3)	0.54837 (4)	0.02739 (12)
N2	0.43754 (17)	−0.1178 (2)	0.5672 (2)	0.0171 (5)
N3	0.43806 (16)	−0.2191 (2)	0.5678 (2)	0.0174 (5)
H5	0.4860	−0.2515	0.6165	0.021*
N4	0.29129 (18)	−0.2149 (2)	0.4244 (3)	0.0217 (6)
H6	0.2951	−0.1507	0.4317	0.026*
H7	0.2414	−0.2430	0.3741	0.026*
N5	0.2515 (2)	0.0381 (3)	0.3981 (4)	0.0491 (10)
N1	0.65560 (17)	−0.0418 (2)	0.7786 (3)	0.0197 (5)
H4	0.7108	−0.0486	0.8329	0.024*
O	0.61642 (14)	−0.20772 (17)	0.7432 (2)	0.0200 (5)
S	0.36470 (5)	−0.39515 (6)	0.48661 (8)	0.02291 (19)

	U11	U22	U33	U12	U13	U23
C9	0.0139 (15)	0.0224 (17)	0.0165 (14)	−0.0033 (12)	0.0098 (13)	−0.0014 (12)
C10	0.0273 (19)	0.0265 (19)	0.0264 (18)	−0.0018 (15)	0.0126 (16)	−0.0003 (15)
C11	0.0214 (18)	0.0231 (18)	0.035 (2)	0.0042 (14)	0.0134 (17)	0.0086 (15)
C6	0.0129 (14)	0.0219 (16)	0.0136 (14)	−0.0017 (12)	0.0077 (12)	−0.0009 (12)
C5	0.0157 (15)	0.0187 (15)	0.0156 (14)	0.0004 (12)	0.0097 (13)	0.0004 (12)
C4	0.0239 (17)	0.0175 (16)	0.0227 (16)	0.0048 (13)	0.0160 (15)	0.0041 (13)
C3	0.0248 (17)	0.0163 (16)	0.0259 (17)	−0.0049 (13)	0.0173 (15)	−0.0006 (13)
C2	0.0138 (15)	0.0238 (17)	0.0244 (17)	−0.0037 (13)	0.0096 (14)	−0.0032 (13)
C1	0.0149 (15)	0.0230 (16)	0.0164 (14)	−0.0006 (12)	0.0099 (13)	−0.0005 (12)
C8	0.0124 (15)	0.0271 (18)	0.0147 (14)	−0.0001 (13)	0.0072 (13)	0.0000 (12)
C7	0.0119 (14)	0.0188 (15)	0.0128 (13)	0.0001 (11)	0.0068 (12)	−0.0005 (11)
Br	0.0271 (2)	0.01948 (18)	0.0320 (2)	0.00440 (14)	0.01693 (16)	0.00453 (14)
N2	0.0164 (13)	0.0179 (13)	0.0172 (13)	0.0003 (10)	0.0107 (12)	0.0007 (10)
N3	0.0101 (12)	0.0179 (13)	0.0187 (13)	0.0011 (10)	0.0066 (11)	0.0003 (10)
N4	0.0130 (13)	0.0167 (13)	0.0283 (15)	−0.0002 (11)	0.0097 (12)	0.0017 (11)
N5	0.0247 (19)	0.046 (2)	0.052 (2)	−0.0026 (16)	0.0130 (18)	0.0101 (19)
N1	0.0110 (12)	0.0191 (14)	0.0223 (13)	−0.0005 (10)	0.0073 (11)	−0.0002 (11)
O	0.0133 (11)	0.0176 (11)	0.0212 (11)	0.0014 (9)	0.0072 (10)	0.0005 (9)
S	0.0140 (4)	0.0176 (4)	0.0273 (4)	0.0001 (3)	0.0084 (3)	0.0001 (3)

C9—N4	1.305 (4)	C3—C2	1.419 (5)
C9—N3	1.370 (4)	C3—H2	0.9300
C9—S	1.681 (3)	C2—C1	1.369 (5)
C10—C11	1.451 (5)	C2—H1	0.9300
C10—H8	0.9600	C1—N1	1.412 (4)
C10—H9	0.9600	C8—O	1.217 (4)
C10—H10	0.9600	C8—O	1.217 (4)
C11—N5	1.142 (5)	C8—N1	1.346 (4)
C11—N5	1.142 (5)	C8—C7	1.510 (4)
C6—C5	1.386 (4)	C7—N2	1.285 (4)
C6—C1	1.398 (4)	N2—N3	1.352 (4)
C6—C7	1.455 (4)	N3—H5	0.8600
C5—C4	1.399 (5)	N4—H6	0.8600
C5—H3	0.9300	N4—H7	0.8600
C4—C3	1.389 (5)	N1—H4	0.8600
C4—Br	1.894 (3)
N4—C9—N3	116.5 (3)	C1—C2—H1	121.0
N4—C9—S	125.9 (2)	C3—C2—H1	121.0
N3—C9—S	117.6 (2)	C2—C1—C6	121.6 (3)
C11—C10—H8	109.5	C2—C1—N1	129.0 (3)
C11—C10—H9	109.5	C6—C1—N1	109.4 (3)
H8—C10—H9	109.5	O—C8—O	0.00 (5)
C11—C10—H10	109.5	O—C8—N1	127.3 (3)
H8—C10—H10	109.5	O—C8—N1	127.3 (3)
H9—C10—H10	109.5	O—C8—C7	126.6 (3)
N5—C11—N5	0.0 (8)	O—C8—C7	126.6 (3)
N5—C11—C10	179.2 (5)	N1—C8—C7	106.1 (3)
N5—C11—C10	179.2 (5)	N2—C7—C6	125.9 (3)
C5—C6—C1	121.7 (3)	N2—C7—C8	127.7 (3)
C5—C6—C7	131.7 (3)	C6—C7—C8	106.3 (3)
C1—C6—C7	106.6 (3)	C7—N2—N3	117.8 (3)
C6—C5—C4	116.6 (3)	N2—N3—C9	119.0 (3)
C6—C5—H3	121.7	N2—N3—H5	120.5
C4—C5—H3	121.7	C9—N3—H5	120.5
C3—C4—C5	122.5 (3)	C9—N4—H6	120.0
C3—C4—Br	118.8 (3)	C9—N4—H7	120.0
C5—C4—Br	118.6 (2)	H6—N4—H7	120.0
C4—C3—C2	119.6 (3)	C8—N1—C1	111.6 (3)
C4—C3—H2	120.2	C8—N1—H4	124.2
C2—C3—H2	120.2	C1—N1—H4	124.2
C1—C2—C3	117.9 (3)
C1—C6—C5—C4	−0.6 (4)	O—C8—C7—N2	0.2 (5)
C7—C6—C5—C4	−180.0 (3)	N1—C8—C7—N2	−178.7 (3)
C6—C5—C4—C3	0.3 (4)	O—C8—C7—C6	179.1 (3)
C6—C5—C4—Br	−178.6 (2)	O—C8—C7—C6	179.1 (3)
C5—C4—C3—C2	0.3 (5)	N1—C8—C7—C6	0.2 (3)
Br—C4—C3—C2	179.2 (2)	C6—C7—N2—N3	179.4 (3)
C4—C3—C2—C1	−0.7 (5)	C8—C7—N2—N3	−1.9 (4)
C3—C2—C1—C6	0.4 (5)	C7—N2—N3—C9	−176.9 (3)
C3—C2—C1—N1	179.9 (3)	N4—C9—N3—N2	−3.6 (4)
C5—C6—C1—C2	0.3 (5)	S—C9—N3—N2	176.5 (2)
C7—C6—C1—C2	179.8 (3)	C10—C11—N5—N5	0(12)
C5—C6—C1—N1	−179.3 (3)	O—C8—N1—C1	−179.0 (3)
C7—C6—C1—N1	0.2 (3)	O—C8—N1—C1	−179.0 (3)
C5—C6—C7—N2	−1.8 (5)	C7—C8—N1—C1	−0.1 (3)
C1—C6—C7—N2	178.7 (3)	C2—C1—N1—C8	−179.6 (3)
C5—C6—C7—C8	179.2 (3)	C6—C1—N1—C8	0.0 (3)
C1—C6—C7—C8	−0.2 (3)	N1—C8—O—O	0.0 (2)
O—C8—C7—N2	0.2 (5)	C7—C8—O—O	0.00 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H5···O	0.86	2.10	2.769 (3)	134
N4—H6···N5	0.86	2.61	3.438 (5)	161
N4—H7···Oi	0.86	2.05	2.906 (4)	173
N1—H4···Sii	0.86	2.50	3.350 (3)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H5⋯O	0.86	2.10	2.769 (3)	134
N4—H6⋯N5	0.86	2.61	3.438 (5)	161
N4—H7⋯Oi	0.86	2.05	2.906 (4)	173
N1—H4⋯Sii	0.86	2.50	3.350 (3)	169

Symmetry codes: (i) ; (ii) .