5-Bromo-2-hy-droxy-benzaldehyde thio-semicarbazone.

The mol-ecule of the title compound, C(8)H(8)BrN(3)OS, is close to being planar, with maximum deviations of -0.127 (3) and 0.135 (5) Å for the N atoms of the -NH- and NH(2)- groups, respectively. Intra-molecular N-H⋯N and O-H⋯N hydrogen bonds to the same acceptor N atom generate S(5) and S(6) ring motifs. In the crystal structure, mol-ecules are connected into [010] chains by pairs of N-H⋯S hydrogen bonds with R(2) (2)(8) graph-set motifs. The crystal used for data collection was found to be an inversion twin.

Related literature

For background on the biological activities and pharmaceutical properties of thio­semicarbazones and their derivatives, see: Casas et al. (2000 ▶); Ferrari et al. (2000 ▶); Maccioni et al. (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C8H8BrN3OS

M = 274.14

Orthorhombic,

a = 4.4564 (2) Å

b = 8.3515 (3) Å

c = 27.7153 (14) Å

V = 1031.50 (8) Å3

Z = 4

Mo Kα radiation

μ = 4.16 mm−1

T = 296 K

0.13 × 0.09 × 0.05 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.614, T max = 0.819

9532 measured reflections

1934 independent reflections

1782 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.063

S = 1.04

1934 reflections

144 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), with 744 Freidel pairs

Flack parameter: 0.477 (11)

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043357/hb5704sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043357/hb5704Isup2.hkl

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

C8H8BrN3OS	F(000) = 544
Mr = 274.14	Dx = 1.765 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 17874 reflections
a = 4.4564 (2) Å	θ = 1.5–26.1°
b = 8.3515 (3) Å	µ = 4.16 mm−1
c = 27.7153 (14) Å	T = 296 K
V = 1031.50 (8) Å3	Prism, colourless
Z = 4	0.13 × 0.09 × 0.05 mm

Stoe IPDS II diffractometer	1934 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1782 reflections with I > 2σ(I)
plane graphite	Rint = 0.037
Detector resolution: 6.67 pixels mm-1	θmax = 25.6°, θmin = 2.6°
ω scans	h = −5→5
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.614, Tmax = 0.819	l = −33→33
9532 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.063	w = 1/[σ2(Fo2) + (0.0281P)2 + 0.5533P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1934 reflections	Δρmax = 0.54 e Å−3
144 parameters	Δρmin = −0.29 e Å−3
4 restraints	Absolute structure: Flack (1983), with 744 Freidel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.477 (11)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.80875 (10)	−0.32853 (5)	0.06313 (1)	0.0606 (1)
S1	−0.5577 (2)	0.35791 (11)	0.26412 (3)	0.0517 (3)
O1	0.2883 (6)	0.3331 (3)	0.08454 (10)	0.0596 (9)
N1	−0.0227 (7)	0.2201 (3)	0.16022 (10)	0.0407 (9)
N2	−0.2226 (8)	0.2237 (3)	0.19824 (9)	0.0408 (9)
N3	−0.2703 (13)	0.4940 (4)	0.19194 (14)	0.0786 (16)
C1	0.4380 (8)	−0.0920 (4)	0.10693 (12)	0.0416 (10)
C2	0.6401 (7)	−0.1207 (4)	0.07038 (11)	0.0420 (10)
C3	0.7260 (8)	0.0001 (5)	0.03956 (13)	0.0486 (11)
C4	0.6033 (8)	0.1505 (5)	0.04464 (12)	0.0485 (11)
C5	0.3981 (7)	0.1819 (5)	0.08111 (11)	0.0418 (10)
C6	0.3119 (8)	0.0589 (4)	0.11293 (11)	0.0382 (9)
C7	0.0966 (8)	0.0836 (4)	0.15148 (11)	0.0389 (10)
C8	−0.3365 (8)	0.3610 (4)	0.21496 (11)	0.0416 (10)
H1	0.38530	−0.17450	0.12780	0.0500*
HN2	−0.323 (12)	0.587 (3)	0.2025 (16)	0.089 (16)*
HN1	−0.260 (9)	0.135 (3)	0.2114 (12)	0.050 (11)*
H3	0.86620	−0.01980	0.01540	0.0580*
HO1	0.169 (8)	0.334 (6)	0.1064 (12)	0.071 (14)*
H4	0.65840	0.23180	0.02350	0.0580*
HN3	−0.144 (9)	0.486 (5)	0.1681 (12)	0.071 (14)*
H7	0.04290	−0.00320	0.17060	0.0470*

	U11	U22	U33	U12	U13	U23
Br1	0.0606 (2)	0.0575 (2)	0.0638 (2)	0.0057 (2)	0.0074 (2)	−0.0153 (2)
S1	0.0657 (6)	0.0400 (5)	0.0495 (5)	−0.0007 (5)	0.0199 (4)	−0.0055 (4)
O1	0.0646 (16)	0.0493 (14)	0.0649 (15)	0.007 (2)	0.0180 (14)	0.0102 (14)
N1	0.0400 (16)	0.0458 (16)	0.0364 (13)	−0.0052 (13)	0.0067 (12)	−0.0039 (11)
N2	0.0436 (18)	0.0372 (14)	0.0415 (14)	−0.0028 (13)	0.0117 (13)	−0.0030 (11)
N3	0.122 (4)	0.0397 (17)	0.074 (2)	0.011 (2)	0.051 (3)	0.0063 (17)
C1	0.0408 (17)	0.0454 (19)	0.0387 (17)	−0.0065 (16)	0.0004 (15)	−0.0037 (15)
C2	0.0341 (18)	0.0532 (19)	0.0386 (16)	−0.0029 (14)	0.0002 (13)	−0.0098 (14)
C3	0.038 (2)	0.065 (2)	0.0428 (17)	−0.0032 (18)	0.0111 (15)	0.0010 (16)
C4	0.0427 (19)	0.062 (2)	0.0407 (16)	−0.0058 (19)	0.0012 (13)	0.0095 (17)
C5	0.0368 (17)	0.0475 (19)	0.0411 (15)	−0.0069 (17)	0.0005 (12)	0.0020 (15)
C6	0.0320 (14)	0.0477 (18)	0.0350 (15)	−0.0045 (17)	−0.0008 (15)	−0.0019 (13)
C7	0.0374 (19)	0.0462 (18)	0.0332 (15)	−0.0033 (15)	0.0027 (13)	−0.0010 (14)
C8	0.0465 (18)	0.0381 (18)	0.0402 (15)	−0.0006 (17)	0.0002 (15)	−0.0030 (13)

Br1—C2	1.902 (3)	C1—C2	1.377 (5)
S1—C8	1.682 (3)	C1—C6	1.390 (5)
O1—C5	1.358 (5)	C2—C3	1.376 (5)
O1—HO1	0.81 (3)	C3—C4	1.377 (6)
N1—N2	1.380 (4)	C4—C5	1.388 (5)
N1—C7	1.281 (4)	C5—C6	1.407 (5)
N2—C8	1.337 (4)	C6—C7	1.451 (5)
N3—C8	1.315 (5)	C1—H1	0.9300
N2—HN1	0.84 (3)	C3—H3	0.9300
N3—HN2	0.86 (3)	C4—H4	0.9300
N3—HN3	0.87 (4)	C7—H7	0.9300
C5—O1—HO1	107 (4)	O1—C5—C4	117.7 (3)
N2—N1—C7	115.6 (3)	C5—C6—C7	122.6 (3)
N1—N2—C8	121.9 (3)	C1—C6—C5	118.5 (3)
C8—N2—HN1	122 (2)	C1—C6—C7	119.0 (3)
N1—N2—HN1	116 (2)	N1—C7—C6	122.7 (3)
HN2—N3—HN3	120 (4)	N2—C8—N3	118.1 (3)
C8—N3—HN2	122 (3)	S1—C8—N2	119.4 (3)
C8—N3—HN3	117 (3)	S1—C8—N3	122.5 (3)
C2—C1—C6	120.7 (3)	C2—C1—H1	120.00
Br1—C2—C3	119.6 (3)	C6—C1—H1	120.00
C1—C2—C3	120.7 (3)	C2—C3—H3	120.00
Br1—C2—C1	119.7 (2)	C4—C3—H3	120.00
C2—C3—C4	119.7 (3)	C3—C4—H4	120.00
C3—C4—C5	120.6 (4)	C5—C4—H4	120.00
C4—C5—C6	119.9 (4)	N1—C7—H7	119.00
O1—C5—C6	122.5 (3)	C6—C7—H7	119.00
C7—N1—N2—C8	172.0 (3)	C2—C3—C4—C5	1.2 (5)
N2—N1—C7—C6	−179.8 (3)	C3—C4—C5—O1	179.2 (3)
N1—N2—C8—S1	−175.2 (3)	C3—C4—C5—C6	−0.6 (5)
N1—N2—C8—N3	4.9 (5)	C4—C5—C6—C1	0.4 (5)
C2—C1—C6—C7	179.1 (3)	O1—C5—C6—C1	−179.5 (3)
C2—C1—C6—C5	−0.7 (5)	O1—C5—C6—C7	0.7 (5)
C6—C1—C2—Br1	180.0 (3)	C4—C5—C6—C7	−179.4 (3)
C6—C1—C2—C3	1.2 (5)	C1—C6—C7—N1	177.9 (3)
Br1—C2—C3—C4	179.8 (3)	C5—C6—C7—N1	−2.3 (5)
C1—C2—C3—C4	−1.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···N1	0.81 (3)	1.97 (4)	2.685 (4)	149 (5)
N3—HN3···N1	0.87 (4)	2.30 (4)	2.688 (5)	107 (3)
N2—HN1···S1i	0.84 (3)	2.55 (3)	3.373 (3)	168 (3)
N3—HN2···S1ii	0.86 (3)	2.50 (3)	3.363 (4)	176 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—HO1⋯N1	0.81 (3)	1.97 (4)	2.685 (4)	149 (5)
N3—HN3⋯N1	0.87 (4)	2.30 (4)	2.688 (5)	107 (3)
N2—HN1⋯S1i	0.84 (3)	2.55 (3)	3.373 (3)	168 (3)
N3—HN2⋯S1ii	0.86 (3)	2.50 (3)	3.363 (4)	176 (6)

Symmetry codes: (i) ; (ii) .