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In the title mol­ecule, C8H8BrN3O2S, there are two intra­molecular hydrogen bonds, one involving the hydrazo group and the O atom of the hydroxyl group, and the other involving the amino group and the N atom of the hydrazo group. In the crystal structure, inter­molecular O—H...S, N—H...S and N—H...O hydrogen bonds connect mol­ecules into a two-dimensional network perpendicular to the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033211/lh2450sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033211/lh2450Isup2.hkl
Contains datablock I

CCDC reference: 657740

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.058
  • wR factor = 0.168
  • Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT230_ALERT_2_C Hirshfeld Test Diff for C3 - C4 .. 6.20 su PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT420_ALERT_2_C D-H Without Acceptor N3 - H3B ... ? PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O2 .. 3.32 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

We have already reported the crystal structures of active esters and other related ligands containing salicyl groups i.e. ethyl 5-bromosalicylate (Jin & Xiao, 2005) and methyl 5-bromosalicylate (Xiao et al., 2005). Part of our studies is to find new methods to synthesize derivatives of 5-bromo sylicylic acid e.g. di-4-(5-bromo salicyloyl) hydrazino-bithiazole. In this paper we report the crystal structure of the title compound.

The title molecule (Fig. 1) contains two intramolecular hydrogen bonds. These are between the hydrazo group and the O atom of the hydroxyl group, and the amino group and the N atom of the hydrazo group. Bond lengths and angles show normal values (Allen et al., 1987). The atoms C1—C6 lie in a plane with an r.m.s deviation of 0.0099 Å. In the crystal structure, molecules are linked by intermolecular O—H···S, N—H···S and N—H···O hydrogen bonds to form a two-dimensional network perpendicular to the c axis (Fig. 2).

Related literature top

For related crystal structures, see: Jin & Xiao (2005); Xiao et al. (2005).

For related literature, see: Allen et al. (1987).

Experimental top

5-Bromo salicylhydrazide (24.8 g, 0.10 mol) and KSCN (14.4 g, 0.20 mol) were added to 100 ml of water at 273 K and stirred for 10 minutes. Then 20 ml of concentrated hydrochloric acid were added, and stirred for 1 h. The reaction mixture was slowly warmed to 366 K and stirred for a further 8 h. After staying for 1 h in a refrigerator, the resulting light-yellow precipitate was filtered and rinsed with water to pH6. A light-yellow solid formed was recrystallized from warm water to give 23.2 g (80% yield) of 4-(5-bromo salicyloyl) thiosemicarbazide. A plate-like crystal suitable for X-ray analysis was grown from a solution of the title compound in methanol at room temperature by slow evaporation.

Refinement top

The hydroxyl, hydrazo and amino H atoms were located in a difference Fourier map and their positions were refined. All other H atoms were included in the riding-model approximation, with C—H distances of 0.93 Å. The isotropic displacement parameters were set equal to 1.2Ueq of the carrier atom for the aromatic and hydrazo and amino H atoms, and to 1.5Ueq of the carrier for hydroxyl H atoms.

Structure description top

We have already reported the crystal structures of active esters and other related ligands containing salicyl groups i.e. ethyl 5-bromosalicylate (Jin & Xiao, 2005) and methyl 5-bromosalicylate (Xiao et al., 2005). Part of our studies is to find new methods to synthesize derivatives of 5-bromo sylicylic acid e.g. di-4-(5-bromo salicyloyl) hydrazino-bithiazole. In this paper we report the crystal structure of the title compound.

The title molecule (Fig. 1) contains two intramolecular hydrogen bonds. These are between the hydrazo group and the O atom of the hydroxyl group, and the amino group and the N atom of the hydrazo group. Bond lengths and angles show normal values (Allen et al., 1987). The atoms C1—C6 lie in a plane with an r.m.s deviation of 0.0099 Å. In the crystal structure, molecules are linked by intermolecular O—H···S, N—H···S and N—H···O hydrogen bonds to form a two-dimensional network perpendicular to the c axis (Fig. 2).

For related crystal structures, see: Jin & Xiao (2005); Xiao et al. (2005).

For related literature, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure showing ellipsoids at 30% probability level.
[Figure 2] Fig. 2. The packing of the title compound showing hydrogen bonds as dashed lines.
4-(5-Bromo-2-hydroxybenzoyl)thiosemicarbazide top
Crystal data top
C8H8BrN3O2SZ = 2
Mr = 290.14F(000) = 288
Triclinic, P1Dx = 1.808 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.4937 (5) ÅCell parameters from 1175 reflections
b = 8.6731 (10) Åθ = 2.5–26.7°
c = 14.4036 (17) ŵ = 4.03 mm1
α = 101.341 (2)°T = 292 K
β = 91.787 (2)°Plate, colorless
γ = 103.660 (2)°0.25 × 0.18 × 0.15 mm
V = 533.06 (11) Å3
Data collection top
Bruker SMART CCD
diffractometer
1896 independent reflections
Radiation source: fine-focus sealed tube1492 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 25.3°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 55
Tmin = 0.422, Tmax = 0.547k = 1010
3551 measured reflectionsl = 1716
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0918P)2 + 0.5449P]
where P = (Fo2 + 2Fc2)/3
1896 reflections(Δ/σ)max < 0.001
151 parametersΔρmax = 0.83 e Å3
5 restraintsΔρmin = 0.62 e Å3
Crystal data top
C8H8BrN3O2Sγ = 103.660 (2)°
Mr = 290.14V = 533.06 (11) Å3
Triclinic, P1Z = 2
a = 4.4937 (5) ÅMo Kα radiation
b = 8.6731 (10) ŵ = 4.03 mm1
c = 14.4036 (17) ÅT = 292 K
α = 101.341 (2)°0.25 × 0.18 × 0.15 mm
β = 91.787 (2)°
Data collection top
Bruker SMART CCD
diffractometer
1896 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1492 reflections with I > 2σ(I)
Tmin = 0.422, Tmax = 0.547Rint = 0.028
3551 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0585 restraints
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.83 e Å3
1896 reflectionsΔρmin = 0.62 e Å3
151 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.40000 (18)1.27910 (9)0.54471 (5)0.0549 (3)
C10.9979 (13)0.9875 (7)0.2863 (4)0.0301 (13)
C20.8402 (14)1.0883 (7)0.2499 (4)0.0320 (14)
C30.8572 (15)1.2431 (7)0.2997 (5)0.0390 (15)
H30.75251.30850.27500.047*
C41.0256 (16)1.3012 (8)0.3847 (6)0.0474 (18)
H41.04011.40720.41680.057*
C51.1756 (15)1.2044 (8)0.4241 (5)0.0400 (16)
C61.1646 (15)1.0498 (8)0.3748 (5)0.0386 (15)
H61.26970.98580.40080.046*
C71.0080 (14)0.8197 (7)0.2383 (4)0.0291 (13)
C80.6261 (14)0.4642 (7)0.1119 (4)0.0292 (13)
N10.8087 (12)0.7505 (6)0.1619 (4)0.0332 (12)
H1A0.713 (13)0.807 (7)0.129 (4)0.040*
N20.8288 (13)0.6018 (6)0.1093 (4)0.0365 (12)
H2A0.977 (12)0.605 (8)0.070 (4)0.044*
N30.4082 (13)0.4717 (6)0.1724 (5)0.0435 (14)
H3A0.371 (16)0.567 (5)0.197 (5)0.052*
H3B0.300 (15)0.376 (5)0.176 (5)0.052*
O10.6661 (12)1.0276 (5)0.1664 (4)0.0481 (12)
H10.64 (2)1.087 (9)0.132 (5)0.072*
O21.1829 (11)0.7491 (6)0.2675 (3)0.0460 (12)
S10.6597 (4)0.28795 (18)0.04272 (12)0.0371 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0649 (6)0.0472 (5)0.0377 (5)0.0050 (4)0.0034 (3)0.0023 (3)
C10.034 (3)0.025 (3)0.029 (3)0.005 (2)0.008 (3)0.000 (2)
C20.036 (3)0.023 (3)0.033 (3)0.004 (3)0.002 (3)0.000 (3)
C30.044 (4)0.027 (3)0.044 (4)0.008 (3)0.000 (3)0.004 (3)
C40.051 (4)0.026 (3)0.064 (5)0.008 (3)0.024 (4)0.005 (3)
C50.041 (4)0.036 (4)0.041 (4)0.003 (3)0.007 (3)0.010 (3)
C60.037 (4)0.037 (4)0.045 (4)0.010 (3)0.009 (3)0.016 (3)
C70.035 (3)0.023 (3)0.027 (3)0.005 (3)0.003 (3)0.002 (2)
C80.037 (3)0.023 (3)0.026 (3)0.010 (2)0.008 (2)0.001 (2)
N10.043 (3)0.022 (3)0.034 (3)0.015 (2)0.002 (2)0.002 (2)
N20.046 (3)0.023 (3)0.039 (3)0.011 (2)0.006 (2)0.001 (2)
N30.045 (3)0.022 (3)0.063 (4)0.011 (2)0.011 (3)0.004 (3)
O10.070 (3)0.026 (2)0.046 (3)0.014 (2)0.015 (2)0.004 (2)
O20.059 (3)0.040 (3)0.041 (3)0.025 (2)0.005 (2)0.000 (2)
S10.0479 (10)0.0216 (8)0.0394 (9)0.0088 (7)0.0003 (7)0.0009 (6)
Geometric parameters (Å, º) top
Br1—C51.896 (7)C7—O21.215 (7)
C1—C61.399 (9)C7—N11.342 (8)
C1—C21.412 (9)C8—N21.327 (8)
C1—C71.495 (8)C8—N31.337 (8)
C2—O11.354 (8)C8—S11.694 (6)
C2—C31.376 (9)N1—N21.386 (7)
C3—C41.359 (10)N1—H1A0.91 (3)
C3—H30.9300N2—H2A0.89 (3)
C4—C51.383 (10)N3—H3A0.88 (3)
C4—H40.9300N3—H3B0.87 (3)
C5—C61.377 (9)O1—H10.81 (4)
C6—H60.9300
C6—C1—C2117.6 (5)C1—C6—H6119.5
C6—C1—C7116.4 (5)O2—C7—N1121.9 (6)
C2—C1—C7126.0 (6)O2—C7—C1122.1 (6)
O1—C2—C3121.1 (6)N1—C7—C1115.9 (5)
O1—C2—C1118.5 (5)N2—C8—N3117.3 (5)
C3—C2—C1120.5 (6)N2—C8—S1119.7 (5)
C4—C3—C2120.5 (6)N3—C8—S1123.0 (4)
C4—C3—H3119.7C7—N1—N2118.2 (5)
C2—C3—H3119.7C7—N1—H1A124 (4)
C3—C4—C5120.7 (7)N2—N1—H1A114 (4)
C3—C4—H4119.7C8—N2—N1122.5 (5)
C5—C4—H4119.7C8—N2—H2A121 (5)
C6—C5—C4119.6 (7)N1—N2—H2A116 (5)
C6—C5—Br1118.7 (5)C8—N3—H3A120 (5)
C4—C5—Br1121.7 (6)C8—N3—H3B112 (5)
C5—C6—C1121.0 (6)H3A—N3—H3B128 (7)
C5—C6—H6119.5C2—O1—H1120 (7)
C6—C1—C2—O1177.0 (5)C2—C1—C6—C50.4 (8)
C7—C1—C2—O14.0 (8)C7—C1—C6—C5178.7 (5)
C6—C1—C2—C31.2 (8)C6—C1—C7—O29.7 (8)
C7—C1—C2—C3177.8 (5)C2—C1—C7—O2169.3 (6)
O1—C2—C3—C4178.1 (6)C6—C1—C7—N1169.2 (5)
C1—C2—C3—C40.1 (9)C2—C1—C7—N111.8 (8)
C2—C3—C4—C51.9 (10)O2—C7—N1—N27.3 (8)
C3—C4—C5—C62.7 (9)C1—C7—N1—N2173.8 (5)
C3—C4—C5—Br1177.7 (5)N3—C8—N2—N14.3 (9)
C4—C5—C6—C11.5 (9)S1—C8—N2—N1177.9 (4)
Br1—C5—C6—C1178.9 (4)C7—N1—N2—C8106.4 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1i0.81 (4)2.34 (4)3.144 (5)169 (8)
N1—H1A···S1ii0.91 (3)2.81 (5)3.481 (6)132 (5)
N2—H2A···S1iii0.89 (3)2.49 (4)3.331 (5)158 (6)
N3—H3A···O2iv0.88 (3)2.08 (4)2.938 (7)164 (7)
N1—H1A···O10.91 (3)1.95 (6)2.618 (7)129 (6)
N3—H3A···N10.88 (3)2.36 (7)2.686 (7)102 (5)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) x+2, y+1, z; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC8H8BrN3O2S
Mr290.14
Crystal system, space groupTriclinic, P1
Temperature (K)292
a, b, c (Å)4.4937 (5), 8.6731 (10), 14.4036 (17)
α, β, γ (°)101.341 (2), 91.787 (2), 103.660 (2)
V3)533.06 (11)
Z2
Radiation typeMo Kα
µ (mm1)4.03
Crystal size (mm)0.25 × 0.18 × 0.15
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.422, 0.547
No. of measured, independent and
observed [I > 2σ(I)] reflections
3551, 1896, 1492
Rint0.028
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.168, 1.11
No. of reflections1896
No. of parameters151
No. of restraints5
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.83, 0.62

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1i0.81 (4)2.34 (4)3.144 (5)169 (8)
N1—H1A···S1ii0.91 (3)2.81 (5)3.481 (6)132 (5)
N2—H2A···S1iii0.89 (3)2.49 (4)3.331 (5)158 (6)
N3—H3A···O2iv0.88 (3)2.08 (4)2.938 (7)164 (7)
N1—H1A···O10.91 (3)1.95 (6)2.618 (7)129 (6)
N3—H3A···N10.88 (3)2.36 (7)2.686 (7)102 (5)
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) x+2, y+1, z; (iv) x1, y, z.
 

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