Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033211/lh2450sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033211/lh2450Isup2.hkl |
CCDC reference: 657740
Key indicators
- Single-crystal X-ray study
- T = 292 K
- Mean (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
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.
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.
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).
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.
Fig. 1. The molecular structure showing ellipsoids at 30% probability level. | |
Fig. 2. The packing of the title compound showing hydrogen bonds as dashed lines. |
C8H8BrN3O2S | Z = 2 |
Mr = 290.14 | F(000) = 288 |
Triclinic, P1 | Dx = 1.808 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.4937 (5) Å | Cell parameters from 1175 reflections |
b = 8.6731 (10) Å | θ = 2.5–26.7° |
c = 14.4036 (17) Å | µ = 4.03 mm−1 |
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 |
Bruker SMART CCD diffractometer | 1896 independent reflections |
Radiation source: fine-focus sealed tube | 1492 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
φ and ω scans | θmax = 25.3°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→5 |
Tmin = 0.422, Tmax = 0.547 | k = −10→10 |
3551 measured reflections | l = −17→16 |
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H 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 parameters | Δρmax = 0.83 e Å−3 |
5 restraints | Δρmin = −0.62 e Å−3 |
C8H8BrN3O2S | γ = 103.660 (2)° |
Mr = 290.14 | V = 533.06 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.4937 (5) Å | Mo Kα radiation |
b = 8.6731 (10) Å | µ = 4.03 mm−1 |
c = 14.4036 (17) Å | T = 292 K |
α = 101.341 (2)° | 0.25 × 0.18 × 0.15 mm |
β = 91.787 (2)° |
Bruker SMART CCD diffractometer | 1896 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1492 reflections with I > 2σ(I) |
Tmin = 0.422, Tmax = 0.547 | Rint = 0.028 |
3551 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 5 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.83 e Å−3 |
1896 reflections | Δρmin = −0.62 e Å−3 |
151 parameters |
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 | ||
Br1 | 1.40000 (18) | 1.27910 (9) | 0.54471 (5) | 0.0549 (3) | |
C1 | 0.9979 (13) | 0.9875 (7) | 0.2863 (4) | 0.0301 (13) | |
C2 | 0.8402 (14) | 1.0883 (7) | 0.2499 (4) | 0.0320 (14) | |
C3 | 0.8572 (15) | 1.2431 (7) | 0.2997 (5) | 0.0390 (15) | |
H3 | 0.7525 | 1.3085 | 0.2750 | 0.047* | |
C4 | 1.0256 (16) | 1.3012 (8) | 0.3847 (6) | 0.0474 (18) | |
H4 | 1.0401 | 1.4072 | 0.4168 | 0.057* | |
C5 | 1.1756 (15) | 1.2044 (8) | 0.4241 (5) | 0.0400 (16) | |
C6 | 1.1646 (15) | 1.0498 (8) | 0.3748 (5) | 0.0386 (15) | |
H6 | 1.2697 | 0.9858 | 0.4008 | 0.046* | |
C7 | 1.0080 (14) | 0.8197 (7) | 0.2383 (4) | 0.0291 (13) | |
C8 | 0.6261 (14) | 0.4642 (7) | 0.1119 (4) | 0.0292 (13) | |
N1 | 0.8087 (12) | 0.7505 (6) | 0.1619 (4) | 0.0332 (12) | |
H1A | 0.713 (13) | 0.807 (7) | 0.129 (4) | 0.040* | |
N2 | 0.8288 (13) | 0.6018 (6) | 0.1093 (4) | 0.0365 (12) | |
H2A | 0.977 (12) | 0.605 (8) | 0.070 (4) | 0.044* | |
N3 | 0.4082 (13) | 0.4717 (6) | 0.1724 (5) | 0.0435 (14) | |
H3A | 0.371 (16) | 0.567 (5) | 0.197 (5) | 0.052* | |
H3B | 0.300 (15) | 0.376 (5) | 0.176 (5) | 0.052* | |
O1 | 0.6661 (12) | 1.0276 (5) | 0.1664 (4) | 0.0481 (12) | |
H1 | 0.64 (2) | 1.087 (9) | 0.132 (5) | 0.072* | |
O2 | 1.1829 (11) | 0.7491 (6) | 0.2675 (3) | 0.0460 (12) | |
S1 | 0.6597 (4) | 0.28795 (18) | 0.04272 (12) | 0.0371 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0649 (6) | 0.0472 (5) | 0.0377 (5) | −0.0050 (4) | −0.0034 (3) | −0.0023 (3) |
C1 | 0.034 (3) | 0.025 (3) | 0.029 (3) | 0.005 (2) | 0.008 (3) | 0.000 (2) |
C2 | 0.036 (3) | 0.023 (3) | 0.033 (3) | 0.004 (3) | 0.002 (3) | 0.000 (3) |
C3 | 0.044 (4) | 0.027 (3) | 0.044 (4) | 0.008 (3) | 0.000 (3) | 0.004 (3) |
C4 | 0.051 (4) | 0.026 (3) | 0.064 (5) | 0.008 (3) | 0.024 (4) | 0.005 (3) |
C5 | 0.041 (4) | 0.036 (4) | 0.041 (4) | 0.003 (3) | 0.007 (3) | 0.010 (3) |
C6 | 0.037 (4) | 0.037 (4) | 0.045 (4) | 0.010 (3) | 0.009 (3) | 0.016 (3) |
C7 | 0.035 (3) | 0.023 (3) | 0.027 (3) | 0.005 (3) | 0.003 (3) | 0.002 (2) |
C8 | 0.037 (3) | 0.023 (3) | 0.026 (3) | 0.010 (2) | −0.008 (2) | 0.001 (2) |
N1 | 0.043 (3) | 0.022 (3) | 0.034 (3) | 0.015 (2) | −0.002 (2) | −0.002 (2) |
N2 | 0.046 (3) | 0.023 (3) | 0.039 (3) | 0.011 (2) | 0.006 (2) | −0.001 (2) |
N3 | 0.045 (3) | 0.022 (3) | 0.063 (4) | 0.011 (2) | 0.011 (3) | 0.004 (3) |
O1 | 0.070 (3) | 0.026 (2) | 0.046 (3) | 0.014 (2) | −0.015 (2) | 0.004 (2) |
O2 | 0.059 (3) | 0.040 (3) | 0.041 (3) | 0.025 (2) | −0.005 (2) | 0.000 (2) |
S1 | 0.0479 (10) | 0.0216 (8) | 0.0394 (9) | 0.0088 (7) | 0.0003 (7) | 0.0009 (6) |
Br1—C5 | 1.896 (7) | C7—O2 | 1.215 (7) |
C1—C6 | 1.399 (9) | C7—N1 | 1.342 (8) |
C1—C2 | 1.412 (9) | C8—N2 | 1.327 (8) |
C1—C7 | 1.495 (8) | C8—N3 | 1.337 (8) |
C2—O1 | 1.354 (8) | C8—S1 | 1.694 (6) |
C2—C3 | 1.376 (9) | N1—N2 | 1.386 (7) |
C3—C4 | 1.359 (10) | N1—H1A | 0.91 (3) |
C3—H3 | 0.9300 | N2—H2A | 0.89 (3) |
C4—C5 | 1.383 (10) | N3—H3A | 0.88 (3) |
C4—H4 | 0.9300 | N3—H3B | 0.87 (3) |
C5—C6 | 1.377 (9) | O1—H1 | 0.81 (4) |
C6—H6 | 0.9300 | ||
C6—C1—C2 | 117.6 (5) | C1—C6—H6 | 119.5 |
C6—C1—C7 | 116.4 (5) | O2—C7—N1 | 121.9 (6) |
C2—C1—C7 | 126.0 (6) | O2—C7—C1 | 122.1 (6) |
O1—C2—C3 | 121.1 (6) | N1—C7—C1 | 115.9 (5) |
O1—C2—C1 | 118.5 (5) | N2—C8—N3 | 117.3 (5) |
C3—C2—C1 | 120.5 (6) | N2—C8—S1 | 119.7 (5) |
C4—C3—C2 | 120.5 (6) | N3—C8—S1 | 123.0 (4) |
C4—C3—H3 | 119.7 | C7—N1—N2 | 118.2 (5) |
C2—C3—H3 | 119.7 | C7—N1—H1A | 124 (4) |
C3—C4—C5 | 120.7 (7) | N2—N1—H1A | 114 (4) |
C3—C4—H4 | 119.7 | C8—N2—N1 | 122.5 (5) |
C5—C4—H4 | 119.7 | C8—N2—H2A | 121 (5) |
C6—C5—C4 | 119.6 (7) | N1—N2—H2A | 116 (5) |
C6—C5—Br1 | 118.7 (5) | C8—N3—H3A | 120 (5) |
C4—C5—Br1 | 121.7 (6) | C8—N3—H3B | 112 (5) |
C5—C6—C1 | 121.0 (6) | H3A—N3—H3B | 128 (7) |
C5—C6—H6 | 119.5 | C2—O1—H1 | 120 (7) |
C6—C1—C2—O1 | −177.0 (5) | C2—C1—C6—C5 | −0.4 (8) |
C7—C1—C2—O1 | 4.0 (8) | C7—C1—C6—C5 | 178.7 (5) |
C6—C1—C2—C3 | 1.2 (8) | C6—C1—C7—O2 | −9.7 (8) |
C7—C1—C2—C3 | −177.8 (5) | C2—C1—C7—O2 | 169.3 (6) |
O1—C2—C3—C4 | 178.1 (6) | C6—C1—C7—N1 | 169.2 (5) |
C1—C2—C3—C4 | −0.1 (9) | C2—C1—C7—N1 | −11.8 (8) |
C2—C3—C4—C5 | −1.9 (10) | O2—C7—N1—N2 | −7.3 (8) |
C3—C4—C5—C6 | 2.7 (9) | C1—C7—N1—N2 | 173.8 (5) |
C3—C4—C5—Br1 | −177.7 (5) | N3—C8—N2—N1 | −4.3 (9) |
C4—C5—C6—C1 | −1.5 (9) | S1—C8—N2—N1 | 177.9 (4) |
Br1—C5—C6—C1 | 178.9 (4) | C7—N1—N2—C8 | 106.4 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···S1i | 0.81 (4) | 2.34 (4) | 3.144 (5) | 169 (8) |
N1—H1A···S1ii | 0.91 (3) | 2.81 (5) | 3.481 (6) | 132 (5) |
N2—H2A···S1iii | 0.89 (3) | 2.49 (4) | 3.331 (5) | 158 (6) |
N3—H3A···O2iv | 0.88 (3) | 2.08 (4) | 2.938 (7) | 164 (7) |
N1—H1A···O1 | 0.91 (3) | 1.95 (6) | 2.618 (7) | 129 (6) |
N3—H3A···N1 | 0.88 (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) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C8H8BrN3O2S |
Mr | 290.14 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 533.06 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.03 |
Crystal size (mm) | 0.25 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.422, 0.547 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3551, 1896, 1492 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.168, 1.11 |
No. of reflections | 1896 |
No. of parameters | 151 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.83, −0.62 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···S1i | 0.81 (4) | 2.34 (4) | 3.144 (5) | 169 (8) |
N1—H1A···S1ii | 0.91 (3) | 2.81 (5) | 3.481 (6) | 132 (5) |
N2—H2A···S1iii | 0.89 (3) | 2.49 (4) | 3.331 (5) | 158 (6) |
N3—H3A···O2iv | 0.88 (3) | 2.08 (4) | 2.938 (7) | 164 (7) |
N1—H1A···O1 | 0.91 (3) | 1.95 (6) | 2.618 (7) | 129 (6) |
N3—H3A···N1 | 0.88 (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) x−1, y, z. |
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).