Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042006/bg2091sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042006/bg2091Isup2.hkl |
CCDC reference: 663664
An anhydrous ethanol solution (50 ml) of thiophene-2-carbaldehyde (1.12 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 4-bromobenzohydrazide (2.14 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N2, whereupon a red precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give the pure compound (I) in a 92% yield. Red single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution.
The N-bound H atom was located in a difference Fourier map and its positional parameters were refined, with Uiso(H) = 1.2Ueq(N). C-bound H atoms were included in calculated positions, with C—H = 0.93 (aromatic) or 0.96 Å (methyl), and refined using a riding model, with Uiso(H) = 1.2Ueq(C) for aromatic H or 1.5Ueq(C) for methyl H atoms.
In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of the active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al.,2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and crystal structure of the title compound, (I) (Fig. 1). The geometric parameters are normal. The two main groups in the molecule are planar within experimental error (maximum deviations from the l.s. planes: 0.0069 (2) Å for S1 in the thiophen ring, and 0.0117 (3) Å in the benzene group. The dihedral angle between these two planes is 22.10 (3)°·The molecular structure is stabilized by a weak intermolecular N—H···O hydrogen bond to form a zigzag packing arrangement, as illustraed in Fig.2 and table 1.
For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
C12H9BrN2OS | F(000) = 1232 |
Mr = 309.18 | Dx = 1.662 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3032 reflections |
a = 12.807 (6) Å | θ = 2.3–24.0° |
b = 7.803 (4) Å | µ = 3.48 mm−1 |
c = 24.734 (11) Å | T = 294 K |
V = 2471.9 (19) Å3 | Block, red |
Z = 8 | 0.22 × 0.20 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 2525 independent reflections |
Radiation source: fine-focus sealed tube | 1626 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
φ and ω scans | θmax = 26.4°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→15 |
Tmin = 0.49, Tmax = 0.57 | k = −4→9 |
13066 measured reflections | l = −30→30 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.074P)2 + 2.5533P] where P = (Fo2 + 2Fc2)/3 |
2525 reflections | (Δ/σ)max = 0.001 |
158 parameters | Δρmax = 0.60 e Å−3 |
1 restraint | Δρmin = −0.72 e Å−3 |
C12H9BrN2OS | V = 2471.9 (19) Å3 |
Mr = 309.18 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.807 (6) Å | µ = 3.48 mm−1 |
b = 7.803 (4) Å | T = 294 K |
c = 24.734 (11) Å | 0.22 × 0.20 × 0.16 mm |
Bruker SMART CCD area-detector diffractometer | 2525 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1626 reflections with I > 2σ(I) |
Tmin = 0.49, Tmax = 0.57 | Rint = 0.056 |
13066 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 1 restraint |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.60 e Å−3 |
2525 reflections | Δρmin = −0.72 e Å−3 |
158 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 | 0.92242 (5) | 1.05663 (8) | 0.62759 (2) | 0.0745 (3) | |
S1 | 0.70401 (13) | 0.4410 (2) | 0.23687 (6) | 0.0801 (5) | |
O1 | 0.8747 (2) | 0.4971 (4) | 0.41694 (12) | 0.0445 (7) | |
N1 | 0.7283 (3) | 0.5996 (5) | 0.34649 (13) | 0.0429 (8) | |
N2 | 0.7489 (3) | 0.6861 (4) | 0.39387 (14) | 0.0434 (8) | |
C1 | 0.6256 (6) | 0.4326 (8) | 0.1825 (2) | 0.0818 (19) | |
H1 | 0.6381 | 0.3622 | 0.1529 | 0.098* | |
C2 | 0.5439 (5) | 0.5367 (7) | 0.1862 (2) | 0.0765 (18) | |
H2 | 0.4944 | 0.5456 | 0.1588 | 0.092* | |
C3 | 0.5375 (3) | 0.6311 (5) | 0.23339 (15) | 0.0386 (9) | |
H3 | 0.4846 | 0.7075 | 0.2425 | 0.046* | |
C4 | 0.6293 (4) | 0.5892 (5) | 0.26673 (17) | 0.0447 (10) | |
C5 | 0.6557 (3) | 0.6618 (6) | 0.31812 (16) | 0.0456 (10) | |
H5 | 0.6187 | 0.7562 | 0.3308 | 0.055* | |
C6 | 0.8247 (3) | 0.6283 (5) | 0.42666 (15) | 0.0365 (9) | |
C7 | 0.8448 (3) | 0.7303 (5) | 0.47612 (15) | 0.0372 (9) | |
C8 | 0.9451 (3) | 0.7347 (6) | 0.49632 (19) | 0.0493 (11) | |
H8 | 0.9976 | 0.6730 | 0.4792 | 0.059* | |
C9 | 0.9682 (4) | 0.8297 (6) | 0.54165 (19) | 0.0573 (13) | |
H9 | 1.0362 | 0.8340 | 0.5548 | 0.069* | |
C10 | 0.8900 (4) | 0.9180 (5) | 0.56724 (17) | 0.0463 (11) | |
C11 | 0.7888 (3) | 0.9092 (6) | 0.54958 (17) | 0.0475 (11) | |
H11 | 0.7358 | 0.9650 | 0.5683 | 0.057* | |
C12 | 0.7673 (3) | 0.8164 (5) | 0.50373 (17) | 0.0454 (10) | |
H12 | 0.6990 | 0.8115 | 0.4910 | 0.054* | |
H2A | 0.710 (3) | 0.781 (3) | 0.3991 (17) | 0.045 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0907 (5) | 0.0819 (5) | 0.0510 (3) | −0.0025 (3) | −0.0156 (3) | −0.0265 (3) |
S1 | 0.0900 (11) | 0.0857 (11) | 0.0647 (9) | 0.0106 (9) | −0.0062 (8) | −0.0259 (8) |
O1 | 0.0443 (16) | 0.0409 (15) | 0.0483 (17) | 0.0057 (14) | −0.0006 (14) | −0.0114 (13) |
N1 | 0.049 (2) | 0.0407 (19) | 0.0392 (19) | −0.0004 (16) | −0.0042 (16) | −0.0104 (16) |
N2 | 0.052 (2) | 0.039 (2) | 0.0396 (18) | 0.0076 (17) | −0.0075 (17) | −0.0123 (16) |
C1 | 0.129 (5) | 0.075 (4) | 0.041 (3) | −0.031 (4) | −0.002 (3) | −0.014 (3) |
C2 | 0.094 (4) | 0.067 (4) | 0.069 (4) | −0.026 (3) | −0.034 (3) | 0.027 (3) |
C3 | 0.050 (2) | 0.0297 (19) | 0.036 (2) | −0.0009 (18) | −0.0087 (19) | 0.0031 (17) |
C4 | 0.054 (3) | 0.041 (2) | 0.039 (2) | −0.004 (2) | −0.005 (2) | −0.0002 (18) |
C5 | 0.053 (3) | 0.042 (2) | 0.042 (2) | 0.003 (2) | −0.001 (2) | −0.0065 (19) |
C6 | 0.039 (2) | 0.034 (2) | 0.036 (2) | −0.0035 (18) | 0.0050 (17) | −0.0034 (17) |
C7 | 0.042 (2) | 0.035 (2) | 0.035 (2) | −0.0008 (18) | −0.0033 (17) | −0.0019 (16) |
C8 | 0.041 (2) | 0.051 (3) | 0.056 (3) | 0.010 (2) | −0.005 (2) | −0.013 (2) |
C9 | 0.048 (3) | 0.065 (3) | 0.058 (3) | 0.004 (2) | −0.019 (2) | −0.018 (2) |
C10 | 0.062 (3) | 0.041 (2) | 0.035 (2) | −0.001 (2) | −0.010 (2) | −0.0032 (19) |
C11 | 0.053 (3) | 0.049 (3) | 0.041 (2) | 0.006 (2) | 0.000 (2) | −0.007 (2) |
C12 | 0.040 (2) | 0.054 (3) | 0.042 (2) | 0.004 (2) | −0.0024 (18) | −0.008 (2) |
Br1—C10 | 1.890 (4) | C4—C5 | 1.432 (6) |
S1—C4 | 1.673 (5) | C5—H5 | 0.9300 |
S1—C1 | 1.679 (6) | C6—C7 | 1.482 (5) |
O1—C6 | 1.231 (5) | C7—C8 | 1.379 (5) |
N1—C5 | 1.263 (5) | C7—C12 | 1.379 (5) |
N1—N2 | 1.378 (5) | C8—C9 | 1.376 (6) |
N2—C6 | 1.344 (5) | C8—H8 | 0.9300 |
N2—H2A | 0.90 (3) | C9—C10 | 1.370 (6) |
C1—C2 | 1.328 (9) | C9—H9 | 0.9300 |
C1—H1 | 0.9300 | C10—C11 | 1.369 (6) |
C2—C3 | 1.383 (7) | C11—C12 | 1.374 (6) |
C2—H2 | 0.9300 | C11—H11 | 0.9300 |
C3—C4 | 1.473 (6) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | ||
C4—S1—C1 | 92.2 (3) | O1—C6—C7 | 121.2 (4) |
C5—N1—N2 | 115.1 (3) | N2—C6—C7 | 116.3 (3) |
C6—N2—N1 | 119.2 (3) | C8—C7—C12 | 118.6 (4) |
C6—N2—H2A | 126 (3) | C8—C7—C6 | 118.3 (4) |
N1—N2—H2A | 115 (3) | C12—C7—C6 | 123.1 (4) |
C2—C1—S1 | 113.1 (4) | C9—C8—C7 | 120.6 (4) |
C2—C1—H1 | 123.4 | C9—C8—H8 | 119.7 |
S1—C1—H1 | 123.4 | C7—C8—H8 | 119.7 |
C1—C2—C3 | 115.5 (5) | C10—C9—C8 | 119.4 (4) |
C1—C2—H2 | 122.3 | C10—C9—H9 | 120.3 |
C3—C2—H2 | 122.3 | C8—C9—H9 | 120.3 |
C2—C3—C4 | 107.9 (4) | C11—C10—C9 | 121.3 (4) |
C2—C3—H3 | 126.1 | C11—C10—Br1 | 119.2 (3) |
C4—C3—H3 | 126.1 | C9—C10—Br1 | 119.5 (3) |
C5—C4—C3 | 126.7 (4) | C10—C11—C12 | 118.7 (4) |
C5—C4—S1 | 122.0 (3) | C10—C11—H11 | 120.7 |
C3—C4—S1 | 111.3 (3) | C12—C11—H11 | 120.7 |
N1—C5—C4 | 121.0 (4) | C11—C12—C7 | 121.4 (4) |
N1—C5—H5 | 119.5 | C11—C12—H12 | 119.3 |
C4—C5—H5 | 119.5 | C7—C12—H12 | 119.3 |
O1—C6—N2 | 122.5 (4) | ||
C5—N1—N2—C6 | 179.7 (4) | N2—C6—C7—C8 | −148.6 (4) |
C4—S1—C1—C2 | −0.6 (5) | O1—C6—C7—C12 | −145.9 (4) |
S1—C1—C2—C3 | −0.4 (7) | N2—C6—C7—C12 | 33.4 (6) |
C1—C2—C3—C4 | 1.5 (6) | C12—C7—C8—C9 | −3.0 (7) |
C2—C3—C4—C5 | 177.8 (4) | C6—C7—C8—C9 | 179.0 (4) |
C2—C3—C4—S1 | −1.9 (5) | C7—C8—C9—C10 | 1.1 (7) |
C1—S1—C4—C5 | −178.3 (4) | C8—C9—C10—C11 | 2.1 (7) |
C1—S1—C4—C3 | 1.4 (4) | C8—C9—C10—Br1 | −177.2 (4) |
N2—N1—C5—C4 | 177.2 (4) | C9—C10—C11—C12 | −3.2 (7) |
C3—C4—C5—N1 | 170.2 (4) | Br1—C10—C11—C12 | 176.1 (3) |
S1—C4—C5—N1 | −10.2 (6) | C10—C11—C12—C7 | 1.2 (7) |
N1—N2—C6—O1 | −2.5 (6) | C8—C7—C12—C11 | 1.8 (6) |
N1—N2—C6—C7 | 178.3 (3) | C6—C7—C12—C11 | 179.8 (4) |
O1—C6—C7—C8 | 32.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.90 (3) | 2.05 (3) | 2.953 (4) | 176 (4) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C12H9BrN2OS |
Mr | 309.18 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 12.807 (6), 7.803 (4), 24.734 (11) |
V (Å3) | 2471.9 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.48 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.49, 0.57 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13066, 2525, 1626 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.148, 1.03 |
No. of reflections | 2525 |
No. of parameters | 158 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.72 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.90 (3) | 2.05 (3) | 2.953 (4) | 176 (4) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of the active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al.,2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and crystal structure of the title compound, (I) (Fig. 1). The geometric parameters are normal. The two main groups in the molecule are planar within experimental error (maximum deviations from the l.s. planes: 0.0069 (2) Å for S1 in the thiophen ring, and 0.0117 (3) Å in the benzene group. The dihedral angle between these two planes is 22.10 (3)°·The molecular structure is stabilized by a weak intermolecular N—H···O hydrogen bond to form a zigzag packing arrangement, as illustraed in Fig.2 and table 1.