Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039694/at2371sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039694/at2371Isup2.hkl |
CCDC reference: 660294
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean (C-C) = 0.003 Å
- R factor = 0.050
- wR factor = 0.097
- Data-to-parameter ratio = 17.4
checkCIF/PLATON results
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0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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
For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).
An anhydrous ethanol solution (50 ml) of thiophene-2-carbohydrazide (1.42 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of 2,4-dichlorobenzaldehyde (1.75 g, 10 mmol), and the mixture was stirred at 350 K for 6 h under N2, whereupon a yellow precipitate appeared. The product was isolated, recrystallized from anhydrous ethanol and then dried in vacuo to give pure compound (I) in 85% yield. Yellow 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 refined freely. C-bound H atoms were included in calculated positions, with C—H = 0.95 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
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 Schiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).
In the structure of the title molecule, (I) (Fig. 1), the geometric parameters are normal. The thiophene ring system (C9—C12/S1) is planar, with an r.m.s. deviation for fitted atoms of 0.0032 (5) Å; the benzene group (C1—C6) is also planar, with an r.m.s. deviation of 0.0053 (2) Å. The dihedral angle between these planes is 14.30 (3)°.
The molecules are linked via weak intermolecular N—H···O hydrogen bond, forming an extended supramolecule (Table 1). The molecules associate to form a supramolecular structure, as illustrated in Fig. 2.
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: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2005); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).
C12H8Cl2N2OS | F(000) = 608 |
Mr = 299.16 | Dx = 1.628 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2966 reflections |
a = 5.6320 (11) Å | θ = 1.9–28.0° |
b = 16.664 (3) Å | µ = 0.69 mm−1 |
c = 13.077 (3) Å | T = 113 K |
β = 96.10 (3)° | Block, yellow |
V = 1220.3 (4) Å3 | 0.10 × 0.06 × 0.04 mm |
Z = 4 |
Rigaku Saturn diffractometer | 2911 independent reflections |
Radiation source: rotating anode | 2370 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.064 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 2.0° |
ω scans | h = −7→6 |
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2005) | k = −21→21 |
Tmin = 0.934, Tmax = 0.973 | l = −15→17 |
9849 measured reflections |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0332P)2 + 0.3458P] where P = (Fo2 + 2Fc2)/3 |
2911 reflections | (Δ/σ)max = 0.001 |
167 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C12H8Cl2N2OS | V = 1220.3 (4) Å3 |
Mr = 299.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6320 (11) Å | µ = 0.69 mm−1 |
b = 16.664 (3) Å | T = 113 K |
c = 13.077 (3) Å | 0.10 × 0.06 × 0.04 mm |
β = 96.10 (3)° |
Rigaku Saturn diffractometer | 2911 independent reflections |
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2005) | 2370 reflections with I > 2σ(I) |
Tmin = 0.934, Tmax = 0.973 | Rint = 0.064 |
9849 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.097 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.32 e Å−3 |
2911 reflections | Δρmin = −0.36 e Å−3 |
167 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 | ||
Cl1 | 1.20133 (11) | 0.60285 (4) | 0.68221 (5) | 0.02104 (16) | |
Cl2 | 0.84737 (12) | 0.82985 (4) | 0.42176 (4) | 0.02250 (17) | |
S1 | 0.16921 (11) | 0.87926 (4) | 0.83555 (5) | 0.02168 (17) | |
O1 | −0.1664 (3) | 1.00868 (11) | 0.60854 (13) | 0.0212 (4) | |
N1 | 0.3309 (4) | 0.88243 (13) | 0.63613 (15) | 0.0168 (5) | |
N2 | 0.1711 (4) | 0.94002 (14) | 0.59904 (16) | 0.0187 (5) | |
H2 | 0.164 (5) | 0.956 (2) | 0.535 (2) | 0.042 (9)* | |
C1 | 0.6565 (4) | 0.75502 (16) | 0.69296 (18) | 0.0186 (5) | |
H1 | 0.5405 | 0.7671 | 0.7384 | 0.022* | |
C2 | 0.8196 (4) | 0.69461 (16) | 0.71835 (18) | 0.0189 (6) | |
H2A | 0.8139 | 0.6645 | 0.7797 | 0.023* | |
C3 | 0.9920 (4) | 0.67847 (16) | 0.65305 (18) | 0.0166 (5) | |
C4 | 1.0012 (4) | 0.72071 (16) | 0.56257 (18) | 0.0175 (5) | |
H4 | 1.1207 | 0.7094 | 0.5185 | 0.021* | |
C5 | 0.8331 (4) | 0.77977 (16) | 0.53762 (17) | 0.0164 (5) | |
C6 | 0.6578 (4) | 0.79905 (16) | 0.60175 (18) | 0.0167 (5) | |
C7 | 0.4807 (4) | 0.86188 (16) | 0.57394 (18) | 0.0173 (5) | |
H7 | 0.4771 | 0.8877 | 0.5090 | 0.021* | |
C8 | −0.0114 (4) | 0.96340 (16) | 0.65136 (18) | 0.0173 (5) | |
C9 | −0.0280 (4) | 0.93785 (15) | 0.75774 (18) | 0.0168 (5) | |
C10 | −0.2147 (4) | 0.96278 (17) | 0.80989 (18) | 0.0197 (6) | |
H10 | −0.3423 | 0.9953 | 0.7801 | 0.024* | |
C11 | −0.1964 (5) | 0.93495 (17) | 0.91240 (19) | 0.0227 (6) | |
H11 | −0.3099 | 0.9465 | 0.9591 | 0.027* | |
C12 | 0.0027 (5) | 0.88965 (17) | 0.9365 (2) | 0.0238 (6) | |
H12 | 0.0445 | 0.8664 | 1.0022 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0206 (3) | 0.0192 (4) | 0.0233 (3) | 0.0029 (3) | 0.0022 (2) | 0.0010 (3) |
Cl2 | 0.0298 (4) | 0.0213 (4) | 0.0172 (3) | 0.0001 (3) | 0.0065 (3) | 0.0026 (3) |
S1 | 0.0198 (3) | 0.0241 (4) | 0.0212 (3) | 0.0033 (3) | 0.0022 (3) | 0.0060 (3) |
O1 | 0.0196 (9) | 0.0229 (11) | 0.0212 (9) | 0.0041 (8) | 0.0023 (7) | 0.0066 (8) |
N1 | 0.0159 (11) | 0.0151 (12) | 0.0193 (10) | −0.0005 (9) | 0.0006 (8) | 0.0006 (9) |
N2 | 0.0200 (11) | 0.0179 (12) | 0.0183 (11) | 0.0031 (9) | 0.0030 (9) | 0.0025 (9) |
C1 | 0.0194 (13) | 0.0189 (14) | 0.0178 (12) | −0.0023 (11) | 0.0034 (10) | −0.0004 (10) |
C2 | 0.0232 (14) | 0.0168 (14) | 0.0166 (12) | −0.0015 (11) | 0.0020 (10) | 0.0017 (10) |
C3 | 0.0157 (12) | 0.0143 (14) | 0.0194 (12) | 0.0001 (10) | 0.0004 (10) | −0.0030 (10) |
C4 | 0.0161 (12) | 0.0169 (14) | 0.0198 (12) | −0.0033 (11) | 0.0026 (10) | −0.0027 (10) |
C5 | 0.0190 (13) | 0.0157 (14) | 0.0144 (11) | −0.0058 (11) | 0.0010 (10) | −0.0006 (10) |
C6 | 0.0152 (12) | 0.0163 (14) | 0.0186 (12) | −0.0008 (10) | 0.0021 (10) | −0.0029 (10) |
C7 | 0.0198 (13) | 0.0141 (13) | 0.0176 (12) | −0.0018 (11) | 0.0003 (10) | 0.0038 (10) |
C8 | 0.0172 (12) | 0.0128 (13) | 0.0218 (12) | −0.0054 (10) | 0.0016 (10) | −0.0001 (10) |
C9 | 0.0147 (12) | 0.0145 (14) | 0.0208 (12) | −0.0024 (10) | 0.0003 (10) | 0.0010 (10) |
C10 | 0.0190 (13) | 0.0196 (15) | 0.0201 (12) | 0.0001 (11) | 0.0008 (10) | 0.0008 (11) |
C11 | 0.0234 (14) | 0.0238 (16) | 0.0215 (13) | −0.0002 (12) | 0.0050 (11) | 0.0014 (11) |
C12 | 0.0241 (14) | 0.0261 (16) | 0.0212 (13) | 0.0004 (12) | 0.0020 (11) | 0.0057 (11) |
Cl1—C3 | 1.740 (3) | C3—C4 | 1.383 (3) |
Cl2—C5 | 1.739 (2) | C4—C5 | 1.381 (3) |
S1—C12 | 1.707 (3) | C4—H4 | 0.9500 |
S1—C9 | 1.727 (3) | C5—C6 | 1.399 (3) |
O1—C8 | 1.241 (3) | C6—C7 | 1.465 (4) |
N1—C7 | 1.279 (3) | C7—H7 | 0.9500 |
N1—N2 | 1.369 (3) | C8—C9 | 1.467 (3) |
N2—C8 | 1.351 (3) | C9—C10 | 1.377 (3) |
N2—H2 | 0.88 (3) | C10—C11 | 1.412 (3) |
C1—C2 | 1.379 (4) | C10—H10 | 0.9500 |
C1—C6 | 1.401 (3) | C11—C12 | 1.361 (4) |
C1—H1 | 0.9500 | C11—H11 | 0.9500 |
C2—C3 | 1.386 (3) | C12—H12 | 0.9500 |
C2—H2A | 0.9500 | ||
C12—S1—C9 | 91.51 (13) | C5—C6—C7 | 121.4 (2) |
C7—N1—N2 | 114.6 (2) | C1—C6—C7 | 121.4 (2) |
C8—N2—N1 | 122.0 (2) | N1—C7—C6 | 120.7 (2) |
C8—N2—H2 | 116 (2) | N1—C7—H7 | 119.6 |
N1—N2—H2 | 121 (2) | C6—C7—H7 | 119.6 |
C2—C1—C6 | 121.6 (2) | O1—C8—N2 | 118.9 (2) |
C2—C1—H1 | 119.2 | O1—C8—C9 | 119.4 (2) |
C6—C1—H1 | 119.2 | N2—C8—C9 | 121.7 (2) |
C1—C2—C3 | 119.1 (2) | C10—C9—C8 | 120.7 (2) |
C1—C2—H2A | 120.5 | C10—C9—S1 | 110.85 (18) |
C3—C2—H2A | 120.5 | C8—C9—S1 | 128.38 (19) |
C4—C3—C2 | 121.4 (2) | C9—C10—C11 | 112.9 (2) |
C4—C3—Cl1 | 118.03 (19) | C9—C10—H10 | 123.6 |
C2—C3—Cl1 | 120.56 (19) | C11—C10—H10 | 123.6 |
C5—C4—C3 | 118.6 (2) | C12—C11—C10 | 112.1 (2) |
C5—C4—H4 | 120.7 | C12—C11—H11 | 123.9 |
C3—C4—H4 | 120.7 | C10—C11—H11 | 123.9 |
C4—C5—C6 | 122.1 (2) | C11—C12—S1 | 112.6 (2) |
C4—C5—Cl2 | 116.99 (19) | C11—C12—H12 | 123.7 |
C6—C5—Cl2 | 120.9 (2) | S1—C12—H12 | 123.7 |
C5—C6—C1 | 117.2 (2) | ||
C7—N1—N2—C8 | 174.2 (2) | C5—C6—C7—N1 | −175.6 (2) |
C6—C1—C2—C3 | 1.5 (4) | C1—C6—C7—N1 | 5.4 (4) |
C1—C2—C3—C4 | −1.0 (4) | N1—N2—C8—O1 | −171.5 (2) |
C1—C2—C3—Cl1 | 179.94 (19) | N1—N2—C8—C9 | 9.6 (4) |
C2—C3—C4—C5 | −0.3 (4) | O1—C8—C9—C10 | 0.8 (4) |
Cl1—C3—C4—C5 | 178.72 (18) | N2—C8—C9—C10 | 179.6 (2) |
C3—C4—C5—C6 | 1.3 (4) | O1—C8—C9—S1 | −177.0 (2) |
C3—C4—C5—Cl2 | −178.62 (19) | N2—C8—C9—S1 | 1.9 (4) |
C4—C5—C6—C1 | −0.8 (4) | C12—S1—C9—C10 | −0.6 (2) |
Cl2—C5—C6—C1 | 179.06 (19) | C12—S1—C9—C8 | 177.3 (2) |
C4—C5—C6—C7 | −180.0 (2) | C8—C9—C10—C11 | −177.7 (2) |
Cl2—C5—C6—C7 | −0.1 (3) | S1—C9—C10—C11 | 0.4 (3) |
C2—C1—C6—C5 | −0.6 (4) | C9—C10—C11—C12 | 0.1 (4) |
C2—C1—C6—C7 | 178.5 (2) | C10—C11—C12—S1 | −0.5 (3) |
N2—N1—C7—C6 | −178.0 (2) | C9—S1—C12—C11 | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.88 (3) | 1.96 (3) | 2.843 (3) | 177 (3) |
Symmetry code: (i) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H8Cl2N2OS |
Mr | 299.16 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 113 |
a, b, c (Å) | 5.6320 (11), 16.664 (3), 13.077 (3) |
β (°) | 96.10 (3) |
V (Å3) | 1220.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.10 × 0.06 × 0.04 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (CrystalClear, Rigaku/MSC, 2005) |
Tmin, Tmax | 0.934, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9849, 2911, 2370 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.659 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.097, 1.10 |
No. of reflections | 2911 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.36 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalStructure (Rigaku/MSC, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.88 (3) | 1.96 (3) | 2.843 (3) | 177 (3) |
Symmetry code: (i) −x, −y+2, −z+1. |
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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 Schiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I).
In the structure of the title molecule, (I) (Fig. 1), the geometric parameters are normal. The thiophene ring system (C9—C12/S1) is planar, with an r.m.s. deviation for fitted atoms of 0.0032 (5) Å; the benzene group (C1—C6) is also planar, with an r.m.s. deviation of 0.0053 (2) Å. The dihedral angle between these planes is 14.30 (3)°.
The molecules are linked via weak intermolecular N—H···O hydrogen bond, forming an extended supramolecule (Table 1). The molecules associate to form a supramolecular structure, as illustrated in Fig. 2.