Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030255/dn2206sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030255/dn2206Isup2.hkl |
CCDC reference: 655032
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.022
- wR factor = 0.060
- Data-to-parameter ratio = 14.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT322_ALERT_2_C Check Hybridisation of S2 in Main Residue . ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. S2 .. 2.97 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.20 From the CIF: _reflns_number_total 1839 Count of symmetry unique reflns 1003 Completeness (_total/calc) 183.35% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 836 Fraction of Friedel pairs measured 0.833 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Johnson et al. (1996); Kim & Shin (1999); Wang & Zheng (2007). [Please provide revised scheme with the second S atom shown.]
Under nitrogen, a mixture of 5-chlorothiophene-2-carbaldehyde (1.67 g,10 mmol), Na2SO4 (3.0 g) and 5-methylthiazol-2-amine (1.58 g, 10 mmol) in absolute ethanol (20 ml) was refluxed for about 12 h to yield a yellow precipitate. The product was collected by vacuum filtration and washed with ethanol. The crude solid was redissolved in CH2Cl2 (100 ml) and washed with water (2 x 15 ml) and brine (8 ml). After drying over Na2SO4, the solvent was removed under vacuum, and a yellow solid was isolated in 92% yield (3.1 g). Colourless single crystals of the Schiff base, (I), suitable for X-ray analysis were grown from CH2Cl2 and absolute ethanol (4:1) by slow evaporation of the solvents at room temperature over a period of about one week.
All H atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.98 Å (methyl) with Uiso(H) = xUeq(C) where x = 1.2 for aromatic H and 1.5 for methyl H.
Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes, (Johnson et al., 1996; Alizadeh et al.,1999; Wang & Zheng, 2007). Schiff bases that have solvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optically active) materials (Alemi & Shaabani, 2000). They are also useful in the asymmetric oxidation of methyl phenyl sulfide and are enantioselective (Kim & Shin, 1999). In this paper, we report the synthesis and crystal structure of the title compound, (I).
The title compound is roughly planar with the two thiophene rings twisted by only (Fig. 1). The bond lengths and bond angles are usual for such compounds. The crystal packing is governed by weak C—H···S interactions (Table 1) forming chains parallel to the c axis and very weak slipped π–π stacking between the thiophene rings with centroid to centroid distance of 3.947 Å and interplanar distance of 3.651 Å resulting in an offset angle of 22.3°.
For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Johnson et al. (1996); Kim & Shin (1999); Wang & Zheng (2007). [Please provide revised scheme with the second S atom shown.]
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); 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, 1998); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Probability displacement ellipsoids are drawn at the 30% level. |
C9H7ClN2S2 | F(000) = 248 |
Mr = 242.74 | Dx = 1.499 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1839 reflections |
a = 3.9472 (4) Å | θ = 3.5–25.2° |
b = 23.281 (2) Å | µ = 0.70 mm−1 |
c = 6.0379 (6) Å | T = 298 K |
β = 104.214 (1)° | Block, colourless |
V = 537.87 (9) Å3 | 0.31 × 0.25 × 0.19 mm |
Z = 2 |
Bruker APEX area-detector diffractometer | 1839 independent reflections |
Radiation source: fine-focus sealed tube | 1766 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 25.2°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −4→4 |
Tmin = 0.812, Tmax = 0.878 | k = −24→27 |
3269 measured reflections | l = −7→7 |
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)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.060 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.0225P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1839 reflections | Δρmax = 0.18 e Å−3 |
128 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 836 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.04 (6) |
C9H7ClN2S2 | V = 537.87 (9) Å3 |
Mr = 242.74 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 3.9472 (4) Å | µ = 0.70 mm−1 |
b = 23.281 (2) Å | T = 298 K |
c = 6.0379 (6) Å | 0.31 × 0.25 × 0.19 mm |
β = 104.214 (1)° |
Bruker APEX area-detector diffractometer | 1839 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1766 reflections with I > 2σ(I) |
Tmin = 0.812, Tmax = 0.878 | Rint = 0.027 |
3269 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.060 | Δρmax = 0.18 e Å−3 |
S = 1.06 | Δρmin = −0.12 e Å−3 |
1839 reflections | Absolute structure: Flack (1983), with 836 Friedel pairs |
128 parameters | Absolute structure parameter: 0.04 (6) |
1 restraint |
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 | ||
C1 | 1.4257 (6) | 0.94947 (11) | 1.1100 (4) | 0.0662 (6) | |
H1A | 1.5326 | 0.9797 | 1.0429 | 0.099* | |
H1B | 1.5992 | 0.9311 | 1.2282 | 0.099* | |
H1C | 1.2463 | 0.9653 | 1.1742 | 0.099* | |
C2 | 1.2681 (5) | 0.90636 (10) | 0.9303 (4) | 0.0501 (4) | |
C3 | 1.2361 (6) | 0.90871 (10) | 0.7032 (4) | 0.0564 (5) | |
H3 | 1.3129 | 0.9405 | 0.6359 | 0.068* | |
C4 | 1.0034 (5) | 0.82366 (9) | 0.7061 (3) | 0.0469 (4) | |
C5 | 0.7404 (5) | 0.75947 (9) | 0.4337 (4) | 0.0491 (4) | |
H5 | 0.7667 | 0.7873 | 0.3286 | 0.059* | |
C6 | 0.5772 (5) | 0.70562 (9) | 0.3507 (4) | 0.0486 (5) | |
C7 | 0.4437 (7) | 0.68890 (11) | 0.1310 (4) | 0.0634 (6) | |
H7 | 0.4465 | 0.7120 | 0.0059 | 0.076* | |
C8 | 0.3010 (6) | 0.63335 (11) | 0.1111 (4) | 0.0657 (6) | |
H8 | 0.1995 | 0.6156 | −0.0274 | 0.079* | |
C9 | 0.3287 (5) | 0.60889 (9) | 0.3165 (4) | 0.0542 (5) | |
Cl1 | 0.18698 (18) | 0.54193 (3) | 0.36876 (14) | 0.0784 (2) | |
N1 | 0.8487 (4) | 0.77019 (7) | 0.6444 (3) | 0.0496 (4) | |
N2 | 1.0867 (5) | 0.86277 (8) | 0.5751 (3) | 0.0559 (4) | |
S1 | 0.52770 (13) | 0.65240 (2) | 0.53993 (8) | 0.05352 (14) | |
S2 | 1.10583 (13) | 0.84148 (2) | 0.99287 (8) | 0.05410 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0655 (13) | 0.0622 (16) | 0.0671 (14) | −0.0105 (11) | 0.0090 (11) | −0.0118 (11) |
C2 | 0.0461 (9) | 0.0458 (11) | 0.0565 (11) | 0.0005 (9) | 0.0092 (8) | −0.0018 (9) |
C3 | 0.0657 (12) | 0.0436 (11) | 0.0586 (12) | −0.0054 (10) | 0.0127 (10) | 0.0040 (9) |
C4 | 0.0496 (10) | 0.0436 (11) | 0.0476 (10) | 0.0025 (8) | 0.0120 (8) | 0.0017 (8) |
C5 | 0.0520 (10) | 0.0441 (11) | 0.0520 (11) | 0.0007 (8) | 0.0139 (8) | 0.0065 (8) |
C6 | 0.0501 (10) | 0.0447 (12) | 0.0503 (11) | 0.0024 (8) | 0.0113 (8) | 0.0041 (8) |
C7 | 0.0821 (14) | 0.0542 (14) | 0.0505 (12) | −0.0005 (11) | 0.0095 (11) | 0.0023 (10) |
C8 | 0.0766 (15) | 0.0574 (15) | 0.0548 (12) | −0.0005 (10) | 0.0001 (10) | −0.0081 (10) |
C9 | 0.0478 (10) | 0.0431 (11) | 0.0702 (13) | 0.0012 (8) | 0.0118 (9) | −0.0054 (9) |
Cl1 | 0.0752 (4) | 0.0445 (3) | 0.1166 (5) | −0.0065 (3) | 0.0253 (3) | 0.0009 (3) |
N1 | 0.0539 (9) | 0.0418 (10) | 0.0522 (10) | −0.0004 (7) | 0.0114 (7) | 0.0020 (7) |
N2 | 0.0713 (11) | 0.0466 (11) | 0.0492 (9) | −0.0048 (8) | 0.0134 (8) | 0.0021 (7) |
S1 | 0.0612 (3) | 0.0480 (3) | 0.0502 (3) | −0.0033 (2) | 0.0115 (2) | 0.0039 (2) |
S2 | 0.0625 (3) | 0.0525 (3) | 0.0464 (2) | −0.0058 (2) | 0.0117 (2) | 0.0024 (2) |
C1—C2 | 1.496 (3) | C5—N1 | 1.264 (3) |
C1—H1A | 0.9600 | C5—C6 | 1.442 (3) |
C1—H1B | 0.9600 | C5—H5 | 0.9300 |
C1—H1C | 0.9600 | C6—C7 | 1.358 (3) |
C2—C3 | 1.347 (3) | C6—S1 | 1.729 (2) |
C2—S2 | 1.719 (2) | C7—C8 | 1.404 (4) |
C3—N2 | 1.366 (3) | C7—H7 | 0.9300 |
C3—H3 | 0.9300 | C8—C9 | 1.345 (3) |
C4—N2 | 1.300 (3) | C8—H8 | 0.9300 |
C4—N1 | 1.396 (3) | C9—Cl1 | 1.712 (2) |
C4—S2 | 1.729 (2) | C9—S1 | 1.715 (2) |
C2—C1—H1A | 109.5 | C6—C5—H5 | 118.9 |
C2—C1—H1B | 109.5 | C7—C6—C5 | 128.4 (2) |
H1A—C1—H1B | 109.5 | C7—C6—S1 | 111.11 (17) |
C2—C1—H1C | 109.5 | C5—C6—S1 | 120.45 (16) |
H1A—C1—H1C | 109.5 | C6—C7—C8 | 113.5 (2) |
H1B—C1—H1C | 109.5 | C6—C7—H7 | 123.2 |
C3—C2—C1 | 129.0 (2) | C8—C7—H7 | 123.2 |
C3—C2—S2 | 108.21 (16) | C9—C8—C7 | 111.8 (2) |
C1—C2—S2 | 122.77 (17) | C9—C8—H8 | 124.1 |
C2—C3—N2 | 117.6 (2) | C7—C8—H8 | 124.1 |
C2—C3—H3 | 121.2 | C8—C9—Cl1 | 126.84 (18) |
N2—C3—H3 | 121.2 | C8—C9—S1 | 113.16 (17) |
N2—C4—N1 | 128.43 (19) | Cl1—C9—S1 | 120.00 (14) |
N2—C4—S2 | 114.16 (15) | C5—N1—C4 | 117.54 (17) |
N1—C4—S2 | 117.41 (14) | C4—N2—C3 | 110.04 (18) |
N1—C5—C6 | 122.24 (18) | C9—S1—C6 | 90.44 (11) |
N1—C5—H5 | 118.9 | C2—S2—C4 | 89.94 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···S2i | 0.93 | 2.97 | 3.834 (2) | 155 |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C9H7ClN2S2 |
Mr | 242.74 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 298 |
a, b, c (Å) | 3.9472 (4), 23.281 (2), 6.0379 (6) |
β (°) | 104.214 (1) |
V (Å3) | 537.87 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.70 |
Crystal size (mm) | 0.31 × 0.25 × 0.19 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.812, 0.878 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3269, 1839, 1766 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.060, 1.06 |
No. of reflections | 1839 |
No. of parameters | 128 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.12 |
Absolute structure | Flack (1983), with 836 Friedel pairs |
Absolute structure parameter | 0.04 (6) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···S2i | 0.93 | 2.97 | 3.834 (2) | 155.0 |
Symmetry code: (i) x, y, z−1. |
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Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes, (Johnson et al., 1996; Alizadeh et al.,1999; Wang & Zheng, 2007). Schiff bases that have solvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optically active) materials (Alemi & Shaabani, 2000). They are also useful in the asymmetric oxidation of methyl phenyl sulfide and are enantioselective (Kim & Shin, 1999). In this paper, we report the synthesis and crystal structure of the title compound, (I).
The title compound is roughly planar with the two thiophene rings twisted by only (Fig. 1). The bond lengths and bond angles are usual for such compounds. The crystal packing is governed by weak C—H···S interactions (Table 1) forming chains parallel to the c axis and very weak slipped π–π stacking between the thiophene rings with centroid to centroid distance of 3.947 Å and interplanar distance of 3.651 Å resulting in an offset angle of 22.3°.