Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020211/dn2165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020211/dn2165Isup2.hkl |
CCDC reference: 647703
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.084
- Data-to-parameter ratio = 16.4
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.922 0.938 Tmin and Tmax expected: 0.348 0.404 RR = 1.140 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.13 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.43 PLAT322_ALERT_2_C Check Hybridisation of S2 in Main Residue . ? PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. N1 .. 3.19 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.431 Tmax scaled 0.404 Tmin scaled 0.397
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For general background, see: Johnson et al., 1996; Alizadeh et al., 1999; Alemi et al., 2000; Kim et al., 1999.
Under nitrogen, a mixture of 5-methylthiazol-2-amine (1.63 g,8 mmol), Na2SO4 (3.0 g) and 5-bromo-2-thiophenecarboxaldehyde(1.52 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*10 ml)and brine(10 ml). After dried over Na2SO4, the solvent was removed under vacuum, and yellow solid was isolated in yield 92% (3.1 g). Yellow single crystals of the compound suitable for X-ray analysis were grown from CH2Cl2 and absolute ethanol(4:1) by slow evaporation of the solvent at room temperature over a period of about a week.
All H atoms were placed in calculated positions, C—H = 0.93Å (Caromatic) or 0.96 Å (CH3) and treated as riding on their parent atoms, with Uiso(H) =1.2Ueq(Caromatic) and Uiso(H) = 1.5Ueq(CH3).
Schiff base ligands have significant importance in chemistry, specially in the development of Schiff base complexes, because Schiff base ligands are potentially capable of forming stable complexes with metal ions (Johnson et al., 1996; Alizadeh et al., 1999). Schiff bases that have solvent dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optical active) materials (Alemi et al., 2000). They are also useful in asymmetric oxidation of methyl phenyl sulfide and enantioselective (Kim et al., 1999). In this paper, we report the synthesis and crystal structure of the title compound (I).
The molecular structure of the title compound (Fig. 1) contains one intramolecular hydrogen bonds [C5—H5\···S2](Table 1). The C5—N1 bond lengths is 1.277 (3) Å, indicative of standard C=N double bond. The other C—N, C—S and C—C distances show no remarkable features. A supramolecular network is formed by C—H···N intermolecular hydrogen bonding and weak π-π interactions. The centroid-to-centroid and interplanar distances between adjacent rings (Symmetry code: 1 - x, 2 - y, -z) are 3.712 (4) and 3.556 (3) Å, respectively.
For general background, see: Johnson et al., 1996; Alizadeh et al., 1999; Alemi et al., 2000; Kim et al., 1999.
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 structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 50% probability displacement ellipsoids. |
C9H7BrN2S2 | F(000) = 568 |
Mr = 287.20 | Dx = 1.753 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2100 reflections |
a = 9.5515 (10) Å | θ = 1.7–28.0° |
b = 10.9177 (11) Å | µ = 4.12 mm−1 |
c = 10.9141 (11) Å | T = 298 K |
β = 107.06 (10)° | Block, colourless |
V = 1088.03 (19) Å3 | 0.36 × 0.22 × 0.22 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 2096 independent reflections |
Radiation source: fine-focus sealed tube | 1622 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
φ and ω scans | θmax = 26.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.922, Tmax = 0.938 | k = −12→13 |
6883 measured reflections | l = −13→13 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0459P)2] where P = (Fo2 + 2Fc2)/3 |
2096 reflections | (Δ/σ)max < 0.001 |
128 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
C9H7BrN2S2 | V = 1088.03 (19) Å3 |
Mr = 287.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.5515 (10) Å | µ = 4.12 mm−1 |
b = 10.9177 (11) Å | T = 298 K |
c = 10.9141 (11) Å | 0.36 × 0.22 × 0.22 mm |
β = 107.06 (10)° |
Bruker APEXII area-detector diffractometer | 2096 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1622 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.938 | Rint = 0.067 |
6883 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.73 e Å−3 |
2096 reflections | Δρmin = −0.53 e Å−3 |
128 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 | 0.59314 (4) | 1.23977 (3) | 0.17687 (4) | 0.06274 (16) | |
C1 | 0.4366 (3) | 1.1433 (3) | 0.0801 (3) | 0.0458 (7) | |
C2 | 0.3745 (3) | 1.1446 (3) | −0.0481 (3) | 0.0527 (8) | |
H2 | 0.4021 | 1.1968 | −0.1042 | 0.063* | |
C3 | 0.2627 (3) | 1.0568 (3) | −0.0855 (3) | 0.0520 (7) | |
H3 | 0.2081 | 1.0445 | −0.1704 | 0.062* | |
C4 | 0.2416 (3) | 0.9918 (3) | 0.0131 (3) | 0.0432 (7) | |
C5 | 0.1400 (3) | 0.8926 (3) | 0.0063 (3) | 0.0453 (7) | |
H5 | 0.0812 | 0.8673 | −0.0737 | 0.054* | |
C6 | 0.0274 (3) | 0.7426 (2) | 0.0921 (3) | 0.0401 (6) | |
C7 | −0.0887 (3) | 0.5910 (3) | 0.1508 (3) | 0.0568 (8) | |
H7 | −0.1098 | 0.5375 | 0.2094 | 0.068* | |
C8 | −0.1607 (3) | 0.5841 (3) | 0.0254 (3) | 0.0462 (7) | |
C9 | −0.2806 (4) | 0.4988 (3) | −0.0419 (3) | 0.0684 (9) | |
H9A | −0.2957 | 0.4395 | 0.0179 | 0.103* | |
H9B | −0.2541 | 0.4577 | −0.1096 | 0.103* | |
H9C | −0.3692 | 0.5444 | −0.0773 | 0.103* | |
N1 | 0.1279 (2) | 0.8383 (2) | 0.1063 (2) | 0.0426 (5) | |
N2 | 0.0168 (3) | 0.6793 (3) | 0.1898 (2) | 0.0547 (7) | |
S1 | 0.36114 (8) | 1.03825 (6) | 0.15710 (7) | 0.0455 (2) | |
S2 | −0.09293 (8) | 0.69442 (7) | −0.05398 (7) | 0.0467 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0652 (3) | 0.0450 (2) | 0.0753 (3) | −0.01064 (14) | 0.0164 (2) | −0.00415 (16) |
C1 | 0.0477 (17) | 0.0379 (16) | 0.0550 (19) | 0.0027 (12) | 0.0202 (15) | 0.0012 (13) |
C2 | 0.064 (2) | 0.0484 (18) | 0.0535 (19) | 0.0008 (15) | 0.0297 (17) | 0.0066 (15) |
C3 | 0.0604 (19) | 0.0592 (19) | 0.0378 (16) | −0.0002 (15) | 0.0167 (14) | −0.0006 (14) |
C4 | 0.0431 (16) | 0.0445 (16) | 0.0416 (15) | 0.0041 (12) | 0.0118 (13) | −0.0020 (13) |
C5 | 0.0427 (16) | 0.0500 (18) | 0.0411 (17) | 0.0009 (13) | 0.0093 (14) | −0.0054 (14) |
C6 | 0.0403 (15) | 0.0451 (17) | 0.0348 (15) | 0.0055 (12) | 0.0107 (12) | −0.0012 (12) |
C7 | 0.0583 (19) | 0.066 (2) | 0.052 (2) | −0.0056 (16) | 0.0244 (16) | 0.0121 (16) |
C8 | 0.0475 (16) | 0.0448 (17) | 0.0487 (18) | 0.0023 (13) | 0.0177 (15) | −0.0004 (13) |
C9 | 0.068 (2) | 0.062 (2) | 0.074 (2) | −0.0127 (17) | 0.0188 (19) | −0.0009 (18) |
N1 | 0.0442 (13) | 0.0475 (14) | 0.0360 (13) | −0.0008 (10) | 0.0115 (11) | −0.0016 (11) |
N2 | 0.0578 (16) | 0.0718 (18) | 0.0350 (14) | −0.0071 (14) | 0.0144 (12) | 0.0068 (13) |
S1 | 0.0506 (4) | 0.0430 (4) | 0.0410 (4) | −0.0008 (3) | 0.0105 (3) | 0.0022 (3) |
S2 | 0.0559 (5) | 0.0444 (4) | 0.0360 (4) | −0.0034 (3) | 0.0074 (3) | 0.0011 (3) |
Br1—C1 | 1.880 (3) | C6—N2 | 1.299 (4) |
C1—C2 | 1.350 (4) | C6—N1 | 1.397 (3) |
C1—S1 | 1.702 (3) | C6—S2 | 1.750 (3) |
C2—C3 | 1.403 (4) | C7—C8 | 1.342 (4) |
C2—H2 | 0.9300 | C7—N2 | 1.370 (4) |
C3—C4 | 1.353 (4) | C7—H7 | 0.9300 |
C3—H3 | 0.9300 | C8—C9 | 1.491 (4) |
C4—C5 | 1.442 (4) | C8—S2 | 1.718 (3) |
C4—S1 | 1.725 (3) | C9—H9A | 0.9600 |
C5—N1 | 1.277 (3) | C9—H9B | 0.9600 |
C5—H5 | 0.9300 | C9—H9C | 0.9600 |
C2—C1—S1 | 113.4 (2) | N1—C6—S2 | 124.9 (2) |
C2—C1—Br1 | 127.7 (2) | C8—C7—N2 | 117.8 (3) |
S1—C1—Br1 | 118.84 (17) | C8—C7—H7 | 121.1 |
C1—C2—C3 | 111.1 (3) | N2—C7—H7 | 121.1 |
C1—C2—H2 | 124.5 | C7—C8—C9 | 128.8 (3) |
C3—C2—H2 | 124.5 | C7—C8—S2 | 108.6 (2) |
C4—C3—C2 | 113.9 (3) | C9—C8—S2 | 122.6 (2) |
C4—C3—H3 | 123.1 | C8—C9—H9A | 109.5 |
C2—C3—H3 | 123.1 | C8—C9—H9B | 109.5 |
C3—C4—C5 | 127.5 (3) | H9A—C9—H9B | 109.5 |
C3—C4—S1 | 110.9 (2) | C8—C9—H9C | 109.5 |
C5—C4—S1 | 121.6 (2) | H9A—C9—H9C | 109.5 |
N1—C5—C4 | 122.2 (3) | H9B—C9—H9C | 109.5 |
N1—C5—H5 | 118.9 | C5—N1—C6 | 119.0 (3) |
C4—C5—H5 | 118.9 | C6—N2—C7 | 110.3 (3) |
N2—C6—N1 | 121.6 (3) | C1—S1—C4 | 90.63 (14) |
N2—C6—S2 | 113.6 (2) | C8—S2—C6 | 89.72 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···S2 | 0.93 | 2.57 | 3.034 (3) | 112 |
C5—H5···N2i | 0.93 | 2.52 | 3.398 (4) | 157 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H7BrN2S2 |
Mr | 287.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.5515 (10), 10.9177 (11), 10.9141 (11) |
β (°) | 107.06 (10) |
V (Å3) | 1088.03 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.12 |
Crystal size (mm) | 0.36 × 0.22 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.922, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6883, 2096, 1622 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.084, 0.94 |
No. of reflections | 2096 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.53 |
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···S2 | 0.93 | 2.57 | 3.034 (3) | 111.5 |
C5—H5···N2i | 0.93 | 2.52 | 3.398 (4) | 156.7 |
Symmetry code: (i) x, −y+3/2, z−1/2. |
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Schiff base ligands have significant importance in chemistry, specially in the development of Schiff base complexes, because Schiff base ligands are potentially capable of forming stable complexes with metal ions (Johnson et al., 1996; Alizadeh et al., 1999). Schiff bases that have solvent dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optical active) materials (Alemi et al., 2000). They are also useful in asymmetric oxidation of methyl phenyl sulfide and enantioselective (Kim et al., 1999). In this paper, we report the synthesis and crystal structure of the title compound (I).
The molecular structure of the title compound (Fig. 1) contains one intramolecular hydrogen bonds [C5—H5\···S2](Table 1). The C5—N1 bond lengths is 1.277 (3) Å, indicative of standard C=N double bond. The other C—N, C—S and C—C distances show no remarkable features. A supramolecular network is formed by C—H···N intermolecular hydrogen bonding and weak π-π interactions. The centroid-to-centroid and interplanar distances between adjacent rings (Symmetry code: 1 - x, 2 - y, -z) are 3.712 (4) and 3.556 (3) Å, respectively.