Acta Cryst. (2012). E68, o2635 [ doi:10.1107/S1600536812034071 ]
The asymmetric unit of the title compound, C28H22Br2N2O2S2, comprises half of a Schiff base ligand, the whole molecule being generated by a crystallographic inversion center located at the mid-point of the C-C bond of the central methylene segment. Intramolecular O-HN and O-HS hydrogen bonds make S(6) and S(5) ring motifs, respectively. In the crystal, there are no significant intermolecular interactions.
The title compound was synthesized by adding 5-bromosalicylaldehyde (2 mmol) to a solution of 2-(2-(2-aminophenylthio)ethylthio)benzenamine (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Light-yellow needle-like crystals of the title compound, suitable for X-ray structure analysis, were obtained by slow evaporation of a solution in ethanol at room temperature over several days.
The O-bound H atom was located in a difference Fourier map and constrained to refine on the parent atom with Uiso(H) = 1.5Ueq(O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C-H = 0.93 and 0.97 Å for CH and CH2 H atoms, respectively, with Uiso(H) = 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
C28H22Br2N2O2S2 | F(000) = 644 |
Mr = 642.42 | Dx = 1.629 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2098 reflections |
a = 13.9124 (18) Å | θ = 2.5–28.8° |
b = 5.4112 (7) Å | µ = 3.28 mm−1 |
c = 17.409 (2) Å | T = 296 K |
β = 92.444 (7)° | Needle, light-yellow |
V = 1309.4 (3) Å3 | 0.35 × 0.14 × 0.12 mm |
Z = 2 |
Bruker SMART APEXII CCD area-detector diffractometer | 2879 independent reflections |
Radiation source: fine-focus sealed tube | 1277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.093 |
φ and ω scans | θmax = 27.1°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −17→17 |
Tmin = 0.393, Tmax = 0.694 | k = −6→4 |
10754 measured reflections | l = −22→22 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 0.93 | w = 1/[σ2(Fo2) + (0.0347P)2] where P = (Fo2 + 2Fc2)/3 |
2879 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
C28H22Br2N2O2S2 | V = 1309.4 (3) Å3 |
Mr = 642.42 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.9124 (18) Å | µ = 3.28 mm−1 |
b = 5.4112 (7) Å | T = 296 K |
c = 17.409 (2) Å | 0.35 × 0.14 × 0.12 mm |
β = 92.444 (7)° |
Bruker SMART APEXII CCD area-detector diffractometer | 2879 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1277 reflections with I > 2σ(I) |
Tmin = 0.393, Tmax = 0.694 | Rint = 0.093 |
10754 measured reflections | θmax = 27.1° |
R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
wR(F2) = 0.106 | Δρmax = 0.38 e Å−3 |
S = 0.93 | Δρmin = −0.55 e Å−3 |
2879 reflections | Absolute structure: ? |
163 parameters | Flack parameter: ? |
0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.55873 (4) | 1.84843 (11) | 0.63714 (3) | 0.0707 (3) | |
S1 | 0.08346 (11) | 0.7463 (2) | 0.57293 (8) | 0.0622 (4) | |
O1 | 0.2265 (3) | 1.2258 (6) | 0.51696 (19) | 0.0684 (11) | |
H1 | 0.2092 | 1.1303 | 0.5566 | 0.103* | |
N1 | 0.2327 (3) | 0.9977 (8) | 0.6512 (2) | 0.0479 (10) | |
C1 | 0.2994 (4) | 1.3675 (9) | 0.5463 (3) | 0.0502 (13) | |
C2 | 0.3336 (4) | 1.5574 (10) | 0.5026 (3) | 0.0633 (16) | |
H2 | 0.3048 | 1.5889 | 0.4544 | 0.076* | |
C3 | 0.4094 (4) | 1.7013 (9) | 0.5286 (3) | 0.0577 (15) | |
H3 | 0.4322 | 1.8277 | 0.4981 | 0.069* | |
C4 | 0.4522 (3) | 1.6562 (9) | 0.6015 (3) | 0.0492 (13) | |
C5 | 0.4185 (3) | 1.4704 (9) | 0.6453 (3) | 0.0483 (13) | |
H5 | 0.4480 | 1.4404 | 0.6934 | 0.058* | |
C6 | 0.3408 (3) | 1.3230 (8) | 0.6206 (2) | 0.0439 (12) | |
C7 | 0.3043 (4) | 1.1325 (9) | 0.6696 (3) | 0.0510 (13) | |
H7 | 0.3352 | 1.1076 | 0.7174 | 0.061* | |
C8 | 0.1967 (3) | 0.8149 (9) | 0.7006 (3) | 0.0436 (12) | |
C9 | 0.2299 (4) | 0.7718 (10) | 0.7752 (3) | 0.0672 (16) | |
H9 | 0.2797 | 0.8671 | 0.7968 | 0.081* | |
C10 | 0.1892 (4) | 0.5876 (10) | 0.8175 (3) | 0.0692 (17) | |
H10 | 0.2109 | 0.5615 | 0.8681 | 0.083* | |
C11 | 0.1171 (4) | 0.4423 (10) | 0.7861 (3) | 0.0616 (15) | |
H11 | 0.0911 | 0.3157 | 0.8148 | 0.074* | |
C12 | 0.0836 (4) | 0.4857 (10) | 0.7114 (3) | 0.0595 (15) | |
H12 | 0.0338 | 0.3893 | 0.6903 | 0.071* | |
C13 | 0.1228 (3) | 0.6697 (9) | 0.6678 (3) | 0.0447 (12) | |
C14 | 0.0071 (4) | 0.4938 (9) | 0.5431 (2) | 0.0567 (14) | |
H14A | 0.0368 | 0.3379 | 0.5582 | 0.068* | |
H14B | −0.0543 | 0.5063 | 0.5671 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0767 (5) | 0.0794 (5) | 0.0547 (4) | −0.0273 (3) | −0.0120 (3) | 0.0093 (3) |
S1 | 0.0652 (11) | 0.0659 (11) | 0.0537 (9) | −0.0180 (7) | −0.0170 (7) | −0.0023 (7) |
O1 | 0.059 (3) | 0.091 (3) | 0.053 (2) | −0.020 (2) | −0.0163 (19) | 0.0036 (18) |
N1 | 0.042 (3) | 0.054 (3) | 0.047 (2) | −0.011 (2) | −0.006 (2) | −0.007 (2) |
C1 | 0.049 (3) | 0.059 (4) | 0.042 (3) | 0.000 (3) | −0.008 (2) | −0.008 (3) |
C2 | 0.060 (4) | 0.085 (5) | 0.043 (3) | 0.002 (3) | −0.014 (3) | 0.016 (3) |
C3 | 0.060 (4) | 0.070 (4) | 0.042 (3) | −0.008 (3) | −0.008 (3) | 0.010 (3) |
C4 | 0.048 (3) | 0.057 (4) | 0.042 (3) | −0.009 (3) | 0.001 (2) | −0.003 (3) |
C5 | 0.046 (4) | 0.060 (4) | 0.038 (3) | −0.007 (3) | −0.009 (2) | 0.003 (3) |
C6 | 0.042 (3) | 0.052 (4) | 0.037 (3) | 0.001 (3) | −0.001 (2) | 0.003 (3) |
C7 | 0.056 (4) | 0.057 (4) | 0.039 (3) | −0.007 (3) | −0.006 (3) | 0.003 (3) |
C8 | 0.039 (3) | 0.047 (4) | 0.045 (3) | −0.008 (3) | 0.001 (2) | −0.001 (3) |
C9 | 0.064 (4) | 0.084 (5) | 0.052 (4) | −0.023 (3) | −0.009 (3) | 0.007 (3) |
C10 | 0.068 (5) | 0.083 (5) | 0.056 (4) | −0.011 (3) | −0.002 (3) | 0.013 (3) |
C11 | 0.060 (4) | 0.061 (4) | 0.064 (4) | −0.008 (3) | 0.004 (3) | 0.013 (3) |
C12 | 0.048 (4) | 0.067 (4) | 0.062 (4) | −0.014 (3) | −0.007 (3) | 0.001 (3) |
C13 | 0.036 (3) | 0.047 (3) | 0.051 (3) | 0.003 (3) | −0.002 (2) | 0.000 (3) |
C14 | 0.048 (3) | 0.060 (4) | 0.062 (3) | −0.009 (3) | −0.003 (3) | −0.005 (3) |
Br1—C4 | 1.894 (5) | C6—C7 | 1.444 (6) |
S1—C13 | 1.766 (5) | C7—H7 | 0.9300 |
S1—C14 | 1.793 (5) | C8—C9 | 1.379 (6) |
O1—C1 | 1.354 (5) | C8—C13 | 1.397 (6) |
O1—H1 | 0.9026 | C9—C10 | 1.376 (6) |
N1—C7 | 1.265 (5) | C9—H9 | 0.9300 |
N1—C8 | 1.416 (5) | C10—C11 | 1.369 (7) |
C1—C2 | 1.377 (6) | C10—H10 | 0.9300 |
C1—C6 | 1.413 (6) | C11—C12 | 1.383 (6) |
C2—C3 | 1.373 (6) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C12—C13 | 1.379 (6) |
C3—C4 | 1.399 (6) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C14—C14i | 1.508 (8) |
C4—C5 | 1.358 (6) | C14—H14A | 0.9700 |
C5—C6 | 1.396 (6) | C14—H14B | 0.9700 |
C5—H5 | 0.9300 | ||
C13—S1—C14 | 104.3 (2) | C9—C8—C13 | 120.1 (5) |
C1—O1—H1 | 104.8 | C9—C8—N1 | 125.2 (5) |
C7—N1—C8 | 123.0 (4) | C13—C8—N1 | 114.7 (4) |
O1—C1—C2 | 119.0 (4) | C10—C9—C8 | 119.8 (5) |
O1—C1—C6 | 121.3 (5) | C10—C9—H9 | 120.1 |
C2—C1—C6 | 119.7 (5) | C8—C9—H9 | 120.1 |
C3—C2—C1 | 121.3 (5) | C11—C10—C9 | 120.9 (5) |
C3—C2—H2 | 119.3 | C11—C10—H10 | 119.5 |
C1—C2—H2 | 119.3 | C9—C10—H10 | 119.5 |
C2—C3—C4 | 119.4 (5) | C10—C11—C12 | 119.3 (5) |
C2—C3—H3 | 120.3 | C10—C11—H11 | 120.3 |
C4—C3—H3 | 120.3 | C12—C11—H11 | 120.3 |
C5—C4—C3 | 119.7 (5) | C13—C12—C11 | 121.0 (5) |
C5—C4—Br1 | 120.4 (4) | C13—C12—H12 | 119.5 |
C3—C4—Br1 | 119.9 (4) | C11—C12—H12 | 119.5 |
C4—C5—C6 | 122.0 (4) | C12—C13—C8 | 118.8 (4) |
C4—C5—H5 | 119.0 | C12—C13—S1 | 124.8 (4) |
C6—C5—H5 | 119.0 | C8—C13—S1 | 116.3 (4) |
C5—C6—C1 | 117.7 (4) | C14i—C14—S1 | 107.8 (4) |
C5—C6—C7 | 120.8 (4) | C14i—C14—H14A | 110.2 |
C1—C6—C7 | 121.5 (4) | S1—C14—H14A | 110.2 |
N1—C7—C6 | 123.7 (5) | C14i—C14—H14B | 110.2 |
N1—C7—H7 | 118.1 | S1—C14—H14B | 110.2 |
C6—C7—H7 | 118.1 | H14A—C14—H14B | 108.5 |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.90 | 1.81 | 2.641 (5) | 151 |
O1—H1···S1 | 0.90 | 2.74 | 3.436 (4) | 135 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.90 | 1.81 | 2.641 (5) | 151 |
O1—H1···S1 | 0.90 | 2.74 | 3.436 (4) | 135 |
HK thanks PNU for financial support. MNT thanks GC University of Sargodha, Pakistan for the research facility.
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Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Kargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, o614.
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Spek, A. L. (2009). Acta Cryst. D65, 148–155.
In continuation of our work on the crystal structures of Schiff base ligands (Kargar et al., 2011; Kia et al., 2010), we synthesized and determined the X-ray crystal structure of the title compound.
The asymmetric unit of the title compound, Fig. 1, comprises half of a Schiff base ligand. The whole molecule is generated by a crystallographic inversion center located in the middle of the C14—C14i bond of the methylene segment [Symmetry code: (i) -x, -y+1, -z+1]. The bond lengths (Allen et al., 1987) and angles are within the normal ranges. Intramolecular O—H···N and O—H···S hydrogen bonds make S(6) and S(5) ring motifs, respectively (Table 1; Bernstein et al., 1995).
There are no significant intermolecular interactions in the crystal structure.