organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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4-Bromo-2-[(E)-(2-{2-[(2-{[(E)-5-bromo-2-hy­dr­oxy­benzyl­­idene]amino}­phen­yl)sulfan­yl]ethyl­sulfan­yl}phen­yl)imino­meth­yl]phenol

aDepartment of Chemistry, Payame Noor University, PO Box 19395-3697 Tehran, I. R. of IRAN, bDepartment of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran, and cDepartment of Physics, University of Sargodha, Punjab, Pakistan
*Correspondence e-mail: zsrkk@yahoo.com, dmntahir_uos@yahoo.com

(Received 22 July 2012; accepted 31 July 2012; online 4 August 2012)

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—H⋯N and O—H⋯S hydrogen bonds make S(6) and S(5) ring motifs, respectively. In the crystal, there are no significant inter­molecular inter­actions.

Related literature

For standard bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). For hydrogen-bond motifs, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). For background to Schiff base ligands see, for example: Kargar et al. (2011[Kargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, o614.]); Kia et al. (2010[Kia, R., Kargar, H., Tahir, M. N. & Kianoosh, F. (2010). Acta Cryst. E66, o2296.]).

[Scheme 1]

Experimental

Crystal data
  • C28H22Br2N2O2S2

  • Mr = 642.42

  • Monoclinic, P 21 /c

  • a = 13.9124 (18) Å

  • b = 5.4112 (7) Å

  • c = 17.409 (2) Å

  • β = 92.444 (7)°

  • V = 1309.4 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 3.28 mm−1

  • T = 296 K

  • 0.35 × 0.14 × 0.12 mm

Data collection
  • Bruker SMART APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.393, Tmax = 0.694

  • 10754 measured reflections

  • 2879 independent reflections

  • 1277 reflections with I > 2σ(I)

  • Rint = 0.093

Refinement
  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.106

  • S = 0.93

  • 2879 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.55 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

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.

Related literature top

For standard bond lengths, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For background to Schiff base ligands see, for example: Kargar et al. (2011); Kia et al. (2010).

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids and the atomic numbering [symmetry code for A: -x, -y + 1, -z + 1]. Dashed lines show the intramolecular interactions
4-Bromo-2-[(E)-(2-{2-[(2-{[(E)-5-bromo-2- hydroxybenzylidene]amino}phenyl)sulfanyl]ethylsulfanyl}phenyl)iminomethyl]phenol top
Crystal data top
C28H22Br2N2O2S2F(000) = 644
Mr = 642.42Dx = 1.629 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2098 reflections
a = 13.9124 (18) Åθ = 2.5–28.8°
b = 5.4112 (7) ŵ = 3.28 mm1
c = 17.409 (2) ÅT = 296 K
β = 92.444 (7)°Needle, light-yellow
V = 1309.4 (3) Å30.35 × 0.14 × 0.12 mm
Z = 2
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
2879 independent reflections
Radiation source: fine-focus sealed tube1277 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.093
ϕ and ω scansθmax = 27.1°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1717
Tmin = 0.393, Tmax = 0.694k = 64
10754 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-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 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
C28H22Br2N2O2S2V = 1309.4 (3) Å3
Mr = 642.42Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.9124 (18) ŵ = 3.28 mm1
b = 5.4112 (7) ÅT = 296 K
c = 17.409 (2) Å0.35 × 0.14 × 0.12 mm
β = 92.444 (7)°
Data collection top
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 = 0.694Rint = 0.093
10754 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 0.93Δρmax = 0.38 e Å3
2879 reflectionsΔρmin = 0.55 e Å3
163 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.55873 (4)1.84843 (11)0.63714 (3)0.0707 (3)
S10.08346 (11)0.7463 (2)0.57293 (8)0.0622 (4)
O10.2265 (3)1.2258 (6)0.51696 (19)0.0684 (11)
H10.20921.13030.55660.103*
N10.2327 (3)0.9977 (8)0.6512 (2)0.0479 (10)
C10.2994 (4)1.3675 (9)0.5463 (3)0.0502 (13)
C20.3336 (4)1.5574 (10)0.5026 (3)0.0633 (16)
H20.30481.58890.45440.076*
C30.4094 (4)1.7013 (9)0.5286 (3)0.0577 (15)
H30.43221.82770.49810.069*
C40.4522 (3)1.6562 (9)0.6015 (3)0.0492 (13)
C50.4185 (3)1.4704 (9)0.6453 (3)0.0483 (13)
H50.44801.44040.69340.058*
C60.3408 (3)1.3230 (8)0.6206 (2)0.0439 (12)
C70.3043 (4)1.1325 (9)0.6696 (3)0.0510 (13)
H70.33521.10760.71740.061*
C80.1967 (3)0.8149 (9)0.7006 (3)0.0436 (12)
C90.2299 (4)0.7718 (10)0.7752 (3)0.0672 (16)
H90.27970.86710.79680.081*
C100.1892 (4)0.5876 (10)0.8175 (3)0.0692 (17)
H100.21090.56150.86810.083*
C110.1171 (4)0.4423 (10)0.7861 (3)0.0616 (15)
H110.09110.31570.81480.074*
C120.0836 (4)0.4857 (10)0.7114 (3)0.0595 (15)
H120.03380.38930.69030.071*
C130.1228 (3)0.6697 (9)0.6678 (3)0.0447 (12)
C140.0071 (4)0.4938 (9)0.5431 (2)0.0567 (14)
H14A0.03680.33790.55820.068*
H14B0.05430.50630.56710.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0767 (5)0.0794 (5)0.0547 (4)0.0273 (3)0.0120 (3)0.0093 (3)
S10.0652 (11)0.0659 (11)0.0537 (9)0.0180 (7)0.0170 (7)0.0023 (7)
O10.059 (3)0.091 (3)0.053 (2)0.020 (2)0.0163 (19)0.0036 (18)
N10.042 (3)0.054 (3)0.047 (2)0.011 (2)0.006 (2)0.007 (2)
C10.049 (3)0.059 (4)0.042 (3)0.000 (3)0.008 (2)0.008 (3)
C20.060 (4)0.085 (5)0.043 (3)0.002 (3)0.014 (3)0.016 (3)
C30.060 (4)0.070 (4)0.042 (3)0.008 (3)0.008 (3)0.010 (3)
C40.048 (3)0.057 (4)0.042 (3)0.009 (3)0.001 (2)0.003 (3)
C50.046 (4)0.060 (4)0.038 (3)0.007 (3)0.009 (2)0.003 (3)
C60.042 (3)0.052 (4)0.037 (3)0.001 (3)0.001 (2)0.003 (3)
C70.056 (4)0.057 (4)0.039 (3)0.007 (3)0.006 (3)0.003 (3)
C80.039 (3)0.047 (4)0.045 (3)0.008 (3)0.001 (2)0.001 (3)
C90.064 (4)0.084 (5)0.052 (4)0.023 (3)0.009 (3)0.007 (3)
C100.068 (5)0.083 (5)0.056 (4)0.011 (3)0.002 (3)0.013 (3)
C110.060 (4)0.061 (4)0.064 (4)0.008 (3)0.004 (3)0.013 (3)
C120.048 (4)0.067 (4)0.062 (4)0.014 (3)0.007 (3)0.001 (3)
C130.036 (3)0.047 (3)0.051 (3)0.003 (3)0.002 (2)0.000 (3)
C140.048 (3)0.060 (4)0.062 (3)0.009 (3)0.003 (3)0.005 (3)
Geometric parameters (Å, º) top
Br1—C41.894 (5)C6—C71.444 (6)
S1—C131.766 (5)C7—H70.9300
S1—C141.793 (5)C8—C91.379 (6)
O1—C11.354 (5)C8—C131.397 (6)
O1—H10.9026C9—C101.376 (6)
N1—C71.265 (5)C9—H90.9300
N1—C81.416 (5)C10—C111.369 (7)
C1—C21.377 (6)C10—H100.9300
C1—C61.413 (6)C11—C121.383 (6)
C2—C31.373 (6)C11—H110.9300
C2—H20.9300C12—C131.379 (6)
C3—C41.399 (6)C12—H120.9300
C3—H30.9300C14—C14i1.508 (8)
C4—C51.358 (6)C14—H14A0.9700
C5—C61.396 (6)C14—H14B0.9700
C5—H50.9300
C13—S1—C14104.3 (2)C9—C8—C13120.1 (5)
C1—O1—H1104.8C9—C8—N1125.2 (5)
C7—N1—C8123.0 (4)C13—C8—N1114.7 (4)
O1—C1—C2119.0 (4)C10—C9—C8119.8 (5)
O1—C1—C6121.3 (5)C10—C9—H9120.1
C2—C1—C6119.7 (5)C8—C9—H9120.1
C3—C2—C1121.3 (5)C11—C10—C9120.9 (5)
C3—C2—H2119.3C11—C10—H10119.5
C1—C2—H2119.3C9—C10—H10119.5
C2—C3—C4119.4 (5)C10—C11—C12119.3 (5)
C2—C3—H3120.3C10—C11—H11120.3
C4—C3—H3120.3C12—C11—H11120.3
C5—C4—C3119.7 (5)C13—C12—C11121.0 (5)
C5—C4—Br1120.4 (4)C13—C12—H12119.5
C3—C4—Br1119.9 (4)C11—C12—H12119.5
C4—C5—C6122.0 (4)C12—C13—C8118.8 (4)
C4—C5—H5119.0C12—C13—S1124.8 (4)
C6—C5—H5119.0C8—C13—S1116.3 (4)
C5—C6—C1117.7 (4)C14i—C14—S1107.8 (4)
C5—C6—C7120.8 (4)C14i—C14—H14A110.2
C1—C6—C7121.5 (4)S1—C14—H14A110.2
N1—C7—C6123.7 (5)C14i—C14—H14B110.2
N1—C7—H7118.1S1—C14—H14B110.2
C6—C7—H7118.1H14A—C14—H14B108.5
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.901.812.641 (5)151
O1—H1···S10.902.743.436 (4)135

Experimental details

Crystal data
Chemical formulaC28H22Br2N2O2S2
Mr642.42
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)13.9124 (18), 5.4112 (7), 17.409 (2)
β (°) 92.444 (7)
V3)1309.4 (3)
Z2
Radiation typeMo Kα
µ (mm1)3.28
Crystal size (mm)0.35 × 0.14 × 0.12
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.393, 0.694
No. of measured, independent and
observed [I > 2σ(I)] reflections
10754, 2879, 1277
Rint0.093
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.106, 0.93
No. of reflections2879
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.55

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.901.812.641 (5)151
O1—H1···S10.902.743.436 (4)135
 

Footnotes

Present address: Structural Dynamics of (Bio)Chemical Systems, Max Planck Institute for Biophysical Chemistry, Am Fassberg 11 37077 Göttingen, Germany.

Acknowledgements

HK thanks PNU for financial support. MNT thanks GC University of Sargodha, Pakistan for the research facility.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science
First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationKargar, H., Kia, R., Pahlavani, E. & Tahir, M. N. (2011). Acta Cryst. E67, o614.  Web of Science CSD CrossRef IUCr Journals
First citationKia, R., Kargar, H., Tahir, M. N. & Kianoosh, F. (2010). Acta Cryst. E66, o2296.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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