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The Schiff base ligand in the title complex, [Pt(C9H8BrN2S2)2], is deprotonated from its tautomeric thiol form and coordinated to PtII via the mercapto S and [beta]-N atoms. The configuration about PtII is a perfect square-planar, with two equivalent Pt-N [2.023 (3) Å] and Pt-S [2.293 (1) Å] bonds. The phenyl ring is twisted against the coordination moiety Pt1/N1/N1'/S2'/S2 by 31.8 (2)°, due to the steric hindrance induced by ortho-substituted bulky Br atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827019901611X/qa0193sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827019901611X/qa0193Isup2.hkl
Contains datablock I

CCDC reference: 140853

Comment top

Organometallic compounds have recently received considerable attention as potential non-linear optical materials due to the various excited states present in these systems, as well as the ability to manipulate metal-organic ligand interactions (Long, 1995). Thiosemicabazones and their derivatives are known to coordinate readily with a variety of transition metal ions to afford stable metal complexes (Ali & Livingstone, 1974; Podhye & Kauffman, 1985). As part of our continuing studies on the syntheses and non-linear optical properties (including optical limiting) of Schiff base complexes containing mixed N,S donors (Tian et al., 1997; Zhu, Chen et al., 1999; Zhu, Liu et al., 1999), we report herein the structure of title compound, (I), the PtII complex with a bidentate Schiff base ligand derived from S-methyl dithiocarbazate.

The molecular structure of [Pt(C9H8BrN2S2)2] consists of monomeric complex units. The Pt atom lies on a centre of symmetry with a perfect square-planar geometry with two equivalent Pt—N and Pt—S bonds; PtII is situated in the coordination plane. The bond lengths of Pt—N [2.023 (3) Å] and of Pt—S [2.2934 (12) Å] are normal (Clement et al., 1996). The ligand has a cis–cis conformation, strictly resembling its analogues [Pt{N(CH2Ph)NC(S)SMe}2] (Fares et al., 1987) and [Pt(PhL1-2H)2] (Dessy & Fares, 1980). The bond distances and bond angles are also not very different from those found in the analogues, the only significant difference being the Pt1—N1 distance [1.937 (4) and 1.966 (4) Å, respectively observed for the analogues] and related to the σ influence of the phenyl group. The Schiff base loses a proton from its tautomeric thiol form on cordination and acts as a singly charged bidentate ligand, coordinating to PtII via the mercapto-S and β-N atoms. The phenyl ring is twisted against the coordination moieties Pt1/N1/N1i/S2/S2i [symmetry code: (i) −x, 1 − y, −z] by 31.8°, which is attributed to the steric hindrance induced by ortho-substituted bulky Br atom.

The S-methyldithiocarbazate, N2C(S)SMe, group is planar with a maximum out-of-plane deviation of 0.013 (3) Å for N1. The Br atom deviates 0.043 (1) Å from the planarity of the phenyl ring.

Experimental top

The title compound, [Pt(C9H8BrN2S2)2], was synthesized by refluxing an equivalent molar ratio of PtCl2 and the Schiff-base ligand (prepared by condensation of 2-bromobenzaldehyde with S-methyl dithiocarbazate) in CH3CN. Single crystals suitable for X-ray diffraction were obtained by evaporation of ether into a THF solution.

Refinement top

The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. The temperature factors of C3, C4 and C5 are slightly higher. The highest peak and the deepest hole are located neat Pt atom.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Bis(2-Bromobenzaldehyde S-methyl dithiocabazate)Pt(II) top
Crystal data top
[Pt(C9H8BrN2S2)2]Dx = 2.23 Mg m3
Mr = 771.50Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 8192 reflections
a = 7.9739 (1) Åθ = 2.0–28.3°
b = 14.1721 (2) ŵ = 9.94 mm1
c = 20.3772 (2) ÅT = 293 K
V = 2302.76 (5) Å3Slab, red
Z = 40.34 × 0.24 × 0.10 mm
F(000) = 1456
Data collection top
Siemens SMART CCD area-detector
diffractometer
2865 independent reflections
Radiation source: fine-focus sealed tube2191 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 8.33 pixels mm-1θmax = 28.3°, θmin = 2.0°
ω scansh = 1010
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 1818
Tmin = 0.070, Tmax = 0.370l = 2722
14693 measured reflections
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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0405P)2 + 3.2007P]
where P = (Fo2 + 2Fc2)/3
2865 reflections(Δ/σ)max < 0.001
133 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = 2.06 e Å3
Crystal data top
[Pt(C9H8BrN2S2)2]V = 2302.76 (5) Å3
Mr = 771.50Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 7.9739 (1) ŵ = 9.94 mm1
b = 14.1721 (2) ÅT = 293 K
c = 20.3772 (2) Å0.34 × 0.24 × 0.10 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer
2865 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2191 reflections with I > 2σ(I)
Tmin = 0.070, Tmax = 0.370Rint = 0.042
14693 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.07Δρmax = 0.88 e Å3
2865 reflectionsΔρmin = 2.06 e Å3
133 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.00000.50000.00000.02923 (9)
Br10.03190 (8)0.47696 (4)0.26737 (3)0.05158 (15)
S10.0603 (2)0.83018 (8)0.01676 (6)0.0495 (3)
S20.03328 (19)0.63491 (8)0.06077 (5)0.0457 (3)
N10.0224 (4)0.5922 (2)0.07533 (16)0.0305 (7)
N20.0029 (4)0.6897 (3)0.06569 (18)0.0331 (8)
C10.1050 (5)0.6285 (3)0.19033 (18)0.0307 (8)
C20.1893 (6)0.7143 (3)0.1839 (2)0.0428 (10)
H2A0.21200.73840.14240.051*
C30.2394 (6)0.7637 (4)0.2396 (3)0.0568 (16)
H3A0.29690.82040.23510.068*
C40.2051 (8)0.7301 (4)0.3006 (3)0.0640 (16)
H4A0.23620.76490.33730.077*
C50.1266 (7)0.6468 (4)0.3084 (2)0.0554 (14)
H5A0.10560.62390.35040.066*
C60.0766 (5)0.5945 (3)0.25352 (19)0.0351 (9)
C70.0660 (6)0.5681 (3)0.13423 (17)0.0332 (9)
H7A0.07360.50360.14190.040*
C80.0282 (6)0.7120 (4)0.00497 (19)0.0354 (10)
C90.0340 (7)0.8924 (4)0.0597 (3)0.0538 (13)
H9A0.04960.95880.05260.081*
H9B0.11530.87030.09090.081*
H9C0.07680.88130.07640.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.04440 (16)0.02661 (14)0.01668 (13)0.00150 (8)0.00263 (8)0.00162 (7)
Br10.0602 (3)0.0506 (3)0.0440 (3)0.0113 (2)0.0105 (2)0.0166 (2)
S10.0888 (10)0.0294 (5)0.0303 (5)0.0051 (6)0.0079 (6)0.0023 (4)
S20.0864 (9)0.0306 (6)0.0202 (5)0.0012 (5)0.0074 (5)0.0004 (4)
N10.046 (2)0.0253 (17)0.0198 (16)0.0004 (13)0.0037 (13)0.0031 (13)
N20.049 (2)0.0256 (17)0.0247 (17)0.0020 (13)0.0033 (14)0.0015 (14)
C10.038 (2)0.0289 (19)0.0258 (19)0.0039 (16)0.0051 (16)0.0046 (15)
C20.049 (3)0.035 (2)0.045 (3)0.0012 (19)0.011 (2)0.0054 (19)
C30.055 (3)0.042 (3)0.074 (4)0.004 (2)0.024 (3)0.025 (2)
C40.074 (4)0.069 (4)0.049 (4)0.021 (3)0.024 (3)0.037 (3)
C50.064 (3)0.078 (4)0.025 (2)0.025 (3)0.009 (2)0.015 (2)
C60.040 (2)0.042 (2)0.0231 (19)0.0131 (18)0.0026 (16)0.0004 (16)
C70.052 (3)0.0260 (19)0.0211 (19)0.0005 (18)0.0047 (17)0.0018 (15)
C80.052 (3)0.028 (2)0.026 (2)0.0016 (18)0.0018 (18)0.0013 (15)
C90.088 (4)0.033 (2)0.040 (3)0.001 (2)0.001 (3)0.006 (2)
Geometric parameters (Å, º) top
Pt1—N12.023 (3)N1—N21.411 (5)
Pt1—N1i2.023 (3)N2—C81.293 (5)
Pt1—S2i2.2934 (12)C1—C61.393 (5)
Pt1—S22.293 (1)C1—C21.395 (6)
Br1—C61.898 (5)C1—C71.461 (5)
S1—C81.751 (5)C2—C31.394 (7)
S1—C91.803 (5)C3—C41.358 (8)
S2—C81.729 (5)C4—C51.345 (8)
N1—C71.295 (5)C5—C61.400 (6)
N1—Pt1—N1i180.0 (1)C6—C1—C7119.1 (4)
N1—Pt1—S2i96.8 (1)C2—C1—C7122.6 (4)
N1i—Pt1—S2i83.2 (1)C3—C2—C1119.9 (5)
N1—Pt1—S283.2 (1)C4—C3—C2120.8 (5)
N1i—Pt1—S296.8 (1)C5—C4—C3120.7 (5)
S2i—Pt1—S2180.0 (1)C4—C5—C6120.1 (5)
C8—S1—C9103.4 (2)C1—C6—C5120.6 (4)
C8—S2—Pt196.07 (16)C1—C6—Br1121.0 (3)
C7—N1—N2115.2 (3)C5—C6—Br1118.4 (4)
C7—N1—Pt1123.9 (3)N1—C7—C1128.9 (4)
N2—N1—Pt1120.9 (2)N2—C8—S2126.2 (4)
C8—N2—N1113.3 (4)N2—C8—S1119.9 (4)
C6—C1—C2117.8 (4)S2—C8—S1113.9 (2)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Pt(C9H8BrN2S2)2]
Mr771.50
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)293
a, b, c (Å)7.9739 (1), 14.1721 (2), 20.3772 (2)
V3)2302.76 (5)
Z4
Radiation typeMo Kα
µ (mm1)9.94
Crystal size (mm)0.34 × 0.24 × 0.10
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.070, 0.370
No. of measured, independent and
observed [I > 2σ(I)] reflections
14693, 2865, 2191
Rint0.042
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.084, 1.07
No. of reflections2865
No. of parameters133
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.88, 2.06

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
Pt1—N12.023 (3)S2—C81.729 (5)
Pt1—S22.293 (1)N1—C71.295 (5)
Br1—C61.898 (5)N1—N21.411 (5)
S1—C81.751 (5)N2—C81.293 (5)
S1—C91.803 (5)
N1—Pt1—N1i180.0 (1)N1—Pt1—S283.2 (1)
N1—Pt1—S2i96.8 (1)N1i—Pt1—S296.8 (1)
N1i—Pt1—S2i83.2 (1)S2i—Pt1—S2180.0 (1)
Symmetry code: (i) x, y+1, z.
 

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