Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827019901611X/qa0193sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827019901611X/qa0193Isup2.hkl |
CCDC reference: 140853
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.
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.
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).
[Pt(C9H8BrN2S2)2] | Dx = 2.23 Mg m−3 |
Mr = 771.50 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8192 reflections |
a = 7.9739 (1) Å | θ = 2.0–28.3° |
b = 14.1721 (2) Å | µ = 9.94 mm−1 |
c = 20.3772 (2) Å | T = 293 K |
V = 2302.76 (5) Å3 | Slab, red |
Z = 4 | 0.34 × 0.24 × 0.10 mm |
F(000) = 1456 |
Siemens SMART CCD area-detector diffractometer | 2865 independent reflections |
Radiation source: fine-focus sealed tube | 2191 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.0° |
ω scans | h = −10→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −18→18 |
Tmin = 0.070, Tmax = 0.370 | l = −27→22 |
14693 measured reflections |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.084 | H-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 parameters | Δρmax = 0.88 e Å−3 |
0 restraints | Δρmin = −2.06 e Å−3 |
[Pt(C9H8BrN2S2)2] | V = 2302.76 (5) Å3 |
Mr = 771.50 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.9739 (1) Å | µ = 9.94 mm−1 |
b = 14.1721 (2) Å | T = 293 K |
c = 20.3772 (2) Å | 0.34 × 0.24 × 0.10 mm |
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 = 0.370 | Rint = 0.042 |
14693 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.88 e Å−3 |
2865 reflections | Δρmin = −2.06 e Å−3 |
133 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 | ||
Pt1 | 0.0000 | 0.5000 | 0.0000 | 0.02923 (9) | |
Br1 | 0.03190 (8) | 0.47696 (4) | 0.26737 (3) | 0.05158 (15) | |
S1 | 0.0603 (2) | 0.83018 (8) | −0.01676 (6) | 0.0495 (3) | |
S2 | 0.03328 (19) | 0.63491 (8) | −0.06077 (5) | 0.0457 (3) | |
N1 | −0.0224 (4) | 0.5922 (2) | 0.07533 (16) | 0.0305 (7) | |
N2 | 0.0029 (4) | 0.6897 (3) | 0.06569 (18) | 0.0331 (8) | |
C1 | −0.1050 (5) | 0.6285 (3) | 0.19033 (18) | 0.0307 (8) | |
C2 | −0.1893 (6) | 0.7143 (3) | 0.1839 (2) | 0.0428 (10) | |
H2A | −0.2120 | 0.7384 | 0.1424 | 0.051* | |
C3 | −0.2394 (6) | 0.7637 (4) | 0.2396 (3) | 0.0568 (16) | |
H3A | −0.2969 | 0.8204 | 0.2351 | 0.068* | |
C4 | −0.2051 (8) | 0.7301 (4) | 0.3006 (3) | 0.0640 (16) | |
H4A | −0.2362 | 0.7649 | 0.3373 | 0.077* | |
C5 | −0.1266 (7) | 0.6468 (4) | 0.3084 (2) | 0.0554 (14) | |
H5A | −0.1056 | 0.6239 | 0.3504 | 0.066* | |
C6 | −0.0766 (5) | 0.5945 (3) | 0.25352 (19) | 0.0351 (9) | |
C7 | −0.0660 (6) | 0.5681 (3) | 0.13423 (17) | 0.0332 (9) | |
H7A | −0.0736 | 0.5036 | 0.1419 | 0.040* | |
C8 | 0.0282 (6) | 0.7120 (4) | 0.00497 (19) | 0.0354 (10) | |
C9 | 0.0340 (7) | 0.8924 (4) | 0.0597 (3) | 0.0538 (13) | |
H9A | 0.0496 | 0.9588 | 0.0526 | 0.081* | |
H9B | 0.1153 | 0.8703 | 0.0909 | 0.081* | |
H9C | −0.0768 | 0.8813 | 0.0764 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.04440 (16) | 0.02661 (14) | 0.01668 (13) | 0.00150 (8) | 0.00263 (8) | −0.00162 (7) |
Br1 | 0.0602 (3) | 0.0506 (3) | 0.0440 (3) | −0.0113 (2) | −0.0105 (2) | 0.0166 (2) |
S1 | 0.0888 (10) | 0.0294 (5) | 0.0303 (5) | −0.0051 (6) | 0.0079 (6) | 0.0023 (4) |
S2 | 0.0864 (9) | 0.0306 (6) | 0.0202 (5) | −0.0012 (5) | 0.0074 (5) | −0.0004 (4) |
N1 | 0.046 (2) | 0.0253 (17) | 0.0198 (16) | 0.0004 (13) | 0.0037 (13) | −0.0031 (13) |
N2 | 0.049 (2) | 0.0256 (17) | 0.0247 (17) | −0.0020 (13) | 0.0033 (14) | −0.0015 (14) |
C1 | 0.038 (2) | 0.0289 (19) | 0.0258 (19) | −0.0039 (16) | 0.0051 (16) | −0.0046 (15) |
C2 | 0.049 (3) | 0.035 (2) | 0.045 (3) | −0.0012 (19) | 0.011 (2) | −0.0054 (19) |
C3 | 0.055 (3) | 0.042 (3) | 0.074 (4) | −0.004 (2) | 0.024 (3) | −0.025 (2) |
C4 | 0.074 (4) | 0.069 (4) | 0.049 (4) | −0.021 (3) | 0.024 (3) | −0.037 (3) |
C5 | 0.064 (3) | 0.078 (4) | 0.025 (2) | −0.025 (3) | 0.009 (2) | −0.015 (2) |
C6 | 0.040 (2) | 0.042 (2) | 0.0231 (19) | −0.0131 (18) | 0.0026 (16) | −0.0004 (16) |
C7 | 0.052 (3) | 0.0260 (19) | 0.0211 (19) | −0.0005 (18) | 0.0047 (17) | −0.0018 (15) |
C8 | 0.052 (3) | 0.028 (2) | 0.026 (2) | 0.0016 (18) | 0.0018 (18) | 0.0013 (15) |
C9 | 0.088 (4) | 0.033 (2) | 0.040 (3) | 0.001 (2) | 0.001 (3) | −0.006 (2) |
Pt1—N1 | 2.023 (3) | N1—N2 | 1.411 (5) |
Pt1—N1i | 2.023 (3) | N2—C8 | 1.293 (5) |
Pt1—S2i | 2.2934 (12) | C1—C6 | 1.393 (5) |
Pt1—S2 | 2.293 (1) | C1—C2 | 1.395 (6) |
Br1—C6 | 1.898 (5) | C1—C7 | 1.461 (5) |
S1—C8 | 1.751 (5) | C2—C3 | 1.394 (7) |
S1—C9 | 1.803 (5) | C3—C4 | 1.358 (8) |
S2—C8 | 1.729 (5) | C4—C5 | 1.345 (8) |
N1—C7 | 1.295 (5) | C5—C6 | 1.400 (6) |
N1—Pt1—N1i | 180.0 (1) | C6—C1—C7 | 119.1 (4) |
N1—Pt1—S2i | 96.8 (1) | C2—C1—C7 | 122.6 (4) |
N1i—Pt1—S2i | 83.2 (1) | C3—C2—C1 | 119.9 (5) |
N1—Pt1—S2 | 83.2 (1) | C4—C3—C2 | 120.8 (5) |
N1i—Pt1—S2 | 96.8 (1) | C5—C4—C3 | 120.7 (5) |
S2i—Pt1—S2 | 180.0 (1) | C4—C5—C6 | 120.1 (5) |
C8—S1—C9 | 103.4 (2) | C1—C6—C5 | 120.6 (4) |
C8—S2—Pt1 | 96.07 (16) | C1—C6—Br1 | 121.0 (3) |
C7—N1—N2 | 115.2 (3) | C5—C6—Br1 | 118.4 (4) |
C7—N1—Pt1 | 123.9 (3) | N1—C7—C1 | 128.9 (4) |
N2—N1—Pt1 | 120.9 (2) | N2—C8—S2 | 126.2 (4) |
C8—N2—N1 | 113.3 (4) | N2—C8—S1 | 119.9 (4) |
C6—C1—C2 | 117.8 (4) | S2—C8—S1 | 113.9 (2) |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Pt(C9H8BrN2S2)2] |
Mr | 771.50 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 7.9739 (1), 14.1721 (2), 20.3772 (2) |
V (Å3) | 2302.76 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.94 |
Crystal size (mm) | 0.34 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.070, 0.370 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14693, 2865, 2191 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.084, 1.07 |
No. of reflections | 2865 |
No. of parameters | 133 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −2.06 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
Pt1—N1 | 2.023 (3) | S2—C8 | 1.729 (5) |
Pt1—S2 | 2.293 (1) | N1—C7 | 1.295 (5) |
Br1—C6 | 1.898 (5) | N1—N2 | 1.411 (5) |
S1—C8 | 1.751 (5) | N2—C8 | 1.293 (5) |
S1—C9 | 1.803 (5) | ||
N1—Pt1—N1i | 180.0 (1) | N1—Pt1—S2 | 83.2 (1) |
N1—Pt1—S2i | 96.8 (1) | N1i—Pt1—S2 | 96.8 (1) |
N1i—Pt1—S2i | 83.2 (1) | S2i—Pt1—S2 | 180.0 (1) |
Symmetry code: (i) −x, −y+1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
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.