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In the title compounds, trans-[PtI2(C11H14N2OS)2], (I), and trans-[PtBr2(C11H14N2OS)2], (II), respectively, intramolecular N—H...O (propyl­amine side) hydrogen bonds in the potentially bidentate thio­urea ligands lock the carbonyl O atoms into six-membered rings, determining the S-mono­dentate mode of coordination of these ligands. Intramolecular N—H...X (X is I or Br) interactions (benzoyl­amine side) lead to slight distortions of the PtII coordination spheres from ideal square-planar geometry. The PtII ion is located on an inversion centre in both structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104014933/jz1636sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014933/jz1636Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104014933/jz1636IIsup3.hkl
Contains datablock II

CCDC references: 248134; 248135

Comment top

The compounds generally described as N,N-dialkyl- (HL1) and N-alkyl-N'-aroylthioureas (H2L2) have been found to display very different modes of coordination to PtII (Koch, 2001). HL1 ligands [R12NC(S)NHC(O)R2, where R1 = alkyl and R2 = aryl] coordinate to this metal centre via both the S and O atoms with the loss of the thioamidic H atom, forming predominantly cis isomers, several of which have been structurally characterized (Irving et al., 1993; Mautjana et al., 2003; Sacht et al., 2000). The structure of only one example of a trans complex has been reported to date (Koch et al., 1994). H2L2 molecules [R1NHC(S)NHC(O)R2, where R1 = alkyl and R2 = aryl] coordinate to PtX42− (X is I, Br or Cl) to form significant quantities of both cis- and trans-[Pt(H2L2—S)2X2] isomers (Koch et al., 1999). In the only structurally characterized complex of PtII with an H2L2 ligand, cis-bis(N-propyl-N'-benzoylthiourea)dichloroplatinum(II) (Bourne & Koch, 1993), it was shown that the coordination of the ligand is directed by an intramolecular N—H···O hydrogen bond and occurs, without loss of an H atom, via the S atom only. No structural data are available for a trans complex [Cambridge Structural Database (CSD), Version?; Allen, 2002].

In the last decade we have studied the coordination chemistry of these molecules with PtII and PdII as part of our interest in developing practically useful analytical and process chemical applications for these compounds (Koch, 2001; Mautjana et al., 2003). We present here the crystal structures of the title compounds, (I) and (II) (Figs. 1 and 2), the first two examples of trans complexes of PtII with an N-alkyl-N'-aroylthiourea ligand, H2L2. \sch

Both compounds crystallize in space group P1, with the PtII ion located on an inversion centre, but they are not isostructural. Because of the inversion symmetry, both PtS2X2 moieties are strictly planar.

The molecular structure of (I) and (II) reveals that, despite the potentially bidentate nature of the ligand (N-propyl-N'-benzoylthiourea, H2L2a), only the S-atom coordinates to the metal, while the carbonyl O atom is locked into an O/C/N/C/N/H ring by means of an intramolecular N2—H7···O1 hydrogen bond (Tables 2 and 4), similar to that in the previously reported compounds cis-bis(N-propyl-N'-benzoylthiourea)dichloroplatinum(II) (Bourne & Koch, 1993) and trans-bis(N-propyl-N'-benzoylthiourea)dibromopalladium(II) (Koch et al., 1999). The six-membered O1/C7/N1/C8/N2/H7 rings in both structures are virtually planar, with maximum deviations from planarity of 0.013 (4) Å for atom N1 in (I) and 0.050 (24) Å for atom H7 in (II).

The Pt—I and Pt—S bond lengths for (I) [2.617 (2) and 2.315 (6) Å, respectively] compare well with the corresponding distances in the previously reported trans-PtII complexes of S-donor ligands and iodide, [Pt{C2H5NHC(S)OC2H5}2I2] [Pt—I 2.610 (2) and Pt—S 2.314 (4) Å; Bardi et al., 1987], [Pt{(CH3)2S}2I2] [Pt—I 2.604 (1) and Pt—S 2.310 (2) Å; Lövqvist et al., 1996] and [Pt{(C4H9)2NC(S)NHC(O)Ph}2I2] [Pt—I 2.608 (2) and Pt—S 2.294 (3) Å; Koch & Bourne, 1998]. The Pt—Br and Pt—S bond distances in (II) [2.440 (4) and 2.305 (8) Å, respectively] are somewhat longer than the corresponding distances in trans-bis(1,4-oxathian)dibromoplatinum(II) [Pt—Br 2.420 (1) and Pt—S 2.281 (3) Å; Barnes et al., 1977]. The latter is the only trans-PtII complex of S-donor ligands and Br reported in the CSD (Version?).

The torsion angles in Tables 1 and 3 illustrate that there is no distortion of the thiourea ligands in compounds (I) and (II). The atoms of the central carbonyl-thiourea moieties, O1/C7/N1/C8/S1/N2, are nearly planar, with deviations of less than 0.04 Å for (I) and (II). The carbonyl-thiourea moiety (O1/C7/N1/C8/S1/N2) in (I) is tilted at an angle of 68.96 (3)° to the coordination plane, while the corresponding angle in (II) is 54.17 (7)°. These angles allow for the relatively short interatomic distances of 3.597 (2) Å between atoms N1 and I1 in (I), and 3.289 (3) Å between atoms N1 and Br1 in (II). The sums of the van der Waals radii for the N···I and N···Br contacts are ca 3.65 and 3.45 Å, respectively (Huheey et al., 1993), so the corresponding distances in (I) and (II) indicate intramolecular N1—H6···I1 and N1—H6···Br1 hydrogen bonds (Tables 2 and 4). Such interactions also account for the distortions of the coordination spheres of the PtII centres from ideal square-planar geometry, leading to angles slightly larger than 90° for S1—Pt1—I1 [92.03 (2)°] and S1—Pt1—Br1 [94.40 (3)°].

The intramolecular N—H···O hydrogen bond in (I) and (II) is also observed in the free ligand N-propyl-N'-benzoylthiourea, H2L2a (Dago et al., 1989). Analogous intramolecular N—H···O interactions are a common phenomenon in related molecules which, as in H2L2a, feature a central carbonyl-thiourea moiety –NHC(S)NHC(O)-; examples include molecules such as N-(n-butyl)-N'-benzoylthiourea (Koch et al., 1995), N-(2-pyridyl)-N'-benzoylthiourea (Kaminsky et al., 2002), N-benzoylthiourea (Wagner et al., 2003), N-(p-bromophenyl)-N'-benzoylthiourea (Yamin & Yusof, 2003), 3-(3-benzoylthioureido)propionic acid (Yusof & Yamin, 2003), N-Benzoyl-N'-(2-hydroxyethyl)thiourea (Zhang Xian et al., 2003), and N-ethoxycarbonyl-N'-phenylthiourea (Zhang Wei et al., 2003).

In conclusion, for the H2L2 ligand, the relatively stable six-membered O/C/N/C/N/H hydrogen-bonded ring persists upon coordination to `softer' transition metal ions, without the loss of an H atom. This is confirmed by observations on (I) and (II) in this paper, and can be seen in several related structures recently published, e.g. [(Cu(PhNHC(S)NHC(O)C3H5)2Cl) 2] (Černak et al., 1991), [Rh(C3H7NHC(S)NHC(O)Ph)(C8H12)Cl] (Cauzzi et al., 1995), trans-[Pd(C3H7NHC(S)NHC(O)Ph)2Br2] (Koch et al., 1999), [(Cu(C5NH4NHC(S)NHC(O)Ph)Cl2)2] (Li et al., 2002), and [Cu(CH3PhNHC(S)NHC(O)OC2H5)2Cl] (Zhang Xian & Wei, 2003).

Experimental top

Reaction of PtX42− (X is I, Br or Cl) with N-propyl-N'-benzoylthiourea (H2L2a) leads to cis:trans isomer mixtures, cis- and trans-[Pt(H2L2a—S)2X2] (X is I, Br or Cl), the equilibrium ratios of which were determined by 1H NMR spectroscopy in a previous study to be 5:95, 42:58 and 68:32, for X = I, Br or Cl, respectively (Koch et al., 1999). In the present study, the ligand H2L2a and complexes cis- and trans-[Pt(H2L2a—S)2X2] (X is I or Br) were synthesized, recrystallized and characterized as previously reported by Koch et al. (1999). All reagents and solvents were commercially available and all were used without further purification, except for the acetone used in the ligand synthesis, which was distilled before use. 195Pt NMR spectra of the products show resonances at δPt −4846 p.p.m. and −4670 p.p.m. for trans- and cis-[Pt(H2L2a—S)2I2], respectively, and at δPt −3662 p.p.m. and −3681 p.p.m. for trans- and cis-[Pt(H2L2a—S)2Br2], respectively, confirming the presence of both isomers. However, good quality crystals of only the dominant trans isomers could be isolated by recrystallization from chloroform-ethanol (Ratio?); suitable crystals of the cis-complexes could not be obtained. The 195Pt NMR spectra were recorded in CDCl3 on a Varian INOVA 600 MHz s pectrometer (128 MHz, 303 K); 195Pt chemical shifts are quoted relative to external H2PtCl6 (500 mg ml−1 in 30% v/v D2O-1M HCl).

Refinement top

H atoms involved in hydrogen bonding, i.e. those attached to N atoms, were located in a difference electron-density map and refined isotropically. All other H atoms were placed in geometrically calculated positions, with C—H = 0.99 (for –CH2–), 0.98 (for –CH3) or 0.95 Å (for phenyl), and refined using a riding model, with Uiso(H) = 1.2Ueq(parent) (for –CH2– and phenyl) or 1.5Ueq(parent) (for –CH3). In compound (II), the highest peak and deepest hole in the residual electron-density function, at distances of 0.91 and 0.99 Å, respectively, from the Pt atom, are unusually high, possibly due to residual absorption errors inherent in the use of empirical absorption corrections.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 1999); software used to prepare material for publication: X-SEED.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Primed atoms are at the symmetry position (1 − x, −y, −z).
[Figure 2] Fig. 2. The molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Primed atoms are at the symmetry position (1 − x, 1 − y, 1 − z).
(I) trans-diiodobis(N-propyl-N'-benzoylthiourea-κS)platinum(II) top
Crystal data top
[PtI2(C11H14N2OS)2]Z = 1
Mr = 893.49F(000) = 420
Triclinic, P1Dx = 2.164 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3485 (4) ÅCell parameters from 7162 reflections
b = 10.2458 (6) Åθ = 2–26°
c = 10.5738 (6) ŵ = 7.55 mm1
α = 67.725 (1)°T = 100 K
β = 74.742 (1)°Plate, brown
γ = 70.468 (1)°0.30 × 0.24 × 0.17 mm
V = 685.76 (7) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2682 independent reflections
Radiation source: fine-focus sealed tube2673 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 99
Tmin = 0.13, Tmax = 0.28k = 1212
7162 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.015H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.037 w = 1/[σ2(Fo2) + (0.0174P)2 + 0.2796P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
2682 reflectionsΔρmax = 0.85 e Å3
161 parametersΔρmin = 0.59 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: heavy-atom methodExtinction coefficient: 0.0036 (3)
Crystal data top
[PtI2(C11H14N2OS)2]γ = 70.468 (1)°
Mr = 893.49V = 685.76 (7) Å3
Triclinic, P1Z = 1
a = 7.3485 (4) ÅMo Kα radiation
b = 10.2458 (6) ŵ = 7.55 mm1
c = 10.5738 (6) ÅT = 100 K
α = 67.725 (1)°0.30 × 0.24 × 0.17 mm
β = 74.742 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2682 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
2673 reflections with I > 2σ(I)
Tmin = 0.13, Tmax = 0.28Rint = 0.019
7162 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0150 restraints
wR(F2) = 0.037H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.85 e Å3
2682 reflectionsΔρmin = 0.59 e Å3
161 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
Pt10.50000.00000.00000.01248 (6)
I10.84105 (2)0.050892 (16)0.154830 (16)0.01674 (6)
S10.34518 (9)0.13826 (6)0.19142 (6)0.01675 (13)
O10.3762 (3)0.19915 (19)0.38308 (19)0.0222 (4)
N10.4385 (3)0.1234 (2)0.2266 (2)0.0162 (4)
N20.2555 (3)0.0733 (2)0.3808 (2)0.0154 (4)
C10.5718 (4)0.3794 (3)0.2169 (3)0.0158 (5)
C20.5683 (4)0.4889 (3)0.2630 (3)0.0179 (5)
H10.49410.46510.33370.021*
C30.6715 (4)0.6317 (3)0.2068 (3)0.0209 (6)
H20.66630.70590.23780.025*
C40.7826 (4)0.6670 (3)0.1053 (3)0.0206 (6)
H30.85460.76510.06730.025*
C50.7885 (4)0.5582 (3)0.0594 (3)0.0198 (5)
H40.86510.58240.01000.024*
C60.6833 (4)0.4145 (3)0.1139 (3)0.0180 (5)
H50.68680.34070.08170.022*
C70.4550 (4)0.2285 (3)0.2833 (3)0.0169 (5)
C80.3454 (3)0.0235 (3)0.2730 (2)0.0136 (5)
C90.1445 (4)0.2251 (3)0.4347 (3)0.0163 (5)
H80.23510.28870.47640.020*
H90.05300.25650.35790.020*
C100.0308 (4)0.2413 (3)0.5426 (3)0.0183 (5)
H100.06180.17930.49990.022*
H110.12240.20690.61770.022*
C110.0818 (4)0.3991 (3)0.6033 (3)0.0229 (6)
H120.18010.43080.53050.034*
H130.14670.40690.67680.034*
H140.00890.46130.64170.034*
H60.492 (4)0.146 (3)0.162 (3)0.008 (7)*
H70.257 (4)0.013 (3)0.417 (3)0.009 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01325 (8)0.01143 (8)0.01451 (8)0.00146 (5)0.00516 (5)0.00557 (5)
I10.01440 (10)0.01722 (10)0.01966 (10)0.00353 (7)0.00263 (7)0.00760 (7)
S10.0203 (3)0.0134 (3)0.0185 (3)0.0000 (2)0.0094 (2)0.0069 (2)
O10.0262 (10)0.0181 (9)0.0262 (10)0.0025 (8)0.0139 (8)0.0078 (8)
N10.0174 (11)0.0156 (10)0.0174 (11)0.0004 (8)0.0094 (9)0.0062 (9)
N20.0189 (11)0.0131 (10)0.0167 (11)0.0024 (9)0.0064 (9)0.0068 (9)
C10.0131 (12)0.0156 (12)0.0182 (12)0.0031 (10)0.0026 (10)0.0052 (10)
C20.0150 (12)0.0191 (13)0.0219 (13)0.0048 (10)0.0031 (10)0.0087 (10)
C30.0190 (13)0.0169 (13)0.0281 (14)0.0048 (10)0.0007 (11)0.0106 (11)
C40.0192 (13)0.0153 (12)0.0225 (13)0.0025 (10)0.0008 (10)0.0045 (10)
C50.0173 (13)0.0212 (13)0.0199 (13)0.0037 (10)0.0059 (10)0.0046 (10)
C60.0200 (13)0.0178 (12)0.0193 (13)0.0078 (10)0.0029 (10)0.0071 (10)
C70.0152 (13)0.0171 (12)0.0201 (13)0.0052 (10)0.0036 (10)0.0066 (10)
C80.0125 (12)0.0136 (11)0.0152 (12)0.0033 (9)0.0026 (9)0.0048 (9)
C90.0177 (13)0.0136 (12)0.0170 (12)0.0013 (10)0.0055 (10)0.0048 (10)
C100.0205 (13)0.0173 (12)0.0180 (13)0.0056 (10)0.0056 (10)0.0042 (10)
C110.0213 (14)0.0236 (14)0.0204 (13)0.0020 (11)0.0079 (11)0.0036 (11)
Geometric parameters (Å, º) top
Pt1—S1i2.3148 (6)C3—C41.385 (4)
Pt1—S12.3148 (6)C3—H20.9500
Pt1—I1i2.6167 (2)C4—C51.391 (4)
Pt1—I12.6167 (2)C4—H30.9500
S1—C81.701 (2)C5—C61.388 (4)
O1—C71.226 (3)C5—H40.9500
N1—C71.377 (3)C6—H50.9500
N1—C81.380 (3)C9—C101.515 (3)
N1—H60.80 (3)C9—H80.9900
N2—C81.314 (3)C9—H90.9900
N2—C91.461 (3)C10—C111.519 (3)
N2—H70.84 (3)C10—H100.9900
C1—C21.393 (3)C10—H110.9900
C1—C61.400 (4)C11—H120.9800
C1—C71.492 (3)C11—H130.9800
C2—C31.380 (4)C11—H140.9800
C2—H10.9500
S1i—Pt1—S1180.0C5—C6—C1119.5 (2)
S1i—Pt1—I1i92.033 (17)C5—C6—H5120.3
S1—Pt1—I1i87.967 (17)C1—C6—H5120.3
S1i—Pt1—I187.967 (17)O1—C7—N1121.4 (2)
S1—Pt1—I192.033 (17)O1—C7—C1121.8 (2)
I1i—Pt1—I1180.0N1—C7—C1116.8 (2)
C8—S1—Pt1108.10 (8)N2—C8—N1118.8 (2)
C7—N1—C8127.3 (2)N2—C8—S1120.49 (18)
C7—N1—H6118.6 (19)N1—C8—S1120.67 (18)
C8—N1—H6114.0 (19)N2—C9—C10110.4 (2)
C8—N2—C9123.5 (2)N2—C9—H8109.6
C8—N2—H7117.9 (17)C10—C9—H8109.6
C9—N2—H7118.5 (17)N2—C9—H9109.6
C2—C1—C6119.5 (2)C10—C9—H9109.6
C2—C1—C7116.7 (2)H8—C9—H9108.1
C6—C1—C7123.8 (2)C9—C10—C11111.5 (2)
C3—C2—C1120.6 (2)C9—C10—H10109.3
C3—C2—H1119.7C11—C10—H10109.3
C1—C2—H1119.7C9—C10—H11109.3
C2—C3—C4120.1 (2)C11—C10—H11109.3
C2—C3—H2119.9H10—C10—H11108.0
C4—C3—H2119.9C10—C11—H12109.5
C3—C4—C5119.8 (2)C10—C11—H13109.5
C3—C4—H3120.1H12—C11—H13109.5
C5—C4—H3120.1C10—C11—H14109.5
C6—C5—C4120.6 (2)H12—C11—H14109.5
C6—C5—H4119.7H13—C11—H14109.5
C4—C5—H4119.7
S1i—Pt1—S1—C8103 (6)C2—C1—C7—O17.3 (4)
I1i—Pt1—S1—C8109.67 (9)C6—C1—C7—O1172.1 (2)
I1—Pt1—S1—C870.33 (9)C2—C1—C7—N1172.2 (2)
C6—C1—C2—C30.8 (4)C6—C1—C7—N18.3 (4)
C7—C1—C2—C3179.7 (2)C9—N2—C8—N1177.0 (2)
C1—C2—C3—C41.1 (4)C9—N2—C8—S12.5 (3)
C2—C3—C4—C50.6 (4)C7—N1—C8—N22.1 (4)
C3—C4—C5—C60.2 (4)C7—N1—C8—S1178.4 (2)
C4—C5—C6—C10.5 (4)Pt1—S1—C8—N2175.87 (17)
C2—C1—C6—C50.0 (4)Pt1—S1—C8—N13.7 (2)
C7—C1—C6—C5179.4 (2)C8—N2—C9—C10170.2 (2)
C8—N1—C7—O13.2 (4)N2—C9—C10—C11178.4 (2)
C8—N1—C7—C1177.2 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H7···O10.84 (3)1.98 (3)2.639 (3)134 (2)
N1—H6···I10.80 (3)3.06 (3)3.600 (2)127 (2)
(II) trans-dibromobis(N-propyl-N'-benzoylthiourea-κS)platinum(II) top
Crystal data top
[PtBr2(C11H14N2OS)2]Z = 1
Mr = 799.51F(000) = 384
Triclinic, P1Dx = 2.071 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.6641 (11) ÅCell parameters from 6491 reflections
b = 8.8178 (11) Åθ = 2–26°
c = 9.7472 (12) ŵ = 8.78 mm1
α = 104.609 (2)°T = 100 K
β = 112.263 (2)°Prism, orange
γ = 98.663 (2)°0.24 × 0.22 × 0.18 mm
V = 641.18 (14) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2490 independent reflections
Radiation source: fine-focus sealed tube2398 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1010
Tmin = 0.14, Tmax = 0.21k = 1010
6491 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0416P)2 + 0.0891P]
where P = (Fo2 + 2Fc2)/3
2490 reflections(Δ/σ)max = 0.001
160 parametersΔρmax = 2.68 e Å3
0 restraintsΔρmin = 1.20 e Å3
Crystal data top
[PtBr2(C11H14N2OS)2]γ = 98.663 (2)°
Mr = 799.51V = 641.18 (14) Å3
Triclinic, P1Z = 1
a = 8.6641 (11) ÅMo Kα radiation
b = 8.8178 (11) ŵ = 8.78 mm1
c = 9.7472 (12) ÅT = 100 K
α = 104.609 (2)°0.24 × 0.22 × 0.18 mm
β = 112.263 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2490 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
2398 reflections with I > 2σ(I)
Tmin = 0.14, Tmax = 0.21Rint = 0.022
6491 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 2.68 e Å3
2490 reflectionsΔρmin = 1.20 e Å3
160 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
Pt10.50000.50000.50000.01584 (8)
Br10.54977 (5)0.74468 (4)0.71389 (4)0.02076 (10)
S10.35639 (12)0.32718 (11)0.58216 (10)0.0219 (2)
O10.7002 (3)0.3755 (3)1.0841 (3)0.0229 (5)
N10.6258 (4)0.4579 (4)0.8699 (3)0.0186 (6)
N20.4177 (4)0.2293 (3)0.8240 (4)0.0184 (6)
C10.9001 (5)0.6052 (4)1.1052 (4)0.0181 (7)
C21.0086 (5)0.6159 (4)1.2585 (4)0.0202 (7)
H10.97480.54091.30370.024*
C31.1646 (5)0.7356 (4)1.3441 (4)0.0226 (8)
H21.23850.74241.44770.027*
C41.2132 (5)0.8454 (4)1.2790 (4)0.0251 (8)
H31.32020.92801.33850.030*
C51.1072 (5)0.8359 (4)1.1280 (4)0.0226 (8)
H41.14090.91261.08440.027*
C60.9515 (5)0.7145 (4)1.0398 (4)0.0198 (7)
H50.88030.70620.93490.024*
C70.7361 (4)0.4705 (4)1.0217 (4)0.0182 (7)
C80.4737 (5)0.3384 (4)0.7712 (4)0.0180 (7)
C90.2639 (5)0.0901 (4)0.7280 (4)0.0197 (7)
H80.27320.02760.63300.024*
H90.15930.12960.69330.024*
C100.2464 (5)0.0197 (4)0.8210 (4)0.0201 (7)
H100.24540.04470.91960.024*
H110.34750.06490.84950.024*
C110.0807 (5)0.1585 (4)0.7261 (4)0.0237 (8)
H120.01940.11370.69790.036*
H130.07130.22700.78920.036*
H140.08320.22420.62990.036*
H70.474 (6)0.240 (5)0.918 (5)0.030 (12)*
H60.651 (6)0.524 (6)0.836 (6)0.037 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01729 (12)0.01509 (11)0.01016 (11)0.00006 (7)0.00315 (8)0.00333 (8)
Br10.0263 (2)0.01749 (19)0.01393 (19)0.00335 (15)0.00610 (16)0.00365 (15)
S10.0221 (5)0.0221 (4)0.0131 (4)0.0041 (4)0.0033 (4)0.0056 (3)
O10.0236 (13)0.0244 (13)0.0169 (13)0.0004 (11)0.0058 (11)0.0094 (11)
N10.0205 (15)0.0175 (15)0.0131 (15)0.0003 (12)0.0050 (13)0.0043 (12)
N20.0208 (16)0.0176 (14)0.0120 (15)0.0008 (12)0.0046 (13)0.0036 (12)
C10.0204 (17)0.0158 (16)0.0146 (17)0.0049 (14)0.0072 (14)0.0002 (13)
C20.0243 (19)0.0190 (17)0.0166 (18)0.0081 (15)0.0080 (15)0.0050 (14)
C30.0216 (18)0.0229 (18)0.0151 (17)0.0061 (15)0.0020 (15)0.0026 (14)
C40.0193 (18)0.0220 (18)0.025 (2)0.0012 (15)0.0078 (16)0.0004 (15)
C50.0220 (18)0.0218 (18)0.0239 (19)0.0033 (15)0.0121 (16)0.0060 (15)
C60.0186 (17)0.0216 (17)0.0168 (18)0.0038 (14)0.0075 (15)0.0038 (14)
C70.0198 (18)0.0182 (16)0.0157 (17)0.0065 (14)0.0073 (15)0.0045 (14)
C80.0195 (17)0.0171 (16)0.0137 (17)0.0022 (14)0.0062 (14)0.0023 (13)
C90.0213 (18)0.0166 (16)0.0151 (17)0.0013 (14)0.0058 (15)0.0029 (13)
C100.0215 (18)0.0200 (17)0.0180 (18)0.0028 (14)0.0084 (15)0.0071 (14)
C110.0239 (19)0.0192 (17)0.0231 (19)0.0010 (15)0.0076 (16)0.0077 (15)
Geometric parameters (Å, º) top
Pt1—S12.3046 (9)C3—C41.380 (5)
Pt1—S1i2.3046 (9)C3—H20.9500
Pt1—Br12.4407 (4)C4—C51.381 (5)
Pt1—Br1i2.4407 (4)C4—H30.9500
S1—C81.702 (4)C5—C61.388 (5)
O1—C71.220 (4)C5—H40.9500
N1—C81.372 (4)C6—H50.9500
N1—C71.389 (5)C9—C101.511 (5)
N1—H60.78 (5)C9—H80.9900
N2—C81.313 (4)C9—H90.9900
N2—C91.463 (4)C10—C111.519 (5)
N2—H70.83 (5)C10—H100.9900
C1—C61.388 (5)C10—H110.9900
C1—C21.402 (5)C11—H120.9800
C1—C71.490 (5)C11—H130.9800
C2—C31.382 (5)C11—H140.9800
C2—H10.9500
S1—Pt1—S1i180.0C5—C6—C1119.9 (3)
S1—Pt1—Br194.43 (3)C5—C6—H5120.0
S1i—Pt1—Br185.57 (3)C1—C6—H5120.0
S1—Pt1—Br1i85.57 (3)O1—C7—N1121.5 (3)
S1i—Pt1—Br1i94.43 (3)O1—C7—C1121.5 (3)
Br1—Pt1—Br1i180.0N1—C7—C1117.0 (3)
C8—S1—Pt1113.44 (13)N2—C8—N1119.0 (3)
C8—N1—C7125.9 (3)N2—C8—S1119.2 (3)
C8—N1—H6116 (4)N1—C8—S1121.8 (3)
C7—N1—H6118 (4)N2—C9—C10110.5 (3)
C8—N2—C9124.3 (3)N2—C9—H8109.5
C8—N2—H7117 (3)C10—C9—H8109.5
C9—N2—H7118 (3)N2—C9—H9109.5
C6—C1—C2119.5 (3)C10—C9—H9109.5
C6—C1—C7124.5 (3)H8—C9—H9108.1
C2—C1—C7115.9 (3)C9—C10—C11110.9 (3)
C3—C2—C1120.0 (3)C9—C10—H10109.5
C3—C2—H1120.0C11—C10—H10109.5
C1—C2—H1120.0C9—C10—H11109.5
C4—C3—C2120.0 (3)C11—C10—H11109.5
C4—C3—H2120.0H10—C10—H11108.0
C2—C3—H2120.0C10—C11—H12109.5
C3—C4—C5120.4 (3)C10—C11—H13109.5
C3—C4—H3119.8H12—C11—H13109.5
C5—C4—H3119.8C10—C11—H14109.5
C4—C5—C6120.1 (3)H12—C11—H14109.5
C4—C5—H4120.0H13—C11—H14109.5
C6—C5—H4120.0
S1i—Pt1—S1—C884 (100)C6—C1—C7—O1178.0 (3)
Br1—Pt1—S1—C855.98 (13)C2—C1—C7—O10.3 (5)
Br1i—Pt1—S1—C8124.02 (13)C6—C1—C7—N12.0 (5)
C6—C1—C2—C30.6 (5)C2—C1—C7—N1179.6 (3)
C7—C1—C2—C3179.1 (3)C9—N2—C8—N1175.9 (3)
C1—C2—C3—C40.5 (5)C9—N2—C8—S13.8 (5)
C2—C3—C4—C50.5 (5)C7—N1—C8—N24.3 (5)
C3—C4—C5—C60.7 (5)C7—N1—C8—S1175.3 (3)
C4—C5—C6—C11.8 (5)Pt1—S1—C8—N2169.7 (2)
C2—C1—C6—C51.7 (5)Pt1—S1—C8—N19.9 (3)
C7—C1—C6—C5180.0 (3)C8—N2—C9—C10174.5 (3)
C8—N1—C7—O13.4 (6)N2—C9—C10—C11176.2 (3)
C8—N1—C7—C1176.7 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H7···O10.83 (5)1.95 (5)2.603 (4)135 (4)
N1—H6···Br10.78 (5)2.62 (5)3.290 (3)145 (4)

Experimental details

(I)(II)
Crystal data
Chemical formula[PtI2(C11H14N2OS)2][PtBr2(C11H14N2OS)2]
Mr893.49799.51
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)100100
a, b, c (Å)7.3485 (4), 10.2458 (6), 10.5738 (6)8.6641 (11), 8.8178 (11), 9.7472 (12)
α, β, γ (°)67.725 (1), 74.742 (1), 70.468 (1)104.609 (2), 112.263 (2), 98.663 (2)
V3)685.76 (7)641.18 (14)
Z11
Radiation typeMo KαMo Kα
µ (mm1)7.558.78
Crystal size (mm)0.30 × 0.24 × 0.170.24 × 0.22 × 0.18
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Multi-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.13, 0.280.14, 0.21
No. of measured, independent and
observed [I > 2σ(I)] reflections
7162, 2682, 2673 6491, 2490, 2398
Rint0.0190.022
(sin θ/λ)max1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.015, 0.037, 1.06 0.024, 0.060, 1.06
No. of reflections26822490
No. of parameters161160
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.85, 0.592.68, 1.20

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 1999), X-SEED.

Selected geometric parameters (Å, º) for (I) top
Pt1—S12.3148 (6)N1—C71.377 (3)
Pt1—I12.6167 (2)N1—C81.380 (3)
S1—C81.701 (2)N2—C81.314 (3)
O1—C71.226 (3)
S1—Pt1—I192.033 (17)O1—C7—N1121.4 (2)
I1i—Pt1—I1180.0N2—C8—N1118.8 (2)
C8—S1—Pt1108.10 (8)N2—C8—S1120.49 (18)
C7—N1—C8127.3 (2)
C2—C1—C7—N1172.2 (2)C7—N1—C8—S1178.4 (2)
C7—N1—C8—N22.1 (4)C8—N2—C9—C10170.2 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H7···O10.84 (3)1.98 (3)2.639 (3)134 (2)
N1—H6···I10.80 (3)3.06 (3)3.600 (2)127 (2)
Selected geometric parameters (Å, º) for (II) top
Pt1—S12.3046 (9)N1—C81.372 (4)
Pt1—Br12.4407 (4)N1—C71.389 (5)
S1—C81.702 (4)N2—C81.313 (4)
O1—C71.220 (4)
S1—Pt1—Br194.43 (3)O1—C7—N1121.5 (3)
Br1—Pt1—Br1i180.0N2—C8—N1119.0 (3)
C8—S1—Pt1113.44 (13)N2—C8—S1119.2 (3)
C8—N1—C7125.9 (3)
C2—C1—C7—N1179.6 (3)C7—N1—C8—S1175.3 (3)
C7—N1—C8—N24.3 (5)C8—N2—C9—C10174.5 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N2—H7···O10.83 (5)1.95 (5)2.603 (4)135 (4)
N1—H6···Br10.78 (5)2.62 (5)3.290 (3)145 (4)
 

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