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Acta Cryst. (2007). E63, m1898-m1899    [ doi:10.1107/S1600536807028206 ]

Dichloridobis[N-(diphenylphosphino)isopropylamine-[kappa]P]platinum(II) chloroform solvate

G. M. Brown, M. R. J. Elsegood, J. R. Evans, N. M. Sanchez Ballester, M. B. Smith and K. Blann

Abstract top

The cis isomer of the square-planar title complex has been crystallized as the chloroform solvate, [PtCl2(C15H18NP)2]·CHCl3. Comparison of the Pt-P and Pt-Cl bond lengths and the Cl-Pt-Cl and P-Pt-P angles with the known compounds cis-{Ph2PN(H)R'}2PtCl2 reveals that the R' substituents have negligible effects on these structural parameters. Intramolecular N-H...Cl and intermolecular Pt-Cl...H-CCl3 hydrogen bonds are evident in the title structure.

Comment top

Secondary aminophosphines are useful ligands in coordination and organometallic chemistry (Gaw et al., 1999). Depending on the R' group these phosphorus(III) ligands may either be P-monodentate, R2PN(H)R', (Clarke et al., 2003; Slawin et al., 2005; Slawin et al., 1999) or P/P'-didentate, R2PN(H)R'N(H)PR2, (Bergamini et al., 2004; Lindner et al., 2000; Ly et al., 1997). For many of these ligands the Ph2P group has been widely employed whereas R' has been various substituents e.g. CH2CH═CH2 (II), CH(CH3)C(O)OCH3 (III), Ph (Priya et al., 2003; Slawin et al., 1999, 2005). These ligands coordinate readily to d8 square-planar metal centres including palladium(II) and platinum(II). Both cis-and trans- geometric isomers of {R2PN(H)R'}2MCl2 have previously been structurally characterized (Browning & Farrar, 1995; Burrows et al., 2000; Priya et al., 2003; Slawin et al., 2005; Slawin et al., 1999). For trans-{R2PN(H)R'}2MCl2 complexes two intramolecular H-bonds between both NH moieties and terminal chlorides are observed. Some of these ligands e.g. Ph2PN(H)R (R = Ph, tBu) complex also with Group 6 metals to give cis- and/or trans-{Ph2PN(H)R}2M(CO)4 (M = Cr, Mo, W) but with the more sterically hindered aminophosphine (2,4,6-Me3C6H2)2PN(H)Ph no coordination was observed (Kühl et al., 2001; Priya et al., 2003).

The structure of (I) (Fig. 1 and Table 2) exhibits an essentially square-planar, cis- geometry comprising two chloride and two Ph2PN(H)iPr ligands around the platinum(II) metal centre. In (I) the Pt—P and Pt—Cl bond lengths are typical and compare favourably with those reported for the related complexes (II) and (III) (Table 2). The angles around the platinum coordination sphere in (I) vary from 84.75 (2)° [Cl—Pt—Cl] to 96.03 (2)° [P—Pt—P]. The P—N bond distances for (I) are similar to those in (II) and (III) and are shorter than those expected for a single P—N bond. This suggests some delocalization of electron density. Complex (I) displays an intramolecular H-bond between the secondary amine and a terminal bound chloride ligand. This leads to disparity between the Pt(1)—P(1)—N(1) and Pt(1)—P(2)—N(2) bond angles [109.00 (8)° versus. 116.04 (8)° respectively]. The chloroform hydrogen forms a bifurcated H-bond to the two Pt-coordinated chlorides.

In summary, we have shown that the aminophosphine Ph2PN(H)iPr complexes to platinum(II) to afford the cis-isomer {Ph2PN(H)iPr}2PtCl2 with typical Pt—P/Pt—Cl/P—N bond lengths and Cl—Pt—Cl/P—Pt—P bond angles.

Related literature top

Functionalized tertiary phosphines with secondary amine groups have been used in coordination and organometallic chemistry (see Gaw et al., 1999; Kühl et al., 2001). For structures of square-planar dichloroplatinum(II) complexes with similar ligands see also Slawin et al. (2005) and Priya et al. (2003).

For related literature, see: Bergamini et al. (2004); Browning & Farrar (1995); Burrows et al. (2000); Clarke et al. (2003); Lindner et al. (2000); Ly et al. (1997); Slawin et al. (1999).

Experimental top

Preparation of (I). To a CH2Cl2 (10 ml) solution of PtCl2(cod) (0.046 g, 0.123 mmol) was added Ph2PN(H)iPr (0.066 g, 0.244 mmol). The solution was stirred for 1 h and the volume reduced to ca 2 ml under reduced pressure. Addition of petroleum ether (b.p. 60–80 °C, 20 ml) gave (I) which was collected by suction filtration and dried in vacuo. Yield: 0.045 g, 49%. Selected data: 31P{1H}/(CDCl3): 30.4 p.p.m.., 1J(PtP) 3952 Hz. 1H/(CDCl3): 7.61–7.27 (m, arom. H), 3.89 [t, 2J(PH) 21 Hz, NH], 2.65 (m, CH), 0.69 [d, 3J(HH) 6.4 Hz, CH3] p.p.m.. FT—IR/(KBr pellet): νNH 3363, 3262, νPtCl 310, 284 cm−1. Found: C, 44.41; H, 4.24; N, 3.26. C30H36Cl2N2P2Pt·CH2Cl2 requires C, 44.51; H, 4.58; N, 3.35%. Colourless block crystals of (I) were obtained by slow diffusion of petroleum ether (b.p. 60–80 °C) into a CHCl3 solution.

Refinement top

Aromatic H atoms were placed in geometric positions (C—H distance = 0.95 Å for aryl H; 0.98 Å for methyl H; and 1.00 Å for methine H) using a riding model. NH coordinates were freely refined. Uiso values were set to 1.2Ueq (1.5Ueq for methyl H and NH).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The schematic structures of some cis-{Ph2PN(H)R'}2PtCl2 compounds.
Dichloridobis[N-(diphenylphosphino)isopropylamine-κP]platinum(II) chloroform solvate top
Crystal data top
[PtCl2(C15H18NP)2]·CHCl3F000 = 1720
Mr = 871.91Dx = 1.657 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 13577 reflections
a = 11.5142 (4) Åθ = 2.3–28.9º
b = 14.5440 (5) ŵ = 4.51 mm−1
c = 21.5825 (8) ÅT = 150 (2) K
β = 104.795 (2)ºBlock, colourless
V = 3494.4 (2) Å30.34 × 0.24 × 0.14 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		8350 independent reflections
Radiation source: sealed tube6863 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 150(2) Kθmax = 29.0º
ω rotation with narrow frames scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −14→15
Tmin = 0.287, Tmax = 0.531k = −18→17
26733 measured reflectionsl = −27→29
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: geom except NH coords freely refined
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.044  w = 1/[σ2(Fo2) + (0.0136P)2 + 2.3257P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
8350 reflectionsΔρmax = 1.14 e Å−3
380 parametersΔρmin = −0.75 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: heavy-atom method
Crystal data top
[PtCl2(C15H18NP)2]·CHCl3V = 3494.4 (2) Å3
Mr = 871.91Z = 4
Monoclinic, P21/nMo Kα
a = 11.5142 (4) ŵ = 4.51 mm−1
b = 14.5440 (5) ÅT = 150 (2) K
c = 21.5825 (8) Å0.34 × 0.24 × 0.14 mm
β = 104.795 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		8350 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		6863 reflections with I > 2σ(I)
Tmin = 0.287, Tmax = 0.531Rint = 0.027
26733 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0222 restraints
wR(F2) = 0.044H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 1.14 e Å−3
8350 reflectionsΔρmin = −0.75 e Å−3
380 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
Pt10.610678 (8)0.266739 (7)0.607682 (4)0.01569 (3)
Cl10.40601 (5)0.23034 (5)0.59963 (3)0.02215 (13)
Cl20.62839 (6)0.27216 (5)0.71855 (3)0.02706 (14)
P10.58363 (5)0.25957 (4)0.50050 (3)0.01643 (13)
P20.81064 (6)0.28418 (4)0.63150 (3)0.01808 (14)
N10.4412 (2)0.23747 (16)0.46669 (10)0.0239 (5)
H10.397 (2)0.237 (2)0.4910 (12)0.036*
C10.3803 (2)0.23277 (19)0.39797 (12)0.0249 (6)
H1A0.44300.22930.37340.030*
C20.3042 (3)0.1459 (2)0.38439 (14)0.0401 (8)
H2A0.35520.09200.39860.060*
H2B0.26700.14120.33830.060*
H2C0.24140.14850.40760.060*
C30.3063 (3)0.3187 (2)0.37732 (13)0.0373 (7)
H3A0.24670.32480.40240.056*
H3B0.26520.31430.33170.056*
H3C0.35920.37260.38460.056*
C40.6650 (2)0.16705 (17)0.47293 (11)0.0191 (5)
C50.7616 (2)0.17847 (19)0.44604 (12)0.0236 (6)
H50.79010.23850.44090.028*
C60.8167 (3)0.1026 (2)0.42654 (13)0.0300 (7)
H60.88200.11110.40760.036*
C70.7766 (3)0.0151 (2)0.43462 (14)0.0345 (7)
H70.8141−0.03660.42100.041*
C80.6825 (3)0.0023 (2)0.46236 (14)0.0350 (7)
H80.6559−0.05810.46840.042*
C90.6266 (3)0.07774 (19)0.48150 (13)0.0280 (6)
H90.56170.06870.50060.034*
C100.6209 (2)0.36412 (17)0.46285 (11)0.0180 (5)
C110.6288 (2)0.44695 (18)0.49622 (12)0.0220 (6)
H110.62390.44710.53950.026*
C120.6440 (2)0.52958 (19)0.46646 (14)0.0275 (6)
H120.64910.58570.48950.033*
C130.6516 (3)0.53001 (19)0.40386 (14)0.0296 (7)
H130.66150.58650.38370.036*
C140.6449 (2)0.44817 (19)0.37024 (13)0.0278 (6)
H140.65130.44860.32720.033*
C150.6288 (2)0.36561 (19)0.39924 (12)0.0237 (6)
H150.62320.30980.37580.028*
N20.86725 (19)0.31830 (16)0.57158 (10)0.0215 (5)
H20.822 (2)0.3539 (17)0.5452 (12)0.032*
C160.9961 (2)0.3428 (2)0.58081 (13)0.0298 (6)
H161.04370.31060.62010.036*
C171.0398 (3)0.3090 (3)0.52374 (16)0.0471 (9)
H17A1.02780.24230.51910.071*
H17B1.12540.32310.53070.071*
H17C0.99420.33970.48470.071*
C181.0154 (3)0.4455 (2)0.59066 (16)0.0452 (9)
H18A0.96640.47840.55350.068*
H18B1.10040.46000.59550.068*
H18C0.99200.46440.62930.068*
C190.8767 (2)0.17142 (18)0.65314 (12)0.0220 (6)
C200.9065 (2)0.11735 (19)0.60665 (14)0.0285 (6)
H200.90260.14240.56550.034*
C210.9421 (3)0.0269 (2)0.61997 (16)0.0379 (8)
H210.9621−0.00980.58780.046*
C220.9486 (3)−0.0103 (2)0.67930 (17)0.0394 (8)
H220.9731−0.07240.68800.047*
C230.9196 (3)0.0426 (2)0.72611 (16)0.0369 (8)
H230.92480.01700.76720.044*
C240.8827 (2)0.1333 (2)0.71358 (14)0.0284 (6)
H240.86160.16930.74580.034*
C250.8729 (2)0.36076 (18)0.69854 (12)0.0205 (5)
C260.9837 (2)0.34360 (19)0.74212 (12)0.0246 (6)
H261.02360.28680.74070.030*
C271.0353 (3)0.4093 (2)0.78732 (13)0.0305 (7)
H271.11020.39710.81690.037*
C280.9783 (3)0.4925 (2)0.78963 (13)0.0301 (6)
H281.01380.53730.82080.036*
C290.8696 (3)0.5102 (2)0.74632 (13)0.0306 (7)
H290.83120.56780.74730.037*
C300.8164 (2)0.44455 (19)0.70155 (13)0.0257 (6)
H300.74070.45690.67270.031*
C310.3502 (3)0.2155 (2)0.74824 (13)0.0354 (7)
H310.41020.21010.72210.042*
Cl30.42136 (9)0.18738 (8)0.82838 (4)0.0609 (3)
Cl40.23036 (8)0.13999 (7)0.71669 (4)0.0556 (2)
Cl50.29746 (8)0.32944 (6)0.74342 (4)0.0493 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.01498 (5)0.01740 (5)0.01464 (5)−0.00012 (4)0.00371 (3)0.00047 (4)
Cl10.0184 (3)0.0288 (3)0.0201 (3)−0.0045 (3)0.0065 (2)−0.0015 (3)
Cl20.0228 (3)0.0432 (4)0.0154 (3)−0.0049 (3)0.0052 (2)−0.0001 (3)
P10.0161 (3)0.0173 (3)0.0157 (3)0.0000 (2)0.0036 (2)−0.0004 (3)
P20.0161 (3)0.0212 (4)0.0169 (3)0.0001 (3)0.0042 (2)0.0006 (3)
N10.0203 (11)0.0353 (13)0.0162 (10)−0.0040 (10)0.0050 (9)−0.0020 (10)
C10.0213 (13)0.0349 (15)0.0166 (12)−0.0032 (12)0.0012 (10)−0.0002 (12)
C20.0420 (19)0.044 (2)0.0284 (16)−0.0153 (15)−0.0019 (14)−0.0034 (14)
C30.0355 (17)0.048 (2)0.0226 (14)0.0060 (14)−0.0025 (13)−0.0002 (14)
C40.0219 (13)0.0183 (13)0.0162 (12)0.0028 (10)0.0033 (10)−0.0008 (10)
C50.0250 (14)0.0233 (15)0.0217 (13)0.0029 (11)0.0044 (11)−0.0015 (11)
C60.0291 (15)0.0351 (18)0.0270 (15)0.0092 (13)0.0092 (12)−0.0015 (13)
C70.0412 (18)0.0295 (17)0.0299 (16)0.0142 (14)0.0039 (14)−0.0067 (13)
C80.0440 (19)0.0194 (16)0.0387 (17)0.0017 (13)0.0051 (14)−0.0034 (13)
C90.0312 (16)0.0236 (16)0.0296 (15)−0.0017 (12)0.0087 (12)0.0014 (12)
C100.0157 (12)0.0196 (14)0.0181 (12)0.0001 (10)0.0033 (10)0.0018 (10)
C110.0210 (13)0.0253 (15)0.0202 (13)0.0009 (11)0.0062 (11)0.0011 (11)
C120.0313 (16)0.0177 (15)0.0353 (16)0.0023 (12)0.0117 (13)0.0001 (12)
C130.0330 (16)0.0224 (15)0.0370 (16)0.0038 (12)0.0153 (13)0.0098 (13)
C140.0319 (16)0.0326 (17)0.0204 (13)0.0026 (12)0.0095 (12)0.0056 (12)
C150.0269 (14)0.0241 (15)0.0210 (13)0.0000 (11)0.0075 (11)−0.0005 (11)
N20.0176 (11)0.0263 (13)0.0206 (11)−0.0017 (9)0.0047 (9)0.0021 (9)
C160.0205 (14)0.0417 (18)0.0282 (15)−0.0060 (12)0.0082 (12)−0.0008 (13)
C170.0329 (18)0.069 (2)0.046 (2)−0.0164 (17)0.0225 (15)−0.0153 (18)
C180.0405 (19)0.049 (2)0.052 (2)−0.0213 (16)0.0220 (16)−0.0053 (17)
C190.0156 (12)0.0220 (14)0.0270 (14)−0.0005 (10)0.0030 (11)0.0003 (11)
C200.0224 (14)0.0292 (16)0.0316 (15)0.0082 (12)0.0028 (12)0.0002 (12)
C210.0268 (16)0.0337 (18)0.048 (2)0.0099 (13)−0.0002 (14)−0.0082 (15)
C220.0229 (15)0.0242 (16)0.065 (2)0.0033 (12)0.0002 (15)0.0080 (16)
C230.0244 (15)0.0379 (19)0.0449 (19)−0.0013 (13)0.0024 (14)0.0177 (15)
C240.0232 (14)0.0304 (17)0.0316 (15)−0.0022 (12)0.0071 (12)0.0043 (13)
C250.0198 (13)0.0232 (14)0.0187 (12)−0.0004 (11)0.0053 (10)−0.0007 (11)
C260.0228 (14)0.0248 (15)0.0254 (14)0.0009 (11)0.0047 (11)−0.0010 (11)
C270.0229 (14)0.0396 (18)0.0254 (14)−0.0025 (12)−0.0006 (12)−0.0023 (13)
C280.0323 (16)0.0312 (17)0.0257 (14)−0.0085 (13)0.0050 (12)−0.0082 (13)
C290.0343 (17)0.0245 (16)0.0335 (16)0.0019 (12)0.0096 (13)−0.0043 (13)
C300.0220 (14)0.0287 (16)0.0251 (14)0.0024 (11)0.0034 (11)0.0005 (12)
C310.0321 (16)0.051 (2)0.0259 (15)−0.0043 (14)0.0136 (13)−0.0023 (14)
Cl30.0603 (6)0.0896 (8)0.0323 (4)0.0058 (5)0.0105 (4)0.0095 (5)
Cl40.0532 (5)0.0645 (6)0.0539 (5)−0.0265 (5)0.0226 (4)−0.0134 (5)
Cl50.0398 (5)0.0538 (6)0.0555 (5)−0.0010 (4)0.0145 (4)−0.0067 (4)
Geometric parameters (Å, °) top
Pt1—P22.2417 (6)C14—C151.388 (4)
Pt1—P12.2564 (6)C14—H140.9500
Pt1—Cl22.3503 (6)C15—H150.9500
Pt1—Cl12.3780 (6)N2—C161.489 (3)
P1—N11.648 (2)N2—H20.845 (17)
P1—C41.824 (3)C16—C181.517 (4)
P1—C101.826 (3)C16—C171.526 (4)
P2—N21.666 (2)C16—H161.0000
P2—C191.818 (3)C17—H17A0.9800
P2—C251.821 (3)C17—H17B0.9800
N1—C11.471 (3)C17—H17C0.9800
N1—H10.815 (17)C18—H18A0.9800
C1—C31.514 (4)C18—H18B0.9800
C1—C21.523 (4)C18—H18C0.9800
C1—H1A1.0000C19—C201.385 (4)
C2—H2A0.9800C19—C241.403 (4)
C2—H2B0.9800C20—C211.386 (4)
C2—H2C0.9800C20—H200.9500
C3—H3A0.9800C21—C221.374 (4)
C3—H3B0.9800C21—H210.9500
C3—H3C0.9800C22—C231.377 (5)
C4—C51.389 (3)C22—H220.9500
C4—C91.399 (4)C23—C241.392 (4)
C5—C61.391 (4)C23—H230.9500
C5—H50.9500C24—H240.9500
C6—C71.380 (4)C25—C301.391 (4)
C6—H60.9500C25—C261.401 (3)
C7—C81.378 (4)C26—C271.386 (4)
C7—H70.9500C26—H260.9500
C8—C91.387 (4)C27—C281.384 (4)
C8—H80.9500C27—H270.9500
C9—H90.9500C28—C291.381 (4)
C10—C111.395 (4)C28—H280.9500
C10—C151.399 (3)C29—C301.385 (4)
C11—C121.394 (4)C29—H290.9500
C11—H110.9500C30—H300.9500
C12—C131.376 (4)C31—Cl51.758 (3)
C12—H120.9500C31—Cl41.759 (3)
C13—C141.386 (4)C31—Cl31.763 (3)
C13—H130.9500C31—H311.0000
P2—Pt1—P196.03 (2)C13—C14—C15120.2 (3)
P2—Pt1—Cl286.89 (2)C13—C14—H14119.9
P1—Pt1—Cl2177.05 (2)C15—C14—H14119.9
P2—Pt1—Cl1169.29 (2)C14—C15—C10120.4 (2)
P1—Pt1—Cl192.29 (2)C14—C15—H15119.8
Cl2—Pt1—Cl184.75 (2)C10—C15—H15119.8
N1—P1—C4104.36 (12)C16—N2—P2122.79 (18)
N1—P1—C10106.61 (11)C16—N2—H2112 (2)
C4—P1—C10105.69 (11)P2—N2—H2114 (2)
N1—P1—Pt1108.91 (8)N2—C16—C18111.0 (2)
C4—P1—Pt1114.87 (8)N2—C16—C17109.7 (2)
C10—P1—Pt1115.54 (8)C18—C16—C17111.3 (3)
N2—P2—C19104.32 (12)N2—C16—H16108.2
N2—P2—C25106.38 (12)C18—C16—H16108.2
C19—P2—C25107.08 (12)C17—C16—H16108.2
N2—P2—Pt1116.00 (8)C16—C17—H17A109.5
C19—P2—Pt1107.13 (8)C16—C17—H17B109.5
C25—P2—Pt1115.09 (8)H17A—C17—H17B109.5
C1—N1—P1128.26 (17)C16—C17—H17C109.5
C1—N1—H1116 (2)H17A—C17—H17C109.5
P1—N1—H1115 (2)H17B—C17—H17C109.5
N1—C1—C3110.2 (2)C16—C18—H18A109.5
N1—C1—C2109.6 (2)C16—C18—H18B109.5
C3—C1—C2112.0 (2)H18A—C18—H18B109.5
N1—C1—H1A108.3C16—C18—H18C109.5
C3—C1—H1A108.3H18A—C18—H18C109.5
C2—C1—H1A108.3H18B—C18—H18C109.5
C1—C2—H2A109.5C20—C19—C24119.1 (3)
C1—C2—H2B109.5C20—C19—P2119.4 (2)
H2A—C2—H2B109.5C24—C19—P2120.9 (2)
C1—C2—H2C109.5C19—C20—C21120.2 (3)
H2A—C2—H2C109.5C19—C20—H20119.9
H2B—C2—H2C109.5C21—C20—H20119.9
C1—C3—H3A109.5C22—C21—C20120.7 (3)
C1—C3—H3B109.5C22—C21—H21119.7
H3A—C3—H3B109.5C20—C21—H21119.7
C1—C3—H3C109.5C21—C22—C23119.8 (3)
H3A—C3—H3C109.5C21—C22—H22120.1
H3B—C3—H3C109.5C23—C22—H22120.1
C5—C4—C9118.7 (2)C22—C23—C24120.4 (3)
C5—C4—P1125.5 (2)C22—C23—H23119.8
C9—C4—P1115.8 (2)C24—C23—H23119.8
C4—C5—C6120.5 (3)C23—C24—C19119.7 (3)
C4—C5—H5119.7C23—C24—H24120.2
C6—C5—H5119.7C19—C24—H24120.2
C7—C6—C5120.0 (3)C30—C25—C26118.8 (2)
C7—C6—H6120.0C30—C25—P2118.63 (19)
C5—C6—H6120.0C26—C25—P2122.0 (2)
C8—C7—C6120.3 (3)C27—C26—C25120.2 (3)
C8—C7—H7119.8C27—C26—H26119.9
C6—C7—H7119.8C25—C26—H26119.9
C7—C8—C9119.9 (3)C28—C27—C26120.4 (3)
C7—C8—H8120.0C28—C27—H27119.8
C9—C8—H8120.0C26—C27—H27119.8
C8—C9—C4120.6 (3)C29—C28—C27119.6 (3)
C8—C9—H9119.7C29—C28—H28120.2
C4—C9—H9119.7C27—C28—H28120.2
C11—C10—C15118.8 (2)C28—C29—C30120.5 (3)
C11—C10—P1118.78 (19)C28—C29—H29119.8
C15—C10—P1122.08 (19)C30—C29—H29119.8
C12—C11—C10120.4 (2)C29—C30—C25120.5 (3)
C12—C11—H11119.8C29—C30—H30119.7
C10—C11—H11119.8C25—C30—H30119.7
C13—C12—C11120.2 (3)Cl5—C31—Cl4109.92 (17)
C13—C12—H12119.9Cl5—C31—Cl3110.11 (16)
C11—C12—H12119.9Cl4—C31—Cl3110.91 (17)
C12—C13—C14120.1 (3)Cl5—C31—H31108.6
C12—C13—H13120.0Cl4—C31—H31108.6
C14—C13—H13120.0Cl3—C31—H31108.6
P2—Pt1—P1—N1175.27 (9)P1—C10—C11—C12−172.9 (2)
Cl1—Pt1—P1—N12.01 (10)C10—C11—C12—C13−0.2 (4)
P2—Pt1—P1—C458.67 (10)C11—C12—C13—C14−0.3 (4)
Cl1—Pt1—P1—C4−114.59 (9)C12—C13—C14—C150.9 (4)
P2—Pt1—P1—C10−64.82 (9)C13—C14—C15—C10−0.9 (4)
Cl1—Pt1—P1—C10121.92 (9)C11—C10—C15—C140.3 (4)
P1—Pt1—P2—N218.14 (10)P1—C10—C15—C14173.2 (2)
Cl2—Pt1—P2—N2−162.27 (10)C19—P2—N2—C16−69.1 (2)
Cl1—Pt1—P2—N2159.01 (14)C25—P2—N2—C1643.9 (2)
P1—Pt1—P2—C19−97.86 (9)Pt1—P2—N2—C16173.29 (18)
Cl2—Pt1—P2—C1981.73 (9)P2—N2—C16—C18−94.6 (3)
Cl1—Pt1—P2—C1943.02 (16)P2—N2—C16—C17141.9 (2)
P1—Pt1—P2—C25143.22 (10)N2—P2—C19—C20−29.7 (2)
Cl2—Pt1—P2—C25−37.19 (10)C25—P2—C19—C20−142.2 (2)
Cl1—Pt1—P2—C25−75.90 (16)Pt1—P2—C19—C2093.8 (2)
C4—P1—N1—C1−61.4 (3)N2—P2—C19—C24159.1 (2)
C10—P1—N1—C150.2 (3)C25—P2—C19—C2446.6 (2)
Pt1—P1—N1—C1175.5 (2)Pt1—P2—C19—C24−77.4 (2)
P1—N1—C1—C3−103.9 (3)C24—C19—C20—C21−0.2 (4)
P1—N1—C1—C2132.4 (2)P2—C19—C20—C21−171.5 (2)
N1—P1—C4—C5130.0 (2)C19—C20—C21—C22−0.2 (4)
C10—P1—C4—C517.7 (3)C20—C21—C22—C230.0 (5)
Pt1—P1—C4—C5−110.9 (2)C21—C22—C23—C240.5 (5)
N1—P1—C4—C9−51.5 (2)C22—C23—C24—C19−0.9 (4)
C10—P1—C4—C9−163.73 (19)C20—C19—C24—C230.7 (4)
Pt1—P1—C4—C967.7 (2)P2—C19—C24—C23172.0 (2)
C9—C4—C5—C61.7 (4)N2—P2—C25—C3084.6 (2)
P1—C4—C5—C6−179.8 (2)C19—P2—C25—C30−164.3 (2)
C4—C5—C6—C7−0.9 (4)Pt1—P2—C25—C30−45.4 (2)
C5—C6—C7—C8−0.4 (4)N2—P2—C25—C26−86.8 (2)
C6—C7—C8—C90.9 (4)C19—P2—C25—C2624.3 (2)
C7—C8—C9—C40.0 (4)Pt1—P2—C25—C26143.23 (19)
C5—C4—C9—C8−1.2 (4)C30—C25—C26—C270.1 (4)
P1—C4—C9—C8−179.9 (2)P2—C25—C26—C27171.5 (2)
N1—P1—C10—C11102.8 (2)C25—C26—C27—C28−0.4 (4)
C4—P1—C10—C11−146.55 (19)C26—C27—C28—C29−0.3 (4)
Pt1—P1—C10—C11−18.4 (2)C27—C28—C29—C301.3 (4)
N1—P1—C10—C15−70.1 (2)C28—C29—C30—C25−1.5 (4)
C4—P1—C10—C1540.5 (2)C26—C25—C30—C290.8 (4)
Pt1—P1—C10—C15168.73 (18)P2—C25—C30—C29−170.9 (2)
C15—C10—C11—C120.2 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.815 (17)2.32 (2)3.000 (2)141 (3)
C31—H31···Cl11.002.653.435 (3)136
C31—H31···Cl21.002.693.521 (3)141
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.815 (17)2.32 (2)3.000 (2)141 (3)
C31—H31···Cl11.002.653.435 (3)136
C31—H31···Cl21.002.693.521 (3)141
Table 2
Selected geometric parameters (Å, °) for (I) and a comparison with (II) and (III) top
(I)(II)(III)
Pt—P2.2565 (6), 2.2416 (6)2.2625 (10), 2.251 (9)2.221 (2) [2.253 (2)]
2.254 (2) [2.239 (2)]
Pt—Cl2.3779 (6), 2.3503 (6)2.3644 (10), 2.3649 (12)2.348 (2) [2.254 (2)]
2.362 (2) [2.353 (2)]
P—N1.647 (2), 1.665 (2)1.663 (3), 1.660 (4)1.667 (8) [1.634 (8)]
1.686 (9) [1.669 (8)]
P—Pt—P96.03 (2)98.81 (4)102.3 (1) [95.4 (1)]
Cl—Pt—Cl84.75 (2)84.53 (4)86.6 (1) [86.6 (1)]
Notes: (I) this work (R = iPr); (II) Slawin et al. (2005) (R = CH2CH═CH2); (III) Priya et al. (2003), two molecules present in the asymmetric unit (R = Ph).
Acknowledgements top

We would like to acknowledge the EPSRC, Sasol Technology (Pty) Ltd and Loughborough University for the provision of studentships (GMB, NMSB).

references
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