Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028206/fj2039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028206/fj2039Isup2.hkl |
CCDC reference: 654758
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- R factor = 0.022
- wR factor = 0.043
- Data-to-parameter ratio = 22.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.61 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C31 PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2 ... ?
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: ... Smith: synthetic chemistry supervisor Elsegood: crystallographic supervisor Sanchez-Ballester: Wrote most of the paper in cif Evans: MChem student learning how to write in cif and synthesised the complex Brown: made the ligand Blann: Industrial supervisor |
PUBL022_ALERT_1_A There is a mismatched ~ on line 272 Slawin <i>et al.</i>, 1999). For <i>trans</i>-{R~2~PN(H)R'}~2~MCl~2 If you require a ~ then it should be escaped with a \, i.e. \~ Otherwise there must be a matching closing ~, e.g. C~2~H~4~ PUBL022_ALERT_1_A There is a mismatched ~ on line 273 ~complexes If you require a ~ then it should be escaped with a \, i.e. \~ Otherwise there must be a matching closing ~, e.g. C~2~H~4~
3 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
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).
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.
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).
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.
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).
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.
[PtCl2(C15H18NP)2]·CHCl3 | F(000) = 1720 |
Mr = 871.91 | Dx = 1.657 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 13577 reflections |
a = 11.5142 (4) Å | θ = 2.3–28.9° |
b = 14.5440 (5) Å | µ = 4.51 mm−1 |
c = 21.5825 (8) Å | T = 150 K |
β = 104.795 (2)° | Block, colourless |
V = 3494.4 (2) Å3 | 0.34 × 0.24 × 0.14 mm |
Z = 4 |
Bruker SMART 1000 CCD diffractometer | 8350 independent reflections |
Radiation source: sealed tube | 6863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω rotation with narrow frames scans | θmax = 29.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −14→15 |
Tmin = 0.287, Tmax = 0.531 | k = −18→17 |
26733 measured reflections | l = −27→29 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: geom except NH coords freely refined |
wR(F2) = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0136P)2 + 2.3257P] where P = (Fo2 + 2Fc2)/3 |
8350 reflections | (Δ/σ)max = 0.002 |
380 parameters | Δρmax = 1.14 e Å−3 |
2 restraints | Δρmin = −0.75 e Å−3 |
[PtCl2(C15H18NP)2]·CHCl3 | V = 3494.4 (2) Å3 |
Mr = 871.91 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.5142 (4) Å | µ = 4.51 mm−1 |
b = 14.5440 (5) Å | T = 150 K |
c = 21.5825 (8) Å | 0.34 × 0.24 × 0.14 mm |
β = 104.795 (2)° |
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 = 0.531 | Rint = 0.027 |
26733 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 2 restraints |
wR(F2) = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 1.14 e Å−3 |
8350 reflections | Δρmin = −0.75 e Å−3 |
380 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 | 0.610678 (8) | 0.266739 (7) | 0.607682 (4) | 0.01569 (3) | |
Cl1 | 0.40601 (5) | 0.23034 (5) | 0.59963 (3) | 0.02215 (13) | |
Cl2 | 0.62839 (6) | 0.27216 (5) | 0.71855 (3) | 0.02706 (14) | |
P1 | 0.58363 (5) | 0.25957 (4) | 0.50050 (3) | 0.01643 (13) | |
P2 | 0.81064 (6) | 0.28418 (4) | 0.63150 (3) | 0.01808 (14) | |
N1 | 0.4412 (2) | 0.23747 (16) | 0.46669 (10) | 0.0239 (5) | |
H1 | 0.397 (2) | 0.237 (2) | 0.4910 (12) | 0.036* | |
C1 | 0.3803 (2) | 0.23277 (19) | 0.39797 (12) | 0.0249 (6) | |
H1A | 0.4430 | 0.2293 | 0.3734 | 0.030* | |
C2 | 0.3042 (3) | 0.1459 (2) | 0.38439 (14) | 0.0401 (8) | |
H2A | 0.3552 | 0.0920 | 0.3986 | 0.060* | |
H2B | 0.2670 | 0.1412 | 0.3383 | 0.060* | |
H2C | 0.2414 | 0.1485 | 0.4076 | 0.060* | |
C3 | 0.3063 (3) | 0.3187 (2) | 0.37732 (13) | 0.0373 (7) | |
H3A | 0.2467 | 0.3248 | 0.4024 | 0.056* | |
H3B | 0.2652 | 0.3143 | 0.3317 | 0.056* | |
H3C | 0.3592 | 0.3726 | 0.3846 | 0.056* | |
C4 | 0.6650 (2) | 0.16705 (17) | 0.47293 (11) | 0.0191 (5) | |
C5 | 0.7616 (2) | 0.17847 (19) | 0.44604 (12) | 0.0236 (6) | |
H5 | 0.7901 | 0.2385 | 0.4409 | 0.028* | |
C6 | 0.8167 (3) | 0.1026 (2) | 0.42654 (13) | 0.0300 (7) | |
H6 | 0.8820 | 0.1111 | 0.4076 | 0.036* | |
C7 | 0.7766 (3) | 0.0151 (2) | 0.43462 (14) | 0.0345 (7) | |
H7 | 0.8141 | −0.0366 | 0.4210 | 0.041* | |
C8 | 0.6825 (3) | 0.0023 (2) | 0.46236 (14) | 0.0350 (7) | |
H8 | 0.6559 | −0.0581 | 0.4684 | 0.042* | |
C9 | 0.6266 (3) | 0.07774 (19) | 0.48150 (13) | 0.0280 (6) | |
H9 | 0.5617 | 0.0687 | 0.5006 | 0.034* | |
C10 | 0.6209 (2) | 0.36412 (17) | 0.46285 (11) | 0.0180 (5) | |
C11 | 0.6288 (2) | 0.44695 (18) | 0.49622 (12) | 0.0220 (6) | |
H11 | 0.6239 | 0.4471 | 0.5395 | 0.026* | |
C12 | 0.6440 (2) | 0.52958 (19) | 0.46646 (14) | 0.0275 (6) | |
H12 | 0.6491 | 0.5857 | 0.4895 | 0.033* | |
C13 | 0.6516 (3) | 0.53001 (19) | 0.40386 (14) | 0.0296 (7) | |
H13 | 0.6615 | 0.5865 | 0.3837 | 0.036* | |
C14 | 0.6449 (2) | 0.44817 (19) | 0.37024 (13) | 0.0278 (6) | |
H14 | 0.6513 | 0.4486 | 0.3272 | 0.033* | |
C15 | 0.6288 (2) | 0.36561 (19) | 0.39924 (12) | 0.0237 (6) | |
H15 | 0.6232 | 0.3098 | 0.3758 | 0.028* | |
N2 | 0.86725 (19) | 0.31830 (16) | 0.57158 (10) | 0.0215 (5) | |
H2 | 0.822 (2) | 0.3539 (17) | 0.5452 (12) | 0.032* | |
C16 | 0.9961 (2) | 0.3428 (2) | 0.58081 (13) | 0.0298 (6) | |
H16 | 1.0437 | 0.3106 | 0.6201 | 0.036* | |
C17 | 1.0398 (3) | 0.3090 (3) | 0.52374 (16) | 0.0471 (9) | |
H17A | 1.0278 | 0.2423 | 0.5191 | 0.071* | |
H17B | 1.1254 | 0.3231 | 0.5307 | 0.071* | |
H17C | 0.9942 | 0.3397 | 0.4847 | 0.071* | |
C18 | 1.0154 (3) | 0.4455 (2) | 0.59066 (16) | 0.0452 (9) | |
H18A | 0.9664 | 0.4784 | 0.5535 | 0.068* | |
H18B | 1.1004 | 0.4600 | 0.5955 | 0.068* | |
H18C | 0.9920 | 0.4644 | 0.6293 | 0.068* | |
C19 | 0.8767 (2) | 0.17142 (18) | 0.65314 (12) | 0.0220 (6) | |
C20 | 0.9065 (2) | 0.11735 (19) | 0.60665 (14) | 0.0285 (6) | |
H20 | 0.9026 | 0.1424 | 0.5655 | 0.034* | |
C21 | 0.9421 (3) | 0.0269 (2) | 0.61997 (16) | 0.0379 (8) | |
H21 | 0.9621 | −0.0098 | 0.5878 | 0.046* | |
C22 | 0.9486 (3) | −0.0103 (2) | 0.67930 (17) | 0.0394 (8) | |
H22 | 0.9731 | −0.0724 | 0.6880 | 0.047* | |
C23 | 0.9196 (3) | 0.0426 (2) | 0.72611 (16) | 0.0369 (8) | |
H23 | 0.9248 | 0.0170 | 0.7672 | 0.044* | |
C24 | 0.8827 (2) | 0.1333 (2) | 0.71358 (14) | 0.0284 (6) | |
H24 | 0.8616 | 0.1693 | 0.7458 | 0.034* | |
C25 | 0.8729 (2) | 0.36076 (18) | 0.69854 (12) | 0.0205 (5) | |
C26 | 0.9837 (2) | 0.34360 (19) | 0.74212 (12) | 0.0246 (6) | |
H26 | 1.0236 | 0.2868 | 0.7407 | 0.030* | |
C27 | 1.0353 (3) | 0.4093 (2) | 0.78732 (13) | 0.0305 (7) | |
H27 | 1.1102 | 0.3971 | 0.8169 | 0.037* | |
C28 | 0.9783 (3) | 0.4925 (2) | 0.78963 (13) | 0.0301 (6) | |
H28 | 1.0138 | 0.5373 | 0.8208 | 0.036* | |
C29 | 0.8696 (3) | 0.5102 (2) | 0.74632 (13) | 0.0306 (7) | |
H29 | 0.8312 | 0.5678 | 0.7473 | 0.037* | |
C30 | 0.8164 (2) | 0.44455 (19) | 0.70155 (13) | 0.0257 (6) | |
H30 | 0.7407 | 0.4569 | 0.6727 | 0.031* | |
C31 | 0.3502 (3) | 0.2155 (2) | 0.74824 (13) | 0.0354 (7) | |
H31 | 0.4102 | 0.2101 | 0.7221 | 0.042* | |
Cl3 | 0.42136 (9) | 0.18738 (8) | 0.82838 (4) | 0.0609 (3) | |
Cl4 | 0.23036 (8) | 0.13999 (7) | 0.71669 (4) | 0.0556 (2) | |
Cl5 | 0.29746 (8) | 0.32944 (6) | 0.74342 (4) | 0.0493 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.01498 (5) | 0.01740 (5) | 0.01464 (5) | −0.00012 (4) | 0.00371 (3) | 0.00047 (4) |
Cl1 | 0.0184 (3) | 0.0288 (3) | 0.0201 (3) | −0.0045 (3) | 0.0065 (2) | −0.0015 (3) |
Cl2 | 0.0228 (3) | 0.0432 (4) | 0.0154 (3) | −0.0049 (3) | 0.0052 (2) | −0.0001 (3) |
P1 | 0.0161 (3) | 0.0173 (3) | 0.0157 (3) | 0.0000 (2) | 0.0036 (2) | −0.0004 (3) |
P2 | 0.0161 (3) | 0.0212 (4) | 0.0169 (3) | 0.0001 (3) | 0.0042 (2) | 0.0006 (3) |
N1 | 0.0203 (11) | 0.0353 (13) | 0.0162 (10) | −0.0040 (10) | 0.0050 (9) | −0.0020 (10) |
C1 | 0.0213 (13) | 0.0349 (15) | 0.0166 (12) | −0.0032 (12) | 0.0012 (10) | −0.0002 (12) |
C2 | 0.0420 (19) | 0.044 (2) | 0.0284 (16) | −0.0153 (15) | −0.0019 (14) | −0.0034 (14) |
C3 | 0.0355 (17) | 0.048 (2) | 0.0226 (14) | 0.0060 (14) | −0.0025 (13) | −0.0002 (14) |
C4 | 0.0219 (13) | 0.0183 (13) | 0.0162 (12) | 0.0028 (10) | 0.0033 (10) | −0.0008 (10) |
C5 | 0.0250 (14) | 0.0233 (15) | 0.0217 (13) | 0.0029 (11) | 0.0044 (11) | −0.0015 (11) |
C6 | 0.0291 (15) | 0.0351 (18) | 0.0270 (15) | 0.0092 (13) | 0.0092 (12) | −0.0015 (13) |
C7 | 0.0412 (18) | 0.0295 (17) | 0.0299 (16) | 0.0142 (14) | 0.0039 (14) | −0.0067 (13) |
C8 | 0.0440 (19) | 0.0194 (16) | 0.0387 (17) | 0.0017 (13) | 0.0051 (14) | −0.0034 (13) |
C9 | 0.0312 (16) | 0.0236 (16) | 0.0296 (15) | −0.0017 (12) | 0.0087 (12) | 0.0014 (12) |
C10 | 0.0157 (12) | 0.0196 (14) | 0.0181 (12) | 0.0001 (10) | 0.0033 (10) | 0.0018 (10) |
C11 | 0.0210 (13) | 0.0253 (15) | 0.0202 (13) | 0.0009 (11) | 0.0062 (11) | 0.0011 (11) |
C12 | 0.0313 (16) | 0.0177 (15) | 0.0353 (16) | 0.0023 (12) | 0.0117 (13) | 0.0001 (12) |
C13 | 0.0330 (16) | 0.0224 (15) | 0.0370 (16) | 0.0038 (12) | 0.0153 (13) | 0.0098 (13) |
C14 | 0.0319 (16) | 0.0326 (17) | 0.0204 (13) | 0.0026 (12) | 0.0095 (12) | 0.0056 (12) |
C15 | 0.0269 (14) | 0.0241 (15) | 0.0210 (13) | 0.0000 (11) | 0.0075 (11) | −0.0005 (11) |
N2 | 0.0176 (11) | 0.0263 (13) | 0.0206 (11) | −0.0017 (9) | 0.0047 (9) | 0.0021 (9) |
C16 | 0.0205 (14) | 0.0417 (18) | 0.0282 (15) | −0.0060 (12) | 0.0082 (12) | −0.0008 (13) |
C17 | 0.0329 (18) | 0.069 (2) | 0.046 (2) | −0.0164 (17) | 0.0225 (15) | −0.0153 (18) |
C18 | 0.0405 (19) | 0.049 (2) | 0.052 (2) | −0.0213 (16) | 0.0220 (16) | −0.0053 (17) |
C19 | 0.0156 (12) | 0.0220 (14) | 0.0270 (14) | −0.0005 (10) | 0.0030 (11) | 0.0003 (11) |
C20 | 0.0224 (14) | 0.0292 (16) | 0.0316 (15) | 0.0082 (12) | 0.0028 (12) | 0.0002 (12) |
C21 | 0.0268 (16) | 0.0337 (18) | 0.048 (2) | 0.0099 (13) | −0.0002 (14) | −0.0082 (15) |
C22 | 0.0229 (15) | 0.0242 (16) | 0.065 (2) | 0.0033 (12) | 0.0002 (15) | 0.0080 (16) |
C23 | 0.0244 (15) | 0.0379 (19) | 0.0449 (19) | −0.0013 (13) | 0.0024 (14) | 0.0177 (15) |
C24 | 0.0232 (14) | 0.0304 (17) | 0.0316 (15) | −0.0022 (12) | 0.0071 (12) | 0.0043 (13) |
C25 | 0.0198 (13) | 0.0232 (14) | 0.0187 (12) | −0.0004 (11) | 0.0053 (10) | −0.0007 (11) |
C26 | 0.0228 (14) | 0.0248 (15) | 0.0254 (14) | 0.0009 (11) | 0.0047 (11) | −0.0010 (11) |
C27 | 0.0229 (14) | 0.0396 (18) | 0.0254 (14) | −0.0025 (12) | −0.0006 (12) | −0.0023 (13) |
C28 | 0.0323 (16) | 0.0312 (17) | 0.0257 (14) | −0.0085 (13) | 0.0050 (12) | −0.0082 (13) |
C29 | 0.0343 (17) | 0.0245 (16) | 0.0335 (16) | 0.0019 (12) | 0.0096 (13) | −0.0043 (13) |
C30 | 0.0220 (14) | 0.0287 (16) | 0.0251 (14) | 0.0024 (11) | 0.0034 (11) | 0.0005 (12) |
C31 | 0.0321 (16) | 0.051 (2) | 0.0259 (15) | −0.0043 (14) | 0.0136 (13) | −0.0023 (14) |
Cl3 | 0.0603 (6) | 0.0896 (8) | 0.0323 (4) | 0.0058 (5) | 0.0105 (4) | 0.0095 (5) |
Cl4 | 0.0532 (5) | 0.0645 (6) | 0.0539 (5) | −0.0265 (5) | 0.0226 (4) | −0.0134 (5) |
Cl5 | 0.0398 (5) | 0.0538 (6) | 0.0555 (5) | −0.0010 (4) | 0.0145 (4) | −0.0067 (4) |
Pt1—P2 | 2.2417 (6) | C14—C15 | 1.388 (4) |
Pt1—P1 | 2.2564 (6) | C14—H14 | 0.9500 |
Pt1—Cl2 | 2.3503 (6) | C15—H15 | 0.9500 |
Pt1—Cl1 | 2.3780 (6) | N2—C16 | 1.489 (3) |
P1—N1 | 1.648 (2) | N2—H2 | 0.845 (17) |
P1—C4 | 1.824 (3) | C16—C18 | 1.517 (4) |
P1—C10 | 1.826 (3) | C16—C17 | 1.526 (4) |
P2—N2 | 1.666 (2) | C16—H16 | 1.0000 |
P2—C19 | 1.818 (3) | C17—H17A | 0.9800 |
P2—C25 | 1.821 (3) | C17—H17B | 0.9800 |
N1—C1 | 1.471 (3) | C17—H17C | 0.9800 |
N1—H1 | 0.815 (17) | C18—H18A | 0.9800 |
C1—C3 | 1.514 (4) | C18—H18B | 0.9800 |
C1—C2 | 1.523 (4) | C18—H18C | 0.9800 |
C1—H1A | 1.0000 | C19—C20 | 1.385 (4) |
C2—H2A | 0.9800 | C19—C24 | 1.403 (4) |
C2—H2B | 0.9800 | C20—C21 | 1.386 (4) |
C2—H2C | 0.9800 | C20—H20 | 0.9500 |
C3—H3A | 0.9800 | C21—C22 | 1.374 (4) |
C3—H3B | 0.9800 | C21—H21 | 0.9500 |
C3—H3C | 0.9800 | C22—C23 | 1.377 (5) |
C4—C5 | 1.389 (3) | C22—H22 | 0.9500 |
C4—C9 | 1.399 (4) | C23—C24 | 1.392 (4) |
C5—C6 | 1.391 (4) | C23—H23 | 0.9500 |
C5—H5 | 0.9500 | C24—H24 | 0.9500 |
C6—C7 | 1.380 (4) | C25—C30 | 1.391 (4) |
C6—H6 | 0.9500 | C25—C26 | 1.401 (3) |
C7—C8 | 1.378 (4) | C26—C27 | 1.386 (4) |
C7—H7 | 0.9500 | C26—H26 | 0.9500 |
C8—C9 | 1.387 (4) | C27—C28 | 1.384 (4) |
C8—H8 | 0.9500 | C27—H27 | 0.9500 |
C9—H9 | 0.9500 | C28—C29 | 1.381 (4) |
C10—C11 | 1.395 (4) | C28—H28 | 0.9500 |
C10—C15 | 1.399 (3) | C29—C30 | 1.385 (4) |
C11—C12 | 1.394 (4) | C29—H29 | 0.9500 |
C11—H11 | 0.9500 | C30—H30 | 0.9500 |
C12—C13 | 1.376 (4) | C31—Cl5 | 1.758 (3) |
C12—H12 | 0.9500 | C31—Cl4 | 1.759 (3) |
C13—C14 | 1.386 (4) | C31—Cl3 | 1.763 (3) |
C13—H13 | 0.9500 | C31—H31 | 1.0000 |
P2—Pt1—P1 | 96.03 (2) | C13—C14—C15 | 120.2 (3) |
P2—Pt1—Cl2 | 86.89 (2) | C13—C14—H14 | 119.9 |
P1—Pt1—Cl2 | 177.05 (2) | C15—C14—H14 | 119.9 |
P2—Pt1—Cl1 | 169.29 (2) | C14—C15—C10 | 120.4 (2) |
P1—Pt1—Cl1 | 92.29 (2) | C14—C15—H15 | 119.8 |
Cl2—Pt1—Cl1 | 84.75 (2) | C10—C15—H15 | 119.8 |
N1—P1—C4 | 104.36 (12) | C16—N2—P2 | 122.79 (18) |
N1—P1—C10 | 106.61 (11) | C16—N2—H2 | 112 (2) |
C4—P1—C10 | 105.69 (11) | P2—N2—H2 | 114 (2) |
N1—P1—Pt1 | 108.91 (8) | N2—C16—C18 | 111.0 (2) |
C4—P1—Pt1 | 114.87 (8) | N2—C16—C17 | 109.7 (2) |
C10—P1—Pt1 | 115.54 (8) | C18—C16—C17 | 111.3 (3) |
N2—P2—C19 | 104.32 (12) | N2—C16—H16 | 108.2 |
N2—P2—C25 | 106.38 (12) | C18—C16—H16 | 108.2 |
C19—P2—C25 | 107.08 (12) | C17—C16—H16 | 108.2 |
N2—P2—Pt1 | 116.00 (8) | C16—C17—H17A | 109.5 |
C19—P2—Pt1 | 107.13 (8) | C16—C17—H17B | 109.5 |
C25—P2—Pt1 | 115.09 (8) | H17A—C17—H17B | 109.5 |
C1—N1—P1 | 128.26 (17) | C16—C17—H17C | 109.5 |
C1—N1—H1 | 116 (2) | H17A—C17—H17C | 109.5 |
P1—N1—H1 | 115 (2) | H17B—C17—H17C | 109.5 |
N1—C1—C3 | 110.2 (2) | C16—C18—H18A | 109.5 |
N1—C1—C2 | 109.6 (2) | C16—C18—H18B | 109.5 |
C3—C1—C2 | 112.0 (2) | H18A—C18—H18B | 109.5 |
N1—C1—H1A | 108.3 | C16—C18—H18C | 109.5 |
C3—C1—H1A | 108.3 | H18A—C18—H18C | 109.5 |
C2—C1—H1A | 108.3 | H18B—C18—H18C | 109.5 |
C1—C2—H2A | 109.5 | C20—C19—C24 | 119.1 (3) |
C1—C2—H2B | 109.5 | C20—C19—P2 | 119.4 (2) |
H2A—C2—H2B | 109.5 | C24—C19—P2 | 120.9 (2) |
C1—C2—H2C | 109.5 | C19—C20—C21 | 120.2 (3) |
H2A—C2—H2C | 109.5 | C19—C20—H20 | 119.9 |
H2B—C2—H2C | 109.5 | C21—C20—H20 | 119.9 |
C1—C3—H3A | 109.5 | C22—C21—C20 | 120.7 (3) |
C1—C3—H3B | 109.5 | C22—C21—H21 | 119.7 |
H3A—C3—H3B | 109.5 | C20—C21—H21 | 119.7 |
C1—C3—H3C | 109.5 | C21—C22—C23 | 119.8 (3) |
H3A—C3—H3C | 109.5 | C21—C22—H22 | 120.1 |
H3B—C3—H3C | 109.5 | C23—C22—H22 | 120.1 |
C5—C4—C9 | 118.7 (2) | C22—C23—C24 | 120.4 (3) |
C5—C4—P1 | 125.5 (2) | C22—C23—H23 | 119.8 |
C9—C4—P1 | 115.8 (2) | C24—C23—H23 | 119.8 |
C4—C5—C6 | 120.5 (3) | C23—C24—C19 | 119.7 (3) |
C4—C5—H5 | 119.7 | C23—C24—H24 | 120.2 |
C6—C5—H5 | 119.7 | C19—C24—H24 | 120.2 |
C7—C6—C5 | 120.0 (3) | C30—C25—C26 | 118.8 (2) |
C7—C6—H6 | 120.0 | C30—C25—P2 | 118.63 (19) |
C5—C6—H6 | 120.0 | C26—C25—P2 | 122.0 (2) |
C8—C7—C6 | 120.3 (3) | C27—C26—C25 | 120.2 (3) |
C8—C7—H7 | 119.8 | C27—C26—H26 | 119.9 |
C6—C7—H7 | 119.8 | C25—C26—H26 | 119.9 |
C7—C8—C9 | 119.9 (3) | C28—C27—C26 | 120.4 (3) |
C7—C8—H8 | 120.0 | C28—C27—H27 | 119.8 |
C9—C8—H8 | 120.0 | C26—C27—H27 | 119.8 |
C8—C9—C4 | 120.6 (3) | C29—C28—C27 | 119.6 (3) |
C8—C9—H9 | 119.7 | C29—C28—H28 | 120.2 |
C4—C9—H9 | 119.7 | C27—C28—H28 | 120.2 |
C11—C10—C15 | 118.8 (2) | C28—C29—C30 | 120.5 (3) |
C11—C10—P1 | 118.78 (19) | C28—C29—H29 | 119.8 |
C15—C10—P1 | 122.08 (19) | C30—C29—H29 | 119.8 |
C12—C11—C10 | 120.4 (2) | C29—C30—C25 | 120.5 (3) |
C12—C11—H11 | 119.8 | C29—C30—H30 | 119.7 |
C10—C11—H11 | 119.8 | C25—C30—H30 | 119.7 |
C13—C12—C11 | 120.2 (3) | Cl5—C31—Cl4 | 109.92 (17) |
C13—C12—H12 | 119.9 | Cl5—C31—Cl3 | 110.11 (16) |
C11—C12—H12 | 119.9 | Cl4—C31—Cl3 | 110.91 (17) |
C12—C13—C14 | 120.1 (3) | Cl5—C31—H31 | 108.6 |
C12—C13—H13 | 120.0 | Cl4—C31—H31 | 108.6 |
C14—C13—H13 | 120.0 | Cl3—C31—H31 | 108.6 |
P2—Pt1—P1—N1 | 175.27 (9) | P1—C10—C11—C12 | −172.9 (2) |
Cl1—Pt1—P1—N1 | 2.01 (10) | C10—C11—C12—C13 | −0.2 (4) |
P2—Pt1—P1—C4 | 58.67 (10) | C11—C12—C13—C14 | −0.3 (4) |
Cl1—Pt1—P1—C4 | −114.59 (9) | C12—C13—C14—C15 | 0.9 (4) |
P2—Pt1—P1—C10 | −64.82 (9) | C13—C14—C15—C10 | −0.9 (4) |
Cl1—Pt1—P1—C10 | 121.92 (9) | C11—C10—C15—C14 | 0.3 (4) |
P1—Pt1—P2—N2 | 18.14 (10) | P1—C10—C15—C14 | 173.2 (2) |
Cl2—Pt1—P2—N2 | −162.27 (10) | C19—P2—N2—C16 | −69.1 (2) |
Cl1—Pt1—P2—N2 | 159.01 (14) | C25—P2—N2—C16 | 43.9 (2) |
P1—Pt1—P2—C19 | −97.86 (9) | Pt1—P2—N2—C16 | 173.29 (18) |
Cl2—Pt1—P2—C19 | 81.73 (9) | P2—N2—C16—C18 | −94.6 (3) |
Cl1—Pt1—P2—C19 | 43.02 (16) | P2—N2—C16—C17 | 141.9 (2) |
P1—Pt1—P2—C25 | 143.22 (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—C20 | 93.8 (2) |
C4—P1—N1—C1 | −61.4 (3) | N2—P2—C19—C24 | 159.1 (2) |
C10—P1—N1—C1 | 50.2 (3) | C25—P2—C19—C24 | 46.6 (2) |
Pt1—P1—N1—C1 | 175.5 (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—C2 | 132.4 (2) | P2—C19—C20—C21 | −171.5 (2) |
N1—P1—C4—C5 | 130.0 (2) | C19—C20—C21—C22 | −0.2 (4) |
C10—P1—C4—C5 | 17.7 (3) | C20—C21—C22—C23 | 0.0 (5) |
Pt1—P1—C4—C5 | −110.9 (2) | C21—C22—C23—C24 | 0.5 (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—C23 | 0.7 (4) |
Pt1—P1—C4—C9 | 67.7 (2) | P2—C19—C24—C23 | 172.0 (2) |
C9—C4—C5—C6 | 1.7 (4) | N2—P2—C25—C30 | 84.6 (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—C9 | 0.9 (4) | C19—P2—C25—C26 | 24.3 (2) |
C7—C8—C9—C4 | 0.0 (4) | Pt1—P2—C25—C26 | 143.23 (19) |
C5—C4—C9—C8 | −1.2 (4) | C30—C25—C26—C27 | 0.1 (4) |
P1—C4—C9—C8 | −179.9 (2) | P2—C25—C26—C27 | 171.5 (2) |
N1—P1—C10—C11 | 102.8 (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—C30 | 1.3 (4) |
N1—P1—C10—C15 | −70.1 (2) | C28—C29—C30—C25 | −1.5 (4) |
C4—P1—C10—C15 | 40.5 (2) | C26—C25—C30—C29 | 0.8 (4) |
Pt1—P1—C10—C15 | 168.73 (18) | P2—C25—C30—C29 | −170.9 (2) |
C15—C10—C11—C12 | 0.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.82 (2) | 2.32 (2) | 3.000 (2) | 141 (3) |
C31—H31···Cl1 | 1.00 | 2.65 | 3.435 (3) | 136 |
C31—H31···Cl2 | 1.00 | 2.69 | 3.521 (3) | 141 |
Experimental details
Crystal data | |
Chemical formula | [PtCl2(C15H18NP)2]·CHCl3 |
Mr | 871.91 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 11.5142 (4), 14.5440 (5), 21.5825 (8) |
β (°) | 104.795 (2) |
V (Å3) | 3494.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.51 |
Crystal size (mm) | 0.34 × 0.24 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.287, 0.531 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26733, 8350, 6863 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.044, 1.04 |
No. of reflections | 8350 |
No. of parameters | 380 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.14, −0.75 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Bruker, 2000), SHELXTL and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.815 (17) | 2.32 (2) | 3.000 (2) | 141 (3) |
C31—H31···Cl1 | 1.00 | 2.65 | 3.435 (3) | 136 |
C31—H31···Cl2 | 1.00 | 2.69 | 3.521 (3) | 141 |
(I) | (II) | (III) | |
Pt—P | 2.2565 (6), 2.2416 (6) | 2.2625 (10), 2.251 (9) | 2.221 (2) [2.253 (2)] |
2.254 (2) [2.239 (2)] | |||
Pt—Cl | 2.3779 (6), 2.3503 (6) | 2.3644 (10), 2.3649 (12) | 2.348 (2) [2.254 (2)] |
2.362 (2) [2.353 (2)] | |||
P—N | 1.647 (2), 1.665 (2) | 1.663 (3), 1.660 (4) | 1.667 (8) [1.634 (8)] |
1.686 (9) [1.669 (8)] | |||
P—Pt—P | 96.03 (2) | 98.81 (4) | 102.3 (1) [95.4 (1)] |
Cl—Pt—Cl | 84.75 (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). |
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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.