Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046636/sj2365sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046636/sj2365Isup2.hkl |
CCDC reference: 667106
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean (C-C) = 0.008 Å
- R factor = 0.029
- wR factor = 0.068
- Data-to-parameter ratio = 18.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Pt1 - I1 .. 12.43 su
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.28 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 2 I1 -PT1 -P1 -C11 -128.40 0.60 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 5 I1 -PT1 -P1 -C21 105.30 0.60 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 8 I1 -PT1 -P1 -C1 -9.80 0.70 1.555 1.555 1.555 1.555 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Pt1 (9) 2.68
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 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 0 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For general background, see Hudson et al. (1968); for a related structure, see Parkin et al. (1991).
Crystals of the complex I were obtained as an unexpected by-product of the reaction of Pt(dppe)Cl2 with a Grignard reagent, IMg(CH2)6MgI in diethyl ether solution. The title compound was also prepared by the reaction of NaI with Pt(dppe)Cl2 in refluxing acetone solution for 4 h. 31P NMR indicated a singlet at 46.2 p.p.m. with platinum satellites (JPt—P = 3368 Hz). A mixture containing 0.248 g (0.373 mmol) of cis-Pt(dppe)Cl2 and 0.112 g (0.747 mmol) of NaI in 20 ml of acetone was refluxed for 4 h. Removal of solvent in high vacuum and recrystallize from a mixture of CH2Cl2 and n-hexane (1:1) led to the isolation of the complex I as a light yellow crystalline solid (0.296 g, 93%). Anal. Calc. for C26H24I2P2Pt: C, 36.86; H, 2.86; Found: C, 36.82; H, 2.89. Mass spectral data: M+ = 846.9; Pt(dppe)I+ = 719.9; Pt(dppe)+ = 595.
The structure was solved by the Patterson method. All H atoms were placed in idealized positions in a riding model with d(C—H) = 0.95 Å for aromatic H atoms and d(C—H) = 0.99 Å for the CH2 group and assigned Uiso(H)=1.2Ueq(C). The highest peak of 2.05 e Å-3 is located at 1.69 Å from I1. The deepest hole of -0.89 e Å-3 is located at 0.81 Å from I1.
The preparation of the title compound, cis-[PtI2(dppe)], was studied initially by Hudson et al. (1968). Parkin et al. (1991) reported the first and only crystal structure of the PtI2(dppe) molecule as a dichloromethane solvated complex co-crystallized with an iodine molecule, namely 3[PtI2(dppe)]·I2·2CH2Cl2 (monoclinic space group P21/n, a = 8.593 (2) Å, b = 28.194 (16) Å, c = 36.206 (9) Å, β = 91.50 (2)°, Z = 12, CSD Refcode LAGBOK). However, there are no atomic coordinates available in the CSD (Version 5.28, 2007). We present here a well refined bis-dichloromethane solvated crystal structure of the title compound, [PtI2(dppe)]·2CH2Cl2, (I) (Fig. 1). Here the complex crystallized in the space group Pccn with Z = 4. The molecule of PtI2(dppe) lies on a twofold rotation axis passing through Pt atom and the mid-point of the C1—C1i bond [symmetry code: (i) 3/2 - x, 3/2 - y, z]. Thus, in addition to Pt on the special position c in Wyckoff notation, the asymmetric unit consists of one I1 atom and half of the ligand comprising P1, the ethane C1 and the C11—C16 and C21—C26 phenyl rings attached to P1 together with one CH2Cl2 solvent molecule which is on a general position.
The coordination of Pt is a slight tetrahedral distortion from a square-planar arrangement with the sum of angles at Pt being 360.0 (2)°. The Pt—P distance and P—Pt—P angle are 2.242 (1) Å and 86.31 (6)° respectively; the Pt—I distance and I—Pt—I angle are 2.6484 (4) Å and 92.32 (2)° respectively; other important bond lengths and angles are in Table 1. A search of cis-dihalide complexes of the type M(dppe)X2 [where M = Ni, Pd and Pt; dppe = 1,2-bis(diphenylphosphino)ethane; X = Cl, Br and I] in the CSD (Version 5.28, 2007) reveals 23 entries. This resulted in the following statistics: the average distances of Pt—Cl (4 entries), Pd—Cl (3 entries) and Ni—Cl (10 entries) are 2.356 Å, 2.362 Å and 2.200 Å respectively; the average Ni—Br distances (2 entries) are 2.330 Å and the average Pd—I (2 entries) and Ni—I distances (1 entry) are 2.658 Å and 2.527 Å respectively. Intermolecular contacts of the type C(1)—H(1 A)···I(1) are present with a C···I distance of 3.873 (5) Å (details in Table 2). These interconnect the title molecules into columns propagated in the [001] direction.
For general background, see Hudson et al. (1968); for a related structure, see Parkin et al. (1991).
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[PtI2(C26H24P2)]·2CH2Cl2 | F(000) = 1912 |
Mr = 1017.13 | Dx = 2.026 Mg m−3 |
Orthorhombic, Pccn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ab 2ac | Cell parameters from 67782 reflections |
a = 12.7385 (2) Å | θ = 2.8–25.7° |
b = 15.6542 (3) Å | µ = 6.49 mm−1 |
c = 16.7194 (3) Å | T = 113 K |
V = 3334.03 (10) Å3 | Needle, yellow |
Z = 4 | 0.09 × 0.08 × 0.05 mm |
Nonius Kappa CCD diffractometer | 3156 independent reflections |
Radiation source: fine-focus sealed tube | 2527 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
1.2° φ scans, and ω | θmax = 25.7°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −15→15 |
Tmin = 0.616, Tmax = 0.737 | k = −19→19 |
67782 measured reflections | l = −20→20 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0323P)2 + 6.3267P] where P = (Fo2 + 2Fc2)/3 |
3156 reflections | (Δ/σ)max = 0.001 |
168 parameters | Δρmax = 2.05 e Å−3 |
0 restraints | Δρmin = −0.90 e Å−3 |
[PtI2(C26H24P2)]·2CH2Cl2 | V = 3334.03 (10) Å3 |
Mr = 1017.13 | Z = 4 |
Orthorhombic, Pccn | Mo Kα radiation |
a = 12.7385 (2) Å | µ = 6.49 mm−1 |
b = 15.6542 (3) Å | T = 113 K |
c = 16.7194 (3) Å | 0.09 × 0.08 × 0.05 mm |
Nonius Kappa CCD diffractometer | 3156 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2527 reflections with I > 2σ(I) |
Tmin = 0.616, Tmax = 0.737 | Rint = 0.082 |
67782 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.12 | Δρmax = 2.05 e Å−3 |
3156 reflections | Δρmin = −0.90 e Å−3 |
168 parameters |
Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of φ and ω scans of 1.2°, 30 s per °, 2 iterations. |
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 | 0.7500 | 0.7500 | 0.212727 (15) | 0.02157 (9) | |
I1 | 0.81688 (3) | 0.85922 (2) | 0.322442 (19) | 0.03005 (11) | |
Cl1A | 0.3632 (2) | 0.84723 (12) | 0.26536 (13) | 0.0849 (7) | |
Cl2A | 0.41394 (18) | 0.79969 (12) | 0.42948 (12) | 0.0718 (6) | |
P1 | 0.69591 (10) | 0.66250 (8) | 0.11491 (7) | 0.0234 (3) | |
C1 | 0.6997 (4) | 0.7235 (3) | 0.0217 (3) | 0.0259 (11) | |
H1A | 0.6991 | 0.6843 | −0.0248 | 0.031* | |
H1B | 0.6377 | 0.7614 | 0.0180 | 0.031* | |
C11 | 0.5636 (4) | 0.6218 (3) | 0.1242 (3) | 0.0263 (11) | |
C12 | 0.5399 (4) | 0.5360 (3) | 0.1280 (3) | 0.0319 (12) | |
H12 | 0.5945 | 0.4950 | 0.1229 | 0.038* | |
C13 | 0.4379 (4) | 0.5088 (4) | 0.1390 (3) | 0.0356 (13) | |
H13 | 0.4231 | 0.4494 | 0.1416 | 0.043* | |
C14 | 0.3577 (4) | 0.5667 (4) | 0.1463 (3) | 0.0377 (13) | |
H14 | 0.2877 | 0.5477 | 0.1546 | 0.045* | |
C15 | 0.3796 (5) | 0.6530 (4) | 0.1414 (3) | 0.0422 (14) | |
H15 | 0.3243 | 0.6935 | 0.1454 | 0.051* | |
C16 | 0.4827 (4) | 0.6808 (4) | 0.1307 (3) | 0.0367 (13) | |
H16 | 0.4975 | 0.7402 | 0.1278 | 0.044* | |
C21 | 0.7835 (4) | 0.5730 (3) | 0.0982 (3) | 0.0245 (11) | |
C22 | 0.8669 (4) | 0.5580 (4) | 0.1500 (3) | 0.0363 (13) | |
H22 | 0.8767 | 0.5937 | 0.1953 | 0.044* | |
C23 | 0.9358 (5) | 0.4916 (4) | 0.1358 (3) | 0.0424 (15) | |
H23 | 0.9921 | 0.4812 | 0.1718 | 0.051* | |
C24 | 0.9230 (5) | 0.4405 (4) | 0.0696 (3) | 0.0385 (14) | |
H24 | 0.9713 | 0.3956 | 0.0596 | 0.046* | |
C25 | 0.8405 (4) | 0.4540 (4) | 0.0178 (3) | 0.0394 (14) | |
H25 | 0.8314 | 0.4178 | −0.0273 | 0.047* | |
C26 | 0.7706 (4) | 0.5204 (4) | 0.0315 (3) | 0.0338 (13) | |
H26 | 0.7142 | 0.5301 | −0.0045 | 0.041* | |
C1A | 0.4117 (8) | 0.7672 (5) | 0.3296 (5) | 0.089 (3) | |
H1A1 | 0.3671 | 0.7156 | 0.3246 | 0.106* | |
H1A2 | 0.4837 | 0.7516 | 0.3128 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.02113 (14) | 0.02447 (15) | 0.01910 (14) | −0.00048 (12) | 0.000 | 0.000 |
I1 | 0.03385 (19) | 0.03157 (19) | 0.02474 (18) | −0.00589 (15) | 0.00190 (14) | −0.00346 (14) |
Cl1A | 0.1160 (18) | 0.0525 (11) | 0.0860 (14) | 0.0233 (11) | −0.0591 (14) | −0.0198 (10) |
Cl2A | 0.0926 (15) | 0.0549 (11) | 0.0679 (12) | 0.0121 (11) | −0.0133 (11) | −0.0114 (9) |
P1 | 0.0227 (7) | 0.0264 (7) | 0.0211 (6) | 0.0015 (5) | −0.0011 (5) | 0.0007 (5) |
C1 | 0.028 (3) | 0.028 (3) | 0.022 (2) | 0.002 (2) | −0.003 (2) | −0.004 (2) |
C11 | 0.028 (3) | 0.032 (3) | 0.019 (2) | −0.001 (2) | −0.003 (2) | 0.002 (2) |
C12 | 0.032 (3) | 0.028 (3) | 0.036 (3) | 0.000 (2) | −0.002 (2) | 0.002 (2) |
C13 | 0.033 (3) | 0.035 (3) | 0.039 (3) | −0.009 (3) | 0.002 (3) | 0.002 (3) |
C14 | 0.033 (3) | 0.043 (4) | 0.037 (3) | −0.010 (3) | −0.005 (2) | −0.003 (3) |
C15 | 0.030 (3) | 0.050 (4) | 0.047 (3) | 0.004 (3) | 0.000 (3) | −0.009 (3) |
C16 | 0.027 (3) | 0.034 (3) | 0.049 (3) | −0.004 (2) | −0.001 (3) | −0.003 (3) |
C21 | 0.024 (2) | 0.020 (2) | 0.029 (3) | −0.004 (2) | 0.005 (2) | 0.001 (2) |
C22 | 0.035 (3) | 0.045 (3) | 0.029 (3) | 0.004 (3) | −0.003 (2) | −0.007 (2) |
C23 | 0.036 (3) | 0.050 (4) | 0.041 (3) | 0.016 (3) | −0.005 (3) | −0.003 (3) |
C24 | 0.040 (3) | 0.033 (3) | 0.043 (3) | 0.013 (3) | 0.004 (3) | −0.001 (3) |
C25 | 0.042 (3) | 0.036 (3) | 0.040 (3) | 0.006 (3) | 0.003 (3) | −0.009 (3) |
C26 | 0.034 (3) | 0.036 (3) | 0.032 (3) | 0.002 (2) | −0.005 (2) | −0.004 (2) |
C1A | 0.116 (8) | 0.072 (6) | 0.078 (6) | 0.046 (5) | −0.045 (6) | −0.023 (4) |
Pt1—P1 | 2.2418 (13) | C14—C15 | 1.382 (8) |
Pt1—P1i | 2.2418 (13) | C14—H14 | 0.9500 |
Pt1—I1 | 2.6484 (4) | C15—C16 | 1.395 (8) |
Pt1—I1i | 2.6484 (4) | C15—H15 | 0.9500 |
Cl1A—C1A | 1.762 (8) | C16—H16 | 0.9500 |
Cl2A—C1A | 1.747 (8) | C21—C22 | 1.391 (7) |
P1—C1 | 1.829 (5) | C21—C26 | 1.396 (7) |
P1—C11 | 1.808 (5) | C22—C23 | 1.381 (8) |
P1—C21 | 1.813 (5) | C22—H22 | 0.9500 |
C1—C1i | 1.526 (10) | C23—C24 | 1.374 (8) |
C1—H1A | 0.9900 | C23—H23 | 0.9500 |
C1—H1B | 0.9900 | C24—C25 | 1.378 (8) |
C11—C12 | 1.379 (7) | C24—H24 | 0.9500 |
C11—C16 | 1.389 (7) | C25—C26 | 1.388 (7) |
C12—C13 | 1.379 (7) | C25—H25 | 0.9500 |
C12—H12 | 0.9500 | C26—H26 | 0.9500 |
C13—C14 | 1.372 (8) | C1A—H1A1 | 0.9900 |
C13—H13 | 0.9500 | C1A—H1A2 | 0.9900 |
P1—Pt1—P1i | 86.31 (6) | C14—C15—C16 | 120.2 (6) |
P1—Pt1—I1 | 176.99 (3) | C14—C15—H15 | 119.9 |
P1i—Pt1—I1 | 90.69 (3) | C16—C15—H15 | 119.9 |
P1—Pt1—I1i | 90.69 (3) | C11—C16—C15 | 120.1 (5) |
P1i—Pt1—I1i | 176.99 (3) | C11—C16—H16 | 120.0 |
I1—Pt1—I1i | 92.321 (16) | C15—C16—H16 | 120.0 |
C11—P1—C21 | 108.3 (2) | C22—C21—C26 | 119.2 (5) |
C11—P1—C1 | 106.4 (2) | C22—C21—P1 | 120.3 (4) |
C21—P1—C1 | 104.8 (2) | C26—C21—P1 | 120.4 (4) |
C11—P1—Pt1 | 116.04 (16) | C23—C22—C21 | 120.3 (5) |
C21—P1—Pt1 | 113.30 (17) | C23—C22—H22 | 119.8 |
C1—P1—Pt1 | 107.13 (17) | C21—C22—H22 | 119.8 |
C1i—C1—P1 | 107.8 (3) | C24—C23—C22 | 120.1 (5) |
C1i—C1—H1A | 110.1 | C24—C23—H23 | 120.0 |
P1—C1—H1A | 110.1 | C22—C23—H23 | 120.0 |
C1i—C1—H1B | 110.1 | C23—C24—C25 | 120.5 (5) |
P1—C1—H1B | 110.1 | C23—C24—H24 | 119.7 |
H1A—C1—H1B | 108.5 | C25—C24—H24 | 119.7 |
C12—C11—C16 | 118.8 (5) | C24—C25—C26 | 119.9 (5) |
C12—C11—P1 | 123.5 (4) | C24—C25—H25 | 120.0 |
C16—C11—P1 | 117.7 (4) | C26—C25—H25 | 120.0 |
C11—C12—C13 | 120.9 (5) | C25—C26—C21 | 119.9 (5) |
C11—C12—H12 | 119.6 | C25—C26—H26 | 120.0 |
C13—C12—H12 | 119.6 | C21—C26—H26 | 120.0 |
C14—C13—C12 | 120.7 (5) | Cl2A—C1A—Cl1A | 112.4 (4) |
C14—C13—H13 | 119.7 | Cl2A—C1A—H1A1 | 109.1 |
C12—C13—H13 | 119.7 | Cl1A—C1A—H1A1 | 109.1 |
C13—C14—C15 | 119.4 (5) | Cl2A—C1A—H1A2 | 109.1 |
C13—C14—H14 | 120.3 | Cl1A—C1A—H1A2 | 109.1 |
C15—C14—H14 | 120.3 | H1A1—C1A—H1A2 | 107.9 |
P1i—Pt1—P1—C11 | −131.36 (19) | C11—C12—C13—C14 | 0.2 (8) |
I1—Pt1—P1—C11 | −128.4 (6) | C12—C13—C14—C15 | 0.8 (8) |
I1i—Pt1—P1—C11 | 48.80 (18) | C13—C14—C15—C16 | −1.2 (9) |
P1i—Pt1—P1—C21 | 102.38 (18) | C12—C11—C16—C15 | 0.4 (8) |
I1—Pt1—P1—C21 | 105.3 (6) | P1—C11—C16—C15 | −177.3 (4) |
I1i—Pt1—P1—C21 | −77.47 (17) | C14—C15—C16—C11 | 0.6 (9) |
P1i—Pt1—P1—C1 | −12.74 (17) | C11—P1—C21—C22 | −122.6 (4) |
I1—Pt1—P1—C1 | −9.8 (7) | C1—P1—C21—C22 | 124.2 (4) |
I1i—Pt1—P1—C1 | 167.41 (18) | Pt1—P1—C21—C22 | 7.7 (5) |
C11—P1—C1—C1i | 166.3 (4) | C11—P1—C21—C26 | 60.1 (5) |
C21—P1—C1—C1i | −79.1 (4) | C1—P1—C21—C26 | −53.1 (5) |
Pt1—P1—C1—C1i | 41.6 (5) | Pt1—P1—C21—C26 | −169.6 (4) |
C21—P1—C11—C12 | 7.6 (5) | C26—C21—C22—C23 | −0.5 (8) |
C1—P1—C11—C12 | 119.9 (4) | P1—C21—C22—C23 | −177.8 (4) |
Pt1—P1—C11—C12 | −121.1 (4) | C21—C22—C23—C24 | 0.9 (9) |
C21—P1—C11—C16 | −174.8 (4) | C22—C23—C24—C25 | −1.2 (9) |
C1—P1—C11—C16 | −62.5 (5) | C23—C24—C25—C26 | 1.1 (9) |
Pt1—P1—C11—C16 | 56.5 (4) | C24—C25—C26—C21 | −0.6 (8) |
C16—C11—C12—C13 | −0.8 (8) | C22—C21—C26—C25 | 0.3 (8) |
P1—C11—C12—C13 | 176.8 (4) | P1—C21—C26—C25 | 177.6 (4) |
Symmetry code: (i) −x+3/2, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···I1ii | 0.99 | 3.04 | 3.873 (5) | 143 |
Symmetry code: (ii) x, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [PtI2(C26H24P2)]·2CH2Cl2 |
Mr | 1017.13 |
Crystal system, space group | Orthorhombic, Pccn |
Temperature (K) | 113 |
a, b, c (Å) | 12.7385 (2), 15.6542 (3), 16.7194 (3) |
V (Å3) | 3334.03 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 6.49 |
Crystal size (mm) | 0.09 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Nonius Kappa CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.616, 0.737 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 67782, 3156, 2527 |
Rint | 0.082 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.068, 1.12 |
No. of reflections | 3156 |
No. of parameters | 168 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.05, −0.90 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001).
Pt1—P1 | 2.2418 (13) | Pt1—I1 | 2.6484 (4) |
P1—Pt1—P1i | 86.31 (6) | P1i—Pt1—I1 | 90.69 (3) |
P1—Pt1—I1 | 176.99 (3) | P1—Pt1—I1i | 90.69 (3) |
Symmetry code: (i) −x+3/2, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···I1ii | 0.99 | 3.04 | 3.873 (5) | 142.5 |
Symmetry code: (ii) x, −y+3/2, z−1/2. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The preparation of the title compound, cis-[PtI2(dppe)], was studied initially by Hudson et al. (1968). Parkin et al. (1991) reported the first and only crystal structure of the PtI2(dppe) molecule as a dichloromethane solvated complex co-crystallized with an iodine molecule, namely 3[PtI2(dppe)]·I2·2CH2Cl2 (monoclinic space group P21/n, a = 8.593 (2) Å, b = 28.194 (16) Å, c = 36.206 (9) Å, β = 91.50 (2)°, Z = 12, CSD Refcode LAGBOK). However, there are no atomic coordinates available in the CSD (Version 5.28, 2007). We present here a well refined bis-dichloromethane solvated crystal structure of the title compound, [PtI2(dppe)]·2CH2Cl2, (I) (Fig. 1). Here the complex crystallized in the space group Pccn with Z = 4. The molecule of PtI2(dppe) lies on a twofold rotation axis passing through Pt atom and the mid-point of the C1—C1i bond [symmetry code: (i) 3/2 - x, 3/2 - y, z]. Thus, in addition to Pt on the special position c in Wyckoff notation, the asymmetric unit consists of one I1 atom and half of the ligand comprising P1, the ethane C1 and the C11—C16 and C21—C26 phenyl rings attached to P1 together with one CH2Cl2 solvent molecule which is on a general position.
The coordination of Pt is a slight tetrahedral distortion from a square-planar arrangement with the sum of angles at Pt being 360.0 (2)°. The Pt—P distance and P—Pt—P angle are 2.242 (1) Å and 86.31 (6)° respectively; the Pt—I distance and I—Pt—I angle are 2.6484 (4) Å and 92.32 (2)° respectively; other important bond lengths and angles are in Table 1. A search of cis-dihalide complexes of the type M(dppe)X2 [where M = Ni, Pd and Pt; dppe = 1,2-bis(diphenylphosphino)ethane; X = Cl, Br and I] in the CSD (Version 5.28, 2007) reveals 23 entries. This resulted in the following statistics: the average distances of Pt—Cl (4 entries), Pd—Cl (3 entries) and Ni—Cl (10 entries) are 2.356 Å, 2.362 Å and 2.200 Å respectively; the average Ni—Br distances (2 entries) are 2.330 Å and the average Pd—I (2 entries) and Ni—I distances (1 entry) are 2.658 Å and 2.527 Å respectively. Intermolecular contacts of the type C(1)—H(1 A)···I(1) are present with a C···I distance of 3.873 (5) Å (details in Table 2). These interconnect the title molecules into columns propagated in the [001] direction.