Dichloro­[(5,6:12,13-η⁴)-penta­cyclo­[8.4.0.0^3,8.0^4,14.0^7,11]­tetra­deca-5,12-diene]platinum(II)

The title compound, [PtCl₂(C₁₄H₁₆)], contains a square-planar d⁸ platinum(II) center which is coordinated by two Cl atoms and the double bonds of a rigid polycyclic ligand containing a 1,4-cyclo­octa­diene subunit. This compound is an inter­esting substrate for additional mechanistic studies of catalytically active metal complexes.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.056
• wR factor = 0.146
• Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT410_ALERT_2_B Short Intra H...H Contact  H2B    ..  H9B     ..       1.86 Ang.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.42
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         12

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Dichloro[(5,6,12,13-η)-pentacyclo[8.4.0.0^3,8.0^4,14.0^7,11]tetradeca- 5,12-diene]platinum(II)

Crystal data

[PtCl2(C14H16)]	F(000) = 848
Mr = 450.26	Dx = 2.479 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 6.6686 (10) Å	θ = 4.7–16.8°
b = 13.648 (3) Å	µ = 25.58 mm^−1
c = 13.321 (3) Å	T = 295 K
β = 95.794 (18)°	Polyhedron, light brown
V = 1206.2 (4) Å^3	0.32 × 0.26 × 0.16 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.086
non–profiled ω/2θ scans	θmax = 70.0°, θmin = 4.7°
Absorption correction: analytical (see. N.W. Alcock (1970). Cryst. Computing, p271)	h = −8→0
Tmin = 0.019, Tmax = 0.141	k = 0→16
2494 measured reflections	l = −16→16
2287 independent reflections	3 standard reflections every 60 min
2222 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.1018P)^2 + 4.3395P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.056	(Δ/σ)max < 0.001
wR(F^2) = 0.146	Δρmax = 5.65 e Å^−3
S = 1.20	Δρmin = −2.33 e Å^−3
2287 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
155 parameters	Extinction coefficient: 0.0037 (3)
0 restraints

Special details

Experimental. 1H NMR (CD2Cl2, 500?MHz): δ = 5.54 (broad s with Pt satellites, 5-, 6-, 12-, 13-H), 3.65 (broad s, 4-, 7-, 11-, 14-H), 2.36 (d, 2-, 9-Hendo), 2.14 (broad s, 1-, 3-, 8-, 10-H), 1.13 (d, 2-, 9-Hexo)p.p.m.; 2 J2endo,2exo = 2 J9endo,9exo = 12.5?Hz, JPt,H = 37?Hz; 13 C NMR (CD2Cl2, 125.7?MHz): δ = 99.0 (C-5, -6, -12, -13), 54.1 (C-4, -7, -11, -14), 39.6 (C-1, -3, -8, -10), 33.3 (C-2, -9)p.p.m.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pt	0.13680 (4)	0.08579 (2)	0.12378 (2)	0.0272 (3)
Cl1	−0.1517 (3)	0.01191 (15)	0.16546 (19)	0.0451 (5)
Cl2	0.3173 (3)	−0.05358 (15)	0.17382 (17)	0.0418 (5)
C6	−0.0109 (11)	0.2273 (6)	0.1275 (6)	0.0305 (15)
H6	−0.082	0.2025	0.1785	0.037*
C7	0.1364 (12)	0.3094 (6)	0.1488 (6)	0.0314 (16)
H7	0.1129	0.3392	0.2135	0.038*
C1	0.4121 (13)	0.3074 (6)	−0.0379 (7)	0.0380 (18)
H1	0.539	0.3042	−0.069	0.046*
C11	0.3637 (12)	0.2812 (6)	0.1524 (6)	0.0315 (16)
H11	0.4299	0.3001	0.2186	0.038*
C5	−0.0399 (12)	0.1885 (6)	0.0297 (7)	0.0328 (17)
H5	−0.1262	0.1357	0.015	0.039*
C9	0.3123 (13)	0.4402 (6)	0.0822 (8)	0.0397 (19)
H9A	0.3356	0.469	0.1489	0.048*
H9B	0.3297	0.4895	0.0313	0.048*
C10	0.4461 (12)	0.3492 (6)	0.0706 (6)	0.0336 (17)
H10	0.5887	0.3648	0.0887	0.04*
C3	0.0721 (13)	0.3481 (6)	−0.0448 (7)	0.0375 (18)
H3	−0.0506	0.3754	−0.0809	0.045*
C12	0.4079 (11)	0.1738 (6)	0.1356 (6)	0.0297 (15)
H12	0.4564	0.1337	0.1891	0.036*
C14	0.3020 (13)	0.2066 (6)	−0.0447 (6)	0.0337 (16)
H14	0.3261	0.1761	−0.109	0.04*
C13	0.3743 (12)	0.1369 (6)	0.0389 (7)	0.0326 (16)
H13	0.3957	0.071	0.0258	0.039*
C8	0.1069 (13)	0.3899 (6)	0.0651 (7)	0.0327 (16)
H8	−0.0014	0.4352	0.0785	0.039*
C4	0.0707 (13)	0.2338 (6)	−0.0496 (6)	0.0351 (17)
H4	0.0054	0.2138	−0.1157	0.042*
C2	0.2567 (14)	0.3697 (6)	−0.1012 (6)	0.0386 (18)
H2A	0.2374	0.3479	−0.1708	0.046*
H2B	0.2919	0.4387	−0.0989	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt	0.0286 (3)	0.0239 (3)	0.0286 (3)	−0.00016 (9)	0.00041 (17)	0.00155 (9)
Cl1	0.0385 (11)	0.0361 (10)	0.0613 (14)	−0.0060 (8)	0.0084 (9)	0.0113 (9)
Cl2	0.0444 (11)	0.0295 (10)	0.0492 (12)	0.0061 (8)	−0.0059 (9)	0.0062 (8)
C6	0.027 (4)	0.029 (4)	0.035 (4)	0.003 (3)	0.007 (3)	0.003 (3)
C7	0.040 (4)	0.028 (4)	0.026 (3)	−0.002 (3)	0.007 (3)	0.000 (3)
C1	0.038 (4)	0.036 (4)	0.042 (5)	−0.003 (3)	0.010 (3)	0.007 (3)
C11	0.036 (4)	0.028 (4)	0.029 (4)	−0.004 (3)	−0.002 (3)	0.003 (3)
C5	0.030 (4)	0.030 (4)	0.036 (4)	0.003 (3)	−0.007 (3)	0.006 (3)
C9	0.042 (5)	0.024 (4)	0.053 (5)	−0.001 (3)	0.002 (4)	0.001 (4)
C10	0.037 (4)	0.024 (4)	0.042 (4)	−0.007 (3)	0.008 (3)	0.002 (3)
C3	0.039 (4)	0.031 (4)	0.041 (5)	0.001 (3)	−0.003 (3)	0.007 (3)
C12	0.028 (3)	0.028 (4)	0.033 (4)	−0.001 (3)	0.000 (3)	0.009 (3)
C14	0.043 (4)	0.029 (4)	0.029 (4)	−0.002 (3)	0.007 (3)	0.001 (3)
C13	0.031 (4)	0.026 (3)	0.043 (4)	0.003 (3)	0.014 (3)	0.003 (3)
C8	0.038 (4)	0.025 (3)	0.037 (4)	0.005 (3)	0.007 (3)	0.005 (3)
C4	0.046 (5)	0.034 (4)	0.024 (4)	−0.001 (3)	−0.007 (3)	0.000 (3)
C2	0.054 (5)	0.033 (4)	0.029 (4)	−0.009 (4)	0.002 (3)	0.005 (3)

Geometric parameters (Å, º)

Pt—C5	2.151 (8)	C5—H5	0.93
Pt—C13	2.153 (7)	C9—C8	1.528 (12)
Pt—C12	2.163 (7)	C9—C10	1.546 (12)
Pt—C6	2.171 (7)	C9—H9A	0.97
Pt—Cl1	2.290 (2)	C9—H9B	0.97
Pt—Cl2	2.3129 (19)	C10—H10	0.98
C6—C5	1.402 (12)	C3—C2	1.534 (13)
C6—C7	1.498 (11)	C3—C4	1.562 (11)
C6—H6	0.93	C3—C8	1.567 (12)
C7—C11	1.560 (11)	C3—H3	0.98
C7—C8	1.562 (11)	C12—C13	1.380 (12)
C7—H7	0.98	C12—H12	0.93
C1—C2	1.527 (12)	C14—C13	1.507 (11)
C1—C10	1.550 (12)	C14—C4	1.581 (12)
C1—C14	1.557 (11)	C14—H14	0.98
C1—H1	0.98	C13—H13	0.93
C11—C12	1.516 (11)	C8—H8	0.98
C11—C10	1.572 (11)	C4—H4	0.98
C11—H11	0.98	C2—H2A	0.97
C5—C4	1.484 (12)	C2—H2B	0.97
C5—Pt—C13	82.7 (3)	H9A—C9—H9B	109.8
C5—Pt—C12	94.9 (3)	C9—C10—C1	110.9 (7)
C13—Pt—C12	37.3 (3)	C9—C10—C11	99.2 (7)
C5—Pt—C6	37.8 (3)	C1—C10—C11	113.7 (6)
C13—Pt—C6	94.8 (3)	C9—C10—H10	110.9
C12—Pt—C6	83.2 (3)	C1—C10—H10	110.9
C5—Pt—Cl1	90.2 (2)	C11—C10—H10	110.9
C13—Pt—Cl1	162.0 (3)	C2—C3—C4	100.0 (7)
C12—Pt—Cl1	160.7 (2)	C2—C3—C8	109.7 (7)
C6—Pt—Cl1	89.5 (2)	C4—C3—C8	113.7 (7)
C5—Pt—Cl2	160.5 (2)	C2—C3—H3	111
C13—Pt—Cl2	91.6 (2)	C4—C3—H3	111
C12—Pt—Cl2	91.6 (2)	C8—C3—H3	111
C6—Pt—Cl2	161.7 (2)	C13—C12—C11	118.4 (7)
Cl1—Pt—Cl2	89.63 (8)	C13—C12—Pt	71.0 (4)
C5—C6—C7	119.0 (7)	C11—C12—Pt	112.0 (5)
C5—C6—Pt	70.3 (4)	C13—C12—H12	120.8
C7—C6—Pt	112.3 (5)	C11—C12—H12	120.8
C5—C6—H6	120.5	Pt—C12—H12	87.3
C7—C6—H6	120.5	C13—C14—C1	113.7 (7)
Pt—C6—H6	87.6	C13—C14—C4	114.6 (6)
C6—C7—C11	115.9 (6)	C1—C14—C4	104.3 (6)
C6—C7—C8	111.0 (7)	C13—C14—H14	108
C11—C7—C8	104.4 (6)	C1—C14—H14	108
C6—C7—H7	108.4	C4—C14—H14	108
C11—C7—H7	108.4	C12—C13—C14	118.0 (7)
C8—C7—H7	108.4	C12—C13—Pt	71.7 (4)
C2—C1—C10	109.8 (7)	C14—C13—Pt	113.3 (5)
C2—C1—C14	99.8 (7)	C12—C13—H13	121
C10—C1—C14	113.8 (6)	C14—C13—H13	121
C2—C1—H1	111	Pt—C13—H13	85.4
C10—C1—H1	111	C9—C8—C7	99.4 (7)
C14—C1—H1	111	C9—C8—C3	110.4 (7)
C12—C11—C7	115.9 (6)	C7—C8—C3	114.0 (7)
C12—C11—C10	112.4 (7)	C9—C8—H8	110.8
C7—C11—C10	103.8 (6)	C7—C8—H8	110.8
C12—C11—H11	108.1	C3—C8—H8	110.8
C7—C11—H11	108.1	C5—C4—C3	112.8 (7)
C10—C11—H11	108.1	C5—C4—C14	115.2 (6)
C6—C5—C4	118.2 (7)	C3—C4—C14	103.4 (7)
C6—C5—Pt	71.9 (4)	C5—C4—H4	108.4
C4—C5—Pt	113.8 (5)	C3—C4—H4	108.4
C6—C5—H5	120.9	C14—C4—H4	108.4
C4—C5—H5	120.9	C1—C2—C3	99.0 (6)
Pt—C5—H5	84.8	C1—C2—H2A	112
C8—C9—C10	98.2 (7)	C3—C2—H2A	112
C8—C9—H9A	112.1	C1—C2—H2B	112
C10—C9—H9A	112.1	C3—C2—H2B	112
C8—C9—H9B	112.1	H2A—C2—H2B	109.7
C10—C9—H9B	112.1