Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809052660/nk2017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536809052660/nk2017Isup2.hkl |
CCDC reference: 766669
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.016 Å
- R factor = 0.032
- wR factor = 0.067
- Data-to-parameter ratio = 24.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Pt1 -- Br1 .. 8.75 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C8 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Pt1 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang .. 16 PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C3 - C4 ... 1.41 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C1 - C2 ... 1.33 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C5 - C6 ... 1.37 Ang. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 4 PLAT234_ALERT_4_C Large Hirshfeld Difference C6 -- C7 .. 0.17 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 6
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.49 From the CIF: _reflns_number_total 2514 Count of symmetry unique reflns 1491 Completeness (_total/calc) 168.61% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1023 Fraction of Friedel pairs measured 0.686 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 11 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 7 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To a solution of cyclooctadienedimethylplatinum(II) (0.1677 g, 0.503 mmol) in CH2Cl2/MeOH (15 ml/15 ml) was added acetyl bromide (0.0740 g, 0.602 mmol), and stirred for 5 h at room temperature. The solvent was removed under vacuum, the residue was washed with pentane and dried, to give a white powder (0.1611 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a methanol solution.
H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.98 (CH), 0.97 (CH2) or 0.96 (CH3) Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C)]. The highest peak (0.92 e Å-3) and the deepest hole (-1.27 e Å-3) in the difference Fourier map are located 0.95 and 0.56 Å from the atoms Pt1 and Br1, respectively.
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms. |
[PtBr(CH3)(C8H12)] | F(000) = 728 |
Mr = 398.21 | Dx = 2.624 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3683 reflections |
a = 7.1013 (15) Å | θ = 2.4–28.4° |
b = 11.184 (2) Å | µ = 17.82 mm−1 |
c = 12.691 (3) Å | T = 296 K |
V = 1007.9 (4) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.22 × 0.12 mm |
Bruker SMART 1000 CCD diffractometer | 2514 independent reflections |
Radiation source: fine-focus sealed tube | 1988 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
ω scans | θmax = 28.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −8→9 |
Tmin = 0.537, Tmax = 1.000 | k = −15→8 |
7369 measured reflections | l = −15→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0196P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2514 reflections | Δρmax = 0.92 e Å−3 |
101 parameters | Δρmin = −1.27 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1023 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (3) |
[PtBr(CH3)(C8H12)] | V = 1007.9 (4) Å3 |
Mr = 398.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.1013 (15) Å | µ = 17.82 mm−1 |
b = 11.184 (2) Å | T = 296 K |
c = 12.691 (3) Å | 0.25 × 0.22 × 0.12 mm |
Bruker SMART 1000 CCD diffractometer | 2514 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1988 reflections with I > 2σ(I) |
Tmin = 0.537, Tmax = 1.000 | Rint = 0.041 |
7369 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.067 | Δρmax = 0.92 e Å−3 |
S = 1.04 | Δρmin = −1.27 e Å−3 |
2514 reflections | Absolute structure: Flack (1983), 1023 Friedel pairs |
101 parameters | Absolute structure parameter: −0.02 (3) |
0 restraints |
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 | 0.14514 (4) | 0.09470 (4) | 0.38595 (2) | 0.03996 (10) | |
Br1 | −0.13276 (14) | 0.10500 (13) | 0.27310 (7) | 0.0679 (3) | |
C1 | 0.0998 (13) | −0.1007 (10) | 0.4243 (7) | 0.052 (2) | |
H1 | 0.0112 | −0.1408 | 0.3768 | 0.063* | |
C2 | 0.0164 (14) | −0.0373 (11) | 0.5001 (7) | 0.059 (3) | |
H2 | −0.1215 | −0.0403 | 0.5006 | 0.071* | |
C3 | 0.109 (2) | −0.0160 (13) | 0.6061 (8) | 0.091 (4) | |
H3A | 0.0092 | −0.0039 | 0.6575 | 0.110* | |
H3B | 0.1742 | −0.0887 | 0.6258 | 0.110* | |
C4 | 0.2370 (16) | 0.0801 (14) | 0.6157 (9) | 0.091 (4) | |
H4A | 0.3361 | 0.0563 | 0.6640 | 0.109* | |
H4B | 0.1715 | 0.1472 | 0.6474 | 0.109* | |
C5 | 0.3254 (13) | 0.1214 (11) | 0.5168 (7) | 0.066 (3) | |
H5 | 0.3742 | 0.2032 | 0.5213 | 0.079* | |
C6 | 0.4194 (13) | 0.0527 (11) | 0.4448 (9) | 0.060 (3) | |
H6 | 0.5218 | 0.0947 | 0.4086 | 0.072* | |
C7 | 0.4495 (15) | −0.0771 (15) | 0.4554 (9) | 0.082 (4) | |
H7A | 0.4850 | −0.0929 | 0.5279 | 0.098* | |
H7B | 0.5562 | −0.0985 | 0.4116 | 0.098* | |
C8 | 0.2914 (17) | −0.1587 (11) | 0.4282 (9) | 0.083 (4) | |
H8A | 0.2879 | −0.2229 | 0.4795 | 0.099* | |
H8B | 0.3171 | −0.1943 | 0.3600 | 0.099* | |
C9 | 0.2351 (11) | 0.2549 (9) | 0.3069 (7) | 0.043 (2) | |
H9A | 0.3702 | 0.2569 | 0.3041 | 0.064* | |
H9B | 0.1900 | 0.3235 | 0.3447 | 0.064* | |
H9C | 0.1854 | 0.2558 | 0.2365 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03947 (15) | 0.03876 (19) | 0.04166 (15) | −0.0015 (2) | −0.00064 (15) | 0.00082 (18) |
Br1 | 0.0593 (5) | 0.0812 (9) | 0.0631 (5) | 0.0112 (9) | −0.0145 (5) | 0.0043 (6) |
C1 | 0.062 (6) | 0.030 (5) | 0.065 (6) | −0.018 (6) | −0.020 (4) | 0.009 (5) |
C2 | 0.055 (6) | 0.064 (8) | 0.059 (6) | −0.017 (6) | 0.006 (5) | 0.012 (6) |
C3 | 0.130 (11) | 0.100 (11) | 0.045 (6) | 0.011 (10) | 0.012 (7) | 0.012 (7) |
C4 | 0.079 (7) | 0.128 (14) | 0.066 (7) | 0.002 (10) | −0.021 (6) | −0.017 (11) |
C5 | 0.057 (6) | 0.078 (10) | 0.063 (6) | −0.004 (7) | −0.025 (5) | −0.024 (6) |
C6 | 0.035 (5) | 0.059 (8) | 0.086 (7) | −0.008 (5) | −0.013 (5) | 0.009 (6) |
C7 | 0.060 (6) | 0.095 (12) | 0.089 (8) | 0.020 (9) | −0.017 (6) | −0.003 (9) |
C8 | 0.106 (10) | 0.045 (8) | 0.097 (9) | 0.009 (8) | −0.006 (7) | 0.006 (7) |
C9 | 0.038 (4) | 0.029 (6) | 0.061 (5) | −0.008 (5) | 0.004 (4) | 0.007 (5) |
Pt1—C5 | 2.118 (8) | C4—H4A | 0.9700 |
Pt1—C6 | 2.138 (9) | C4—H4B | 0.9700 |
Pt1—C9 | 2.151 (9) | C5—C6 | 1.367 (14) |
Pt1—C2 | 2.261 (10) | C5—H5 | 0.9800 |
Pt1—C1 | 2.262 (11) | C6—C7 | 1.473 (18) |
Pt1—Br1 | 2.4410 (11) | C6—H6 | 0.9800 |
C1—C2 | 1.334 (13) | C7—C8 | 1.488 (17) |
C1—C8 | 1.508 (14) | C7—H7A | 0.9700 |
C1—H1 | 0.9800 | C7—H7B | 0.9700 |
C2—C3 | 1.515 (13) | C8—H8A | 0.9700 |
C2—H2 | 0.9800 | C8—H8B | 0.9700 |
C3—C4 | 1.415 (17) | C9—H9A | 0.9600 |
C3—H3A | 0.9700 | C9—H9B | 0.9600 |
C3—H3B | 0.9700 | C9—H9C | 0.9600 |
C4—C5 | 1.478 (14) | ||
C5—Pt1—C6 | 37.5 (4) | C5—C4—H4A | 108.3 |
C5—Pt1—C9 | 93.9 (4) | C3—C4—H4B | 108.3 |
C6—Pt1—C9 | 94.3 (4) | C5—C4—H4B | 108.3 |
C5—Pt1—C2 | 80.5 (4) | H4A—C4—H4B | 107.4 |
C6—Pt1—C2 | 90.1 (4) | C6—C5—C4 | 126.8 (12) |
C9—Pt1—C2 | 164.3 (4) | C6—C5—Pt1 | 72.1 (5) |
C5—Pt1—C1 | 93.1 (4) | C4—C5—Pt1 | 111.4 (7) |
C6—Pt1—C1 | 80.9 (4) | C6—C5—H5 | 113.1 |
C9—Pt1—C1 | 161.4 (4) | C4—C5—H5 | 113.1 |
C2—Pt1—C1 | 34.3 (3) | Pt1—C5—H5 | 113.1 |
C5—Pt1—Br1 | 160.4 (3) | C5—C6—C7 | 124.3 (11) |
C6—Pt1—Br1 | 162.1 (3) | C5—C6—Pt1 | 70.4 (5) |
C9—Pt1—Br1 | 85.8 (2) | C7—C6—Pt1 | 112.3 (7) |
C2—Pt1—Br1 | 94.6 (2) | C5—C6—H6 | 114.0 |
C1—Pt1—Br1 | 93.3 (2) | C7—C6—H6 | 114.0 |
C2—C1—C8 | 127.3 (9) | Pt1—C6—H6 | 114.0 |
C2—C1—Pt1 | 72.8 (7) | C6—C7—C8 | 118.3 (10) |
C8—C1—Pt1 | 107.1 (7) | C6—C7—H7A | 107.7 |
C2—C1—H1 | 113.7 | C8—C7—H7A | 107.7 |
C8—C1—H1 | 113.7 | C6—C7—H7B | 107.7 |
Pt1—C1—H1 | 113.7 | C8—C7—H7B | 107.7 |
C1—C2—C3 | 122.1 (10) | H7A—C7—H7B | 107.1 |
C1—C2—Pt1 | 72.9 (6) | C7—C8—C1 | 115.1 (10) |
C3—C2—Pt1 | 107.0 (8) | C7—C8—H8A | 108.5 |
C1—C2—H2 | 115.5 | C1—C8—H8A | 108.5 |
C3—C2—H2 | 115.5 | C7—C8—H8B | 108.5 |
Pt1—C2—H2 | 115.5 | C1—C8—H8B | 108.5 |
C4—C3—C2 | 118.3 (10) | H8A—C8—H8B | 107.5 |
C4—C3—H3A | 107.7 | Pt1—C9—H9A | 109.5 |
C2—C3—H3A | 107.7 | Pt1—C9—H9B | 109.5 |
C4—C3—H3B | 107.7 | H9A—C9—H9B | 109.5 |
C2—C3—H3B | 107.7 | Pt1—C9—H9C | 109.5 |
H3A—C3—H3B | 107.1 | H9A—C9—H9C | 109.5 |
C3—C4—C5 | 116.0 (10) | H9B—C9—H9C | 109.5 |
C3—C4—H4A | 108.3 | ||
C5—Pt1—C1—C2 | 68.1 (6) | C9—Pt1—C5—C6 | −92.0 (7) |
C6—Pt1—C1—C2 | 103.7 (6) | C2—Pt1—C5—C6 | 102.8 (7) |
C9—Pt1—C1—C2 | −179.9 (9) | C1—Pt1—C5—C6 | 70.7 (7) |
Br1—Pt1—C1—C2 | −93.3 (5) | Br1—Pt1—C5—C6 | 179.4 (7) |
C5—Pt1—C1—C8 | −56.6 (7) | C6—Pt1—C5—C4 | −123.3 (13) |
C6—Pt1—C1—C8 | −21.0 (7) | C9—Pt1—C5—C4 | 144.7 (9) |
C9—Pt1—C1—C8 | 55.4 (13) | C2—Pt1—C5—C4 | −20.6 (9) |
C2—Pt1—C1—C8 | −124.7 (9) | C1—Pt1—C5—C4 | −52.6 (9) |
Br1—Pt1—C1—C8 | 142.0 (7) | Br1—Pt1—C5—C4 | 56.1 (15) |
C8—C1—C2—C3 | −0.9 (18) | C4—C5—C6—C7 | −0.5 (16) |
Pt1—C1—C2—C3 | −99.6 (10) | Pt1—C5—C6—C7 | −104.2 (10) |
C8—C1—C2—Pt1 | 98.8 (11) | C4—C5—C6—Pt1 | 103.7 (9) |
C5—Pt1—C2—C1 | −110.0 (6) | C9—Pt1—C6—C5 | 90.8 (7) |
C6—Pt1—C2—C1 | −73.7 (6) | C2—Pt1—C6—C5 | −74.1 (7) |
C9—Pt1—C2—C1 | 179.9 (11) | C1—Pt1—C6—C5 | −107.3 (8) |
Br1—Pt1—C2—C1 | 89.1 (5) | Br1—Pt1—C6—C5 | −179.4 (8) |
C5—Pt1—C2—C3 | 9.2 (8) | C5—Pt1—C6—C7 | 120.0 (12) |
C6—Pt1—C2—C3 | 45.6 (8) | C9—Pt1—C6—C7 | −149.1 (9) |
C9—Pt1—C2—C3 | −60.9 (16) | C2—Pt1—C6—C7 | 45.9 (9) |
C1—Pt1—C2—C3 | 119.2 (10) | C1—Pt1—C6—C7 | 12.7 (9) |
Br1—Pt1—C2—C3 | −151.7 (8) | Br1—Pt1—C6—C7 | −59.4 (15) |
C1—C2—C3—C4 | 84.4 (16) | C5—C6—C7—C8 | 79.3 (14) |
Pt1—C2—C3—C4 | 4.3 (14) | Pt1—C6—C7—C8 | −1.6 (14) |
C2—C3—C4—C5 | −22.8 (17) | C6—C7—C8—C1 | −17.9 (16) |
C3—C4—C5—C6 | −53.1 (15) | C2—C1—C8—C7 | −54.7 (15) |
C3—C4—C5—Pt1 | 30.0 (14) | Pt1—C1—C8—C7 | 26.4 (12) |
Experimental details
Crystal data | |
Chemical formula | [PtBr(CH3)(C8H12)] |
Mr | 398.21 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 7.1013 (15), 11.184 (2), 12.691 (3) |
V (Å3) | 1007.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 17.82 |
Crystal size (mm) | 0.25 × 0.22 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.537, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7369, 2514, 1988 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.671 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.067, 1.04 |
No. of reflections | 2514 |
No. of parameters | 101 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −1.27 |
Absolute structure | Flack (1983), 1023 Friedel pairs |
Absolute structure parameter | −0.02 (3) |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
In the title complex, [PtBr(CH3)(C8H12)], the central PtII ion lies in a distorted square-planar environment defined by the Br and methyl C atoms and the two mid-points (M1, M2) of the π-coordinated double bonds of cycloocta-1,5-diene (cod) ligand (M1 and M2 denote the mid-points of the olefinic bonds C1—C2 and C5—C6, respectively) (Fig. 1). The Pt, Br, C9 atoms and the mid-points lie in a coordination plane with the largest deviation of 0.018 Å (M2) from the least-squares plane, and with bond angles in the range of 85.4°–94.5°. Because of the different trans influences of the Br atom and the methyl group, the Pt—C bonds trans to C9 of the methyl group (2.261 (10)–2.262 (11) Å) are longer than those trans to the Br atom (2.118 (8)–2.138 (9) Å). The cod ligand coordinates to the Pt atom in the twist-boat conformation with the coordinated double-bond lengths of 1.334 (13) and 1.367 (14) Å, and the cod ring angles lie in the range of 115.1 (10)°–127.3 (9)°.