Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103020869/ob1141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020869/ob1141Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103020869/ob1141IIsup3.hkl |
CCDC references: 226097; 226098
[PtCl2(bpy)] was prepared according to the method reported by Morgan & Burstall (1934). [PtCl2(phen)] was prepared in a similar way, using phen as a starting material. The resulting yellow precipitates of [PtCl2(bpy)] and [PtCl2(phen)] were recrystallized from acetone and N,N-dimethylformamide, respectively. An aqueous suspension of [PtCl2(bpy)] (0.33 g, 0.78 mmol) containing (1R,2R)-1,2-diaminocyclohexane (0.089 g, 0.78 mmol) was refluxed for 3 h. To the resulting clear yellow solution was added an aqueous solution of an excess amount of NH4PF6 (0.30 g, 1.8 mmol). The solution was left to stand at room temperature, and pale-yellow needle-shaped crystals of (I) were produced (yield 52%). The complex (II) was obtained in a similar manner, using [PtCl2(phen)]. Recrystallization from methanol/acetone gave pale-yellow needle-shaped crystals (yield 57%).
For (I), 1H NMR (DMSO-d6, δ, p.p.m.): 1.19 (5, 2H, CH2), 1.39 (4, 2H, CH2), 1.58 (d, 2H, CH2), 2.05 (s, 2H, CH2), 2.57 (s, 2H, CH), 6.36 (t, 2H, NH2), 6.90 (d, 2H, NH2), 7.97 (t, 2H, bpy), 8.57 (t, 2H, bpy), 8.76 (d, 4H, bpy); IR (KBr, cm−1): 892.19, 563.28 (νPF6). For (II), 1H NMR (DMSO-d6, δ, p.p.m.): 1.22 (d, 2H, CH2), 1.45 (d, 2H, CH2), 1.61 (d, 2H, CH2), 2.11 (d, 2H, CH2), 6.55 (d, 2H, NH2), 7.15 (d, 2H, NH2), 8.31 (dd, 2H, phen), 8.37 (s, 2H, phen), 9.19 (d, 4H, bpy); IR (KBr, cm−1): 861.32, 557.50 (νPF6).
H atoms were positioned geometrically and fixed [Uiso(H) = Ueq(parent atom)]. The PLATON/ADDSYM (Spec, 2002) results suggested the existence of a pseudo-centre of symmetry for both crystal structures. The pseudo-space groups of (I) and (II) are C2/c and Pnma, respectively. However, these were rejected because both structures contain the chiral ligand. The absolute structures of (I) and (II) were assigned based on the known chirality of the (1R,2R)-1,2-diaminocyclohexane ligand and were confirmed by anomalous dispersion effects. The crystal structure of (II) has voids of 42 Å3 without detectable electron density (> 0.5 e Å−3). The Dm of (II) is consistent with the crystal containing no solvent molecules.
For both compounds, data collection: CrystalClear (Rigaku MSC/SSI, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation/Rigaku, 2000); program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
[Pt(C6H14N2)(C10H8N2)](PF6)2 | F(000) = 1448 |
Mr = 755.40 | Dx = 2.249 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.7107 Å |
a = 15.534 (1) Å | Cell parameters from 4092 reflections |
b = 17.448 (2) Å | θ = 3.1–27.5° |
c = 8.2424 (7) Å | µ = 6.52 mm−1 |
β = 93.256 (4)° | T = 173 K |
V = 2230.4 (3) Å3 | Needle, pale yellow |
Z = 4 | 0.68 × 0.20 × 0.16 mm |
Rigaku/MSC Mercury CCD diffractometer | 4820 reflections with I > 2σ(I) |
Detector resolution: 14.62 pixels mm-1 | Rint = 0.050 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: numerical (Higashi, 1999) | h = −17→20 |
Tmin = 0.254, Tmax = 0.713 | k = −22→22 |
8699 measured reflections | l = −10→10 |
5075 independent reflections |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0273P)2 + 6.5862P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.032 | (Δ/σ)max = 0.024 |
wR(F2) = 0.077 | Δρmax = 1.63 e Å−3 |
S = 1.04 | Δρmin = −2.16 e Å−3 |
5075 reflections | Absolute structure: Flack (1983), 2446 Friedel pairs |
317 parameters | Absolute structure parameter: 0.04 (2) |
H-atom parameters not refined |
[Pt(C6H14N2)(C10H8N2)](PF6)2 | V = 2230.4 (3) Å3 |
Mr = 755.40 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 15.534 (1) Å | µ = 6.52 mm−1 |
b = 17.448 (2) Å | T = 173 K |
c = 8.2424 (7) Å | 0.68 × 0.20 × 0.16 mm |
β = 93.256 (4)° |
Rigaku/MSC Mercury CCD diffractometer | 5075 independent reflections |
Absorption correction: numerical (Higashi, 1999) | 4820 reflections with I > 2σ(I) |
Tmin = 0.254, Tmax = 0.713 | Rint = 0.050 |
8699 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters not refined |
wR(F2) = 0.077 | Δρmax = 1.63 e Å−3 |
S = 1.04 | Δρmin = −2.16 e Å−3 |
5075 reflections | Absolute structure: Flack (1983), 2446 Friedel pairs |
317 parameters | Absolute structure parameter: 0.04 (2) |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.0000 | 0.33474 (1) | 0.5000 | 0.0177 (1) | |
Pt2 | 0.0000 | 0.00743 (1) | 0.0000 | 0.0173 (1) | |
P1 | −0.1614 (2) | 0.4510 (2) | 1.0169 (4) | 0.0339 (7) | |
P2 | −0.3408 (2) | 0.3943 (2) | 0.4791 (4) | 0.0358 (8) | |
F1 | −0.2250 (9) | 0.5035 (10) | 1.107 (1) | 0.136 (6) | |
F2 | −0.1953 (5) | 0.4875 (7) | 0.8474 (9) | 0.074 (4) | |
F3 | −0.0891 (7) | 0.5138 (7) | 1.026 (1) | 0.093 (4) | |
F4 | −0.1001 (6) | 0.3985 (5) | 0.9188 (9) | 0.054 (2) | |
F5 | −0.1249 (5) | 0.4139 (5) | 1.1831 (9) | 0.050 (2) | |
F6 | −0.2329 (6) | 0.3903 (8) | 1.005 (1) | 0.102 (4) | |
F7 | −0.2700 (8) | 0.3498 (9) | 0.386 (1) | 0.125 (6) | |
F8 | −0.3049 (5) | 0.3571 (6) | 0.6467 (9) | 0.064 (3) | |
F9 | −0.4072 (8) | 0.3292 (8) | 0.445 (1) | 0.101 (4) | |
F10 | −0.4087 (5) | 0.4437 (5) | 0.5756 (8) | 0.046 (2) | |
F11 | −0.3743 (6) | 0.4369 (5) | 0.3163 (8) | 0.052 (2) | |
F12 | −0.2741 (5) | 0.4657 (5) | 0.511 (1) | 0.064 (2) | |
N1 | −0.0725 (7) | 0.2468 (6) | 0.569 (1) | 0.028 (2) | |
N2 | −0.0796 (6) | 0.4230 (6) | 0.559 (1) | 0.022 (2) | |
N3 | 0.0726 (5) | 0.0962 (6) | −0.075 (1) | 0.018 (2) | |
N4 | 0.0747 (8) | −0.0809 (7) | −0.072 (1) | 0.034 (3) | |
C1 | −0.1481 (8) | 0.2524 (8) | 0.641 (2) | 0.034 (3) | |
C2 | −0.1918 (8) | 0.1887 (8) | 0.696 (2) | 0.039 (3) | |
C3 | −0.1587 (9) | 0.1177 (8) | 0.670 (2) | 0.040 (3) | |
C4 | −0.0813 (9) | 0.1114 (7) | 0.592 (2) | 0.032 (3) | |
C5 | −0.0385 (7) | 0.1766 (6) | 0.537 (1) | 0.026 (3) | |
C6 | −0.0310 (5) | 0.4972 (4) | 0.5681 (10) | 0.026 (2) | |
C7 | −0.091 (1) | 0.5666 (8) | 0.555 (2) | 0.042 (3) | |
C8 | −0.0334 (9) | 0.6385 (6) | 0.565 (1) | 0.052 (3) | |
C9 | 0.1441 (7) | 0.0899 (7) | −0.156 (1) | 0.030 (2) | |
C10 | 0.1900 (9) | 0.1541 (8) | −0.200 (2) | 0.042 (3) | |
C11 | 0.1583 (8) | 0.2262 (8) | −0.169 (2) | 0.035 (3) | |
C12 | 0.0824 (9) | 0.2333 (7) | −0.091 (1) | 0.030 (3) | |
C13 | 0.0415 (7) | 0.1684 (7) | −0.047 (1) | 0.020 (2) | |
C14 | 0.0487 (5) | −0.1549 (4) | 0.0013 (10) | 0.022 (1) | |
C15 | 0.0810 (9) | −0.2255 (8) | −0.082 (2) | 0.031 (2) | |
C16 | 0.0484 (7) | −0.2979 (5) | −0.003 (1) | 0.038 (2) | |
H1 | −0.1725 | 0.3019 | 0.6577 | 0.0340* | |
H2 | −0.2402 | 0.1943 | 0.7512 | 0.0391* | |
H3 | −0.1922 | 0.0723 | 0.6984 | 0.0401* | |
H4 | −0.0519 | 0.0599 | 0.5830 | 0.0320* | |
H5 | −0.0727 | 0.4270 | 0.6842 | 0.0222* | |
H6 | −0.1335 | 0.4146 | 0.5306 | 0.0222* | |
H7 | 0.0015 | 0.4997 | 0.6691 | 0.0261* | |
H8 | −0.1243 | 0.5655 | 0.4547 | 0.0415* | |
H9 | −0.1288 | 0.5664 | 0.6422 | 0.0415* | |
H10 | −0.0686 | 0.6822 | 0.5509 | 0.0525* | |
H11 | −0.0043 | 0.6390 | 0.6694 | 0.0525* | |
H12 | 0.1636 | 0.0403 | −0.1808 | 0.0297* | |
H13 | 0.2474 | 0.1482 | −0.2558 | 0.0417* | |
H14 | 0.1847 | 0.2704 | −0.2054 | 0.0348* | |
H15 | 0.0636 | 0.2815 | −0.0619 | 0.0298* | |
H16 | 0.0686 | −0.0854 | −0.1879 | 0.0336* | |
H17 | 0.1334 | −0.0707 | −0.0410 | 0.0336* | |
H18 | 0.0700 | −0.1561 | 0.1140 | 0.0222* | |
H19 | 0.0618 | −0.2247 | −0.1925 | 0.0312* | |
H20 | 0.1425 | −0.2256 | −0.0726 | 0.0312* | |
H21 | 0.0726 | −0.2999 | 0.1049 | 0.0385* | |
H22 | 0.0647 | −0.3407 | −0.0626 | 0.0385* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0173 (3) | 0.0136 (3) | 0.0218 (3) | 0.0000 | −0.0027 (3) | 0.0000 |
Pt2 | 0.0183 (3) | 0.0126 (3) | 0.0205 (3) | 0.0000 | −0.0040 (3) | 0.0000 |
P1 | 0.036 (2) | 0.036 (2) | 0.030 (1) | 0.011 (1) | 0.000 (1) | 0.004 (1) |
P2 | 0.040 (2) | 0.043 (2) | 0.025 (1) | 0.018 (2) | 0.000 (1) | 0.005 (1) |
F1 | 0.21 (1) | 0.14 (1) | 0.063 (5) | 0.14 (1) | 0.069 (7) | 0.038 (7) |
F2 | 0.054 (5) | 0.13 (1) | 0.041 (4) | 0.046 (6) | 0.017 (4) | 0.038 (5) |
F3 | 0.125 (9) | 0.031 (4) | 0.121 (7) | −0.029 (6) | −0.021 (7) | 0.010 (5) |
F4 | 0.072 (5) | 0.040 (4) | 0.051 (4) | 0.022 (4) | 0.019 (4) | 0.005 (4) |
F5 | 0.067 (5) | 0.043 (4) | 0.037 (4) | 0.006 (3) | −0.028 (4) | −0.001 (3) |
F6 | 0.039 (4) | 0.19 (1) | 0.073 (5) | −0.047 (6) | −0.010 (4) | 0.051 (7) |
F7 | 0.17 (1) | 0.14 (1) | 0.076 (6) | 0.125 (9) | 0.080 (7) | 0.061 (7) |
F8 | 0.062 (5) | 0.088 (8) | 0.040 (4) | 0.038 (5) | 0.003 (4) | 0.033 (4) |
F9 | 0.16 (1) | 0.038 (5) | 0.095 (6) | −0.036 (7) | −0.049 (7) | 0.009 (5) |
F10 | 0.040 (3) | 0.046 (4) | 0.052 (4) | 0.013 (3) | 0.014 (3) | 0.008 (4) |
F11 | 0.097 (6) | 0.030 (3) | 0.026 (3) | 0.009 (3) | −0.018 (4) | −0.002 (3) |
F12 | 0.044 (4) | 0.085 (5) | 0.060 (4) | −0.020 (4) | −0.023 (4) | 0.024 (4) |
N1 | 0.033 (6) | 0.019 (5) | 0.031 (5) | 0.007 (4) | −0.003 (4) | 0.004 (4) |
N2 | 0.016 (4) | 0.018 (4) | 0.032 (4) | 0.012 (3) | −0.001 (3) | 0.003 (3) |
N3 | 0.009 (4) | 0.018 (5) | 0.028 (4) | −0.009 (3) | −0.006 (3) | 0.004 (4) |
N4 | 0.041 (6) | 0.020 (5) | 0.042 (5) | −0.007 (4) | 0.018 (5) | −0.001 (4) |
C1 | 0.025 (5) | 0.027 (6) | 0.049 (6) | 0.006 (4) | −0.004 (4) | 0.011 (5) |
C2 | 0.023 (6) | 0.044 (8) | 0.050 (7) | −0.010 (5) | 0.004 (5) | 0.019 (6) |
C3 | 0.042 (8) | 0.027 (7) | 0.050 (8) | −0.017 (6) | −0.003 (6) | 0.015 (6) |
C4 | 0.034 (6) | 0.019 (5) | 0.041 (7) | 0.004 (5) | −0.009 (5) | 0.007 (5) |
C5 | 0.025 (5) | 0.010 (4) | 0.040 (6) | −0.006 (4) | −0.016 (5) | 0.009 (4) |
C6 | 0.040 (4) | 0.018 (3) | 0.020 (4) | 0.003 (3) | 0.004 (3) | 0.000 (3) |
C7 | 0.054 (8) | 0.020 (5) | 0.052 (7) | 0.016 (5) | 0.017 (5) | 0.005 (4) |
C8 | 0.097 (9) | 0.014 (4) | 0.048 (6) | 0.012 (4) | 0.017 (6) | 0.012 (4) |
C9 | 0.026 (5) | 0.023 (6) | 0.040 (5) | −0.005 (4) | 0.005 (4) | 0.000 (4) |
C10 | 0.042 (8) | 0.034 (7) | 0.050 (7) | −0.007 (6) | 0.007 (6) | −0.001 (6) |
C11 | 0.035 (7) | 0.031 (7) | 0.037 (6) | −0.010 (6) | −0.007 (5) | 0.005 (5) |
C12 | 0.043 (7) | 0.019 (5) | 0.026 (5) | −0.016 (5) | −0.010 (5) | 0.002 (4) |
C13 | 0.026 (5) | 0.020 (5) | 0.014 (4) | 0.004 (4) | −0.004 (4) | 0.000 (3) |
C14 | 0.033 (4) | 0.012 (3) | 0.021 (3) | 0.002 (2) | 0.001 (3) | 0.001 (3) |
C15 | 0.030 (4) | 0.022 (5) | 0.042 (5) | 0.005 (4) | 0.005 (4) | 0.005 (4) |
C16 | 0.055 (5) | 0.019 (4) | 0.043 (5) | 0.011 (3) | 0.012 (4) | 0.005 (4) |
Pt1—N1 | 2.005 (11) | C3—H3 | 0.985 |
Pt1—N2 | 2.052 (10) | C4—C5 | 1.41 (2) |
Pt2—N3 | 2.033 (9) | C4—H4 | 1.011 |
Pt2—N4 | 2.037 (12) | C5—C5i | 1.38 (2) |
P1—F1 | 1.57 (1) | C6—C6i | 1.52 (2) |
P1—F2 | 1.597 (9) | C6—C7 | 1.53 (2) |
P1—F3 | 1.57 (1) | C6—H7 | 0.949 |
P1—F4 | 1.577 (9) | C7—C8 | 1.54 (2) |
P1—F5 | 1.590 (8) | C7—H8 | 0.956 |
P1—F6 | 1.53 (1) | C7—H9 | 0.953 |
P2—F7 | 1.58 (1) | C8—C8i | 1.53 (2) |
P2—F8 | 1.599 (9) | C8—H10 | 0.942 |
P2—F9 | 1.55 (1) | C8—H11 | 0.951 |
P2—F10 | 1.607 (9) | C9—C10 | 1.39 (2) |
P2—F11 | 1.595 (8) | C9—H12 | 0.944 |
P2—F12 | 1.632 (9) | C10—C11 | 1.38 (2) |
N1—C1 | 1.35 (2) | C10—H13 | 1.033 |
N1—C5 | 1.36 (2) | C11—C12 | 1.38 (2) |
N2—C6 | 1.50 (1) | C11—H14 | 0.929 |
N2—H5 | 1.031 | C12—C13 | 1.36 (2) |
N2—H6 | 0.869 | C12—H15 | 0.928 |
N3—C9 | 1.33 (1) | C13—C13ii | 1.54 (2) |
N3—C13 | 1.37 (2) | C14—C14ii | 1.51 (2) |
N4—C14 | 1.49 (1) | C14—C15 | 1.51 (2) |
N4—H16 | 0.961 | C14—H18 | 0.968 |
N4—H17 | 0.949 | C15—C16 | 1.52 (2) |
C1—C2 | 1.39 (2) | C15—H19 | 0.941 |
C1—H1 | 0.956 | C15—H20 | 0.954 |
C2—C3 | 1.36 (2) | C16—C16ii | 1.51 (2) |
C2—H2 | 0.908 | C16—H21 | 0.944 |
C3—C4 | 1.40 (2) | C16—H22 | 0.936 |
Pt1···F5iii | 3.453 (8) | F6···C15viii | 3.57 (2) |
Pt1···F5iv | 3.453 (8) | F8···N4viii | 3.25 (2) |
Pt2···F11v | 3.398 (8) | F8···C15viii | 3.27 (2) |
Pt2···F11vi | 3.398 (8) | F9···F9xi | 3.07 (2) |
F1···F11vii | 3.19 (2) | F9···C8xii | 3.45 (2) |
F1···C9viii | 3.26 (2) | F9···F10xi | 3.48 (1) |
F1···C3ix | 3.31 (2) | F10···N4viii | 2.96 (1) |
F1···F12vii | 3.52 (1) | F10···F10xi | 3.03 (1) |
F2···C9viii | 3.07 (2) | F10···C4xiii | 3.23 (2) |
F2···C10viii | 3.42 (2) | F10···C9viii | 3.45 (1) |
F3···F3iv | 2.82 (2) | F10···F11xi | 3.54 (1) |
F3···C16x | 3.35 (2) | F11···C3xiii | 3.20 (2) |
F3···F4iv | 3.57 (1) | F11···C4xiii | 3.22 (2) |
F4···F4iv | 3.31 (2) | F11···C14xiv | 3.22 (1) |
F5···F7vii | 3.09 (2) | F11···N4xiv | 3.26 (1) |
F5···N2vii | 3.14 (1) | F12···C3xiii | 3.19 (2) |
F5···C6iv | 3.41 (1) | F12···C4xiii | 3.47 (2) |
F6···N4viii | 3.06 (2) | N1···C12vii | 3.59 (2) |
F6···F7vii | 3.30 (1) | N3···C4iii | 3.55 (2) |
F6···C14viii | 3.48 (1) | C4···C13vii | 3.59 (2) |
F6···F11vii | 3.56 (1) | C5···C13vii | 3.58 (2) |
N1—Pt1—N1i | 80.1 (6) | C3—C2—H2 | 120.5 |
N1—Pt1—N2 | 98.7 (4) | C2—C3—C4 | 119 (1) |
N1—Pt1—N2i | 176.5 (4) | C2—C3—H3 | 119.1 |
N2—Pt1—N2i | 82.7 (6) | C4—C3—H3 | 121.6 |
N3—Pt2—N3ii | 80.8 (5) | C3—C4—C5 | 121 (1) |
N3—Pt2—N4 | 98.8 (4) | C3—C4—H4 | 120.5 |
N3—Pt2—N4ii | 178.8 (4) | C5—C4—H4 | 118.2 |
N4—Pt2—N4ii | 81.7 (7) | N1—C5—C4 | 118 (1) |
F1—P1—F2 | 89.8 (6) | N1—C5—C5i | 116.2 (7) |
F1—P1—F3 | 92.2 (7) | C4—C5—C5i | 125.6 (7) |
F1—P1—F4 | 177.4 (5) | N2—C6—C6i | 107.7 (6) |
F1—P1—F5 | 91.8 (5) | N2—C6—C7 | 112.3 (9) |
F1—P1—F6 | 87.6 (7) | N2—C6—H7 | 108.9 |
F2—P1—F3 | 87.8 (6) | C6i—C6—C7 | 111.0 (8) |
F2—P1—F4 | 87.8 (5) | C6i—C6—H7 | 108.7 |
F2—P1—F5 | 178.2 (5) | C7—C6—H7 | 108.3 |
F2—P1—F6 | 91.1 (6) | C6—C7—C8 | 107 (1) |
F3—P1—F4 | 88.8 (6) | C6—C7—H8 | 110.0 |
F3—P1—F5 | 91.4 (6) | C6—C7—H9 | 110.2 |
F3—P1—F6 | 178.9 (6) | C8—C7—H8 | 110.2 |
F4—P1—F5 | 90.6 (4) | C8—C7—H9 | 110.5 |
F4—P1—F6 | 91.4 (6) | H8—C7—H9 | 108.7 |
F5—P1—F6 | 89.7 (5) | C7—C8—C8i | 112.3 (8) |
F7—P2—F8 | 90.1 (5) | C7—C8—H10 | 108.8 |
F7—P2—F9 | 91.5 (7) | C7—C8—H11 | 107.3 |
F7—P2—F10 | 176.6 (6) | C8i—C8—H10 | 109.2 |
F7—P2—F11 | 91.3 (5) | C8i—C8—H11 | 109.1 |
F7—P2—F12 | 90.0 (6) | H10—C8—H11 | 110.1 |
F8—P2—F9 | 93.1 (6) | N3—C9—C10 | 121 (1) |
F8—P2—F10 | 89.9 (4) | N3—C9—H12 | 118.2 |
F8—P2—F11 | 176.2 (5) | C10—C9—H12 | 120.5 |
F8—P2—F12 | 89.0 (5) | C9—C10—C11 | 119 (1) |
F9—P2—F10 | 91.9 (6) | C9—C10—H13 | 120.4 |
F9—P2—F11 | 90.4 (5) | C11—C10—H13 | 119.9 |
F9—P2—F12 | 177.4 (6) | C10—C11—C12 | 119 (1) |
F10—P2—F11 | 88.6 (4) | C10—C11—H14 | 121.9 |
F10—P2—F12 | 86.6 (5) | C12—C11—H14 | 118.7 |
F11—P2—F12 | 87.4 (5) | C11—C12—C13 | 118 (1) |
Pt1—N1—C1 | 125.9 (9) | C11—C12—H15 | 119.5 |
Pt1—N1—C5 | 113.8 (8) | C13—C12—H15 | 121.7 |
C1—N1—C5 | 120 (1) | N3—C13—C12 | 122 (1) |
Pt1—N2—C6 | 110.5 (6) | N3—C13—C13ii | 113.4 (6) |
Pt1—N2—H5 | 104.9 | C12—C13—C13ii | 123.6 (7) |
Pt1—N2—H6 | 113.1 | N4—C14—C14ii | 106.7 (6) |
C6—N2—H5 | 82.5 | N4—C14—C15 | 114.8 (9) |
C6—N2—H6 | 129.4 | N4—C14—H18 | 108.7 |
H5—N2—H6 | 109.2 | C14ii—C14—C15 | 110.5 (7) |
Pt2—N3—C9 | 125.6 (8) | C14ii—C14—H18 | 107.5 |
Pt2—N3—C13 | 116.1 (7) | C15—C14—H18 | 108.4 |
C9—N3—C13 | 118.2 (10) | C14—C15—C16 | 110 (1) |
Pt2—N4—C14 | 111.5 (8) | C14—C15—H19 | 109.5 |
Pt2—N4—H16 | 109.0 | C14—C15—H20 | 108.7 |
Pt2—N4—H17 | 109.6 | C16—C15—H19 | 109.4 |
C14—N4—H16 | 108.6 | C16—C15—H20 | 108.6 |
C14—N4—H17 | 109.5 | H19—C15—H20 | 109.8 |
H16—N4—H17 | 108.6 | C15—C16—C16ii | 111.7 (8) |
N1—C1—C2 | 122 (1) | C15—C16—H21 | 108.0 |
N1—C1—H1 | 119.4 | C15—C16—H22 | 109.2 |
C2—C1—H1 | 118.1 | C16ii—C16—H21 | 108.4 |
C1—C2—C3 | 118 (1) | C16ii—C16—H22 | 108.4 |
C1—C2—H2 | 120.7 | H21—C16—H22 | 111.2 |
Symmetry codes: (i) −x, y, −z+1; (ii) −x, y, −z; (iii) x, y, z−1; (iv) −x, y, −z+2; (v) x+1/2, y−1/2, z; (vi) −x−1/2, y−1/2, −z; (vii) x, y, z+1; (viii) x−1/2, y+1/2, z+1; (ix) −x−1/2, y+1/2, −z+2; (x) −x, y+1, −z+1; (xi) −x−1, y, −z+1; (xii) −x−1/2, y−1/2, −z+1; (xiii) −x−1/2, y+1/2, −z+1; (xiv) x−1/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···F2 | 1.031 | 2.612 | 3.26 (1) | 120.2 |
N2—H5···F4 | 1.031 | 2.064 | 3.03 (1) | 154.6 |
N2—H6···F5iii | 0.869 | 2.875 | 3.14 (1) | 100.0 |
N2—H6···F7 | 0.869 | 2.629 | 3.46 (1) | 159.3 |
N2—H6···F12 | 0.869 | 2.356 | 3.11 (1) | 146.0 |
N4—H17···F6xv | 0.949 | 2.198 | 3.06 (1) | 150.7 |
N4—H17···F11v | 0.949 | 2.957 | 3.26 (1) | 100.4 |
N4—H16···F8xv | 0.961 | 2.651 | 3.25 (1) | 120.2 |
N4—H16···F10xv | 0.961 | 2.064 | 2.97 (1) | 155.5 |
Symmetry codes: (iii) x, y, z−1; (v) x+1/2, y−1/2, z; (xv) x+1/2, y−1/2, z−1. |
[Pt(C6H14N2)(C12H8N2)](PF6)2 | Dx = 2.094 Mg m−3 Dm = 2.01 (2) Mg m−3 Dm measured by flotation in bromoform/CCl4 at 303 K |
Mr = 779.42 | Mo Kα radiation, λ = 0.7107 Å |
Orthorhombic, P212121 | Cell parameters from 9155 reflections |
a = 7.3142 (5) Å | θ = 3.1–27.5° |
b = 18.2738 (5) Å | µ = 5.91 mm−1 |
c = 18.4925 (5) Å | T = 293 K |
V = 2471.7 (2) Å3 | Needle, pale yellow |
Z = 4 | 0.70 × 0.14 × 0.10 mm |
F(000) = 1496 |
Rigaku/MSC Mercury CCD diffractometer | 5485 reflections with I > 2σ(I) |
Detector resolution: 7.32 pixels mm-1 | Rint = 0.044 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: numerical (Higashi, 1999) | h = −9→9 |
Tmin = 0.514, Tmax = 0.782 | k = −18→23 |
26208 measured reflections | l = −23→24 |
5570 independent reflections |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0393P)2 + 5.6317P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.047 | (Δ/σ)max = −0.034 |
wR(F2) = 0.105 | Δρmax = 1.81 e Å−3 |
S = 1.26 | Δρmin = −0.79 e Å−3 |
5570 reflections | Absolute structure: Flack (1983), 2413 Friedel pairs |
334 parameters | Absolute structure parameter: 0.21 (2) |
H-atom parameters not refined |
[Pt(C6H14N2)(C12H8N2)](PF6)2 | V = 2471.7 (2) Å3 |
Mr = 779.42 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.3142 (5) Å | µ = 5.91 mm−1 |
b = 18.2738 (5) Å | T = 293 K |
c = 18.4925 (5) Å | 0.70 × 0.14 × 0.10 mm |
Rigaku/MSC Mercury CCD diffractometer | 5570 independent reflections |
Absorption correction: numerical (Higashi, 1999) | 5485 reflections with I > 2σ(I) |
Tmin = 0.514, Tmax = 0.782 | Rint = 0.044 |
26208 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters not refined |
wR(F2) = 0.105 | Δρmax = 1.81 e Å−3 |
S = 1.26 | Δρmin = −0.79 e Å−3 |
5570 reflections | Absolute structure: Flack (1983), 2413 Friedel pairs |
334 parameters | Absolute structure parameter: 0.21 (2) |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.25431 (5) | 0.72160 (1) | 0.18271 (1) | 0.03859 (9) | |
P1 | 0.7442 (5) | 0.8860 (1) | 0.3055 (1) | 0.0561 (5) | |
P2 | 0.2367 (5) | 1.0514 (1) | 0.2494 (1) | 0.0624 (6) | |
F1 | 0.592 (1) | 0.8628 (7) | 0.2498 (6) | 0.095 (4) | |
F2 | 0.898 (1) | 0.8679 (6) | 0.2455 (6) | 0.086 (3) | |
F3 | 0.741 (2) | 0.9675 (3) | 0.2756 (3) | 0.090 (2) | |
F4 | 0.892 (1) | 0.9062 (7) | 0.3637 (5) | 0.096 (3) | |
F5 | 0.586 (1) | 0.9091 (7) | 0.3592 (6) | 0.105 (4) | |
F6 | 0.741 (2) | 0.8063 (4) | 0.3344 (6) | 0.145 (4) | |
F7 | 0.081 (1) | 1.0366 (6) | 0.1942 (5) | 0.094 (3) | |
F8 | 0.389 (1) | 1.0329 (6) | 0.1874 (7) | 0.101 (3) | |
F9 | 0.229 (2) | 1.1349 (4) | 0.2292 (5) | 0.123 (3) | |
F10 | 0.3941 (10) | 1.0707 (6) | 0.3062 (7) | 0.107 (4) | |
F11 | 0.0892 (9) | 1.0682 (4) | 0.3088 (6) | 0.076 (2) | |
F12 | 0.239 (1) | 0.9682 (3) | 0.2718 (3) | 0.080 (2) | |
N1 | 0.264 (2) | 0.6588 (3) | 0.0932 (3) | 0.042 (1) | |
N2 | 0.258 (2) | 0.8018 (3) | 0.1085 (3) | 0.047 (1) | |
N3 | 0.239 (2) | 0.7859 (3) | 0.2728 (3) | 0.045 (1) | |
N4 | 0.259 (2) | 0.6391 (3) | 0.2574 (3) | 0.050 (1) | |
C1 | 0.269 (2) | 0.5874 (5) | 0.0877 (5) | 0.064 (3) | |
C2 | 0.257 (4) | 0.5528 (5) | 0.0196 (5) | 0.103 (5) | |
C3 | 0.253 (3) | 0.5927 (5) | −0.0422 (5) | 0.084 (3) | |
C4 | 0.262 (2) | 0.6679 (4) | −0.0389 (4) | 0.055 (2) | |
C5 | 0.259 (3) | 0.7163 (6) | −0.1004 (5) | 0.081 (3) | |
C6 | 0.251 (2) | 0.7882 (5) | −0.0921 (4) | 0.060 (2) | |
C7 | 0.255 (3) | 0.8221 (4) | −0.0209 (4) | 0.058 (2) | |
C8 | 0.263 (3) | 0.8978 (5) | −0.0094 (5) | 0.073 (3) | |
C9 | 0.267 (3) | 0.9233 (4) | 0.0616 (5) | 0.082 (4) | |
C10 | 0.246 (2) | 0.8739 (4) | 0.1173 (4) | 0.066 (3) | |
C11 | 0.252 (2) | 0.7760 (4) | 0.0382 (3) | 0.044 (2) | |
C12 | 0.264 (2) | 0.6994 (4) | 0.0301 (4) | 0.043 (2) | |
C13 | 0.199 (1) | 0.7406 (5) | 0.3388 (4) | 0.050 (2) | |
C14 | 0.239 (2) | 0.7774 (5) | 0.4082 (4) | 0.058 (2) | |
C15 | 0.222 (2) | 0.7258 (6) | 0.4693 (5) | 0.073 (4) | |
C16 | 0.313 (2) | 0.6557 (7) | 0.4623 (5) | 0.085 (4) | |
C17 | 0.274 (2) | 0.6171 (5) | 0.3908 (4) | 0.060 (3) | |
C18 | 0.308 (1) | 0.6706 (5) | 0.3298 (4) | 0.048 (2) | |
H1 | 0.2941 | 0.5596 | 0.1294 | 0.0636* | |
H2 | 0.2300 | 0.5015 | 0.0173 | 0.1031* | |
H3 | 0.2670 | 0.5690 | −0.0878 | 0.0841* | |
H4 | 0.2652 | 0.6958 | −0.1480 | 0.0809* | |
H5 | 0.2529 | 0.8182 | −0.1341 | 0.0600* | |
H6 | 0.2803 | 0.9303 | −0.0489 | 0.0730* | |
H7 | 0.2674 | 0.9740 | 0.0712 | 0.0821* | |
H8 | 0.2356 | 0.8925 | 0.1651 | 0.0659* | |
H9 | 0.3426 | 0.8078 | 0.2788 | 0.0454* | |
H10 | 0.1567 | 0.8179 | 0.2674 | 0.0454* | |
H11 | 0.1580 | 0.6182 | 0.2597 | 0.0496* | |
H12 | 0.3424 | 0.6077 | 0.2454 | 0.0496* | |
H13 | 0.0733 | 0.7286 | 0.3378 | 0.0502* | |
H14 | 0.3592 | 0.7980 | 0.4066 | 0.0577* | |
H15 | 0.1533 | 0.8162 | 0.4154 | 0.0577* | |
H16 | 0.2842 | 0.7466 | 0.5095 | 0.0731* | |
H17 | 0.0999 | 0.7182 | 0.4790 | 0.0731* | |
H18 | 0.4278 | 0.6577 | 0.4728 | 0.0851* | |
H19 | 0.2439 | 0.6243 | 0.4984 | 0.0851* | |
H20 | 0.3663 | 0.5785 | 0.3873 | 0.0604* | |
H21 | 0.1594 | 0.5971 | 0.3876 | 0.0604* | |
H22 | 0.4346 | 0.6829 | 0.3291 | 0.0482* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0401 (1) | 0.0458 (1) | 0.0299 (1) | −0.0001 (3) | −0.0007 (2) | 0.00104 (9) |
P1 | 0.051 (1) | 0.058 (1) | 0.059 (1) | −0.003 (2) | −0.005 (2) | −0.0016 (8) |
P2 | 0.055 (1) | 0.056 (1) | 0.076 (1) | 0.002 (2) | −0.003 (2) | −0.0157 (10) |
F1 | 0.056 (4) | 0.141 (9) | 0.088 (7) | −0.025 (5) | −0.005 (4) | −0.054 (7) |
F2 | 0.058 (4) | 0.113 (8) | 0.088 (7) | 0.001 (4) | 0.003 (4) | −0.026 (6) |
F3 | 0.112 (5) | 0.068 (3) | 0.090 (4) | 0.014 (6) | 0.028 (7) | 0.003 (3) |
F4 | 0.088 (5) | 0.148 (10) | 0.053 (5) | −0.018 (6) | −0.021 (4) | −0.019 (6) |
F5 | 0.081 (5) | 0.14 (1) | 0.091 (7) | 0.004 (6) | 0.027 (5) | 0.005 (7) |
F6 | 0.166 (9) | 0.073 (4) | 0.196 (9) | 0.028 (8) | 0.03 (1) | 0.043 (5) |
F7 | 0.080 (4) | 0.128 (7) | 0.072 (6) | 0.010 (5) | −0.019 (4) | −0.009 (6) |
F8 | 0.085 (5) | 0.111 (7) | 0.108 (8) | −0.014 (5) | 0.018 (5) | −0.030 (7) |
F9 | 0.153 (9) | 0.063 (3) | 0.153 (7) | −0.018 (7) | −0.02 (1) | 0.010 (4) |
F10 | 0.059 (4) | 0.139 (8) | 0.124 (9) | −0.008 (4) | −0.007 (5) | −0.066 (8) |
F11 | 0.063 (3) | 0.069 (4) | 0.096 (7) | 0.008 (3) | 0.017 (4) | −0.014 (5) |
F12 | 0.081 (4) | 0.061 (3) | 0.100 (4) | 0.007 (5) | 0.003 (6) | −0.005 (3) |
N1 | 0.046 (4) | 0.043 (3) | 0.036 (2) | 0.008 (4) | −0.001 (4) | −0.003 (2) |
N2 | 0.058 (4) | 0.049 (3) | 0.035 (3) | 0.011 (5) | −0.005 (5) | 0.004 (2) |
N3 | 0.047 (4) | 0.054 (3) | 0.035 (3) | 0.007 (6) | −0.001 (4) | 0.001 (2) |
N4 | 0.060 (4) | 0.050 (3) | 0.039 (3) | 0.002 (6) | −0.003 (6) | 0.006 (2) |
C1 | 0.082 (7) | 0.054 (4) | 0.055 (4) | 0.000 (7) | 0.005 (7) | 0.000 (3) |
C2 | 0.19 (1) | 0.053 (5) | 0.063 (5) | −0.04 (1) | 0.03 (1) | −0.013 (4) |
C3 | 0.138 (10) | 0.067 (5) | 0.048 (4) | 0.03 (1) | 0.02 (1) | −0.017 (4) |
C4 | 0.066 (6) | 0.058 (4) | 0.040 (3) | 0.003 (7) | −0.017 (7) | −0.006 (3) |
C5 | 0.101 (9) | 0.100 (8) | 0.042 (4) | 0.02 (1) | 0.035 (7) | −0.007 (4) |
C6 | 0.072 (5) | 0.077 (5) | 0.031 (3) | −0.008 (10) | −0.008 (7) | 0.018 (3) |
C7 | 0.072 (5) | 0.057 (4) | 0.043 (3) | 0.014 (8) | 0.000 (8) | 0.009 (3) |
C8 | 0.096 (8) | 0.064 (5) | 0.059 (5) | 0.001 (10) | −0.001 (10) | 0.031 (4) |
C9 | 0.15 (1) | 0.047 (4) | 0.047 (4) | 0.042 (9) | 0.024 (9) | 0.001 (3) |
C10 | 0.102 (7) | 0.047 (4) | 0.049 (4) | −0.039 (8) | 0.015 (8) | 0.001 (3) |
C11 | 0.053 (4) | 0.055 (4) | 0.025 (3) | 0.022 (7) | −0.012 (5) | 0.001 (2) |
C12 | 0.036 (4) | 0.058 (4) | 0.035 (3) | 0.000 (5) | 0.003 (4) | −0.003 (3) |
C13 | 0.044 (4) | 0.075 (5) | 0.032 (3) | 0.001 (4) | 0.006 (3) | −0.001 (4) |
C14 | 0.068 (5) | 0.074 (5) | 0.031 (3) | 0.028 (8) | −0.007 (5) | 0.001 (3) |
C15 | 0.10 (1) | 0.078 (6) | 0.046 (4) | −0.020 (8) | −0.022 (6) | 0.006 (4) |
C16 | 0.14 (1) | 0.080 (7) | 0.035 (4) | −0.002 (7) | −0.010 (6) | 0.020 (4) |
C17 | 0.075 (8) | 0.068 (5) | 0.039 (3) | −0.003 (6) | −0.006 (5) | 0.017 (3) |
C18 | 0.049 (4) | 0.065 (5) | 0.030 (3) | −0.011 (4) | 0.000 (3) | 0.007 (3) |
Pt1—N1 | 2.015 (5) | C3—H3 | 0.953 |
Pt1—N2 | 2.008 (6) | C4—C5 | 1.44 (1) |
Pt1—N3 | 2.042 (6) | C4—C12 | 1.400 (10) |
Pt1—N4 | 2.046 (6) | C5—C6 | 1.32 (1) |
P1—F1 | 1.576 (10) | C5—H4 | 0.957 |
P1—F2 | 1.614 (10) | C6—C7 | 1.46 (1) |
P1—F3 | 1.590 (6) | C6—H5 | 0.950 |
P1—F4 | 1.570 (10) | C7—C8 | 1.40 (1) |
P1—F5 | 1.58 (1) | C7—C11 | 1.380 (10) |
P1—F6 | 1.551 (8) | C8—C9 | 1.39 (1) |
P2—F7 | 1.553 (10) | C8—H6 | 0.950 |
P2—F8 | 1.64 (1) | C9—C10 | 1.38 (1) |
P2—F9 | 1.572 (7) | C9—H7 | 0.943 |
P2—F10 | 1.60 (1) | C10—H8 | 0.951 |
P2—F11 | 1.569 (9) | C11—C12 | 1.41 (1) |
P2—F12 | 1.575 (6) | C13—C14 | 1.48 (1) |
N1—C1 | 1.31 (1) | C13—C18 | 1.52 (1) |
N1—C12 | 1.383 (9) | C13—H13 | 0.947 |
N2—C10 | 1.331 (10) | C14—C15 | 1.48 (1) |
N2—C11 | 1.384 (8) | C14—H14 | 0.956 |
N3—C13 | 1.50 (1) | C14—H15 | 0.956 |
N3—H9 | 0.864 | C15—C16 | 1.45 (2) |
N3—H10 | 0.844 | C15—H16 | 0.951 |
N4—C18 | 1.50 (1) | C15—H17 | 0.921 |
N4—H11 | 0.834 | C16—C17 | 1.53 (1) |
N4—H12 | 0.864 | C16—H18 | 0.859 |
C1—C2 | 1.41 (1) | C16—H19 | 1.017 |
C1—H1 | 0.941 | C17—C18 | 1.51 (1) |
C2—C3 | 1.35 (1) | C17—H20 | 0.978 |
C2—H2 | 0.960 | C17—H21 | 0.917 |
C3—C4 | 1.38 (1) | C18—H22 | 0.951 |
F1···C5i | 3.35 (2) | F7···N4vi | 3.24 (2) |
F2···N3ii | 2.95 (1) | F7···C17vi | 3.37 (2) |
F2···F12ii | 3.13 (1) | F8···C17iii | 3.24 (2) |
F2···C5i | 3.26 (2) | F8···C18iii | 3.36 (1) |
F2···C10ii | 3.48 (2) | F8···N4iii | 3.38 (2) |
F2···F7ii | 3.49 (2) | F9···N4vi | 3.58 (2) |
F3···F7ii | 3.17 (1) | F9···C6vii | 3.59 (1) |
F3···N4iii | 3.193 (8) | F10···N4iii | 3.06 (2) |
F3···F11ii | 3.20 (1) | F10···C1iii | 3.16 (2) |
F3···C1iii | 3.35 (1) | F10···C6vii | 3.36 (1) |
F4···F12ii | 3.26 (1) | F10···N1iii | 3.51 (1) |
F4···F11ii | 3.45 (1) | F11···N4vi | 3.11 (2) |
F4···C16iv | 3.46 (1) | F11···C1vi | 3.27 (2) |
F4···C14ii | 3.56 (2) | F11···C6vii | 3.41 (1) |
F5···C1iii | 3.56 (2) | F11···N1vi | 3.56 (1) |
F6···F9v | 3.35 (1) | F11···C8vii | 3.59 (1) |
F6···C13ii | 3.56 (2) | C3···C9viii | 3.59 (3) |
N1—Pt1—N2 | 81.6 (2) | C3—C4—C5 | 125.3 (8) |
N1—Pt1—N3 | 178.8 (5) | C3—C4—C12 | 116.8 (7) |
N1—Pt1—N4 | 97.7 (2) | C5—C4—C12 | 117.8 (7) |
N2—Pt1—N3 | 97.9 (2) | C4—C5—C6 | 121.2 (8) |
N2—Pt1—N4 | 178.1 (6) | C4—C5—H4 | 118.9 |
N3—Pt1—N4 | 82.8 (2) | C6—C5—H4 | 119.8 |
F1—P1—F2 | 89.4 (5) | C5—C6—C7 | 121.7 (7) |
F1—P1—F3 | 90.9 (6) | C5—C6—H5 | 118.4 |
F1—P1—F4 | 177.1 (6) | C7—C6—H5 | 119.6 |
F1—P1—F5 | 88.0 (5) | C6—C7—C8 | 123.9 (7) |
F1—P1—F6 | 87.8 (7) | C6—C7—C11 | 117.2 (7) |
F2—P1—F3 | 87.9 (5) | C8—C7—C11 | 118.9 (7) |
F2—P1—F4 | 92.2 (5) | C7—C8—C9 | 118.3 (8) |
F2—P1—F5 | 174.7 (6) | C7—C8—H6 | 120.4 |
F2—P1—F6 | 93.2 (7) | C9—C8—H6 | 120.9 |
F3—P1—F4 | 91.5 (6) | C8—C9—C10 | 118.9 (8) |
F3—P1—F5 | 87.6 (6) | C8—C9—H7 | 120.5 |
F3—P1—F6 | 178.3 (8) | C10—C9—H7 | 120.1 |
F4—P1—F5 | 90.6 (5) | N2—C10—C9 | 123.3 (8) |
F4—P1—F6 | 89.7 (7) | N2—C10—H8 | 118.3 |
F5—P1—F6 | 91.3 (7) | C9—C10—H8 | 118.0 |
F7—P2—F8 | 90.2 (5) | N2—C11—C7 | 122.4 (6) |
F7—P2—F9 | 89.1 (7) | N2—C11—C12 | 115.8 (6) |
F7—P2—F10 | 177.2 (6) | N1—C12—C4 | 123.3 (7) |
F7—P2—F11 | 89.4 (5) | N1—C12—C11 | 116.3 (6) |
F7—P2—F12 | 90.6 (5) | C4—C12—C11 | 120.3 (6) |
F8—P2—F9 | 93.4 (6) | N3—C13—C14 | 114.6 (8) |
F8—P2—F10 | 90.8 (5) | N3—C13—C18 | 105.9 (7) |
F8—P2—F11 | 179.3 (5) | N3—C13—H13 | 107.5 |
F8—P2—F12 | 88.8 (5) | C14—C13—C18 | 112.0 (7) |
F9—P2—F10 | 88.3 (6) | C14—C13—H13 | 108.3 |
F9—P2—F11 | 87.2 (6) | C18—C13—H13 | 108.3 |
F9—P2—F12 | 177.8 (6) | C13—C14—C15 | 110.9 (8) |
F10—P2—F11 | 89.6 (5) | C13—C14—H14 | 109.4 |
F10—P2—F12 | 92.0 (5) | C13—C14—H15 | 109.2 |
F11—P2—F12 | 90.6 (4) | C15—C14—H14 | 110.7 |
PT1—N1—C1 | 129.3 (5) | C15—C14—H15 | 108.2 |
PT1—N1—C12 | 112.8 (4) | H14—C14—H15 | 108.4 |
C1—N1—C12 | 117.9 (6) | C14—C15—C16 | 117.2 (10) |
PT1—N2—C10 | 129.7 (5) | C14—C15—H16 | 107.6 |
PT1—N2—C11 | 113.2 (4) | C14—C15—H17 | 109.2 |
C10—N2—C11 | 116.8 (6) | C16—C15—H16 | 101.6 |
PT1—N3—C13 | 110.8 (5) | C16—C15—H17 | 109.3 |
PT1—N3—H9 | 108.8 | H16—C15—H17 | 111.9 |
PT1—N3—H10 | 109.9 | C15—C16—C17 | 113.5 (10) |
C13—N3—H9 | 108.7 | C15—C16—H18 | 113.0 |
C13—N3—H10 | 109.8 | C15—C16—H19 | 102.1 |
H9—N3—H10 | 108.7 | C17—C16—H18 | 113.6 |
PT1—N4—C18 | 108.9 (5) | C17—C16—H19 | 102.3 |
PT1—N4—H11 | 110.7 | H18—C16—H19 | 111.2 |
PT1—N4—H12 | 109.1 | C16—C17—C18 | 108.5 (8) |
C18—N4—H11 | 110.1 | C16—C17—H20 | 105.1 |
C18—N4—H12 | 108.4 | C16—C17—H21 | 114.5 |
H11—N4—H12 | 109.6 | C18—C17—H20 | 107.6 |
N1—C1—C2 | 120.9 (8) | C18—C17—H21 | 111.1 |
N1—C1—H1 | 118.7 | H20—C17—H21 | 109.8 |
C2—C1—H1 | 120.1 | N4—C18—C13 | 107.2 (7) |
C1—C2—C3 | 120.8 (9) | N4—C18—C17 | 112.2 (7) |
C1—C2—H2 | 119.3 | N4—C18—H22 | 108.2 |
C3—C2—H2 | 119.0 | C13—C18—C17 | 112.0 (7) |
C2—C3—C4 | 119.9 (8) | C13—C18—H22 | 108.2 |
C2—C3—H3 | 120.0 | C17—C18—H22 | 108.8 |
C4—C3—H3 | 119.1 |
Symmetry codes: (i) x+1/2, −y+3/2, −z; (ii) x+1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1/2, −y+3/2, −z+1; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y+1/2, −z+1/2; (vii) −x+1/2, −y+2, z+1/2; (viii) x−1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···F1 | 0.864 | 2.149 | 2.97 (1) | 158.1 |
N3—H9···F12 | 0.864 | 3.031 | 3.331 (7) | 102.8 |
N3—H10···F2ix | 0.844 | 2.139 | 2.95 (1) | 161.4 |
N4—H11···F7x | 0.834 | 2.452 | 3.24 (1) | 158.2 |
N4—H11···F9x | 0.834 | 2.851 | 3.58 (2) | 146.7 |
N4—H11···F11x | 0.834 | 2.390 | 3.11 (1) | 145.2 |
Symmetry codes: (ix) x−1, y, z; (x) −x, y−1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pt(C6H14N2)(C10H8N2)](PF6)2 | [Pt(C6H14N2)(C12H8N2)](PF6)2 |
Mr | 755.40 | 779.42 |
Crystal system, space group | Monoclinic, C2 | Orthorhombic, P212121 |
Temperature (K) | 173 | 293 |
a, b, c (Å) | 15.534 (1), 17.448 (2), 8.2424 (7) | 7.3142 (5), 18.2738 (5), 18.4925 (5) |
α, β, γ (°) | 90, 93.256 (4), 90 | 90, 90, 90 |
V (Å3) | 2230.4 (3) | 2471.7 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.52 | 5.91 |
Crystal size (mm) | 0.68 × 0.20 × 0.16 | 0.70 × 0.14 × 0.10 |
Data collection | ||
Diffractometer | Rigaku/MSC Mercury CCD diffractometer | Rigaku/MSC Mercury CCD diffractometer |
Absorption correction | Numerical (Higashi, 1999) | Numerical (Higashi, 1999) |
Tmin, Tmax | 0.254, 0.713 | 0.514, 0.782 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8699, 5075, 4820 | 26208, 5570, 5485 |
Rint | 0.050 | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.04 | 0.047, 0.105, 1.26 |
No. of reflections | 5075 | 5570 |
No. of parameters | 317 | 334 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.63, −2.16 | 1.81, −0.79 |
Absolute structure | Flack (1983), 2446 Friedel pairs | Flack (1983), 2413 Friedel pairs |
Absolute structure parameter | 0.04 (2) | 0.21 (2) |
Computer programs: CrystalClear (Rigaku MSC/SSI, 2001), CrystalClear, TEXSAN (Molecular Structure Corporation/Rigaku, 2000), SIR92 (Altomare, 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.
Pt1—N1 | 2.005 (11) | Pt2—N3 | 2.033 (9) |
Pt1—N2 | 2.052 (10) | Pt2—N4 | 2.037 (12) |
N1—Pt1—N1i | 80.1 (6) | N3—Pt2—N3ii | 80.8 (5) |
N1—Pt1—N2 | 98.7 (4) | N3—Pt2—N4 | 98.8 (4) |
N1—Pt1—N2i | 176.5 (4) | N3—Pt2—N4ii | 178.8 (4) |
N2—Pt1—N2i | 82.7 (6) | N4—Pt2—N4ii | 81.7 (7) |
Symmetry codes: (i) −x, y, −z+1; (ii) −x, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H5···F2 | 1.031 | 2.612 | 3.26 (1) | 120.2 |
N2—H5···F4 | 1.031 | 2.064 | 3.03 (1) | 154.6 |
N2—H6···F5iii | 0.869 | 2.875 | 3.14 (1) | 100.0 |
N2—H6···F7 | 0.869 | 2.629 | 3.46 (1) | 159.3 |
N2—H6···F12 | 0.869 | 2.356 | 3.11 (1) | 146.0 |
N4—H17···F6iv | 0.949 | 2.198 | 3.06 (1) | 150.7 |
N4—H17···F11v | 0.949 | 2.957 | 3.26 (1) | 100.4 |
N4—H16···F8iv | 0.961 | 2.651 | 3.25 (1) | 120.2 |
N4—H16···F10iv | 0.961 | 2.064 | 2.97 (1) | 155.5 |
Symmetry codes: (iii) x, y, z−1; (iv) x+1/2, y−1/2, z−1; (v) x+1/2, y−1/2, z. |
Pt1—N1 | 2.015 (5) | Pt1—N3 | 2.042 (6) |
Pt1—N2 | 2.008 (6) | Pt1—N4 | 2.046 (6) |
N1—Pt1—N2 | 81.6 (2) | N2—Pt1—N3 | 97.9 (2) |
N1—Pt1—N3 | 178.8 (5) | N2—Pt1—N4 | 178.1 (6) |
N1—Pt1—N4 | 97.7 (2) | N3—Pt1—N4 | 82.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H9···F1 | 0.864 | 2.149 | 2.97 (1) | 158.1 |
N3—H9···F12 | 0.864 | 3.031 | 3.331 (7) | 102.8 |
N3—H10···F2i | 0.844 | 2.139 | 2.95 (1) | 161.4 |
N4—H11···F7ii | 0.834 | 2.452 | 3.24 (1) | 158.2 |
N4—H11···F9ii | 0.834 | 2.851 | 3.58 (2) | 146.7 |
N4—H11···F11ii | 0.834 | 2.390 | 3.11 (1) | 145.2 |
Symmetry codes: (i) x−1, y, z; (ii) −x, y−1/2, −z+1/2. |
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Square-planar PtII complexes containing α-diimine ligands such as 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) form various stacking structures based on the Pt···Pt and/or π–π interactions. For example, [PtCl2(bpy)] is known to form two columnar stacking structures, viz. the red form with a Pt···Pt linear chain (Connick et al., 1996; Osborn & Rogers, 1974) and the yellow form with a π–π stack (Herber et al., 1994). However, the complexes containing a non-planar ligand, such as ethylenediamine (en), should have difficulty in taking a columnar structure because of the steric effect of the en ligand and the positive charge of the complex. We have previously reported that [Pt(α-diimine)(en)]2+ (α-diimine is bpy and phen) forms a ladder-type stacking structure, which is constructed via π–π stacking on the α-diimine ligands and hydrogen bonding between the en ligand and the counter-anion (Kato et al., 1999). In order to expand the structual chemistry of this type of platinum complex, we have synthesized new PtII complexes containing a more bulky chiral ligand, (1R,2R)-1,2-diaminocyclohexane (RR-chxn). In this paper, the crystal structures of [Pt(bpy)(RR-chxn)](PF6)2, (I), and [Pt(phen)(RR-chxn)](PF6)2, (II), are reported.
Fig. 1 shows the molecular structure of one of the two independent [Pt(bpy)(RR-chxn)]2+ ions in (I). This ion has a twofold axis through the Pt atom, intersecting the bpy and RR-chxn ligands. The coordination geometry is almost planar, including the bpy ligand, while the cyclohexane ring takes a stable chair conformation. The geometries of the two independent complexes are very similar to one another, being related by the pseudo-center of symmetry, except for diaminocyclohexane with the RR-configuration. The complex cations are stacked on the bpy ligands, and the PF6− ions are located near the RR-chxn ligands, as shown in Fig. 2. The crystal structure is similar to that of the corresponding en complex [Pt(bpy)(en)](PF6)2 (Kato et al., 1997). As shown in Fig. 3, the geometry of the platinum complex in (II) is very similar to that in (I), although the crystal packing is somewhat different.
In the crystal structures of both (I) and (II), ladder-type structures similar to those found in the corresponding en complexes are formed. Fig. 4 shows the ladder-type stacking in (II). The dihedral angles and the interplanar spacings between neighboring bpy and phen ligands are 0.5 (1) ° and 3.53 (1) Å for (I), and 1.8 (2) ° and 3.66 (2) Å for (II), respectively. Such a loose π–π stacking would be controlled by the counter-anion. In fact, we found that the larger anion, PF6−, expanded the interplanar spacing between the phen ligands in the ladder structure for the [Pt(en)(phen)]2+ complex compared to that in the case containing the smaller anion, Cl− (Kato et al., 1999). The PF6− anions form hydrogen bonds with the RR-chxn ligands, thus linking the PtII complexes on every other step. As a remarkable characteristic, we reported that [Pt(bpy)(en)]2+ acts as a host molecule and takes up free phen preferentially, thus forming a tight integrated stack (Kato et al., 2001). The complexes containing bulky R,R-chxn are expected to include larger guests, because (I) and (II) have more space between the complexes in the stack than complexes containing the en ligand.