Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008249/ob6234sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008249/ob6234Isup2.hkl |
CCDC reference: 214571
To a solution of dmtpy (286 mg, 0.61 mmol) in tetrahydrofuran (12 ml) was added a solution of [Cu(NCMe)4](PF6) (226 mg, 0.61 mmol) in MeCN (5 ml) at room temperature. The reaction mixture was stirred for 10 min and dried in vacuo. The residue was recrystallized from MeCN/ether to give dark red crystals of (I). Yield: 26 mg (6.2%). Elemental analysis, calculated for C35H34CuF6N4P: C 58.45, H 4.77, N 7.79%; found: C 58.78, H 4.50, N 7.88%.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLEASE PROVIDE; software used to prepare material for publication: SHELXL97.
[Cu(C2H3N)(C33H31N3)](PF6) | F(000) = 1480 |
Mr = 719.17 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 11.317 (3) Å | Cell parameters from 25 reflections |
b = 23.592 (4) Å | θ = 29.2–30.0° |
c = 12.873 (2) Å | µ = 0.75 mm−1 |
β = 92.450 (16)° | T = 296 K |
V = 3433.7 (11) Å3 | Block, dark red |
Z = 4 | 0.50 × 0.30 × 0.20 mm |
Rigaku AFC-5R diffractometer | 2104 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.150 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω–2θ scans | h = 0→13 |
Absorption correction: Ψ scan (North, 1968) | k = 0→30 |
Tmin = 0.842, Tmax = 0.998 | l = −16→16 |
7686 measured reflections | 3 standard reflections every 150 reflections |
7302 independent reflections | intensity decay: 0.2% |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.227 | H-atom parameters constrained |
S = 0.91 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
7302 reflections | (Δ/σ)max < 0.001 |
425 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[Cu(C2H3N)(C33H31N3)](PF6) | V = 3433.7 (11) Å3 |
Mr = 719.17 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.317 (3) Å | µ = 0.75 mm−1 |
b = 23.592 (4) Å | T = 296 K |
c = 12.873 (2) Å | 0.50 × 0.30 × 0.20 mm |
β = 92.450 (16)° |
Rigaku AFC-5R diffractometer | 2104 reflections with I > 2σ(I) |
Absorption correction: Ψ scan (North, 1968) | Rint = 0.150 |
Tmin = 0.842, Tmax = 0.998 | 3 standard reflections every 150 reflections |
7686 measured reflections | intensity decay: 0.2% |
7302 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.227 | H-atom parameters constrained |
S = 0.91 | Δρmax = 0.50 e Å−3 |
7302 reflections | Δρmin = −0.58 e Å−3 |
425 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 | ||
Cu1 | 0.05468 (7) | 0.10159 (4) | 0.17286 (6) | 0.0525 (3) | |
P1 | 0.0440 (2) | 0.42579 (10) | 0.19005 (16) | 0.0636 (6) | |
F1 | 0.0048 (6) | 0.4646 (4) | 0.2806 (4) | 0.165 (3) | |
F2 | −0.0705 (7) | 0.3931 (5) | 0.1877 (6) | 0.227 (5) | |
F3 | 0.1021 (9) | 0.3872 (3) | 0.2710 (5) | 0.182 (4) | |
F4 | 0.0829 (6) | 0.3895 (2) | 0.0968 (4) | 0.121 (2) | |
F5 | 0.1619 (7) | 0.4580 (5) | 0.1919 (6) | 0.204 (4) | |
F6 | −0.0092 (8) | 0.4681 (3) | 0.1096 (5) | 0.179 (4) | |
N1 | 0.1947 (5) | 0.0958 (3) | 0.2571 (4) | 0.0665 (18) | |
N11 | 0.1095 (5) | 0.1199 (2) | 0.0108 (4) | 0.0430 (14) | |
N21 | −0.0775 (5) | 0.0687 (2) | 0.0837 (4) | 0.0448 (14) | |
N31 | −0.0997 (5) | 0.1041 (3) | 0.2751 (4) | 0.0522 (14) | |
C1 | 0.2767 (7) | 0.1005 (4) | 0.3073 (6) | 0.066 (2) | |
C2 | 0.3835 (8) | 0.1043 (4) | 0.3752 (7) | 0.100 (3) | |
H2A | 0.4484 | 0.0868 | 0.3416 | 0.120* | |
H2B | 0.3705 | 0.0850 | 0.4394 | 0.120* | |
H2C | 0.4016 | 0.1434 | 0.3890 | 0.120* | |
C12 | 0.0470 (6) | 0.0852 (3) | −0.0564 (5) | 0.0449 (17) | |
C13 | 0.0867 (6) | 0.0718 (3) | −0.1553 (5) | 0.0487 (18) | |
H13 | 0.0422 | 0.0487 | −0.2006 | 0.058* | |
C14 | 0.1931 (7) | 0.0937 (3) | −0.1829 (5) | 0.062 (2) | |
H14 | 0.2224 | 0.0845 | −0.2472 | 0.075* | |
C15 | 0.2573 (7) | 0.1291 (3) | −0.1164 (6) | 0.057 (2) | |
H15 | 0.3291 | 0.1443 | −0.1353 | 0.069* | |
C16 | 0.2114 (6) | 0.1416 (3) | −0.0200 (5) | 0.0459 (17) | |
C22 | −0.0676 (6) | 0.0652 (3) | −0.0190 (5) | 0.0434 (17) | |
C23 | −0.1594 (7) | 0.0453 (3) | −0.0831 (6) | 0.058 (2) | |
H23 | −0.1508 | 0.0426 | −0.1544 | 0.070* | |
C24 | −0.2635 (7) | 0.0295 (3) | −0.0404 (7) | 0.069 (2) | |
H24 | −0.3257 | 0.0155 | −0.0825 | 0.083* | |
C25 | −0.2751 (6) | 0.0345 (3) | 0.0657 (6) | 0.057 (2) | |
H25 | −0.3444 | 0.0235 | 0.0963 | 0.068* | |
C26 | −0.1806 (6) | 0.0564 (3) | 0.1253 (6) | 0.0502 (19) | |
C32 | −0.1853 (6) | 0.0693 (3) | 0.2398 (6) | 0.0521 (18) | |
C33 | −0.2717 (7) | 0.0479 (4) | 0.3003 (7) | 0.076 (2) | |
H33 | −0.3290 | 0.0230 | 0.2735 | 0.091* | |
C34 | −0.2692 (8) | 0.0653 (4) | 0.4045 (7) | 0.095 (3) | |
H34 | −0.3254 | 0.0516 | 0.4486 | 0.113* | |
C35 | −0.1872 (8) | 0.1013 (4) | 0.4405 (7) | 0.084 (3) | |
H35 | −0.1880 | 0.1138 | 0.5090 | 0.101* | |
C36 | −0.0989 (7) | 0.1205 (3) | 0.3752 (6) | 0.064 (2) | |
C41 | 0.2746 (6) | 0.1814 (3) | 0.0541 (5) | 0.0564 (19) | |
C42 | 0.3887 (7) | 0.1693 (4) | 0.0936 (6) | 0.066 (2) | |
C43 | 0.4444 (7) | 0.2095 (4) | 0.1593 (7) | 0.076 (3) | |
H43 | 0.5210 | 0.2024 | 0.1852 | 0.091* | |
C44 | 0.3908 (9) | 0.2583 (4) | 0.1866 (6) | 0.079 (3) | |
C45 | 0.2799 (8) | 0.2677 (4) | 0.1469 (7) | 0.077 (2) | |
H45 | 0.2420 | 0.3009 | 0.1656 | 0.093* | |
C46 | 0.2201 (7) | 0.2312 (3) | 0.0809 (6) | 0.062 (2) | |
C47 | 0.4515 (8) | 0.1136 (4) | 0.0687 (8) | 0.105 (3) | |
H47A | 0.5284 | 0.1131 | 0.1032 | 0.126* | |
H47B | 0.4596 | 0.1107 | −0.0050 | 0.126* | |
H47C | 0.4058 | 0.0823 | 0.0924 | 0.126* | |
C48 | 0.4586 (10) | 0.3010 (5) | 0.2525 (8) | 0.123 (4) | |
H48A | 0.4088 | 0.3329 | 0.2653 | 0.147* | |
H48B | 0.5267 | 0.3133 | 0.2168 | 0.147* | |
H48C | 0.4835 | 0.2838 | 0.3175 | 0.147* | |
C49 | 0.0995 (8) | 0.2489 (4) | 0.0354 (9) | 0.117 (4) | |
H49A | 0.0683 | 0.2194 | −0.0093 | 0.141* | |
H49B | 0.1073 | 0.2832 | −0.0040 | 0.141* | |
H49C | 0.0468 | 0.2553 | 0.0907 | 0.141* | |
C51 | −0.0073 (7) | 0.1608 (4) | 0.4120 (5) | 0.059 (2) | |
C52 | 0.0810 (8) | 0.1451 (4) | 0.4845 (6) | 0.079 (3) | |
C53 | 0.1665 (9) | 0.1871 (6) | 0.5163 (7) | 0.103 (4) | |
H53 | 0.2250 | 0.1775 | 0.5662 | 0.123* | |
C54 | 0.1652 (9) | 0.2405 (6) | 0.4760 (8) | 0.095 (3) | |
C55 | 0.0800 (9) | 0.2548 (4) | 0.4041 (7) | 0.086 (3) | |
H55 | 0.0790 | 0.2912 | 0.3763 | 0.103* | |
C56 | −0.0070 (7) | 0.2158 (4) | 0.3706 (6) | 0.069 (2) | |
C57 | 0.0887 (11) | 0.0851 (5) | 0.5281 (8) | 0.129 (4) | |
H57A | 0.1550 | 0.0824 | 0.5769 | 0.155* | |
H57B | 0.0986 | 0.0587 | 0.4723 | 0.155* | |
H57C | 0.0173 | 0.0764 | 0.5625 | 0.155* | |
C58 | 0.2561 (10) | 0.2856 (6) | 0.5135 (9) | 0.151 (5) | |
H58A | 0.3108 | 0.2691 | 0.5640 | 0.181* | |
H58B | 0.2157 | 0.3167 | 0.5446 | 0.181* | |
H58C | 0.2985 | 0.2991 | 0.4554 | 0.181* | |
C59 | −0.1021 (9) | 0.2362 (4) | 0.2920 (7) | 0.105 (3) | |
H59A | −0.0868 | 0.2748 | 0.2736 | 0.126* | |
H59B | −0.1782 | 0.2336 | 0.3220 | 0.126* | |
H59C | −0.1013 | 0.2129 | 0.2308 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0464 (5) | 0.0594 (6) | 0.0510 (5) | −0.0025 (5) | −0.0062 (4) | −0.0069 (5) |
P1 | 0.0659 (15) | 0.0672 (14) | 0.0580 (14) | 0.0154 (12) | 0.0076 (11) | 0.0014 (12) |
F1 | 0.171 (6) | 0.230 (8) | 0.090 (4) | 0.121 (6) | −0.035 (4) | −0.077 (5) |
F2 | 0.154 (7) | 0.362 (13) | 0.171 (7) | −0.152 (8) | 0.079 (6) | −0.080 (8) |
F3 | 0.283 (10) | 0.143 (6) | 0.119 (5) | 0.092 (7) | −0.027 (6) | 0.025 (5) |
F4 | 0.155 (5) | 0.104 (4) | 0.109 (4) | 0.037 (4) | 0.048 (4) | −0.024 (3) |
F5 | 0.146 (7) | 0.294 (11) | 0.171 (7) | −0.114 (7) | −0.003 (6) | −0.006 (8) |
F6 | 0.289 (10) | 0.147 (6) | 0.096 (4) | 0.115 (7) | −0.051 (5) | −0.006 (4) |
N1 | 0.049 (4) | 0.099 (5) | 0.051 (4) | 0.010 (4) | −0.002 (3) | −0.006 (4) |
N11 | 0.044 (3) | 0.038 (3) | 0.047 (3) | 0.002 (3) | −0.002 (3) | −0.002 (3) |
N21 | 0.040 (3) | 0.041 (3) | 0.054 (4) | −0.003 (3) | −0.002 (3) | −0.010 (3) |
N31 | 0.057 (4) | 0.054 (4) | 0.046 (3) | −0.001 (3) | 0.005 (3) | −0.014 (3) |
C1 | 0.052 (5) | 0.083 (6) | 0.063 (5) | 0.005 (5) | −0.002 (4) | −0.002 (5) |
C2 | 0.084 (6) | 0.100 (7) | 0.111 (7) | −0.001 (6) | −0.040 (6) | −0.004 (6) |
C12 | 0.052 (4) | 0.039 (4) | 0.043 (4) | 0.007 (3) | −0.002 (3) | −0.005 (3) |
C13 | 0.067 (5) | 0.040 (4) | 0.038 (4) | 0.007 (4) | −0.007 (4) | −0.004 (3) |
C14 | 0.083 (6) | 0.064 (6) | 0.042 (4) | 0.002 (5) | 0.022 (4) | 0.005 (4) |
C15 | 0.067 (5) | 0.048 (5) | 0.059 (5) | 0.002 (4) | 0.020 (4) | 0.003 (4) |
C16 | 0.048 (4) | 0.039 (4) | 0.051 (4) | −0.002 (3) | 0.003 (3) | −0.001 (3) |
C22 | 0.043 (4) | 0.034 (4) | 0.053 (4) | 0.004 (3) | −0.005 (3) | −0.006 (3) |
C23 | 0.057 (5) | 0.056 (5) | 0.060 (5) | 0.004 (4) | −0.015 (4) | −0.006 (4) |
C24 | 0.056 (5) | 0.074 (6) | 0.076 (6) | −0.011 (4) | −0.015 (5) | −0.014 (5) |
C25 | 0.038 (4) | 0.051 (5) | 0.080 (6) | 0.001 (3) | −0.008 (4) | −0.005 (4) |
C26 | 0.045 (4) | 0.036 (4) | 0.070 (5) | 0.004 (3) | −0.006 (4) | −0.008 (3) |
C32 | 0.043 (4) | 0.055 (5) | 0.059 (5) | −0.003 (4) | 0.012 (4) | −0.008 (4) |
C33 | 0.061 (5) | 0.079 (6) | 0.089 (6) | −0.019 (5) | 0.023 (5) | −0.017 (5) |
C34 | 0.086 (7) | 0.118 (8) | 0.083 (7) | −0.038 (6) | 0.048 (6) | −0.022 (6) |
C35 | 0.091 (7) | 0.096 (7) | 0.069 (5) | −0.028 (6) | 0.033 (5) | −0.018 (5) |
C36 | 0.061 (5) | 0.070 (6) | 0.063 (5) | −0.001 (4) | 0.015 (4) | −0.008 (4) |
C41 | 0.056 (5) | 0.061 (5) | 0.053 (4) | −0.007 (4) | 0.015 (4) | 0.004 (4) |
C42 | 0.049 (5) | 0.072 (6) | 0.076 (5) | −0.003 (4) | 0.000 (4) | −0.001 (5) |
C43 | 0.047 (5) | 0.095 (7) | 0.084 (6) | −0.012 (5) | −0.010 (4) | 0.024 (6) |
C44 | 0.094 (7) | 0.079 (7) | 0.065 (5) | −0.021 (6) | 0.004 (5) | −0.014 (5) |
C45 | 0.076 (6) | 0.073 (6) | 0.084 (6) | −0.009 (5) | 0.008 (5) | −0.008 (5) |
C46 | 0.056 (5) | 0.051 (5) | 0.080 (5) | −0.008 (4) | −0.001 (4) | −0.017 (4) |
C47 | 0.072 (6) | 0.109 (9) | 0.134 (9) | 0.005 (6) | 0.001 (6) | −0.002 (7) |
C48 | 0.151 (10) | 0.117 (9) | 0.098 (8) | −0.058 (8) | −0.018 (7) | −0.023 (7) |
C49 | 0.090 (7) | 0.083 (7) | 0.176 (11) | 0.034 (6) | −0.028 (7) | −0.052 (7) |
C51 | 0.067 (5) | 0.073 (6) | 0.039 (4) | −0.007 (5) | 0.012 (4) | −0.010 (4) |
C52 | 0.100 (7) | 0.099 (8) | 0.038 (5) | −0.013 (6) | −0.003 (5) | 0.002 (5) |
C53 | 0.082 (7) | 0.178 (12) | 0.046 (6) | −0.003 (8) | −0.017 (5) | −0.023 (7) |
C54 | 0.083 (7) | 0.136 (11) | 0.066 (7) | −0.025 (7) | 0.007 (5) | −0.019 (7) |
C55 | 0.091 (7) | 0.089 (7) | 0.077 (6) | −0.012 (6) | 0.005 (5) | −0.020 (5) |
C56 | 0.070 (5) | 0.084 (7) | 0.052 (5) | −0.004 (5) | 0.003 (4) | −0.029 (5) |
C57 | 0.148 (11) | 0.164 (13) | 0.074 (7) | 0.008 (9) | −0.013 (7) | 0.019 (7) |
C58 | 0.107 (9) | 0.217 (15) | 0.128 (10) | −0.062 (9) | −0.005 (7) | −0.066 (10) |
C59 | 0.120 (8) | 0.084 (7) | 0.108 (7) | 0.004 (6) | −0.039 (7) | −0.027 (6) |
Cu1—N1 | 1.886 (6) | C35—C36 | 1.408 (11) |
Cu1—N21 | 2.003 (5) | C35—H35 | 0.9300 |
Cu1—N31 | 2.232 (5) | C36—C51 | 1.471 (10) |
Cu1—N11 | 2.244 (5) | C41—C46 | 1.378 (10) |
P1—F2 | 1.507 (7) | C41—C42 | 1.396 (10) |
P1—F3 | 1.512 (6) | C42—C43 | 1.403 (11) |
P1—F5 | 1.535 (7) | C42—C47 | 1.534 (12) |
P1—F6 | 1.542 (6) | C43—C44 | 1.355 (12) |
P1—F4 | 1.554 (5) | C43—H43 | 0.9300 |
P1—F1 | 1.561 (5) | C44—C45 | 1.353 (11) |
N1—C1 | 1.114 (8) | C44—C48 | 1.505 (11) |
N11—C16 | 1.338 (8) | C45—C46 | 1.369 (10) |
N11—C12 | 1.367 (8) | C45—H45 | 0.9300 |
N21—C22 | 1.333 (8) | C46—C49 | 1.521 (11) |
N21—C26 | 1.336 (8) | C47—H47A | 0.9600 |
N31—C32 | 1.336 (8) | C47—H47B | 0.9600 |
N31—C36 | 1.346 (9) | C47—H47C | 0.9600 |
C1—C2 | 1.463 (10) | C48—H48A | 0.9600 |
C2—H2A | 0.9600 | C48—H48B | 0.9600 |
C2—H2B | 0.9600 | C48—H48C | 0.9600 |
C2—H2C | 0.9600 | C49—H49A | 0.9600 |
C12—C13 | 1.403 (9) | C49—H49B | 0.9600 |
C12—C22 | 1.480 (9) | C49—H49C | 0.9600 |
C13—C14 | 1.372 (10) | C51—C52 | 1.388 (11) |
C13—H13 | 0.9300 | C51—C56 | 1.402 (11) |
C14—C15 | 1.381 (10) | C52—C53 | 1.433 (13) |
C14—H14 | 0.9300 | C52—C57 | 1.524 (13) |
C15—C16 | 1.397 (9) | C53—C54 | 1.364 (15) |
C15—H15 | 0.9300 | C53—H53 | 0.9300 |
C16—C41 | 1.497 (9) | C54—C55 | 1.350 (12) |
C22—C23 | 1.381 (9) | C54—C58 | 1.543 (14) |
C23—C24 | 1.372 (10) | C55—C56 | 1.403 (11) |
C23—H23 | 0.9300 | C55—H55 | 0.9300 |
C24—C25 | 1.383 (10) | C56—C59 | 1.523 (11) |
C24—H24 | 0.9300 | C57—H57A | 0.9600 |
C25—C26 | 1.389 (9) | C57—H57B | 0.9600 |
C25—H25 | 0.9300 | C57—H57C | 0.9600 |
C26—C32 | 1.508 (10) | C58—H58A | 0.9600 |
C32—C33 | 1.372 (10) | C58—H58B | 0.9600 |
C33—C34 | 1.402 (11) | C58—H58C | 0.9600 |
C33—H33 | 0.9300 | C59—H59A | 0.9600 |
C34—C35 | 1.327 (11) | C59—H59B | 0.9600 |
C34—H34 | 0.9300 | C59—H59C | 0.9600 |
N1—Cu1—N21 | 152.8 (3) | C34—C35—H35 | 120.0 |
N1—Cu1—N31 | 108.8 (2) | C36—C35—H35 | 120.0 |
N21—Cu1—N31 | 76.3 (2) | N31—C36—C35 | 120.2 (7) |
N1—Cu1—N11 | 106.8 (2) | N31—C36—C51 | 118.0 (7) |
N21—Cu1—N11 | 76.8 (2) | C35—C36—C51 | 121.7 (7) |
N31—Cu1—N11 | 142.9 (2) | C46—C41—C42 | 120.0 (7) |
F2—P1—F3 | 93.1 (6) | C46—C41—C16 | 119.1 (7) |
F2—P1—F5 | 178.9 (7) | C42—C41—C16 | 120.9 (7) |
F3—P1—F5 | 86.3 (5) | C41—C42—C43 | 117.8 (8) |
F2—P1—F6 | 90.4 (6) | C41—C42—C47 | 121.9 (8) |
F3—P1—F6 | 176.2 (5) | C43—C42—C47 | 120.3 (8) |
F5—P1—F6 | 90.2 (5) | C44—C43—C42 | 122.4 (8) |
F2—P1—F4 | 88.5 (4) | C44—C43—H43 | 118.8 |
F3—P1—F4 | 94.1 (4) | C42—C43—H43 | 118.8 |
F5—P1—F4 | 90.6 (5) | C45—C44—C43 | 117.4 (8) |
F6—P1—F4 | 87.3 (3) | C45—C44—C48 | 123.1 (10) |
F2—P1—F1 | 92.5 (5) | C43—C44—C48 | 119.4 (10) |
F3—P1—F1 | 88.2 (4) | C44—C45—C46 | 123.9 (9) |
F5—P1—F1 | 88.4 (5) | C44—C45—H45 | 118.1 |
F6—P1—F1 | 90.4 (4) | C46—C45—H45 | 118.1 |
F4—P1—F1 | 177.5 (4) | C45—C46—C41 | 118.5 (8) |
C1—N1—Cu1 | 170.2 (8) | C45—C46—C49 | 118.5 (8) |
C16—N11—C12 | 118.2 (6) | C41—C46—C49 | 122.8 (7) |
C16—N11—Cu1 | 128.7 (4) | C42—C47—H47A | 109.5 |
C12—N11—Cu1 | 108.5 (4) | C42—C47—H47B | 109.5 |
C22—N21—C26 | 119.7 (6) | H47A—C47—H47B | 109.5 |
C22—N21—Cu1 | 120.0 (4) | C42—C47—H47C | 109.5 |
C26—N21—Cu1 | 119.9 (5) | H47A—C47—H47C | 109.5 |
C32—N31—C36 | 118.5 (6) | H47B—C47—H47C | 109.5 |
C32—N31—Cu1 | 111.0 (4) | C44—C48—H48A | 109.5 |
C36—N31—Cu1 | 126.8 (5) | C44—C48—H48B | 109.5 |
N1—C1—C2 | 177.6 (10) | H48A—C48—H48B | 109.5 |
C1—C2—H2A | 109.5 | C44—C48—H48C | 109.5 |
C1—C2—H2B | 109.5 | H48A—C48—H48C | 109.5 |
H2A—C2—H2B | 109.5 | H48B—C48—H48C | 109.5 |
C1—C2—H2C | 109.5 | C46—C49—H49A | 109.5 |
H2A—C2—H2C | 109.5 | C46—C49—H49B | 109.5 |
H2B—C2—H2C | 109.5 | H49A—C49—H49B | 109.5 |
N11—C12—C13 | 122.1 (6) | C46—C49—H49C | 109.5 |
N11—C12—C22 | 114.9 (6) | H49A—C49—H49C | 109.5 |
C13—C12—C22 | 122.9 (6) | H49B—C49—H49C | 109.5 |
C14—C13—C12 | 118.0 (7) | C52—C51—C56 | 119.4 (8) |
C14—C13—H13 | 121.0 | C52—C51—C36 | 121.3 (8) |
C12—C13—H13 | 121.0 | C56—C51—C36 | 119.3 (7) |
C13—C14—C15 | 120.8 (7) | C51—C52—C53 | 117.7 (9) |
C13—C14—H14 | 119.6 | C51—C52—C57 | 121.7 (9) |
C15—C14—H14 | 119.6 | C53—C52—C57 | 120.6 (9) |
C14—C15—C16 | 118.3 (7) | C54—C53—C52 | 122.3 (9) |
C14—C15—H15 | 120.9 | C54—C53—H53 | 118.8 |
C16—C15—H15 | 120.9 | C52—C53—H53 | 118.8 |
N11—C16—C15 | 122.6 (6) | C55—C54—C53 | 119.2 (10) |
N11—C16—C41 | 116.5 (6) | C55—C54—C58 | 119.3 (12) |
C15—C16—C41 | 120.8 (6) | C53—C54—C58 | 121.5 (11) |
N21—C22—C23 | 121.4 (6) | C54—C55—C56 | 121.2 (10) |
N21—C22—C12 | 114.5 (5) | C54—C55—H55 | 119.4 |
C23—C22—C12 | 124.1 (7) | C56—C55—H55 | 119.4 |
C24—C23—C22 | 119.3 (7) | C51—C56—C55 | 120.2 (8) |
C24—C23—H23 | 120.3 | C51—C56—C59 | 122.1 (8) |
C22—C23—H23 | 120.3 | C55—C56—C59 | 117.7 (9) |
C23—C24—C25 | 119.4 (7) | C52—C57—H57A | 109.5 |
C23—C24—H24 | 120.3 | C52—C57—H57B | 109.5 |
C25—C24—H24 | 120.3 | H57A—C57—H57B | 109.5 |
C24—C25—C26 | 118.3 (7) | C52—C57—H57C | 109.5 |
C24—C25—H25 | 120.8 | H57A—C57—H57C | 109.5 |
C26—C25—H25 | 120.8 | H57B—C57—H57C | 109.5 |
N21—C26—C25 | 121.6 (7) | C54—C58—H58A | 109.5 |
N21—C26—C32 | 114.6 (6) | C54—C58—H58B | 109.5 |
C25—C26—C32 | 123.8 (7) | H58A—C58—H58B | 109.5 |
N31—C32—C33 | 123.9 (7) | C54—C58—H58C | 109.5 |
N31—C32—C26 | 113.6 (6) | H58A—C58—H58C | 109.5 |
C33—C32—C26 | 122.4 (7) | H58B—C58—H58C | 109.5 |
C32—C33—C34 | 116.7 (8) | C56—C59—H59A | 109.5 |
C32—C33—H33 | 121.7 | C56—C59—H59B | 109.5 |
C34—C33—H33 | 121.7 | H59A—C59—H59B | 109.5 |
C35—C34—C33 | 120.5 (8) | C56—C59—H59C | 109.5 |
C35—C34—H34 | 119.7 | H59A—C59—H59C | 109.5 |
C33—C34—H34 | 119.7 | H59B—C59—H59C | 109.5 |
C34—C35—C36 | 120.1 (8) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H3N)(C33H31N3)](PF6) |
Mr | 719.17 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 11.317 (3), 23.592 (4), 12.873 (2) |
β (°) | 92.450 (16) |
V (Å3) | 3433.7 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.75 |
Crystal size (mm) | 0.50 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | Ψ scan (North, 1968) |
Tmin, Tmax | 0.842, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7686, 7302, 2104 |
Rint | 0.150 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.227, 0.91 |
No. of reflections | 7302 |
No. of parameters | 425 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.58 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLEASE PROVIDE, SHELXL97.
Cu1—N1 | 1.886 (6) | Cu1—N31 | 2.232 (5) |
Cu1—N21 | 2.003 (5) | Cu1—N11 | 2.244 (5) |
N1—Cu1—N21 | 152.8 (3) | N1—Cu1—N11 | 106.8 (2) |
N1—Cu1—N31 | 108.8 (2) | N21—Cu1—N11 | 76.8 (2) |
N21—Cu1—N31 | 76.3 (2) | N31—Cu1—N11 | 142.9 (2) |
Design of N-chelating ligands with various bulky substituents is essential approach in developing N-chelating metal catalysts for polymerization. For example, Johnson et al. (1995) have reported highly efficient Pd and Ni catalysts with α-diimino ligands for the polymerization of ethylene and α-olefin. It was also reported that the control of bulkiness in pyridine bisimino ligands (3 N coordination) contribute to polymerization by their Fe and Co catalysts (Small et al., 1998; Britovsek et al., 1998). Here, we determined the crystal structure of the title compound (I) to show the effect of the steric hindrance of the bulky terpyridine ligand 6,6''-dimesityl-2,2':6',2''-terpyridine (dmtpy), which perturbs the metal coordination geometry.
The Cu complex in (I) gives a distorted square planar coordination with four N atoms from dmtpy and acetonitrile molecules because of the extremely bulky terpyridyl ligand. The Cu1—N21 bond distance of 2.003 (5) Å for the central pyridine ring is shorter than those for the pyridine rings of the both side, 2.232 (5) Å and 2.244 (5) Å (Table 1). The Cu1 atom lies nearly on the plane of the central pyridine ring (C24···N21—Cu1, 176.8 (3)°). While, the Cu center aligned apart from the pyridine rings of the both side (C14···N11—Cu1, 155.7 (3)°, C34···N31—Cu1, 158.7 (3)°). The N21—Cu1—N1 bond angle is 152.8 (3)° and the Cu1 ion is located 0.625 (1) Å apart from the N11/N21/N31 plane. The bulkiness of dimesityl groups in the 6,6''- positions of terpyridine ligands distrupts the square planar coordination geometry forward to highly distorted tetrahedral one. Our ligand design of bulky derivatization in terpyridine ligands successfully induces a distortion in Cu(I) coordination geometry (Fig. 2).