Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805038778/su6247sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805038778/su6247Isup2.hkl |
CCDC reference: 296675
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.014 Å
- Disorder in solvent or counterion
- R factor = 0.077
- wR factor = 0.197
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.738 0.884 Tmin(prime) and Tmax expected: 0.835 0.884 RR(prime) = 0.884 Please check that your absorption correction is appropriate. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.88 PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT214_ALERT_2_C Atom F4' (Anion/Solvent) ADP max/min Ratio 4.90 prolat PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.94 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C11 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C18 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for C38 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2' PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C38' PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for B1 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 47.00 Perc. PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 14 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 40.20 Deg. F2' -B1 -F3 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 39.50 Deg. F4 -B1 -F4' 1.555 1.555 1.555
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 18 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion
Reaction of equimolar amounts of [Cu(CH3CN)4]BF4, phen and dppm in dichloromethane under a dinitrogen atmosphere gave an orange solution. Yellow crystals of (I), suitable for X-ray diffraction analysis, were obtained by vapour diffusion of diethyl ether into the dichloromethane solution.
All H atoms were positioned geometrically and treated as riding atoms, with C—H bond distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C). The tetrafluoroborate anion and solvent dichloromethane molecules are disordered, with occupanices of 0.768:0.232 for the tetrafluoroborate anion and 0.5:0.5 for dichloromethane. [Please state how these occupancies were derived, and give s.u. values if appropriate]
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Cu2(C25H22P2)2(C12H8N2)2](BF4)2·2CH2Cl2 | Z = 1 |
Mr = 1599.69 | F(000) = 816 |
Triclinic, P1 | Dx = 1.453 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.318 (5) Å | Cell parameters from 703 reflections |
b = 12.461 (5) Å | θ = 2.7–24.2° |
c = 14.710 (6) Å | µ = 0.88 mm−1 |
α = 104.177 (7)° | T = 293 K |
β = 103.851 (7)° | Block, yellow |
γ = 105.822 (7)° | 0.20 × 0.16 × 0.14 mm |
V = 1827.8 (13) Å3 |
Bruker SMART CCD area-detector diffractometer | 6403 independent reflections |
Radiation source: fine-focus sealed tube | 3689 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.738, Tmax = 0.884 | k = −14→14 |
9428 measured reflections | l = −17→13 |
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)] = 0.077 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0856P)2] where P = (Fo2 + 2Fc2)/3 |
6403 reflections | (Δ/σ)max = 0.001 |
515 parameters | Δρmax = 0.66 e Å−3 |
92 restraints | Δρmin = −0.52 e Å−3 |
[Cu2(C25H22P2)2(C12H8N2)2](BF4)2·2CH2Cl2 | γ = 105.822 (7)° |
Mr = 1599.69 | V = 1827.8 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.318 (5) Å | Mo Kα radiation |
b = 12.461 (5) Å | µ = 0.88 mm−1 |
c = 14.710 (6) Å | T = 293 K |
α = 104.177 (7)° | 0.20 × 0.16 × 0.14 mm |
β = 103.851 (7)° |
Bruker SMART CCD area-detector diffractometer | 6403 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3689 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 0.884 | Rint = 0.048 |
9428 measured reflections |
R[F2 > 2σ(F2)] = 0.077 | 92 restraints |
wR(F2) = 0.197 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.66 e Å−3 |
6403 reflections | Δρmin = −0.52 e Å−3 |
515 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 | Occ. (<1) | |
Cu1 | 0.99584 (8) | −0.02796 (7) | 0.15235 (6) | 0.0364 (3) | |
P1 | 0.80859 (16) | −0.00694 (15) | 0.08425 (13) | 0.0332 (4) | |
P2 | 0.86027 (16) | 0.08853 (15) | −0.08881 (13) | 0.0338 (4) | |
N1 | 1.1252 (5) | 0.0867 (5) | 0.2937 (4) | 0.0389 (14) | |
N2 | 0.9575 (5) | −0.1363 (5) | 0.2407 (4) | 0.0410 (14) | |
C1 | 0.6776 (6) | −0.1349 (6) | 0.0806 (5) | 0.0367 (16) | |
C2 | 0.6313 (7) | −0.2418 (6) | 0.0052 (5) | 0.0436 (17) | |
H2 | 0.6621 | −0.2483 | −0.0484 | 0.052* | |
C3 | 0.5402 (8) | −0.3392 (6) | 0.0077 (6) | 0.057 (2) | |
H3 | 0.5093 | −0.4101 | −0.0446 | 0.068* | |
C4 | 0.4949 (8) | −0.3328 (7) | 0.0862 (7) | 0.060 (2) | |
H4 | 0.4336 | −0.3988 | 0.0880 | 0.072* | |
C5 | 0.5410 (8) | −0.2279 (8) | 0.1620 (7) | 0.065 (2) | |
H5 | 0.5108 | −0.2230 | 0.2159 | 0.079* | |
C6 | 0.6307 (7) | −0.1296 (6) | 0.1607 (5) | 0.050 (2) | |
H6 | 0.6605 | −0.0590 | 0.2132 | 0.060* | |
C7 | 0.7751 (7) | 0.1179 (6) | 0.1527 (5) | 0.0386 (16) | |
C8 | 0.6541 (7) | 0.1301 (7) | 0.1265 (6) | 0.0512 (19) | |
H8 | 0.5868 | 0.0719 | 0.0725 | 0.061* | |
C9 | 0.6315 (8) | 0.2265 (7) | 0.1790 (6) | 0.058 (2) | |
H9 | 0.5501 | 0.2334 | 0.1599 | 0.070* | |
C10 | 0.7282 (10) | 0.3102 (8) | 0.2578 (7) | 0.075 (3) | |
H10 | 0.7135 | 0.3754 | 0.2930 | 0.090* | |
C11 | 0.8468 (11) | 0.3008 (9) | 0.2864 (8) | 0.099 (4) | |
H11 | 0.9128 | 0.3594 | 0.3411 | 0.119* | |
C12 | 0.8707 (8) | 0.2035 (7) | 0.2344 (6) | 0.062 (2) | |
H12 | 0.9520 | 0.1969 | 0.2553 | 0.075* | |
C13 | 0.7511 (6) | −0.0096 (5) | −0.0443 (4) | 0.0350 (16) | |
H13A | 0.6721 | 0.0090 | −0.0533 | 0.042* | |
H13B | 0.7273 | −0.0901 | −0.0875 | 0.042* | |
C14 | 0.9151 (7) | 0.2360 (6) | 0.0013 (5) | 0.0435 (18) | |
C15 | 0.8307 (8) | 0.2965 (6) | 0.0163 (6) | 0.053 (2) | |
H15 | 0.7427 | 0.2611 | −0.0204 | 0.064* | |
C16 | 0.8761 (11) | 0.4065 (8) | 0.0839 (7) | 0.077 (3) | |
H16 | 0.8185 | 0.4458 | 0.0930 | 0.092* | |
C17 | 1.0016 (14) | 0.4594 (9) | 0.1376 (9) | 0.103 (4) | |
H17 | 1.0296 | 0.5347 | 0.1838 | 0.123* | |
C18 | 1.0910 (11) | 0.4060 (10) | 0.1269 (8) | 0.101 (4) | |
H18 | 1.1785 | 0.4447 | 0.1641 | 0.121* | |
C19 | 1.0467 (8) | 0.2909 (8) | 0.0579 (7) | 0.067 (2) | |
H19 | 1.1048 | 0.2518 | 0.0501 | 0.080* | |
C20 | 0.7426 (7) | 0.0968 (6) | −0.1942 (5) | 0.0388 (17) | |
C21 | 0.6306 (7) | 0.0044 (7) | −0.2531 (5) | 0.0483 (19) | |
H21 | 0.6067 | −0.0638 | −0.2364 | 0.058* | |
C22 | 0.5514 (9) | 0.0128 (9) | −0.3391 (6) | 0.069 (3) | |
H22 | 0.4749 | −0.0496 | −0.3790 | 0.083* | |
C23 | 0.5875 (11) | 0.1129 (10) | −0.3634 (7) | 0.076 (3) | |
H23 | 0.5359 | 0.1182 | −0.4205 | 0.091* | |
C24 | 0.6979 (10) | 0.2043 (9) | −0.3050 (7) | 0.072 (3) | |
H24 | 0.7208 | 0.2723 | −0.3222 | 0.086* | |
C25 | 0.7761 (8) | 0.1986 (7) | −0.2213 (6) | 0.057 (2) | |
H25 | 0.8518 | 0.2623 | −0.1820 | 0.068* | |
C26 | 1.2106 (7) | 0.1941 (7) | 0.3188 (6) | 0.053 (2) | |
H26 | 1.2117 | 0.2302 | 0.2705 | 0.063* | |
C27 | 1.2995 (8) | 0.2560 (8) | 0.4146 (7) | 0.072 (3) | |
H27 | 1.3579 | 0.3317 | 0.4292 | 0.086* | |
C28 | 1.2995 (9) | 0.2054 (9) | 0.4846 (7) | 0.074 (3) | |
H28 | 1.3582 | 0.2461 | 0.5485 | 0.089* | |
C29 | 1.2123 (8) | 0.0919 (8) | 0.4628 (6) | 0.056 (2) | |
C30 | 1.2057 (11) | 0.0318 (11) | 0.5331 (7) | 0.082 (3) | |
H30 | 1.2618 | 0.0691 | 0.5981 | 0.098* | |
C31 | 1.1208 (11) | −0.0770 (11) | 0.5073 (7) | 0.080 (3) | |
H31 | 1.1186 | −0.1133 | 0.5554 | 0.096* | |
C32 | 1.0322 (9) | −0.1407 (8) | 0.4078 (7) | 0.061 (2) | |
C33 | 0.9421 (11) | −0.2540 (9) | 0.3768 (8) | 0.078 (3) | |
H33 | 0.9364 | −0.2942 | 0.4221 | 0.093* | |
C34 | 0.8626 (9) | −0.3067 (8) | 0.2820 (8) | 0.073 (3) | |
H34 | 0.8014 | −0.3824 | 0.2615 | 0.088* | |
C35 | 0.8740 (8) | −0.2451 (6) | 0.2152 (6) | 0.055 (2) | |
H35 | 0.8202 | −0.2824 | 0.1495 | 0.066* | |
C36 | 1.0356 (7) | −0.0833 (7) | 0.3367 (5) | 0.0425 (18) | |
C37 | 1.1269 (7) | 0.0345 (6) | 0.3649 (5) | 0.0401 (17) | |
B1 | 0.4744 (8) | 0.4840 (7) | 0.2831 (6) | 0.074 (3) | |
F1 | 0.4161 (9) | 0.5642 (8) | 0.2711 (9) | 0.140 (5) | 0.768 (13) |
F2 | 0.5084 (12) | 0.4955 (9) | 0.3801 (5) | 0.147 (5) | 0.768 (13) |
F3 | 0.5775 (9) | 0.5057 (10) | 0.2501 (10) | 0.135 (5) | 0.768 (13) |
F4 | 0.3952 (10) | 0.3723 (7) | 0.2289 (7) | 0.123 (5) | 0.768 (13) |
C38 | 0.6879 (18) | 0.4342 (11) | 0.509 (4) | 0.18 (2) | 0.50 |
H38A | 0.6672 | 0.4622 | 0.4533 | 0.221* | 0.50 |
H38B | 0.6409 | 0.4572 | 0.5530 | 0.221* | 0.50 |
Cl1 | 0.6469 (9) | 0.2806 (7) | 0.4677 (6) | 0.128 (3) | 0.50 |
Cl2 | 0.8548 (12) | 0.4923 (10) | 0.5721 (10) | 0.238 (6) | 0.50 |
F1' | 0.417 (3) | 0.542 (3) | 0.339 (2) | 0.159 (15) | 0.232 (13) |
F2' | 0.6048 (12) | 0.540 (2) | 0.319 (2) | 0.14 (2) | 0.232 (13) |
F3' | 0.425 (3) | 0.476 (3) | 0.1870 (13) | 0.172 (16) | 0.232 (13) |
F4' | 0.446 (3) | 0.3717 (18) | 0.288 (3) | 0.26 (4) | 0.232 (13) |
C38' | 0.7130 (16) | 0.4286 (11) | 0.518 (2) | 0.081 (8) | 0.50 |
H38C | 0.7026 | 0.4546 | 0.5827 | 0.097* | 0.50 |
H38D | 0.6340 | 0.4174 | 0.4674 | 0.097* | 0.50 |
Cl1' | 0.7454 (11) | 0.2970 (8) | 0.5010 (8) | 0.161 (4) | 0.50 |
Cl2' | 0.8466 (7) | 0.5331 (5) | 0.5107 (5) | 0.113 (2) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0324 (5) | 0.0429 (5) | 0.0379 (5) | 0.0136 (4) | 0.0136 (4) | 0.0179 (4) |
P1 | 0.0313 (10) | 0.0389 (10) | 0.0327 (10) | 0.0119 (8) | 0.0143 (8) | 0.0142 (8) |
P2 | 0.0307 (10) | 0.0402 (10) | 0.0340 (10) | 0.0128 (8) | 0.0121 (8) | 0.0164 (8) |
N1 | 0.034 (3) | 0.042 (3) | 0.043 (4) | 0.017 (3) | 0.011 (3) | 0.013 (3) |
N2 | 0.035 (3) | 0.044 (3) | 0.050 (4) | 0.014 (3) | 0.019 (3) | 0.022 (3) |
C1 | 0.032 (4) | 0.048 (4) | 0.036 (4) | 0.019 (3) | 0.011 (3) | 0.019 (3) |
C2 | 0.046 (4) | 0.049 (4) | 0.036 (4) | 0.015 (4) | 0.014 (3) | 0.016 (4) |
C3 | 0.060 (5) | 0.037 (4) | 0.061 (6) | 0.004 (4) | 0.015 (4) | 0.017 (4) |
C4 | 0.046 (5) | 0.051 (5) | 0.090 (7) | 0.010 (4) | 0.028 (5) | 0.035 (5) |
C5 | 0.068 (6) | 0.080 (6) | 0.082 (7) | 0.031 (5) | 0.051 (5) | 0.052 (6) |
C6 | 0.058 (5) | 0.050 (4) | 0.051 (5) | 0.020 (4) | 0.031 (4) | 0.019 (4) |
C7 | 0.040 (4) | 0.044 (4) | 0.028 (4) | 0.011 (3) | 0.012 (3) | 0.009 (3) |
C8 | 0.036 (4) | 0.058 (5) | 0.053 (5) | 0.019 (4) | 0.006 (4) | 0.013 (4) |
C9 | 0.051 (5) | 0.075 (6) | 0.065 (6) | 0.042 (5) | 0.026 (5) | 0.023 (5) |
C10 | 0.084 (7) | 0.076 (6) | 0.069 (7) | 0.048 (6) | 0.025 (6) | 0.007 (5) |
C11 | 0.087 (8) | 0.088 (7) | 0.078 (8) | 0.036 (6) | 0.002 (6) | −0.030 (6) |
C12 | 0.047 (5) | 0.078 (6) | 0.052 (5) | 0.037 (4) | 0.003 (4) | −0.001 (5) |
C13 | 0.035 (4) | 0.036 (4) | 0.030 (4) | 0.008 (3) | 0.010 (3) | 0.012 (3) |
C14 | 0.046 (4) | 0.041 (4) | 0.044 (5) | 0.011 (4) | 0.016 (4) | 0.019 (3) |
C15 | 0.057 (5) | 0.044 (4) | 0.058 (5) | 0.018 (4) | 0.022 (4) | 0.013 (4) |
C16 | 0.088 (8) | 0.055 (6) | 0.081 (7) | 0.025 (5) | 0.024 (6) | 0.014 (5) |
C17 | 0.117 (11) | 0.053 (6) | 0.101 (9) | 0.005 (7) | 0.032 (8) | −0.005 (6) |
C18 | 0.069 (7) | 0.076 (7) | 0.099 (9) | −0.021 (6) | 0.007 (6) | 0.001 (7) |
C19 | 0.045 (5) | 0.077 (6) | 0.070 (6) | 0.014 (5) | 0.015 (4) | 0.021 (5) |
C20 | 0.047 (4) | 0.053 (4) | 0.031 (4) | 0.028 (4) | 0.021 (3) | 0.020 (4) |
C21 | 0.050 (5) | 0.061 (5) | 0.039 (5) | 0.029 (4) | 0.014 (4) | 0.016 (4) |
C22 | 0.058 (6) | 0.099 (7) | 0.043 (5) | 0.035 (5) | 0.005 (4) | 0.014 (5) |
C23 | 0.095 (8) | 0.122 (9) | 0.046 (6) | 0.074 (7) | 0.025 (6) | 0.047 (6) |
C24 | 0.081 (7) | 0.098 (7) | 0.063 (6) | 0.049 (6) | 0.025 (5) | 0.049 (6) |
C25 | 0.058 (5) | 0.074 (5) | 0.053 (5) | 0.029 (4) | 0.023 (4) | 0.036 (4) |
C26 | 0.036 (4) | 0.050 (5) | 0.064 (6) | 0.014 (4) | 0.007 (4) | 0.016 (4) |
C27 | 0.054 (6) | 0.053 (5) | 0.076 (7) | 0.015 (4) | −0.005 (5) | −0.006 (5) |
C28 | 0.069 (6) | 0.080 (7) | 0.050 (6) | 0.032 (6) | −0.001 (5) | −0.002 (5) |
C29 | 0.054 (5) | 0.074 (6) | 0.044 (5) | 0.037 (5) | 0.012 (4) | 0.014 (5) |
C30 | 0.098 (8) | 0.113 (9) | 0.044 (6) | 0.062 (7) | 0.016 (5) | 0.025 (6) |
C31 | 0.102 (8) | 0.132 (9) | 0.055 (7) | 0.075 (8) | 0.044 (6) | 0.057 (7) |
C32 | 0.076 (6) | 0.085 (6) | 0.061 (6) | 0.050 (5) | 0.043 (5) | 0.045 (5) |
C33 | 0.103 (8) | 0.084 (7) | 0.089 (8) | 0.044 (6) | 0.059 (7) | 0.061 (6) |
C34 | 0.076 (7) | 0.056 (5) | 0.109 (9) | 0.023 (5) | 0.046 (6) | 0.048 (6) |
C35 | 0.053 (5) | 0.045 (5) | 0.073 (6) | 0.016 (4) | 0.023 (4) | 0.030 (4) |
C36 | 0.046 (4) | 0.064 (5) | 0.040 (5) | 0.033 (4) | 0.025 (4) | 0.028 (4) |
C37 | 0.039 (4) | 0.052 (4) | 0.037 (4) | 0.027 (4) | 0.016 (3) | 0.013 (4) |
B1 | 0.065 (8) | 0.093 (9) | 0.060 (8) | 0.030 (7) | 0.019 (6) | 0.020 (7) |
F1 | 0.147 (9) | 0.157 (9) | 0.200 (12) | 0.111 (7) | 0.087 (8) | 0.108 (9) |
F2 | 0.210 (12) | 0.127 (8) | 0.062 (6) | 0.032 (8) | 0.001 (6) | 0.031 (5) |
F3 | 0.107 (8) | 0.136 (9) | 0.197 (14) | 0.049 (7) | 0.098 (9) | 0.061 (9) |
F4 | 0.137 (8) | 0.095 (7) | 0.085 (7) | 0.003 (6) | 0.037 (6) | −0.013 (5) |
C38 | 0.18 (2) | 0.19 (2) | 0.19 (2) | 0.068 (13) | 0.057 (12) | 0.062 (12) |
Cl1 | 0.159 (6) | 0.103 (4) | 0.122 (5) | 0.024 (4) | 0.047 (5) | 0.060 (4) |
Cl2 | 0.178 (8) | 0.246 (9) | 0.233 (9) | 0.034 (7) | 0.024 (7) | 0.071 (8) |
F1' | 0.159 (15) | 0.159 (15) | 0.159 (15) | 0.056 (5) | 0.052 (5) | 0.053 (5) |
F2' | 0.08 (2) | 0.15 (3) | 0.16 (4) | 0.024 (19) | 0.07 (2) | −0.03 (3) |
F3' | 0.172 (16) | 0.172 (16) | 0.172 (16) | 0.061 (6) | 0.057 (5) | 0.057 (5) |
F4' | 0.21 (5) | 0.24 (6) | 0.24 (6) | −0.10 (4) | 0.04 (4) | 0.17 (5) |
C38' | 0.070 (10) | 0.090 (12) | 0.089 (12) | 0.037 (8) | 0.023 (8) | 0.033 (8) |
Cl1' | 0.198 (8) | 0.159 (6) | 0.177 (7) | 0.071 (6) | 0.089 (6) | 0.108 (5) |
Cl2' | 0.101 (4) | 0.091 (4) | 0.107 (5) | 0.004 (3) | 0.021 (4) | 0.011 (4) |
Cu1—N1 | 2.111 (5) | C19—H19 | 0.9300 |
Cu1—N2 | 2.124 (5) | C20—C21 | 1.368 (9) |
Cu1—P1 | 2.231 (2) | C20—C25 | 1.403 (9) |
Cu1—P2i | 2.269 (2) | C21—C22 | 1.409 (11) |
P1—C7 | 1.821 (7) | C21—H21 | 0.9300 |
P1—C13 | 1.836 (6) | C22—C23 | 1.364 (12) |
P1—C1 | 1.837 (7) | C22—H22 | 0.9300 |
P2—C14 | 1.820 (7) | C23—C24 | 1.352 (12) |
P2—C20 | 1.831 (7) | C23—H23 | 0.9300 |
P2—C13 | 1.845 (6) | C24—C25 | 1.365 (11) |
P2—Cu1i | 2.269 (2) | C24—H24 | 0.9300 |
N1—C26 | 1.319 (8) | C25—H25 | 0.9300 |
N1—C37 | 1.360 (8) | C26—C27 | 1.399 (11) |
N2—C35 | 1.325 (8) | C26—H26 | 0.9300 |
N2—C36 | 1.356 (9) | C27—C28 | 1.333 (12) |
C1—C2 | 1.377 (9) | C27—H27 | 0.9300 |
C1—C6 | 1.398 (9) | C28—C29 | 1.393 (12) |
C2—C3 | 1.377 (9) | C28—H28 | 0.9300 |
C2—H2 | 0.9300 | C29—C37 | 1.404 (10) |
C3—C4 | 1.365 (10) | C29—C30 | 1.422 (12) |
C3—H3 | 0.9300 | C30—C31 | 1.329 (13) |
C4—C5 | 1.364 (11) | C30—H30 | 0.9300 |
C4—H4 | 0.9300 | C31—C32 | 1.439 (13) |
C5—C6 | 1.369 (10) | C31—H31 | 0.9300 |
C5—H5 | 0.9300 | C32—C33 | 1.386 (12) |
C6—H6 | 0.9300 | C32—C36 | 1.406 (10) |
C7—C12 | 1.368 (9) | C33—C34 | 1.347 (12) |
C7—C8 | 1.391 (10) | C33—H33 | 0.9300 |
C8—C9 | 1.383 (10) | C34—C35 | 1.395 (11) |
C8—H8 | 0.9300 | C34—H34 | 0.9300 |
C9—C10 | 1.345 (11) | C35—H35 | 0.9300 |
C9—H9 | 0.9300 | C36—C37 | 1.437 (10) |
C10—C11 | 1.354 (13) | B1—F2 | 1.346 (8) |
C10—H10 | 0.9300 | B1—F4 | 1.346 (8) |
C11—C12 | 1.397 (11) | B1—F2' | 1.353 (10) |
C11—H11 | 0.9300 | B1—F3 | 1.354 (8) |
C12—H12 | 0.9300 | B1—F1' | 1.356 (10) |
C13—H13A | 0.9700 | B1—F3' | 1.360 (10) |
C13—H13B | 0.9700 | B1—F1 | 1.362 (8) |
C14—C15 | 1.392 (10) | B1—F4' | 1.370 (10) |
C14—C19 | 1.397 (11) | C38—Cl2 | 1.743 (10) |
C15—C16 | 1.355 (11) | C38—Cl1 | 1.748 (10) |
C15—H15 | 0.9300 | C38—H38A | 0.9700 |
C16—C17 | 1.332 (14) | C38—H38B | 0.9700 |
C16—H16 | 0.9300 | C38'—Cl1' | 1.748 (10) |
C17—C18 | 1.372 (15) | C38'—Cl2' | 1.753 (10) |
C17—H17 | 0.9300 | C38'—H38C | 0.9700 |
C18—C19 | 1.410 (12) | C38'—H38D | 0.9700 |
C18—H18 | 0.9300 | ||
N1—Cu1—N2 | 79.2 (2) | C22—C21—H21 | 120.0 |
N1—Cu1—P1 | 121.60 (15) | C23—C22—C21 | 119.7 (9) |
N2—Cu1—P1 | 106.47 (16) | C23—C22—H22 | 120.2 |
N1—Cu1—P2i | 98.91 (15) | C21—C22—H22 | 120.2 |
N2—Cu1—P2i | 102.78 (15) | C24—C23—C22 | 120.4 (8) |
P1—Cu1—P2i | 133.33 (8) | C24—C23—H23 | 119.8 |
C7—P1—C13 | 102.5 (3) | C22—C23—H23 | 119.8 |
C7—P1—C1 | 102.8 (3) | C23—C24—C25 | 121.1 (9) |
C13—P1—C1 | 100.2 (3) | C23—C24—H24 | 119.5 |
C7—P1—Cu1 | 117.3 (2) | C25—C24—H24 | 119.5 |
C13—P1—Cu1 | 124.0 (2) | C24—C25—C20 | 120.1 (8) |
C1—P1—Cu1 | 106.9 (2) | C24—C25—H25 | 119.9 |
C14—P2—C20 | 102.6 (3) | C20—C25—H25 | 119.9 |
C14—P2—C13 | 106.0 (3) | N1—C26—C27 | 123.1 (8) |
C20—P2—C13 | 100.8 (3) | N1—C26—H26 | 118.5 |
C14—P2—Cu1i | 119.2 (2) | C27—C26—H26 | 118.5 |
C20—P2—Cu1i | 105.0 (2) | C28—C27—C26 | 119.3 (9) |
C13—P2—Cu1i | 120.2 (2) | C28—C27—H27 | 120.4 |
C26—N1—C37 | 117.5 (6) | C26—C27—H27 | 120.4 |
C26—N1—Cu1 | 129.3 (5) | C27—C28—C29 | 120.5 (9) |
C37—N1—Cu1 | 112.9 (4) | C27—C28—H28 | 119.8 |
C35—N2—C36 | 117.7 (6) | C29—C28—H28 | 119.8 |
C35—N2—Cu1 | 130.0 (5) | C28—C29—C37 | 117.1 (8) |
C36—N2—Cu1 | 112.3 (4) | C28—C29—C30 | 124.0 (9) |
C2—C1—C6 | 117.6 (6) | C37—C29—C30 | 118.8 (8) |
C2—C1—P1 | 122.0 (5) | C31—C30—C29 | 121.1 (9) |
C6—C1—P1 | 120.1 (5) | C31—C30—H30 | 119.5 |
C3—C2—C1 | 121.1 (7) | C29—C30—H30 | 119.5 |
C3—C2—H2 | 119.4 | C30—C31—C32 | 122.5 (9) |
C1—C2—H2 | 119.4 | C30—C31—H31 | 118.7 |
C4—C3—C2 | 120.7 (7) | C32—C31—H31 | 118.7 |
C4—C3—H3 | 119.6 | C33—C32—C36 | 117.3 (9) |
C2—C3—H3 | 119.6 | C33—C32—C31 | 124.9 (9) |
C5—C4—C3 | 118.8 (7) | C36—C32—C31 | 117.8 (8) |
C5—C4—H4 | 120.6 | C34—C33—C32 | 120.8 (8) |
C3—C4—H4 | 120.6 | C34—C33—H33 | 119.6 |
C4—C5—C6 | 121.5 (7) | C32—C33—H33 | 119.6 |
C4—C5—H5 | 119.3 | C33—C34—C35 | 118.5 (8) |
C6—C5—H5 | 119.3 | C33—C34—H34 | 120.7 |
C5—C6—C1 | 120.3 (7) | C35—C34—H34 | 120.7 |
C5—C6—H6 | 119.9 | N2—C35—C34 | 123.3 (8) |
C1—C6—H6 | 119.9 | N2—C35—H35 | 118.3 |
C12—C7—C8 | 117.6 (6) | C34—C35—H35 | 118.3 |
C12—C7—P1 | 119.7 (6) | N2—C36—C32 | 122.3 (7) |
C8—C7—P1 | 122.7 (5) | N2—C36—C37 | 118.0 (6) |
C9—C8—C7 | 121.6 (7) | C32—C36—C37 | 119.6 (7) |
C9—C8—H8 | 119.2 | N1—C37—C29 | 122.5 (7) |
C7—C8—H8 | 119.2 | N1—C37—C36 | 117.3 (6) |
C10—C9—C8 | 119.4 (8) | C29—C37—C36 | 120.2 (7) |
C10—C9—H9 | 120.3 | F2—B1—F4 | 109.5 (8) |
C8—C9—H9 | 120.3 | F2—B1—F2' | 75.0 (14) |
C9—C10—C11 | 120.8 (8) | F4—B1—F2' | 134.4 (14) |
C9—C10—H10 | 119.6 | F2—B1—F3 | 112.9 (8) |
C11—C10—H10 | 119.6 | F4—B1—F3 | 106.6 (8) |
C10—C11—C12 | 120.4 (9) | F2'—B1—F3 | 40.2 (11) |
C10—C11—H11 | 119.8 | F2—B1—F1' | 62.6 (15) |
C12—C11—H11 | 119.8 | F4—B1—F1' | 111.5 (15) |
C7—C12—C11 | 120.2 (8) | F2'—B1—F1' | 110.3 (11) |
C7—C12—H12 | 119.9 | F3—B1—F1' | 140.7 (14) |
C11—C12—H12 | 119.9 | F2—B1—F3' | 171.5 (15) |
P1—C13—P2 | 118.9 (3) | F4—B1—F3' | 70.4 (15) |
P1—C13—H13A | 107.6 | F2'—B1—F3' | 111.4 (11) |
P2—C13—H13A | 107.6 | F3—B1—F3' | 74.7 (14) |
P1—C13—H13B | 107.6 | F1'—B1—F3' | 109.3 (11) |
P2—C13—H13B | 107.6 | F2—B1—F1 | 107.2 (7) |
H13A—C13—H13B | 107.0 | F4—B1—F1 | 112.3 (8) |
C15—C14—C19 | 118.6 (7) | F2'—B1—F1 | 109.0 (16) |
C15—C14—P2 | 122.5 (6) | F3—B1—F1 | 108.4 (8) |
C19—C14—P2 | 118.9 (6) | F1'—B1—F1 | 47.7 (15) |
C16—C15—C14 | 120.5 (8) | F3'—B1—F1 | 65.8 (15) |
C16—C15—H15 | 119.8 | F2—B1—F4' | 73.6 (17) |
C14—C15—H15 | 119.8 | F4—B1—F4' | 39.5 (15) |
C17—C16—C15 | 121.1 (10) | F2'—B1—F4' | 109.3 (11) |
C17—C16—H16 | 119.4 | F3—B1—F4' | 107.2 (16) |
C15—C16—H16 | 119.4 | F1'—B1—F4' | 108.1 (11) |
C16—C17—C18 | 122.0 (10) | F3'—B1—F4' | 108.4 (11) |
C16—C17—H17 | 119.0 | F1—B1—F4' | 140.4 (16) |
C18—C17—H17 | 119.0 | Cl2—C38—Cl1 | 105.8 (8) |
C17—C18—C19 | 118.3 (10) | Cl2—C38—H38A | 110.6 |
C17—C18—H18 | 120.8 | Cl1—C38—H38A | 110.6 |
C19—C18—H18 | 120.8 | Cl2—C38—H38B | 110.6 |
C14—C19—C18 | 119.6 (9) | Cl1—C38—H38B | 110.6 |
C14—C19—H19 | 120.2 | H38A—C38—H38B | 108.7 |
C18—C19—H19 | 120.2 | Cl1'—C38'—Cl2' | 106.5 (7) |
C21—C20—C25 | 118.8 (7) | Cl1'—C38'—H38C | 110.4 |
C21—C20—P2 | 123.1 (5) | Cl2'—C38'—H38C | 110.4 |
C25—C20—P2 | 117.8 (6) | Cl1'—C38'—H38D | 110.4 |
C20—C21—C22 | 119.9 (8) | Cl2'—C38'—H38D | 110.4 |
C20—C21—H21 | 120.0 | H38C—C38'—H38D | 108.6 |
N1—Cu1—P1—C7 | 3.0 (3) | Cu1i—P2—C14—C19 | −24.5 (7) |
N2—Cu1—P1—C7 | 90.3 (3) | C19—C14—C15—C16 | 0.5 (11) |
P2i—Cu1—P1—C7 | −143.1 (2) | P2—C14—C15—C16 | −179.7 (6) |
N1—Cu1—P1—C13 | 132.9 (3) | C14—C15—C16—C17 | −0.1 (14) |
N2—Cu1—P1—C13 | −139.8 (3) | C15—C16—C17—C18 | 0.5 (18) |
P2i—Cu1—P1—C13 | −13.2 (3) | C16—C17—C18—C19 | −1.1 (19) |
N1—Cu1—P1—C1 | −111.7 (3) | C15—C14—C19—C18 | −1.1 (12) |
N2—Cu1—P1—C1 | −24.4 (3) | P2—C14—C19—C18 | 179.0 (7) |
P2i—Cu1—P1—C1 | 102.2 (2) | C17—C18—C19—C14 | 1.5 (15) |
N2—Cu1—N1—C26 | 177.2 (6) | C14—P2—C20—C21 | −143.2 (6) |
P1—Cu1—N1—C26 | −80.0 (6) | C13—P2—C20—C21 | −34.0 (6) |
P2i—Cu1—N1—C26 | 75.7 (6) | Cu1i—P2—C20—C21 | 91.5 (6) |
N2—Cu1—N1—C37 | 4.5 (4) | C14—P2—C20—C25 | 43.5 (6) |
P1—Cu1—N1—C37 | 107.3 (4) | C13—P2—C20—C25 | 152.7 (5) |
P2i—Cu1—N1—C37 | −96.9 (4) | Cu1i—P2—C20—C25 | −81.8 (5) |
N1—Cu1—N2—C35 | 179.0 (6) | C25—C20—C21—C22 | 0.0 (11) |
P1—Cu1—N2—C35 | 59.0 (6) | P2—C20—C21—C22 | −173.3 (6) |
P2i—Cu1—N2—C35 | −84.2 (6) | C20—C21—C22—C23 | 0.5 (12) |
N1—Cu1—N2—C36 | −3.3 (4) | C21—C22—C23—C24 | −0.8 (13) |
P1—Cu1—N2—C36 | −123.3 (4) | C22—C23—C24—C25 | 0.6 (14) |
P2i—Cu1—N2—C36 | 93.5 (4) | C23—C24—C25—C20 | −0.2 (13) |
C7—P1—C1—C2 | 152.2 (6) | C21—C20—C25—C24 | −0.1 (11) |
C13—P1—C1—C2 | 46.8 (6) | P2—C20—C25—C24 | 173.5 (6) |
Cu1—P1—C1—C2 | −83.6 (6) | C37—N1—C26—C27 | −1.3 (10) |
C7—P1—C1—C6 | −34.2 (6) | Cu1—N1—C26—C27 | −173.6 (6) |
C13—P1—C1—C6 | −139.6 (6) | N1—C26—C27—C28 | 0.2 (13) |
Cu1—P1—C1—C6 | 89.9 (6) | C26—C27—C28—C29 | 0.2 (14) |
C6—C1—C2—C3 | 1.2 (11) | C27—C28—C29—C37 | 0.5 (13) |
P1—C1—C2—C3 | 174.9 (6) | C27—C28—C29—C30 | −179.8 (9) |
C1—C2—C3—C4 | −1.1 (12) | C28—C29—C30—C31 | −179.5 (9) |
C2—C3—C4—C5 | 0.3 (13) | C37—C29—C30—C31 | 0.2 (13) |
C3—C4—C5—C6 | 0.3 (13) | C29—C30—C31—C32 | 0.7 (15) |
C4—C5—C6—C1 | −0.1 (13) | C30—C31—C32—C33 | 179.8 (9) |
C2—C1—C6—C5 | −0.6 (11) | C30—C31—C32—C36 | −1.1 (13) |
P1—C1—C6—C5 | −174.4 (6) | C36—C32—C33—C34 | 0.7 (13) |
C13—P1—C7—C12 | −129.8 (6) | C31—C32—C33—C34 | 179.8 (9) |
C1—P1—C7—C12 | 126.6 (6) | C32—C33—C34—C35 | 0.8 (14) |
Cu1—P1—C7—C12 | 9.6 (7) | C36—N2—C35—C34 | 0.3 (11) |
C13—P1—C7—C8 | 51.2 (6) | Cu1—N2—C35—C34 | 178.0 (6) |
C1—P1—C7—C8 | −52.4 (6) | C33—C34—C35—N2 | −1.4 (13) |
Cu1—P1—C7—C8 | −169.4 (5) | C35—N2—C36—C32 | 1.3 (10) |
C12—C7—C8—C9 | 1.8 (11) | Cu1—N2—C36—C32 | −176.8 (5) |
P1—C7—C8—C9 | −179.1 (6) | C35—N2—C36—C37 | 179.7 (6) |
C7—C8—C9—C10 | −0.6 (12) | Cu1—N2—C36—C37 | 1.7 (7) |
C8—C9—C10—C11 | −0.4 (15) | C33—C32—C36—N2 | −1.8 (11) |
C9—C10—C11—C12 | 0.1 (17) | C31—C32—C36—N2 | 179.0 (7) |
C8—C7—C12—C11 | −2.1 (12) | C33—C32—C36—C37 | 179.8 (7) |
P1—C7—C12—C11 | 178.8 (8) | C31—C32—C36—C37 | 0.7 (11) |
C10—C11—C12—C7 | 1.2 (16) | C26—N1—C37—C29 | 2.0 (10) |
C7—P1—C13—P2 | 83.7 (4) | Cu1—N1—C37—C29 | 175.6 (5) |
C1—P1—C13—P2 | −170.6 (4) | C26—N1—C37—C36 | −178.7 (6) |
Cu1—P1—C13—P2 | −52.1 (5) | Cu1—N1—C37—C36 | −5.1 (7) |
C14—P2—C13—P1 | −51.9 (5) | C28—C29—C37—N1 | −1.6 (11) |
C20—P2—C13—P1 | −158.5 (4) | C30—C29—C37—N1 | 178.7 (7) |
Cu1i—P2—C13—P1 | 87.0 (4) | C28—C29—C37—C36 | 179.1 (7) |
C20—P2—C14—C15 | 40.2 (6) | C30—C29—C37—C36 | −0.6 (11) |
C13—P2—C14—C15 | −65.0 (7) | N2—C36—C37—N1 | 2.4 (9) |
Cu1i—P2—C14—C15 | 155.6 (5) | C32—C36—C37—N1 | −179.2 (6) |
C20—P2—C14—C19 | −139.9 (6) | N2—C36—C37—C29 | −178.3 (6) |
C13—P2—C14—C19 | 114.8 (6) | C32—C36—C37—C29 | 0.2 (10) |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C25H22P2)2(C12H8N2)2](BF4)2·2CH2Cl2 |
Mr | 1599.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.318 (5), 12.461 (5), 14.710 (6) |
α, β, γ (°) | 104.177 (7), 103.851 (7), 105.822 (7) |
V (Å3) | 1827.8 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.20 × 0.16 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.738, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9428, 6403, 3689 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.077, 0.197, 1.08 |
No. of reflections | 6403 |
No. of parameters | 515 |
No. of restraints | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.52 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Cu1—N1 | 2.111 (5) | Cu1—P1 | 2.231 (2) |
Cu1—N2 | 2.124 (5) | Cu1—P2i | 2.269 (2) |
N1—Cu1—N2 | 79.2 (2) | N1—Cu1—P2i | 98.91 (15) |
N1—Cu1—P1 | 121.60 (15) | N2—Cu1—P2i | 102.78 (15) |
N2—Cu1—P1 | 106.47 (16) | P1—Cu1—P2i | 133.33 (8) |
Symmetry code: (i) −x+2, −y, −z. |
The four-electron-donor diphosphine ligand, bis(diphenylphosphino)methane (dppm), is a very efficient bridging bidentate ligand and can form polynuclear complexes with most metal ions (Puddephatt, 1983; Morton & Orpen, 1992). Copper(I) complexes with dppm have received the most attention, due to their diverse coordination geometry and rich photophysical properties (Jitendra et al., 1999; Yam et al., 2001). Here, we report the preparation and crystal structure determination of the title compound, (I), a new dinuclear copper(I) complex with dppm.
The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. Compound (I) consists of a centrosymmetric dimer of [Cu(phen)(dppm)]+ cations (phen is 1,10-phenanthroline), tetrafluoroborate anions and solvent dichloromethane molecules. The two Cu centres are bridged by two dppm ligands to form a centrosymmetric eight-membered Cu2P4C2 ring. The remaining coordination sites on each Cu atom are occpuied by two N atoms of a phen ligand. The CuI atoms adopt a distorted tetrahedral coordination geometry, with the angles around the Cu atoms ranging from 79.2 (2)° for N1—Cu1—N2 to 133.33 (8)° for P1—Cu1—P2A.
Compound (I) can be regarded as similar to [Cu2(µ2-dppm)2(phen)2](PF6)2·2(CH3COCH3) (Kitagawa et al., 1991). The Cu—N and Cu—P bond distance are within the normal ranges (Reference for standard values?) and similar to those in the above-mentioned complex. The Cu···Cu separation of 4.720 (5) Å is shorter than that in the trinuclear complexes [Cu3(dppm)3(µ3-X)2]+ (X is Cl, Br and I; Jitendra et al., 1999).