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Acta Cryst. (2007). E63, m2096    [ doi:10.1107/S1600536807032539 ]

Bis[[mu]-bis(diphenylphosphino)methane-[kappa]2P:P']bis[(2,2'-bipyridine-[kappa]2N,N')copper(I)] bis(tetrafluoridoborate) diethyl ether disolvate

J. Mo, S.-M. Zhang, W.-Z. Ge and J.-H. Liu

Abstract top

The dinuclear cation of the title complex, [Cu2(C25H22P2)2(C10H8N2)2](BF4)2·2C4H10O, lies on a centre of inversion. Each CuI atom is coordinated by 2,2'-bipyridine (bpy) and bis(diphenylphosphino)methane (dppm) ligands, and has a distorted tetrahedral coordination geometry. The distance between the two CuI atoms separated by two dppm bridging ligands is 4.671 (3) Å. The solvent molecule and anion are each disordered over two positions; the site occupancy factor ratios are ca 0.56:0.44 and 0.6:0.4, respectively

Comment top

d10 polynuclear copper complexes generally exhibit rich luminescence and recently have attracted much attention on both a theoretical and a spectroscopic level (Pan et al., 2006; Pyykkö & Mendizabal, 1998; Ryu et al., 1993). A series of luminescent dinuclear d10 complexes with bridging phosphane ligands have been studied (Harvey et al., 1997; King et al., 1989; Perreault et al., 1992; Che et al., 2000). Here, we report crystal structure of [Cu2(dppm)2(bpy)2](BF4)2.2C4H10O, (I).

The Cu atom in (I) (Fig. 1) has a distorted tetrahedral coordination geometry involving two N atoms of 2,2'-bipyridine ligand and two P atoms of two (diphenylphosphino)methane ligand. The Cu—N bond lengths are 2.080 (3) and 2.109 (3) Å, while the Cu—P bonds are 2.272 (1) and 2.227 (1)Å [2 - x, 1 - y, -z](Table 1). The two CuI ions in (I) are doubly bridged by two (diphenylphosphino)methane ligands. There are no Cu—Cu bonds, as the measured distance (rCu···Cu = 4.471 (3) Å) is greater than the sum of the van der Waals radii (rvdW(Cu) = 1.40 Å).

Related literature top

For related literature, see: Che et al. (2000); Harvey et al. (1997); Ho & Bau (1983); King et al. (1989); Pan et al. (2006); Perreault et al. (1992); Pyykkö & Mendizabal (1998); Ryu et al. (1993).

Experimental top

A 10 ml me thanolic solution of 2,2'-bipyridine (0.078 g, 0.5 mmol, i.e. large excess) was added to a 20 mL me thanolic suspension of [Cu3(dppm)3(OH)](BF4)2 (0.0767 g, 0.05 mmol) (Ho & Bau, 1983) under N2 atmosphere. The mixture was stirred for 2 days. The filtrate was kept in diethyl ether atmosphere for two weeks, yellow crystals suitable for X-ray diffraction were formed.

Refinement top

All hydrogen atoms were generated geometrically (C—H bond lengths fixed at 0.93 Å), assigned appropriated isotropic thermal parameters, Uiso(H) = 1.2Ueq(C). The (BF4)- anions are disordered, F—B distances were restrained to 1.36 (1) Å. The ethyl ether molecules are disordered over two sites, the C···O and C···C distances were restrained to ensure a reasonable geometry.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: XP.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound showing the atom-numbering scheme and displacement ellipsoids drawn at the 40% probability level. The symmetry code for the unlabelled atoms is (2 - x, 1 - y, -z). Free (BF4)- anions are not shown.
Bis[µ-bis(diphenylphosphino)methane-κ2P:P'] bis[(2,2'-bipyridine-κ2N,N')copper(I)] bis(tetrafluoridoborate) diethyl ether disolvate top
Crystal data top
[Cu2(C25H22P2)2(C10H8N2)2](BF4)2·2C4H10OF(000) = 1584
Mr = 1530.09Dx = 1.357 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2605 reflections
a = 14.942 (5) Åθ = 3.0–26.4°
b = 13.432 (4) ŵ = 0.72 mm−1
c = 19.734 (6) ÅT = 294 K
β = 108.970 (6)°Block, yellow
V = 3746 (2) Å30.22 × 0.18 × 0.16 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		6602 independent reflections
Radiation source: fine-focus sealed tube4337 reflections with I > 2σ(I)
graphiteRint = 0.043
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→17
Tmin = 0.857, Tmax = 0.895k = −15→15
19160 measured reflectionsl = −23→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0582P)2 + 2.5517P]
where P = (Fo2 + 2Fc2)/3
6602 reflections(Δ/σ)max = 0.002
534 parametersΔρmax = 0.40 e Å−3
60 restraintsΔρmin = −0.31 e Å−3
Crystal data top
[Cu2(C25H22P2)2(C10H8N2)2](BF4)2·2C4H10OV = 3746 (2) Å3
Mr = 1530.09Z = 2
Monoclinic, P21/nMo Kα radiation
a = 14.942 (5) ŵ = 0.72 mm−1
b = 13.432 (4) ÅT = 294 K
c = 19.734 (6) Å0.22 × 0.18 × 0.16 mm
β = 108.970 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		6602 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4337 reflections with I > 2σ(I)
Tmin = 0.857, Tmax = 0.895Rint = 0.043
19160 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.40 e Å−3
S = 1.04Δρmin = −0.31 e Å−3
6602 reflectionsAbsolute structure: ?
534 parametersFlack parameter: ?
60 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.89350 (3)0.40826 (4)0.03928 (2)0.04066 (16)
P11.03081 (7)0.45536 (8)0.12368 (5)0.0379 (2)
P21.14667 (7)0.62233 (7)0.07772 (5)0.0375 (2)
N10.7958 (2)0.4649 (3)0.08405 (17)0.0475 (8)
N20.8587 (2)0.2798 (3)0.08685 (16)0.0490 (8)
C11.0103 (3)0.4376 (3)0.20948 (19)0.0435 (10)
C21.0196 (3)0.3430 (4)0.2392 (2)0.0608 (12)
H21.04350.29150.21860.073*
C30.9941 (4)0.3247 (5)0.2986 (3)0.0835 (17)
H31.00080.26100.31800.100*
C40.9592 (5)0.3989 (6)0.3295 (3)0.102 (2)
H40.94220.38610.37000.122*
C50.9491 (4)0.4928 (5)0.3008 (3)0.0912 (18)
H50.92490.54350.32180.109*
C60.9749 (3)0.5131 (4)0.2402 (2)0.0611 (12)
H60.96810.57690.22090.073*
C71.1341 (3)0.3783 (3)0.1327 (2)0.0433 (9)
C81.1349 (3)0.3209 (3)0.0746 (2)0.0602 (12)
H81.08360.32260.03250.072*
C91.2120 (4)0.2610 (4)0.0791 (3)0.0836 (16)
H91.21260.22260.04000.100*
C101.2877 (4)0.2588 (4)0.1416 (4)0.0833 (16)
H101.33960.21860.14460.100*
C111.2874 (3)0.3146 (4)0.1988 (3)0.0683 (14)
H111.33910.31260.24070.082*
C121.2114 (3)0.3739 (3)0.1953 (2)0.0522 (11)
H121.21150.41150.23490.063*
C131.0725 (3)0.5853 (3)0.13178 (19)0.0419 (9)
H13A1.01740.62850.11910.050*
H13B1.10790.59780.18170.050*
C141.2651 (3)0.5858 (3)0.1340 (2)0.0412 (9)
C151.3211 (3)0.5318 (4)0.1053 (2)0.0602 (12)
H151.29860.51410.05720.072*
C161.4115 (3)0.5026 (4)0.1473 (3)0.0801 (16)
H161.44900.46510.12750.096*
C171.4449 (4)0.5295 (4)0.2179 (3)0.0793 (16)
H171.50510.51000.24610.095*
C181.3902 (3)0.5849 (4)0.2470 (3)0.0691 (14)
H181.41370.60370.29490.083*
C191.3001 (3)0.6131 (3)0.2056 (2)0.0569 (11)
H191.26280.65040.22580.068*
C201.1524 (3)0.7576 (3)0.08989 (19)0.0441 (10)
C211.2357 (3)0.8070 (3)0.0957 (2)0.0610 (12)
H211.28910.77040.09720.073*
C221.2411 (4)0.9089 (4)0.0993 (3)0.0800 (16)
H221.29800.94100.10390.096*
C231.1627 (6)0.9626 (4)0.0960 (3)0.099 (2)
H231.16591.03170.09780.118*
C241.0790 (5)0.9161 (4)0.0902 (3)0.0911 (18)
H241.02580.95350.08820.109*
C251.0738 (4)0.8137 (3)0.0875 (3)0.0640 (13)
H251.01700.78220.08400.077*
C260.7694 (3)0.5600 (4)0.0828 (2)0.0627 (12)
H260.79020.60480.05520.075*
C270.7126 (4)0.5950 (5)0.1205 (3)0.0807 (16)
H270.69440.66150.11800.097*
C280.6842 (4)0.5284 (6)0.1613 (3)0.094 (2)
H280.64590.54950.18740.113*
C290.7113 (4)0.4309 (5)0.1644 (3)0.0818 (17)
H290.69250.38590.19300.098*
C300.7671 (3)0.4002 (4)0.1244 (2)0.0553 (12)
C310.7986 (3)0.2970 (4)0.1233 (2)0.0541 (11)
C320.7680 (4)0.2190 (5)0.1572 (3)0.0801 (16)
H320.72700.23100.18310.096*
C330.7994 (4)0.1252 (5)0.1518 (3)0.0911 (19)
H330.77840.07240.17320.109*
C340.8606 (4)0.1078 (4)0.1155 (3)0.0785 (16)
H340.88280.04390.11220.094*
C350.8889 (3)0.1871 (3)0.0839 (2)0.0601 (12)
H350.93120.17570.05900.072*
B10.3873 (4)0.7013 (4)0.6889 (4)0.104 (3)
F10.4849 (4)0.7197 (6)0.7232 (5)0.147 (4)0.610 (11)
F20.3676 (7)0.7312 (8)0.6190 (4)0.122 (3)0.610 (11)
F30.3700 (6)0.6049 (4)0.6941 (4)0.112 (3)0.610 (11)
F40.3431 (5)0.7569 (5)0.7258 (3)0.105 (3)0.610 (11)
F1'0.3974 (9)0.7667 (8)0.6416 (7)0.097 (4)0.390 (11)
F2'0.2924 (7)0.6907 (12)0.6820 (9)0.178 (7)0.390 (11)
F3'0.4112 (11)0.6097 (7)0.6678 (8)0.145 (6)0.390 (11)
F4'0.4378 (13)0.7177 (14)0.7567 (6)0.250 (11)0.390 (11)
O10.9395 (6)0.3004 (6)0.4884 (4)0.111 (4)0.565 (13)
C360.8268 (11)0.4325 (12)0.4737 (10)0.154 (7)0.565 (13)
H36A0.81280.49110.49630.231*0.565 (13)
H36B0.77630.38530.46630.231*0.565 (13)
H36C0.83340.45010.42840.231*0.565 (13)
C370.9196 (10)0.3860 (10)0.5220 (8)0.132 (6)0.565 (13)
H37A0.97090.43360.53020.158*0.565 (13)
H37B0.91360.36840.56800.158*0.565 (13)
C381.0271 (10)0.2522 (11)0.5241 (11)0.174 (9)0.565 (13)
H38A1.03830.25240.57530.208*0.565 (13)
H38B1.07830.28840.51510.208*0.565 (13)
C391.0260 (11)0.1472 (10)0.4984 (10)0.140 (7)0.565 (13)
H39A1.08530.11580.52340.210*0.565 (13)
H39B1.01660.14720.44790.210*0.565 (13)
H39C0.97550.11130.50750.210*0.565 (13)
O1'0.9797 (12)0.3255 (13)0.5339 (14)0.282 (14)0.435 (13)
C36'0.878 (2)0.4681 (16)0.486 (2)0.26 (2)0.435 (13)
H36D0.81310.48940.47240.388*0.435 (13)
H36E0.90170.47730.44720.388*0.435 (13)
H36F0.91490.50660.52680.388*0.435 (13)
C37'0.8839 (11)0.3579 (14)0.5071 (14)0.132 (9)0.435 (13)
H37C0.85390.34760.54330.159*0.435 (13)
H37D0.85010.31850.46540.159*0.435 (13)
C38'0.9885 (14)0.2185 (13)0.5302 (11)0.136 (9)0.435 (13)
H38C0.92650.18920.50820.163*0.435 (13)
H38D1.01480.19160.57820.163*0.435 (13)
C39'1.0519 (12)0.1928 (14)0.4870 (8)0.095 (6)0.435 (13)
H39D1.06080.12200.48740.142*0.435 (13)
H39E1.11200.22500.50750.142*0.435 (13)
H39F1.02320.21510.43850.142*0.435 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0417 (3)0.0494 (3)0.0327 (3)−0.0030 (2)0.0147 (2)0.0003 (2)
P10.0407 (5)0.0450 (6)0.0298 (5)−0.0031 (4)0.0139 (4)0.0015 (4)
P20.0400 (5)0.0418 (6)0.0323 (5)−0.0020 (4)0.0139 (4)0.0004 (4)
N10.0436 (18)0.059 (2)0.0419 (19)−0.0036 (17)0.0164 (16)−0.0069 (16)
N20.054 (2)0.056 (2)0.0365 (18)−0.0080 (17)0.0140 (16)0.0053 (16)
C10.042 (2)0.062 (3)0.0276 (19)−0.0058 (19)0.0123 (17)0.0022 (18)
C20.065 (3)0.077 (3)0.042 (2)−0.006 (2)0.019 (2)0.017 (2)
C30.095 (4)0.102 (5)0.056 (3)−0.007 (3)0.029 (3)0.028 (3)
C40.117 (5)0.149 (7)0.057 (3)−0.011 (5)0.052 (4)0.027 (4)
C50.101 (4)0.130 (6)0.060 (3)0.003 (4)0.049 (3)−0.013 (4)
C60.066 (3)0.079 (3)0.044 (2)0.000 (2)0.026 (2)0.000 (2)
C70.047 (2)0.042 (2)0.045 (2)−0.0052 (18)0.0205 (19)0.0032 (18)
C80.061 (3)0.064 (3)0.057 (3)0.006 (2)0.021 (2)−0.005 (2)
C90.093 (4)0.072 (4)0.095 (4)0.019 (3)0.043 (4)−0.014 (3)
C100.071 (4)0.071 (4)0.117 (5)0.026 (3)0.042 (4)0.019 (3)
C110.056 (3)0.076 (4)0.070 (3)0.010 (3)0.016 (3)0.028 (3)
C120.049 (2)0.061 (3)0.046 (2)0.000 (2)0.013 (2)0.013 (2)
C130.049 (2)0.045 (2)0.037 (2)−0.0013 (18)0.0205 (18)−0.0009 (17)
C140.041 (2)0.043 (2)0.039 (2)−0.0022 (18)0.0124 (17)0.0020 (18)
C150.046 (2)0.077 (3)0.053 (3)0.002 (2)0.010 (2)−0.001 (2)
C160.052 (3)0.099 (4)0.085 (4)0.015 (3)0.016 (3)0.001 (3)
C170.050 (3)0.088 (4)0.080 (4)−0.002 (3)−0.006 (3)0.016 (3)
C180.064 (3)0.075 (3)0.049 (3)−0.013 (3)−0.008 (2)0.010 (2)
C190.064 (3)0.057 (3)0.046 (2)−0.008 (2)0.012 (2)−0.005 (2)
C200.060 (3)0.043 (2)0.033 (2)−0.004 (2)0.0193 (19)−0.0005 (17)
C210.069 (3)0.053 (3)0.059 (3)−0.016 (2)0.018 (2)0.006 (2)
C220.102 (4)0.058 (3)0.082 (4)−0.030 (3)0.031 (3)−0.001 (3)
C230.168 (7)0.046 (3)0.101 (5)−0.016 (4)0.070 (5)−0.001 (3)
C240.131 (5)0.052 (3)0.113 (5)0.017 (3)0.072 (4)−0.001 (3)
C250.086 (3)0.047 (3)0.074 (3)0.002 (2)0.046 (3)−0.004 (2)
C260.052 (3)0.074 (4)0.060 (3)−0.003 (2)0.015 (2)−0.018 (2)
C270.064 (3)0.092 (4)0.090 (4)0.004 (3)0.029 (3)−0.035 (3)
C280.063 (3)0.139 (6)0.094 (4)−0.004 (4)0.042 (3)−0.046 (4)
C290.061 (3)0.124 (5)0.073 (3)−0.019 (3)0.040 (3)−0.017 (3)
C300.040 (2)0.089 (4)0.039 (2)−0.015 (2)0.0163 (19)−0.009 (2)
C310.046 (2)0.076 (3)0.040 (2)−0.016 (2)0.014 (2)0.006 (2)
C320.068 (3)0.107 (5)0.071 (3)−0.015 (3)0.031 (3)0.020 (3)
C330.089 (4)0.090 (5)0.091 (4)−0.023 (4)0.023 (4)0.035 (4)
C340.090 (4)0.063 (3)0.072 (3)0.000 (3)0.013 (3)0.025 (3)
C350.068 (3)0.060 (3)0.048 (3)−0.001 (2)0.012 (2)0.012 (2)
B10.094 (6)0.087 (6)0.145 (8)0.034 (5)0.057 (6)0.046 (6)
F10.103 (5)0.167 (6)0.176 (7)−0.011 (4)0.051 (5)−0.010 (5)
F20.131 (7)0.137 (7)0.113 (5)0.028 (5)0.057 (5)0.022 (5)
F30.136 (6)0.061 (4)0.147 (6)−0.006 (3)0.055 (4)0.009 (3)
F40.133 (6)0.105 (5)0.108 (5)0.040 (4)0.080 (4)0.024 (3)
F1'0.097 (7)0.072 (6)0.142 (9)−0.001 (5)0.067 (6)0.023 (6)
F2'0.161 (9)0.189 (11)0.207 (11)−0.017 (8)0.093 (8)0.043 (8)
F3'0.169 (9)0.090 (7)0.180 (10)0.013 (6)0.063 (7)0.009 (6)
F4'0.261 (14)0.261 (14)0.235 (13)−0.019 (10)0.092 (9)−0.018 (9)
O10.116 (6)0.120 (7)0.077 (5)0.026 (5)0.003 (4)0.013 (4)
C360.161 (10)0.152 (10)0.162 (10)0.022 (8)0.070 (8)−0.010 (8)
C370.140 (10)0.135 (10)0.108 (9)−0.039 (8)0.024 (8)0.009 (8)
C380.168 (12)0.172 (12)0.168 (11)0.004 (9)0.036 (9)0.006 (9)
C390.128 (10)0.150 (10)0.133 (10)0.013 (8)0.030 (7)0.011 (8)
O1'0.281 (16)0.279 (16)0.283 (17)0.025 (10)0.088 (10)−0.028 (10)
C36'0.25 (2)0.27 (2)0.25 (2)0.008 (10)0.092 (12)−0.009 (10)
C37'0.127 (12)0.173 (13)0.112 (11)−0.034 (9)0.060 (9)−0.001 (9)
C38'0.139 (11)0.124 (12)0.133 (11)−0.022 (9)0.030 (9)0.014 (8)
C39'0.099 (9)0.087 (9)0.084 (8)0.015 (7)0.009 (7)0.017 (7)
Geometric parameters (Å, °) top
Cu1—N12.080 (3)C23—H230.9300
Cu1—N22.109 (3)C24—C251.377 (7)
Cu1—P2i2.2268 (12)C24—H240.9300
Cu1—P12.2720 (12)C25—H250.9300
P1—C71.819 (4)C26—C271.380 (7)
P1—C11.831 (4)C26—H260.9300
P1—C131.843 (4)C27—C281.361 (8)
P2—C141.824 (4)C27—H270.9300
P2—C201.831 (4)C28—C291.366 (8)
P2—C131.839 (4)C28—H280.9300
P2—Cu1i2.2267 (12)C29—C301.385 (6)
N1—C261.335 (6)C29—H290.9300
N1—C301.340 (5)C30—C311.467 (6)
N2—C351.331 (5)C31—C321.398 (6)
N2—C311.340 (5)C32—C331.361 (8)
C1—C61.372 (6)C32—H320.9300
C1—C21.387 (6)C33—C341.353 (8)
C2—C31.367 (6)C33—H330.9300
C2—H20.9300C34—C351.370 (6)
C3—C41.357 (8)C34—H340.9300
C3—H30.9300C35—H350.9300
C4—C51.371 (8)B1—F4'1.324 (9)
C4—H40.9300B1—F1'1.325 (9)
C5—C61.397 (6)B1—F31.331 (7)
C5—H50.9300B1—F41.356 (7)
C6—H60.9300B1—F21.374 (8)
C7—C81.385 (6)B1—F3'1.383 (9)
C7—C121.391 (5)B1—F2'1.388 (9)
C8—C91.383 (6)B1—F11.416 (7)
C8—H80.9300O1—C371.408 (9)
C9—C101.377 (7)O1—C381.425 (9)
C9—H90.9300C36—C371.537 (9)
C10—C111.357 (7)C36—H36A0.9600
C10—H100.9300C36—H36B0.9600
C11—C121.370 (6)C36—H36C0.9600
C11—H110.9300C37—H37A0.9700
C12—H120.9300C37—H37B0.9700
C13—H13A0.9700C38—C391.497 (10)
C13—H13B0.9700C38—H38A0.9700
C14—C151.361 (6)C38—H38B0.9700
C14—C191.388 (5)C39—H39A0.9600
C15—C161.392 (6)C39—H39B0.9600
C15—H150.9300C39—H39C0.9600
C16—C171.366 (7)O1'—C37'1.424 (10)
C16—H160.9300O1'—C38'1.446 (10)
C17—C181.361 (7)C36'—C37'1.530 (10)
C17—H170.9300C36'—H36D0.9600
C18—C191.382 (6)C36'—H36E0.9600
C18—H180.9300C36'—H36F0.9600
C19—H190.9300C37'—H37C0.9700
C20—C211.382 (6)C37'—H37D0.9700
C20—C251.384 (6)C38'—C39'1.507 (10)
C21—C221.372 (7)C38'—H38C0.9700
C21—H210.9300C38'—H38D0.9700
C22—C231.360 (8)C39'—H39D0.9600
C22—H220.9300C39'—H39E0.9600
C23—C241.369 (8)C39'—H39F0.9600
N1—Cu1—N278.56 (14)C28—C27—C26117.3 (6)
N1—Cu1—P2i121.20 (9)C28—C27—H27121.3
N2—Cu1—P2i106.75 (9)C26—C27—H27121.3
N1—Cu1—P1100.25 (9)C27—C28—C29120.9 (5)
N2—Cu1—P1101.31 (9)C27—C28—H28119.6
P2i—Cu1—P1133.33 (4)C29—C28—H28119.6
C7—P1—C1103.12 (18)C28—C29—C30118.9 (6)
C7—P1—C13106.19 (17)C28—C29—H29120.5
C1—P1—C13101.34 (18)C30—C29—H29120.5
C7—P1—Cu1116.65 (13)N1—C30—C29121.0 (5)
C1—P1—Cu1105.00 (12)N1—C30—C31115.9 (4)
C13—P1—Cu1121.76 (13)C29—C30—C31123.1 (5)
C14—P2—C20101.10 (18)N2—C31—C32120.5 (5)
C14—P2—C13102.87 (18)N2—C31—C30116.5 (4)
C20—P2—C13101.71 (17)C32—C31—C30123.0 (4)
C14—P2—Cu1i117.56 (13)C33—C32—C31118.8 (5)
C20—P2—Cu1i107.72 (12)C33—C32—H32120.6
C13—P2—Cu1i122.78 (13)C31—C32—H32120.6
C26—N1—C30118.8 (4)C34—C33—C32120.8 (5)
C26—N1—Cu1125.9 (3)C34—C33—H33119.6
C30—N1—Cu1114.8 (3)C32—C33—H33119.6
C35—N2—C31118.7 (4)C33—C34—C35117.9 (5)
C35—N2—Cu1127.5 (3)C33—C34—H34121.0
C31—N2—Cu1113.7 (3)C35—C34—H34121.0
C6—C1—C2119.3 (4)N2—C35—C34123.2 (5)
C6—C1—P1121.1 (3)N2—C35—H35118.4
C2—C1—P1119.1 (3)C34—C35—H35118.4
C3—C2—C1120.6 (5)F4'—B1—F1'116.4 (9)
C3—C2—H2119.7F4'—B1—F398.3 (10)
C1—C2—H2119.7F1'—B1—F3140.2 (8)
C4—C3—C2120.5 (5)F4'—B1—F465.3 (9)
C4—C3—H3119.8F1'—B1—F4101.6 (7)
C2—C3—H3119.8F3—B1—F4110.7 (6)
C3—C4—C5119.8 (5)F4'—B1—F2146.4 (10)
C3—C4—H4120.1F1'—B1—F230.1 (6)
C5—C4—H4120.1F3—B1—F2112.2 (7)
C4—C5—C6120.6 (6)F4—B1—F2113.3 (6)
C4—C5—H5119.7F4'—B1—F3'109.5 (9)
C6—C5—H5119.7F1'—B1—F3'106.2 (8)
C1—C6—C5119.2 (5)F3—B1—F3'39.9 (6)
C1—C6—H6120.4F4—B1—F3'150.5 (8)
C5—C6—H6120.4F2—B1—F3'87.1 (8)
C8—C7—C12118.9 (4)F4'—B1—F2'110.1 (9)
C8—C7—P1118.1 (3)F1'—B1—F2'110.2 (8)
C12—C7—P1122.9 (3)F3—B1—F2'71.9 (7)
C9—C8—C7120.1 (5)F4—B1—F2'56.5 (7)
C9—C8—H8119.9F2—B1—F2'93.0 (8)
C7—C8—H8119.9F3'—B1—F2'103.5 (8)
C10—C9—C8119.6 (5)F4'—B1—F147.8 (8)
C10—C9—H9120.2F1'—B1—F183.5 (7)
C8—C9—H9120.2F3—B1—F1109.2 (6)
C11—C10—C9120.6 (5)F4—B1—F1104.6 (6)
C11—C10—H10119.7F2—B1—F1106.3 (7)
C9—C10—H10119.7F3'—B1—F188.5 (7)
C10—C11—C12120.4 (5)F2'—B1—F1157.8 (9)
C10—C11—H11119.8C37—O1—C38116.0 (8)
C12—C11—H11119.8C37—C36—H36A109.5
C11—C12—C7120.3 (4)C37—C36—H36B109.5
C11—C12—H12119.8H36A—C36—H36B109.5
C7—C12—H12119.8C37—C36—H36C109.5
P2—C13—P1117.1 (2)H36A—C36—H36C109.5
P2—C13—H13A108.0H36B—C36—H36C109.5
P1—C13—H13A108.0O1—C37—C36109.0 (9)
P2—C13—H13B108.0O1—C37—H37A109.9
P1—C13—H13B108.0C36—C37—H37A109.9
H13A—C13—H13B107.3O1—C37—H37B109.9
C15—C14—C19119.0 (4)C36—C37—H37B109.9
C15—C14—P2119.7 (3)H37A—C37—H37B108.3
C19—C14—P2121.3 (3)O1—C38—C39110.7 (9)
C14—C15—C16120.7 (4)O1—C38—H38A109.5
C14—C15—H15119.6C39—C38—H38A109.5
C16—C15—H15119.6O1—C38—H38B109.5
C17—C16—C15119.6 (5)C39—C38—H38B109.5
C17—C16—H16120.2H38A—C38—H38B108.1
C15—C16—H16120.2C38—C39—H39A109.5
C18—C17—C16120.3 (5)C38—C39—H39B109.5
C18—C17—H17119.8H39A—C39—H39B109.5
C16—C17—H17119.8C38—C39—H39C109.5
C17—C18—C19120.2 (5)H39A—C39—H39C109.5
C17—C18—H18119.9H39B—C39—H39C109.5
C19—C18—H18119.9C37'—O1'—C38'112.4 (11)
C18—C19—C14120.1 (5)C37'—C36'—H36D109.5
C18—C19—H19119.9C37'—C36'—H36E109.5
C14—C19—H19119.9H36D—C36'—H36E109.5
C21—C20—C25118.2 (4)C37'—C36'—H36F109.5
C21—C20—P2119.3 (3)H36D—C36'—H36F109.5
C25—C20—P2122.3 (3)H36E—C36'—H36F109.5
C22—C21—C20121.4 (5)O1'—C37'—C36'111.1 (11)
C22—C21—H21119.3O1'—C37'—H37C109.4
C20—C21—H21119.3C36'—C37'—H37C109.4
C23—C22—C21119.3 (5)O1'—C37'—H37D109.4
C23—C22—H22120.3C36'—C37'—H37D109.4
C21—C22—H22120.3H37C—C37'—H37D108.0
C22—C23—C24120.8 (5)O1'—C38'—C39'109.8 (10)
C22—C23—H23119.6O1'—C38'—H38C109.7
C24—C23—H23119.6C39'—C38'—H38C109.7
C23—C24—C25119.8 (6)O1'—C38'—H38D109.7
C23—C24—H24120.1C39'—C38'—H38D109.7
C25—C24—H24120.1H38C—C38'—H38D108.2
C24—C25—C20120.4 (5)C38'—C39'—H39D109.5
C24—C25—H25119.8C38'—C39'—H39E109.5
C20—C25—H25119.8H39D—C39'—H39E109.5
N1—C26—C27123.1 (5)C38'—C39'—H39F109.5
N1—C26—H26118.5H39D—C39'—H39F109.5
C27—C26—H26118.5H39E—C39'—H39F109.5
N1—Cu1—P1—C7152.08 (17)Cu1i—P2—C14—C15−7.4 (4)
N2—Cu1—P1—C771.83 (17)C20—P2—C14—C1955.0 (4)
P2i—Cu1—P1—C7−54.52 (15)C13—P2—C14—C19−49.9 (4)
N1—Cu1—P1—C138.66 (18)Cu1i—P2—C14—C19171.9 (3)
N2—Cu1—P1—C1−41.59 (18)C19—C14—C15—C161.1 (7)
P2i—Cu1—P1—C1−167.94 (15)P2—C14—C15—C16−179.7 (4)
N1—Cu1—P1—C13−75.26 (17)C14—C15—C16—C17−0.7 (8)
N2—Cu1—P1—C13−155.50 (17)C15—C16—C17—C18−0.3 (8)
P2i—Cu1—P1—C1378.15 (15)C16—C17—C18—C190.9 (8)
N2—Cu1—N1—C26177.6 (3)C17—C18—C19—C14−0.5 (7)
P2i—Cu1—N1—C26−79.6 (3)C15—C14—C19—C18−0.5 (6)
P1—Cu1—N1—C2678.0 (3)P2—C14—C19—C18−179.7 (3)
N2—Cu1—N1—C305.9 (3)C14—P2—C20—C2136.8 (4)
P2i—Cu1—N1—C30108.7 (3)C13—P2—C20—C21142.6 (3)
P1—Cu1—N1—C30−93.7 (3)Cu1i—P2—C20—C21−87.1 (3)
N1—Cu1—N2—C35176.5 (4)C14—P2—C20—C25−148.7 (3)
P2i—Cu1—N2—C3557.1 (3)C13—P2—C20—C25−42.9 (4)
P1—Cu1—N2—C35−85.2 (3)Cu1i—P2—C20—C2587.4 (3)
N1—Cu1—N2—C31−3.0 (3)C25—C20—C21—C220.2 (6)
P2i—Cu1—N2—C31−122.4 (2)P2—C20—C21—C22174.9 (4)
P1—Cu1—N2—C3195.3 (3)C20—C21—C22—C23−1.0 (8)
C7—P1—C1—C6146.7 (3)C21—C22—C23—C240.9 (9)
C13—P1—C1—C636.9 (4)C22—C23—C24—C25−0.1 (10)
Cu1—P1—C1—C6−90.7 (3)C23—C24—C25—C20−0.6 (8)
C7—P1—C1—C2−41.4 (4)C21—C20—C25—C240.6 (7)
C13—P1—C1—C2−151.2 (3)P2—C20—C25—C24−173.9 (4)
Cu1—P1—C1—C281.3 (3)C30—N1—C26—C27−0.9 (6)
C6—C1—C2—C3−0.1 (6)Cu1—N1—C26—C27−172.3 (3)
P1—C1—C2—C3−172.2 (4)N1—C26—C27—C281.0 (7)
C1—C2—C3—C40.0 (8)C26—C27—C28—C290.0 (8)
C2—C3—C4—C50.2 (9)C27—C28—C29—C30−1.0 (8)
C3—C4—C5—C6−0.3 (10)C26—N1—C30—C29−0.2 (6)
C2—C1—C6—C50.1 (6)Cu1—N1—C30—C29172.1 (3)
P1—C1—C6—C5172.0 (4)C26—N1—C30—C31179.9 (3)
C4—C5—C6—C10.1 (8)Cu1—N1—C30—C31−7.8 (4)
C1—P1—C7—C8137.7 (3)C28—C29—C30—N11.1 (7)
C13—P1—C7—C8−116.2 (3)C28—C29—C30—C31−179.0 (4)
Cu1—P1—C7—C823.2 (4)C35—N2—C31—C32−0.2 (6)
C1—P1—C7—C12−41.8 (4)Cu1—N2—C31—C32179.3 (3)
C13—P1—C7—C1264.4 (4)C35—N2—C31—C30−179.6 (4)
Cu1—P1—C7—C12−156.3 (3)Cu1—N2—C31—C30−0.1 (4)
C12—C7—C8—C9−0.5 (7)N1—C30—C31—N25.2 (5)
P1—C7—C8—C9−179.9 (4)C29—C30—C31—N2−174.7 (4)
C7—C8—C9—C100.1 (8)N1—C30—C31—C32−174.1 (4)
C8—C9—C10—C110.0 (8)C29—C30—C31—C326.0 (6)
C9—C10—C11—C120.2 (8)N2—C31—C32—C33−0.9 (7)
C10—C11—C12—C7−0.6 (7)C30—C31—C32—C33178.4 (5)
C8—C7—C12—C110.7 (6)C31—C32—C33—C341.4 (8)
P1—C7—C12—C11−179.8 (3)C32—C33—C34—C35−0.9 (8)
C14—P2—C13—P1−85.4 (2)C31—N2—C35—C340.8 (6)
C20—P2—C13—P1170.2 (2)Cu1—N2—C35—C34−178.6 (3)
Cu1i—P2—C13—P150.0 (3)C33—C34—C35—N2−0.3 (7)
C7—P1—C13—P248.3 (3)C38—O1—C37—C36175.7 (16)
C1—P1—C13—P2155.7 (2)C37—O1—C38—C39160.8 (17)
Cu1—P1—C13—P2−88.6 (2)C38'—O1'—C37'—C36'−160 (2)
C20—P2—C14—C15−124.2 (4)C37'—O1'—C38'—C39'123 (2)
C13—P2—C14—C15130.9 (3)
Symmetry codes: (i) −x+2, −y+1, −z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N12.080 (3)Cu1—P2i2.2268 (12)
Cu1—N22.109 (3)Cu1—P12.2720 (12)
N1—Cu1—N278.56 (14)P2i—Cu1—P1133.33 (4)
Symmetry codes: (i) −x+2, −y+1, −z.
Acknowledgements top

We thank Henan Agricultural University and Heilongjiang August First Land Reclamation University for the generous support of this study.

references
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