catena-Poly[[[acetonitrile­copper(I)]-bis­[μ-bis­(diphenyl­phosphino)methane-κ2P:P′]-copper(I)-μ-1,2-di-4-pyridy­l­ethene] bis­(tetra­fluoridoborate)]

Wang, Y.; Gan, X.; Jishu, C.

doi:10.1107/S1600536809040896

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1358

https://doi.org/10.1107/S1600536809040896

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catena-Poly[[[acetonitrilecopper(I)]-bis[μ-bis(diphenylphosphino)methane-κ²P:P′]-copper(I)-μ-1,2-di-4-pyridylethene] bis(tetrafluoridoborate)]

Yufei Wang,^a Xin Gan ^a ^* and Chen Jishu ^b

^aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, People's Republic of China, and ^bDepartment of Chemistry and Life Science, Qujing Normal College, Qujing 655011, People's Republic of China
^*Correspondence e-mail: quanli99@126.com

(Received 13 September 2009; accepted 7 October 2009; online 13 October 2009)

The title dinuclear copper(I) complex, {[Cu₂(C₂H₃N)(C₁₂H₁₀N₂)(C₂₅H₂₂P₂)₂](BF₄)₂}_n, contains 1,2-di-4-pyridylethene, bis(diphenylphosphino)methane and acetonitrile ligands. The two Cu atoms, one with an N₂P₂ ligand set and the other with an NP₂ ligand set, are bridged by two bis(diphenylphosphino)methane ligands, forming an eight-membered ring.

Related literature

For the synthesis and structures of related compounds, see: Engelhardt et al. (1985 ); Fu et al. (2007 ).

Experimental

Crystal data

[Cu₂(C₂H₃N)(C₁₂H₁₀N₂)(C₂₅H₂₂P₂)₂](BF₄)₂
M_r = 1292.71
Triclinic, $[P \overline 1]$
a = 11.146 (7) Å
b = 14.818 (9) Å
c = 18.532 (11) Å
α = 87.368 (10)°
β = 86.963 (11)°
γ = 84.992 (10)°
V = 3042 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 298 K
0.19 × 0.17 × 0.13 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.852, T_max = 0.895
15646 measured reflections
10398 independent reflections
4625 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.152
S = 1.00
10398 reflections
749 parameters
39 restraints
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N3	2.050 (7)
Cu1—N1	2.135 (6)
Cu1—P2	2.279 (2)
Cu1—P1	2.283 (2)
Cu2—N2	2.060 (6)
Cu2—P3	2.239 (2)
Cu2—P4	2.251 (2)

P2—Cu1—P1	125.82 (9)
P3—Cu2—P4	142.34 (8)

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809040896/jh2105sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040896/jh2105Isup2.hkl

checkCIF report

Comment top

The two copper atoms adopt different coordination geometries (Figure 1), one adopting a planar trigonal configuration and the other adopting a distroted tetrahedral geometry by the additional coordination of acetonitrile. The resulting NCu and N₂Cu fragments are bridged by bis(diphenylphosphino)methane ligands and form a 1D chain (Fig. 1) furtherly linked together through C-H···π to form 2D network (Fig. 2). Similar compounds were obtained by Fu (Fu et al., 2007, Engelhardt et al., 1985). The average Cu-N and Cu-P distances are 2.082 Å and 2.263 Å, respectively, which are within the range of reference (Fu et al., 2007). And the P-Cu-P angles of 125.82 (9) °, 142.34 (8) ° are larger than 115.85 (9)° (Engelhardt et al., 1985).

Related literature top

For the synthesis and structures of related compounds, see: Engelhardt et al. (1985); Fu et al. (2007).

Experimental top

Under nitrogen atmosphere, a mixture of bis(diphenylphosphino)methane (0.386 g, 1 mmol) and [Cu(CH₃CN)₄]BF₄ (0.315 g, 1 mmol) in dichloromethane (30 mL) was stirred for 2 h at room temperature. Then 1,2-di-4-pyridylethene (0.091 g, 0.5 mmol) was added to the solution with stirring. After stirring the resulting solution for another 12 h, the solvents were removed and the residue was obtained. The pale yellow crystals were obtained by slow diffusion of diethyl ether into a dichloromethane solution of the complex.

Structure description top

For the synthesis and structures of related compounds, see: Engelhardt et al. (1985); Fu et al. (2007).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. One-dimensional chain formed by Cu-N bonds (solid lines).
	Fig. 2. Two-dimensional network formed by connections between the chains through C—H···π interactions.

catena-Poly[[[acetonitrilecopper(I)]-bis[µ- bis(diphenylphosphino)methane-κ²P:P']-copper(I)- µ-1,2-di-4-pyridylethene] bis(tetrafluoridoborate)] top

Crystal data top

[Cu₂(C₂H₃N)(C₁₂H₁₀N₂)(C₂₅H₂₂P₂)₂](BF₄)₂	Z = 2
M_r = 1292.71	F(000) = 1324
Triclinic, P1	D_x = 1.411 Mg m⁻³
a = 11.146 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.818 (9) Å	Cell parameters from 2198 reflections
c = 18.532 (11) Å	θ = 3.2–21.0°
α = 87.368 (10)°	µ = 0.87 mm⁻¹
β = 86.963 (11)°	T = 298 K
γ = 84.992 (10)°	Block, yellow
V = 3042 (3) Å³	0.19 × 0.17 × 0.13 mm

Data collection top

Bruker SMART diffractometer	10398 independent reflections
Radiation source: fine-focus sealed tube	4625 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→7
T_min = 0.852, T_max = 0.895	k = −17→17
15646 measured reflections	l = −22→21

Refinement top

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0373P)²] where P = (F_o² + 2F_c²)/3
10398 reflections	(Δ/σ)_max = 0.001
749 parameters	Δρ_max = 1.01 e Å⁻³
39 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cu₂(C₂H₃N)(C₁₂H₁₀N₂)(C₂₅H₂₂P₂)₂](BF₄)₂	γ = 84.992 (10)°
M_r = 1292.71	V = 3042 (3) Å³
Triclinic, P1	Z = 2
a = 11.146 (7) Å	Mo Kα radiation
b = 14.818 (9) Å	µ = 0.87 mm⁻¹
c = 18.532 (11) Å	T = 298 K
α = 87.368 (10)°	0.19 × 0.17 × 0.13 mm
β = 86.963 (11)°

Data collection top

Bruker SMART diffractometer	10398 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4625 reflections with I > 2σ(I)
T_min = 0.852, T_max = 0.895	R_int = 0.061
15646 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	39 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.00	Δρ_max = 1.01 e Å⁻³
10398 reflections	Δρ_min = −0.44 e Å⁻³
749 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
Cu1	0.27700 (8)	0.57866 (6)	0.24838 (5)	0.0411 (3)
Cu2	0.04993 (8)	0.81487 (6)	0.24358 (5)	0.0474 (3)
B1	0.7566 (10)	0.6129 (7)	0.2537 (6)	0.067 (3)
B2	0.3676 (15)	0.0452 (9)	0.2281 (9)	0.139 (7)
F1	0.8510 (5)	0.6714 (5)	0.2510 (3)	0.117 (2)
F2	0.6789 (5)	0.6318 (4)	0.3101 (3)	0.0938 (17)
F3	0.6988 (5)	0.6232 (4)	0.1921 (3)	0.1012 (19)
F4	0.7995 (6)	0.5214 (5)	0.2598 (4)	0.166 (3)
F5	0.4366 (8)	0.0476 (6)	0.2825 (5)	0.192 (4)
F6	0.2843 (9)	0.1165 (7)	0.2408 (6)	0.224 (4)
F7	0.3061 (6)	−0.0289 (4)	0.2262 (3)	0.120 (2)
F8	0.4247 (10)	0.0703 (8)	0.1707 (5)	0.229 (4)
N1	0.4004 (6)	0.4605 (4)	0.2560 (3)	0.0439 (16)
N2	−0.0458 (6)	0.9402 (4)	0.2449 (3)	0.0474 (16)
N3	0.3895 (6)	0.6814 (4)	0.2418 (3)	0.0436 (16)
P1	0.18562 (17)	0.56636 (12)	0.14230 (10)	0.0389 (5)
P2	0.18580 (17)	0.57121 (12)	0.36125 (10)	0.0402 (5)
P3	0.06244 (17)	0.76465 (12)	0.13110 (11)	0.0424 (5)
P4	0.05932 (17)	0.76720 (13)	0.36037 (11)	0.0437 (5)
C1	0.3610 (8)	0.3770 (5)	0.2611 (4)	0.057 (2)
H1	0.2779	0.3735	0.2639	0.068*
C2	0.4310 (9)	0.2974 (5)	0.2625 (5)	0.068 (3)
H2	0.3965	0.2423	0.2660	0.082*
C3	0.5518 (10)	0.2997 (6)	0.2586 (4)	0.064 (3)
C4	0.6005 (7)	0.3836 (6)	0.2543 (4)	0.053 (2)
H4	0.6835	0.3872	0.2525	0.063*
C5	0.5201 (7)	0.4630 (5)	0.2528 (4)	0.046 (2)
H5	0.5518	0.5191	0.2494	0.055*
C6	−0.1647 (8)	0.9443 (5)	0.2425 (4)	0.058 (2)
H6	−0.2005	0.8907	0.2374	0.070*
C7	−0.2378 (7)	1.0234 (6)	0.2471 (4)	0.065 (2)
H7	−0.3211	1.0226	0.2462	0.078*
C8	−0.1878 (9)	1.1032 (6)	0.2530 (4)	0.059 (2)
C9	−0.0659 (8)	1.1002 (5)	0.2536 (4)	0.066 (3)
H9	−0.0282	1.1533	0.2571	0.079*
C10	0.0007 (8)	1.0197 (5)	0.2491 (4)	0.062 (2)
H10	0.0841	1.0197	0.2490	0.074*
C11	−0.3744 (9)	1.2097 (6)	0.2578 (5)	0.076 (3)
H11	−0.4172	1.1584	0.2591	0.092*
C12	−0.2620 (10)	1.1961 (7)	0.2555 (5)	0.079 (3)
H12	−0.2188	1.2471	0.2553	0.095*
C13	0.0543 (6)	0.6422 (4)	0.1200 (4)	0.0437 (19)
H13A	−0.0141	0.6232	0.1496	0.052*
H13B	0.0376	0.6337	0.0700	0.052*
C14	0.1318 (7)	0.4541 (5)	0.1332 (4)	0.0420 (19)
C15	0.0127 (7)	0.4378 (5)	0.1429 (4)	0.057 (2)
H15	−0.0452	0.4856	0.1516	0.068*
C16	−0.0220 (9)	0.3501 (7)	0.1397 (5)	0.086 (3)
H16	−0.1027	0.3396	0.1480	0.103*
C17	0.0615 (11)	0.2789 (6)	0.1244 (5)	0.079 (3)
H17	0.0387	0.2203	0.1213	0.095*
C18	0.1802 (10)	0.2974 (6)	0.1140 (4)	0.073 (3)
H18	0.2385	0.2502	0.1041	0.088*
C19	0.2142 (8)	0.3822 (5)	0.1176 (4)	0.067 (3)
H19	0.2951	0.3923	0.1093	0.081*
C20	0.2829 (6)	0.5734 (4)	0.0609 (4)	0.0394 (18)
C21	0.3966 (7)	0.6086 (5)	0.0635 (4)	0.051 (2)
H21	0.4234	0.6236	0.1077	0.061*
C22	0.4675 (7)	0.6207 (5)	0.0020 (4)	0.056 (2)
H22	0.5389	0.6482	0.0046	0.068*
C23	0.4357 (8)	0.5934 (5)	−0.0630 (4)	0.061 (2)
H23	0.4862	0.5993	−0.1043	0.073*
C24	0.3240 (8)	0.5561 (6)	−0.0659 (4)	0.065 (2)
H24	0.2997	0.5374	−0.1096	0.078*
C25	0.2520 (7)	0.5473 (5)	−0.0053 (4)	0.053 (2)
H25	0.1787	0.5226	−0.0086	0.064*
C26	0.1855 (6)	0.7985 (4)	0.0709 (4)	0.0395 (18)
C27	0.1913 (7)	0.7824 (5)	−0.0034 (4)	0.051 (2)
H27	0.1323	0.7514	−0.0228	0.061*
C28	0.2841 (9)	0.8123 (6)	−0.0474 (5)	0.065 (2)
H28	0.2865	0.8026	−0.0967	0.077*
C29	0.3739 (8)	0.8567 (6)	−0.0191 (6)	0.076 (3)
H29	0.4374	0.8756	−0.0489	0.091*
C30	0.3685 (7)	0.8729 (5)	0.0539 (6)	0.062 (2)
H30	0.4283	0.9031	0.0733	0.075*
C31	0.2757 (7)	0.8447 (5)	0.0974 (4)	0.053 (2)
H31	0.2726	0.8568	0.1463	0.063*
C32	−0.0722 (7)	0.8126 (5)	0.0853 (4)	0.051 (2)
C33	−0.1728 (8)	0.7703 (5)	0.0819 (4)	0.058 (2)
H33	−0.1736	0.7107	0.1001	0.069*
C34	−0.2757 (8)	0.8122 (6)	0.0522 (5)	0.071 (3)
H34	−0.3460	0.7824	0.0540	0.085*
C35	−0.2744 (8)	0.8942 (7)	0.0215 (5)	0.089 (3)
H35	−0.3410	0.9196	−0.0028	0.107*
C36	−0.1746 (9)	0.9421 (6)	0.0252 (5)	0.086 (3)
H36	−0.1762	1.0021	0.0079	0.103*
C37	−0.0730 (8)	0.9002 (6)	0.0547 (5)	0.079 (3)
H37	−0.0036	0.9308	0.0542	0.095*
C38	0.0500 (6)	0.6457 (4)	0.3867 (4)	0.049 (2)
H38A	0.0353	0.6400	0.4388	0.058*
H38B	−0.0187	0.6245	0.3645	0.058*
C39	0.1300 (7)	0.4593 (5)	0.3766 (4)	0.049 (2)
C40	0.0297 (8)	0.4385 (6)	0.3444 (4)	0.064 (2)
H40	−0.0177	0.4843	0.3208	0.077*
C41	−0.0033 (10)	0.3502 (8)	0.3460 (6)	0.102 (4)
H41	−0.0726	0.3381	0.3236	0.122*
C42	0.0629 (12)	0.2815 (7)	0.3793 (5)	0.092 (4)
H42	0.0416	0.2222	0.3788	0.110*
C43	0.1606 (11)	0.3010 (6)	0.4133 (5)	0.092 (3)
H43	0.2065	0.2547	0.4372	0.111*
C44	0.1940 (9)	0.3887 (6)	0.4133 (5)	0.078 (3)
H44	0.2606	0.4005	0.4383	0.093*
C45	0.2827 (7)	0.5788 (4)	0.4352 (4)	0.0406 (19)
C46	0.2484 (8)	0.5600 (5)	0.5079 (4)	0.060 (2)
H46	0.1726	0.5398	0.5188	0.071*
C47	0.3213 (9)	0.5700 (6)	0.5632 (4)	0.063 (2)
H47	0.2954	0.5552	0.6105	0.075*
C48	0.4328 (9)	0.6016 (5)	0.5495 (5)	0.062 (2)
H48	0.4818	0.6106	0.5872	0.074*
C49	0.4699 (8)	0.6195 (5)	0.4797 (5)	0.062 (2)
H49	0.5456	0.6402	0.4695	0.075*
C50	0.3962 (8)	0.6074 (5)	0.4233 (4)	0.051 (2)
H50	0.4247	0.6190	0.3760	0.062*
C51	0.1817 (7)	0.8027 (5)	0.4107 (4)	0.048 (2)
C52	0.1880 (8)	0.7839 (5)	0.4865 (4)	0.057 (2)
H52	0.1293	0.7523	0.5116	0.069*
C53	0.2820 (9)	0.8128 (6)	0.5225 (5)	0.068 (3)
H53	0.2881	0.7987	0.5717	0.082*
C54	0.3647 (9)	0.8613 (6)	0.4871 (7)	0.074 (3)
H54	0.4271	0.8808	0.5121	0.089*
C55	0.3583 (8)	0.8822 (5)	0.4150 (6)	0.068 (3)
H55	0.4167	0.9154	0.3911	0.082*
C56	0.2644 (7)	0.8540 (5)	0.3768 (5)	0.057 (2)
H56	0.2585	0.8705	0.3280	0.068*
C57	−0.0764 (7)	0.8199 (5)	0.4061 (4)	0.049 (2)
C58	−0.0741 (8)	0.8976 (6)	0.4431 (5)	0.084 (3)
H58	−0.0010	0.9216	0.4488	0.101*
C59	−0.1805 (9)	0.9410 (7)	0.4721 (6)	0.096 (3)
H59	−0.1778	0.9944	0.4963	0.115*
C60	−0.2890 (9)	0.9062 (7)	0.4654 (6)	0.099 (3)
H60	−0.3598	0.9354	0.4849	0.119*
C61	−0.2917 (8)	0.8273 (6)	0.4294 (5)	0.082 (3)
H61	−0.3650	0.8031	0.4247	0.098*
C62	−0.1892 (8)	0.7843 (6)	0.4007 (4)	0.068 (2)
H62	−0.1930	0.7306	0.3770	0.081*
C63	0.4518 (7)	0.7361 (5)	0.2385 (4)	0.045 (2)
C64	0.5343 (8)	0.8084 (6)	0.2355 (5)	0.082 (3)
H64A	0.5945	0.7979	0.1971	0.123*
H64B	0.5727	0.8086	0.2806	0.123*
H64C	0.4897	0.8659	0.2267	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0400 (6)	0.0310 (5)	0.0509 (6)	0.0062 (4)	−0.0044 (5)	−0.0040 (4)
Cu2	0.0430 (6)	0.0369 (6)	0.0598 (7)	0.0136 (5)	−0.0053 (5)	−0.0046 (4)
B1	0.069 (8)	0.065 (8)	0.065 (8)	−0.005 (7)	0.002 (7)	−0.003 (6)
B2	0.148 (18)	0.038 (9)	0.23 (2)	−0.026 (10)	0.023 (17)	−0.003 (11)
F1	0.095 (3)	0.162 (4)	0.101 (3)	−0.046 (3)	0.000 (3)	−0.020 (3)
F2	0.085 (4)	0.101 (4)	0.098 (4)	−0.025 (3)	0.024 (3)	−0.030 (3)
F3	0.112 (5)	0.108 (5)	0.092 (4)	−0.045 (4)	−0.021 (4)	0.001 (3)
F4	0.094 (5)	0.143 (7)	0.247 (8)	0.063 (5)	−0.006 (5)	0.016 (6)
F5	0.183 (9)	0.185 (9)	0.227 (9)	−0.105 (7)	−0.089 (7)	0.032 (7)
F6	0.207 (8)	0.130 (6)	0.338 (9)	−0.019 (6)	−0.028 (7)	−0.032 (6)
F7	0.130 (5)	0.063 (4)	0.169 (6)	−0.018 (4)	−0.015 (4)	−0.015 (4)
F8	0.224 (8)	0.289 (9)	0.189 (7)	−0.141 (7)	0.021 (6)	0.004 (6)
N1	0.040 (4)	0.037 (4)	0.054 (4)	0.012 (3)	−0.006 (3)	−0.012 (3)
N2	0.044 (4)	0.028 (4)	0.068 (5)	0.010 (3)	−0.006 (4)	−0.002 (3)
N3	0.048 (4)	0.042 (4)	0.040 (4)	0.012 (3)	−0.012 (3)	−0.009 (3)
P1	0.0406 (12)	0.0274 (11)	0.0478 (12)	0.0075 (9)	−0.0082 (10)	−0.0054 (9)
P2	0.0415 (12)	0.0320 (11)	0.0454 (12)	0.0094 (9)	−0.0062 (10)	−0.0040 (9)
P3	0.0364 (12)	0.0313 (11)	0.0576 (14)	0.0068 (9)	−0.0045 (10)	0.0021 (9)
P4	0.0377 (12)	0.0374 (12)	0.0543 (13)	0.0088 (10)	−0.0010 (10)	−0.0081 (10)
C1	0.063 (6)	0.036 (5)	0.071 (6)	0.001 (5)	−0.004 (5)	−0.007 (4)
C2	0.066 (7)	0.029 (5)	0.108 (8)	0.013 (5)	−0.004 (6)	−0.010 (5)
C3	0.088 (8)	0.062 (7)	0.035 (5)	0.034 (6)	−0.003 (5)	−0.007 (4)
C4	0.034 (5)	0.077 (7)	0.044 (5)	0.018 (5)	−0.005 (4)	−0.012 (4)
C5	0.052 (6)	0.040 (5)	0.045 (5)	0.006 (4)	0.001 (4)	−0.005 (4)
C6	0.055 (6)	0.026 (5)	0.095 (7)	−0.004 (4)	−0.009 (5)	−0.012 (4)
C7	0.035 (5)	0.075 (7)	0.079 (7)	0.023 (5)	0.001 (5)	0.001 (5)
C8	0.078 (7)	0.042 (5)	0.054 (6)	0.017 (5)	−0.008 (5)	−0.005 (4)
C9	0.062 (7)	0.034 (5)	0.100 (7)	0.011 (5)	−0.016 (6)	−0.004 (5)
C10	0.071 (6)	0.036 (5)	0.077 (6)	0.008 (5)	−0.010 (5)	−0.002 (4)
C11	0.083 (8)	0.056 (6)	0.086 (7)	0.012 (6)	−0.001 (6)	0.003 (5)
C12	0.082 (8)	0.078 (7)	0.071 (7)	0.029 (6)	−0.010 (6)	−0.008 (5)
C13	0.034 (4)	0.045 (5)	0.051 (5)	0.004 (4)	−0.007 (4)	0.004 (4)
C14	0.047 (5)	0.033 (4)	0.046 (5)	−0.005 (4)	−0.008 (4)	0.004 (3)
C15	0.050 (6)	0.051 (6)	0.071 (6)	−0.004 (5)	−0.009 (5)	−0.001 (4)
C16	0.074 (7)	0.061 (7)	0.124 (9)	−0.029 (6)	0.007 (6)	0.006 (6)
C17	0.109 (9)	0.039 (6)	0.095 (8)	−0.018 (6)	−0.027 (7)	0.004 (5)
C18	0.103 (9)	0.045 (6)	0.072 (7)	0.010 (6)	−0.014 (6)	−0.020 (5)
C19	0.067 (6)	0.033 (5)	0.101 (7)	0.007 (5)	0.001 (5)	−0.018 (5)
C20	0.029 (5)	0.028 (4)	0.060 (5)	0.012 (3)	−0.006 (4)	−0.011 (4)
C21	0.060 (6)	0.052 (5)	0.039 (5)	0.005 (4)	0.002 (4)	−0.003 (4)
C22	0.055 (6)	0.051 (5)	0.063 (6)	−0.006 (4)	0.004 (5)	−0.009 (4)
C23	0.060 (6)	0.072 (6)	0.047 (6)	0.004 (5)	0.012 (5)	−0.013 (4)
C24	0.059 (6)	0.085 (7)	0.049 (6)	0.005 (5)	−0.005 (5)	−0.013 (5)
C25	0.058 (6)	0.053 (5)	0.049 (5)	−0.001 (4)	0.001 (5)	−0.011 (4)
C26	0.034 (5)	0.025 (4)	0.058 (5)	0.006 (3)	−0.007 (4)	0.002 (4)
C27	0.054 (6)	0.038 (5)	0.059 (6)	0.005 (4)	−0.012 (5)	−0.001 (4)
C28	0.065 (7)	0.061 (6)	0.062 (6)	0.011 (5)	0.009 (6)	0.012 (5)
C29	0.040 (6)	0.076 (7)	0.106 (9)	0.003 (5)	0.018 (6)	0.030 (6)
C30	0.032 (5)	0.051 (6)	0.103 (8)	−0.004 (4)	−0.007 (5)	0.012 (5)
C31	0.038 (5)	0.046 (5)	0.072 (6)	0.005 (4)	−0.016 (5)	0.009 (4)
C32	0.046 (5)	0.030 (5)	0.075 (6)	0.008 (4)	−0.002 (4)	0.004 (4)
C33	0.053 (6)	0.047 (5)	0.071 (6)	0.005 (5)	−0.017 (5)	0.012 (4)
C34	0.046 (6)	0.057 (6)	0.110 (8)	−0.005 (5)	−0.015 (5)	0.012 (5)
C35	0.048 (7)	0.106 (9)	0.107 (8)	0.016 (6)	−0.028 (6)	0.035 (7)
C36	0.065 (6)	0.062 (5)	0.126 (7)	0.006 (5)	−0.017 (5)	0.044 (5)
C37	0.045 (6)	0.050 (6)	0.139 (9)	0.002 (5)	−0.014 (6)	0.021 (6)
C38	0.038 (5)	0.042 (5)	0.065 (5)	0.010 (4)	−0.010 (4)	−0.011 (4)
C39	0.056 (6)	0.040 (5)	0.049 (5)	0.003 (4)	0.004 (4)	0.001 (4)
C40	0.059 (6)	0.046 (6)	0.087 (7)	0.004 (5)	−0.020 (5)	0.006 (5)
C41	0.093 (9)	0.066 (8)	0.154 (11)	−0.029 (7)	−0.033 (8)	−0.012 (7)
C42	0.136 (11)	0.055 (7)	0.089 (8)	−0.038 (8)	0.000 (8)	−0.012 (6)
C43	0.142 (11)	0.034 (6)	0.101 (8)	−0.001 (6)	−0.018 (8)	−0.003 (5)
C44	0.092 (8)	0.054 (6)	0.088 (7)	0.000 (6)	−0.034 (6)	0.009 (5)
C45	0.032 (5)	0.023 (4)	0.066 (6)	0.012 (3)	−0.012 (4)	−0.005 (4)
C46	0.069 (6)	0.053 (5)	0.055 (6)	0.004 (5)	0.000 (5)	−0.006 (4)
C47	0.078 (7)	0.066 (6)	0.043 (6)	0.004 (5)	−0.006 (5)	−0.013 (4)
C48	0.073 (7)	0.058 (6)	0.056 (6)	0.005 (5)	−0.028 (5)	−0.010 (5)
C49	0.064 (6)	0.048 (5)	0.074 (7)	0.006 (4)	−0.013 (6)	−0.002 (5)
C50	0.056 (6)	0.050 (5)	0.045 (5)	0.014 (4)	−0.014 (5)	0.000 (4)
C51	0.037 (5)	0.041 (5)	0.062 (6)	0.009 (4)	0.008 (4)	−0.010 (4)
C52	0.059 (6)	0.045 (5)	0.065 (6)	0.012 (4)	−0.006 (5)	−0.014 (4)
C53	0.076 (7)	0.057 (6)	0.072 (7)	0.026 (5)	−0.036 (6)	−0.021 (5)
C54	0.045 (6)	0.053 (6)	0.127 (10)	0.008 (5)	−0.023 (7)	−0.023 (6)
C55	0.044 (6)	0.052 (6)	0.107 (8)	−0.004 (5)	0.009 (6)	−0.012 (6)
C56	0.044 (5)	0.042 (5)	0.085 (6)	−0.009 (4)	0.013 (5)	−0.013 (4)
C57	0.049 (5)	0.032 (5)	0.064 (6)	0.018 (4)	−0.004 (4)	−0.010 (4)
C58	0.045 (6)	0.051 (6)	0.157 (10)	0.022 (5)	−0.006 (6)	−0.041 (6)
C59	0.073 (6)	0.073 (6)	0.143 (7)	−0.005 (5)	0.011 (6)	−0.042 (5)
C60	0.059 (7)	0.082 (8)	0.158 (10)	0.011 (6)	0.012 (7)	−0.060 (7)
C61	0.037 (6)	0.077 (7)	0.130 (9)	0.009 (5)	0.004 (6)	−0.031 (6)
C62	0.048 (6)	0.071 (6)	0.084 (7)	0.004 (5)	−0.005 (5)	−0.030 (5)
C63	0.039 (5)	0.037 (5)	0.058 (5)	−0.001 (4)	−0.006 (4)	−0.002 (4)
C64	0.070 (7)	0.056 (6)	0.124 (8)	−0.013 (5)	−0.006 (6)	−0.014 (5)

Geometric parameters (Å, º) top

Cu1—N3	2.050 (7)	C24—C25	1.353 (10)
Cu1—N1	2.135 (6)	C24—H24	0.9300
Cu1—P2	2.279 (2)	C25—H25	0.9300
Cu1—P1	2.283 (2)	C26—C31	1.386 (9)
Cu2—N2	2.060 (6)	C26—C27	1.405 (9)
Cu2—P3	2.239 (2)	C27—C28	1.375 (10)
Cu2—P4	2.251 (2)	C27—H27	0.9300
B1—F3	1.338 (10)	C28—C29	1.383 (11)
B1—F2	1.344 (10)	C28—H28	0.9300
B1—F4	1.400 (10)	C29—C30	1.381 (11)
B1—F1	1.418 (10)	C29—H29	0.9300
B2—F8	1.268 (13)	C30—C31	1.360 (10)
B2—F5	1.304 (15)	C30—H30	0.9300
B2—F7	1.347 (12)	C31—H31	0.9300
B2—F6	1.364 (13)	C32—C33	1.338 (9)
N1—C5	1.335 (8)	C32—C37	1.392 (10)
N1—C1	1.347 (8)	C33—C34	1.384 (10)
N2—C6	1.325 (9)	C33—H33	0.9300
N2—C10	1.335 (9)	C34—C35	1.319 (11)
N3—C63	1.110 (8)	C34—H34	0.9300
P1—C20	1.815 (7)	C35—C36	1.377 (11)
P1—C13	1.820 (7)	C35—H35	0.9300
P1—C14	1.834 (7)	C36—C37	1.371 (10)
P2—C45	1.803 (7)	C36—H36	0.9300
P2—C39	1.827 (8)	C37—H37	0.9300
P2—C38	1.847 (7)	C38—H38A	0.9700
P3—C26	1.812 (7)	C38—H38B	0.9700
P3—C32	1.836 (8)	C39—C40	1.360 (10)
P3—C13	1.846 (7)	C39—C44	1.386 (10)
P4—C51	1.820 (8)	C40—C41	1.388 (11)
P4—C57	1.826 (7)	C40—H40	0.9300
P4—C38	1.855 (7)	C41—C42	1.350 (12)
C1—C2	1.357 (10)	C41—H41	0.9300
C1—H1	0.9300	C42—C43	1.346 (12)
C2—C3	1.348 (11)	C42—H42	0.9300
C2—H2	0.9300	C43—C44	1.382 (11)
C3—C4	1.396 (11)	C43—H43	0.9300
C3—C11ⁱ	1.506 (11)	C44—H44	0.9300
C4—C5	1.415 (10)	C45—C50	1.374 (10)
C4—H4	0.9300	C45—C46	1.402 (9)
C5—H5	0.9300	C46—C47	1.362 (10)
C6—C7	1.372 (10)	C46—H46	0.9300
C6—H6	0.9300	C47—C48	1.373 (11)
C7—C8	1.361 (10)	C47—H47	0.9300
C7—H7	0.9300	C48—C49	1.360 (10)
C8—C9	1.356 (11)	C48—H48	0.9300
C8—C12	1.545 (11)	C49—C50	1.390 (9)
C9—C10	1.352 (10)	C49—H49	0.9300
C9—H9	0.9300	C50—H50	0.9300
C10—H10	0.9300	C51—C56	1.356 (9)
C11—C12	1.250 (10)	C51—C52	1.424 (9)
C11—C3ⁱⁱ	1.506 (11)	C52—C53	1.380 (10)
C11—H11	0.9300	C52—H52	0.9300
C12—H12	0.9300	C53—C54	1.344 (11)
C13—H13A	0.9700	C53—H53	0.9300
C13—H13B	0.9700	C54—C55	1.362 (11)
C14—C15	1.371 (10)	C54—H54	0.9300
C14—C19	1.375 (10)	C55—C56	1.398 (10)
C15—C16	1.393 (11)	C55—H55	0.9300
C15—H15	0.9300	C56—H56	0.9300
C16—C17	1.373 (12)	C57—C58	1.370 (10)
C16—H16	0.9300	C57—C62	1.416 (10)
C17—C18	1.377 (12)	C58—C59	1.393 (11)
C17—H17	0.9300	C58—H58	0.9300
C18—C19	1.349 (10)	C59—C60	1.370 (11)
C18—H18	0.9300	C59—H59	0.9300
C19—H19	0.9300	C60—C61	1.377 (11)
C20—C25	1.373 (9)	C60—H60	0.9300
C20—C21	1.415 (9)	C61—C62	1.354 (11)
C21—C22	1.367 (9)	C61—H61	0.9300
C21—H21	0.9300	C62—H62	0.9300
C22—C23	1.362 (9)	C63—C64	1.468 (10)
C22—H22	0.9300	C64—H64A	0.9600
C23—C24	1.411 (10)	C64—H64B	0.9600
C23—H23	0.9300	C64—H64C	0.9600

N3—Cu1—N1	102.5 (2)	C23—C24—H24	119.8
N3—Cu1—P2	109.40 (16)	C24—C25—C20	122.5 (8)
N1—Cu1—P2	99.37 (17)	C24—C25—H25	118.7
N3—Cu1—P1	111.69 (16)	C20—C25—H25	118.7
N1—Cu1—P1	104.49 (16)	C31—C26—C27	117.9 (7)
P2—Cu1—P1	125.82 (9)	C31—C26—P3	119.9 (6)
N2—Cu2—P3	109.65 (17)	C27—C26—P3	122.1 (6)
N2—Cu2—P4	105.34 (17)	C28—C27—C26	120.0 (8)
P3—Cu2—P4	142.34 (8)	C28—C27—H27	120.0
F3—B1—F2	109.8 (9)	C26—C27—H27	120.0
F3—B1—F4	106.2 (8)	C27—C28—C29	120.6 (8)
F2—B1—F4	108.7 (8)	C27—C28—H28	119.7
F3—B1—F1	109.4 (8)	C29—C28—H28	119.7
F2—B1—F1	110.3 (8)	C30—C29—C28	119.5 (8)
F4—B1—F1	112.3 (9)	C30—C29—H29	120.2
F8—B2—F5	108.9 (13)	C28—C29—H29	120.2
F8—B2—F7	117.9 (14)	C31—C30—C29	120.0 (8)
F5—B2—F7	115.8 (12)	C31—C30—H30	120.0
F8—B2—F6	103.6 (12)	C29—C30—H30	120.0
F5—B2—F6	101.8 (13)	C30—C31—C26	121.9 (8)
F7—B2—F6	106.6 (12)	C30—C31—H31	119.0
C5—N1—C1	115.4 (7)	C26—C31—H31	119.0
C5—N1—Cu1	123.5 (5)	C33—C32—C37	117.1 (7)
C1—N1—Cu1	121.0 (5)	C33—C32—P3	124.2 (6)
C6—N2—C10	115.5 (7)	C37—C32—P3	118.6 (7)
C6—N2—Cu2	118.5 (5)	C32—C33—C34	122.1 (8)
C10—N2—Cu2	126.0 (6)	C32—C33—H33	119.0
C63—N3—Cu1	178.9 (6)	C34—C33—H33	119.0
C20—P1—C13	102.9 (3)	C35—C34—C33	120.2 (8)
C20—P1—C14	100.0 (3)	C35—C34—H34	119.9
C13—P1—C14	102.4 (3)	C33—C34—H34	119.9
C20—P1—Cu1	115.6 (2)	C34—C35—C36	120.1 (8)
C13—P1—Cu1	120.4 (2)	C34—C35—H35	120.0
C14—P1—Cu1	112.9 (2)	C36—C35—H35	120.0
C45—P2—C39	103.4 (3)	C37—C36—C35	119.1 (8)
C45—P2—C38	103.6 (3)	C37—C36—H36	120.4
C39—P2—C38	101.2 (3)	C35—C36—H36	120.4
C45—P2—Cu1	115.8 (3)	C36—C37—C32	121.0 (8)
C39—P2—Cu1	108.5 (2)	C36—C37—H37	119.5
C38—P2—Cu1	122.0 (2)	C32—C37—H37	119.5
C26—P3—C32	103.3 (3)	P2—C38—P4	114.6 (4)
C26—P3—C13	106.5 (3)	P2—C38—H38A	108.6
C32—P3—C13	101.3 (3)	P4—C38—H38A	108.6
C26—P3—Cu2	117.8 (3)	P2—C38—H38B	108.6
C32—P3—Cu2	107.8 (3)	P4—C38—H38B	108.6
C13—P3—Cu2	118.0 (2)	H38A—C38—H38B	107.6
C51—P4—C57	103.9 (3)	C40—C39—C44	116.5 (8)
C51—P4—C38	105.3 (3)	C40—C39—P2	120.4 (6)
C57—P4—C38	101.9 (3)	C44—C39—P2	122.6 (7)
C51—P4—Cu2	117.5 (3)	C39—C40—C41	121.3 (8)
C57—P4—Cu2	105.6 (2)	C39—C40—H40	119.4
C38—P4—Cu2	120.3 (2)	C41—C40—H40	119.4
N1—C1—C2	126.1 (8)	C42—C41—C40	121.5 (10)
N1—C1—H1	117.0	C42—C41—H41	119.3
C2—C1—H1	117.0	C40—C41—H41	119.3
C3—C2—C1	118.6 (8)	C43—C42—C41	118.2 (10)
C3—C2—H2	120.7	C43—C42—H42	120.9
C1—C2—H2	120.7	C41—C42—H42	120.9
C2—C3—C4	119.1 (8)	C42—C43—C44	121.2 (10)
C2—C3—C11ⁱ	116.6 (9)	C42—C43—H43	119.4
C4—C3—C11ⁱ	124.3 (9)	C44—C43—H43	119.4
C3—C4—C5	118.2 (8)	C43—C44—C39	121.3 (9)
C3—C4—H4	120.9	C43—C44—H44	119.4
C5—C4—H4	120.9	C39—C44—H44	119.4
N1—C5—C4	122.6 (7)	C50—C45—C46	115.2 (7)
N1—C5—H5	118.7	C50—C45—P2	120.8 (6)
C4—C5—H5	118.7	C46—C45—P2	123.9 (6)
N2—C6—C7	123.5 (7)	C47—C46—C45	122.9 (8)
N2—C6—H6	118.3	C47—C46—H46	118.5
C7—C6—H6	118.3	C45—C46—H46	118.5
C8—C7—C6	119.6 (8)	C46—C47—C48	120.4 (8)
C8—C7—H7	120.2	C46—C47—H47	119.8
C6—C7—H7	120.2	C48—C47—H47	119.8
C9—C8—C7	117.5 (8)	C49—C48—C47	118.5 (8)
C9—C8—C12	119.0 (9)	C49—C48—H48	120.8
C7—C8—C12	123.4 (9)	C47—C48—H48	120.8
C10—C9—C8	119.8 (8)	C48—C49—C50	120.9 (8)
C10—C9—H9	120.1	C48—C49—H49	119.5
C8—C9—H9	120.1	C50—C49—H49	119.5
N2—C10—C9	124.2 (8)	C45—C50—C49	122.1 (8)
N2—C10—H10	117.9	C45—C50—H50	118.9
C9—C10—H10	117.9	C49—C50—H50	118.9
C12—C11—C3ⁱⁱ	127.2 (10)	C56—C51—C52	118.6 (7)
C12—C11—H11	116.4	C56—C51—P4	119.7 (6)
C3ⁱⁱ—C11—H11	116.4	C52—C51—P4	121.6 (6)
C11—C12—C8	126.5 (10)	C53—C52—C51	119.5 (8)
C11—C12—H12	116.8	C53—C52—H52	120.2
C8—C12—H12	116.8	C51—C52—H52	120.2
P1—C13—P3	117.6 (4)	C54—C53—C52	120.5 (9)
P1—C13—H13A	107.9	C54—C53—H53	119.7
P3—C13—H13A	107.9	C52—C53—H53	119.7
P1—C13—H13B	107.9	C53—C54—C55	120.9 (9)
P3—C13—H13B	107.9	C53—C54—H54	119.6
H13A—C13—H13B	107.2	C55—C54—H54	119.6
C15—C14—C19	118.0 (7)	C54—C55—C56	120.1 (8)
C15—C14—P1	123.0 (6)	C54—C55—H55	119.9
C19—C14—P1	119.0 (6)	C56—C55—H55	119.9
C14—C15—C16	120.5 (8)	C51—C56—C55	120.3 (8)
C14—C15—H15	119.8	C51—C56—H56	119.9
C16—C15—H15	119.8	C55—C56—H56	119.9
C17—C16—C15	120.8 (9)	C58—C57—C62	117.8 (7)
C17—C16—H16	119.6	C58—C57—P4	121.5 (7)
C15—C16—H16	119.6	C62—C57—P4	120.6 (6)
C16—C17—C18	117.5 (9)	C57—C58—C59	120.4 (8)
C16—C17—H17	121.3	C57—C58—H58	119.8
C18—C17—H17	121.3	C59—C58—H58	119.8
C19—C18—C17	121.8 (9)	C60—C59—C58	120.9 (9)
C19—C18—H18	119.1	C60—C59—H59	119.6
C17—C18—H18	119.1	C58—C59—H59	119.6
C18—C19—C14	121.4 (9)	C59—C60—C61	119.0 (9)
C18—C19—H19	119.3	C59—C60—H60	120.5
C14—C19—H19	119.3	C61—C60—H60	120.5
C25—C20—C21	116.6 (7)	C62—C61—C60	121.0 (9)
C25—C20—P1	123.5 (6)	C62—C61—H61	119.5
C21—C20—P1	119.9 (5)	C60—C61—H61	119.5
C22—C21—C20	121.0 (7)	C61—C62—C57	120.9 (8)
C22—C21—H21	119.5	C61—C62—H62	119.6
C20—C21—H21	119.5	C57—C62—H62	119.6
C23—C22—C21	121.4 (8)	N3—C63—C64	179.1 (8)
C23—C22—H22	119.3	C63—C64—H64A	109.5
C21—C22—H22	119.3	C63—C64—H64B	109.5
C22—C23—C24	117.9 (8)	H64A—C64—H64B	109.5
C22—C23—H23	121.0	C63—C64—H64C	109.5
C24—C23—H23	121.0	H64A—C64—H64C	109.5
C25—C24—C23	120.4 (8)	H64B—C64—H64C	109.5
C25—C24—H24	119.8

Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂H₃N)(C₁₂H₁₀N₂)(C₂₅H₂₂P₂)₂](BF₄)₂
M_r	1292.71
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	11.146 (7), 14.818 (9), 18.532 (11)
α, β, γ (°)	87.368 (10), 86.963 (11), 84.992 (10)
V (Å³)	3042 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.19 × 0.17 × 0.13

Data collection
Diffractometer	Bruker SMART
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.852, 0.895
No. of measured, independent and observed [I > 2σ(I)] reflections	15646, 10398, 4625
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.152, 1.00
No. of reflections	10398
No. of parameters	749
No. of restraints	39
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.44

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—N3	2.050 (7)	Cu2—N2	2.060 (6)
Cu1—N1	2.135 (6)	Cu2—P3	2.239 (2)
Cu1—P2	2.279 (2)	Cu2—P4	2.251 (2)
Cu1—P1	2.283 (2)

P2—Cu1—P1	125.82 (9)	P3—Cu2—P4	142.34 (8)

Acknowledgements

We acknowledge the National Natural Science Foundation of China (20761006).

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Engelhardt, L. M., Pakawatchai, C., White, A. H. & Healy, P. C. (1985). J. Chem. Soc. Dalton Trans. pp. 125–133. CSD CrossRef Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Fu, W. F., Gan, X., Jian, J., Chen, Y., Yuan, M., Chi, S. M., Yu, M. M. & Xiong, S. X. (2007). Inorg. Chim. Acta, 360, 2758–2766. Web of Science CSD CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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