[μ-1,2-Bis(diphenyl­phosphino)ethane-κ2P:P′]bis­{[1,2-bis­(diphenyl­phosphino)ethane-κ2P,P′]cyanidocopper(I)} methanol disolvate

Wang, R.; Xiao, Y.-L.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536810029545

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m1032

https://doi.org/10.1107/S1600536810029545

Open

access

[μ-1,2-Bis(diphenylphosphino)ethane-κ²P:P′]bis{[1,2-bis(diphenylphosphino)ethane-κ²P,P′]cyanidocopper(I)} methanol disolvate

Rong Wang,^a Ye-Lan Xiao,^a Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^b

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and ^bBeijing Key Laboratory for Terahertz Spectroscopy and Imaging, Key Laboratory of Terahertz Optoelectronics, Ministry of Education, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: jinqh204@163.com

(Received 5 July 2010; accepted 25 July 2010; online 31 July 2010)

The title centrosymmetric complex, [Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₃OH, consists of two five-membered [Cu(dppe)CN] rings [dppe is 1,2-bis(diphenylphosphino)ethane] bridged by one μ₂-dppe ligand, and two methanol solvent molecules. The angles around the central metal atom indicate that each Cu^I atom is located in the center of a distorted tetrahedron. The coordination sphere of each Cu^I atom is formed by three P atoms from two dppe ligands, and one C atom from the cyanide ligand. The crystal structure is stabilized by O—H⋯N hydrogen bonds, which are formed by the O—H donor group from methanol and the N-atom acceptor from a cyanide ligand.

Related literature

For related structures, see: Jin et al. (2009 ); Effendy et al. (2006 ); Sivasankar et al. (2004 ); Di Nicola et al. (2006 ); Saravanabharathi et al. (2002 ). For general background to the photophysical properties of similar compounds, see: Cingolani et al. (2005 ); Song et al. (2007 ).

Experimental

Crystal data

[Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₄O
M_r = 1438.38
Monoclinic, C 2/c
a = 23.423 (2) Å
b = 17.7912 (16) Å
c = 17.6614 (18) Å
β = 92.194 (1)°
V = 7354.6 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 298 K
0.44 × 0.40 × 0.25 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.732, T_max = 0.833
18242 measured reflections
6494 independent reflections
4140 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.149
S = 1.06
6494 reflections
425 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	2.02	2.829 (11)	171
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810029545/su2196sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029545/su2196Isup2.hkl

checkCIF report

Comment top

Copper(I) complexes containing the diphosphine ligands bis(diphenylphosphinoethane)(Dppe) are extensively studied because of their interesting structures and photophysical properties (Cingolani et al., 2005; Song et al., 2007). dppe is a very efficient bridging bidentate ligand and its chelating tendency is very suitable to lock the metal atom. As a part of the extension of our study on the systematic structural chemistry of copper(I) complexes with ligands containing phosphine and nitrogen atoms (Jin et al., 2009), we synthesized the new title complex, (1), in the presence of (NH₄)₂WS₄ and 1,10-phenanthroline.

The molecular structure of complex (1) is depicted in Fig. 1. It consists of two five-membered [Cu(dppe)CN] rings that are bridged by one µ₂-dppe ligand, and two methanol solvent molecules. The copper atom is four-coordinated by three P-atoms from two dppe ligands, and one C-atom from the cyanide ion. The Cu—P distances of 2.2832 (12) Å, 2.3041 (13) Å and 2.3291 (12) Å are longer than those in complex [Cu₂(dppe)₃(CN)₂].2(CH₃CN) (2), which vary from 2.2784 (4) to 2.3158 (4) Å (Effendy et al., 2006), but are almost equal to those in complex [Cu₂(dppe)₃(CN)₂] (3), which vary from 2.2808 (8) to 2.3276 (8) Å (Saravanabharathi et al., 2002). The Cu—C distance of 1.952 (6)Å in complex (1) is shorter than the same distance observed in complexes (2) and (3); 1.975 (2) Å and 1.964 (4) Å, respectively.

In (1) the P—Cu—C angles are in the range 107.59 (14) - 119.11 (14)°, and the P—Cu—P angles are in the range 89.03 (4) - 115.07 (5)°. This confirms the distored tetrahedral environment around the copper(I) atom. These values are very close to those observed for complex (3), where the P—Cu—C angles range from 107.05 (9) to 120.73 (9)°, and the P—Cu—P angles are in the range 89.22 (3) - 115.16 (3) °.

Though both (NH₄)₂WS₄ and 1,10-phenanthroline were starting materials in the prepartion of (1), they do not appear in the final product. This may be related to the solvent methanol because the O—H donor from methanol can form an O—H···N hydrogen bond with the N atom from the cyanide anion (Table 1), and this can stablize the molecular structure of the complex.

The crystal structure of complex (1) is similar with that of complex (2). Other similar complexes are adducts CuX:dppe:X, where X is a simple inorganic anion, for example, a halide (Effendy et al., 2006; Di Nicola et al., 2006), thiocyanate (Saravanabharathi et al., 2002), nitrate (Saravanabharathi et al., 2002), perchlorate (Sivasankar et al., 2004; Jin et al., 2009) and tetrafluoroborate (Jin et al., 2009).

Related literature top

For related structures, see: Jin et al. (2009); Effendy et al. (2006); Sivasankar et al. (2004); Di Nicola et al. (2006); Saravanabharathi et al. (2002). For general background to the photophysical properties of similar compounds, see: Cingolani et al. (2005); Song et al. (2007).

Experimental top

A mixture of CuCN, bis(diphenylphosphinoethane), (NH₄)₂WS₄ and 1,10-Phenanthroline, in the molar ratio of 3:3:1:1 in CH₂Cl₂ and MeOH (10 ml,V/V=1/1), was stirred for 4 h at RT, then filtered. Subsequent slow evaporation of the filtrate resulted in the formation of yellow crystals of complex (1). Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

Structure description top

For related structures, see: Jin et al. (2009); Effendy et al. (2006); Sivasankar et al. (2004); Di Nicola et al. (2006); Saravanabharathi et al. (2002). For general background to the photophysical properties of similar compounds, see: Cingolani et al. (2005); Song et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of complex (1), with the displacement ellipsoids drawn at the 50% probability level [Symmetry code: (i) = -x+1/2, -y+1/2, -z+1; Hydrogen atoms have been omitted for clarity].

[µ-1,2-Bis(diphenylphosphino)ethane-κ²P:P']bis{[1,2- bis(diphenylphosphino)ethane-κ²P,P']cyanidocopper(I)} methanol disolvate top

Crystal data top

[Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₄O	F(000) = 3000
M_r = 1438.38	D_x = 1.299 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4634 reflections
a = 23.423 (2) Å	θ = 2.3–27.3°
b = 17.7912 (16) Å	µ = 0.76 mm⁻¹
c = 17.6614 (18) Å	T = 298 K
β = 92.194 (1)°	Block, yellow
V = 7354.6 (12) Å³	0.44 × 0.40 × 0.25 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	6494 independent reflections
Radiation source: fine-focus sealed tube	4140 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
phi and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→27
T_min = 0.732, T_max = 0.833	k = −21→21
18242 measured reflections	l = −17→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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.063P)² + 16.0608P] where P = (F_o² + 2F_c²)/3
6494 reflections	(Δ/σ)_max = 0.001
425 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₄O	V = 7354.6 (12) Å³
M_r = 1438.38	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 23.423 (2) Å	µ = 0.76 mm⁻¹
b = 17.7912 (16) Å	T = 298 K
c = 17.6614 (18) Å	0.44 × 0.40 × 0.25 mm
β = 92.194 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6494 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4140 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.833	R_int = 0.044
18242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.063P)² + 16.0608P] where P = (F_o² + 2F_c²)/3
6494 reflections	Δρ_max = 0.63 e Å⁻³
425 parameters	Δρ_min = −0.39 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cu1	0.26534 (2)	0.24069 (3)	0.29813 (3)	0.03662 (18)
N1	0.3058 (2)	0.4054 (3)	0.3181 (3)	0.0646 (13)
O1	0.0834 (4)	0.0342 (6)	0.6565 (6)	0.243 (5)
H1	0.1155	0.0494	0.6686	0.292*
P1	0.28874 (4)	0.17964 (6)	0.40872 (6)	0.0305 (3)
P2	0.30147 (5)	0.18670 (7)	0.18979 (7)	0.0372 (3)
P3	0.17430 (5)	0.21480 (7)	0.25132 (7)	0.0379 (3)
C1	0.2892 (2)	0.3452 (3)	0.3102 (3)	0.0437 (11)
C2	0.28034 (17)	0.2350 (2)	0.4956 (2)	0.0332 (10)
H2A	0.2907	0.2038	0.5391	0.040*
H2B	0.3066	0.2771	0.4954	0.040*
C3	0.25244 (17)	0.0913 (2)	0.4259 (2)	0.0328 (10)
C4	0.2433 (2)	0.0433 (3)	0.3649 (3)	0.0463 (12)
H4	0.2558	0.0573	0.3175	0.056*
C5	0.2161 (2)	−0.0251 (3)	0.3731 (3)	0.0608 (15)
H5	0.2103	−0.0566	0.3315	0.073*
C6	0.1977 (2)	−0.0462 (3)	0.4427 (4)	0.0640 (15)
H6	0.1798	−0.0924	0.4486	0.077*
C7	0.2057 (2)	0.0011 (3)	0.5039 (3)	0.0594 (14)
H7	0.1926	−0.0126	0.5510	0.071*
C8	0.2332 (2)	0.0687 (3)	0.4953 (3)	0.0460 (12)
H8	0.2389	0.0999	0.5372	0.055*
C9	0.36466 (17)	0.1560 (2)	0.4211 (2)	0.0359 (10)
C10	0.4037 (2)	0.1964 (3)	0.3819 (3)	0.0572 (14)
H10	0.3912	0.2327	0.3472	0.069*
C11	0.4621 (2)	0.1835 (4)	0.3935 (4)	0.0745 (18)
H11	0.4882	0.2116	0.3670	0.089*
C12	0.4810 (2)	0.1305 (4)	0.4432 (3)	0.0676 (17)
H12	0.5200	0.1215	0.4501	0.081*
C13	0.4429 (2)	0.0898 (3)	0.4834 (3)	0.0628 (15)
H13	0.4559	0.0538	0.5181	0.075*
C14	0.3848 (2)	0.1026 (3)	0.4721 (3)	0.0504 (13)
H14	0.3590	0.0747	0.4993	0.060*
C15	0.23651 (19)	0.1723 (3)	0.1290 (3)	0.0456 (12)
H15A	0.2270	0.2188	0.1028	0.055*
H15B	0.2441	0.1345	0.0912	0.055*
C16	0.18567 (19)	0.1475 (3)	0.1747 (3)	0.0438 (11)
H16A	0.1929	0.0979	0.1958	0.053*
H16B	0.1516	0.1447	0.1417	0.053*
C17	0.33868 (19)	0.0963 (3)	0.1854 (2)	0.0412 (11)
C18	0.3107 (2)	0.0287 (3)	0.1734 (3)	0.0490 (12)
H18	0.2711	0.0283	0.1672	0.059*
C19	0.3406 (2)	−0.0385 (3)	0.1706 (3)	0.0584 (14)
H19	0.3209	−0.0833	0.1623	0.070*
C20	0.3982 (3)	−0.0392 (3)	0.1797 (3)	0.0651 (16)
H20	0.4181	−0.0844	0.1777	0.078*
C21	0.4273 (2)	0.0267 (4)	0.1920 (4)	0.0714 (17)
H21	0.4670	0.0264	0.1980	0.086*
C22	0.3977 (2)	0.0938 (3)	0.1953 (3)	0.0593 (14)
H22	0.4177	0.1382	0.2045	0.071*
C23	0.3481 (2)	0.2435 (3)	0.1316 (3)	0.0455 (12)
C24	0.3554 (2)	0.2283 (3)	0.0564 (3)	0.0606 (14)
H24	0.3343	0.1901	0.0328	0.073*
C25	0.3935 (3)	0.2691 (4)	0.0156 (4)	0.0784 (19)
H25	0.3973	0.2592	−0.0357	0.094*
C26	0.4252 (3)	0.3234 (4)	0.0498 (4)	0.082 (2)
H26	0.4515	0.3501	0.0222	0.099*
C27	0.4192 (2)	0.3396 (3)	0.1245 (4)	0.0757 (18)
H27	0.4411	0.3772	0.1478	0.091*
C28	0.3801 (2)	0.2995 (3)	0.1655 (3)	0.0556 (14)
H28	0.3755	0.3106	0.2164	0.067*
C29	0.11966 (19)	0.1722 (3)	0.3079 (3)	0.0464 (12)
C30	0.0944 (3)	0.1036 (3)	0.2908 (4)	0.0761 (18)
H30	0.1061	0.0757	0.2496	0.091*
C31	0.0515 (3)	0.0769 (4)	0.3358 (5)	0.101 (2)
H31	0.0338	0.0313	0.3240	0.122*
C32	0.0350 (3)	0.1166 (4)	0.3970 (4)	0.098 (2)
H32	0.0069	0.0974	0.4274	0.117*
C33	0.0592 (3)	0.1842 (4)	0.4141 (4)	0.084 (2)
H33	0.0473	0.2115	0.4555	0.101*
C34	0.1015 (2)	0.2122 (3)	0.3699 (3)	0.0597 (14)
H34	0.1180	0.2584	0.3817	0.072*
C35	0.13433 (19)	0.2891 (3)	0.2004 (3)	0.0423 (11)
C36	0.1637 (2)	0.3484 (3)	0.1707 (3)	0.0548 (13)
H36	0.2032	0.3509	0.1779	0.066*
C37	0.1351 (3)	0.4045 (3)	0.1302 (3)	0.0707 (17)
H37	0.1554	0.4440	0.1096	0.085*
C38	0.0765 (3)	0.4017 (3)	0.1204 (3)	0.0716 (17)
H38	0.0573	0.4398	0.0940	0.086*
C39	0.0469 (2)	0.3436 (3)	0.1492 (3)	0.0648 (16)
H39	0.0073	0.3419	0.1419	0.078*
C40	0.0750 (2)	0.2864 (3)	0.1895 (3)	0.0530 (13)
H40	0.0544	0.2467	0.2090	0.064*
C41	0.0678 (5)	0.0611 (8)	0.5868 (8)	0.200 (6)
H41A	0.0315	0.0859	0.5890	0.300*
H41B	0.0648	0.0202	0.5514	0.300*
H41C	0.0960	0.0961	0.5707	0.300*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0365 (3)	0.0446 (3)	0.0287 (3)	0.0026 (2)	0.0002 (2)	0.0009 (2)
N1	0.084 (4)	0.054 (3)	0.057 (3)	−0.012 (3)	0.006 (2)	−0.007 (2)
O1	0.204 (9)	0.280 (12)	0.241 (12)	−0.122 (8)	−0.036 (8)	0.110 (9)
P1	0.0297 (6)	0.0359 (6)	0.0260 (6)	0.0033 (5)	0.0006 (4)	−0.0011 (5)
P2	0.0374 (7)	0.0460 (7)	0.0284 (6)	0.0033 (5)	0.0041 (5)	−0.0016 (5)
P3	0.0319 (6)	0.0469 (7)	0.0346 (7)	0.0047 (5)	−0.0016 (5)	−0.0020 (5)
C1	0.045 (3)	0.057 (3)	0.029 (3)	0.005 (2)	0.003 (2)	0.003 (2)
C2	0.036 (2)	0.036 (2)	0.027 (2)	0.0024 (19)	−0.0035 (18)	−0.0043 (18)
C3	0.031 (2)	0.040 (2)	0.028 (2)	0.0052 (18)	−0.0047 (18)	−0.0014 (19)
C4	0.054 (3)	0.051 (3)	0.034 (3)	0.002 (2)	0.001 (2)	0.000 (2)
C5	0.074 (4)	0.052 (3)	0.056 (4)	−0.009 (3)	−0.010 (3)	−0.014 (3)
C6	0.068 (4)	0.049 (3)	0.075 (4)	−0.012 (3)	−0.005 (3)	0.006 (3)
C7	0.073 (4)	0.053 (3)	0.053 (4)	−0.007 (3)	0.009 (3)	0.012 (3)
C8	0.057 (3)	0.044 (3)	0.037 (3)	−0.004 (2)	0.003 (2)	−0.002 (2)
C9	0.031 (2)	0.045 (3)	0.032 (2)	0.006 (2)	0.0013 (19)	−0.008 (2)
C10	0.041 (3)	0.078 (4)	0.053 (3)	0.000 (3)	0.001 (2)	0.009 (3)
C11	0.043 (3)	0.108 (5)	0.073 (4)	−0.015 (3)	0.009 (3)	0.004 (4)
C12	0.036 (3)	0.098 (5)	0.067 (4)	0.012 (3)	−0.005 (3)	−0.013 (4)
C13	0.049 (3)	0.078 (4)	0.060 (4)	0.019 (3)	−0.014 (3)	−0.002 (3)
C14	0.040 (3)	0.058 (3)	0.052 (3)	0.007 (2)	−0.004 (2)	0.002 (3)
C15	0.051 (3)	0.052 (3)	0.034 (3)	0.011 (2)	−0.006 (2)	−0.008 (2)
C16	0.040 (3)	0.049 (3)	0.042 (3)	0.007 (2)	−0.002 (2)	−0.007 (2)
C17	0.042 (3)	0.053 (3)	0.029 (3)	0.007 (2)	0.003 (2)	−0.001 (2)
C18	0.045 (3)	0.057 (3)	0.046 (3)	0.009 (2)	0.006 (2)	−0.001 (2)
C19	0.063 (4)	0.052 (3)	0.061 (4)	0.006 (3)	0.003 (3)	−0.002 (3)
C20	0.066 (4)	0.062 (4)	0.068 (4)	0.022 (3)	0.005 (3)	0.007 (3)
C21	0.048 (3)	0.087 (5)	0.079 (5)	0.020 (3)	−0.001 (3)	0.008 (4)
C22	0.049 (3)	0.062 (4)	0.066 (4)	0.005 (3)	−0.002 (3)	0.003 (3)
C23	0.048 (3)	0.051 (3)	0.039 (3)	0.013 (2)	0.012 (2)	0.006 (2)
C24	0.068 (4)	0.070 (4)	0.045 (3)	0.009 (3)	0.014 (3)	0.007 (3)
C25	0.083 (5)	0.097 (5)	0.058 (4)	0.020 (4)	0.032 (3)	0.018 (4)
C26	0.075 (5)	0.084 (5)	0.091 (5)	0.007 (4)	0.043 (4)	0.032 (4)
C27	0.065 (4)	0.069 (4)	0.095 (5)	−0.005 (3)	0.025 (4)	0.010 (4)
C28	0.056 (3)	0.061 (3)	0.051 (3)	−0.001 (3)	0.017 (3)	0.005 (3)
C29	0.038 (3)	0.052 (3)	0.049 (3)	0.006 (2)	0.000 (2)	0.001 (2)
C30	0.070 (4)	0.074 (4)	0.086 (5)	−0.009 (3)	0.030 (4)	−0.008 (4)
C31	0.105 (6)	0.086 (5)	0.117 (7)	−0.027 (4)	0.046 (5)	−0.007 (5)
C32	0.094 (5)	0.106 (6)	0.097 (6)	−0.017 (5)	0.049 (4)	0.000 (5)
C33	0.076 (4)	0.107 (6)	0.072 (5)	−0.001 (4)	0.027 (4)	−0.006 (4)
C34	0.054 (3)	0.075 (4)	0.051 (3)	−0.004 (3)	0.007 (3)	−0.005 (3)
C35	0.042 (3)	0.047 (3)	0.037 (3)	0.007 (2)	−0.006 (2)	−0.007 (2)
C36	0.050 (3)	0.060 (3)	0.053 (3)	0.002 (3)	−0.011 (3)	0.003 (3)
C37	0.075 (4)	0.064 (4)	0.071 (4)	−0.004 (3)	−0.020 (3)	0.015 (3)
C38	0.075 (4)	0.069 (4)	0.069 (4)	0.019 (3)	−0.026 (3)	0.009 (3)
C39	0.048 (3)	0.077 (4)	0.068 (4)	0.018 (3)	−0.015 (3)	0.003 (3)
C40	0.044 (3)	0.062 (3)	0.052 (3)	0.006 (3)	−0.007 (2)	−0.001 (3)
C41	0.166 (12)	0.229 (14)	0.204 (16)	−0.004 (10)	−0.006 (10)	0.052 (12)

Geometric parameters (Å, º) top

Cu1—C1	1.951 (6)	C17—C22	1.387 (6)
Cu1—P1	2.2832 (12)	C18—C19	1.388 (6)
Cu1—P3	2.3041 (13)	C18—H18	0.9300
Cu1—P2	2.3291 (12)	C19—C20	1.355 (7)
N1—C1	1.146 (6)	C19—H19	0.9300
O1—C41	1.358 (12)	C20—C21	1.370 (8)
O1—H1	0.8200	C20—H20	0.9300
P1—C3	1.818 (4)	C21—C22	1.383 (7)
P1—C9	1.832 (4)	C21—H21	0.9300
P1—C2	1.840 (4)	C22—H22	0.9300
P2—C17	1.832 (5)	C23—C28	1.370 (7)
P2—C23	1.833 (5)	C23—C24	1.372 (7)
P2—C15	1.846 (5)	C24—C25	1.375 (8)
P3—C29	1.818 (5)	C24—H24	0.9300
P3—C16	1.835 (5)	C25—C26	1.348 (9)
P3—C35	1.835 (5)	C25—H25	0.9300
C2—C2ⁱ	1.532 (8)	C26—C27	1.363 (9)
C2—H2A	0.9700	C26—H26	0.9300
C2—H2B	0.9700	C27—C28	1.387 (7)
C3—C8	1.382 (6)	C27—H27	0.9300
C3—C4	1.386 (6)	C28—H28	0.9300
C4—C5	1.384 (7)	C29—C30	1.384 (7)
C4—H4	0.9300	C29—C34	1.386 (7)
C5—C6	1.371 (7)	C30—C31	1.391 (8)
C5—H5	0.9300	C30—H30	0.9300
C6—C7	1.378 (7)	C31—C32	1.360 (9)
C6—H6	0.9300	C31—H31	0.9300
C7—C8	1.375 (7)	C32—C33	1.358 (9)
C7—H7	0.9300	C32—H32	0.9300
C8—H8	0.9300	C33—C34	1.377 (8)
C9—C10	1.372 (6)	C33—H33	0.9300
C9—C14	1.381 (6)	C34—H34	0.9300
C10—C11	1.394 (7)	C35—C36	1.374 (7)
C10—H10	0.9300	C35—C40	1.396 (6)
C11—C12	1.352 (8)	C36—C37	1.387 (7)
C11—H11	0.9300	C36—H36	0.9300
C12—C13	1.368 (8)	C37—C38	1.376 (8)
C12—H12	0.9300	C37—H37	0.9300
C13—C14	1.387 (6)	C38—C39	1.355 (8)
C13—H13	0.9300	C38—H38	0.9300
C14—H14	0.9300	C39—C40	1.393 (7)
C15—C16	1.529 (6)	C39—H39	0.9300
C15—H15A	0.9700	C40—H40	0.9300
C15—H15B	0.9700	C41—H41A	0.9600
C16—H16A	0.9700	C41—H41B	0.9600
C16—H16B	0.9700	C41—H41C	0.9600
C17—C18	1.381 (6)

C1—Cu1—P1	107.59 (14)	H16A—C16—H16B	108.2
C1—Cu1—P3	119.11 (14)	C18—C17—C22	117.1 (4)
P1—Cu1—P3	113.60 (5)	C18—C17—P2	123.1 (4)
C1—Cu1—P2	111.79 (14)	C22—C17—P2	119.7 (4)
P1—Cu1—P2	115.07 (5)	C17—C18—C19	121.2 (5)
P3—Cu1—P2	89.03 (4)	C17—C18—H18	119.4
C41—O1—H1	109.5	C19—C18—H18	119.4
C3—P1—C9	103.88 (19)	C20—C19—C18	120.4 (5)
C3—P1—C2	104.93 (19)	C20—C19—H19	119.8
C9—P1—C2	99.06 (18)	C18—C19—H19	119.8
C3—P1—Cu1	117.12 (14)	C19—C20—C21	119.9 (5)
C9—P1—Cu1	114.28 (15)	C19—C20—H20	120.1
C2—P1—Cu1	115.39 (14)	C21—C20—H20	120.1
C17—P2—C23	99.5 (2)	C20—C21—C22	119.9 (5)
C17—P2—C15	103.7 (2)	C20—C21—H21	120.1
C23—P2—C15	104.3 (2)	C22—C21—H21	120.1
C17—P2—Cu1	125.84 (15)	C21—C22—C17	121.5 (5)
C23—P2—Cu1	118.46 (16)	C21—C22—H22	119.3
C15—P2—Cu1	102.56 (15)	C17—C22—H22	119.3
C29—P3—C16	105.0 (2)	C28—C23—C24	118.8 (5)
C29—P3—C35	102.3 (2)	C28—C23—P2	118.9 (4)
C16—P3—C35	101.2 (2)	C24—C23—P2	122.2 (4)
C29—P3—Cu1	123.19 (17)	C23—C24—C25	120.7 (6)
C16—P3—Cu1	103.70 (15)	C23—C24—H24	119.7
C35—P3—Cu1	118.66 (16)	C25—C24—H24	119.7
N1—C1—Cu1	176.6 (5)	C26—C25—C24	120.1 (6)
C2ⁱ—C2—P1	113.6 (4)	C26—C25—H25	120.0
C2ⁱ—C2—H2A	108.8	C24—C25—H25	120.0
P1—C2—H2A	108.8	C25—C26—C27	120.6 (6)
C2ⁱ—C2—H2B	108.8	C25—C26—H26	119.7
P1—C2—H2B	108.8	C27—C26—H26	119.7
H2A—C2—H2B	107.7	C26—C27—C28	119.5 (6)
C8—C3—C4	117.7 (4)	C26—C27—H27	120.2
C8—C3—P1	124.8 (3)	C28—C27—H27	120.2
C4—C3—P1	117.5 (3)	C23—C28—C27	120.4 (6)
C5—C4—C3	121.2 (5)	C23—C28—H28	119.8
C5—C4—H4	119.4	C27—C28—H28	119.8
C3—C4—H4	119.4	C30—C29—C34	118.9 (5)
C6—C5—C4	119.9 (5)	C30—C29—P3	123.5 (4)
C6—C5—H5	120.1	C34—C29—P3	117.6 (4)
C4—C5—H5	120.1	C29—C30—C31	119.3 (6)
C5—C6—C7	119.8 (5)	C29—C30—H30	120.3
C5—C6—H6	120.1	C31—C30—H30	120.3
C7—C6—H6	120.1	C32—C31—C30	120.7 (7)
C8—C7—C6	119.9 (5)	C32—C31—H31	119.7
C8—C7—H7	120.1	C30—C31—H31	119.7
C6—C7—H7	120.1	C33—C32—C31	120.5 (6)
C7—C8—C3	121.5 (5)	C33—C32—H32	119.7
C7—C8—H8	119.2	C31—C32—H32	119.7
C3—C8—H8	119.2	C32—C33—C34	119.8 (6)
C10—C9—C14	118.2 (4)	C32—C33—H33	120.1
C10—C9—P1	118.9 (4)	C34—C33—H33	120.1
C14—C9—P1	122.8 (3)	C33—C34—C29	120.8 (6)
C9—C10—C11	120.6 (5)	C33—C34—H34	119.6
C9—C10—H10	119.7	C29—C34—H34	119.6
C11—C10—H10	119.7	C36—C35—C40	118.9 (4)
C12—C11—C10	120.4 (5)	C36—C35—P3	119.1 (4)
C12—C11—H11	119.8	C40—C35—P3	122.0 (4)
C10—C11—H11	119.8	C35—C36—C37	120.6 (5)
C11—C12—C13	120.1 (5)	C35—C36—H36	119.7
C11—C12—H12	120.0	C37—C36—H36	119.7
C13—C12—H12	120.0	C38—C37—C36	119.9 (6)
C12—C13—C14	119.7 (5)	C38—C37—H37	120.0
C12—C13—H13	120.1	C36—C37—H37	120.0
C14—C13—H13	120.1	C39—C38—C37	120.3 (5)
C9—C14—C13	121.0 (5)	C39—C38—H38	119.9
C9—C14—H14	119.5	C37—C38—H38	119.9
C13—C14—H14	119.5	C38—C39—C40	120.6 (5)
C16—C15—P2	112.0 (3)	C38—C39—H39	119.7
C16—C15—H15A	109.2	C40—C39—H39	119.7
P2—C15—H15A	109.2	C39—C40—C35	119.7 (5)
C16—C15—H15B	109.2	C39—C40—H40	120.2
P2—C15—H15B	109.2	C35—C40—H40	120.2
H15A—C15—H15B	107.9	O1—C41—H41A	109.5
C15—C16—P3	109.8 (3)	O1—C41—H41B	109.5
C15—C16—H16A	109.7	H41A—C41—H41B	109.5
P3—C16—H16A	109.7	O1—C41—H41C	109.5
C15—C16—H16B	109.7	H41A—C41—H41C	109.5
P3—C16—H16B	109.7	H41B—C41—H41C	109.5

C1—Cu1—P1—C3	160.9 (2)	P2—C15—C16—P3	54.5 (4)
P3—Cu1—P1—C3	26.84 (16)	C29—P3—C16—C15	−172.6 (3)
P2—Cu1—P1—C3	−73.77 (16)	C35—P3—C16—C15	81.3 (3)
C1—Cu1—P1—C9	−77.3 (2)	Cu1—P3—C16—C15	−42.1 (3)
P3—Cu1—P1—C9	148.63 (15)	C23—P2—C17—C18	−135.9 (4)
P2—Cu1—P1—C9	48.02 (16)	C15—P2—C17—C18	−28.6 (4)
C1—Cu1—P1—C2	36.6 (2)	Cu1—P2—C17—C18	88.2 (4)
P3—Cu1—P1—C2	−97.46 (15)	C23—P2—C17—C22	45.0 (4)
P2—Cu1—P1—C2	161.93 (15)	C15—P2—C17—C22	152.3 (4)
C1—Cu1—P2—C17	130.6 (2)	Cu1—P2—C17—C22	−90.8 (4)
P1—Cu1—P2—C17	7.5 (2)	C22—C17—C18—C19	−0.9 (7)
P3—Cu1—P2—C17	−108.3 (2)	P2—C17—C18—C19	−179.9 (4)
C1—Cu1—P2—C23	2.0 (2)	C17—C18—C19—C20	0.2 (8)
P1—Cu1—P2—C23	−121.14 (18)	C18—C19—C20—C21	0.1 (9)
P3—Cu1—P2—C23	123.13 (18)	C19—C20—C21—C22	0.3 (9)
C1—Cu1—P2—C15	−112.1 (2)	C20—C21—C22—C17	−1.1 (9)
P1—Cu1—P2—C15	124.81 (16)	C18—C17—C22—C21	1.3 (8)
P3—Cu1—P2—C15	9.07 (16)	P2—C17—C22—C21	−179.6 (4)
C1—Cu1—P3—C29	−112.1 (2)	C17—P2—C23—C28	−112.0 (4)
P1—Cu1—P3—C29	16.2 (2)	C15—P2—C23—C28	141.1 (4)
P2—Cu1—P3—C29	133.3 (2)	Cu1—P2—C23—C28	28.0 (4)
C1—Cu1—P3—C16	129.4 (2)	C17—P2—C23—C24	63.0 (4)
P1—Cu1—P3—C16	−102.25 (17)	C15—P2—C23—C24	−43.9 (5)
P2—Cu1—P3—C16	14.82 (17)	Cu1—P2—C23—C24	−157.0 (4)
C1—Cu1—P3—C35	18.2 (2)	C28—C23—C24—C25	−0.8 (8)
P1—Cu1—P3—C35	146.56 (17)	P2—C23—C24—C25	−175.8 (4)
P2—Cu1—P3—C35	−96.37 (17)	C23—C24—C25—C26	1.7 (9)
C3—P1—C2—C2ⁱ	−72.9 (4)	C24—C25—C26—C27	−1.4 (10)
C9—P1—C2—C2ⁱ	−180.0 (4)	C25—C26—C27—C28	0.3 (10)
Cu1—P1—C2—C2ⁱ	57.6 (4)	C24—C23—C28—C27	−0.3 (8)
C9—P1—C3—C8	92.8 (4)	P2—C23—C28—C27	174.8 (4)
C2—P1—C3—C8	−10.7 (4)	C26—C27—C28—C23	0.6 (9)
Cu1—P1—C3—C8	−140.2 (3)	C16—P3—C29—C30	−0.7 (5)
C9—P1—C3—C4	−87.4 (4)	C35—P3—C29—C30	104.6 (5)
C2—P1—C3—C4	169.1 (3)	Cu1—P3—C29—C30	−118.6 (5)
Cu1—P1—C3—C4	39.7 (4)	C16—P3—C29—C34	−178.7 (4)
C8—C3—C4—C5	−0.2 (7)	C35—P3—C29—C34	−73.4 (4)
P1—C3—C4—C5	179.9 (4)	Cu1—P3—C29—C34	63.4 (4)
C3—C4—C5—C6	−0.1 (8)	C34—C29—C30—C31	0.3 (9)
C4—C5—C6—C7	0.9 (8)	P3—C29—C30—C31	−177.6 (5)
C5—C6—C7—C8	−1.3 (8)	C29—C30—C31—C32	−1.3 (12)
C6—C7—C8—C3	1.0 (8)	C30—C31—C32—C33	1.7 (13)
C4—C3—C8—C7	−0.2 (7)	C31—C32—C33—C34	−1.0 (12)
P1—C3—C8—C7	179.6 (4)	C32—C33—C34—C29	0.0 (10)
C3—P1—C9—C10	151.4 (4)	C30—C29—C34—C33	0.3 (9)
C2—P1—C9—C10	−100.6 (4)	P3—C29—C34—C33	178.4 (5)
Cu1—P1—C9—C10	22.6 (4)	C29—P3—C35—C36	159.4 (4)
C3—P1—C9—C14	−33.0 (4)	C16—P3—C35—C36	−92.4 (4)
C2—P1—C9—C14	74.9 (4)	Cu1—P3—C35—C36	20.2 (4)
Cu1—P1—C9—C14	−161.8 (3)	C29—P3—C35—C40	−22.0 (4)
C14—C9—C10—C11	0.0 (8)	C16—P3—C35—C40	86.2 (4)
P1—C9—C10—C11	175.7 (4)	Cu1—P3—C35—C40	−161.3 (3)
C9—C10—C11—C12	0.6 (9)	C40—C35—C36—C37	−0.3 (8)
C10—C11—C12—C13	−1.1 (9)	P3—C35—C36—C37	178.3 (4)
C11—C12—C13—C14	1.0 (9)	C35—C36—C37—C38	1.0 (9)
C10—C9—C14—C13	−0.1 (7)	C36—C37—C38—C39	−1.1 (9)
P1—C9—C14—C13	−175.7 (4)	C37—C38—C39—C40	0.6 (9)
C12—C13—C14—C9	−0.4 (8)	C38—C39—C40—C35	0.1 (8)
C17—P2—C15—C16	93.9 (3)	C36—C35—C40—C39	−0.2 (7)
C23—P2—C15—C16	−162.3 (3)	P3—C35—C40—C39	−178.8 (4)
Cu1—P2—C15—C16	−38.3 (3)

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.02	2.829 (11)	171

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(CN)₂(C₂₆H₂₄P₂)₃]·2CH₄O
M_r	1438.38
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	23.423 (2), 17.7912 (16), 17.6614 (18)
β (°)	92.194 (1)
V (Å³)	7354.6 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.44 × 0.40 × 0.25

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.732, 0.833
No. of measured, independent and observed [I > 2σ(I)] reflections	18242, 6494, 4140
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.149, 1.06
No. of reflections	6494
No. of parameters	425
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.063P)² + 16.0608P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.39

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.82	2.02	2.829 (11)	171

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Acknowledgements

This work was supported by the National Keystone Basic Research Program (973 Program – grant Nos. 2007CB310408 and 2006CB302901), the Funding Project for Academic Human Resources Development in Institutions of Higher Learning Under the Jurisdiction of the Beijing Municipality and the State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences.

References

Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cingolani, A., Di Nicola, C., Effendy, Pettinari, C., Skelton, B. W., Somers, N. & White, A. H. (2005). Inorg. Chim. Acta, 358, 748–762. Web of Science CSD CrossRef CAS Google Scholar
Di Nicola, C., Koutsantonis, G. A., Pettinari, C., Skelton, B. W., Somers, N. & White, A. H. (2006). Inorg. Chim. Acta, 359, 2159–2169. CrossRef CAS Google Scholar
Effendy, Di Nicola, C., Pettinari, C., Pizzabiocca, A., Skelton, B. W., Somers, N. & White, A. H. (2006). Inorg. Chim. Acta, 359, 64–80. Web of Science CSD CrossRef CAS Google Scholar
Jin, Q. H., Chen, L. M., Li, P. Z., Deng, S. F. & Wang, R. (2009). Inorg. Chim. Acta, 362, 5224–5230. Web of Science CSD CrossRef CAS Google Scholar
Saravanabharathi, D., Monika, Venugopalan, P. & Samuelson, A.G. (2002). Polyhedron, 21, 2433–2443. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sivasankar, C., Nethaji, M. & Samuelson, A. G. (2004). Inorg. Chim. Commun. 7, 238–240. Web of Science CSD CrossRef CAS Google Scholar
Song, L., Lin, P., Li, Z. H., Li, J. R., Du, S. W. & Wu, X. T. (2007). Polyhedron, 26, 1199–1204. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m1032

https://doi.org/10.1107/S1600536810029545

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)