Poly[di-μ3-chlorido-di-μ2-chlorido-{μ4-N,N,N′,N′-tetra­kis­[(diphenyl­phosphan­yl)meth­yl]benzene-1,4-diamine-κ4P:P′:P′′:P′′′}tetra­copper(II)]

Liu, J.-Q.; Zhang, Y.; Lü, Y.-J.; Jiang, Z.-J.

doi:10.1107/S1600536812010860

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m430

doi:10.1107/S1600536812010860

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Poly[di-μ₃-chlorido-di-μ₂-chlorido-{μ₄-N,N,N′,N′-tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine-κ⁴P:P′:P′′:P′′′}tetracopper(II)]

Jia-Qin Liu,^a Yan Zhang,^a Ya-Jing Lü ^a and Zhen-Jü Jiang ^a ^*

^aSchool of Physics and Chemistry, Xihua University, Chengdu 610039, People's Republic of China
^*Correspondence e-mail: liujq67@yahoo.com.cn

(Received 12 January 2012; accepted 12 March 2012; online 17 March 2012)

In the title complex, [Cu₄Cl₄(C₅₈H₅₂N₂P₄)]_n, four Cu^II atoms are held together via two doubly bridging and two triply bridging chlorides, forming a stair-like Cu₄Cl₄ core having crystallographically imposed inversion symmetry, while the benzene-1,4-diamine ligand (with a crystallographic inversion center at the centroid) acts in a tetradentate coordination mode, bridging two adjacent Cu₄Cl₄ cores, resulting in a chain along the a-axis direction. One Cu atom has a distorted tetrahedral geometry, coordinated by one P atom, one μ₂-Cl and two μ₃-Cl atoms, while the second Cu atom adopts a trigonal geometry, coordinated by one P atom, one μ₂-Cl and one μ₃-Cl atoms.

Related literature

For the structures and properties of Cu^I complexes containing polyphosphine ligands, see: Li et al. (2009 ); Kohl et al. (2006 ); Wang et al. (2008 ); Hou et al.(2011 ); Ni et al. (2011 ). For the synthesis of Cu(I) complexes with diphosphine ligands, see: Saravanabharathi et al. (2002 ); Sivasankar et al. (2004 ).

Experimental

Crystal data

[Cu₄Cl₄(C₅₈H₅₂N₂P₄)]
M_r = 1296.86
Monoclinic, P 2₁ /c
a = 10.298 (7) Å
b = 17.649 (12) Å
c = 18.009 (9) Å
β = 123.94 (3)°
V = 2715 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.90 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.852, T_max = 1.000
15819 measured reflections
5333 independent reflections
3089 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.143
S = 0.94
5333 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—P1	2.1998 (19)
Cu1—Cl2	2.3975 (19)
Cu1—Cl1	2.4140 (17)
Cu1—Cl1ⁱ	2.565 (2)
Cu2—P2ⁱⁱ	2.188 (2)
Cu2—Cl2	2.3062 (18)
Cu2—Cl1	2.3255 (18)
Symmetry codes: (i) -x-1, -y, -z+1; (ii) -x, -y, -z+1.

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536812010860/zq2150sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010860/zq2150Isup2.hkl

checkCIF report

Comment top

Recently, Cu^I complexes containing multiphosphine ligands have received much attention so far due to their special structures, novel reactivity, as well as catalytic and luminescent properties (Kohl et al., 2006; Wang et al., 2008; Hou et al., 2011; Ni et al., 2011). However, synthesis of Cu^I complexes with tetraphosphine ligands have been virtually not explored, though a great number of Cu(I) complexes with diphosphines were reported (Saravanabharathi et al., 2002; Sivasankar et al., 2004; Li et al., 2009). Herein, we report the synthesis and crystal structure of a new Cu^I complex with the tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine ligand (dpppda), the title complex [Cu₄Cl₄(dpppda)]_n.

The asymmetric unit of the title complex, [Cu₂Cl₂(C₂₉H₂₆NP₂)]_n, contains two copper ions, two chlorine atoms and one half of the N,N,N',N'-tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine ligand (dpppda). Four copper atoms are held together via two doubly bridging and two triply-bridging chlorides to form a stair-like Cu₄Cl₄ core having a crystallographically imposed centrosymmetry, while the N,N,N',N'-tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine ligand (with a crystallographic inversion center at the midpoint of the central phenyl ring) acts as a tetradentate coordination mode to bridge two adjacent Cu₄Cl₄ cores resulting in a one-dimentional chain. The structure of the title complex is anologous to the reported complex [Cu₄I₄(dpppda)] (Li et al., 2009). Cu1 has a distorted tetrahedral geometry, coordinated by one P atom, one µ₂-Cl and two µ₃-Cl atoms, while Cu2 adopts a trigonal geometry, coordinated by one P atom, one µ₂-Cl and one µ₃-Cl atoms. The mean Cu—Cl and Cu—P bond distances are 2.40 (1) and 2.19 (2) Å, respectively.

Related literature top

For the structures and properties of Cu^I complexes containing multiphosphine ligands, see: Li et al. (2009); Kohl et al. (2006); Wang et al. (2008); Hou et al.(2011); Ni et al. (2011). For the synthesis of Cu(I) complexes with diphosphine ligands, see: Saravanabharathi et al. (2002); Sivasankar et al. (2004).

Experimental top

CuCl (0.0198 g, 0.2 mmol) was added with stirring to a solution of N,N,N',N'-tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine (0.0900 g, 0.10 mmol) in DMF (5 ml), and the resulting solution was allowed to stir for 1 h at room temperature. Slow diffusion of diethyl ether into the solution give colourless block crystals suitable for X-ray analysis after three days.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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. The structure of the title compound with displacement ellipsoids drawn at the 20% probability level. Hydrogen atoms are omitted for clarity. [symmetry code: (A) 1-x, -y, 1-z; (B) -x, -y, 1-z; (C) -1+x, y, z.]

Poly[di-µ₃-chlorido-di-µ₂-chlorido-{µ₄- N,N,N',N'- tetrakis[(diphenylphosphanyl)methyl]benzene-1,4-diamine- κ⁴P:P':P'':P'''}tetracopper(II)] top

Crystal data top

[Cu₄Cl₄(C₅₈H₅₂N₂P₄)]	F(000) = 1316
M_r = 1296.86	D_x = 1.586 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5682 reflections
a = 10.298 (7) Å	θ = 2.8–26.3°
b = 17.649 (12) Å	µ = 1.90 mm⁻¹
c = 18.009 (9) Å	T = 296 K
β = 123.94 (3)°	Block, colourless
V = 2715 (3) Å³	0.20 × 0.15 × 0.13 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	5333 independent reflections
Radiation source: fine-focus sealed tube	3089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→9
T_min = 0.852, T_max = 1.000	k = −19→21
15819 measured reflections	l = −21→22

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
5333 reflections	(Δ/σ)_max = 0.001
325 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[Cu₄Cl₄(C₅₈H₅₂N₂P₄)]	V = 2715 (3) Å³
M_r = 1296.86	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.298 (7) Å	µ = 1.90 mm⁻¹
b = 17.649 (12) Å	T = 296 K
c = 18.009 (9) Å	0.20 × 0.15 × 0.13 mm
β = 123.94 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5333 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3089 reflections with I > 2σ(I)
T_min = 0.852, T_max = 1.000	R_int = 0.085
15819 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.94	Δρ_max = 0.70 e Å⁻³
5333 reflections	Δρ_min = −0.62 e Å⁻³
325 parameters

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	−0.45394 (8)	0.04466 (4)	0.43168 (4)	0.0540 (2)
Cu2	−0.15464 (7)	0.07255 (4)	0.62081 (4)	0.0487 (2)
Cl1	−0.30501 (14)	−0.03659 (7)	0.56069 (8)	0.0417 (3)
Cl2	−0.32846 (15)	0.15805 (7)	0.51454 (9)	0.0526 (4)
P1	−0.52339 (15)	0.01608 (8)	0.29527 (8)	0.0402 (3)
P2	−0.07631 (15)	−0.08176 (7)	0.25371 (8)	0.0367 (3)
N1	−0.2438 (4)	−0.0268 (2)	0.3202 (2)	0.0397 (10)
C1	−0.1055 (6)	0.0562 (3)	0.4500 (3)	0.0370 (12)
H1A	−0.1767	0.0948	0.4172	0.044*
C2	−0.1233 (5)	−0.0133 (3)	0.4094 (3)	0.0336 (11)
C3	−0.0155 (6)	−0.0698 (3)	0.4619 (3)	0.0364 (11)
H3A	−0.0251	−0.1175	0.4372	0.044*
C4	−0.3712 (5)	0.0258 (3)	0.2699 (3)	0.0393 (12)
H4A	−0.4193	0.0173	0.2064	0.047*
H4B	−0.3304	0.0771	0.2835	0.047*
C5	−0.5742 (6)	−0.0830 (3)	0.2617 (3)	0.0430 (13)
C6	−0.6482 (7)	−0.1100 (4)	0.1736 (4)	0.0658 (18)
H6A	−0.6962	−0.0752	0.1269	0.079*
C7	−0.6531 (8)	−0.1842 (4)	0.1535 (5)	0.077 (2)
H7A	−0.7037	−0.1999	0.0943	0.092*
C8	−0.5818 (8)	−0.2361 (4)	0.2222 (5)	0.087 (2)
H8A	−0.5802	−0.2870	0.2094	0.104*
C9	−0.5123 (8)	−0.2134 (4)	0.3103 (4)	0.088 (2)
H9A	−0.4684	−0.2490	0.3562	0.105*
C10	−0.5089 (7)	−0.1380 (3)	0.3292 (4)	0.0647 (17)
H10A	−0.4619	−0.1230	0.3884	0.078*
C11	−0.6787 (6)	0.0772 (3)	0.2085 (3)	0.0481 (14)
C12	−0.7157 (8)	0.0836 (4)	0.1220 (4)	0.078 (2)
H12A	−0.6607	0.0545	0.1053	0.094*
C13	−0.8307 (9)	0.1312 (4)	0.0603 (4)	0.099 (3)
H13A	−0.8583	0.1319	0.0015	0.118*
C14	−0.9051 (8)	0.1783 (4)	0.0868 (5)	0.086 (2)
H14A	−0.9836	0.2108	0.0454	0.103*
C15	−0.8645 (7)	0.1776 (4)	0.1730 (5)	0.0743 (19)
H15A	−0.9118	0.2110	0.1910	0.089*
C16	−0.7513 (7)	0.1263 (3)	0.2341 (4)	0.0647 (17)
H16A	−0.7245	0.1253	0.2927	0.078*
C17	−0.2353 (5)	−0.0931 (3)	0.2727 (3)	0.0402 (12)
H17A	−0.3346	−0.0990	0.2156	0.048*
H17B	−0.2165	−0.1385	0.3077	0.048*
C18	−0.1096 (5)	−0.1626 (2)	0.1820 (3)	0.0352 (11)
C19	−0.2520 (6)	−0.1996 (3)	0.1284 (3)	0.0516 (14)
H19A	−0.3385	−0.1823	0.1271	0.062*
C20	−0.2680 (7)	−0.2612 (3)	0.0773 (4)	0.0551 (15)
H20A	−0.3647	−0.2849	0.0418	0.066*
C21	−0.1420 (7)	−0.2879 (3)	0.0785 (4)	0.0525 (14)
H21A	−0.1526	−0.3296	0.0441	0.063*
C22	−0.0008 (7)	−0.2525 (3)	0.1307 (4)	0.0548 (15)
H22A	0.0849	−0.2699	0.1312	0.066*
C23	0.0160 (6)	−0.1911 (3)	0.1827 (3)	0.0453 (13)
H23A	0.1138	−0.1685	0.2190	0.054*
C24	−0.1553 (6)	0.0012 (3)	0.1797 (3)	0.0430 (13)
C25	−0.1172 (7)	0.0719 (3)	0.2188 (4)	0.0545 (15)
H25A	−0.0423	0.0769	0.2798	0.065*
C26	−0.1918 (8)	0.1364 (3)	0.1661 (5)	0.0701 (19)
H26A	−0.1672	0.1840	0.1928	0.084*
C27	−0.2981 (8)	0.1301 (4)	0.0776 (4)	0.0710 (19)
H27A	−0.3477	0.1732	0.0435	0.085*
C28	−0.3334 (8)	0.0610 (4)	0.0378 (4)	0.0714 (19)
H28A	−0.4057	0.0570	−0.0237	0.086*
C29	−0.2629 (7)	−0.0035 (3)	0.0880 (4)	0.0607 (17)
H29A	−0.2878	−0.0505	0.0599	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0651 (5)	0.0619 (5)	0.0341 (4)	0.0056 (3)	0.0270 (4)	0.0001 (3)
Cu2	0.0389 (4)	0.0554 (4)	0.0406 (4)	−0.0038 (3)	0.0154 (3)	−0.0054 (3)
Cl1	0.0392 (7)	0.0407 (7)	0.0396 (7)	−0.0005 (5)	0.0187 (6)	0.0031 (5)
Cl2	0.0503 (8)	0.0430 (8)	0.0577 (9)	0.0049 (6)	0.0259 (7)	0.0008 (6)
P1	0.0376 (8)	0.0506 (9)	0.0318 (7)	0.0042 (6)	0.0190 (6)	0.0011 (6)
P2	0.0355 (7)	0.0419 (8)	0.0322 (7)	−0.0021 (6)	0.0185 (6)	−0.0041 (6)
N1	0.038 (2)	0.043 (2)	0.035 (2)	0.0018 (19)	0.018 (2)	−0.0083 (18)
C1	0.040 (3)	0.038 (3)	0.032 (3)	0.001 (2)	0.020 (2)	0.004 (2)
C2	0.035 (3)	0.039 (3)	0.029 (2)	−0.002 (2)	0.019 (2)	−0.001 (2)
C3	0.046 (3)	0.031 (3)	0.040 (3)	−0.006 (2)	0.030 (3)	−0.006 (2)
C4	0.041 (3)	0.048 (3)	0.026 (2)	−0.002 (2)	0.017 (2)	0.001 (2)
C5	0.035 (3)	0.055 (3)	0.047 (3)	−0.004 (2)	0.027 (3)	−0.008 (3)
C6	0.066 (4)	0.079 (5)	0.044 (3)	−0.022 (3)	0.026 (3)	−0.010 (3)
C7	0.083 (5)	0.070 (5)	0.087 (5)	−0.034 (4)	0.053 (4)	−0.037 (4)
C8	0.068 (5)	0.058 (4)	0.119 (7)	−0.011 (4)	0.044 (5)	−0.022 (5)
C9	0.088 (5)	0.063 (5)	0.066 (5)	0.000 (4)	0.014 (4)	0.005 (4)
C10	0.064 (4)	0.058 (4)	0.054 (4)	−0.006 (3)	0.021 (3)	0.000 (3)
C11	0.044 (3)	0.064 (4)	0.034 (3)	0.010 (3)	0.021 (3)	0.003 (2)
C12	0.093 (5)	0.090 (5)	0.047 (4)	0.045 (4)	0.037 (4)	0.017 (3)
C13	0.123 (7)	0.107 (6)	0.053 (4)	0.055 (5)	0.041 (5)	0.022 (4)
C14	0.065 (5)	0.106 (6)	0.064 (5)	0.027 (4)	0.021 (4)	0.022 (4)
C15	0.075 (5)	0.072 (5)	0.083 (5)	0.027 (4)	0.048 (4)	0.016 (4)
C16	0.064 (4)	0.070 (4)	0.057 (4)	0.018 (3)	0.032 (3)	0.015 (3)
C17	0.040 (3)	0.047 (3)	0.036 (3)	−0.001 (2)	0.023 (2)	−0.002 (2)
C18	0.038 (3)	0.034 (3)	0.034 (3)	0.000 (2)	0.020 (2)	−0.001 (2)
C19	0.043 (3)	0.058 (4)	0.053 (3)	−0.005 (3)	0.026 (3)	−0.017 (3)
C20	0.052 (4)	0.061 (4)	0.056 (4)	−0.018 (3)	0.033 (3)	−0.022 (3)
C21	0.068 (4)	0.043 (3)	0.056 (4)	−0.006 (3)	0.040 (3)	−0.011 (3)
C22	0.052 (4)	0.053 (4)	0.065 (4)	0.005 (3)	0.036 (3)	−0.007 (3)
C23	0.040 (3)	0.048 (3)	0.050 (3)	0.000 (2)	0.027 (3)	−0.007 (2)
C24	0.043 (3)	0.046 (3)	0.041 (3)	−0.004 (2)	0.025 (3)	−0.004 (2)
C25	0.062 (4)	0.048 (3)	0.053 (3)	−0.011 (3)	0.032 (3)	−0.009 (3)
C26	0.090 (5)	0.035 (3)	0.085 (5)	−0.005 (3)	0.048 (4)	−0.002 (3)
C27	0.077 (5)	0.056 (4)	0.068 (4)	0.006 (3)	0.033 (4)	0.021 (3)
C28	0.077 (5)	0.067 (5)	0.046 (4)	0.000 (3)	0.020 (3)	0.008 (3)
C29	0.074 (4)	0.048 (4)	0.046 (3)	−0.003 (3)	0.025 (3)	−0.004 (3)

Geometric parameters (Å, º) top

Cu1—P1	2.1998 (19)	C10—H10A	0.9300
Cu1—Cl2	2.3975 (19)	C11—C16	1.381 (7)
Cu1—Cl1	2.4140 (17)	C11—C12	1.386 (8)
Cu1—Cl1ⁱ	2.565 (2)	C12—C13	1.369 (8)
Cu2—P2ⁱⁱ	2.188 (2)	C12—H12A	0.9300
Cu2—Cl2	2.3062 (18)	C13—C14	1.382 (9)
Cu2—Cl1	2.3255 (18)	C13—H13A	0.9300
Cl1—Cu1ⁱ	2.565 (2)	C14—C15	1.364 (9)
P1—C5	1.828 (5)	C14—H14A	0.9300
P1—C11	1.837 (5)	C15—C16	1.399 (7)
P1—C4	1.869 (5)	C15—H15A	0.9300
P2—C18	1.824 (5)	C16—H16A	0.9300
P2—C24	1.836 (5)	C17—H17A	0.9700
P2—C17	1.861 (5)	C17—H17B	0.9700
P2—Cu2ⁱⁱ	2.188 (2)	C18—C23	1.381 (7)
N1—C2	1.397 (5)	C18—C19	1.389 (6)
N1—C4	1.442 (6)	C19—C20	1.374 (7)
N1—C17	1.479 (6)	C19—H19A	0.9300
C1—C3ⁱⁱ	1.386 (6)	C20—C21	1.368 (8)
C1—C2	1.387 (6)	C20—H20A	0.9300
C1—H1A	0.9300	C21—C22	1.364 (7)
C2—C3	1.396 (6)	C21—H21A	0.9300
C3—C1ⁱⁱ	1.386 (6)	C22—C23	1.378 (7)
C3—H3A	0.9300	C22—H22A	0.9300
C4—H4A	0.9700	C23—H23A	0.9300
C4—H4B	0.9700	C24—C25	1.378 (7)
C5—C10	1.400 (7)	C24—C29	1.386 (7)
C5—C6	1.405 (7)	C25—C26	1.404 (7)
C6—C7	1.352 (8)	C25—H25A	0.9300
C6—H6A	0.9300	C26—C27	1.342 (8)
C7—C8	1.377 (9)	C26—H26A	0.9300
C7—H7A	0.9300	C27—C28	1.358 (8)
C8—C9	1.387 (9)	C27—H27A	0.9300
C8—H8A	0.9300	C28—C29	1.380 (7)
C9—C10	1.368 (8)	C28—H28A	0.9300
C9—H9A	0.9300	C29—H29A	0.9300

P1—Cu1—Cl2	127.78 (6)	C16—C11—C12	117.7 (5)
P1—Cu1—Cl1	125.05 (7)	C16—C11—P1	117.4 (4)
Cl2—Cu1—Cl1	93.71 (7)	C12—C11—P1	124.5 (4)
P1—Cu1—Cl1ⁱ	109.03 (6)	C13—C12—C11	122.2 (6)
Cl2—Cu1—Cl1ⁱ	102.38 (6)	C13—C12—H12A	118.9
Cl1—Cu1—Cl1ⁱ	91.68 (6)	C11—C12—H12A	118.9
P2ⁱⁱ—Cu2—Cl2	134.50 (6)	C12—C13—C14	118.9 (7)
P2ⁱⁱ—Cu2—Cl1	126.84 (6)	C12—C13—H13A	120.5
Cl2—Cu2—Cl1	98.57 (7)	C14—C13—H13A	120.5
Cu2—Cl1—Cu1	81.73 (6)	C15—C14—C13	120.7 (6)
Cu2—Cl1—Cu1ⁱ	115.71 (6)	C15—C14—H14A	119.6
Cu1—Cl1—Cu1ⁱ	88.32 (6)	C13—C14—H14A	119.6
Cu2—Cl2—Cu1	82.49 (7)	C14—C15—C16	119.5 (6)
C5—P1—C11	109.2 (2)	C14—C15—H15A	120.2
C5—P1—C4	97.5 (2)	C16—C15—H15A	120.2
C11—P1—C4	100.9 (2)	C11—C16—C15	120.8 (6)
C5—P1—Cu1	116.30 (18)	C11—C16—H16A	119.6
C11—P1—Cu1	113.65 (18)	C15—C16—H16A	119.6
C4—P1—Cu1	117.26 (16)	N1—C17—P2	111.4 (3)
C18—P2—C24	106.1 (2)	N1—C17—H17A	109.4
C18—P2—C17	102.1 (2)	P2—C17—H17A	109.4
C24—P2—C17	98.1 (2)	N1—C17—H17B	109.4
C18—P2—Cu2ⁱⁱ	117.10 (16)	P2—C17—H17B	109.4
C24—P2—Cu2ⁱⁱ	118.43 (17)	H17A—C17—H17B	108.0
C17—P2—Cu2ⁱⁱ	112.24 (17)	C23—C18—C19	117.1 (4)
C2—N1—C4	121.7 (4)	C23—C18—P2	118.3 (4)
C2—N1—C17	119.9 (4)	C19—C18—P2	124.6 (4)
C4—N1—C17	118.2 (4)	C20—C19—C18	121.5 (5)
C3ⁱⁱ—C1—C2	121.7 (4)	C20—C19—H19A	119.2
C3ⁱⁱ—C1—H1A	119.1	C18—C19—H19A	119.2
C2—C1—H1A	119.1	C21—C20—C19	120.2 (5)
C1—C2—C3	117.0 (4)	C21—C20—H20A	119.9
C1—C2—N1	121.9 (4)	C19—C20—H20A	119.9
C3—C2—N1	121.1 (4)	C22—C21—C20	119.3 (5)
C1ⁱⁱ—C3—C2	121.2 (4)	C22—C21—H21A	120.3
C1ⁱⁱ—C3—H3A	119.4	C20—C21—H21A	120.3
C2—C3—H3A	119.4	C21—C22—C23	120.6 (5)
N1—C4—P1	112.3 (3)	C21—C22—H22A	119.7
N1—C4—H4A	109.1	C23—C22—H22A	119.7
P1—C4—H4A	109.1	C22—C23—C18	121.2 (5)
N1—C4—H4B	109.1	C22—C23—H23A	119.4
P1—C4—H4B	109.1	C18—C23—H23A	119.4
H4A—C4—H4B	107.9	C25—C24—C29	118.2 (5)
C10—C5—C6	116.0 (5)	C25—C24—P2	117.9 (4)
C10—C5—P1	117.8 (4)	C29—C24—P2	123.6 (4)
C6—C5—P1	125.0 (4)	C24—C25—C26	119.8 (5)
C7—C6—C5	123.2 (6)	C24—C25—H25A	120.1
C7—C6—H6A	118.4	C26—C25—H25A	120.1
C5—C6—H6A	118.4	C27—C26—C25	120.8 (5)
C6—C7—C8	118.8 (6)	C27—C26—H26A	119.6
C6—C7—H7A	120.6	C25—C26—H26A	119.6
C8—C7—H7A	120.6	C26—C27—C28	120.1 (6)
C7—C8—C9	120.8 (6)	C26—C27—H27A	120.0
C7—C8—H8A	119.6	C28—C27—H27A	120.0
C9—C8—H8A	119.6	C27—C28—C29	120.5 (6)
C10—C9—C8	119.4 (6)	C27—C28—H28A	119.8
C10—C9—H9A	120.3	C29—C28—H28A	119.8
C8—C9—H9A	120.3	C28—C29—C24	120.6 (5)
C9—C10—C5	121.7 (6)	C28—C29—H29A	119.7
C9—C10—H10A	119.1	C24—C29—H29A	119.7
C5—C10—H10A	119.1

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

Experimental details

Crystal data
Chemical formula	[Cu₄Cl₄(C₅₈H₅₂N₂P₄)]
M_r	1296.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.298 (7), 17.649 (12), 18.009 (9)
β (°)	123.94 (3)
V (Å³)	2715 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.90
Crystal size (mm)	0.20 × 0.15 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.852, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15819, 5333, 3089
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.143, 0.94
No. of reflections	5333
No. of parameters	325
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.62

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—P1	2.1998 (19)	Cu2—P2ⁱⁱ	2.188 (2)
Cu1—Cl2	2.3975 (19)	Cu2—Cl2	2.3062 (18)
Cu1—Cl1	2.4140 (17)	Cu2—Cl1	2.3255 (18)
Cu1—Cl1ⁱ	2.565 (2)

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

Acknowledgements

This work was supported by the Key Program of Xihua University (E0913305, E0913307).

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