Poly[di-μ(3)-chlorido-di-μ(2)-chlorido-{μ(4)-N,N,N',N'-tetra-kis-[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine-κ(4)P:P':P'':P'''}tetra-copper(II)].

In the title complex, [Cu(4)Cl(4)(C(58)H(52)N(2)P(4))](n), four Cu(II) atoms are held together via two doubly bridging and two triply bridging chlorides, forming a stair-like Cu(4)Cl(4) core having crystallographically imposed inversion symmetry, while the benzene-1,4-diamine ligand (with a crystallographic inversion center at the centroid) acts in a tetra-dentate coordination mode, bridging two adjacent Cu(4)Cl(4) cores, resulting in a chain along the a-axis direction. One Cu atom has a distorted tetra-hedral geometry, coordinated by one P atom, one μ(2)-Cl and two μ(3)-Cl atoms, while the second Cu atom adopts a trigonal geometry, coordinated by one P atom, one μ(2)-Cl and one μ(3)-Cl atoms.

Related literature

For the structures and properties of CuI 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 = 1296.86

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.143

S = 0.94

5333 reflections

325 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.62 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010860/zq2150sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu4Cl4(C58H52N2P4)]	F(000) = 1316
Mr = 1296.86	Dx = 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

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

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(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
5333 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.62 e Å−3

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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) ; (ii) .