Di-μ3-bromo-di­bromo­tetrakis­[μ-di­phenyl(2-pyridyl)­phosphine)]­tetracopper(I) di­chloro­methane hexasolvate

Zhou, J.-L.; Li, Y.-Z.; Zheng, H.-G.; Xin, X.-Q.; Xu, L.-L.

doi:10.1107/S1600536803005725

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Di-μ₃-bromo-dibromotetrakis[μ-diphenyl(2-pyridyl)phosphine)]tetracopper(I) dichloromethane hexasolvate

J.-L. Zhou, Y.-Z. Li, H.-G. Zheng, X.-Q. Xin and L.-L. Xu

In the title compound, [Cu₄Br₄(C₁₇H₁₄NP)₄]·6CH₂Cl₂, the centrosymmetric Cu₄Br₂ group is in a slightly distorted plane, forming a shuttle-like structure. Each of the Cu^I ions is coordinated by two Br, N and P atoms, with metal–metal bonds between neighbouring Cu atoms.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005725/ob6225sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005725/ob6225Isup2.hkl Contains datablock I

CCDC reference: 209891

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.008 Å
R factor = 0.032
wR factor = 0.157
Data-to-parameter ratio = 17.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

Comment top

The chemistry of transition metal clusters has attracted much attention owing to their relevance to certain biological catalyses and functional materials (Holm et al., 1985; Holm, 1992; Du et al., 1992). Transition metal complexes containing coordinated diphenyl(2-pyridyl)phosphine (PyPPh₂) have been studied for their structural chemistry. Much research has focused on the preparation of model compounds because of their catalytic and non-linear optical properties (Niu et al., 2001). A rich structural diversity of PyPPh₂-containing Cu complexes has been revealed. The PyPPh₂ ligand can coordinate to Cu in different coordination fashions, such as monodentate and bidentate. We present here the structure of the title compound, (I).

The structure of the complex in (I) is centrosymmetric and the two independent Cu atoms are coordinated in different modes (Fig. 1). Atom Cu1 is coordinated by two µ₃-bridging Br atoms, and P and N atoms from PyPPh₂ ligands. Atom Cu2 is coordinated by a terminal Br atom, a µ₃-bridging Br atom, and P and N atoms from PyPPh₂ ligands. There are two different kinds of Br atoms: two are terminal and the other two are µ₃-bridging. The Br1 coordinates to three Cu atoms in a µ₃bridging bond mode, while atom Br2 is terminal. The bond lengths of Br1—Cu1, Br1—Cu2 and Br1—Cu1ⁱ are 2.4645 (8), 2.5721 (8) and 2.8008 (8) Å, respectively (see Table 1 for symmetry code). The average Br—Cu bond length involving µ₃-Br is 2.6125 (8) Å, which is longer than that of the terminal Cu—Br bond [2.4754 (8) Å]. The PyPPh₂ ligand is a bidentate and coordinates to two Cu atoms through its P and N atoms, forming a distorted Cu—Cu—P—C—N pentagon, with the angles ranging from 85.78 (4) to 124.7 (3)°. The average Cu—N bond length is 2.074 (4) Å, which is much shorter than the average Cu—P bond length [2.1920 (14) Å]. There are intermolecular C—H···Cl interactions (Fig. 2).

Experimental top

The title compound, (I), was obtained by the reaction of CuBr (3 mmol, 0.430 g) with diphenyl(2-pyridyl)phosphine (3 mmol, 0.808 g) in CH₂Cl₂ solution (20 ml). The mixture was stirred for 8 h. The resulting solution was subsequently filtered to afford a light-yellow filtrate. Light-yellow crystals of (I) were obtained after several days by laying the filtrate with i-PrOH. Elemental analysis, calculated for Cu₄Br₄(PyPPh₂)₄·6CH₂Cl₂: C 41.60, H 3.21, N 2.62%; found: C 41.62, H 3.20, N 2.64%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure of the complex in (I), shown with 30% probability displacement ellipsoids.
	Fig. 2. The packing diagram of (I), viewed down the a axis. The broken lines indicate C—H···Cl interactions.

Di-µ₃-bromo-dibromotetrakis[µ-diphenyl(2-pyridyl)phosphine)]tetracopper(I) hexakisdichloromethane solvate top

Crystal data top

[Cu₄Br₄(C₁₇H₁₄NP)₄]·6CH₂Cl₂	F(000) = 2120
M_r = 2136.40	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3951 reflections
a = 13.818 (1) Å	θ = 2.2–20.2°
b = 17.793 (2) Å	µ = 3.12 mm⁻¹
c = 19.292 (2) Å	T = 293 K
β = 104.85 (1)°	Strip, light yellow
V = 4584.8 (8) Å³	0.3 × 0.2 × 0.2 mm
Z = 2

Data collection top

Bruker SMART diffractometer	8072 independent reflections
Radiation source: sealed tube	6838 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.007
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→16
T_min = 0.476, T_max = 0.534	k = −21→12
23308 measured reflections	l = −22→20

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.12P)² + 1.99P] where P = (F_o² + 2F_c²)/3
8072 reflections	(Δ/σ)_max < 0.001
460 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Cu₄Br₄(C₁₇H₁₄NP)₄]·6CH₂Cl₂	V = 4584.8 (8) Å³
M_r = 2136.40	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.818 (1) Å	µ = 3.12 mm⁻¹
b = 17.793 (2) Å	T = 293 K
c = 19.292 (2) Å	0.3 × 0.2 × 0.2 mm
β = 104.85 (1)°

Data collection top

Bruker SMART diffractometer	8072 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	6838 reflections with I > 2σ(I)
T_min = 0.476, T_max = 0.534	R_int = 0.007
23308 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.02	Δρ_max = 0.64 e Å⁻³
8072 reflections	Δρ_min = −0.74 e Å⁻³
460 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	0.91632 (5)	0.44876 (3)	0.43243 (3)	0.06064 (18)
Cu2	0.98400 (5)	0.30401 (3)	0.42525 (3)	0.06069 (18)
Br1	1.08113 (4)	0.40829 (3)	0.50636 (2)	0.06077 (16)
Br2	1.10391 (4)	0.19858 (3)	0.43650 (2)	0.06145 (16)
P1	0.78981 (10)	0.39748 (7)	0.46157 (7)	0.0610 (3)
P2	0.94083 (10)	0.33349 (7)	0.30991 (7)	0.0605 (3)
N1	0.9154 (3)	0.4820 (2)	0.3305 (2)	0.0592 (9)
C1	0.9241 (3)	0.4292 (3)	0.2794 (2)	0.0559 (10)
C2	0.9216 (4)	0.4516 (3)	0.2101 (3)	0.0592 (11)
H2	0.9264	0.4160	0.1758	0.071*
C3	0.9118 (4)	0.5278 (3)	0.1919 (3)	0.0624 (11)
H3	0.9111	0.5432	0.1457	0.075*
C4	0.9032 (4)	0.5805 (3)	0.2430 (3)	0.0593 (11)
H4	0.8961	0.6312	0.2309	0.071*
C5	0.9052 (4)	0.5579 (3)	0.3119 (2)	0.0608 (11)
H5	0.8996	0.5934	0.3460	0.073*
C6	0.8176 (4)	0.2897 (3)	0.2652 (3)	0.0605 (12)
C7	0.7389 (4)	0.3288 (3)	0.2218 (2)	0.0583 (11)
H7	0.7456	0.3796	0.2128	0.070*
C8	0.6490 (4)	0.2915 (2)	0.1913 (3)	0.0590 (11)
H8	0.5955	0.3173	0.1617	0.071*
C9	0.6402 (4)	0.2155 (3)	0.2056 (3)	0.0611 (13)
H9	0.5804	0.1906	0.1857	0.073*
C10	0.7184 (4)	0.1772 (3)	0.2487 (3)	0.0598 (12)
H10	0.7116	0.1264	0.2575	0.072*
C11	0.8085 (4)	0.2140 (3)	0.2795 (3)	0.0605 (12)
H11	0.8616	0.1880	0.3092	0.073*
C12	1.0210 (4)	0.2975 (2)	0.2556 (3)	0.0584 (11)
C13	0.9849 (4)	0.2670 (2)	0.1868 (3)	0.0592 (12)
H13	0.9164	0.2611	0.1675	0.071*
C14	1.0522 (4)	0.2457 (2)	0.1477 (3)	0.0617 (12)
H14	1.0288	0.2249	0.1023	0.074*
C15	1.1542 (4)	0.2555 (2)	0.1767 (3)	0.0595 (12)
H15	1.1991	0.2417	0.1504	0.071*
C16	1.1895 (4)	0.2859 (3)	0.2447 (3)	0.0606 (12)
H16	1.2579	0.2923	0.2639	0.073*
C17	1.1229 (4)	0.3068 (2)	0.2842 (3)	0.0622 (12)
H17	1.1467	0.3271	0.3299	0.075*
N2	0.8725 (3)	0.2610 (2)	0.4702 (2)	0.0610 (9)
C18	0.7972 (4)	0.3037 (3)	0.4872 (3)	0.0610 (11)
C19	0.7295 (4)	0.2701 (3)	0.5194 (2)	0.0610 (11)
H19	0.6789	0.2987	0.5303	0.073*
C20	0.7367 (4)	0.1935 (2)	0.5355 (3)	0.0612 (12)
H20	0.6916	0.1711	0.5575	0.073*
C21	0.8119 (4)	0.1509 (3)	0.5185 (3)	0.0598 (12)
H21	0.8170	0.0998	0.5289	0.072*
C22	0.8795 (4)	0.1850 (2)	0.4858 (3)	0.0583 (11)
H22	0.9297	0.1565	0.4745	0.070*
C23	0.7594 (4)	0.4442 (3)	0.5409 (3)	0.0616 (11)
C24	0.8323 (4)	0.4646 (2)	0.6013 (3)	0.0600 (12)
H24	0.8993	0.4554	0.6037	0.072*
C25	0.8058 (4)	0.4991 (3)	0.6588 (3)	0.0622 (13)
H25	0.8551	0.5128	0.6994	0.075*
C26	0.7055 (4)	0.5129 (2)	0.6551 (3)	0.0582 (11)
H26	0.6878	0.5358	0.6934	0.070*
C27	0.6319 (4)	0.4925 (3)	0.5945 (3)	0.0617 (12)
H27	0.5650	0.5018	0.5922	0.074*
C28	0.6583 (4)	0.4581 (3)	0.5370 (3)	0.0591 (12)
H28	0.6090	0.4445	0.4963	0.071*
C29	0.6754 (4)	0.4042 (3)	0.3907 (3)	0.0622 (11)
C30	0.6107 (4)	0.3434 (3)	0.3693 (3)	0.0632 (11)
H30	0.6250	0.2975	0.3927	0.076*
C31	0.5254 (4)	0.3508 (3)	0.3134 (3)	0.0629 (11)
H31	0.4829	0.3100	0.2990	0.076*
C32	0.5035 (4)	0.4199 (3)	0.2789 (3)	0.0621 (11)
H32	0.4460	0.4253	0.2417	0.075*
C33	0.5673 (4)	0.4807 (3)	0.2998 (3)	0.0629 (12)
H33	0.5529	0.5267	0.2765	0.075*
C34	0.6522 (4)	0.4726 (3)	0.3554 (3)	0.0624 (11)
H34	0.6947	0.5135	0.3696	0.075*
C40	0.5738 (4)	0.5898 (3)	0.0406 (3)	0.0627 (13)
H40A	0.6314	0.6124	0.0287	0.075*
H40B	0.5198	0.5830	−0.0023	0.075*
Cl41	0.60511 (9)	0.50282 (6)	0.09416 (6)	0.0613 (3)
Cl42	0.53451 (9)	0.64031 (6)	0.11240 (6)	0.0613 (3)
C50	0.5554 (4)	0.7653 (3)	0.9573 (3)	0.0607 (12)
H50A	0.4870	0.7827	0.9400	0.073*
H50B	0.5570	0.7112	0.9635	0.073*
Cl51	0.62630 (9)	0.81619 (6)	1.03761 (6)	0.0612 (3)
Cl52	0.63845 (9)	0.79866 (6)	0.90207 (6)	0.0609 (3)
C60	0.2384 (4)	0.0633 (3)	0.6282 (3)	0.0617 (12)
H60A	0.2426	0.1172	0.6361	0.074*
H60B	0.2893	0.0376	0.6646	0.074*
Cl61	0.23931 (9)	0.03683 (6)	0.53711 (6)	0.0616 (3)
Cl62	0.11041 (9)	0.02520 (6)	0.61905 (6)	0.0612 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0781 (4)	0.0559 (3)	0.0537 (3)	0.0056 (3)	0.0274 (3)	0.0044 (2)
Cu2	0.0780 (4)	0.0561 (3)	0.0536 (3)	0.0054 (3)	0.0272 (3)	0.0042 (2)
Br1	0.0778 (3)	0.0560 (3)	0.0542 (3)	0.0055 (2)	0.0273 (2)	0.00414 (19)
Br2	0.0790 (3)	0.0561 (3)	0.0553 (3)	0.0060 (2)	0.0282 (2)	0.00446 (19)
P1	0.0763 (8)	0.0569 (7)	0.0548 (7)	0.0004 (6)	0.0261 (6)	0.0009 (5)
P2	0.0777 (8)	0.0554 (7)	0.0535 (6)	0.0055 (6)	0.0263 (6)	0.0042 (5)
N1	0.081 (3)	0.0370 (18)	0.054 (2)	0.0121 (17)	0.0079 (18)	0.0100 (15)
C1	0.075 (3)	0.053 (2)	0.037 (2)	0.010 (2)	0.0099 (19)	0.0058 (18)
C2	0.077 (3)	0.053 (2)	0.060 (3)	−0.010 (2)	0.040 (2)	−0.013 (2)
C3	0.081 (3)	0.049 (2)	0.061 (3)	0.009 (2)	0.024 (2)	0.005 (2)
C4	0.076 (3)	0.055 (3)	0.059 (3)	−0.013 (2)	0.039 (2)	−0.012 (2)
C5	0.079 (3)	0.054 (3)	0.046 (2)	0.019 (2)	0.009 (2)	0.0137 (19)
C6	0.079 (3)	0.055 (3)	0.061 (3)	−0.014 (2)	0.042 (2)	−0.014 (2)
C7	0.076 (3)	0.052 (2)	0.059 (3)	−0.010 (2)	0.039 (2)	−0.012 (2)
C8	0.075 (3)	0.053 (2)	0.062 (3)	−0.013 (2)	0.041 (2)	−0.012 (2)
C9	0.078 (3)	0.054 (3)	0.069 (3)	−0.025 (2)	0.051 (3)	−0.027 (2)
C10	0.077 (3)	0.051 (2)	0.069 (3)	−0.023 (2)	0.050 (3)	−0.025 (2)
C11	0.081 (3)	0.050 (2)	0.068 (3)	−0.026 (2)	0.051 (2)	−0.024 (2)
C12	0.073 (3)	0.053 (3)	0.061 (3)	−0.012 (2)	0.039 (2)	−0.012 (2)
C13	0.078 (3)	0.048 (2)	0.068 (3)	−0.020 (2)	0.049 (2)	−0.022 (2)
C14	0.084 (3)	0.052 (2)	0.068 (3)	−0.024 (2)	0.053 (2)	−0.025 (2)
C15	0.077 (3)	0.051 (2)	0.068 (3)	−0.021 (2)	0.050 (2)	−0.022 (2)
C16	0.080 (3)	0.051 (2)	0.069 (3)	−0.022 (2)	0.052 (2)	−0.022 (2)
C17	0.082 (3)	0.052 (2)	0.070 (3)	−0.024 (2)	0.053 (3)	−0.025 (2)
N2	0.076 (2)	0.057 (2)	0.055 (2)	0.0004 (18)	0.0261 (18)	0.0009 (17)
C18	0.076 (3)	0.057 (3)	0.055 (3)	0.000 (2)	0.026 (2)	0.001 (2)
C19	0.076 (3)	0.057 (3)	0.055 (3)	0.000 (2)	0.026 (2)	0.001 (2)
C20	0.079 (3)	0.050 (2)	0.072 (3)	−0.025 (2)	0.052 (3)	−0.026 (2)
C21	0.078 (3)	0.049 (2)	0.068 (3)	−0.023 (2)	0.048 (2)	−0.023 (2)
C22	0.077 (3)	0.049 (2)	0.066 (3)	−0.020 (2)	0.048 (2)	−0.020 (2)
C23	0.078 (3)	0.056 (3)	0.057 (3)	0.003 (2)	0.026 (2)	0.001 (2)
C24	0.077 (3)	0.052 (2)	0.068 (3)	−0.021 (2)	0.049 (2)	−0.022 (2)
C25	0.082 (3)	0.053 (2)	0.070 (3)	−0.026 (2)	0.055 (3)	−0.026 (2)
C26	0.075 (3)	0.050 (2)	0.064 (3)	−0.021 (2)	0.045 (2)	−0.021 (2)
C27	0.082 (3)	0.050 (2)	0.071 (3)	−0.024 (2)	0.054 (3)	−0.025 (2)
C28	0.077 (3)	0.054 (2)	0.062 (3)	−0.023 (2)	0.047 (2)	−0.024 (2)
C29	0.076 (3)	0.060 (3)	0.057 (3)	0.002 (2)	0.028 (2)	0.003 (2)
C30	0.076 (3)	0.062 (3)	0.057 (3)	0.005 (2)	0.026 (2)	0.001 (2)
C31	0.080 (3)	0.060 (3)	0.055 (3)	0.003 (2)	0.028 (2)	0.001 (2)
C32	0.075 (3)	0.060 (3)	0.056 (3)	0.005 (2)	0.025 (2)	0.004 (2)
C33	0.081 (3)	0.059 (3)	0.055 (3)	0.008 (2)	0.028 (2)	0.003 (2)
C34	0.076 (3)	0.061 (3)	0.056 (3)	0.004 (2)	0.026 (2)	0.002 (2)
C40	0.079 (3)	0.057 (3)	0.069 (3)	−0.024 (2)	0.050 (2)	−0.026 (2)
Cl41	0.0797 (7)	0.0522 (6)	0.0697 (7)	−0.0238 (5)	0.0513 (6)	−0.0236 (5)
Cl42	0.0796 (7)	0.0517 (6)	0.0700 (7)	−0.0237 (5)	0.0510 (6)	−0.0237 (5)
C50	0.079 (3)	0.053 (2)	0.068 (3)	−0.022 (2)	0.049 (2)	−0.022 (2)
Cl51	0.0797 (7)	0.0517 (6)	0.0697 (7)	−0.0237 (5)	0.0509 (6)	−0.0235 (5)
Cl52	0.0788 (7)	0.0522 (6)	0.0687 (7)	−0.0232 (5)	0.0501 (6)	−0.0235 (5)
C60	0.080 (3)	0.053 (2)	0.069 (3)	−0.025 (2)	0.051 (2)	−0.024 (2)
Cl61	0.0802 (7)	0.0525 (6)	0.0701 (7)	−0.0240 (5)	0.0518 (6)	−0.0238 (5)
Cl62	0.0799 (7)	0.0514 (6)	0.0700 (7)	−0.0240 (5)	0.0513 (6)	−0.0237 (5)

Geometric parameters (Å, º) top

Cu1—N1	2.051 (4)	C16—H16	0.9300
Cu1—P1	2.1699 (14)	C17—H17	0.9300
Cu1—Br1	2.4645 (8)	N2—C22	1.383 (6)
Cu1—Cu2	2.7556 (8)	N2—C18	1.394 (6)
Cu1—Br1ⁱ	2.8008 (8)	C18—C19	1.384 (7)
Cu2—N2	2.097 (4)	C19—C20	1.396 (7)
Cu2—P2	2.2140 (14)	C19—H19	0.9300
Cu2—Br2	2.4754 (8)	C20—C21	1.392 (6)
Cu2—Br1	2.5721 (8)	C20—H20	0.9300
Br1—Cu1ⁱ	2.8008 (8)	C21—C22	1.393 (6)
P1—C18	1.736 (5)	C21—H21	0.9300
P1—C29	1.810 (5)	C22—H22	0.9300
P1—C23	1.882 (5)	C23—C24	1.379 (7)
P2—C1	1.798 (5)	C23—C28	1.402 (7)
P2—C12	1.825 (4)	C24—C25	1.396 (6)
P2—C6	1.870 (5)	C24—H24	0.9300
N1—C1	1.389 (6)	C25—C26	1.392 (7)
N1—C5	1.395 (6)	C25—H25	0.9300
C1—C2	1.386 (6)	C26—C27	1.387 (7)
C2—C3	1.399 (7)	C26—H26	0.9300
C2—H2	0.9300	C27—C28	1.394 (6)
C3—C4	1.387 (6)	C27—H27	0.9300
C3—H3	0.9300	C28—H28	0.9300
C4—C5	1.382 (6)	C29—C34	1.391 (7)
C4—H4	0.9300	C29—C30	1.397 (7)
C5—H5	0.9300	C30—C31	1.385 (7)
C6—C7	1.380 (7)	C30—H30	0.9300
C6—C11	1.388 (7)	C31—C32	1.393 (7)
C7—C8	1.398 (7)	C31—H31	0.9300
C7—H7	0.9300	C32—C33	1.389 (7)
C8—C9	1.392 (7)	C32—H32	0.9300
C8—H8	0.9300	C33—C34	1.380 (7)
C9—C10	1.364 (8)	C33—H33	0.9300
C9—H9	0.9300	C34—H34	0.9300
C10—C11	1.397 (7)	C40—Cl42	1.846 (4)
C10—H10	0.9300	C40—Cl41	1.849 (5)
C11—H11	0.9300	C40—H40A	0.9700
C12—C17	1.385 (7)	C40—H40B	0.9700
C12—C13	1.400 (7)	C50—Cl51	1.845 (5)
C13—C14	1.392 (6)	C50—Cl52	1.852 (4)
C13—H13	0.9300	C50—H50A	0.9700
C14—C15	1.388 (7)	C50—H50B	0.9700
C14—H14	0.9300	C60—Cl61	1.823 (4)
C15—C16	1.387 (7)	C60—Cl62	1.860 (4)
C15—H15	0.9300	C60—H60A	0.9700
C16—C17	1.387 (6)	C60—H60B	0.9700

N1—Cu1—P1	124.21 (12)	C16—C15—H15	119.8
N1—Cu1—Br1	114.65 (12)	C14—C15—H15	119.8
P1—Cu1—Br1	114.42 (4)	C15—C16—C17	120.2 (5)
N1—Cu1—Cu2	98.04 (10)	C15—C16—H16	119.9
P1—Cu1—Cu2	85.78 (4)	C17—C16—H16	119.9
Br1—Cu1—Cu2	58.72 (2)	C12—C17—C16	119.8 (5)
N1—Cu1—Br1ⁱ	98.00 (10)	C12—C17—H17	120.1
P1—Cu1—Br1ⁱ	101.33 (4)	C16—C17—H17	120.1
Br1—Cu1—Br1ⁱ	96.40 (2)	C22—N2—C18	119.8 (4)
Cu2—Cu1—Br1ⁱ	154.45 (3)	C22—N2—Cu2	115.4 (3)
N2—Cu2—P2	117.70 (12)	C18—N2—Cu2	124.7 (3)
N2—Cu2—Br2	103.49 (11)	C19—C18—N2	120.1 (4)
P2—Cu2—Br2	105.64 (4)	C19—C18—P1	123.0 (4)
N2—Cu2—Br1	109.64 (11)	N2—C18—P1	116.8 (4)
P2—Cu2—Br1	113.87 (4)	C18—C19—C20	120.2 (5)
Br2—Cu2—Br1	105.08 (3)	C18—C19—H19	119.9
N2—Cu2—Cu1	91.48 (11)	C20—C19—H19	119.9
P2—Cu2—Cu1	79.73 (4)	C21—C20—C19	119.7 (4)
Br2—Cu2—Cu1	158.76 (3)	C21—C20—H20	120.2
Br1—Cu2—Cu1	54.98 (2)	C19—C20—H20	120.2
Cu1—Br1—Cu2	66.30 (2)	C20—C21—C22	119.8 (4)
Cu1—Br1—Cu1ⁱ	83.60 (2)	C20—C21—H21	120.1
Cu2—Br1—Cu1ⁱ	149.30 (3)	C22—C21—H21	120.1
C18—P1—C29	104.8 (2)	N2—C22—C21	120.5 (4)
C18—P1—C23	101.6 (2)	N2—C22—H22	119.8
C29—P1—C23	104.6 (2)	C21—C22—H22	119.8
C18—P1—Cu1	119.03 (19)	C24—C23—C28	120.1 (4)
C29—P1—Cu1	112.46 (17)	C24—C23—P1	122.4 (4)
C23—P1—Cu1	112.84 (17)	C28—C23—P1	117.5 (4)
C1—P2—C12	101.0 (2)	C23—C24—C25	120.2 (5)
C1—P2—C6	102.6 (2)	C23—C24—H24	119.9
C12—P2—C6	101.7 (2)	C25—C24—H24	119.9
C1—P2—Cu2	122.20 (15)	C26—C25—C24	119.8 (5)
C12—P2—Cu2	116.57 (18)	C26—C25—H25	120.1
C6—P2—Cu2	110.10 (16)	C24—C25—H25	120.1
C1—N1—C5	119.5 (4)	C27—C26—C25	120.1 (4)
C1—N1—Cu1	120.4 (3)	C27—C26—H26	119.9
C5—N1—Cu1	120.1 (3)	C25—C26—H26	119.9
C2—C1—N1	120.3 (4)	C26—C27—C28	120.1 (5)
C2—C1—P2	123.9 (3)	C26—C27—H27	120.0
N1—C1—P2	115.8 (3)	C28—C27—H27	120.0
C1—C2—C3	119.8 (4)	C27—C28—C23	119.6 (5)
C1—C2—H2	120.1	C27—C28—H28	120.2
C3—C2—H2	120.1	C23—C28—H28	120.2
C4—C3—C2	119.8 (4)	C34—C29—C30	119.0 (5)
C4—C3—H3	120.1	C34—C29—P1	118.3 (4)
C2—C3—H3	120.1	C30—C29—P1	122.7 (4)
C5—C4—C3	120.1 (4)	C31—C30—C29	120.5 (5)
C5—C4—H4	119.9	C31—C30—H30	119.7
C3—C4—H4	119.9	C29—C30—H30	119.7
C4—C5—N1	120.4 (4)	C30—C31—C32	119.6 (5)
C4—C5—H5	119.8	C30—C31—H31	120.2
N1—C5—H5	119.8	C32—C31—H31	120.2
C7—C6—C11	120.9 (5)	C33—C32—C31	120.3 (5)
C7—C6—P2	123.6 (4)	C33—C32—H32	119.8
C11—C6—P2	115.6 (4)	C31—C32—H32	119.8
C6—C7—C8	119.6 (4)	C34—C33—C32	119.6 (5)
C6—C7—H7	120.2	C34—C33—H33	120.2
C8—C7—H7	120.2	C32—C33—H33	120.2
C9—C8—C7	119.3 (5)	C33—C34—C29	121.0 (5)
C9—C8—H8	120.3	C33—C34—H34	119.5
C7—C8—H8	120.3	C29—C34—H34	119.5
C10—C9—C8	120.7 (4)	Cl42—C40—Cl41	93.4 (2)
C10—C9—H9	119.6	Cl42—C40—H40A	113.0
C8—C9—H9	119.6	Cl41—C40—H40A	113.0
C9—C10—C11	120.4 (5)	Cl42—C40—H40B	113.0
C9—C10—H10	119.8	Cl41—C40—H40B	113.0
C11—C10—H10	119.8	H40A—C40—H40B	110.4
C6—C11—C10	119.1 (5)	Cl51—C50—Cl52	93.0 (2)
C6—C11—H11	120.5	Cl51—C50—H50A	113.1
C10—C11—H11	120.5	Cl52—C50—H50A	113.1
C17—C12—C13	120.3 (4)	Cl51—C50—H50B	113.1
C17—C12—P2	115.7 (3)	Cl52—C50—H50B	113.1
C13—C12—P2	123.9 (4)	H50A—C50—H50B	110.5
C14—C13—C12	119.6 (5)	Cl61—C60—Cl62	93.2 (2)
C14—C13—H13	120.2	Cl61—C60—H60A	113.1
C12—C13—H13	120.2	Cl62—C60—H60A	113.1
C15—C14—C13	119.8 (4)	Cl61—C60—H60B	113.1
C15—C14—H14	120.1	Cl62—C60—H60B	113.1
C13—C14—H14	120.1	H60A—C60—H60B	110.5
C16—C15—C14	120.3 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₄Br₄(C₁₇H₁₄NP)₄]·6CH₂Cl₂
M_r	2136.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.818 (1), 17.793 (2), 19.292 (2)
β (°)	104.85 (1)
V (Å³)	4584.8 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.476, 0.534
No. of measured, independent and observed [I > 2σ(I)] reflections	23308, 8072, 6838
R_int	0.007
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.157, 1.02
No. of reflections	8072
No. of parameters	460
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.74

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.

Selected geometric parameters (Å, º) top

Cu1—N1	2.051 (4)	Cu2—N2	2.097 (4)
Cu1—P1	2.1699 (14)	Cu2—P2	2.2140 (14)
Cu1—Br1	2.4645 (8)	Cu2—Br2	2.4754 (8)
Cu1—Cu2	2.7556 (8)	Cu2—Br1	2.5721 (8)
Cu1—Br1ⁱ	2.8008 (8)

N1—Cu1—P1	124.21 (12)	P2—Cu2—Br2	105.64 (4)
N1—Cu1—Br1	114.65 (12)	N2—Cu2—Br1	109.64 (11)
P1—Cu1—Br1	114.42 (4)	P2—Cu2—Br1	113.87 (4)
N1—Cu1—Cu2	98.04 (10)	Br2—Cu2—Br1	105.08 (3)
P1—Cu1—Cu2	85.78 (4)	N2—Cu2—Cu1	91.48 (11)
Br1—Cu1—Cu2	58.72 (2)	P2—Cu2—Cu1	79.73 (4)
N1—Cu1—Br1ⁱ	98.00 (10)	Br2—Cu2—Cu1	158.76 (3)
P1—Cu1—Br1ⁱ	101.33 (4)	Br1—Cu2—Cu1	54.98 (2)
Br1—Cu1—Br1ⁱ	96.40 (2)	Cu1—Br1—Cu2	66.30 (2)
Cu2—Cu1—Br1ⁱ	154.45 (3)	Cu1—Br1—Cu1ⁱ	83.60 (2)
N2—Cu2—P2	117.70 (12)	Cu2—Br1—Cu1ⁱ	149.30 (3)
N2—Cu2—Br2	103.49 (11)

Symmetry code: (i) −x+2, −y+1, −z+1.

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