Bis(μ-4,4;6,6-bis­(biphenyl-2,2′-diyldi­oxy)-2,2-bis­{2-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]phen­oxy}cyclo­triphosphazene)di-μ-chlorido-bis­[chlorido­copper(II)]

Wu, X.-W.; Wang, X.-Y.; Ma, J.-P.; Dong, Y.-B.

doi:10.1107/S1600536812016285

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m648-m649

doi:10.1107/S1600536812016285

Open

access

Bis(μ-4,4;6,6-bis(biphenyl-2,2′-diyldioxy)-2,2-bis{2-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]phenoxy}cyclotriphosphazene)di-μ-chlorido-bis[chloridocopper(II)]

Xiang-Wen Wu,^a Xiao-Yan Wang,^a Jian-Ping Ma ^a and Yu-Bin Dong ^a ^*

^aCollege of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Engineering Research Center of Pesticide and Medicine Intermediate Clean Production, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: yubindong@sdnu.edu.cn

(Received 28 March 2012; accepted 14 April 2012; online 21 April 2012)

In the crystal of the title compound, [Cu₂Cl₄(C₅₀H₃₂N₉O₈P₃)₂], the binuclear molecule is located across an inversion center. Each Cu²⁺ cation is coordinated by two pyridine N atoms from symmetry-related 4,4;6,6-bis(biphenyl-2,2′-diyldioxy)-2,2-bis{2-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]phenoxy}cyclotriphosphazene (L) ligands, a pair of bridging Cl⁻ anions and a terminal Cl⁻ anion, forming a distorted CuCl₃N₂ square-pyramidal geometry. Weak intramolecular C—H⋯O and intermolecular C—H⋯N interactions occur in the crystal.

Related literature

For our interest in the coordination chemistry of bent organic ligands bridged by five-membered heterocycles such as oxadiazole and triazole, see: Dong et al. (2005 , 2007 ). For the impact of different types of linkages as well as distinct coordinating orientations on the structures of various coordination-driven supramolecular compounds, see: Zhao et al. (2007 ). For bond lengths and angles in related structures, see: Ainscough et al. (2008 ); Du et al. (2010 ). Zhao et al. (2009 ).

Experimental

Crystal data

[Cu₂Cl₄(C₅₀H₃₂N₉O₈P₃)₂]
M_r = 2228.39
Triclinic, $[P \overline 1]$
a = 10.554 (5) Å
b = 14.486 (7) Å
c = 15.551 (8) Å
α = 85.401 (7)°
β = 81.984 (7)°
γ = 89.844 (7)°
V = 2347 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 298 K
0.35 × 0.30 × 0.08 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.779, T_max = 0.942
12440 measured reflections
8593 independent reflections
6217 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.139
S = 1.02
8593 reflections
658 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C26—H26⋯O3	0.93	2.38	3.271 (5)	160
C36—H36⋯N5ⁱ	0.93	2.51	3.396 (6)	159
Symmetry code: (i) x, y+1, z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016285/xu5503sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016285/xu5503Isup2.hkl

checkCIF report

Comment top

In our research, we have a longstanding interest in the coordination chemistry of bent organic ligands bridged by the five-membered heterocycles such as oxadiazole (Dong et al., 2005) and triazole (Dong et al., 2007), especially in how different types of linkages as well as distinct coordinating orientations impact the structures of various coordination-driven supramolecular compounds (Zhao et al., 2007). In this contribution, we present a new ligand containing 1,3,4-oxadiazole and cyclotriphosphazene units, namely, bis(2,2'-dioxybiphenyl)bis(2-phenoxy-5-(4-pyridyl)-1,3,4-oxadiazole) cyclotriphosphazene (L) and the title compound, [CuCl₂(C₅₀H₃₂O₈N₉P₃)]₂ based on it (Scheme 1).

In the crystal of the title compound, [CuCl₂(C₅₀H₃₂O₈N₉P₃)]₂, the binuclear molecule is located across an inversion center (Figure 1). The Cu^II cation is N,N'-chelated by a bis(2,2'-dioxybiphenyl)bis(2-phenoxy-5-(4-pyridyl)-1,3,4-oxadiazole) cyclotriphosphazene (L) ligand, and a pair of bridging Cl^- anions and a terminal Cl^- anion further coordinate to the Cu^II cation to complete the distorted CuCl₃N₂ square-pyramidal geometry (Ainscough et al., 2008). The N8ⁱ-Cu1-N9 angle is 174.68 (1)° and the dihedral angle between C1-C5/N9 and C21ⁱ-C25ⁱ/N8ⁱis 21.272° (Zhao et al., 2009) [symmetry code: i = -x, -y, 1-z]. The corresponding dihedral angles between the planes of the three rings in one 1,3,4-oxadiazole arm are 9.565° (between C1-C5/N9 and C6-C7-O8/N6-N7) and 5.322° (between C6-C7-O8/N6-N7 and C8-C13), and the corresponding dihedral angles of three rings in the other 1,3,4-oxadiazole arm are 30.941° (between C22-C26/N8 and C20-C21-O8/N4-N5) and 12.694° (between C20-C21-O8/N4-N5 and C14-C19). The Cu-N distances range from 2.021 (3) Å to 2.045 Å which are close to those found in {[Cu(4-bpo)(dca)(H₂O)₂](NO₃)(H₂O)}_n (4-bp = 2,5-bis(4-pyridyl)-1,3,4-oxadiazole, dca = N(CN)₂^-) (Du et al., 2010). Moreover, the angles of Cl1-Cu1-Cl2 and Cl1-Cu1-Cl2ⁱ are 167.54 (5)^° and 101.39 (5)°, respectively [symmetry code: i = -x, -y, 1-z]. The bridged Cu-Cl bond length (2.700 (6) Å) is longer than other Cu-Cl bonds (2.261 (9) Å and 2.300 (8) Å) (Ainscough et al., 2008). Additionally, neighbouring Cu^II cations are connected by two bridged chlorine ions into Cu₂Cl₂ loops with a Cu···Cu separation 3.522 (1) Å.

In the solid state, binuclear molecules are linked together by weak intramolecular C—H···O and intermolecular C—H···N interactions into one-dimensional double-chains (Figure 2, Table 1).

Related literature top

For our interest in the coordination chemistry of bent organic ligands bridged by five-membered heterocycles such as oxadiazole and triazole, see: Dong et al. (2005, 2007). For the impact of different types of linkages as well as distinct coordinating orientations on the structures of various coordination-driven supramolecular compounds, see: Zhao et al. (2007). For bond lengths and angles in related structures, see see: Ainscough et al. (2008); Du et al. (2010). Zhao et al. (2009).

Experimental top

Preparation of L:

The solution of 2-phenoxy-5-(4-pyridyl)-1,3,4-oxadiazole (0.50 g, 2.1 mmol) in 30 ml THF was added NaH(50.4 mg, 2.1 mmol), the mixture was stirred for 1 h at room temperature, then [N₃P₃(2,2'-dioxybiphenyl)₂Cl₂](0.574 g, 1 mmol) in 20 ml THF was added. The mixture was heated at reflux over 3 h, allowed to cool, the precipitation was separated by filtration and washed several times with water, then the residue was purified on a silica gel column using CH₂Cl₂:MeOH = 20:1 as the eluent to afford L as a white crystalline solid. IR(KBr pellet, cm^-1): 1608(m), 1540(w), 1477(m), 1435(m), 1410(w),1276(m), 1233(m), 1175(s), 1090(m), 1033(m), 932(w), 890(s), 818(w), 785(m),750(m), 716(m), 701(m), 630(w), 608(m), 532(m), 409(w). ¹H-NMR (300 MHz, 25°C, DMSO-d₆,TMS, p.p.m.): 8.41–8.40(d, 2H, –C₅H₄N), 8.26–8.24(d, 1H, –C₆H₄O),8.02–7.84(d, 2H, –C₅H₄N), 7.76(d, 1H, –C₆H₄O),7.54(t, 1H, p-C₆H₄O), 7. 51–7.39(m, 3H, –C₆H₄O,-C₁₂H₈O₂), 7.28–7.26(m, 4H, –C₁₂H₈O₂),6.98–6.26(d, 3H, –C₆H₄O, –C₁₂H₈O₂).Anal. Calcd. forC₅₀H₃₂N₉O₈P₃: C, 61.29;H, 3.30; N, 12.86. Found: C, 61.33; H, 3.24; N, 12.89.

Preparation of Cu^II compound:

L (49 mg, 0.05 mmol) in CH₂Cl₂ (7 ml) and CuCl₂.2H₂O (9 mg, 0.05 mmol) in CH₃OH (7 ml) were mixed. After about one week, green block-shaped crystals were obtained in 75% yield based on L.

Computing details top

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

Figures top

	Fig. 1. A view of Cu^II compound,showing the coordination around Cu^II. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [symmetry code: (i) -x, -y, -z + 1].
	Fig. 2. A diagram showing weak intermolecular C–H..N interaction.

Bis(µ-4,4;6,6-bis(biphenyl-2,2'-diyldioxy)-2,2-bis{2-[5-(pyridin-4-yl)-1,3,4- oxadiazol-2-yl]phenoxy}cyclotriphosphazene)di-µ-chlorido- bis[chloridocopper(II)] top

Crystal data top

[Cu₂Cl₄(C₅₀H₃₂N₉O₈P₃)₂]	Z = 1
M_r = 2228.39	F(000) = 1134
Triclinic, P1	D_x = 1.577 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.554 (5) Å	Cell parameters from 2838 reflections
b = 14.486 (7) Å	θ = 2.2–24.7°
c = 15.551 (8) Å	µ = 0.75 mm⁻¹
α = 85.401 (7)°	T = 298 K
β = 81.984 (7)°	Block, green
γ = 89.844 (7)°	0.35 × 0.30 × 0.08 mm
V = 2347 (2) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	8593 independent reflections
Radiation source: fine-focus sealed tube	6217 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.779, T_max = 0.942	k = −17→13
12440 measured reflections	l = −18→18

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0629P)² + 0.7991P] where P = (F_o² + 2F_c²)/3
8593 reflections	(Δ/σ)_max = 0.001
658 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cu₂Cl₄(C₅₀H₃₂N₉O₈P₃)₂]	γ = 89.844 (7)°
M_r = 2228.39	V = 2347 (2) Å³
Triclinic, P1	Z = 1
a = 10.554 (5) Å	Mo Kα radiation
b = 14.486 (7) Å	µ = 0.75 mm⁻¹
c = 15.551 (8) Å	T = 298 K
α = 85.401 (7)°	0.35 × 0.30 × 0.08 mm
β = 81.984 (7)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	8593 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	6217 reflections with I > 2σ(I)
T_min = 0.779, T_max = 0.942	R_int = 0.027
12440 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	Δρ_max = 0.51 e Å⁻³
8593 reflections	Δρ_min = −0.48 e Å⁻³
658 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
C1	0.0712 (4)	−0.0313 (3)	0.2710 (3)	0.0457 (11)
H1	0.0268	−0.0868	0.2868	0.055*
C2	0.1569 (4)	−0.0249 (3)	0.1965 (3)	0.0453 (10)
H2	0.1706	−0.0753	0.1629	0.054*
C3	0.2228 (4)	0.0568 (3)	0.1715 (3)	0.0374 (9)
C4	0.2035 (4)	0.1283 (3)	0.2261 (3)	0.0465 (11)
H4	0.2500	0.1833	0.2130	0.056*
C5	0.1149 (4)	0.1168 (3)	0.2994 (3)	0.0478 (11)
H5	0.1009	0.1658	0.3347	0.057*
C6	0.3034 (4)	0.0679 (3)	0.0879 (3)	0.0374 (9)
C7	0.4205 (4)	0.1374 (3)	−0.0201 (2)	0.0362 (9)
C8	0.4932 (4)	0.2111 (3)	−0.0736 (2)	0.0341 (9)
C9	0.5458 (4)	0.1951 (3)	−0.1588 (3)	0.0462 (11)
H9	0.5371	0.1369	−0.1787	0.055*
C10	0.6096 (4)	0.2634 (3)	−0.2131 (3)	0.0518 (12)
H10	0.6462	0.2505	−0.2687	0.062*
C11	0.6206 (4)	0.3511 (3)	−0.1870 (3)	0.0467 (11)
H11	0.6610	0.3979	−0.2254	0.056*
C12	0.5710 (4)	0.3691 (3)	−0.1029 (3)	0.0379 (9)
H12	0.5781	0.4281	−0.0845	0.045*
C13	0.5108 (3)	0.2990 (3)	−0.0465 (2)	0.0317 (9)
C14	0.7375 (3)	0.1807 (2)	0.0721 (2)	0.0295 (8)
C15	0.8049 (4)	0.2253 (3)	−0.0015 (3)	0.0372 (9)
H15	0.7672	0.2738	−0.0314	0.045*
C16	0.9278 (4)	0.1988 (3)	−0.0314 (3)	0.0448 (10)
H16	0.9738	0.2301	−0.0804	0.054*
C17	0.9821 (4)	0.1253 (3)	0.0120 (3)	0.0453 (11)
H17	1.0648	0.1068	−0.0077	0.054*
C18	0.9139 (4)	0.0801 (3)	0.0839 (3)	0.0421 (10)
H18	0.9515	0.0308	0.1128	0.051*
C19	0.7891 (4)	0.1055 (3)	0.1157 (2)	0.0340 (9)
C20	0.7238 (4)	0.0482 (3)	0.1890 (3)	0.0357 (9)
C21	0.5882 (4)	−0.0021 (3)	0.2956 (3)	0.0413 (10)
C22	0.4747 (4)	−0.0044 (3)	0.3607 (3)	0.0408 (10)
C23	0.4200 (5)	−0.0890 (3)	0.3937 (3)	0.0535 (12)
H23	0.4551	−0.1438	0.3742	0.064*
C24	0.3138 (4)	−0.0910 (3)	0.4553 (3)	0.0530 (12)
H24	0.2772	−0.1483	0.4759	0.064*
C25	0.3143 (4)	0.0655 (3)	0.4566 (3)	0.0544 (12)
H25	0.2792	0.1191	0.4788	0.065*
C26	0.4198 (4)	0.0741 (3)	0.3937 (3)	0.0536 (12)
H26	0.4539	0.1323	0.3737	0.064*
C27	0.9432 (3)	0.4069 (2)	0.1586 (2)	0.0302 (8)
C28	1.0052 (4)	0.3287 (3)	0.1306 (3)	0.0423 (10)
H28	0.9665	0.2707	0.1433	0.051*
C29	1.1253 (4)	0.3382 (3)	0.0836 (3)	0.0521 (12)
H29	1.1684	0.2860	0.0641	0.062*
C30	1.1819 (4)	0.4234 (3)	0.0652 (3)	0.0525 (12)
H30	1.2630	0.4289	0.0329	0.063*
C31	1.1200 (4)	0.5013 (3)	0.0940 (3)	0.0440 (10)
H31	1.1596	0.5590	0.0809	0.053*
C32	0.9980 (3)	0.4944 (3)	0.1429 (2)	0.0330 (9)
C33	0.9357 (3)	0.5754 (2)	0.1815 (2)	0.0317 (8)
C34	1.0032 (4)	0.6362 (3)	0.2232 (3)	0.0449 (10)
H34	1.0895	0.6258	0.2264	0.054*
C35	0.9449 (5)	0.7115 (3)	0.2601 (3)	0.0538 (12)
H35	0.9917	0.7507	0.2886	0.065*
C36	0.8176 (5)	0.7291 (3)	0.2551 (3)	0.0557 (13)
H36	0.7788	0.7804	0.2796	0.067*
C37	0.7478 (4)	0.6702 (3)	0.2135 (3)	0.0436 (10)
H37	0.6624	0.6821	0.2086	0.052*
C38	0.8072 (3)	0.5931 (2)	0.1793 (2)	0.0314 (8)
C39	0.4887 (4)	0.3345 (2)	0.4399 (2)	0.0332 (9)
C40	0.6046 (4)	0.3320 (3)	0.4705 (3)	0.0419 (10)
H40	0.6766	0.3081	0.4386	0.050*
C41	0.6109 (4)	0.3662 (3)	0.5505 (3)	0.0494 (11)
H41	0.6879	0.3650	0.5732	0.059*
C42	0.5037 (4)	0.4021 (3)	0.5964 (3)	0.0478 (11)
H42	0.5083	0.4244	0.6504	0.057*
C43	0.3902 (4)	0.4050 (3)	0.5632 (3)	0.0440 (10)
H43	0.3188	0.4302	0.5948	0.053*
C44	0.3791 (4)	0.3712 (3)	0.4831 (2)	0.0356 (9)
C45	0.2570 (4)	0.3736 (3)	0.4468 (3)	0.0378 (9)
C46	0.1428 (4)	0.3526 (4)	0.4998 (3)	0.0613 (13)
H46	0.1432	0.3374	0.5590	0.074*
C47	0.0272 (5)	0.3538 (4)	0.4663 (4)	0.0782 (17)
H47	−0.0488	0.3409	0.5033	0.094*
C48	0.0249 (4)	0.3740 (4)	0.3794 (4)	0.0704 (15)
H48	−0.0522	0.3729	0.3570	0.084*
C49	0.1367 (4)	0.3958 (3)	0.3248 (3)	0.0502 (11)
H49	0.1359	0.4100	0.2655	0.060*
C50	0.2493 (3)	0.3961 (3)	0.3593 (3)	0.0341 (9)
Cl1	−0.18724 (11)	0.15324 (8)	0.35268 (7)	0.0535 (3)
Cl2	−0.02705 (10)	−0.11280 (7)	0.46697 (7)	0.0485 (3)
Cu1	−0.10057 (5)	0.02987 (3)	0.42097 (3)	0.04299 (16)
N1	0.4580 (3)	0.3014 (2)	0.2006 (2)	0.0334 (7)
N2	0.6647 (3)	0.3800 (2)	0.09859 (19)	0.0323 (7)
N3	0.5960 (3)	0.4339 (2)	0.2594 (2)	0.0349 (8)
N4	0.7652 (3)	−0.0316 (2)	0.2173 (3)	0.0536 (10)
N5	0.6752 (4)	−0.0637 (2)	0.2876 (3)	0.0573 (10)
N6	0.3977 (4)	0.0552 (3)	−0.0424 (3)	0.0599 (11)
N7	0.3211 (4)	0.0102 (3)	0.0285 (3)	0.0599 (11)
N8	0.2597 (3)	−0.0152 (2)	0.4874 (2)	0.0429 (8)
N9	0.0475 (3)	0.0384 (2)	0.3230 (2)	0.0422 (8)
O1	0.8252 (2)	0.39650 (16)	0.21153 (16)	0.0315 (6)
O2	0.7351 (2)	0.53487 (16)	0.13627 (16)	0.0332 (6)
O3	0.4819 (2)	0.29617 (16)	0.35980 (16)	0.0348 (6)
O4	0.3585 (2)	0.42701 (16)	0.30209 (16)	0.0328 (6)
O5	0.6110 (2)	0.20458 (16)	0.10054 (16)	0.0322 (6)
O6	0.4665 (2)	0.31792 (16)	0.03865 (16)	0.0306 (6)
O7	0.6120 (2)	0.07148 (17)	0.23493 (17)	0.0354 (6)
O8	0.3621 (2)	0.15034 (17)	0.06086 (16)	0.0357 (6)
P1	0.55400 (9)	0.30498 (6)	0.11381 (6)	0.0272 (2)
P2	0.69841 (9)	0.43337 (6)	0.17686 (6)	0.0290 (2)
P3	0.47897 (9)	0.36458 (6)	0.27569 (6)	0.0295 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (3)	0.031 (2)	0.052 (3)	−0.0080 (19)	0.000 (2)	0.0047 (19)
C2	0.051 (3)	0.037 (2)	0.047 (3)	−0.005 (2)	0.001 (2)	−0.0062 (19)
C3	0.032 (2)	0.039 (2)	0.040 (2)	−0.0045 (17)	−0.0041 (19)	0.0002 (18)
C4	0.051 (3)	0.041 (2)	0.045 (3)	−0.018 (2)	0.001 (2)	−0.002 (2)
C5	0.052 (3)	0.038 (2)	0.051 (3)	−0.008 (2)	0.002 (2)	−0.009 (2)
C6	0.036 (2)	0.036 (2)	0.041 (2)	−0.0054 (18)	−0.0062 (19)	−0.0015 (18)
C7	0.035 (2)	0.043 (2)	0.031 (2)	−0.0004 (18)	−0.0019 (18)	−0.0093 (18)
C8	0.034 (2)	0.039 (2)	0.031 (2)	0.0005 (17)	−0.0085 (18)	−0.0037 (17)
C9	0.051 (3)	0.054 (3)	0.036 (3)	0.000 (2)	−0.007 (2)	−0.012 (2)
C10	0.049 (3)	0.072 (3)	0.031 (3)	−0.003 (2)	0.002 (2)	−0.003 (2)
C11	0.039 (2)	0.059 (3)	0.039 (3)	−0.009 (2)	−0.008 (2)	0.013 (2)
C12	0.037 (2)	0.041 (2)	0.037 (2)	−0.0014 (18)	−0.0115 (19)	0.0049 (18)
C13	0.0245 (19)	0.044 (2)	0.027 (2)	0.0016 (17)	−0.0081 (16)	0.0002 (17)
C14	0.029 (2)	0.030 (2)	0.031 (2)	0.0004 (16)	−0.0055 (17)	−0.0085 (16)
C15	0.039 (2)	0.038 (2)	0.035 (2)	0.0017 (18)	−0.0056 (19)	−0.0047 (18)
C16	0.047 (3)	0.046 (3)	0.039 (2)	−0.002 (2)	0.009 (2)	−0.010 (2)
C17	0.035 (2)	0.048 (3)	0.050 (3)	0.007 (2)	0.006 (2)	−0.009 (2)
C18	0.040 (2)	0.035 (2)	0.050 (3)	0.0127 (19)	−0.004 (2)	−0.0047 (19)
C19	0.035 (2)	0.033 (2)	0.034 (2)	0.0050 (17)	−0.0053 (18)	−0.0079 (17)
C20	0.031 (2)	0.034 (2)	0.043 (2)	0.0031 (17)	−0.0073 (19)	−0.0045 (18)
C21	0.043 (2)	0.035 (2)	0.045 (3)	−0.0003 (19)	−0.003 (2)	0.0003 (19)
C22	0.043 (2)	0.036 (2)	0.042 (3)	−0.0013 (19)	−0.004 (2)	0.0021 (18)
C23	0.065 (3)	0.034 (2)	0.057 (3)	0.001 (2)	0.005 (3)	0.000 (2)
C24	0.062 (3)	0.035 (2)	0.057 (3)	−0.005 (2)	0.009 (2)	0.002 (2)
C25	0.053 (3)	0.030 (2)	0.075 (4)	0.000 (2)	0.010 (3)	−0.004 (2)
C26	0.050 (3)	0.029 (2)	0.075 (3)	−0.006 (2)	0.011 (2)	0.005 (2)
C27	0.028 (2)	0.033 (2)	0.032 (2)	0.0014 (16)	−0.0115 (17)	−0.0037 (16)
C28	0.042 (2)	0.035 (2)	0.053 (3)	0.0091 (19)	−0.015 (2)	−0.013 (2)
C29	0.048 (3)	0.057 (3)	0.055 (3)	0.022 (2)	−0.011 (2)	−0.020 (2)
C30	0.032 (2)	0.075 (3)	0.048 (3)	0.015 (2)	0.005 (2)	−0.002 (2)
C31	0.033 (2)	0.050 (3)	0.047 (3)	0.0009 (19)	−0.004 (2)	0.004 (2)
C32	0.027 (2)	0.035 (2)	0.038 (2)	0.0000 (16)	−0.0070 (17)	−0.0032 (17)
C33	0.030 (2)	0.029 (2)	0.035 (2)	−0.0053 (16)	−0.0026 (17)	0.0024 (16)
C34	0.041 (2)	0.044 (3)	0.050 (3)	−0.013 (2)	−0.010 (2)	0.001 (2)
C35	0.073 (3)	0.035 (2)	0.055 (3)	−0.014 (2)	−0.011 (3)	−0.010 (2)
C36	0.083 (4)	0.029 (2)	0.052 (3)	0.006 (2)	0.002 (3)	−0.007 (2)
C37	0.047 (3)	0.032 (2)	0.050 (3)	0.0112 (19)	−0.004 (2)	−0.0016 (19)
C38	0.037 (2)	0.0268 (19)	0.030 (2)	−0.0067 (16)	−0.0049 (17)	0.0031 (16)
C39	0.042 (2)	0.026 (2)	0.032 (2)	0.0009 (17)	−0.0075 (18)	−0.0056 (16)
C40	0.043 (2)	0.041 (2)	0.042 (3)	0.0095 (19)	−0.010 (2)	−0.0032 (19)
C41	0.055 (3)	0.050 (3)	0.048 (3)	−0.003 (2)	−0.025 (2)	−0.001 (2)
C42	0.069 (3)	0.047 (3)	0.032 (2)	0.000 (2)	−0.019 (2)	−0.0078 (19)
C43	0.056 (3)	0.044 (2)	0.032 (2)	0.005 (2)	−0.003 (2)	−0.0062 (18)
C44	0.043 (2)	0.033 (2)	0.029 (2)	0.0008 (18)	−0.0039 (18)	−0.0014 (16)
C45	0.034 (2)	0.045 (2)	0.033 (2)	−0.0004 (18)	0.0013 (18)	−0.0040 (18)
C46	0.048 (3)	0.090 (4)	0.039 (3)	−0.002 (3)	0.010 (2)	0.010 (2)
C47	0.032 (3)	0.120 (5)	0.074 (4)	−0.003 (3)	0.008 (3)	0.020 (3)
C48	0.033 (3)	0.105 (4)	0.071 (4)	−0.008 (3)	−0.011 (3)	0.009 (3)
C49	0.039 (3)	0.067 (3)	0.045 (3)	−0.002 (2)	−0.010 (2)	0.001 (2)
C50	0.030 (2)	0.035 (2)	0.036 (2)	−0.0014 (17)	−0.0028 (18)	−0.0008 (17)
Cl1	0.0586 (7)	0.0497 (7)	0.0504 (7)	0.0054 (5)	−0.0059 (6)	0.0038 (5)
Cl2	0.0525 (6)	0.0362 (6)	0.0536 (7)	−0.0018 (5)	−0.0003 (5)	0.0037 (5)
Cu1	0.0438 (3)	0.0355 (3)	0.0460 (3)	−0.0034 (2)	0.0028 (2)	0.0034 (2)
N1	0.0297 (17)	0.0375 (18)	0.0327 (18)	−0.0091 (14)	0.0003 (14)	−0.0093 (14)
N2	0.0288 (17)	0.0365 (18)	0.0306 (18)	−0.0071 (14)	0.0017 (14)	−0.0060 (14)
N3	0.0347 (18)	0.0342 (18)	0.0373 (19)	−0.0070 (14)	−0.0036 (15)	−0.0132 (14)
N4	0.051 (2)	0.038 (2)	0.065 (3)	0.0100 (18)	0.008 (2)	0.0075 (18)
N5	0.059 (2)	0.040 (2)	0.064 (3)	0.0108 (19)	0.013 (2)	0.0109 (18)
N6	0.078 (3)	0.049 (2)	0.050 (2)	−0.018 (2)	0.012 (2)	−0.0161 (19)
N7	0.077 (3)	0.048 (2)	0.051 (3)	−0.020 (2)	0.011 (2)	−0.0135 (19)
N8	0.044 (2)	0.0320 (19)	0.049 (2)	−0.0043 (16)	0.0027 (17)	0.0017 (16)
N9	0.043 (2)	0.0317 (19)	0.049 (2)	−0.0015 (15)	0.0023 (17)	−0.0002 (16)
O1	0.0271 (13)	0.0271 (13)	0.0404 (16)	−0.0027 (10)	−0.0078 (12)	0.0023 (11)
O2	0.0288 (14)	0.0320 (14)	0.0402 (16)	−0.0006 (11)	−0.0099 (12)	−0.0021 (11)
O3	0.0455 (16)	0.0297 (14)	0.0301 (15)	0.0030 (12)	−0.0061 (12)	−0.0068 (11)
O4	0.0320 (14)	0.0348 (14)	0.0299 (15)	0.0003 (11)	0.0006 (12)	−0.0006 (11)
O5	0.0244 (13)	0.0305 (14)	0.0415 (16)	0.0024 (11)	−0.0046 (12)	−0.0022 (11)
O6	0.0260 (13)	0.0369 (14)	0.0301 (15)	0.0021 (11)	−0.0057 (11)	−0.0066 (11)
O7	0.0359 (15)	0.0322 (14)	0.0367 (16)	0.0044 (12)	−0.0026 (12)	0.0021 (12)
O8	0.0388 (15)	0.0338 (15)	0.0336 (16)	−0.0073 (12)	−0.0004 (12)	−0.0051 (12)
P1	0.0260 (5)	0.0304 (5)	0.0260 (5)	−0.0018 (4)	−0.0041 (4)	−0.0056 (4)
P2	0.0260 (5)	0.0290 (5)	0.0322 (6)	−0.0027 (4)	−0.0044 (4)	−0.0039 (4)
P3	0.0298 (5)	0.0305 (5)	0.0278 (5)	−0.0019 (4)	−0.0002 (4)	−0.0062 (4)

Geometric parameters (Å, º) top

C1—N9	1.344 (5)	C30—C31	1.377 (6)
C1—C2	1.364 (6)	C30—H30	0.9300
C1—H1	0.9300	C31—C32	1.400 (5)
C2—C3	1.376 (5)	C31—H31	0.9300
C2—H2	0.9300	C32—C33	1.472 (5)
C3—C4	1.387 (5)	C33—C38	1.384 (5)
C3—C6	1.449 (5)	C33—C34	1.389 (5)
C4—C5	1.370 (6)	C34—C35	1.377 (6)
C4—H4	0.9300	C34—H34	0.9300
C5—N9	1.339 (5)	C35—C36	1.378 (6)
C5—H5	0.9300	C35—H35	0.9300
C6—N7	1.289 (5)	C36—C37	1.384 (6)
C6—O8	1.356 (4)	C36—H36	0.9300
C7—N6	1.299 (5)	C37—C38	1.387 (5)
C7—O8	1.349 (4)	C37—H37	0.9300
C7—C8	1.450 (5)	C38—O2	1.405 (4)
C8—C13	1.394 (5)	C39—C40	1.372 (5)
C8—C9	1.401 (5)	C39—C44	1.382 (5)
C9—C10	1.363 (6)	C39—O3	1.414 (4)
C9—H9	0.9300	C40—C41	1.386 (5)
C10—C11	1.375 (6)	C40—H40	0.9300
C10—H10	0.9300	C41—C42	1.375 (6)
C11—C12	1.383 (6)	C41—H41	0.9300
C11—H11	0.9300	C42—C43	1.368 (6)
C12—C13	1.383 (5)	C42—H42	0.9300
C12—H12	0.9300	C43—C44	1.394 (5)
C13—O6	1.390 (4)	C43—H43	0.9300
C14—C15	1.374 (5)	C44—C45	1.477 (5)
C14—C19	1.387 (5)	C45—C46	1.382 (6)
C14—O5	1.399 (4)	C45—C50	1.387 (5)
C15—C16	1.381 (5)	C46—C47	1.391 (7)
C15—H15	0.9300	C46—H46	0.9300
C16—C17	1.380 (6)	C47—C48	1.363 (7)
C16—H16	0.9300	C47—H47	0.9300
C17—C18	1.363 (6)	C48—C49	1.376 (6)
C17—H17	0.9300	C48—H48	0.9300
C18—C19	1.400 (5)	C49—C50	1.371 (5)
C18—H18	0.9300	C49—H49	0.9300
C19—C20	1.448 (5)	C50—O4	1.405 (4)
C20—N4	1.300 (5)	Cl1—Cu1	2.2619 (14)
C20—O7	1.348 (4)	Cl2—Cu1	2.3008 (15)
C21—N5	1.279 (5)	Cl2—Cu1ⁱ	2.7006 (15)
C21—O7	1.366 (5)	Cu1—N9	2.021 (3)
C21—C22	1.455 (6)	Cu1—N8ⁱ	2.045 (4)
C22—C26	1.378 (5)	Cu1—Cl2ⁱ	2.7006 (15)
C22—C23	1.385 (6)	N1—P1	1.568 (3)
C23—C24	1.368 (6)	N1—P3	1.579 (3)
C23—H23	0.9300	N2—P2	1.575 (3)
C24—N8	1.337 (5)	N2—P1	1.578 (3)
C24—H24	0.9300	N3—P2	1.560 (3)
C25—N8	1.329 (5)	N3—P3	1.573 (3)
C25—C26	1.374 (6)	N4—N5	1.395 (5)
C25—H25	0.9300	N6—N7	1.391 (5)
C26—H26	0.9300	N8—Cu1ⁱ	2.045 (4)
C27—C28	1.377 (5)	O1—P2	1.587 (2)
C27—C32	1.384 (5)	O2—P2	1.580 (3)
C27—O1	1.395 (4)	O3—P3	1.580 (3)
C28—C29	1.373 (6)	O4—P3	1.584 (3)
C28—H28	0.9300	O5—P1	1.590 (3)
C29—C30	1.365 (6)	O6—P1	1.587 (2)
C29—H29	0.9300

N9—C1—C2	123.5 (4)	C35—C34—H34	119.4
N9—C1—H1	118.2	C33—C34—H34	119.4
C2—C1—H1	118.2	C34—C35—C36	120.4 (4)
C1—C2—C3	119.3 (4)	C34—C35—H35	119.8
C1—C2—H2	120.4	C36—C35—H35	119.8
C3—C2—H2	120.4	C35—C36—C37	119.7 (4)
C2—C3—C4	118.0 (4)	C35—C36—H36	120.2
C2—C3—C6	119.7 (4)	C37—C36—H36	120.2
C4—C3—C6	122.1 (4)	C36—C37—C38	119.0 (4)
C5—C4—C3	119.1 (4)	C36—C37—H37	120.5
C5—C4—H4	120.5	C38—C37—H37	120.5
C3—C4—H4	120.5	C33—C38—C37	122.2 (3)
N9—C5—C4	123.2 (4)	C33—C38—O2	119.6 (3)
N9—C5—H5	118.4	C37—C38—O2	118.0 (3)
C4—C5—H5	118.4	C40—C39—C44	123.8 (4)
N7—C6—O8	111.7 (4)	C40—C39—O3	117.5 (3)
N7—C6—C3	128.3 (4)	C44—C39—O3	118.6 (3)
O8—C6—C3	119.8 (3)	C39—C40—C41	117.9 (4)
N6—C7—O8	111.7 (4)	C39—C40—H40	121.1
N6—C7—C8	126.8 (4)	C41—C40—H40	121.1
O8—C7—C8	121.4 (3)	C42—C41—C40	120.2 (4)
C13—C8—C9	117.2 (4)	C42—C41—H41	119.9
C13—C8—C7	124.0 (4)	C40—C41—H41	119.9
C9—C8—C7	118.8 (4)	C43—C42—C41	120.3 (4)
C10—C9—C8	121.1 (4)	C43—C42—H42	119.8
C10—C9—H9	119.5	C41—C42—H42	119.8
C8—C9—H9	119.5	C42—C43—C44	121.5 (4)
C9—C10—C11	121.0 (4)	C42—C43—H43	119.3
C9—C10—H10	119.5	C44—C43—H43	119.3
C11—C10—H10	119.5	C39—C44—C43	116.2 (4)
C10—C11—C12	119.4 (4)	C39—C44—C45	121.8 (3)
C10—C11—H11	120.3	C43—C44—C45	122.0 (4)
C12—C11—H11	120.3	C46—C45—C50	116.4 (4)
C13—C12—C11	119.7 (4)	C46—C45—C44	120.6 (4)
C13—C12—H12	120.1	C50—C45—C44	123.0 (4)
C11—C12—H12	120.1	C45—C46—C47	121.2 (5)
C12—C13—O6	118.6 (3)	C45—C46—H46	119.4
C12—C13—C8	121.4 (4)	C47—C46—H46	119.4
O6—C13—C8	120.0 (3)	C48—C47—C46	120.3 (5)
C15—C14—C19	120.9 (3)	C48—C47—H47	119.9
C15—C14—O5	120.8 (3)	C46—C47—H47	119.9
C19—C14—O5	118.0 (3)	C47—C48—C49	120.0 (4)
C14—C15—C16	120.6 (4)	C47—C48—H48	120.0
C14—C15—H15	119.7	C49—C48—H48	120.0
C16—C15—H15	119.7	C50—C49—C48	118.8 (4)
C17—C16—C15	119.5 (4)	C50—C49—H49	120.6
C17—C16—H16	120.3	C48—C49—H49	120.6
C15—C16—H16	120.3	C49—C50—C45	123.2 (4)
C18—C17—C16	119.7 (4)	C49—C50—O4	116.3 (4)
C18—C17—H17	120.2	C45—C50—O4	120.3 (3)
C16—C17—H17	120.2	Cu1—Cl2—Cu1ⁱ	89.14 (5)
C17—C18—C19	122.1 (4)	N9—Cu1—N8ⁱ	174.68 (13)
C17—C18—H18	119.0	N9—Cu1—Cl1	88.10 (10)
C19—C18—H18	119.0	N8ⁱ—Cu1—Cl1	90.93 (10)
C14—C19—C18	117.2 (4)	N9—Cu1—Cl2	88.67 (10)
C14—C19—C20	126.0 (3)	N8ⁱ—Cu1—Cl2	91.18 (10)
C18—C19—C20	116.8 (3)	Cl1—Cu1—Cl2	167.54 (5)
N4—C20—O7	112.5 (4)	N9—Cu1—Cl2ⁱ	94.56 (11)
N4—C20—C19	124.0 (4)	N8ⁱ—Cu1—Cl2ⁱ	90.77 (10)
O7—C20—C19	123.5 (3)	Cl1—Cu1—Cl2ⁱ	101.39 (5)
N5—C21—O7	112.5 (4)	Cl2—Cu1—Cl2ⁱ	90.86 (5)
N5—C21—C22	126.9 (4)	P1—N1—P3	120.96 (19)
O7—C21—C22	120.6 (3)	P2—N2—P1	120.2 (2)
C26—C22—C23	117.5 (4)	P2—N3—P3	121.78 (18)
C26—C22—C21	123.2 (4)	C20—N4—N5	105.9 (3)
C23—C22—C21	119.3 (4)	C21—N5—N4	106.6 (3)
C24—C23—C22	119.2 (4)	C7—N6—N7	106.3 (3)
C24—C23—H23	120.4	C6—N7—N6	106.7 (3)
C22—C23—H23	120.4	C25—N8—C24	116.7 (4)
N8—C24—C23	123.6 (4)	C25—N8—Cu1ⁱ	124.4 (3)
N8—C24—H24	118.2	C24—N8—Cu1ⁱ	118.8 (3)
C23—C24—H24	118.2	C5—N9—C1	116.7 (4)
N8—C25—C26	123.5 (4)	C5—N9—Cu1	122.2 (3)
N8—C25—H25	118.2	C1—N9—Cu1	120.5 (3)
C26—C25—H25	118.2	C27—O1—P2	120.5 (2)
C25—C26—C22	119.4 (4)	C38—O2—P2	120.3 (2)
C25—C26—H26	120.3	C39—O3—P3	118.2 (2)
C22—C26—H26	120.3	C50—O4—P3	124.2 (2)
C28—C27—C32	122.7 (4)	C14—O5—P1	128.2 (2)
C28—C27—O1	118.5 (3)	C13—O6—P1	121.9 (2)
C32—C27—O1	118.5 (3)	C20—O7—C21	102.5 (3)
C29—C28—C27	118.7 (4)	C7—O8—C6	103.6 (3)
C29—C28—H28	120.7	N1—P1—N2	118.73 (16)
C27—C28—H28	120.7	N1—P1—O6	104.80 (15)
C30—C29—C28	120.5 (4)	N2—P1—O6	110.24 (15)
C30—C29—H29	119.7	N1—P1—O5	109.29 (16)
C28—C29—H29	119.7	N2—P1—O5	110.41 (15)
C29—C30—C31	120.5 (4)	O6—P1—O5	101.93 (13)
C29—C30—H30	119.7	N3—P2—N2	117.71 (16)
C31—C30—H30	119.7	N3—P2—O2	111.60 (15)
C30—C31—C32	120.6 (4)	N2—P2—O2	105.09 (16)
C30—C31—H31	119.7	N3—P2—O1	105.30 (16)
C32—C31—H31	119.7	N2—P2—O1	112.52 (15)
C27—C32—C31	116.9 (3)	O2—P2—O1	103.87 (13)
C27—C32—C33	121.6 (3)	N3—P3—N1	118.07 (17)
C31—C32—C33	121.3 (3)	N3—P3—O3	112.23 (16)
C38—C33—C34	117.3 (3)	N1—P3—O3	105.70 (16)
C38—C33—C32	121.5 (3)	N3—P3—O4	104.77 (15)
C34—C33—C32	121.2 (3)	N1—P3—O4	112.16 (15)
C35—C34—C33	121.3 (4)	O3—P3—O4	103.00 (14)

N9—C1—C2—C3	−0.6 (7)	C46—C47—C48—C49	−1.9 (9)
C1—C2—C3—C4	3.1 (6)	C47—C48—C49—C50	0.5 (8)
C1—C2—C3—C6	−173.3 (4)	C48—C49—C50—C45	1.4 (7)
C2—C3—C4—C5	−3.7 (6)	C48—C49—C50—O4	−174.4 (4)
C6—C3—C4—C5	172.6 (4)	C46—C45—C50—C49	−1.8 (6)
C3—C4—C5—N9	1.9 (7)	C44—C45—C50—C49	178.0 (4)
C2—C3—C6—N7	2.3 (7)	C46—C45—C50—O4	173.8 (4)
C4—C3—C6—N7	−173.9 (4)	C44—C45—C50—O4	−6.3 (6)
C2—C3—C6—O8	175.9 (4)	Cu1ⁱ—Cl2—Cu1—N9	94.54 (11)
C4—C3—C6—O8	−0.3 (6)	Cu1ⁱ—Cl2—Cu1—N8ⁱ	−90.78 (11)
N6—C7—C8—C13	177.9 (4)	Cu1ⁱ—Cl2—Cu1—Cl1	169.5 (2)
O8—C7—C8—C13	1.2 (6)	Cu1ⁱ—Cl2—Cu1—Cl2ⁱ	0.0
N6—C7—C8—C9	0.2 (6)	O7—C20—N4—N5	−0.4 (5)
O8—C7—C8—C9	−176.5 (3)	C19—C20—N4—N5	−179.7 (4)
C13—C8—C9—C10	−1.0 (6)	O7—C21—N5—N4	0.0 (5)
C7—C8—C9—C10	176.8 (4)	C22—C21—N5—N4	−179.3 (4)
C8—C9—C10—C11	−2.2 (7)	C20—N4—N5—C21	0.2 (5)
C9—C10—C11—C12	2.9 (6)	O8—C7—N6—N7	−1.0 (5)
C10—C11—C12—C13	−0.2 (6)	C8—C7—N6—N7	−178.0 (4)
C11—C12—C13—O6	177.4 (3)	O8—C6—N7—N6	1.0 (5)
C11—C12—C13—C8	−3.2 (6)	C3—C6—N7—N6	175.0 (4)
C9—C8—C13—C12	3.7 (5)	C7—N6—N7—C6	0.0 (5)
C7—C8—C13—C12	−174.0 (3)	C26—C25—N8—C24	1.1 (7)
C9—C8—C13—O6	−176.8 (3)	C26—C25—N8—Cu1ⁱ	−178.7 (4)
C7—C8—C13—O6	5.5 (5)	C23—C24—N8—C25	−0.1 (7)
C19—C14—C15—C16	−2.9 (6)	C23—C24—N8—Cu1ⁱ	179.8 (4)
O5—C14—C15—C16	−177.2 (3)	C4—C5—N9—C1	0.7 (6)
C14—C15—C16—C17	1.5 (6)	C4—C5—N9—Cu1	−170.6 (3)
C15—C16—C17—C18	−0.2 (6)	C2—C1—N9—C5	−1.4 (6)
C16—C17—C18—C19	0.2 (6)	C2—C1—N9—Cu1	170.1 (3)
C15—C14—C19—C18	2.8 (5)	N8ⁱ—Cu1—N9—C5	133.5 (13)
O5—C14—C19—C18	177.3 (3)	Cl1—Cu1—N9—C5	54.0 (3)
C15—C14—C19—C20	−174.4 (3)	Cl2—Cu1—N9—C5	−138.0 (3)
O5—C14—C19—C20	0.1 (5)	Cl2ⁱ—Cu1—N9—C5	−47.2 (3)
C17—C18—C19—C14	−1.4 (6)	N8ⁱ—Cu1—N9—C1	−37.5 (15)
C17—C18—C19—C20	176.0 (4)	Cl1—Cu1—N9—C1	−117.0 (3)
C14—C19—C20—N4	165.9 (4)	Cl2—Cu1—N9—C1	51.0 (3)
C18—C19—C20—N4	−11.3 (6)	Cl2ⁱ—Cu1—N9—C1	141.8 (3)
C14—C19—C20—O7	−13.3 (6)	C28—C27—O1—P2	−113.1 (3)
C18—C19—C20—O7	169.6 (3)	C32—C27—O1—P2	72.5 (4)
N5—C21—C22—C26	147.9 (5)	C33—C38—O2—P2	71.7 (4)
O7—C21—C22—C26	−31.5 (6)	C37—C38—O2—P2	−112.3 (3)
N5—C21—C22—C23	−30.1 (7)	C40—C39—O3—P3	−103.8 (4)
O7—C21—C22—C23	150.6 (4)	C44—C39—O3—P3	77.0 (4)
C26—C22—C23—C24	1.5 (7)	C49—C50—O4—P3	−116.9 (3)
C21—C22—C23—C24	179.5 (4)	C45—C50—O4—P3	67.1 (4)
C22—C23—C24—N8	−1.3 (7)	C15—C14—O5—P1	−49.2 (4)
N8—C25—C26—C22	−0.9 (8)	C19—C14—O5—P1	136.3 (3)
C23—C22—C26—C25	−0.5 (7)	C12—C13—O6—P1	−89.1 (4)
C21—C22—C26—C25	−178.5 (4)	C8—C13—O6—P1	91.4 (4)
C32—C27—C28—C29	−1.4 (6)	N4—C20—O7—C21	0.5 (4)
O1—C27—C28—C29	−175.6 (3)	C19—C20—O7—C21	179.7 (3)
C27—C28—C29—C30	0.1 (6)	N5—C21—O7—C20	−0.3 (5)
C28—C29—C30—C31	0.5 (7)	C22—C21—O7—C20	179.1 (3)
C29—C30—C31—C32	0.2 (7)	N6—C7—O8—C6	1.5 (4)
C28—C27—C32—C31	1.9 (5)	C8—C7—O8—C6	178.7 (3)
O1—C27—C32—C31	176.1 (3)	N7—C6—O8—C7	−1.6 (4)
C28—C27—C32—C33	−173.3 (3)	C3—C6—O8—C7	−176.1 (3)
O1—C27—C32—C33	0.9 (5)	P3—N1—P1—N2	−6.0 (3)
C30—C31—C32—C27	−1.3 (6)	P3—N1—P1—O6	−129.6 (2)
C30—C31—C32—C33	173.9 (4)	P3—N1—P1—O5	121.8 (2)
C27—C32—C33—C38	−47.2 (5)	P2—N2—P1—N1	14.5 (3)
C31—C32—C33—C38	137.8 (4)	P2—N2—P1—O6	135.4 (2)
C27—C32—C33—C34	131.5 (4)	P2—N2—P1—O5	−112.8 (2)
C31—C32—C33—C34	−43.5 (6)	C13—O6—P1—N1	−162.0 (3)
C38—C33—C34—C35	−0.7 (6)	C13—O6—P1—N2	69.2 (3)
C32—C33—C34—C35	−179.4 (4)	C13—O6—P1—O5	−48.1 (3)
C33—C34—C35—C36	−1.1 (7)	C14—O5—P1—N1	−137.8 (3)
C34—C35—C36—C37	0.7 (7)	C14—O5—P1—N2	−5.5 (3)
C35—C36—C37—C38	1.4 (7)	C14—O5—P1—O6	111.7 (3)
C34—C33—C38—C37	2.8 (6)	P3—N3—P2—N2	15.3 (3)
C32—C33—C38—C37	−178.4 (4)	P3—N3—P2—O2	136.9 (2)
C34—C33—C38—O2	178.6 (3)	P3—N3—P2—O1	−111.0 (2)
C32—C33—C38—O2	−2.6 (5)	P1—N2—P2—N3	−18.9 (3)
C36—C37—C38—C33	−3.3 (6)	P1—N2—P2—O2	−143.86 (19)
C36—C37—C38—O2	−179.1 (4)	P1—N2—P2—O1	103.8 (2)
C44—C39—C40—C41	1.7 (6)	C38—O2—P2—N3	71.1 (3)
O3—C39—C40—C41	−177.6 (3)	C38—O2—P2—N2	−160.3 (3)
C39—C40—C41—C42	−0.6 (6)	C38—O2—P2—O1	−41.9 (3)
C40—C41—C42—C43	−0.6 (7)	C27—O1—P2—N3	−165.3 (2)
C41—C42—C43—C44	0.8 (7)	C27—O1—P2—N2	65.3 (3)
C40—C39—C44—C43	−1.5 (6)	C27—O1—P2—O2	−47.8 (3)
O3—C39—C44—C43	177.8 (3)	P2—N3—P3—N1	−7.1 (3)
C40—C39—C44—C45	179.1 (4)	P2—N3—P3—O3	116.2 (2)
O3—C39—C44—C45	−1.7 (6)	P2—N3—P3—O4	−132.7 (2)
C42—C43—C44—C39	0.2 (6)	P1—N1—P3—N3	2.3 (3)
C42—C43—C44—C45	179.7 (4)	P1—N1—P3—O3	−124.2 (2)
C39—C44—C45—C46	138.6 (4)	P1—N1—P3—O4	124.2 (2)
C43—C44—C45—C46	−40.9 (6)	C39—O3—P3—N3	55.3 (3)
C39—C44—C45—C50	−41.3 (6)	C39—O3—P3—N1	−174.7 (3)
C43—C44—C45—C50	139.3 (4)	C39—O3—P3—O4	−56.9 (3)
C50—C45—C46—C47	0.4 (7)	C50—O4—P3—N3	−148.7 (3)
C44—C45—C46—C47	−179.5 (5)	C50—O4—P3—N1	82.0 (3)
C45—C46—C47—C48	1.5 (9)	C50—O4—P3—O3	−31.2 (3)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···O3	0.93	2.38	3.271 (5)	160
C36—H36···N5ⁱⁱ	0.93	2.51	3.396 (6)	159

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₅₀H₃₂N₉O₈P₃)₂]
M_r	2228.39
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.554 (5), 14.486 (7), 15.551 (8)
α, β, γ (°)	85.401 (7), 81.984 (7), 89.844 (7)
V (Å³)	2347 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.35 × 0.30 × 0.08

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.779, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	12440, 8593, 6217
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.139, 1.02
No. of reflections	8593
No. of parameters	658
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.48

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···O3	0.93	2.38	3.271 (5)	160
C36—H36···N5ⁱ	0.93	2.51	3.396 (6)	159

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

Acknowledgements

This work was supported by the NSFC (Nos. 91027003 and 21072118), the 973 Program (No. 2012CB821705), the PCSIRT, the Shangdong Natural Science Foundation (No. JQ200803) and the Taishan Scholars' Construction Project Special Fund in China.

References

Ainscough, E. W., Brodie, A. M., Davidson, R. J., Moubaraki, B., Murray, K. M., Otter, C. A. & Waterland, M. R. (2008). Inorg. Chem. 47, 9182–9192. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dong, Y.-B., Wang, H.-Y., Ma, J.-P., Shen, D.-Z. & Huang, R.-Q. (2005). Inorg. Chem. 44, 4679–4692. Web of Science CSD CrossRef PubMed CAS Google Scholar
Dong, Y.-B., Wang, P., Ma, J.-P., Wang, H.-Y., Tang, B. & Huang, R.-Q. (2007). J. Am. Chem. Soc. 129, 4872–4873. Web of Science CSD CrossRef PubMed CAS Google Scholar
Du, M., Wang, Q., Li, C.-P., Zhao, X.-J. & Ribas, J. (2010). Cryst. Growth Des. 10, 3285–3296. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, X.-X., Ma, J.-P., Dong, Y.-B., Huang, R.-Q. & Lai, T.-S. (2007). Cryst. Growth Des. 7, 1058–1068. Web of Science CSD CrossRef CAS Google Scholar
Zhao, X.-X., Ma, J.-P., Shen, D.-Z., Dong, Y.-B. & Huang, R.-Q. (2009). CrystEngComm, 11, 1281–1290. Web of Science CSD 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 68| Part 5| May 2012| Pages m648-m649

doi:10.1107/S1600536812016285

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\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(μ-4,4;6,6-bis­­(bi­phenyl-2,2′-diyldi­­oxy)-2,2-bis­­{2-[5-(pyridin-4-yl)-1,3,4-oxa­diazol-2-yl]phen­­oxy}cyclo­triphosphazene)di-μ-chlorido-bis­­[chlorido­copper(II)]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(μ-4,4;6,6-bis(biphenyl-2,2′-diyldioxy)-2,2-bis{2-[5-(pyridin-4-yl)-1,3,4-oxadiazol-2-yl]phenoxy}cyclotriphosphazene)di-μ-chlorido-bis[chloridocopper(II)]