A new copper(II) coordination polymer containing chains of inter­connected paddle-wheel anti­ferromagnetic clusters

The construction of supra­molecular architectures based on inorganic–organic coordination frameworks with weak noncovalent inter­actions has implications for the rational design of functional materials. A new crystalline binuclear copper(II) one-dimensional polymeric chain, namely catena-poly[[[tetra­kis­(μ-4-aza­niumyl­butano­ato-κ²O:O′)dicopper(II)(Cu—Cu)]-μ-chlorido-[di­aqua­dichlo­rido­copper(II)]-μ-chlorido] bis­(perchlorate)], {[Cu₃Cl₄(C₄H₉NO₂)₄(H₂O)₂](ClO₄)₂}_n, was obtained by the reaction of 4-amino­butyric acid (GABA) with CuCl₂·2H₂O in aqueous solution. The structure was established by single-crystal X-ray diffraction and was also characterized by IR spectroscopy and magnetic measurements. The crystal structure consists of [{Cu₂(GABA)₄}{CuCl₄(H₂O)₂}]⁺ cations and isolated perchlorate anions. Two symmetry-related Cu^II centres are bridged via carboxyl­ate O atoms into a classical paddle-wheel configuration, with a Cu...Cu distance of 2.643 (1) Å, while bridging Cl atoms complete the square-pyramidal geometry of the metal atoms. The Cl atoms connect the paddlewheel moieties to a second Cu^II atom lying on an octa­hedral site, resulting in infinite helical chains along the c axis. The packing motif exhibits channels containing free perchlorate anions. The crystal structure is stabilized by hydrogen bonds between the perchlorate anions, the coordinated water mol­ecules and the ammonium groups of the polymeric chains. The magnetic analysis of the title compound indicates a nontrivial anti­ferromagnetic behaviour arising from alternating weak–strong anti­ferromagnetic coupling between neighbouring Cu^II centres.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2008); cell refinement: CrysAlis PRO (Oxford Diffraction, 2008); data reduction: CrysAlis PRO (Oxford Diffraction, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[[tetrakis(µ-4-azaniumylbutanoato-\ κ²O:O')dicopper(II)(Cu—Cu)]-\ µ-chlorido-[diaquadichloridocopper(II)]-µ-chlorido] bis(perchlorate)]

Crystal data

[Cu3Cl4(C4H9NO2)4(H2O)2](ClO4)2	F(000) = 994
Mr = 979.82	Dx = 2.001 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 19042 reflections
a = 12.946 (3) Å	θ = 2.6–27.7°
b = 12.568 (3) Å	µ = 2.52 mm^−1
c = 11.044 (2) Å	T = 100 K
β = 115.18 (3)°	Prism, green
V = 1626.2 (7) Å^3	0.1 × 0.1 × 0.08 mm
Z = 2

Data collection

Oxford Diffraction KappaCCD diffractometer	19050 independent reflections
Radiation source: fine-focus sealed tube	15048 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 27.7°, θmin = 2.6°
Absorption correction: integration (DeTitta, 1985)	h = −16→16
Tmin = 0.720, Tmax = 0.853	k = −16→16
19050 measured reflections	l = −14→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: difference Fourier map
wR(F^2) = 0.109	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0667P)^2] where P = (Fo^2 + 2Fc^2)/3
19050 reflections	(Δ/σ)max < 0.001
217 parameters	Δρmax = 1.26 e Å^−3
3 restraints	Δρmin = −1.92 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.99887 (8)	0.95931 (5)	0.38914 (7)	0.0087 (2)
Cu2	1.00000	1.00000	0.00000	0.0236 (4)
Cl2	0.80176 (13)	0.99175 (15)	−0.11378 (19)	0.0213 (5)
Cl3	0.98967 (15)	0.86597 (11)	0.19198 (15)	0.0141 (4)
O1	1.1161 (4)	0.8638 (4)	0.5140 (5)	0.0208 (17)
O1W	0.9850 (5)	1.1296 (3)	0.1010 (5)	0.0243 (16)
O2	0.8865 (5)	1.0727 (4)	0.2988 (5)	0.0187 (17)
O3	0.8778 (4)	0.8696 (4)	0.3998 (5)	0.0188 (17)
O4	1.1208 (5)	1.0625 (4)	0.4120 (5)	0.0205 (17)
N1	1.2977 (5)	0.5897 (5)	0.9106 (6)	0.0156 (19)
N2	0.7144 (5)	0.5913 (5)	0.6050 (5)	0.0139 (19)
C1	1.1480 (6)	0.8635 (6)	0.6389 (7)	0.010 (2)
C2	1.2308 (6)	0.7758 (5)	0.7141 (7)	0.0139 (19)
C3	1.2774 (7)	0.7837 (6)	0.8644 (8)	0.014 (2)
C4	1.3600 (6)	0.6939 (5)	0.9343 (8)	0.013 (2)
C5	0.8440 (6)	0.8730 (6)	0.4908 (7)	0.013 (2)
C6	0.7515 (6)	0.7943 (5)	0.4807 (7)	0.012 (2)
C7	0.7261 (7)	0.7881 (6)	0.6029 (7)	0.016 (2)
C8	0.6543 (6)	0.6931 (5)	0.6004 (8)	0.014 (2)
Cl1	0.51942 (12)	0.47535 (11)	0.74998 (16)	0.0153 (5)
O5	0.4947 (4)	0.5097 (3)	0.8587 (5)	0.0218 (17)
O6	0.4636 (4)	0.5401 (5)	0.6359 (5)	0.0306 (17)
O7	0.6421 (3)	0.4820 (3)	0.7932 (5)	0.0189 (16)
O8	0.4841 (4)	0.3669 (4)	0.7191 (5)	0.0277 (17)
H1WA	0.98700	1.13870	0.19200	0.0300*
H1A	1.26710	0.57390	0.82180	0.0190*
H1B	1.24090	0.59460	0.93820	0.0190*
H1C	1.34730	0.53750	0.95750	0.0190*
H1WB	0.98210	1.20340	0.06870	0.0300*
H2A	0.69960	0.57060	0.52030	0.0170*
H2B	0.68940	0.54040	0.64480	0.0170*
H2C	0.79090	0.60060	0.65280	0.0170*
H2D	1.19180	0.70640	0.68550	0.0160*
H2E	1.29550	0.77710	0.68880	0.0160*
H3A	1.21320	0.78180	0.89070	0.0170*
H3B	1.31700	0.85280	0.89400	0.0170*
H4A	1.41910	0.69000	0.89990	0.0160*
H4B	1.39850	0.70850	1.03150	0.0160*
H6A	0.77430	0.72260	0.46370	0.0140*
H6B	0.68020	0.81360	0.40220	0.0140*
H7A	0.79900	0.78480	0.68440	0.0190*
H7B	0.68580	0.85370	0.60800	0.0190*
H8A	0.63500	0.69660	0.67800	0.0160*
H8B	0.58210	0.69510	0.51790	0.0160*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0090 (3)	0.0082 (3)	0.0092 (5)	0.0004 (4)	0.0041 (5)	0.0003 (3)
Cu2	0.0205 (5)	0.0270 (6)	0.0234 (8)	0.0014 (7)	0.0095 (8)	−0.0013 (5)
Cl2	0.0209 (7)	0.0233 (8)	0.0184 (10)	−0.0014 (8)	0.0072 (8)	0.0037 (7)
Cl3	0.0136 (7)	0.0187 (7)	0.0110 (8)	0.0012 (7)	0.0062 (8)	−0.0022 (5)
O1	0.025 (3)	0.027 (3)	0.009 (3)	0.015 (3)	0.006 (2)	0.004 (2)
O1W	0.036 (3)	0.021 (2)	0.020 (3)	0.002 (2)	0.016 (3)	0.0000 (19)
O2	0.027 (3)	0.016 (3)	0.010 (3)	0.009 (2)	0.005 (2)	−0.001 (2)
O3	0.019 (3)	0.026 (3)	0.016 (3)	−0.013 (2)	0.012 (2)	−0.010 (2)
O4	0.027 (3)	0.019 (3)	0.023 (3)	−0.011 (2)	0.018 (2)	−0.010 (2)
N1	0.020 (3)	0.009 (4)	0.016 (3)	0.001 (2)	0.006 (3)	0.000 (2)
N2	0.013 (3)	0.018 (4)	0.009 (3)	0.000 (2)	0.003 (2)	0.005 (2)
C1	0.007 (3)	0.008 (4)	0.017 (4)	−0.001 (3)	0.006 (3)	0.003 (3)
C2	0.017 (3)	0.010 (3)	0.014 (4)	0.002 (3)	0.006 (3)	0.000 (3)
C3	0.019 (4)	0.010 (4)	0.012 (4)	0.002 (3)	0.005 (3)	−0.002 (3)
C4	0.013 (3)	0.012 (4)	0.016 (4)	−0.002 (3)	0.007 (3)	−0.001 (3)
C5	0.010 (3)	0.013 (4)	0.016 (4)	0.007 (3)	0.005 (3)	0.006 (3)
C6	0.014 (3)	0.009 (4)	0.012 (4)	−0.002 (2)	0.005 (3)	0.001 (3)
C7	0.017 (4)	0.016 (4)	0.020 (4)	−0.002 (3)	0.013 (3)	0.001 (3)
C8	0.014 (3)	0.011 (4)	0.018 (4)	−0.002 (3)	0.009 (3)	0.001 (3)
Cl1	0.0135 (7)	0.0211 (9)	0.0096 (8)	−0.0012 (6)	0.0033 (7)	−0.0001 (7)
O5	0.016 (3)	0.031 (3)	0.019 (3)	0.0065 (19)	0.008 (2)	−0.004 (2)
O6	0.025 (3)	0.045 (3)	0.015 (3)	0.001 (2)	0.002 (2)	0.020 (3)
O7	0.013 (2)	0.021 (3)	0.024 (3)	0.0007 (19)	0.009 (2)	0.000 (2)
O8	0.031 (3)	0.021 (3)	0.031 (3)	−0.010 (2)	0.013 (3)	−0.008 (2)

Geometric parameters (Å, º)

Cu1—Cl3	2.4312 (18)	N1—H1C	0.9100
Cu1—O1	1.966 (5)	N1—H1A	0.9100
Cu1—O2	1.977 (6)	N2—H2C	0.9100
Cu1—O3	1.975 (6)	N2—H2A	0.9100
Cu1—O4	1.974 (6)	N2—H2B	0.9100
Cu2—Cl2	2.331 (2)	C1—C2	1.515 (10)
Cu2—Cl3	2.7554 (17)	C2—C3	1.509 (11)
Cu2—O1W	2.030 (5)	C3—C4	1.520 (11)
Cu2—Cl2^i	2.331 (2)	C5—C6	1.520 (11)
Cu2—Cl3^i	2.7554 (17)	C6—C7	1.521 (11)
Cu2—O1W^i	2.030 (5)	C7—C8	1.506 (11)
Cl1—O7	1.453 (5)	C2—H2E	0.9900
Cl1—O5	1.434 (5)	C2—H2D	0.9900
Cl1—O6	1.413 (6)	C3—H3B	0.9900
Cl1—O8	1.432 (5)	C3—H3A	0.9900
O1—C1	1.260 (9)	C4—H4A	0.9900
O2—C1^ii	1.256 (10)	C4—H4B	0.9900
O3—C5	1.256 (9)	C6—H6A	0.9900
O4—C5^ii	1.265 (9)	C6—H6B	0.9900
O1W—H1WB	0.9900	C7—H7B	0.9900
O1W—H1WA	1.0000	C7—H7A	0.9900
N1—C4	1.502 (9)	C8—H8A	0.9900
N2—C8	1.487 (9)	C8—H8B	0.9900
N1—H1B	0.9100
Cu1···O1W	3.775 (5)	O8···H2A^x	2.8100
Cu1···N2^iii	3.739 (6)	O8···H2E^xiii	2.8200
Cu1···O3^ii	3.072 (5)	O8···H4B^vii	2.6900
Cu1···O1^ii	3.108 (5)	O8···H8B^x	2.5100
Cu1···O2^ii	3.145 (5)	N1···Cl2^iv	3.214 (6)
Cu1···O4^ii	3.193 (6)	N1···O5^vii	3.074 (8)
Cu1···N1^iii	3.824 (7)	N1···O7^vii	3.155 (8)
Cu1···H1WB^iv	3.2400	N1···Cu1^xii	3.824 (7)
Cu1···H1WA	3.0900	N1···O1^xii	3.075 (9)
Cu1···H1B^iii	3.0200	N1···O5^xv	3.015 (9)
Cu1···H2C^iii	2.9400	N1···O4^xii	2.989 (9)
Cu2···H2D^v	3.5700	N2···O7	2.956 (8)
Cu2···H2D^iii	3.5700	N2···O6^x	3.146 (8)
Cl2···Cl3	3.582 (3)	N2···Cu1^xii	3.739 (6)
Cl2···O1W	3.077 (5)	N2···Cl2^xii	3.245 (6)
Cl2···O6^vi	3.394 (6)	N2···Cl3^xii	3.316 (7)
Cl2···N1^v	3.214 (6)	N2···O2^xii	3.120 (8)
Cl2···O1W^i	3.104 (7)	N2···O3^xii	3.075 (7)
Cl2···N2^iii	3.245 (6)	N1···H2D	2.7000
Cl2···Cl3^i	3.636 (3)	N2···H6A	2.6100
Cl3···O1W^i	3.389 (6)	C1···O7^xvi	2.904 (9)
Cl3···N2^iii	3.316 (7)	C1···C5	3.564 (12)
Cl3···O4	3.373 (5)	C2···Cl3^xii	3.511 (8)
Cl3···O1W	3.455 (4)	C2···O7^xvi	3.089 (8)
Cl3···Cl2	3.582 (3)	C4···O5^xv	3.215 (9)
Cl3···O1	3.221 (5)	C4···O5^vii	3.414 (8)
Cl3···C6^iii	3.590 (8)	C5···C1	3.564 (12)
Cl3···O2	3.357 (6)	C5···O7^iii	3.172 (9)
Cl3···O3	3.193 (6)	C6···Cl3^xii	3.590 (8)
Cl3···Cl2^i	3.636 (3)	C8···O8^x	3.294 (9)
Cl3···C2^iii	3.511 (8)	C8···O6	3.282 (10)
Cl1···H1C^vii	2.9500	C1···H1WA^ii	3.0500
Cl1···H2B	3.0100	C1···H1WB^iv	2.9800
Cl2···H6A^iii	2.8900	C1···H1B^iii	2.9800
Cl2···H2A^iii	2.4900	C2···H1A	2.7600
Cl2···H1A^v	2.3200	C4···H8B^xvii	2.9700
Cl2···H2D^v	2.8200	C6···H2C	3.0000
Cl3···H1WA^iv	3.0900	C6···H2A	2.9700
Cl3···H6A^iii	3.0600	C6···H8A^iii	3.0300
Cl3···H7A^iii	3.0800	H1WA···C1^ii	3.0500
Cl3···H2C^iii	2.4600	H1WA···O4	2.5000
Cl3···H2D^iii	2.8000	H1WA···Cl3^v	3.0900
O1···Cl3	3.221 (5)	H1WA···Cu1	3.0900
O1···N1^iii	3.075 (9)	H1WA···O2	2.2500
O1···O3	2.793 (8)	H1WA···H3A^ii	2.5600
O1···O4	2.751 (7)	H1A···Cl2^iv	2.3200
O1···C5^ii	3.352 (9)	H1A···O5^xv	2.9100
O1···Cu1^ii	3.108 (5)	H1A···C2	2.7600
O1W···Cl2^i	3.104 (7)	H1A···H2D	2.1800
O1W···Cl2	3.077 (5)	H1B···O7^vii	2.8600
O1W···O4	3.234 (7)	H1B···Cu1^xii	3.0200
O1W···Cl3^i	3.389 (6)	H1B···H3A	2.4000
O1W···Cu1	3.775 (5)	H1B···O1^xii	2.1800
O1W···O2	3.046 (9)	H1B···O4^xii	2.4500
O1W···Cl3	3.455 (4)	H1B···C1^xii	2.9800
O2···O1W	3.046 (9)	H1C···H7B^xiii	2.4000
O2···C5^ii	3.338 (10)	H1C···Cl1^vii	2.9500
O2···O3	2.807 (7)	H1C···O5^vii	2.2600
O2···Cu1^ii	3.145 (5)	H1C···O5^xv	2.5900
O2···N2^iii	3.120 (8)	H1C···O7^vii	2.7100
O2···Cl3	3.357 (6)	H1WB···C1^v	2.9800
O2···O4	2.748 (9)	H1WB···O1^v	2.3500
O2···O7^iii	3.213 (8)	H1WB···O3^v	2.6900
O3···O1	2.793 (8)	H1WB···Cu1^v	3.2400
O3···C1	3.370 (9)	H2A···C6	2.9700
O3···N2^iii	3.075 (7)	H2A···H6A	2.3400
O3···Cl3	3.193 (6)	H2A···O6^x	2.5000
O3···Cu1^ii	3.072 (5)	H2A···O8^x	2.8100
O3···O2	2.807 (7)	H2A···Cl2^xii	2.4900
O3···C1^ii	3.380 (9)	H2B···O7	2.1100
O4···C1^ii	3.410 (11)	H2B···O2^xii	2.7800
O4···Cu1^ii	3.193 (6)	H2B···O6	2.8800
O4···O2	2.748 (9)	H2B···H3B^xiii	2.3900
O4···O1W	3.234 (7)	H2B···Cl1	3.0100
O4···N1^iii	2.989 (9)	H2C···C6	3.0000
O4···Cl3	3.373 (5)	H2C···Cl3^xii	2.4600
O4···O1	2.751 (7)	H2C···O2^xii	2.6800
O5···O5^viii	3.075 (7)	H2C···O3^xii	2.5000
O5···N1^vii	3.074 (8)	H2C···H7A	2.3400
O5···N1^ix	3.015 (9)	H2C···Cu1^xii	2.9400
O5···C4^ix	3.215 (9)	H2C···H6A	2.5300
O5···C4^vii	3.414 (8)	H2D···N1	2.7000
O6···N2^x	3.146 (8)	H2D···H1A	2.1800
O6···C8	3.282 (10)	H2D···Cl3^xii	2.8000
O6···Cl2^xi	3.394 (6)	H2D···Cu2^iv	3.5700
O7···O2^xii	3.213 (8)	H2D···Cl2^iv	2.8200
O7···C5^xii	3.172 (9)	H2D···Cu2^xii	3.5700
O7···N2	2.956 (8)	H2E···H4A	2.4500
O7···C2^xiii	3.089 (8)	H2E···O7^xvi	2.6800
O7···N1^vii	3.155 (8)	H2E···O8^xvi	2.8200
O7···C1^xiii	2.904 (9)	H3A···O1^xii	2.8700
O8···C8^x	3.294 (9)	H3A···H1WA^ii	2.5600
O1···H1B^iii	2.1800	H3A···O2^ii	2.6600
O1···H3A^iii	2.8700	H3A···H1B	2.4000
O1···H1WB^iv	2.3500	H3A···O1W^ii	2.8300
O1W···H3A^ii	2.8300	H3B···H2B^xvi	2.3900
O2···H3B^ii	2.7500	H3B···O2^ii	2.7500
O2···H1WA	2.2500	H3B···O6^xvii	2.8700
O2···H2B^iii	2.7800	H3B···O7^xvi	2.8500
O2···H3A^ii	2.6600	H4A···O5^xv	2.5800
O2···H2C^iii	2.6800	H4A···H2E	2.4500
O3···H1WB^iv	2.6900	H4A···H8B^xvii	2.4300
O3···H7A^iii	2.9000	H4B···O8^vii	2.6900
O3···H2C^iii	2.5000	H6A···H2A	2.3400
O4···H7B^ii	2.8100	H6A···H2C	2.5300
O4···H7A^ii	2.6100	H6A···Cl2^xii	2.8900
O4···H1B^iii	2.4500	H6A···N2	2.6100
O4···H1WA	2.5000	H6A···Cl3^xii	3.0600
O5···H1C^vii	2.2600	H6B···H8A^iii	2.2900
O5···H1C^ix	2.5900	H6B···O7^iii	2.7900
O5···H1A^ix	2.9100	H7A···O4^ii	2.6100
O5···H4A^ix	2.5800	H7A···Cl3^xii	3.0800
O6···H3B^xiv	2.8700	H7A···O3^xii	2.9000
O6···H2B	2.8800	H7A···H2C	2.3400
O6···H2A^x	2.5000	H7B···H1C^xvi	2.4000
O6···H8A	2.8500	H7B···O4^ii	2.8100
O7···H2E^xiii	2.6800	H8A···O6	2.8500
O7···H2B	2.1100	H8A···C6^xii	3.0300
O7···H6B^xii	2.7900	H8A···H6B^xii	2.2900
O7···H1B^vii	2.8600	H8B···C4^xiv	2.9700
O7···H3B^xiii	2.8500	H8B···H4A^xiv	2.4300
O7···H1C^vii	2.7100	H8B···O8^x	2.5100
Cl3—Cu1—O1	93.59 (16)	C8—N2—H2A	109.00
Cl3—Cu1—O2	98.67 (16)	C8—N2—H2B	109.00
Cl3—Cu1—O3	92.31 (16)	C8—N2—H2C	109.00
Cl3—Cu1—O4	99.40 (17)	H2B—N2—H2C	109.00
O1—Cu1—O2	167.7 (2)	O2^ii—C1—C2	119.9 (6)
O1—Cu1—O3	90.3 (2)	O1—C1—C2	115.3 (7)
O1—Cu1—O4	88.6 (2)	O1—C1—O2^ii	124.8 (7)
O2—Cu1—O3	90.5 (2)	C1—C2—C3	114.4 (6)
O2—Cu1—O4	88.2 (2)	C2—C3—C4	112.1 (7)
O3—Cu1—O4	168.3 (2)	N1—C4—C3	110.5 (7)
Cl2—Cu2—Cl3	89.13 (7)	O3—C5—O4^ii	125.3 (7)
Cl2—Cu2—O1W	89.49 (19)	O3—C5—C6	116.8 (6)
Cl2—Cu2—Cl2^i	180.00	O4^ii—C5—C6	117.9 (7)
Cl2—Cu2—Cl3^i	90.87 (7)	C5—C6—C7	115.4 (6)
Cl2—Cu2—O1W^i	90.51 (19)	C6—C7—C8	112.9 (6)
Cl3—Cu2—O1W	91.17 (15)	N2—C8—C7	111.8 (7)
Cl2^i—Cu2—Cl3	90.87 (7)	C1—C2—H2D	109.00
Cl3—Cu2—Cl3^i	180.00	C1—C2—H2E	109.00
Cl3—Cu2—O1W^i	88.83 (15)	H2D—C2—H2E	108.00
Cl2^i—Cu2—O1W	90.51 (19)	C3—C2—H2E	109.00
Cl3^i—Cu2—O1W	88.83 (15)	C3—C2—H2D	109.00
O1W—Cu2—O1W^i	180.00	C4—C3—H3A	109.00
Cl2^i—Cu2—Cl3^i	89.13 (7)	C2—C3—H3B	109.00
Cl2^i—Cu2—O1W^i	89.49 (19)	C2—C3—H3A	109.00
Cl3^i—Cu2—O1W^i	91.17 (15)	C4—C3—H3B	109.00
Cu1—Cl3—Cu2	113.22 (6)	H3A—C3—H3B	108.00
O5—Cl1—O8	108.9 (3)	H4A—C4—H4B	108.00
O6—Cl1—O7	109.4 (3)	N1—C4—H4A	110.00
O6—Cl1—O8	110.2 (3)	N1—C4—H4B	110.00
O7—Cl1—O8	109.1 (3)	C3—C4—H4A	109.00
O5—Cl1—O6	111.2 (3)	C3—C4—H4B	110.00
O5—Cl1—O7	108.0 (3)	C5—C6—H6B	108.00
Cu1—O1—C1	124.4 (5)	C7—C6—H6A	108.00
Cu1—O2—C1^ii	122.7 (5)	C5—C6—H6A	108.00
Cu1—O3—C5	125.7 (5)	H6A—C6—H6B	107.00
Cu1—O4—C5^ii	120.6 (6)	C7—C6—H6B	108.00
H1WA—O1W—H1WB	104.00	C8—C7—H7A	109.00
Cu2—O1W—H1WB	124.00	C6—C7—H7B	109.00
Cu2—O1W—H1WA	133.00	C6—C7—H7A	109.00
H1A—N1—H1B	109.00	C8—C7—H7B	109.00
C4—N1—H1A	109.00	H7A—C7—H7B	108.00
C4—N1—H1C	109.00	H8A—C8—H8B	108.00
H1B—N1—H1C	109.00	N2—C8—H8A	109.00
H1A—N1—H1C	110.00	N2—C8—H8B	109.00
C4—N1—H1B	109.00	C7—C8—H8A	109.00
H2A—N2—H2C	110.00	C7—C8—H8B	109.00
H2A—N2—H2B	109.00
O1—Cu1—Cl3—Cu2	−131.91 (18)	Cl2^i—Cu2—Cl3—Cu1	81.65 (9)
O2—Cu1—Cl3—Cu2	46.8 (2)	O1W^i—Cu2—Cl3—Cu1	171.1 (2)
O3—Cu1—Cl3—Cu2	137.66 (17)	Cu1—O1—C1—C2	174.1 (5)
O4—Cu1—Cl3—Cu2	−42.78 (18)	Cu1—O1—C1—O2^ii	−3.6 (11)
Cl3—Cu1—O1—C1	−170.4 (6)	Cu1—O2—C1^ii—O1^ii	0.0 (12)
O3—Cu1—O1—C1	−78.0 (6)	Cu1—O2—C1^ii—C2^ii	177.6 (5)
O4—Cu1—O1—C1	90.3 (6)	Cu1—O3—C5—C6	−178.5 (5)
Cl3—Cu1—O2—C1^ii	172.2 (6)	Cu1—O3—C5—O4^ii	2.9 (11)
O3—Cu1—O2—C1^ii	79.8 (6)	Cu1—O4—C5^ii—O3^ii	2.5 (11)
O4—Cu1—O2—C1^ii	−88.6 (6)	Cu1—O4—C5^ii—C6^ii	−178.9 (5)
Cl3—Cu1—O3—C5	175.4 (6)	O1—C1—C2—C3	173.9 (7)
O1—Cu1—O3—C5	81.8 (6)	O2^ii—C1—C2—C3	−8.3 (11)
O2—Cu1—O3—C5	−85.9 (6)	C1—C2—C3—C4	−179.9 (7)
Cl3—Cu1—O4—C5^ii	−177.9 (5)	C2—C3—C4—N1	−68.8 (9)
O1—Cu1—O4—C5^ii	−84.5 (6)	O3—C5—C6—C7	170.5 (7)
O2—Cu1—O4—C5^ii	83.7 (6)	O4^ii—C5—C6—C7	−10.7 (10)
Cl2—Cu2—Cl3—Cu1	−98.35 (9)	C5—C6—C7—C8	−167.0 (7)
O1W—Cu2—Cl3—Cu1	−8.9 (2)	C6—C7—C8—N2	63.8 (8)

Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+2, −y+2, −z+1; (iii) x, −y+3/2, z−1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+2, y+1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+2, −y+1, −z+2; (viii) −x+1, −y+1, −z+2; (ix) x−1, y, z; (x) −x+1, −y+1, −z+1; (xi) −x+1, y−1/2, −z+1/2; (xii) x, −y+3/2, z+1/2; (xiii) −x+2, y−1/2, −z+3/2; (xiv) x−1, −y+3/2, z−1/2; (xv) x+1, y, z; (xvi) −x+2, y+1/2, −z+3/2; (xvii) x+1, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	1.0000	2.2500	3.046 (9)	135.00
O1W—H1WA···O4	1.0000	2.5000	3.234 (7)	130.00
N1—H1A···Cl2^iv	0.9100	2.3200	3.214 (6)	166.00
N1—H1B···O1^xii	0.9100	2.1800	3.075 (9)	169.00
N1—H1B···O4^xii	0.9100	2.4500	2.989 (9)	118.00
N1—H1C···O5^xv	0.9100	2.5900	3.015 (9)	109.00
N1—H1C···O5^vii	0.9100	2.2600	3.074 (8)	148.00
O1W—H1WB···O1^v	0.9900	2.3500	3.252 (7)	151.00
N2—H2A···O6^x	0.9100	2.5000	3.146 (8)	128.00
N2—H2A···Cl2^xii	0.9100	2.4900	3.245 (6)	140.00
N2—H2B···O7	0.9100	2.1100	2.956 (8)	154.00
N2—H2C···Cl3^xii	0.9100	2.4600	3.316 (7)	157.00
N2—H2C···O3^xii	0.9100	2.5000	3.075 (7)	122.00
C2—H2D···Cl2^iv	0.9900	2.8200	3.708 (7)	149.00
C2—H2D···Cl3^xii	0.9900	2.8000	3.511 (8)	129.00
C4—H4A···O5^xv	0.9900	2.5800	3.215 (9)	122.00
C6—H6A···N2	0.9900	2.6100	3.031 (9)	106.00
C8—H8B···O8^x	0.9900	2.5100	3.294 (9)	136.00

Symmetry codes: (iv) −x+2, y−1/2, −z+1/2; (v) −x+2, y+1/2, −z+1/2; (vii) −x+2, −y+1, −z+2; (x) −x+1, −y+1, −z+1; (xii) x, −y+3/2, z+1/2; (xv) x+1, y, z.