Poly[[μ-aqua-diaqua­bis­(μ-furan-2,5-dicarboxyl­ato-κ2O2:O5)bis­(1,10-phenanthroline-κ2N,N′)dicopper(II)] N,N-dimethyl­formamide monosolvate]

Li, Y.-F.; Qin, X.-L.; Xu, Y.; Yuan, Y.-P.; Gao, W.-Y.

doi:10.1107/S1600536812046041

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1484-m1485

doi:10.1107/S1600536812046041

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Poly[[μ-aqua-diaquabis(μ-furan-2,5-dicarboxylato-κ²O²:O⁵)bis(1,10-phenanthroline-κ²N,N′)dicopper(II)] N,N-dimethylformamide monosolvate]

Ya-Feng Li,^a ^* Xiao-Lin Qin,^a Yue Xu,^a Yong-Peng Yuan ^a and Wen-Yuan Gao ^a

^aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 25 October 2012; accepted 7 November 2012; online 14 November 2012)

The asymmetric unit of the title compound, {[Cu₂(C₆H₂O₅)₂(C₁₂H₈N₂)₂(H₂O)₃]·C₃H₇NO}_n, contains two Cu^II atoms, two furan-2,5-dicarboxylate (L) ligands, two 1,10-phenanthroline (phen) ligands, three coordinating water molecules and one N,N-dimethylformamide solvent molecule. Each Cu^II atom is coordinated by two N atoms from one phen ligand, two O atoms from two L ligands and two water molecules in a distorted octahedral geometry. The main difference between the environments of the two independent Cu atoms is in the Cu—O_water distances, which are 2.415 (2) and 2.639 (2) Å for one Cu^II atom and 2.3560 (19) and 2.911 (4) Å for the other. Ligands L and one independent water molecule bridge the Cu^II atoms, forming corrugated polymeric layers parallel to the ab plane. Intermolecular O—H⋯O and C—H⋯O hydrogen bonds consolidate the crystal packing.

Related literature

For a related structure, see: Li et al. (2012 ).

Experimental

Crystal data

[Cu₂(C₆H₂O₅)₂(C₁₂H₈N₂)₂(H₂O)₃]·C₃H₇NO
M_r = 922.78
Monoclinic, P 2₁ /c
a = 16.620 (3) Å
b = 11.600 (2) Å
c = 20.168 (4) Å
β = 92.41 (3)°
V = 3884.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 293 K
0.35 × 0.20 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.685, T_max = 0.826
36308 measured reflections
8855 independent reflections
6642 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.110
S = 1.05
8855 reflections
561 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O5ⁱ	0.84 (2)	1.88 (2)	2.715 (3)	170 (3)
O1W—H1B⋯O7	0.85 (2)	1.96 (2)	2.729 (3)	151 (3)
O2W—H2A⋯O10ⁱⁱ	0.88 (2)	1.98 (2)	2.729 (3)	143 (2)
O2W—H2B⋯O3Wⁱ	0.86 (2)	1.89 (2)	2.726 (3)	163 (3)
O3W—H3A⋯O2	0.85 (2)	2.14 (3)	2.694 (3)	123 (2)
O3W—H3B⋯O41ⁱⁱⁱ	0.88 (2)	1.88 (2)	2.758 (4)	178 (4)
C3—H3⋯O5ⁱ	0.93	2.53	3.424 (3)	161
C4—H4⋯O2ⁱ	0.93	2.44	3.287 (3)	152
C9—H9⋯O10^iv	0.93	2.33	3.193 (3)	155
C10—H10⋯O7^iv	0.93	2.41	3.324 (3)	168
C15—H15⋯O8^v	0.93	2.42	3.327 (4)	166
C18—H18⋯O5ⁱⁱⁱ	0.93	2.56	3.416 (4)	154
C20—H20⋯O2ⁱⁱⁱ	0.93	2.52	3.230 (4)	133
C21—H21⋯O41	0.93	2.54	3.349 (5)	146
C33—H33⋯O2W^vi	0.93	2.59	3.402 (5)	146
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) -x+1, -y+1, -z; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x, -y+1, -z; (vi) -x+2, -y+1, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046041/cv5353sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046041/cv5353Isup2.hkl

checkCIF report

Comment top

As the analogous structure of BDC (benzene-1,4-dicarboxyl acid), FDA (furan-2,5-dicarboxyl acid) attracts attention owing to the bond angle of two carboxyl groups about 126°. Recently, we utilized furan-2,5-dicarboxyl acid as the ligand to construct coordination polymers (Li et al., 2012). As an extension of that work, herewith we present the crystal structure of the title compound, [[CuL(H₂O)(phen)]₂^.H₂O]_n ^.nDMFA (L = furan-2,5-dicarboxylato, phen = 1,10-phenanthroline, DMFA = N,N-dimethylformamide) (I).

The asymmetric unit of (I) contains two Cu^II cations, two anionic ligands L, two ligands phen, three coordinated water molecules and one DMFA solvent molecule (Fig.1). Each copper center is coordinated by two N atoms from one phen ligand, two O atoms from two ligands L and two water molecules in a distorted octahedral geometry. The main difference in environment of two independent Cu atoms is the difference in Cu—O_water distances, which are equal to 2.415 (2) and 2.639 (2) Å for one Cu atom and 2.3560 (19) and 2.911 (4) Å for another. Ligands L and one independent water molecule bridge copper centers into corrugated polymeric layers prallel to ab plane (Fig.2). Intermolecular O—H···O and C—H···O hydrogen bonds (Table 1) consolidate the crystal packing.

Related literature top

For a related structure, see: Li et al. (2012).

Experimental top

Furan-2,5-dicarboxyl acid (0.0156 g, 0.10 mmol), Cu(NO₃)₂^.3H₂O (0.0244 g, 0.10 mmol), and 1,10-phenanthroline (0.0180, 0.10 mmol) were dissolved in DMFA (5 ml, 75 mmol) under stirring. The mixture with molar ratio of 1 (furan-2,5-dicarboxyl acid): 1 (Cu(NO₃)₂^.3H₂O): 1 (1,10-phenanthroline): 750 DMFA was layed under room temperature for 8 days. The blue block product was collected as a single phase.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of (I), showing the atomic labelling scheme and displacement ellipsoids drawn at the 50% probability level [symmetry codes: (i) 1 + x, y, z; (ii) 1 - x, 0.5 + y, 0.5 - z.]
	Fig. 2. A portion of the crystal packing of (I) viewed along the c axis and showing the coordination environment of Cu centers as polyhedron.

Poly[[µ-aqua-diaquabis(µ-furan-2,5-dicarboxylato- κ²O²:O⁵)bis(1,10-phenanthroline- κ²N,N')dicopper(II)] N,N-dimethylformamide monosolvate] top

Crystal data top

[Cu₂(C₆H₂O₅)₂(C₁₂H₈N₂)₂(H₂O)₃]·C₃H₇NO	F(000) = 1888
M_r = 922.78	D_x = 1.578 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 16.620 (3) Å	θ = 1.2–27.5°
b = 11.600 (2) Å	µ = 1.17 mm⁻¹
c = 20.168 (4) Å	T = 293 K
β = 92.41 (3)°	Block, blue
V = 3884.6 (13) Å³	0.35 × 0.20 × 0.17 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	8855 independent reflections
Radiation source: fine-focus sealed tube	6642 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 1.2°
ω scans	h = −20→21
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→15
T_min = 0.685, T_max = 0.826	l = −26→26
36308 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0551P)² + 1.1821P] where P = (F_o² + 2F_c²)/3
8855 reflections	(Δ/σ)_max = 0.001
561 parameters	Δρ_max = 0.65 e Å⁻³
13 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Cu₂(C₆H₂O₅)₂(C₁₂H₈N₂)₂(H₂O)₃]·C₃H₇NO	V = 3884.6 (13) Å³
M_r = 922.78	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.620 (3) Å	µ = 1.17 mm⁻¹
b = 11.600 (2) Å	T = 293 K
c = 20.168 (4) Å	0.35 × 0.20 × 0.17 mm
β = 92.41 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	8855 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	6642 reflections with I > 2σ(I)
T_min = 0.685, T_max = 0.826	R_int = 0.047
36308 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	13 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.65 e Å⁻³
8855 reflections	Δρ_min = −0.35 e Å⁻³
561 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	0.262045 (16)	0.46824 (3)	0.095417 (14)	0.03123 (9)
Cu2	0.778317 (16)	0.54556 (3)	0.415298 (14)	0.03424 (10)
O1	0.34174 (10)	0.45626 (16)	0.16869 (9)	0.0380 (4)
O2	0.40602 (11)	0.62411 (17)	0.15533 (10)	0.0467 (5)
O3	0.51971 (10)	0.55941 (14)	0.25061 (8)	0.0325 (4)
O4	0.68947 (10)	0.49579 (18)	0.35584 (9)	0.0412 (4)
O5	0.64533 (13)	0.66569 (18)	0.31577 (12)	0.0610 (6)
C1	0.39872 (14)	0.5275 (2)	0.17983 (11)	0.0313 (5)
C2	0.46290 (13)	0.4827 (2)	0.22686 (11)	0.0298 (5)
C3	0.47776 (14)	0.3759 (2)	0.25122 (12)	0.0350 (5)
H3	0.4478	0.3095	0.2425	0.042*
C4	0.54854 (14)	0.3858 (2)	0.29291 (12)	0.0348 (5)
H4	0.5740	0.3267	0.3169	0.042*
C5	0.57159 (14)	0.4961 (2)	0.29108 (11)	0.0305 (5)
C6	0.64101 (15)	0.5605 (2)	0.32343 (12)	0.0345 (5)
O6	0.17981 (10)	0.52844 (16)	0.15262 (9)	0.0369 (4)
O7	0.10622 (13)	0.36742 (18)	0.15767 (12)	0.0588 (6)
O8	0.00890 (10)	0.46740 (14)	0.24548 (8)	0.0315 (4)
O9	−0.14260 (11)	0.57111 (16)	0.34843 (10)	0.0405 (4)
O10	−0.11593 (13)	0.39158 (18)	0.31678 (12)	0.0612 (6)
C7	0.12146 (14)	0.4682 (2)	0.17212 (12)	0.0323 (5)
C8	0.06639 (13)	0.5318 (2)	0.21566 (12)	0.0300 (5)
C9	0.05879 (15)	0.6436 (2)	0.23144 (13)	0.0376 (6)
H9	0.0908	0.7041	0.2176	0.045*
C10	−0.00770 (15)	0.6518 (2)	0.27353 (13)	0.0377 (6)
H10	−0.0277	0.7185	0.2924	0.045*
C11	−0.03577 (13)	0.5440 (2)	0.28061 (11)	0.0297 (5)
C12	−0.10354 (14)	0.4955 (2)	0.31801 (12)	0.0323 (5)
N1	0.19302 (12)	0.4938 (2)	0.01174 (11)	0.0373 (5)
N2	0.34234 (12)	0.4163 (2)	0.02842 (11)	0.0367 (5)
C13	0.11996 (16)	0.5389 (3)	0.00524 (16)	0.0502 (7)
H13	0.0945	0.5630	0.0430	0.060*
C14	0.07967 (19)	0.5515 (3)	−0.05710 (18)	0.0649 (10)
H14	0.0285	0.5841	−0.0602	0.078*
C15	0.1155 (2)	0.5162 (4)	−0.11220 (18)	0.0689 (10)
H15	0.0887	0.5234	−0.1534	0.083*
C16	0.1937 (2)	0.4683 (3)	−0.10785 (15)	0.0551 (8)
C17	0.2383 (3)	0.4298 (4)	−0.16290 (16)	0.0724 (11)
H17	0.2149	0.4340	−0.2055	0.087*
C18	0.3126 (3)	0.3879 (3)	−0.15429 (16)	0.0687 (10)
H18	0.3399	0.3637	−0.1911	0.082*
C19	0.35201 (19)	0.3792 (3)	−0.08942 (15)	0.0514 (7)
C20	0.4306 (2)	0.3379 (3)	−0.07688 (19)	0.0665 (10)
H20	0.4610	0.3124	−0.1116	0.080*
C21	0.4615 (2)	0.3356 (3)	−0.0137 (2)	0.0688 (10)
H21	0.5132	0.3073	−0.0050	0.083*
C22	0.41626 (16)	0.3754 (3)	0.03824 (16)	0.0526 (8)
H22	0.4388	0.3732	0.0812	0.063*
C23	0.31052 (16)	0.4169 (2)	−0.03446 (13)	0.0385 (6)
C24	0.23022 (17)	0.4602 (2)	−0.04374 (13)	0.0396 (6)
N3	0.70653 (14)	0.5346 (2)	0.49399 (11)	0.0441 (6)
N4	0.85693 (13)	0.6052 (2)	0.48709 (12)	0.0446 (5)
C25	0.63292 (18)	0.4888 (4)	0.49529 (17)	0.0615 (9)
H25	0.6080	0.4631	0.4559	0.074*
C26	0.5921 (2)	0.4784 (4)	0.5545 (2)	0.0810 (13)
H26	0.5412	0.4451	0.5542	0.097*
C27	0.6266 (3)	0.5165 (4)	0.6111 (2)	0.0846 (14)
H27	0.5987	0.5114	0.6500	0.101*
C28	0.7044 (3)	0.5642 (3)	0.61325 (16)	0.0701 (11)
C29	0.7473 (3)	0.6017 (4)	0.67048 (18)	0.0837 (14)
H29	0.7229	0.5989	0.7111	0.100*
C30	0.8223 (3)	0.6412 (3)	0.66776 (16)	0.0811 (14)
H30	0.8484	0.6674	0.7066	0.097*
C31	0.8645 (3)	0.6449 (3)	0.60622 (18)	0.0682 (10)
C32	0.9437 (3)	0.6788 (4)	0.5992 (2)	0.0887 (14)
H32	0.9738	0.7038	0.6364	0.106*
C33	0.9790 (3)	0.6765 (4)	0.5388 (3)	0.0861 (14)
H33	1.0323	0.6991	0.5351	0.103*
C34	0.9324 (2)	0.6387 (3)	0.48203 (19)	0.0639 (9)
H34	0.9554	0.6375	0.4408	0.077*
C35	0.8235 (2)	0.6091 (3)	0.54787 (13)	0.0497 (7)
C36	0.74293 (19)	0.5699 (3)	0.55125 (13)	0.0478 (7)
O1W	0.23887 (10)	0.26884 (16)	0.10600 (9)	0.0363 (4)
H1A	0.2766 (12)	0.245 (2)	0.1317 (12)	0.044*
H1B	0.1959 (11)	0.275 (3)	0.1272 (12)	0.044*
O2W	0.81807 (12)	0.34807 (19)	0.43587 (11)	0.0526 (5)
H2A	0.8410 (17)	0.3280 (17)	0.3991 (11)	0.063*
H2B	0.7755 (13)	0.3099 (16)	0.4451 (15)	0.063*
O3W	0.30778 (18)	0.6991 (3)	0.05478 (13)	0.0923 (10)
H3A	0.346 (2)	0.725 (2)	0.0796 (14)	0.111*
H3B	0.324 (2)	0.696 (2)	0.0140 (10)	0.111*
O41	0.6377 (2)	0.3137 (3)	0.07231 (14)	0.1025 (10)
C41	0.6527 (3)	0.2954 (4)	0.1319 (2)	0.0811 (12)
H41	0.6138	0.3170	0.1614	0.097*
N41	0.71914 (18)	0.2478 (3)	0.15731 (15)	0.0652 (8)
C42	0.7841 (3)	0.2158 (4)	0.1167 (2)	0.0884 (13)
H42A	0.7954	0.1352	0.1224	0.106*
H42B	0.8311	0.2599	0.1295	0.106*
H42C	0.7693	0.2309	0.0710	0.106*
C43	0.7313 (3)	0.2344 (5)	0.2284 (2)	0.1029 (17)
H43A	0.7728	0.2862	0.2444	0.123*
H43B	0.7471	0.1565	0.2384	0.123*
H43C	0.6821	0.2517	0.2497	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02015 (14)	0.04554 (19)	0.02800 (15)	0.00042 (11)	0.00089 (11)	−0.00221 (13)
Cu2	0.02092 (15)	0.0551 (2)	0.02665 (15)	−0.00089 (12)	0.00027 (11)	−0.00304 (13)
O1	0.0264 (8)	0.0488 (11)	0.0381 (9)	−0.0065 (7)	−0.0071 (7)	0.0013 (8)
O2	0.0433 (10)	0.0450 (11)	0.0507 (11)	−0.0018 (9)	−0.0121 (9)	0.0099 (9)
O3	0.0292 (8)	0.0323 (9)	0.0350 (9)	−0.0030 (7)	−0.0098 (7)	0.0003 (7)
O4	0.0298 (9)	0.0540 (11)	0.0388 (10)	−0.0016 (8)	−0.0115 (8)	0.0034 (9)
O5	0.0560 (13)	0.0407 (12)	0.0833 (16)	−0.0055 (10)	−0.0351 (12)	−0.0044 (11)
C1	0.0266 (11)	0.0412 (14)	0.0259 (11)	0.0018 (10)	−0.0007 (9)	−0.0059 (10)
C2	0.0228 (10)	0.0384 (13)	0.0280 (11)	−0.0051 (9)	−0.0003 (9)	−0.0043 (10)
C3	0.0319 (12)	0.0349 (13)	0.0380 (13)	−0.0050 (10)	−0.0016 (10)	−0.0012 (11)
C4	0.0323 (12)	0.0369 (13)	0.0350 (12)	0.0014 (10)	−0.0027 (10)	0.0044 (11)
C5	0.0252 (11)	0.0370 (13)	0.0288 (11)	0.0002 (10)	−0.0050 (9)	−0.0004 (10)
C6	0.0302 (12)	0.0430 (15)	0.0296 (12)	−0.0007 (11)	−0.0058 (10)	−0.0038 (11)
O6	0.0271 (8)	0.0448 (11)	0.0395 (9)	−0.0021 (7)	0.0106 (7)	−0.0035 (8)
O7	0.0561 (13)	0.0419 (12)	0.0816 (16)	−0.0090 (10)	0.0394 (12)	−0.0160 (11)
O8	0.0282 (8)	0.0338 (9)	0.0334 (8)	0.0005 (7)	0.0106 (7)	−0.0026 (7)
O9	0.0346 (9)	0.0388 (10)	0.0494 (11)	0.0030 (8)	0.0188 (8)	−0.0034 (8)
O10	0.0621 (13)	0.0383 (11)	0.0867 (16)	−0.0095 (10)	0.0429 (13)	−0.0124 (11)
C7	0.0280 (11)	0.0409 (14)	0.0283 (11)	0.0035 (10)	0.0040 (9)	0.0012 (11)
C8	0.0229 (10)	0.0362 (13)	0.0313 (11)	−0.0007 (9)	0.0056 (9)	0.0054 (10)
C9	0.0326 (12)	0.0360 (14)	0.0448 (14)	−0.0007 (10)	0.0086 (11)	0.0062 (11)
C10	0.0361 (13)	0.0332 (13)	0.0448 (14)	0.0054 (10)	0.0130 (11)	−0.0004 (11)
C11	0.0249 (11)	0.0349 (13)	0.0295 (11)	0.0041 (9)	0.0043 (9)	−0.0009 (10)
C12	0.0268 (11)	0.0376 (14)	0.0328 (12)	0.0001 (10)	0.0045 (10)	−0.0025 (11)
N1	0.0281 (10)	0.0477 (13)	0.0360 (11)	−0.0030 (9)	−0.0001 (9)	0.0071 (10)
N2	0.0289 (10)	0.0427 (12)	0.0391 (11)	−0.0007 (9)	0.0068 (9)	−0.0002 (10)
C13	0.0308 (13)	0.065 (2)	0.0545 (17)	0.0023 (13)	−0.0026 (12)	0.0159 (15)
C14	0.0389 (16)	0.085 (3)	0.069 (2)	−0.0039 (16)	−0.0200 (16)	0.0269 (19)
C15	0.063 (2)	0.090 (3)	0.0510 (19)	−0.016 (2)	−0.0246 (17)	0.0140 (19)
C16	0.063 (2)	0.062 (2)	0.0390 (15)	−0.0121 (16)	−0.0092 (14)	0.0043 (14)
C17	0.102 (3)	0.084 (3)	0.0308 (15)	−0.016 (2)	−0.0045 (18)	−0.0045 (16)
C18	0.098 (3)	0.076 (3)	0.0338 (16)	−0.009 (2)	0.0204 (18)	−0.0112 (16)
C19	0.0619 (19)	0.0504 (18)	0.0436 (16)	−0.0086 (14)	0.0227 (14)	−0.0066 (13)
C20	0.064 (2)	0.070 (2)	0.069 (2)	−0.0006 (17)	0.0360 (19)	−0.0154 (18)
C21	0.0406 (17)	0.081 (3)	0.086 (3)	0.0116 (16)	0.0205 (17)	−0.012 (2)
C22	0.0337 (14)	0.067 (2)	0.0572 (18)	0.0096 (13)	0.0067 (13)	−0.0044 (16)
C23	0.0420 (14)	0.0387 (14)	0.0354 (13)	−0.0076 (11)	0.0082 (11)	−0.0020 (11)
C24	0.0449 (15)	0.0433 (15)	0.0304 (12)	−0.0112 (12)	−0.0012 (11)	0.0015 (11)
N3	0.0367 (12)	0.0621 (16)	0.0340 (11)	0.0132 (11)	0.0054 (9)	0.0039 (11)
N4	0.0375 (12)	0.0483 (14)	0.0468 (13)	0.0019 (10)	−0.0143 (10)	−0.0010 (11)
C25	0.0352 (15)	0.094 (3)	0.0561 (19)	0.0088 (16)	0.0133 (14)	0.0140 (18)
C26	0.052 (2)	0.128 (4)	0.065 (2)	0.020 (2)	0.0275 (19)	0.022 (2)
C27	0.074 (3)	0.121 (4)	0.062 (2)	0.042 (3)	0.038 (2)	0.019 (2)
C28	0.106 (3)	0.071 (2)	0.0335 (15)	0.039 (2)	0.0108 (18)	0.0031 (15)
C29	0.125 (4)	0.086 (3)	0.0391 (19)	0.035 (3)	0.002 (2)	−0.0050 (19)
C30	0.144 (4)	0.067 (2)	0.0304 (16)	0.027 (3)	−0.026 (2)	−0.0117 (15)
C31	0.095 (3)	0.0497 (19)	0.057 (2)	0.0103 (19)	−0.035 (2)	−0.0083 (16)
C32	0.123 (4)	0.070 (3)	0.069 (3)	−0.008 (3)	−0.049 (3)	−0.005 (2)
C33	0.065 (2)	0.071 (3)	0.118 (4)	−0.017 (2)	−0.044 (2)	0.003 (3)
C34	0.0469 (18)	0.068 (2)	0.075 (2)	−0.0107 (16)	−0.0198 (16)	0.0042 (18)
C35	0.073 (2)	0.0410 (15)	0.0330 (14)	0.0157 (15)	−0.0177 (14)	−0.0027 (12)
C36	0.0608 (19)	0.0508 (17)	0.0318 (13)	0.0207 (15)	0.0020 (13)	0.0019 (12)
O1W	0.0258 (8)	0.0385 (10)	0.0445 (10)	−0.0016 (8)	0.0001 (7)	0.0031 (8)
O2W	0.0401 (11)	0.0572 (13)	0.0609 (13)	−0.0075 (9)	0.0050 (10)	0.0044 (11)
O3W	0.087 (2)	0.128 (3)	0.0601 (16)	0.0616 (19)	−0.0142 (14)	−0.0162 (17)
O41	0.115 (2)	0.133 (3)	0.0584 (17)	0.014 (2)	−0.0119 (16)	0.0129 (18)
C41	0.077 (3)	0.102 (3)	0.065 (2)	0.016 (2)	0.005 (2)	−0.004 (2)
N41	0.0630 (17)	0.074 (2)	0.0591 (17)	0.0050 (15)	0.0052 (14)	−0.0023 (15)
C42	0.085 (3)	0.072 (3)	0.111 (3)	−0.008 (2)	0.033 (3)	−0.013 (3)
C43	0.090 (3)	0.149 (5)	0.069 (3)	0.038 (3)	−0.004 (2)	−0.002 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.9475 (18)	C17—C18	1.332 (6)
Cu1—O6	1.9542 (17)	C17—H17	0.9300
Cu1—N1	2.022 (2)	C18—C19	1.442 (5)
Cu1—N2	2.030 (2)	C18—H18	0.9300
Cu1—O1W	2.3560 (19)	C19—C23	1.400 (4)
Cu1—O3W	2.911 (4)	C19—C20	1.404 (5)
Cu2—O9ⁱ	1.9449 (18)	C20—C21	1.353 (5)
Cu2—O4	1.9501 (18)	C20—H20	0.9300
Cu2—N3	2.029 (2)	C21—C22	1.394 (4)
Cu2—N4	2.031 (2)	C21—H21	0.9300
Cu2—O2W	2.415 (2)	C22—H22	0.9300
Cu2—O1Wⁱⁱ	2.639 (2)	C23—C24	1.431 (4)
O1—C1	1.270 (3)	N3—C25	1.335 (4)
O2—C1	1.232 (3)	N3—C36	1.345 (4)
O3—C2	1.369 (3)	N4—C34	1.321 (4)
O3—C5	1.375 (3)	N4—C35	1.368 (4)
O4—C6	1.263 (3)	C25—C26	1.403 (4)
O5—C6	1.233 (3)	C25—H25	0.9300
C1—O2	1.232 (3)	C26—C27	1.332 (6)
C1—C2	1.491 (3)	C26—H26	0.9300
C2—C3	1.352 (3)	C27—C28	1.405 (6)
C3—C4	1.422 (3)	C27—H27	0.9300
C3—H3	0.9300	C28—C29	1.400 (6)
C4—C5	1.337 (4)	C28—C36	1.430 (4)
C4—H4	0.9300	C29—C30	1.332 (6)
C5—C6	1.501 (3)	C29—H29	0.9300
C6—O4	1.263 (3)	C30—C31	1.453 (6)
O6—C7	1.271 (3)	C30—H30	0.9300
O7—C7	1.228 (3)	C31—C32	1.386 (6)
O8—C8	1.371 (3)	C31—C35	1.398 (4)
O8—C11	1.373 (3)	C32—C33	1.374 (6)
O9—C12	1.265 (3)	C32—H32	0.9300
O10—C12	1.223 (3)	C33—C34	1.424 (5)
C7—O7	1.228 (3)	C33—H33	0.9300
C7—C8	1.490 (3)	C34—H34	0.9300
C8—C9	1.343 (4)	C35—C36	1.419 (5)
C9—C10	1.425 (3)	O1W—H1A	0.843 (16)
C9—H9	0.9300	O1W—H1B	0.851 (16)
C10—C11	1.345 (4)	O2W—H2A	0.880 (16)
C10—H10	0.9300	O2W—H2B	0.862 (16)
C11—C12	1.491 (3)	O3W—H3A	0.846 (17)
N1—C13	1.324 (3)	O3W—H3B	0.878 (18)
N1—C24	1.358 (3)	O41—C41	1.236 (5)
N2—C22	1.324 (3)	C41—N41	1.319 (5)
N2—C23	1.353 (3)	C41—H41	0.9300
C13—C14	1.407 (4)	N41—C42	1.431 (5)
C13—H13	0.9300	N41—C43	1.449 (5)
C14—C15	1.347 (5)	C42—H42A	0.9600
C14—H14	0.9300	C42—H42B	0.9600
C15—C16	1.413 (5)	C42—H42C	0.9600
C15—H15	0.9300	C43—H43A	0.9600
C16—C24	1.408 (4)	C43—H43B	0.9600
C16—C17	1.432 (5)	C43—H43C	0.9600

O1—Cu1—O6	92.74 (8)	C16—C15—H15	119.8
O1—Cu1—N1	170.97 (8)	C24—C16—C15	116.3 (3)
O6—Cu1—N1	93.10 (8)	C24—C16—C17	118.3 (3)
O1—Cu1—N2	92.22 (8)	C15—C16—C17	125.4 (3)
O6—Cu1—N2	174.04 (9)	C18—C17—C16	121.3 (3)
N1—Cu1—N2	81.59 (9)	C18—C17—H17	119.3
O1—Cu1—O1W	88.27 (7)	C16—C17—H17	119.3
O6—Cu1—O1W	100.15 (7)	C17—C18—C19	121.8 (3)
N1—Cu1—O1W	97.48 (8)	C17—C18—H18	119.1
N2—Cu1—O1W	83.30 (8)	C19—C18—H18	119.1
O1—Cu1—O3W	95.85 (8)	C23—C19—C20	116.7 (3)
O6—Cu1—O3W	92.00 (7)	C23—C19—C18	118.5 (3)
N1—Cu1—O3W	77.06 (8)	C20—C19—C18	124.8 (3)
N2—Cu1—O3W	84.21 (8)	C21—C20—C19	119.3 (3)
O1W—Cu1—O3W	166.98 (7)	C21—C20—H20	120.3
O9ⁱ—Cu2—O4	97.76 (8)	C19—C20—H20	120.3
O9ⁱ—Cu2—O4	97.76 (8)	C20—C21—C22	120.3 (3)
O4—Cu2—O4	0.00 (13)	C20—C21—H21	119.8
O9ⁱ—Cu2—N3	171.30 (9)	C22—C21—H21	119.8
O4—Cu2—N3	90.43 (9)	N2—C22—C21	122.2 (3)
O4—Cu2—N3	90.43 (9)	N2—C22—H22	118.9
O9ⁱ—Cu2—N4	90.52 (9)	C21—C22—H22	118.9
O4—Cu2—N4	170.84 (9)	N2—C23—C19	123.7 (3)
O4—Cu2—N4	170.84 (9)	N2—C23—C24	116.7 (2)
N3—Cu2—N4	81.11 (10)	C19—C23—C24	119.6 (3)
O9ⁱ—Cu2—O2W	94.34 (7)	N1—C24—C16	123.0 (3)
O4—Cu2—O2W	91.11 (8)	N1—C24—C23	116.6 (2)
O4—Cu2—O2W	91.11 (8)	C16—C24—C23	120.5 (3)
N3—Cu2—O2W	88.39 (9)	C25—N3—C36	118.9 (3)
N4—Cu2—O2W	92.15 (9)	C25—N3—Cu2	127.6 (2)
O9ⁱ—Cu2—O1Wⁱⁱ	79.01 (7)	C36—N3—Cu2	113.2 (2)
O4—Cu2—O1Wⁱⁱ	96.69 (7)	C34—N4—C35	118.8 (3)
O4—Cu2—O1Wⁱⁱ	96.69 (7)	C34—N4—Cu2	129.0 (2)
N3—Cu2—O1Wⁱⁱ	97.21 (8)	C35—N4—Cu2	112.15 (19)
N4—Cu2—O1Wⁱⁱ	81.01 (8)	N3—C25—C26	121.8 (4)
O2W—Cu2—O1Wⁱⁱ	170.34 (6)	N3—C25—H25	119.1
C1—O1—Cu1	124.47 (16)	C26—C25—H25	119.1
C2—O3—C5	105.45 (18)	C27—C26—C25	119.7 (4)
C6—O4—Cu2	126.33 (18)	C27—C26—H26	120.2
O2—C1—O1	127.3 (2)	C25—C26—H26	120.2
O2—C1—O1	127.3 (2)	C26—C27—C28	121.3 (3)
O2—C1—C2	119.5 (2)	C26—C27—H27	119.4
O2—C1—C2	119.5 (2)	C28—C27—H27	119.4
O1—C1—C2	113.2 (2)	C29—C28—C27	125.7 (4)
C3—C2—O3	110.8 (2)	C29—C28—C36	118.4 (4)
C3—C2—C1	131.7 (2)	C27—C28—C36	115.9 (3)
O3—C2—C1	117.4 (2)	C30—C29—C28	121.2 (4)
C2—C3—C4	106.0 (2)	C30—C29—H29	119.4
C2—C3—H3	127.0	C28—C29—H29	119.4
C4—C3—H3	127.0	C29—C30—C31	122.2 (3)
C5—C4—C3	107.0 (2)	C29—C30—H30	118.9
C5—C4—H4	126.5	C31—C30—H30	118.9
C3—C4—H4	126.5	C32—C31—C35	115.4 (4)
C4—C5—O3	110.8 (2)	C32—C31—C30	126.2 (4)
C4—C5—C6	132.9 (2)	C35—C31—C30	118.3 (4)
O3—C5—C6	116.3 (2)	C33—C32—C31	121.8 (4)
O5—C6—O4	127.9 (2)	C33—C32—H32	119.1
O5—C6—O4	127.9 (2)	C31—C32—H32	119.1
O5—C6—C5	119.1 (2)	C32—C33—C34	118.7 (4)
O4—C6—C5	113.0 (2)	C32—C33—H33	120.6
O4—C6—C5	113.0 (2)	C34—C33—H33	120.6
C7—O6—Cu1	123.21 (16)	N4—C34—C33	120.9 (4)
C8—O8—C11	106.02 (18)	N4—C34—H34	119.5
C12—O9—Cu2ⁱⁱⁱ	127.33 (17)	C33—C34—H34	119.5
O7—C7—O6	127.0 (2)	N4—C35—C31	124.2 (3)
O7—C7—O6	127.0 (2)	N4—C35—C36	116.9 (2)
O7—C7—C8	119.0 (2)	C31—C35—C36	118.9 (3)
O7—C7—C8	119.0 (2)	N3—C36—C35	116.6 (2)
O6—C7—C8	113.9 (2)	N3—C36—C28	122.3 (3)
C9—C8—O8	110.3 (2)	C35—C36—C28	121.0 (3)
C9—C8—C7	133.2 (2)	Cu1—O1W—H1A	105 (2)
O8—C8—C7	116.5 (2)	Cu1—O1W—H1B	96 (2)
C8—C9—C10	106.8 (2)	H1A—O1W—H1B	110 (2)
C8—C9—H9	126.6	Cu2—O2W—H2A	103.3 (14)
C10—C9—H9	126.6	Cu2—O2W—H2B	107.6 (14)
C11—C10—C9	106.4 (2)	H2A—O2W—H2B	116 (2)
C11—C10—H10	126.8	Cu1—O3W—H3A	111.3 (17)
C9—C10—H10	126.8	Cu1—O3W—H3B	108.4 (16)
C10—C11—O8	110.5 (2)	H3A—O3W—H3B	108 (2)
C10—C11—C12	132.6 (2)	O41—C41—N41	125.6 (4)
O8—C11—C12	117.0 (2)	O41—C41—H41	117.2
O10—C12—O9	127.1 (2)	N41—C41—H41	117.2
O10—C12—C11	119.4 (2)	C41—N41—C42	121.7 (4)
O9—C12—C11	113.5 (2)	C41—N41—C43	120.6 (3)
C13—N1—C24	118.6 (2)	C42—N41—C43	117.5 (4)
C13—N1—Cu1	128.8 (2)	N41—C42—H42A	109.5
C24—N1—Cu1	112.57 (17)	N41—C42—H42B	109.5
C22—N2—C23	117.8 (2)	H42A—C42—H42B	109.5
C22—N2—Cu1	129.7 (2)	N41—C42—H42C	109.5
C23—N2—Cu1	112.34 (17)	H42A—C42—H42C	109.5
N1—C13—C14	122.0 (3)	H42B—C42—H42C	109.5
N1—C13—H13	119.0	N41—C43—H43A	109.5
C14—C13—H13	119.0	N41—C43—H43B	109.5
C15—C14—C13	119.7 (3)	H43A—C43—H43B	109.5
C15—C14—H14	120.2	N41—C43—H43C	109.5
C13—C14—H14	120.2	H43A—C43—H43C	109.5
C14—C15—C16	120.4 (3)	H43B—C43—H43C	109.5
C14—C15—H15	119.8

O6—Cu1—O1—C1	−101.97 (19)	C13—C14—C15—C16	−1.0 (6)
N2—Cu1—O1—C1	74.7 (2)	C14—C15—C16—C24	0.1 (5)
O1W—Cu1—O1—C1	157.95 (19)	C14—C15—C16—C17	−178.8 (4)
O3W—Cu1—O1—C1	−9.7 (2)	C24—C16—C17—C18	−0.4 (6)
O9ⁱ—Cu2—O4—O4	0.00 (13)	C15—C16—C17—C18	178.5 (4)
N3—Cu2—O4—O4	0.00 (12)	C16—C17—C18—C19	0.0 (6)
O2W—Cu2—O4—O4	0.00 (12)	C17—C18—C19—C23	−0.5 (5)
O1Wⁱⁱ—Cu2—O4—O4	0.00 (13)	C17—C18—C19—C20	−178.9 (4)
O9ⁱ—Cu2—O4—C6	−83.2 (2)	C23—C19—C20—C21	0.5 (5)
O4—Cu2—O4—C6	0 (17)	C18—C19—C20—C21	178.9 (4)
N3—Cu2—O4—C6	93.9 (2)	C19—C20—C21—C22	−0.9 (6)
O2W—Cu2—O4—C6	−177.7 (2)	C23—N2—C22—C21	1.0 (5)
O1Wⁱⁱ—Cu2—O4—C6	−3.4 (2)	Cu1—N2—C22—C21	175.2 (3)
O2—O2—C1—O1	0.0 (2)	C20—C21—C22—N2	0.2 (6)
O2—O2—C1—C2	0.0 (3)	C22—N2—C23—C19	−1.4 (4)
Cu1—O1—C1—O2	13.8 (4)	Cu1—N2—C23—C19	−176.6 (2)
Cu1—O1—C1—O2	13.8 (4)	C22—N2—C23—C24	179.3 (3)
Cu1—O1—C1—C2	−164.53 (15)	Cu1—N2—C23—C24	4.1 (3)
C5—O3—C2—C3	0.2 (3)	C20—C19—C23—N2	0.7 (4)
C5—O3—C2—C1	−178.82 (19)	C18—C19—C23—N2	−177.8 (3)
O2—C1—C2—C3	−166.5 (3)	C20—C19—C23—C24	179.9 (3)
O2—C1—C2—C3	−166.5 (3)	C18—C19—C23—C24	1.4 (4)
O1—C1—C2—C3	11.9 (4)	C13—N1—C24—C16	−1.8 (4)
O2—C1—C2—O3	12.3 (3)	Cu1—N1—C24—C16	179.2 (2)
O2—C1—C2—O3	12.3 (3)	C13—N1—C24—C23	177.2 (3)
O1—C1—C2—O3	−169.3 (2)	Cu1—N1—C24—C23	−1.8 (3)
O3—C2—C3—C4	−0.1 (3)	C15—C16—C24—N1	1.3 (4)
C1—C2—C3—C4	178.7 (2)	C17—C16—C24—N1	−179.7 (3)
C2—C3—C4—C5	0.0 (3)	C15—C16—C24—C23	−177.6 (3)
C3—C4—C5—O3	0.2 (3)	C17—C16—C24—C23	1.4 (4)
C3—C4—C5—C6	−179.4 (3)	N2—C23—C24—N1	−1.6 (4)
C2—O3—C5—C4	−0.2 (3)	C19—C23—C24—N1	179.1 (3)
C2—O3—C5—C6	179.4 (2)	N2—C23—C24—C16	177.4 (3)
O4—O4—C6—O5	0.0 (2)	C19—C23—C24—C16	−1.9 (4)
Cu2—O4—C6—O5	10.0 (4)	O4—Cu2—N3—C25	9.8 (3)
Cu2—O4—C6—O4	0 (100)	O4—Cu2—N3—C25	9.8 (3)
O4—O4—C6—C5	0.00 (13)	N4—Cu2—N3—C25	−173.8 (3)
Cu2—O4—C6—C5	−170.59 (15)	O2W—Cu2—N3—C25	−81.3 (3)
C4—C5—C6—O5	−176.0 (3)	O1Wⁱⁱ—Cu2—N3—C25	106.6 (3)
O3—C5—C6—O5	4.5 (4)	O4—Cu2—N3—C36	−176.3 (2)
C4—C5—C6—O4	4.5 (4)	O4—Cu2—N3—C36	−176.3 (2)
O3—C5—C6—O4	−175.0 (2)	N4—Cu2—N3—C36	0.2 (2)
C4—C5—C6—O4	4.5 (4)	O2W—Cu2—N3—C36	92.6 (2)
O3—C5—C6—O4	−175.0 (2)	O1Wⁱⁱ—Cu2—N3—C36	−79.5 (2)
O1—Cu1—O6—C7	−104.07 (19)	O9ⁱ—Cu2—N4—C34	−3.3 (3)
N1—Cu1—O6—C7	82.8 (2)	N3—Cu2—N4—C34	179.1 (3)
O1W—Cu1—O6—C7	−15.3 (2)	O2W—Cu2—N4—C34	91.1 (3)
O3W—Cu1—O6—C7	159.97 (19)	O1Wⁱⁱ—Cu2—N4—C34	−82.1 (3)
O7—O7—C7—O6	0.0 (3)	O9ⁱ—Cu2—N4—C35	176.79 (19)
O7—O7—C7—C8	0.0 (2)	N3—Cu2—N4—C35	−0.81 (19)
Cu1—O6—C7—O7	−2.0 (4)	O2W—Cu2—N4—C35	−88.8 (2)
Cu1—O6—C7—O7	−2.0 (4)	O1Wⁱⁱ—Cu2—N4—C35	98.01 (19)
Cu1—O6—C7—C8	179.69 (15)	C36—N3—C25—C26	1.1 (5)
C11—O8—C8—C9	0.3 (3)	Cu2—N3—C25—C26	174.8 (3)
C11—O8—C8—C7	−177.9 (2)	N3—C25—C26—C27	1.0 (6)
O7—C7—C8—C9	−167.6 (3)	C25—C26—C27—C28	−1.8 (7)
O7—C7—C8—C9	−167.6 (3)	C26—C27—C28—C29	−176.9 (4)
O6—C7—C8—C9	10.9 (4)	C26—C27—C28—C36	0.5 (6)
O7—C7—C8—O8	10.1 (4)	C27—C28—C29—C30	177.0 (4)
O7—C7—C8—O8	10.1 (4)	C36—C28—C29—C30	−0.3 (6)
O6—C7—C8—O8	−171.4 (2)	C28—C29—C30—C31	−1.8 (7)
O8—C8—C9—C10	−0.3 (3)	C29—C30—C31—C32	−176.4 (4)
C7—C8—C9—C10	177.5 (3)	C29—C30—C31—C35	2.2 (6)
C8—C9—C10—C11	0.2 (3)	C35—C31—C32—C33	−0.3 (6)
C9—C10—C11—O8	0.0 (3)	C30—C31—C32—C33	178.4 (4)
C9—C10—C11—C12	−180.0 (3)	C31—C32—C33—C34	0.4 (6)
C8—O8—C11—C10	−0.2 (3)	C35—N4—C34—C33	1.0 (5)
C8—O8—C11—C12	179.8 (2)	Cu2—N4—C34—C33	−178.9 (3)
Cu2ⁱⁱⁱ—O9—C12—O10	12.0 (4)	C32—C33—C34—N4	−0.7 (6)
Cu2ⁱⁱⁱ—O9—C12—C11	−167.91 (16)	C34—N4—C35—C31	−1.0 (5)
C10—C11—C12—O10	−179.1 (3)	Cu2—N4—C35—C31	178.9 (2)
O8—C11—C12—O10	0.9 (4)	C34—N4—C35—C36	−178.6 (3)
C10—C11—C12—O9	0.8 (4)	Cu2—N4—C35—C36	1.3 (3)
O8—C11—C12—O9	−179.1 (2)	C32—C31—C35—N4	0.7 (5)
O6—Cu1—N1—C13	1.5 (3)	C30—C31—C35—N4	−178.1 (3)
N2—Cu1—N1—C13	−175.8 (3)	C32—C31—C35—C36	178.2 (3)
O1W—Cu1—N1—C13	102.2 (3)	C30—C31—C35—C36	−0.6 (5)
O3W—Cu1—N1—C13	−89.8 (3)	C25—N3—C36—C35	175.0 (3)
O6—Cu1—N1—C24	−179.65 (18)	Cu2—N3—C36—C35	0.4 (3)
N2—Cu1—N1—C24	3.06 (18)	C25—N3—C36—C28	−2.4 (4)
O1W—Cu1—N1—C24	−78.98 (18)	Cu2—N3—C36—C28	−177.0 (2)
O3W—Cu1—N1—C24	89.01 (18)	N4—C35—C36—N3	−1.2 (4)
O1—Cu1—N2—C22	8.2 (3)	C31—C35—C36—N3	−178.9 (3)
N1—Cu1—N2—C22	−178.4 (3)	N4—C35—C36—C28	176.3 (3)
O1W—Cu1—N2—C22	−79.8 (3)	C31—C35—C36—C28	−1.5 (4)
O3W—Cu1—N2—C22	103.9 (3)	C29—C28—C36—N3	179.3 (3)
O1—Cu1—N2—C23	−177.29 (18)	C27—C28—C36—N3	1.6 (5)
N1—Cu1—N2—C23	−3.90 (18)	C29—C28—C36—C35	2.0 (5)
O1W—Cu1—N2—C23	94.72 (18)	C27—C28—C36—C35	−175.7 (3)
O3W—Cu1—N2—C23	−81.63 (18)	O41—O41—C41—N41	0.0 (3)
C24—N1—C13—C14	0.9 (4)	O41—C41—N41—C42	2.6 (7)
Cu1—N1—C13—C14	179.6 (2)	O41—C41—N41—C43	177.8 (5)
N1—C13—C14—C15	0.5 (5)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O5^iv	0.84 (2)	1.88 (2)	2.715 (3)	170 (3)
O1W—H1B···O7	0.85 (2)	1.96 (2)	2.729 (3)	151 (3)
O2W—H2A···O10ⁱ	0.88 (2)	1.98 (2)	2.729 (3)	143 (2)
O2W—H2B···O3W^iv	0.86 (2)	1.89 (2)	2.726 (3)	163 (3)
O3W—H3A···O2	0.85 (2)	2.14 (3)	2.694 (3)	123 (2)
O3W—H3B···O41^v	0.88 (2)	1.88 (2)	2.758 (4)	178 (4)
C3—H3···O5^iv	0.93	2.53	3.424 (3)	161
C4—H4···O2^iv	0.93	2.44	3.287 (3)	152
C9—H9···O10^vi	0.93	2.33	3.193 (3)	155
C10—H10···O7^vi	0.93	2.41	3.324 (3)	168
C15—H15···O8^vii	0.93	2.42	3.327 (4)	166
C18—H18···O5^v	0.93	2.56	3.416 (4)	154
C20—H20···O2^v	0.93	2.52	3.230 (4)	133
C21—H21···O41	0.93	2.54	3.349 (5)	146
C33—H33···O2W^viii	0.93	2.59	3.402 (5)	146

Symmetry codes: (i) x+1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) −x, y+1/2, −z+1/2; (vii) −x, −y+1, −z; (viii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₆H₂O₅)₂(C₁₂H₈N₂)₂(H₂O)₃]·C₃H₇NO
M_r	922.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	16.620 (3), 11.600 (2), 20.168 (4)
β (°)	92.41 (3)
V (Å³)	3884.6 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.35 × 0.20 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.685, 0.826
No. of measured, independent and observed [I > 2σ(I)] reflections	36308, 8855, 6642
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.110, 1.05
No. of reflections	8855
No. of parameters	561
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.35

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O5ⁱ	0.843 (16)	1.880 (17)	2.715 (3)	170 (3)
O1W—H1B···O7	0.851 (16)	1.955 (19)	2.729 (3)	151 (3)
O2W—H2A···O10ⁱⁱ	0.880 (16)	1.98 (2)	2.729 (3)	142.6 (18)
O2W—H2B···O3Wⁱ	0.862 (16)	1.889 (18)	2.726 (3)	163 (3)
O3W—H3A···O2	0.846 (17)	2.14 (3)	2.694 (3)	123 (2)
O3W—H3B···O41ⁱⁱⁱ	0.878 (18)	1.880 (18)	2.758 (4)	178 (4)
C3—H3···O5ⁱ	0.93	2.53	3.424 (3)	161.1
C4—H4···O2ⁱ	0.93	2.44	3.287 (3)	152.3
C9—H9···O10^iv	0.93	2.33	3.193 (3)	155.1
C10—H10···O7^iv	0.93	2.41	3.324 (3)	167.5
C15—H15···O8^v	0.93	2.42	3.327 (4)	166.4
C18—H18···O5ⁱⁱⁱ	0.93	2.56	3.416 (4)	153.5
C20—H20···O2ⁱⁱⁱ	0.93	2.52	3.230 (4)	133.1
C21—H21···O41	0.93	2.54	3.349 (5)	146.0
C33—H33···O2W^vi	0.93	2.59	3.402 (5)	146.2

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+1, −y+1, −z; (iv) −x, y+1/2, −z+1/2; (v) −x, −y+1, −z; (vi) −x+2, −y+1, −z+1.

Acknowledgements

This project was sponsored by the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, Y.-F., Xu, Y., Qin, X.-L., Gao, W.-Y. & Gao, Y. (2012). Acta Cryst. E68, m750. CSD CrossRef IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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