Aqua­malonato(1,10-phenanthroline)copper(II) sesquihydrate

In the title compound, [Cu(C₃H₄O₄)(C₁₂H₈N₂)(H₂O)]·1.5H₂O, there are two complex mol­ecules and three uncoordinated water mol­ecules in the asymmetric unit. In both complex mol­ecules, the Cu atom is five-coordinated by one bidentate 1,10-phenanthroline mol­ecule, one bidentate malonate dianion and one water mol­ecule, resulting in a distorted square-based pyramidal CuN₂O₃ chromophore. The structure is stabilized by O—H...O hydrogen bonds involving both the coordinated and uncoordinated water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.124
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

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Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         20 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.24
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu2         (2)       2.22

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   2 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check


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Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
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Author Response: DIALLO Madina and DIENG Moussa do the synthesis of the compound, obtain the monocrystal and do the analysis. BARRY Aliou Hamady and CHAHRAZED Beghidja resolve the structure of the crystal. GAYE Mohamed and SALL Abdou Salam write the manuscripts.

   1 ALERT level A = Data missing that is essential or data in wrong format
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S1. Comment

The title compound, (I), consists of a mononuclear Cu(II) complex with two neutral molecules in the asymmetric unit (Fig. 1). The Cu(II) ion displays a five coordinated-geometry where the Cu atom is coordinated by two nitrogen atoms of one 1,10-phenanthroline ligand, two oxygen atoms of one non-bridging dicarboxylate group and one oxygen atom of a water molecule (Table 1). Furthermore the largest angles around the Cu(II) centers (β:N1—Cu2—O7=168.67 (8)° and β: N4—Cu1—O2=172.50 (8)°) are slightly larger than the second-largest ones (α: N2—Cu2—O3=164.80 (8)° and α: N3—Cu1—O1=164.14 (9)°). Since the distortion value of the coordination polyhedron, τ=(β-α)/60 is evaluated by the two largest angles in the five coordinated geometry (Addison et al. 1984), the values of τ=0.14 for Cu1 and τ=0.06 for Cu2 which can be compared with the ideal values of 1 for a trigonal-bipyramidal and 0 for a square-pyramidal seem to indicate a distorted square pyramidal geometry around the two Cu centers. Atoms [O1, O2, N4 and N3] and [O3, O7, N1 and N2] consist of a square planar geometry with some deviation from perfect square plane. The apical positions are occupied by O6 and O10 respectively. The malonate ligand afforded two deprotonated carboxylate groups leading to a dinegative charge on the ligand. The structure of (I) is stablisied by O—H···O hydrogen bonds (Table 2).

This structure is comparable to that of [Cu(L-glu)(phen)(H₂O)] (Anitolini et al. 1985) in which the Cu ions also have distorted square-pyramidal coordination geometry comprised of a bidentate phenanthroline ligand and an O,N-bidentate glutamate dianion and an apical coordination water O atom. The Cu—O_water lengths are 2.303 (2) and 2.268 (2) Å in the two molecules, slighly shorter than the value of 2.332 (4) Å observed for Cu—O_water Å in the complex [Cu(Hdapsox)(H₂O)](ClO₄) where H₂dapsox is 2',2'''-(2,6-pyridindiyldiethylidene) dioxamohydrazide (Ivanovic-Burmazovic et al. 1998) but similar to that observed in the complex [Cu₂(mal)₂(IX)(H₂O)₆]_n (Chawla et al. 2004) where IX is 1,4-bis(imidazole-1-yl-methylene)benzene) (2.277 Å).

Related literature

For related structures: see Anitolini et al. (1985); Ivanovic-Burmazovic et al. (1998); Chawla et al., (2004). For related literature, see: Addison et al. (1984); Farrugia (1997).

S2. Experimental

Into an aqueous solution (5 ml) of Cu(NO₃)₂ 3H₂O (0.3011 g, 1.25 mmol) was poured 1.5 ml of a molar solution of Na₂CO₃. The mixture was stirred for 5 minutes and centrifuged. The solid which was isolated was added into a methanolic solution (10 ml) of 1,10-phenanthroline monohydrate (0.2478 g, 1.25 mmol) and malonic acid (0.1301 g, 1.25 mmol). The resulting mixture was heated at 343 K for thirty minutes. The green solution was filtered and then allowed to evaporate slowly in an open atmosphere. After one week, green crystals of (I) were obtained. The crystals were separated, washed with cold methanol and dried (yield: 65%, based on Cu(NO₃)₂ 3H₂O); Anal. Calc. for C₃₀H₃₀Cu₂N₄O₁₃: C, 46.10; H, 3.87; N, 7.17%. Found: C, 46.06; H, 3.85; N, 7.19%.

S3. Refinement

The O-bound H atoms were located in a difference map and refined as riding in their as found relative positions with a fixed U_iso of 0.062 Ų. The C-bound H atoms were placed geometrically (C—H = 0.950.99 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Nonius, 1998); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. View of the asymmetric unit of (I) with displacement ellipsoids plotted at the 50% probability level (arbitrary spheres for the H atoms).

Aquamalonato(1,10-phenanthroline)copper(II) sesquihydrate

Crystal data

[Cu(C3H4O4)(C12H8N2)(H2O)]·1.5H2O	Z = 4
Mr = 390.84	F(000) = 800
Triclinic, P1	Dx = 1.696 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 11.5591 (2) Å	Cell parameters from 12012 reflections
b = 11.7450 (2) Å	θ = 1.0–30.0°
c = 12.5081 (2) Å	µ = 1.47 mm^−1
α = 92.177 (1)°	T = 173 K
β = 105.457 (1)°	Prism, green
γ = 109.1821 (8)°	0.10 × 0.10 × 0.05 mm
V = 1531.06 (5) Å^3

Data collection

Nonius Kappa CCD diffractometer	6592 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 30.0°, θmin = 1.7°
ω and φ scans	h = −16→16
21966 measured reflections	k = −16→15
8939 independent reflections	l = −17→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0621P)^2 + 0.2273P] where P = (Fo^2 + 2Fc^2)/3
8939 reflections	(Δ/σ)max = 0.001
442 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.74 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.83061 (3)	0.35565 (3)	0.64500 (2)	0.03168 (9)
Cu2	0.71496 (3)	0.06782 (3)	0.97437 (2)	0.02830 (9)
O1	0.86279 (19)	0.36223 (17)	0.80482 (13)	0.0398 (4)
O2	0.7194 (2)	0.4471 (2)	0.62900 (14)	0.0491 (5)
O3	0.71195 (19)	0.03964 (18)	0.82197 (13)	0.0404 (4)
O4	0.7521 (2)	−0.03321 (19)	0.67820 (14)	0.0474 (5)
O5	0.84700 (18)	0.42129 (17)	0.96762 (13)	0.0387 (4)
O6	0.6375 (2)	0.5720 (2)	0.68385 (17)	0.0643 (7)
O7	0.78901 (17)	−0.05295 (16)	1.02331 (13)	0.0362 (4)
O8	0.88860 (19)	−0.18133 (18)	1.01234 (15)	0.0441 (5)
O9	0.67258 (18)	0.16762 (18)	0.58759 (15)	0.0442 (5)
O10	0.90425 (16)	0.22466 (16)	1.03827 (13)	0.0348 (4)
O11	0.7673 (2)	0.5795 (2)	1.08301 (16)	0.0530 (5)
O12	0.4202 (2)	0.1567 (2)	0.52647 (18)	0.0660 (6)
O13	0.6054 (2)	0.6153 (2)	0.45161 (19)	0.0718 (7)
N1	0.60609 (19)	0.17145 (19)	0.92857 (15)	0.0289 (4)
N2	0.66727 (19)	0.08302 (19)	1.11745 (15)	0.0300 (4)
N3	0.8475 (2)	0.38116 (18)	0.48948 (15)	0.0307 (4)
N4	0.95203 (19)	0.26891 (19)	0.64407 (15)	0.0302 (4)
C1	0.5672 (2)	0.2071 (2)	1.01363 (18)	0.0281 (5)
C2	1.0673 (3)	0.1905 (3)	0.4113 (2)	0.0458 (7)
H1	1.1170	0.1460	0.3941	0.055*
C3	0.4628 (3)	0.3173 (3)	1.0999 (2)	0.0411 (6)
H2	0.4183	0.3729	1.0956	0.049*
C4	0.8381 (2)	0.4326 (2)	0.86825 (18)	0.0294 (5)
C5	0.8384 (2)	−0.1090 (2)	0.97004 (19)	0.0303 (5)
C6	0.7621 (2)	−0.0238 (2)	0.77940 (18)	0.0310 (5)
C7	1.0521 (3)	0.1971 (2)	0.5215 (2)	0.0374 (6)
C8	0.5733 (2)	0.2109 (2)	0.8310 (2)	0.0361 (6)
H3	0.5992	0.1861	0.7708	0.043*
C9	0.4924 (3)	0.2704 (3)	1.1961 (2)	0.0411 (6)
H4	0.4671	0.2926	1.2577	0.049*
C10	0.4974 (2)	0.2848 (2)	1.0038 (2)	0.0347 (5)
C11	0.7124 (3)	0.5173 (2)	0.7043 (2)	0.0367 (6)
C12	0.4645 (3)	0.3256 (3)	0.8995 (2)	0.0433 (6)
H5	0.4170	0.3788	0.8888	0.052*
C13	1.0119 (3)	0.2465 (3)	0.3323 (2)	0.0444 (7)
H6	1.0219	0.2393	0.2596	0.053*
C14	0.7998 (3)	0.5366 (2)	0.82237 (19)	0.0387 (6)
H7	0.7580	0.5632	0.8731	0.046*
H8	0.8795	0.6053	0.8276	0.046*
C15	0.5996 (2)	0.1581 (2)	1.11580 (18)	0.0277 (5)
C16	0.7976 (3)	0.4437 (2)	0.41560 (19)	0.0360 (6)
H9	0.7485	0.4872	0.4355	0.043*
C17	0.5615 (2)	0.1877 (2)	1.20699 (19)	0.0332 (5)
C18	0.9751 (2)	0.2590 (2)	0.54358 (18)	0.0296 (5)
C19	0.6969 (3)	0.0339 (3)	1.2106 (2)	0.0376 (6)
H10	0.7440	−0.0192	1.2130	0.045*
C20	0.5945 (3)	0.1345 (3)	1.3033 (2)	0.0404 (6)
H11	0.5706	0.1519	1.3674	0.048*
C21	1.1090 (3)	0.1438 (3)	0.6107 (2)	0.0528 (8)
H12	1.1634	0.1013	0.6006	0.063*
C22	0.8396 (3)	−0.0902 (3)	0.8508 (2)	0.0403 (6)
H13	0.9302	−0.0474	0.8542	0.048*
H14	0.8134	−0.1721	0.8086	0.048*
C23	1.0055 (3)	0.2159 (3)	0.72536 (19)	0.0384 (6)
H15	0.9886	0.2208	0.7953	0.046*
C24	0.9179 (2)	0.3201 (2)	0.45969 (18)	0.0293 (5)
C25	0.9382 (2)	0.3168 (2)	0.35420 (19)	0.0341 (5)
C26	0.8837 (3)	0.3834 (3)	0.27801 (19)	0.0396 (6)
H16	0.8943	0.3841	0.2052	0.048*
C27	0.8157 (3)	0.4470 (3)	0.3094 (2)	0.0407 (6)
H17	0.7804	0.4938	0.2589	0.049*
C28	0.6612 (3)	0.0576 (3)	1.3048 (2)	0.0434 (7)
H18	0.6832	0.0204	1.3696	0.052*
C29	0.5015 (3)	0.2878 (3)	0.8138 (2)	0.0430 (6)
H19	0.4788	0.3137	0.7426	0.052*
C30	1.0856 (3)	0.1536 (3)	0.7115 (2)	0.0517 (8)
H20	1.1236	0.1181	0.7718	0.062*
H21	0.6133	0.5993	0.5272	0.062*
H22	0.5357	0.5415	0.4228	0.062*
H23	0.3996	0.2283	0.5323	0.062*
H24	0.3640	0.1262	0.4584	0.062*
H25	0.8137	0.6589	1.0626	0.062*
H26	0.7833	0.5224	1.0522	0.062*
H27	0.9093	0.2935	1.0132	0.062*
H28	0.9674	0.2114	1.0153	0.062*
H29	0.6825	0.1033	0.6230	0.062*
H30	0.5809	0.1432	0.5701	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.04086 (18)	0.04053 (19)	0.02340 (14)	0.02651 (15)	0.00992 (12)	0.00430 (12)
Cu2	0.03470 (17)	0.03519 (18)	0.02483 (14)	0.02200 (14)	0.01212 (12)	0.00651 (11)
O1	0.0572 (12)	0.0509 (12)	0.0259 (8)	0.0380 (10)	0.0119 (8)	0.0046 (7)
O2	0.0648 (13)	0.0685 (14)	0.0297 (9)	0.0510 (12)	0.0057 (8)	−0.0006 (8)
O3	0.0582 (12)	0.0535 (12)	0.0259 (8)	0.0391 (10)	0.0142 (8)	0.0092 (8)
O4	0.0661 (13)	0.0620 (14)	0.0255 (8)	0.0366 (11)	0.0141 (8)	0.0055 (8)
O5	0.0548 (11)	0.0444 (11)	0.0273 (8)	0.0286 (9)	0.0146 (8)	0.0074 (7)
O6	0.0869 (17)	0.0887 (18)	0.0454 (11)	0.0738 (15)	0.0117 (11)	0.0028 (11)
O7	0.0535 (11)	0.0428 (11)	0.0302 (8)	0.0336 (9)	0.0194 (8)	0.0108 (7)
O8	0.0596 (12)	0.0521 (12)	0.0445 (10)	0.0422 (10)	0.0240 (9)	0.0190 (9)
O9	0.0456 (11)	0.0453 (12)	0.0398 (9)	0.0166 (9)	0.0079 (8)	0.0119 (8)
O10	0.0359 (9)	0.0394 (10)	0.0352 (8)	0.0191 (8)	0.0124 (7)	0.0093 (7)
O11	0.0723 (14)	0.0597 (14)	0.0483 (11)	0.0393 (12)	0.0308 (10)	0.0139 (10)
O12	0.0638 (15)	0.0736 (16)	0.0508 (12)	0.0323 (13)	−0.0077 (10)	0.0003 (11)
O13	0.0708 (16)	0.0746 (18)	0.0614 (14)	0.0227 (14)	0.0070 (12)	0.0268 (12)
N1	0.0306 (10)	0.0342 (11)	0.0268 (9)	0.0164 (9)	0.0098 (8)	0.0056 (8)
N2	0.0332 (10)	0.0361 (11)	0.0286 (9)	0.0183 (9)	0.0138 (8)	0.0070 (8)
N3	0.0363 (11)	0.0318 (11)	0.0268 (9)	0.0160 (9)	0.0085 (8)	0.0055 (8)
N4	0.0347 (11)	0.0371 (12)	0.0251 (9)	0.0193 (9)	0.0104 (8)	0.0059 (8)
C1	0.0257 (11)	0.0308 (13)	0.0301 (11)	0.0123 (10)	0.0094 (9)	0.0030 (9)
C2	0.0519 (17)	0.0580 (19)	0.0436 (14)	0.0297 (15)	0.0270 (13)	0.0059 (13)
C3	0.0392 (14)	0.0419 (16)	0.0520 (15)	0.0245 (13)	0.0170 (12)	0.0007 (12)
C4	0.0324 (12)	0.0333 (13)	0.0254 (10)	0.0152 (11)	0.0084 (9)	0.0033 (9)
C5	0.0332 (12)	0.0314 (13)	0.0314 (11)	0.0172 (11)	0.0104 (10)	0.0045 (9)
C6	0.0352 (13)	0.0354 (14)	0.0255 (10)	0.0151 (11)	0.0106 (9)	0.0030 (9)
C7	0.0396 (14)	0.0447 (16)	0.0376 (12)	0.0224 (12)	0.0174 (11)	0.0051 (11)
C8	0.0380 (14)	0.0429 (16)	0.0326 (12)	0.0196 (12)	0.0112 (10)	0.0095 (10)
C9	0.0387 (14)	0.0477 (17)	0.0447 (14)	0.0216 (13)	0.0184 (11)	−0.0056 (12)
C10	0.0323 (13)	0.0347 (14)	0.0424 (13)	0.0175 (11)	0.0125 (10)	0.0041 (10)
C11	0.0455 (15)	0.0423 (15)	0.0332 (12)	0.0267 (13)	0.0145 (11)	0.0088 (11)
C12	0.0421 (15)	0.0402 (16)	0.0566 (16)	0.0257 (13)	0.0145 (13)	0.0131 (12)
C13	0.0512 (17)	0.0552 (18)	0.0359 (13)	0.0210 (14)	0.0248 (12)	0.0052 (12)
C14	0.0581 (17)	0.0343 (14)	0.0293 (11)	0.0244 (13)	0.0114 (11)	0.0045 (10)
C15	0.0268 (11)	0.0265 (12)	0.0307 (11)	0.0099 (10)	0.0097 (9)	0.0015 (9)
C16	0.0438 (15)	0.0357 (14)	0.0313 (11)	0.0193 (12)	0.0085 (10)	0.0069 (10)
C17	0.0308 (12)	0.0386 (14)	0.0313 (11)	0.0117 (11)	0.0127 (10)	−0.0009 (10)
C18	0.0310 (12)	0.0304 (13)	0.0287 (11)	0.0117 (10)	0.0102 (9)	0.0030 (9)
C19	0.0392 (14)	0.0465 (16)	0.0356 (12)	0.0238 (12)	0.0130 (11)	0.0120 (11)
C20	0.0413 (14)	0.0526 (17)	0.0312 (12)	0.0175 (13)	0.0167 (11)	0.0019 (11)
C21	0.0603 (19)	0.074 (2)	0.0484 (15)	0.0495 (18)	0.0222 (14)	0.0155 (15)
C22	0.0518 (16)	0.0550 (17)	0.0331 (12)	0.0365 (14)	0.0200 (11)	0.0131 (11)
C23	0.0467 (15)	0.0491 (16)	0.0290 (11)	0.0278 (13)	0.0123 (11)	0.0101 (11)
C24	0.0323 (12)	0.0289 (12)	0.0260 (10)	0.0098 (10)	0.0089 (9)	0.0022 (9)
C25	0.0360 (13)	0.0369 (14)	0.0271 (11)	0.0084 (11)	0.0114 (10)	0.0019 (10)
C26	0.0432 (15)	0.0462 (16)	0.0261 (11)	0.0096 (13)	0.0119 (10)	0.0084 (10)
C27	0.0456 (15)	0.0421 (16)	0.0314 (12)	0.0149 (13)	0.0060 (11)	0.0141 (11)
C28	0.0482 (16)	0.0593 (19)	0.0282 (12)	0.0228 (14)	0.0139 (11)	0.0153 (11)
C29	0.0451 (15)	0.0505 (17)	0.0422 (14)	0.0262 (14)	0.0132 (12)	0.0196 (12)
C30	0.064 (2)	0.069 (2)	0.0434 (15)	0.0492 (18)	0.0163 (14)	0.0184 (14)

Geometric parameters (Å, º)

Cu1—O2	1.9061 (18)	C3—C10	1.440 (3)
Cu1—O1	1.9270 (16)	C3—H2	0.9500
Cu1—N4	1.989 (2)	C4—C14	1.513 (3)
Cu1—N3	2.0298 (19)	C5—C22	1.519 (3)
Cu1—O9	2.293 (2)	C6—C22	1.514 (3)
Cu2—O3	1.9114 (16)	C7—C18	1.392 (3)
Cu2—O7	1.9246 (16)	C7—C21	1.415 (4)
Cu2—N1	2.017 (2)	C8—C29	1.401 (4)
Cu2—N2	2.0260 (18)	C8—H3	0.9500
Cu2—O10	2.2643 (18)	C9—C17	1.436 (4)
O1—C4	1.273 (3)	C9—H4	0.9500
O5—C4	1.235 (3)	C10—C12	1.408 (4)
O2—C11	1.264 (3)	C11—C14	1.511 (3)
O6—C11	1.219 (3)	C12—C29	1.364 (4)
O7—C5	1.272 (3)	C12—H5	0.9500
O8—C5	1.238 (3)	C13—C25	1.432 (4)
O3—C6	1.263 (3)	C13—H6	0.9500
O4—C6	1.237 (3)	C14—H7	0.9900
O9—H29	0.914	C14—H8	0.9900
O9—H30	0.962	C15—C17	1.398 (3)
O10—H27	0.868	C16—C27	1.399 (3)
O10—H28	0.907	C16—H9	0.9500
O11—H25	0.993	C17—C20	1.398 (4)
O11—H26	0.856	C18—C24	1.432 (3)
O12—H23	0.952	C19—C28	1.394 (4)
O12—H24	0.897	C19—H10	0.9500
O13—H21	0.957	C20—C28	1.365 (4)
O13—H22	0.944	C20—H11	0.9500
N1—C8	1.326 (3)	C21—C30	1.367 (4)
N1—C1	1.362 (3)	C21—H12	0.9500
N2—C19	1.333 (3)	C22—H13	0.9900
N2—C15	1.355 (3)	C22—H14	0.9900
N3—C16	1.331 (3)	C23—C30	1.394 (4)
N3—C24	1.357 (3)	C23—H15	0.9500
N4—C23	1.330 (3)	C24—C25	1.402 (3)
N4—C18	1.361 (3)	C25—C26	1.406 (4)
C1—C10	1.391 (3)	C26—C27	1.364 (4)
C1—C15	1.431 (3)	C26—H16	0.9500
C2—C13	1.346 (4)	C27—H17	0.9500
C2—C7	1.438 (3)	C28—H18	0.9500
C2—H1	0.9500	C29—H19	0.9500
C3—C9	1.350 (4)	C30—H20	0.9500
O2—Cu1—O1	94.22 (7)	C17—C9—H4	119.4
O2—Cu1—N4	172.50 (8)	C1—C10—C12	117.3 (2)
O1—Cu1—N4	92.40 (7)	C1—C10—C3	118.3 (2)
O2—Cu1—N3	90.83 (8)	C12—C10—C3	124.3 (2)
O1—Cu1—N3	164.15 (9)	O6—C11—O2	121.6 (2)
N4—Cu1—N3	81.87 (8)	O6—C11—C14	118.5 (2)
O2—Cu1—O9	96.55 (8)	O2—C11—C14	119.9 (2)
O1—Cu1—O9	99.84 (8)	C29—C12—C10	119.2 (2)
N4—Cu1—O9	85.78 (8)	C29—C12—H5	120.4
N3—Cu1—O9	94.49 (7)	C10—C12—H5	120.4
O3—Cu2—O7	94.75 (7)	C2—C13—C25	122.0 (2)
O3—Cu2—N1	89.31 (7)	C2—C13—H6	119.0
O7—Cu2—N1	168.67 (8)	C25—C13—H6	119.0
O3—Cu2—N2	164.81 (8)	C11—C14—C4	119.5 (2)
O7—Cu2—N2	92.39 (7)	C11—C14—H7	107.4
N1—Cu2—N2	81.31 (8)	C4—C14—H7	107.4
O3—Cu2—O10	99.15 (7)	C11—C14—H8	107.4
O7—Cu2—O10	93.79 (7)	C4—C14—H8	107.4
N1—Cu2—O10	96.00 (7)	H7—C14—H8	107.0
N2—Cu2—O10	93.73 (7)	N2—C15—C17	123.3 (2)
C4—O1—Cu1	126.47 (15)	N2—C15—C1	116.27 (19)
C11—O2—Cu1	127.43 (16)	C17—C15—C1	120.4 (2)
C6—O3—Cu2	129.19 (15)	N3—C16—C27	121.8 (2)
C5—O7—Cu2	127.87 (15)	N3—C16—H9	119.1
Cu1—O9—H29	119.3	C27—C16—H9	119.1
Cu1—O9—H30	131.1	C15—C17—C20	117.2 (2)
Cu2—O10—H27	117.8	C15—C17—C9	118.3 (2)
Cu2—O10—H28	112.6	C20—C17—C9	124.6 (2)
H29—O9—H30	98.1	N4—C18—C7	123.6 (2)
H27—O10—H28	98.2	N4—C18—C24	116.0 (2)
H25—O11—H26	110.1	C7—C18—C24	120.4 (2)
H23—O12—H24	94.7	N2—C19—C28	122.4 (2)
H21—O13—H22	92.2	N2—C19—H10	118.8
C8—N1—C1	118.1 (2)	C28—C19—H10	118.8
C8—N1—Cu2	128.98 (16)	C28—C20—C17	119.6 (2)
C1—N1—Cu2	112.87 (15)	C28—C20—H11	120.2
C19—N2—C15	117.8 (2)	C17—C20—H11	120.2
C19—N2—Cu2	129.25 (17)	C30—C21—C7	119.7 (3)
C15—N2—Cu2	112.89 (15)	C30—C21—H12	120.1
C16—N3—C24	118.3 (2)	C7—C21—H12	120.1
C16—N3—Cu1	129.80 (17)	C6—C22—C5	123.0 (2)
C24—N3—Cu1	111.89 (15)	C6—C22—H13	106.6
C23—N4—C18	118.1 (2)	C5—C22—H13	106.6
C23—N4—Cu1	128.45 (16)	C6—C22—H14	106.6
C18—N4—Cu1	113.33 (15)	C5—C22—H14	106.6
N1—C1—C10	123.3 (2)	H13—C22—H14	106.5
N1—C1—C15	116.3 (2)	N4—C23—C30	122.3 (2)
C10—C1—C15	120.4 (2)	N4—C23—H15	118.8
C13—C2—C7	120.7 (2)	C30—C23—H15	118.8
C13—C2—H1	119.7	N3—C24—C25	123.5 (2)
C7—C2—H1	119.7	N3—C24—C18	116.46 (19)
C9—C3—C10	121.3 (2)	C25—C24—C18	120.1 (2)
C9—C3—H2	119.4	C24—C25—C26	116.8 (2)
C10—C3—H2	119.4	C24—C25—C13	118.0 (2)
O5—C4—O1	122.5 (2)	C26—C25—C13	125.2 (2)
O5—C4—C14	118.1 (2)	C27—C26—C25	119.5 (2)
O1—C4—C14	119.4 (2)	C27—C26—H16	120.2
O8—C5—O7	122.1 (2)	C25—C26—H16	120.2
O8—C5—C22	116.2 (2)	C26—C27—C16	120.2 (2)
O7—C5—C22	121.7 (2)	C26—C27—H17	119.9
O4—C6—O3	121.8 (2)	C16—C27—H17	119.9
O4—C6—C22	117.0 (2)	C20—C28—C19	119.6 (2)
O3—C6—C22	121.23 (19)	C20—C28—H18	120.2
C18—C7—C21	116.6 (2)	C19—C28—H18	120.2
C18—C7—C2	118.7 (2)	C12—C29—C8	119.9 (2)
C21—C7—C2	124.7 (2)	C12—C29—H19	120.1
N1—C8—C29	122.2 (2)	C8—C29—H19	120.1
N1—C8—H3	118.9	C21—C30—C23	119.6 (3)
C29—C8—H3	118.9	C21—C30—H20	120.2
C3—C9—C17	121.3 (2)	C23—C30—H20	120.2
C3—C9—H4	119.4

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H29···O4	0.91	2.08	2.961 (3)	161
O9—H30···O12	0.96	1.85	2.769 (3)	158
O10—H27···O5	0.87	1.91	2.720 (3)	154
O10—H28···O8^i	0.91	1.92	2.824 (3)	172
O11—H25···O8^ii	0.99	1.99	2.983 (3)	174
O11—H26···O5	0.86	1.99	2.831 (3)	167
O12—H23···O13^iii	0.95	1.86	2.800 (3)	168
O12—H24···O4^iv	0.90	1.89	2.780 (3)	169
O13—H21···O6	0.96	1.96	2.915 (3)	177
O13—H22···O6^iii	0.94	2.06	2.952 (3)	156

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