Tetra-μ-1,1′-dimethyl-2,2′-bi-1H-imidazole-bis­[aqua­copper(II)] tetra­nitrate hexa­hydrate

The crystal structure of the title compound, [Cu₂(C₈H₁₀N₄)₄(H₂O)₂](NO₃)₄·6H₂O, contains dinuclear complex cations with twofold rotation symmetry, in which two Cu^II centers are bridged by four 1,1′-dimethyl-2,2′-bi-1H-imidazole ligands. Four N donors define the base of a slightly distorted square pyramid around each Cu^II center, the apical position being occupied by an aqua ligand. The nitrate ions and uncoordinated water mol­ecules form a network of hydrogen bonds, in which the aqua ligands are also involved. The large Cu...Cu separation [3.092 (1) Å] is consistent with the absence of substantial metal–metal inter­actions, as suggested by the normal magnetic moment observed at room temperature.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in solvent or counterion
• R factor = 0.061
• wR factor = 0.164
• Data-to-parameter ratio = 10.9

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.190
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.19

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         20 Ang.
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) .....         20 Ang.
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        N2'
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N3
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      42.00 Perc.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 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
   2 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRC-2 (Ahmed et al., 1973); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (Maris, 2004).

Tetra-µ-1,1'-dimethyl-2,2'-bi-1H-imidazole-bis[aquacopper(II)] tetranitrate hexahydrate

Crystal data

[Cu2(C8H10N4)4(H2O)2](NO3)4·6H2O	F(000) = 2424
Mr = 1168.05	Dx = 1.578 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 21.3104 (2) Å	θ = 20.0–23.0°
b = 22.0240 (2) Å	µ = 1.90 mm^−1
c = 11.0725 (1) Å	T = 293 K
β = 108.865 (1)°	Block, blue
V = 4917.61 (8) Å^3	0.35 × 0.26 × 0.25 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	3670 reflections with I > 2σ(I)
Radiation source: Sealed Tube	Rint = 0.190
Graphite monochromator	θmax = 70.6°, θmin = 3.0°
ω/2θ scans	h = −26→26
Absorption correction: gaussian (ABSORP in NRCVAX; Gabe et al., 1989)	k = −26→26
Tmin = 0.560, Tmax = 0.649	l = −13→13
33942 measured reflections	4 standard reflections every 60 min
4727 independent reflections	intensity decay: 0.2%

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.124P)^2] where P = (Fo^2 + 2Fc^2)/3
4727 reflections	(Δ/σ)max = 0.003
434 parameters	Δρmax = 0.99 e Å^−3
55 restraints	Δρmin = −0.98 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	Occ. (<1)
Cu1	0.05150 (2)	0.25410 (2)	0.88548 (5)	0.0311 (2)
N11	0.16038 (16)	0.17882 (16)	0.6731 (3)	0.0474 (8)
C11	0.1688 (2)	0.1472 (2)	0.5626 (5)	0.0587 (11)
H11A	0.1984	0.1135	0.5914	0.088*
H11B	0.1869	0.1748	0.5154	0.088*
H11C	0.1265	0.1328	0.5086	0.088*
C12	0.10492 (19)	0.18189 (16)	0.7063 (4)	0.0393 (8)
N13	0.11463 (16)	0.21940 (14)	0.8045 (3)	0.0411 (7)
C14	0.1782 (2)	0.24056 (18)	0.8344 (4)	0.0462 (9)
H14	0.1985	0.2678	0.8995	0.055*
C15	0.2065 (2)	0.2153 (2)	0.7535 (5)	0.0542 (10)
H15	0.2495	0.2218	0.7531	0.065*
N21	−0.04323 (18)	0.08720 (14)	0.8670 (4)	0.0503 (8)
C21	−0.0983 (3)	0.0447 (2)	0.8196 (6)	0.0710 (15)
H21A	−0.1149	0.0339	0.8876	0.107*
H21B	−0.0831	0.0088	0.7883	0.107*
H21C	−0.1330	0.0633	0.7517	0.107*
C22	−0.04479 (19)	0.14815 (16)	0.8536 (4)	0.0393 (8)
N23	0.01609 (15)	0.17032 (14)	0.8985 (3)	0.0401 (7)
C24	0.0574 (2)	0.12166 (17)	0.9417 (4)	0.0469 (9)
H24	0.1033	0.1236	0.9781	0.056*
C25	0.0212 (2)	0.07121 (19)	0.9229 (5)	0.0560 (11)
H25	0.0371	0.0320	0.9442	0.067*
N31	0.08823 (18)	0.41991 (14)	0.7358 (3)	0.0486 (8)
C31	0.0880 (3)	0.4620 (2)	0.6340 (5)	0.0639 (13)
H31A	0.1317	0.4782	0.6499	0.096*
H31B	0.0576	0.4946	0.6313	0.096*
H31C	0.0744	0.4410	0.5538	0.096*
C32	0.07780 (18)	0.35938 (16)	0.7265 (4)	0.0399 (8)
N33	0.07365 (15)	0.33807 (13)	0.8355 (3)	0.0401 (7)
C34	0.0813 (2)	0.38667 (17)	0.9162 (4)	0.0492 (10)
H34	0.0799	0.3851	0.9992	0.059*
C35	0.0911 (2)	0.43706 (18)	0.8558 (4)	0.0550 (11)
H35	0.0984	0.4761	0.8894	0.066*
N41	−0.11432 (17)	0.32481 (15)	0.9539 (3)	0.0469 (8)
C41	−0.1787 (2)	0.3543 (2)	0.9201 (5)	0.0626 (12)
H41A	−0.1755	0.3900	0.9716	0.094*
H41B	−0.2105	0.3269	0.9348	0.094*
H41C	−0.1927	0.3656	0.8316	0.094*
C42	−0.07100 (19)	0.32475 (16)	0.8880 (4)	0.0401 (8)
N43	−0.01993 (16)	0.28853 (14)	0.9455 (3)	0.0404 (7)
C44	−0.0321 (2)	0.26486 (19)	1.0508 (4)	0.0461 (9)
H44	−0.0048	0.2377	1.1086	0.055*
C45	−0.0897 (2)	0.2874 (2)	1.0567 (4)	0.0524 (10)
H45	−0.1091	0.2791	1.1190	0.063*
O1	0.12606 (17)	0.25507 (13)	1.0768 (3)	0.0499 (7)
H1A	0.135 (3)	0.2259 (14)	1.125 (4)	0.075*
H1B	0.136 (3)	0.2856 (13)	1.121 (4)	0.075*
O2	0.34449 (19)	0.14740 (16)	0.7583 (4)	0.0634 (8)
H2A	0.326 (3)	0.124 (2)	0.801 (5)	0.095*
H2B	0.3813 (14)	0.133 (3)	0.767 (6)	0.095*
O3	0.1549 (2)	0.1610 (2)	0.2510 (4)	0.0819 (12)
H3A	0.174 (2)	0.130 (2)	0.241 (3)	0.123*
H3B	0.1147 (9)	0.149 (4)	0.236 (7)	0.123*
O4	0.2693 (3)	0.0615 (3)	0.8221 (6)	0.1027 (15)
H4A	0.252 (4)	0.029 (2)	0.794 (8)	0.154*
H4B	0.254 (4)	0.066 (4)	0.881 (6)	0.154*
N1	0.0072 (16)	0.1015 (3)	0.267 (3)	0.050 (5)	0.50
O11	0.0209 (6)	0.1549 (3)	0.258 (2)	0.111 (5)	0.50
O12	−0.0441 (16)	0.0827 (12)	0.195 (3)	0.179 (13)	0.50
O13	0.0539 (12)	0.0710 (8)	0.322 (2)	0.106 (5)	0.50
N2	0.2347 (18)	0.0547 (15)	0.095 (3)	0.110 (12)	0.43
O21	0.219 (3)	0.0545 (16)	0.192 (3)	0.101 (8)	0.43
O22	0.2570 (16)	0.0084 (14)	0.064 (4)	0.134 (10)	0.43
O23	0.2178 (15)	0.0951 (13)	0.017 (2)	0.124 (10)	0.43
N2'	0.2292 (11)	0.0578 (7)	0.1102 (18)	0.084 (6)	0.57
O21'	0.2337 (16)	0.0119 (9)	0.050 (3)	0.181 (13)	0.57
O22'	0.2352 (12)	0.1085 (8)	0.0674 (19)	0.127 (7)	0.57
O23'	0.2211 (17)	0.0528 (12)	0.215 (2)	0.107 (8)	0.57
N3	0.4919 (8)	0.0886 (3)	0.7304 (15)	0.047 (4)	0.50
O31	0.4323 (4)	0.0812 (3)	0.6805 (9)	0.068 (2)	0.50
O32	0.5172 (11)	0.0869 (8)	0.8458 (13)	0.149 (9)	0.50
O33	0.5269 (6)	0.0957 (7)	0.6663 (14)	0.104 (5)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0338 (3)	0.0278 (3)	0.0338 (3)	0.00040 (17)	0.0138 (2)	−0.00021 (17)
N11	0.0379 (17)	0.0528 (19)	0.056 (2)	0.0040 (14)	0.0207 (15)	−0.0056 (15)
C11	0.053 (3)	0.073 (3)	0.058 (3)	0.008 (2)	0.030 (2)	−0.011 (2)
C12	0.041 (2)	0.0362 (18)	0.044 (2)	0.0050 (14)	0.0184 (16)	−0.0001 (14)
N13	0.0423 (17)	0.0358 (15)	0.0461 (17)	−0.0006 (13)	0.0156 (14)	−0.0029 (13)
C14	0.0340 (19)	0.051 (2)	0.053 (2)	−0.0021 (16)	0.0125 (17)	−0.0031 (17)
C15	0.037 (2)	0.061 (3)	0.066 (3)	−0.0005 (18)	0.0191 (19)	−0.004 (2)
N21	0.051 (2)	0.0346 (16)	0.066 (2)	−0.0016 (14)	0.0201 (17)	0.0095 (15)
C21	0.061 (3)	0.039 (2)	0.109 (4)	−0.014 (2)	0.023 (3)	0.002 (2)
C22	0.0411 (19)	0.0353 (17)	0.044 (2)	−0.0029 (14)	0.0178 (16)	0.0023 (15)
N23	0.0402 (17)	0.0376 (15)	0.0429 (17)	0.0024 (12)	0.0141 (13)	0.0024 (13)
C24	0.047 (2)	0.0381 (19)	0.052 (2)	0.0060 (16)	0.0112 (18)	0.0100 (17)
C25	0.058 (3)	0.038 (2)	0.070 (3)	0.0051 (18)	0.017 (2)	0.0146 (19)
N31	0.062 (2)	0.0346 (16)	0.0509 (19)	−0.0081 (15)	0.0204 (16)	−0.0006 (14)
C31	0.090 (4)	0.039 (2)	0.066 (3)	−0.009 (2)	0.030 (3)	0.010 (2)
C32	0.0401 (19)	0.0353 (17)	0.046 (2)	−0.0028 (14)	0.0162 (16)	0.0013 (15)
N33	0.0461 (18)	0.0363 (15)	0.0397 (16)	−0.0014 (13)	0.0165 (14)	−0.0016 (12)
C34	0.066 (3)	0.0378 (19)	0.042 (2)	−0.0017 (18)	0.0144 (19)	−0.0074 (16)
C35	0.076 (3)	0.0353 (19)	0.054 (2)	−0.0069 (19)	0.022 (2)	−0.0081 (17)
N41	0.0503 (19)	0.0489 (18)	0.0485 (19)	0.0072 (15)	0.0256 (16)	−0.0006 (14)
C41	0.050 (3)	0.076 (3)	0.071 (3)	0.016 (2)	0.032 (2)	0.005 (3)
C42	0.044 (2)	0.0336 (17)	0.046 (2)	0.0022 (14)	0.0194 (16)	−0.0030 (14)
N43	0.0477 (18)	0.0368 (15)	0.0392 (16)	0.0034 (13)	0.0174 (13)	0.0015 (12)
C44	0.054 (2)	0.050 (2)	0.038 (2)	0.0052 (18)	0.0204 (18)	0.0035 (16)
C45	0.067 (3)	0.053 (2)	0.046 (2)	0.004 (2)	0.031 (2)	0.0033 (18)
O1	0.0526 (18)	0.0493 (16)	0.0407 (16)	−0.0005 (13)	0.0053 (13)	−0.0019 (11)
O2	0.068 (2)	0.059 (2)	0.067 (2)	0.0034 (16)	0.0266 (18)	−0.0037 (16)
O3	0.086 (3)	0.090 (3)	0.064 (2)	−0.008 (2)	0.017 (2)	0.017 (2)
O4	0.103 (4)	0.105 (4)	0.102 (4)	−0.026 (3)	0.036 (3)	−0.002 (3)
N1	0.064 (13)	0.043 (3)	0.040 (16)	0.004 (5)	0.011 (10)	0.002 (4)
O11	0.145 (15)	0.045 (4)	0.146 (9)	−0.003 (5)	0.053 (15)	0.007 (6)
O12	0.113 (14)	0.21 (2)	0.18 (2)	−0.093 (14)	0.005 (13)	−0.047 (17)
O13	0.106 (12)	0.072 (6)	0.115 (11)	0.037 (7)	0.001 (9)	−0.013 (7)
N2	0.075 (19)	0.16 (3)	0.102 (19)	−0.036 (19)	0.039 (17)	−0.04 (2)
O21	0.15 (2)	0.081 (14)	0.078 (12)	0.006 (13)	0.043 (13)	0.009 (9)
O22	0.107 (12)	0.124 (18)	0.19 (2)	0.008 (10)	0.068 (12)	−0.002 (16)
O23	0.104 (16)	0.17 (2)	0.108 (16)	0.043 (15)	0.044 (13)	0.050 (14)
N2'	0.065 (10)	0.086 (11)	0.101 (15)	−0.003 (7)	0.028 (10)	0.023 (10)
O21'	0.29 (4)	0.140 (19)	0.17 (2)	−0.039 (18)	0.15 (2)	−0.030 (15)
O22'	0.129 (14)	0.123 (11)	0.134 (16)	−0.021 (8)	0.047 (12)	0.041 (12)
O23'	0.119 (14)	0.112 (14)	0.089 (11)	−0.037 (11)	0.032 (9)	−0.008 (9)
N3	0.061 (11)	0.039 (3)	0.035 (13)	0.001 (4)	0.006 (10)	0.007 (4)
O31	0.068 (5)	0.055 (4)	0.088 (6)	−0.006 (4)	0.034 (5)	−0.009 (4)
O32	0.20 (2)	0.131 (14)	0.068 (9)	−0.052 (16)	−0.023 (14)	−0.001 (9)
O33	0.111 (9)	0.113 (8)	0.115 (12)	−0.011 (8)	0.075 (10)	−0.015 (7)

Geometric parameters (Å, º)

Cu1—N13	1.994 (3)	N33—C34	1.370 (5)
Cu1—N23	2.016 (3)	C34—C35	1.347 (6)
Cu1—N33	2.029 (3)	C34—H34	0.9300
Cu1—N43	1.997 (3)	C35—H35	0.9300
Cu1—O1	2.199 (3)	N41—C42	1.349 (5)
N11—C12	1.349 (5)	N41—C45	1.365 (5)
N11—C15	1.356 (5)	N41—C41	1.454 (5)
N11—C11	1.468 (5)	C41—H41A	0.9600
C11—H11A	0.9600	C41—H41B	0.9600
C11—H11B	0.9600	C41—H41C	0.9600
C11—H11C	0.9600	C42—N43	1.333 (5)
C12—N13	1.327 (5)	C42—C32^i	1.446 (5)
C12—C22^i	1.444 (5)	N43—C44	1.377 (5)
N13—C14	1.368 (5)	C44—C45	1.346 (6)
C14—C15	1.351 (6)	C44—H44	0.9300
C14—H14	0.9300	C45—H45	0.9300
C15—H15	0.9300	O1—H1A	0.82 (4)
N21—C22	1.350 (5)	O1—H1B	0.82 (3)
N21—C25	1.357 (6)	O2—H2A	0.87 (6)
N21—C21	1.460 (5)	O2—H2B	0.82 (4)
C21—H21A	0.9600	O3—H3A	0.82 (2)
C21—H21B	0.9600	O3—H3B	0.85 (3)
C21—H21C	0.9600	O4—H4A	0.82 (5)
C22—N23	1.323 (5)	O4—H4B	0.82 (7)
C22—C12^i	1.444 (5)	N1—O12	1.197 (18)
N23—C24	1.372 (5)	N1—O13	1.192 (17)
C24—C25	1.331 (6)	N1—O11	1.223 (14)
C24—H24	0.9300	N2—O22	1.219 (19)
C25—H25	0.9300	N2—O23	1.213 (19)
N31—C32	1.350 (5)	N2—O21	1.236 (17)
N31—C35	1.363 (6)	N2'—O22'	1.236 (6)
N31—C31	1.458 (5)	N2'—O23'	1.235 (6)
C31—H31A	0.9600	N2'—O21'	1.236 (6)
C31—H31B	0.9600	N3—O33	1.195 (18)
C31—H31C	0.9600	N3—O32	1.216 (17)
C32—N33	1.324 (5)	N3—O31	1.221 (16)
C32—C42^i	1.446 (5)
N13—Cu1—N43	173.04 (13)	N31—C31—H31B	109.4
N23—Cu1—N33	168.22 (13)	H31A—C31—H31B	109.5
N13—Cu1—N23	90.22 (13)	N31—C31—H31C	109.5
N13—Cu1—N33	88.66 (13)	H31A—C31—H31C	109.5
N43—Cu1—N23	88.88 (12)	H31B—C31—H31C	109.5
N43—Cu1—N33	90.81 (12)	N33—C32—N31	109.8 (3)
N13—Cu1—O1	93.13 (13)	N33—C32—C42^i	126.5 (3)
N43—Cu1—O1	93.83 (13)	N31—C32—C42^i	123.7 (3)
N23—Cu1—O1	96.34 (12)	C32—N33—C34	106.8 (3)
N33—Cu1—O1	95.43 (12)	C32—N33—Cu1	131.4 (3)
C12—N11—C15	107.7 (3)	C34—N33—Cu1	121.6 (3)
C12—N11—C11	127.2 (4)	C35—C34—N33	108.9 (4)
C15—N11—C11	124.8 (4)	C35—C34—H34	125.5
N11—C11—H11A	109.4	N33—C34—H34	125.5
N11—C11—H11B	109.5	C34—C35—N31	106.9 (3)
H11A—C11—H11B	109.5	C34—C35—H35	126.5
N11—C11—H11C	109.5	N31—C35—H35	126.6
H11A—C11—H11C	109.5	C42—N41—C45	107.8 (3)
H11B—C11—H11C	109.5	C42—N41—C41	128.0 (4)
N13—C12—N11	109.7 (3)	C45—N41—C41	124.1 (4)
N13—C12—C22^i	125.3 (3)	N41—C41—H41A	109.4
N11—C12—C22^i	125.1 (3)	N41—C41—H41B	109.5
C12—N13—C14	106.9 (3)	H41A—C41—H41B	109.5
C12—N13—Cu1	131.1 (3)	N41—C41—H41C	109.5
C14—N13—Cu1	121.3 (3)	H41A—C41—H41C	109.5
C15—C14—N13	108.6 (4)	H41B—C41—H41C	109.5
C15—C14—H14	125.7	N43—C42—N41	109.8 (3)
N13—C14—H14	125.7	N43—C42—C32^i	124.7 (3)
C14—C15—N11	107.2 (4)	N41—C42—C32^i	125.6 (3)
C14—C15—H15	126.4	C42—N43—C44	106.4 (3)
N11—C15—H15	126.4	C42—N43—Cu1	131.4 (3)
C22—N21—C25	107.1 (3)	C44—N43—Cu1	120.7 (3)
C22—N21—C21	127.6 (4)	C45—C44—N43	109.0 (4)
C25—N21—C21	125.0 (4)	C45—C44—H44	125.5
N21—C21—H21A	109.5	N43—C44—H44	125.5
N21—C21—H21B	109.5	C44—C45—N41	107.0 (4)
H21A—C21—H21B	109.5	C44—C45—H45	126.5
N21—C21—H21C	109.5	N41—C45—H45	126.5
H21A—C21—H21C	109.5	Cu1—O1—H1A	125 (4)
H21B—C21—H21C	109.5	Cu1—O1—H1B	124 (4)
N23—C22—N21	109.8 (3)	H1A—O1—H1B	107 (5)
N23—C22—C12^i	126.8 (3)	H2A—O2—H2B	107 (5)
N21—C22—C12^i	123.3 (3)	H3A—O3—H3B	103 (6)
C22—N23—C24	106.5 (3)	H4A—O4—H4B	99 (5)
C22—N23—Cu1	130.9 (3)	O12—N1—O13	125.1 (13)
C24—N23—Cu1	121.8 (3)	O12—N1—O11	118 (2)
C25—C24—N23	108.8 (4)	O13—N1—O11	114 (2)
C25—C24—H24	125.6	O22—N2—O23	118 (2)
N23—C24—H24	125.6	O22—N2—O21	119 (2)
C24—C25—N21	107.8 (4)	O23—N2—O21	122 (3)
C24—C25—H25	126.1	O22'—N2'—O23'	120.4 (9)
N21—C25—H25	126.1	O22'—N2'—O21'	119.7 (10)
C32—N31—C35	107.6 (3)	O23'—N2'—O21'	119.9 (9)
C32—N31—C31	127.6 (4)	O33—N3—O32	119 (2)
C35—N31—C31	124.4 (4)	O33—N3—O31	120.4 (14)
N31—C31—H31A	109.5	O32—N3—O31	121 (2)
C15—N11—C12—N13	0.4 (5)	C35—N31—C32—N33	0.4 (5)
C11—N11—C12—N13	−173.8 (4)	C31—N31—C32—N33	−172.1 (4)
C15—N11—C12—C22^i	−178.1 (4)	C35—N31—C32—C42^i	179.1 (4)
C11—N11—C12—C22^i	7.7 (7)	C31—N31—C32—C42^i	6.7 (7)
N11—C12—N13—C14	−0.2 (4)	N31—C32—N33—C34	0.4 (5)
C22^i—C12—N13—C14	178.3 (4)	C42^i—C32—N33—C34	−178.3 (4)
N11—C12—N13—Cu1	170.0 (3)	N31—C32—N33—Cu1	174.5 (3)
C22^i—C12—N13—Cu1	−11.5 (6)	C42^i—C32—N33—Cu1	−4.3 (6)
N23—Cu1—N13—C12	50.8 (3)	N13—Cu1—N33—C32	46.9 (4)
N33—Cu1—N13—C12	−117.5 (3)	N43—Cu1—N33—C32	−126.1 (4)
O1—Cu1—N13—C12	147.1 (3)	N23—Cu1—N33—C32	−37.7 (8)
N23—Cu1—N13—C14	−140.2 (3)	O1—Cu1—N33—C32	140.0 (3)
N33—Cu1—N13—C14	51.5 (3)	N13—Cu1—N33—C34	−139.7 (3)
O1—Cu1—N13—C14	−43.9 (3)	N43—Cu1—N33—C34	47.2 (3)
C12—N13—C14—C15	−0.1 (5)	N23—Cu1—N33—C34	135.6 (6)
Cu1—N13—C14—C15	−171.5 (3)	O1—Cu1—N33—C34	−46.7 (3)
N13—C14—C15—N11	0.4 (5)	C32—N33—C34—C35	−1.0 (5)
C12—N11—C15—C14	−0.5 (5)	Cu1—N33—C34—C35	−175.8 (3)
C11—N11—C15—C14	173.9 (4)	N33—C34—C35—N31	1.2 (5)
C25—N21—C22—N23	0.3 (5)	C32—N31—C35—C34	−1.0 (5)
C21—N21—C22—N23	−173.8 (4)	C31—N31—C35—C34	171.8 (4)
C25—N21—C22—C12^i	177.9 (4)	C45—N41—C42—N43	0.1 (5)
C21—N21—C22—C12^i	3.8 (7)	C41—N41—C42—N43	−175.1 (4)
N21—C22—N23—C24	0.0 (4)	C45—N41—C42—C32^i	−178.9 (4)
C12^i—C22—N23—C24	−177.5 (4)	C41—N41—C42—C32^i	6.0 (7)
N21—C22—N23—Cu1	169.6 (3)	N41—C42—N43—C44	0.3 (4)
C12^i—C22—N23—Cu1	−7.9 (6)	C32^i—C42—N43—C44	179.3 (4)
N13—Cu1—N23—C22	−122.8 (3)	N41—C42—N43—Cu1	166.0 (3)
N43—Cu1—N23—C22	50.3 (3)	C32^i—C42—N43—Cu1	−15.0 (6)
N33—Cu1—N23—C22	−38.3 (8)	N23—Cu1—N43—C42	−115.9 (3)
O1—Cu1—N23—C22	144.0 (3)	N33—Cu1—N43—C42	52.3 (3)
N13—Cu1—N23—C24	45.5 (3)	O1—Cu1—N43—C42	147.8 (3)
N43—Cu1—N23—C24	−141.4 (3)	N23—Cu1—N43—C44	48.1 (3)
N33—Cu1—N23—C24	130.0 (6)	N33—Cu1—N43—C44	−143.7 (3)
O1—Cu1—N23—C24	−47.7 (3)	O1—Cu1—N43—C44	−48.2 (3)
C22—N23—C24—C25	−0.3 (5)	C42—N43—C44—C45	−0.7 (5)
Cu1—N23—C24—C25	−171.1 (3)	Cu1—N43—C44—C45	−168.2 (3)
N23—C24—C25—N21	0.4 (5)	N43—C44—C45—N41	0.7 (5)
C22—N21—C25—C24	−0.4 (5)	C42—N41—C45—C44	−0.5 (5)
C21—N21—C25—C24	173.9 (5)	C41—N41—C45—C44	174.9 (4)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O3^ii	0.82 (4)	1.94 (4)	2.760 (5)	175 (5)
O1—H1B···O2^iii	0.82 (3)	1.94 (3)	2.757 (5)	173 (5)
O2—H2A···O4	0.87 (6)	1.90 (6)	2.717 (6)	155 (7)
O2—H2B···O31	0.82 (4)	2.02 (4)	2.722 (9)	143 (6)
O2—H2B···O33^iv	0.82 (4)	2.03 (5)	2.833 (15)	166 (6)
O3—H3A···O23′	0.82 (4)	2.04 (5)	2.86 (3)	180 (5)
O3—H3A···O21	0.82 (4)	2.08 (6)	2.89 (5)	173 (3)
O3—H3B···O11	0.85 (3)	2.09 (2)	2.883 (12)	153 (7)
O4—H4A···O23′^v	0.82 (5)	2.02 (3)	2.83 (3)	171 (9)
O4—H4A···O21^v	0.82 (5)	2.15 (7)	2.96 (4)	167 (9)
O4—H4B···O23^ii	0.82 (7)	2.01 (3)	2.81 (3)	168 (9)

Symmetry codes: (ii) x, y, z+1; (iii) −x+1/2, −y+1/2, −z+2; (iv) −x+1, y, −z+3/2; (v) x, −y, z+1/2.