Bis-{(E)-3-[2-(hy-droxy-imino)-propan-amido]-2,2-dimethyl-propan-1-aminium} bis[μ-(E)-N-(3-amino-2,2-dimethyl-prop-yl)-2-(hy-droxy-imino)-propanamido-(2-)]bis-{[(E)-N-(3-amino-2,2-dimethyl-prop-yl)-2-(hy-droxy-imino)-propanamide]-copper(II)} bis-((E)-{3-[2-(hy-droxy-imino)-propanamido]-2,2-dimethyl-prop-yl}carbamate) acetonitrile disolvate.

The reaction between copper(II) nitrate and (E)-N-(3-amino-2,2-dimethyl-prop-yl)-2-(hy-droxy-imino)-propanamide led to the formation of the dinuclear centrosymmetric copper(II) title complex, (C8H18N3O2)2[Cu2(C8H15N3O2)2(C8H17N3O2)2](C9H16N3O4)2·2CH3CN, in which an inversion center is located at the midpoint of the Cu2 unit in the center of the neutral [Cu2(C8H15N3O2)2(C8H17N3O2)2] complex fragment. The Cu(2+) ions are connected by two N-O bridging groups [Cu⋯Cu separation = 4.0608 (5) Å] while the Cu(II) ions are five-coordinated in a square-pyramidal N4O coordination environment. The complex mol-ecule co-crystallizes with two mol-ecules of acetonitrile, two mol-ecules of the protonated ligand (E)-3-[2-(hy-droxy-imino)-propanamido]-2,2-dimethyl-propan-1-aminium and two negatively charged (E)-{3-[2-(hy-droxy-imino)-propanamido]-2,2-dimethyl-prop-yl}carbamate anions, which were probably formed as a result of condensation between (E)-N-(3-amino-2,2-dimethyl-prop-yl)-2-(hy-droxy-imino)-propanamide and hydro-gencarbonate anions. In the crystal, the complex fragment [Cu2(C8H15N3O2)2(C8H17N3O2)2] and the ion pair C8H18N3O2(+.)C9H16N3O4(-) are connected via an extended system of hydrogen bonds.

Related literature

For properties of polynuclear complexes, see: Krämer & Fritsky (2000 ▶); Fritsky et al. (2001 ▶, 2003 ▶); Thompson (2002 ▶); Wörl et al. (2005 ▶); Bauer-Siebenlist et al. (2005 ▶); Thallapally et al. (2010 ▶); Cui et al. (2012 ▶); Beauvais et al. (2000 ▶). For studies of dinuclear copper(II) catecholase activity, see: Demmin et al. (1991 ▶); Monzani et al. (1998 ▶). For use of 2-hy­droxy­imino­propanoic acid derivatives as versatile ligands, see: Fritsky et al. (1998 ▶, 2006 ▶); Kanderal et al. (2005 ▶); Moroz et al. (2008 ▶, 2010 ▶, 2012 ▶); For the τ parameter, see: Addison et al. (1984 ▶). For related structures, see: Duda et al. (1997 ▶); Dobosz et al. (1999 ▶); Mokhir et al. (2002 ▶); Onindo et al. (1995 ▶); Petrusenko et al. (1997 ▶); Sliva et al. (1997 ▶); Dvorkin et al. (1990a ▶,b ▶); Lampeka et al. (1989 ▶); Skopenko et al. (1990 ▶). For carbon dioxide capture, see: Kovbasyuk et al. (1997 ▶); Pavlishchuk et al. (2002 ▶); Nanda et al. (2006 ▶).

Experimental

Crystal data

(C8H18N3O2)2[Cu2(C8H15N3O2)2(C8H17N3O2)2] (C9H16N3O4)2·2C2H3N

M = 1791.14

Triclinic,

a = 9.3077 (3) Å

b = 12.9458 (6) Å

c = 19.8381 (6) Å

α = 107.875 (1)°

β = 98.461 (2)°

γ = 92.718 (2)°

V = 2239.34 (14) Å3

Z = 1

Mo Kα radiation

μ = 0.55 mm−1

T = 120 K

0.17 × 0.14 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.911, T max = 0.944

32405 measured reflections

9811 independent reflections

7089 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.147

S = 1.05

9811 reflections

545 parameters

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −0.70 e Å−3

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681204620X/gg2096sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204620X/gg2096Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C8H18N3O2)2[Cu2(C8H15N3O2)2(C8H17N3O2)2] (C9H16N3O4)2·2C2H3N	Z = 1
Mr = 1791.14	F(000) = 958
Triclinic, P1	Dx = 1.328 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3077 (3) Å	Cell parameters from 23086 reflections
b = 12.9458 (6) Å	θ = 2.9–27.1°
c = 19.8381 (6) Å	µ = 0.55 mm−1
α = 107.875 (1)°	T = 120 K
β = 98.461 (2)°	Block, purple
γ = 92.718 (2)°	0.17 × 0.14 × 0.11 mm
V = 2239.34 (14) Å3

Nonius KappaCCD diffractometer	9811 independent reflections
Radiation source: fine-focus sealed tube	7089 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.074
Detector resolution: 9 pixels mm-1	θmax = 27.1°, θmin = 3.9°
φ scans and ω scans with κ offset	h = −11→11
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −15→16
Tmin = 0.911, Tmax = 0.944	l = −25→25
32405 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0692P)2 + 1.4972P] where P = (Fo2 + 2Fc2)/3
9811 reflections	(Δ/σ)max = 0.001
545 parameters	Δρmax = 0.78 e Å−3
0 restraints	Δρmin = −0.70 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.79591 (4)	0.03835 (3)	0.471381 (19)	0.02474 (11)
O1	0.9971 (2)	0.00520 (16)	0.59142 (11)	0.0270 (4)
O2	0.5459 (2)	−0.20172 (15)	0.49801 (11)	0.0282 (4)
O3	0.8343 (2)	0.32441 (16)	0.44650 (11)	0.0316 (5)
O4	0.5320 (2)	0.59018 (16)	0.43927 (12)	0.0341 (5)
H4O	0.5444	0.6697	0.4459	0.051*
O5	1.0148 (2)	−0.06821 (17)	0.05826 (11)	0.0313 (5)
O6	1.0095 (2)	−0.12422 (16)	0.27643 (11)	0.0292 (4)
H6O	1.0104	−0.0792	0.3216	0.044*
O7	0.5645 (2)	0.13752 (16)	0.00244 (11)	0.0299 (5)
O8	0.3750 (2)	0.14635 (17)	−0.07834 (12)	0.0346 (5)
O9	0.8251 (3)	0.40092 (18)	0.23329 (14)	0.0489 (6)
O10	0.7238 (2)	0.03350 (16)	0.18399 (12)	0.0324 (5)
H10O	0.6854	−0.0205	0.1466	0.049*
N1	0.8683 (3)	−0.02673 (18)	0.54686 (13)	0.0244 (5)
N2	0.6419 (3)	−0.08185 (18)	0.44696 (13)	0.0255 (5)
N3	0.7251 (3)	0.08880 (19)	0.38775 (13)	0.0282 (5)
H3A	0.7873	0.0676	0.3598	0.042*
H3B	0.7311	0.1605	0.3934	0.042*
N4	0.9173 (3)	0.18149 (18)	0.53062 (13)	0.0256 (5)
H4C	0.9301	0.2215	0.4996	0.038*
H4D	1.0061	0.1569	0.5410	0.038*
N5	0.8510 (3)	0.46726 (19)	0.54814 (14)	0.0296 (5)
H5N	0.8229	0.5393	0.5632	0.044*
N6	0.6524 (3)	0.55520 (19)	0.47341 (14)	0.0301 (6)
N7	1.2786 (3)	0.03651 (19)	0.01429 (13)	0.0272 (5)
H7D	1.1936	0.0243	−0.0002	0.041*
H7E	1.3216	−0.0233	0.0095	0.041*
H7F	1.3040	0.0833	−0.0181	0.041*
N8	1.0700 (3)	0.07386 (19)	0.16118 (14)	0.0284 (5)
H8N	1.0818	0.0910	0.2081	0.043*
N9	1.0319 (3)	−0.05481 (19)	0.23722 (13)	0.0263 (5)
N10	0.5814 (3)	0.2593 (2)	−0.05759 (15)	0.0345 (6)
H10N	0.5339	0.2872	−0.0951	0.052*
N11	0.7026 (3)	0.30587 (19)	0.12196 (14)	0.0301 (6)
H11N	0.6605	0.2392	0.0949	0.045*
N12	0.7126 (3)	0.12354 (19)	0.16016 (14)	0.0278 (5)
N13	0.4204 (6)	0.6143 (3)	0.1678 (2)	0.0866 (15)
C1	0.7829 (3)	−0.1065 (2)	0.54971 (15)	0.0255 (6)
C2	0.8168 (4)	−0.1687 (2)	0.60094 (17)	0.0322 (7)
H2A	0.9003	−0.2102	0.5894	0.048*
H2B	0.7318	−0.2191	0.5972	0.048*
H2C	0.8406	−0.1179	0.6501	0.048*
C3	0.6456 (3)	−0.1336 (2)	0.49430 (15)	0.0241 (6)
C4	0.5117 (3)	−0.1048 (2)	0.39132 (16)	0.0272 (6)
H4A	0.4321	−0.0655	0.4125	0.033*
H4B	0.4799	−0.1838	0.3755	0.033*
C5	0.5350 (3)	−0.0719 (2)	0.32556 (16)	0.0262 (6)
C6	0.3899 (4)	−0.0977 (3)	0.27351 (18)	0.0367 (7)
H6A	0.3560	−0.1750	0.2616	0.055*
H6B	0.4035	−0.0818	0.2295	0.055*
H6C	0.3174	−0.0528	0.2960	0.055*
C7	0.6526 (3)	−0.1355 (2)	0.28899 (17)	0.0300 (6)
H7A	0.6203	−0.2137	0.2719	0.045*
H7B	0.7437	−0.1218	0.3236	0.045*
H7C	0.6690	−0.1116	0.2482	0.045*
C8	0.5755 (3)	0.0517 (2)	0.34610 (16)	0.0278 (6)
H8A	0.5670	0.0722	0.3016	0.033*
H8B	0.5045	0.0904	0.3749	0.033*
C9	0.8481 (3)	0.2553 (2)	0.58640 (16)	0.0266 (6)
H9A	0.8221	0.2155	0.6190	0.032*
H9B	0.7560	0.2737	0.5628	0.032*
C10	0.9404 (3)	0.3622 (2)	0.63210 (16)	0.0279 (6)
C11	1.0858 (4)	0.3386 (2)	0.66935 (18)	0.0334 (7)
H11A	1.1402	0.4074	0.7007	0.050*
H11B	1.1433	0.3018	0.6330	0.050*
H11C	1.0668	0.2916	0.6981	0.050*
C12	0.8516 (4)	0.4234 (3)	0.68900 (18)	0.0369 (7)
H12A	0.8324	0.3785	0.7191	0.055*
H12B	0.7587	0.4382	0.6650	0.055*
H12C	0.9071	0.4924	0.7191	0.055*
C13	0.9769 (3)	0.4349 (2)	0.58719 (17)	0.0296 (6)
H13A	1.0370	0.5016	0.6196	0.036*
H13B	1.0370	0.3955	0.5521	0.036*
C14	0.7896 (3)	0.4098 (2)	0.48086 (17)	0.0279 (6)
C15	0.6606 (3)	0.4527 (2)	0.44730 (16)	0.0294 (6)
C16	0.5574 (4)	0.3726 (3)	0.38713 (19)	0.0385 (8)
H16A	0.4661	0.4049	0.3786	0.058*
H16B	0.5371	0.3066	0.3998	0.058*
H16C	0.6013	0.3537	0.3435	0.058*
C17	1.3337 (3)	0.0845 (2)	0.09269 (16)	0.0264 (6)
H17A	1.4401	0.1047	0.0999	0.032*
H17B	1.3188	0.0280	0.1158	0.032*
C18	1.2620 (3)	0.1849 (2)	0.13065 (16)	0.0285 (6)
C19	1.3412 (4)	0.2267 (3)	0.20854 (18)	0.0379 (7)
H19A	1.3309	0.1698	0.2311	0.057*
H19B	1.2985	0.2915	0.2349	0.057*
H19C	1.4449	0.2454	0.2095	0.057*
C20	1.2765 (4)	0.2735 (2)	0.09419 (18)	0.0330 (7)
H20A	1.2375	0.3396	0.1215	0.050*
H20B	1.2216	0.2470	0.0451	0.050*
H20C	1.3796	0.2902	0.0928	0.050*
C21	1.0987 (3)	0.1567 (2)	0.12810 (16)	0.0279 (6)
H21A	1.0561	0.2237	0.1529	0.033*
H21B	1.0494	0.1307	0.0773	0.033*
C22	1.0300 (3)	−0.0316 (2)	0.12427 (16)	0.0258 (6)
C23	1.0066 (3)	−0.1032 (2)	0.16946 (16)	0.0256 (6)
C24	0.9528 (4)	−0.2213 (2)	0.13348 (17)	0.0334 (7)
H24A	1.0145	−0.2662	0.1549	0.050*
H24B	0.9569	−0.2409	0.0820	0.050*
H24C	0.8518	−0.2338	0.1400	0.050*
C25	0.5051 (4)	0.1773 (2)	−0.04470 (17)	0.0299 (7)
C26	0.7333 (4)	0.2957 (3)	−0.02801 (19)	0.0364 (7)
H26A	0.7826	0.3057	−0.0668	0.044*
H26B	0.7782	0.2370	−0.0126	0.044*
C27	0.7646 (3)	0.4020 (3)	0.03606 (19)	0.0345 (7)
C28	0.9282 (4)	0.4177 (3)	0.0648 (2)	0.0469 (9)
H28A	0.9523	0.4873	0.1036	0.070*
H28B	0.9821	0.4177	0.0259	0.070*
H28C	0.9553	0.3579	0.0833	0.070*
C29	0.7196 (4)	0.4993 (3)	0.0118 (2)	0.0422 (8)
H29A	0.6176	0.4845	−0.0124	0.063*
H29B	0.7821	0.5105	−0.0215	0.063*
H29C	0.7301	0.5650	0.0538	0.063*
C30	0.6790 (3)	0.3988 (2)	0.09562 (18)	0.0316 (7)
H30A	0.7069	0.4671	0.1364	0.038*
H30B	0.5736	0.3965	0.0774	0.038*
C31	0.7718 (3)	0.3139 (2)	0.18701 (17)	0.0308 (7)
C32	0.7833 (3)	0.2103 (2)	0.20590 (16)	0.0277 (6)
C33	0.8753 (4)	0.2187 (3)	0.27622 (17)	0.0332 (7)
H33A	0.8243	0.2552	0.3156	0.050*
H33B	0.9686	0.2611	0.2813	0.050*
H33C	0.8932	0.1455	0.2779	0.050*
C35	0.4618 (5)	0.5755 (3)	0.2090 (2)	0.0498 (9)
C34	0.5186 (4)	0.5279 (3)	0.2630 (2)	0.0509 (9)
H34A	0.6131	0.5014	0.2539	0.076*
H34B	0.4502	0.4669	0.2613	0.076*
H34C	0.5313	0.5831	0.3106	0.076*

	U11	U22	U33	U12	U13	U23
Cu1	0.0265 (2)	0.02338 (18)	0.02322 (19)	−0.00097 (13)	0.00151 (14)	0.00753 (13)
O1	0.0222 (10)	0.0343 (10)	0.0229 (10)	0.0009 (8)	0.0021 (8)	0.0076 (8)
O2	0.0275 (11)	0.0248 (9)	0.0332 (12)	0.0000 (8)	0.0076 (9)	0.0096 (8)
O3	0.0405 (13)	0.0261 (10)	0.0273 (11)	0.0055 (9)	0.0080 (9)	0.0059 (9)
O4	0.0378 (13)	0.0279 (10)	0.0354 (12)	0.0057 (9)	0.0006 (10)	0.0107 (9)
O5	0.0335 (12)	0.0354 (11)	0.0243 (11)	−0.0005 (9)	0.0031 (9)	0.0098 (9)
O6	0.0332 (12)	0.0321 (10)	0.0245 (11)	0.0014 (9)	0.0074 (9)	0.0115 (9)
O7	0.0327 (12)	0.0276 (10)	0.0310 (12)	0.0034 (8)	0.0065 (9)	0.0112 (9)
O8	0.0354 (13)	0.0332 (11)	0.0326 (12)	0.0019 (9)	0.0009 (10)	0.0093 (9)
O9	0.0582 (17)	0.0293 (12)	0.0479 (15)	−0.0004 (11)	−0.0110 (12)	0.0058 (11)
O10	0.0368 (12)	0.0290 (10)	0.0321 (12)	−0.0003 (9)	0.0025 (10)	0.0125 (9)
N1	0.0246 (13)	0.0239 (11)	0.0220 (12)	0.0006 (9)	0.0030 (10)	0.0041 (9)
N2	0.0243 (13)	0.0256 (11)	0.0265 (13)	−0.0001 (9)	0.0043 (10)	0.0083 (10)
N3	0.0296 (14)	0.0273 (12)	0.0284 (13)	0.0021 (10)	0.0035 (11)	0.0109 (10)
N4	0.0271 (13)	0.0233 (11)	0.0260 (13)	0.0024 (9)	0.0052 (10)	0.0069 (10)
N5	0.0338 (14)	0.0238 (11)	0.0284 (14)	0.0028 (10)	0.0016 (11)	0.0058 (10)
N6	0.0309 (14)	0.0294 (13)	0.0329 (14)	0.0049 (10)	0.0062 (11)	0.0135 (11)
N7	0.0225 (12)	0.0307 (12)	0.0267 (13)	0.0024 (10)	0.0023 (10)	0.0074 (10)
N8	0.0324 (14)	0.0309 (12)	0.0231 (13)	0.0021 (10)	0.0083 (10)	0.0089 (10)
N9	0.0244 (13)	0.0316 (12)	0.0264 (13)	0.0025 (10)	0.0056 (10)	0.0137 (10)
N10	0.0347 (15)	0.0373 (14)	0.0362 (15)	0.0028 (11)	0.0061 (12)	0.0185 (12)
N11	0.0297 (14)	0.0254 (12)	0.0350 (15)	−0.0005 (10)	0.0038 (11)	0.0104 (11)
N12	0.0257 (13)	0.0279 (12)	0.0317 (14)	0.0023 (10)	0.0052 (11)	0.0118 (11)
N13	0.158 (5)	0.056 (2)	0.046 (2)	0.013 (3)	0.003 (3)	0.0227 (19)
C1	0.0282 (15)	0.0254 (13)	0.0238 (15)	0.0050 (11)	0.0069 (12)	0.0077 (11)
C2	0.0344 (17)	0.0332 (15)	0.0307 (17)	0.0011 (13)	0.0040 (13)	0.0138 (13)
C3	0.0258 (15)	0.0210 (12)	0.0237 (14)	0.0019 (11)	0.0073 (11)	0.0032 (11)
C4	0.0240 (15)	0.0279 (14)	0.0271 (15)	−0.0001 (11)	0.0033 (12)	0.0057 (12)
C5	0.0234 (15)	0.0288 (14)	0.0251 (15)	0.0037 (11)	0.0022 (12)	0.0074 (12)
C6	0.0302 (17)	0.0444 (18)	0.0318 (18)	0.0011 (13)	−0.0025 (13)	0.0106 (14)
C7	0.0311 (16)	0.0296 (14)	0.0271 (16)	0.0034 (12)	0.0067 (13)	0.0049 (12)
C8	0.0250 (15)	0.0310 (14)	0.0272 (16)	0.0050 (12)	0.0012 (12)	0.0101 (12)
C9	0.0270 (15)	0.0273 (14)	0.0247 (15)	0.0005 (11)	0.0060 (12)	0.0067 (12)
C10	0.0285 (16)	0.0262 (14)	0.0265 (15)	0.0006 (11)	0.0044 (12)	0.0051 (12)
C11	0.0329 (17)	0.0278 (14)	0.0341 (17)	−0.0018 (12)	−0.0048 (13)	0.0074 (13)
C12	0.0412 (19)	0.0358 (16)	0.0292 (17)	0.0032 (14)	0.0096 (14)	0.0021 (13)
C13	0.0304 (16)	0.0230 (13)	0.0330 (17)	−0.0002 (11)	0.0028 (13)	0.0069 (12)
C14	0.0314 (16)	0.0240 (13)	0.0310 (16)	0.0008 (11)	0.0075 (13)	0.0120 (12)
C15	0.0345 (17)	0.0279 (14)	0.0258 (16)	0.0003 (12)	0.0068 (13)	0.0082 (12)
C16	0.042 (2)	0.0308 (16)	0.0371 (19)	0.0056 (14)	−0.0031 (15)	0.0072 (14)
C17	0.0220 (14)	0.0324 (14)	0.0256 (15)	0.0024 (11)	0.0038 (11)	0.0105 (12)
C18	0.0265 (16)	0.0297 (14)	0.0289 (16)	0.0002 (12)	0.0063 (12)	0.0083 (12)
C19	0.0328 (18)	0.0425 (18)	0.0328 (18)	−0.0012 (14)	0.0020 (14)	0.0061 (14)
C20	0.0327 (17)	0.0296 (15)	0.0380 (18)	0.0005 (12)	0.0111 (14)	0.0107 (13)
C21	0.0292 (16)	0.0284 (14)	0.0273 (16)	0.0028 (12)	0.0073 (12)	0.0096 (12)
C22	0.0196 (14)	0.0328 (14)	0.0253 (15)	0.0039 (11)	0.0030 (11)	0.0097 (12)
C23	0.0184 (14)	0.0304 (14)	0.0275 (16)	0.0020 (11)	0.0033 (11)	0.0086 (12)
C24	0.0373 (18)	0.0308 (15)	0.0297 (17)	−0.0004 (13)	0.0080 (14)	0.0057 (13)
C25	0.0352 (18)	0.0266 (14)	0.0298 (16)	0.0080 (12)	0.0119 (14)	0.0079 (12)
C26	0.0319 (17)	0.0404 (17)	0.048 (2)	0.0085 (13)	0.0181 (15)	0.0248 (15)
C27	0.0249 (16)	0.0354 (16)	0.050 (2)	0.0013 (12)	0.0072 (14)	0.0231 (15)
C28	0.0253 (17)	0.053 (2)	0.071 (3)	0.0008 (15)	0.0069 (17)	0.034 (2)
C29	0.0353 (19)	0.0374 (17)	0.062 (2)	0.0030 (14)	0.0099 (17)	0.0261 (17)
C30	0.0291 (16)	0.0271 (14)	0.0401 (18)	0.0018 (12)	0.0044 (14)	0.0135 (13)
C31	0.0266 (16)	0.0303 (15)	0.0327 (17)	0.0020 (12)	0.0047 (13)	0.0061 (13)
C32	0.0247 (15)	0.0326 (15)	0.0259 (15)	0.0046 (12)	0.0075 (12)	0.0076 (12)
C33	0.0377 (18)	0.0357 (16)	0.0239 (16)	0.0035 (13)	0.0061 (13)	0.0060 (13)
C35	0.074 (3)	0.0369 (18)	0.037 (2)	0.0001 (18)	0.0112 (19)	0.0097 (16)
C34	0.046 (2)	0.059 (2)	0.052 (2)	0.0056 (18)	0.0101 (18)	0.0238 (19)

Cu1—N1	1.984 (2)	C8—H8A	0.9900
Cu1—N2	1.957 (2)	C8—H8B	0.9900
Cu1—N3	2.000 (2)	C9—C10	1.537 (4)
Cu1—N4	2.041 (2)	C9—H9A	0.9900
Cu1—O1i	2.441 (2)	C9—H9B	0.9900
O1—N1	1.343 (3)	C10—C11	1.535 (4)
O2—C3	1.276 (3)	C10—C13	1.539 (4)
O3—C14	1.234 (3)	C10—C12	1.540 (4)
O4—N6	1.390 (3)	C11—H11A	0.9800
O4—H4O	0.9950	C11—H11B	0.9800
O5—C22	1.232 (4)	C11—H11C	0.9800
O6—N9	1.384 (3)	C12—H12A	0.9800
O6—H6O	0.9050	C12—H12B	0.9800
O7—C25	1.271 (4)	C12—H12C	0.9800
O8—C25	1.275 (4)	C13—H13A	0.9900
O9—C31	1.240 (4)	C13—H13B	0.9900
O10—N12	1.389 (3)	C14—C15	1.499 (4)
O10—H10O	0.8640	C15—C16	1.494 (4)
N1—C1	1.293 (4)	C16—H16A	0.9800
N2—C3	1.308 (4)	C16—H16B	0.9800
N2—C4	1.465 (4)	C16—H16C	0.9800
N3—C8	1.485 (4)	C17—C18	1.526 (4)
N3—H3A	0.8568	C17—H17A	0.9900
N3—H3B	0.8984	C17—H17B	0.9900
N4—C9	1.474 (4)	C18—C19	1.529 (4)
N4—H4C	0.9349	C18—C21	1.536 (4)
N4—H4D	0.9174	C18—C20	1.543 (4)
N5—C14	1.337 (4)	C19—H19A	0.9800
N5—C13	1.458 (4)	C19—H19B	0.9800
N5—H5N	0.9502	C19—H19C	0.9800
N6—C15	1.279 (4)	C20—H20A	0.9800
N7—C17	1.487 (4)	C20—H20B	0.9800
N7—H7D	0.7915	C20—H20C	0.9800
N7—H7E	0.8748	C21—H21A	0.9900
N7—H7F	1.0512	C21—H21B	0.9900
N8—C22	1.341 (4)	C22—C23	1.503 (4)
N8—C21	1.452 (4)	C23—C24	1.499 (4)
N8—H8N	0.8760	C24—H24A	0.9800
N9—C23	1.277 (4)	C24—H24B	0.9800
N10—C25	1.358 (4)	C24—H24C	0.9800
N10—C26	1.445 (4)	C26—C27	1.541 (5)
N10—H10N	0.9806	C26—H26A	0.9900
N11—C31	1.326 (4)	C26—H26B	0.9900
N11—C30	1.465 (4)	C27—C28	1.526 (5)
N11—H11N	0.8987	C27—C30	1.529 (4)
N12—C32	1.283 (4)	C27—C29	1.535 (4)
N13—C35	1.115 (5)	C28—H28A	0.9800
C1—C2	1.488 (4)	C28—H28B	0.9800
C1—C3	1.507 (4)	C28—H28C	0.9800
C2—H2A	0.9800	C29—H29A	0.9800
C2—H2B	0.9800	C29—H29B	0.9800
C2—H2C	0.9800	C29—H29C	0.9800
C4—C5	1.531 (4)	C30—H30A	0.9900
C4—H4A	0.9900	C30—H30B	0.9900
C4—H4B	0.9900	C31—C32	1.504 (4)
C5—C6	1.528 (4)	C32—C33	1.496 (4)
C5—C7	1.535 (4)	C33—H33A	0.9800
C5—C8	1.538 (4)	C33—H33B	0.9800
C6—H6A	0.9800	C33—H33C	0.9800
C6—H6B	0.9800	C35—C34	1.442 (6)
C6—H6C	0.9800	C34—H34A	0.9800
C7—H7A	0.9800	C34—H34B	0.9800
C7—H7B	0.9800	C34—H34C	0.9800
C7—H7C	0.9800
N1—Cu1—N2	81.63 (10)	H12B—C12—H12C	109.5
N1—Cu1—N3	173.95 (10)	N5—C13—C10	115.2 (2)
N1—Cu1—N4	89.54 (10)	N5—C13—H13A	108.5
N2—Cu1—N3	95.35 (10)	C10—C13—H13A	108.5
N2—Cu1—N4	157.75 (10)	N5—C13—H13B	108.5
N3—Cu1—N4	95.10 (10)	C10—C13—H13B	108.5
N6—O4—H4O	112.4	H13A—C13—H13B	107.5
N9—O6—H6O	104.4	O3—C14—N5	122.8 (3)
N12—O10—H10O	103.6	O3—C14—C15	119.9 (3)
C1—N1—O1	120.8 (2)	N5—C14—C15	117.3 (2)
C1—N1—Cu1	114.9 (2)	N6—C15—C16	127.2 (3)
O1—N1—Cu1	124.36 (17)	N6—C15—C14	115.6 (3)
C3—N2—C4	117.5 (2)	C16—C15—C14	117.2 (3)
C3—N2—Cu1	114.07 (19)	C15—C16—H16A	109.5
C4—N2—Cu1	127.20 (18)	C15—C16—H16B	109.5
C8—N3—Cu1	120.40 (18)	H16A—C16—H16B	109.5
C8—N3—H3A	109.0	C15—C16—H16C	109.5
Cu1—N3—H3A	103.3	H16A—C16—H16C	109.5
C8—N3—H3B	101.7	H16B—C16—H16C	109.5
Cu1—N3—H3B	119.6	N7—C17—C18	114.9 (2)
H3A—N3—H3B	101.0	N7—C17—H17A	108.5
C9—N4—Cu1	115.68 (18)	C18—C17—H17A	108.5
C9—N4—H4C	103.7	N7—C17—H17B	108.5
Cu1—N4—H4C	107.6	C18—C17—H17B	108.5
C9—N4—H4D	122.4	H17A—C17—H17B	107.5
Cu1—N4—H4D	100.8	C17—C18—C19	106.8 (2)
H4C—N4—H4D	105.7	C17—C18—C21	111.3 (2)
C14—N5—C13	123.0 (2)	C19—C18—C21	110.2 (2)
C14—N5—H5N	113.3	C17—C18—C20	110.4 (2)
C13—N5—H5N	121.7	C19—C18—C20	110.3 (3)
C15—N6—O4	112.8 (3)	C21—C18—C20	107.8 (2)
C17—N7—H7D	120.2	C18—C19—H19A	109.5
C17—N7—H7E	95.0	C18—C19—H19B	109.5
H7D—N7—H7E	112.0	H19A—C19—H19B	109.5
C17—N7—H7F	116.4	C18—C19—H19C	109.5
H7D—N7—H7F	98.1	H19A—C19—H19C	109.5
H7E—N7—H7F	116.5	H19B—C19—H19C	109.5
C22—N8—C21	124.0 (3)	C18—C20—H20A	109.5
C22—N8—H8N	115.8	C18—C20—H20B	109.5
C21—N8—H8N	120.2	H20A—C20—H20B	109.5
C23—N9—O6	112.8 (2)	C18—C20—H20C	109.5
C25—N10—C26	124.3 (3)	H20A—C20—H20C	109.5
C25—N10—H10N	116.8	H20B—C20—H20C	109.5
C26—N10—H10N	118.2	N8—C21—C18	113.4 (2)
C31—N11—C30	124.3 (3)	N8—C21—H21A	108.9
C31—N11—H11N	116.0	C18—C21—H21A	108.9
C30—N11—H11N	119.4	N8—C21—H21B	108.9
C32—N12—O10	112.4 (2)	C18—C21—H21B	108.9
N1—C1—C2	124.0 (3)	H21A—C21—H21B	107.7
N1—C1—C3	113.6 (2)	O5—C22—N8	123.0 (3)
C2—C1—C3	122.4 (2)	O5—C22—C23	122.0 (3)
C1—C2—H2A	109.5	N8—C22—C23	115.0 (3)
C1—C2—H2B	109.5	N9—C23—C24	125.5 (3)
H2A—C2—H2B	109.5	N9—C23—C22	115.0 (2)
C1—C2—H2C	109.5	C24—C23—C22	119.5 (3)
H2A—C2—H2C	109.5	C23—C24—H24A	109.5
H2B—C2—H2C	109.5	C23—C24—H24B	109.5
O2—C3—N2	126.7 (3)	H24A—C24—H24B	109.5
O2—C3—C1	118.6 (2)	C23—C24—H24C	109.5
N2—C3—C1	114.7 (2)	H24A—C24—H24C	109.5
N2—C4—C5	113.8 (2)	H24B—C24—H24C	109.5
N2—C4—H4A	108.8	O7—C25—O8	122.7 (3)
C5—C4—H4A	108.8	O7—C25—N10	118.6 (3)
N2—C4—H4B	108.8	O8—C25—N10	118.7 (3)
C5—C4—H4B	108.8	N10—C26—C27	116.3 (3)
H4A—C4—H4B	107.7	N10—C26—H26A	108.2
C6—C5—C4	107.9 (2)	C27—C26—H26A	108.2
C6—C5—C7	110.0 (3)	N10—C26—H26B	108.2
C4—C5—C7	110.4 (2)	C27—C26—H26B	108.2
C6—C5—C8	106.5 (2)	H26A—C26—H26B	107.4
C4—C5—C8	111.3 (2)	C28—C27—C30	110.1 (3)
C7—C5—C8	110.7 (2)	C28—C27—C29	109.8 (3)
C5—C6—H6A	109.5	C30—C27—C29	107.0 (3)
C5—C6—H6B	109.5	C28—C27—C26	107.7 (3)
H6A—C6—H6B	109.5	C30—C27—C26	111.9 (2)
C5—C6—H6C	109.5	C29—C27—C26	110.3 (3)
H6A—C6—H6C	109.5	C27—C28—H28A	109.5
H6B—C6—H6C	109.5	C27—C28—H28B	109.5
C5—C7—H7A	109.5	H28A—C28—H28B	109.5
C5—C7—H7B	109.5	C27—C28—H28C	109.5
H7A—C7—H7B	109.5	H28A—C28—H28C	109.5
C5—C7—H7C	109.5	H28B—C28—H28C	109.5
H7A—C7—H7C	109.5	C27—C29—H29A	109.5
H7B—C7—H7C	109.5	C27—C29—H29B	109.5
N3—C8—C5	113.8 (2)	H29A—C29—H29B	109.5
N3—C8—H8A	108.8	C27—C29—H29C	109.5
C5—C8—H8A	108.8	H29A—C29—H29C	109.5
N3—C8—H8B	108.8	H29B—C29—H29C	109.5
C5—C8—H8B	108.8	N11—C30—C27	114.1 (2)
H8A—C8—H8B	107.7	N11—C30—H30A	108.7
N4—C9—C10	115.8 (2)	C27—C30—H30A	108.7
N4—C9—H9A	108.3	N11—C30—H30B	108.7
C10—C9—H9A	108.3	C27—C30—H30B	108.7
N4—C9—H9B	108.3	H30A—C30—H30B	107.6
C10—C9—H9B	108.3	O9—C31—N11	124.4 (3)
H9A—C9—H9B	107.4	O9—C31—C32	118.2 (3)
C11—C10—C9	110.6 (2)	N11—C31—C32	117.4 (3)
C11—C10—C13	107.2 (2)	N12—C32—C33	126.5 (3)
C9—C10—C13	112.6 (2)	N12—C32—C31	116.7 (3)
C11—C10—C12	109.7 (3)	C33—C32—C31	116.8 (3)
C9—C10—C12	107.2 (2)	C32—C33—H33A	109.5
C13—C10—C12	109.5 (2)	C32—C33—H33B	109.5
C10—C11—H11A	109.5	H33A—C33—H33B	109.5
C10—C11—H11B	109.5	C32—C33—H33C	109.5
H11A—C11—H11B	109.5	H33A—C33—H33C	109.5
C10—C11—H11C	109.5	H33B—C33—H33C	109.5
H11A—C11—H11C	109.5	N13—C35—C34	178.4 (5)
H11B—C11—H11C	109.5	C35—C34—H34A	109.5
C10—C12—H12A	109.5	C35—C34—H34B	109.5
C10—C12—H12B	109.5	H34A—C34—H34B	109.5
H12A—C12—H12B	109.5	C35—C34—H34C	109.5
C10—C12—H12C	109.5	H34A—C34—H34C	109.5
H12A—C12—H12C	109.5	H34B—C34—H34C	109.5
N2—Cu1—N1—C1	−5.1 (2)	C12—C10—C13—N5	−60.3 (3)
N4—Cu1—N1—C1	154.4 (2)	C13—N5—C14—O3	0.2 (4)
N2—Cu1—N1—O1	173.3 (2)	C13—N5—C14—C15	179.9 (3)
N4—Cu1—N1—O1	−27.2 (2)	O4—N6—C15—C16	−0.3 (4)
N1—Cu1—N2—C3	9.48 (19)	O4—N6—C15—C14	179.0 (2)
N3—Cu1—N2—C3	−175.8 (2)	O3—C14—C15—N6	−156.0 (3)
N4—Cu1—N2—C3	−58.1 (3)	N5—C14—C15—N6	24.2 (4)
N1—Cu1—N2—C4	176.6 (2)	O3—C14—C15—C16	23.3 (4)
N3—Cu1—N2—C4	−8.7 (2)	N5—C14—C15—C16	−156.5 (3)
N4—Cu1—N2—C4	109.0 (3)	N7—C17—C18—C19	−175.7 (2)
N2—Cu1—N3—C8	15.5 (2)	N7—C17—C18—C21	64.0 (3)
N4—Cu1—N3—C8	−144.8 (2)	N7—C17—C18—C20	−55.7 (3)
N2—Cu1—N4—C9	−18.8 (4)	C22—N8—C21—C18	−99.9 (3)
N1—Cu1—N4—C9	−85.0 (2)	C17—C18—C21—N8	59.0 (3)
N3—Cu1—N4—C9	98.9 (2)	C19—C18—C21—N8	−59.3 (3)
O1—N1—C1—C2	0.2 (4)	C20—C18—C21—N8	−179.8 (2)
Cu1—N1—C1—C2	178.6 (2)	C21—N8—C22—O5	0.5 (4)
O1—N1—C1—C3	−178.1 (2)	C21—N8—C22—C23	179.7 (2)
Cu1—N1—C1—C3	0.3 (3)	O6—N9—C23—C24	2.2 (4)
C4—N2—C3—O2	−1.0 (4)	O6—N9—C23—C22	−179.7 (2)
Cu1—N2—C3—O2	167.4 (2)	O5—C22—C23—N9	177.3 (3)
C4—N2—C3—C1	179.7 (2)	N8—C22—C23—N9	−1.9 (4)
Cu1—N2—C3—C1	−11.9 (3)	O5—C22—C23—C24	−4.5 (4)
N1—C1—C3—O2	−171.6 (2)	N8—C22—C23—C24	176.3 (3)
C2—C1—C3—O2	10.0 (4)	C26—N10—C25—O7	8.3 (4)
N1—C1—C3—N2	7.7 (3)	C26—N10—C25—O8	−174.4 (3)
C2—C1—C3—N2	−170.6 (3)	C25—N10—C26—C27	−102.4 (3)
C3—N2—C4—C5	−161.1 (2)	N10—C26—C27—C28	172.9 (3)
Cu1—N2—C4—C5	32.3 (3)	N10—C26—C27—C30	51.7 (4)
N2—C4—C5—C6	−178.5 (2)	N10—C26—C27—C29	−67.3 (3)
N2—C4—C5—C7	61.3 (3)	C31—N11—C30—C27	111.7 (3)
N2—C4—C5—C8	−62.0 (3)	C28—C27—C30—N11	−64.4 (3)
Cu1—N3—C8—C5	−47.1 (3)	C29—C27—C30—N11	176.4 (3)
C6—C5—C8—N3	−171.1 (2)	C26—C27—C30—N11	55.4 (4)
C4—C5—C8—N3	71.6 (3)	C30—N11—C31—O9	−0.2 (5)
C7—C5—C8—N3	−51.5 (3)	C30—N11—C31—C32	178.6 (3)
Cu1—N4—C9—C10	178.84 (19)	O10—N12—C32—C33	2.8 (4)
N4—C9—C10—C11	−57.4 (3)	O10—N12—C32—C31	−176.9 (2)
N4—C9—C10—C13	62.5 (3)	O9—C31—C32—N12	172.1 (3)
N4—C9—C10—C12	−177.0 (2)	N11—C31—C32—N12	−6.7 (4)
C14—N5—C13—C10	−91.1 (3)	O9—C31—C32—C33	−7.6 (4)
C11—C10—C13—N5	−179.3 (2)	N11—C31—C32—C33	173.6 (3)
C9—C10—C13—N5	58.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O2ii	1.00	1.67	2.574 (3)	150
O6—H6O···O1i	0.91	1.71	2.613 (3)	174
N3—H3A···O1i	0.86	2.45	2.938 (3)	116
N3—H3B···O3	0.90	2.16	2.978 (3)	151
N4—H4C···O3	0.93	2.09	2.908 (3)	145
N4—H4D···O1	0.92	2.47	2.967 (3)	115
N4—H4D···N1i	0.92	2.50	3.123 (3)	126
N7—H7D···O5iii	0.79	2.29	3.002 (3)	149
N7—H7D···O5	0.79	2.60	3.109 (3)	123
N7—H7E···O7iii	0.87	1.84	2.705 (3)	172
N7—H7F···O8iv	1.05	1.82	2.859 (3)	169
N7—H7F···O7iv	1.05	2.43	2.981 (3)	112
N10—H10N···N13v	0.98	2.27	3.107 (5)	143
N11—H11N···O7	0.90	1.95	2.773 (3)	151
O10—H10O···O8vi	0.86	1.77	2.626 (3)	169

Table 1

Selected bond lengths (Å)

Cu1—N1	1.984 (2)
Cu1—N2	1.957 (2)
Cu1—N3	2.000 (2)
Cu1—N4	2.041 (2)
Cu1—O1i	2.441 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O2i	1.00	1.67	2.574 (3)	150
O6—H6O⋯O1ii	0.91	1.71	2.613 (3)	174
N3—H3A⋯O1ii	0.86	2.45	2.938 (3)	116
N3—H3B⋯O3	0.90	2.16	2.978 (3)	151
N4—H4C⋯O3	0.93	2.09	2.908 (3)	145
N4—H4D⋯O1	0.92	2.47	2.967 (3)	115
N4—H4D⋯N1ii	0.92	2.50	3.123 (3)	126
N7—H7D⋯O5iii	0.79	2.29	3.002 (3)	149
N7—H7D⋯O5	0.79	2.60	3.109 (3)	123
N7—H7E⋯O7iii	0.87	1.84	2.705 (3)	172
N7—H7F⋯O8iv	1.05	1.82	2.859 (3)	169
N7—H7F⋯O7iv	1.05	2.43	2.981 (3)	112
N10—H10N⋯N13v	0.98	2.27	3.107 (5)	143
N11—H11N⋯O7	0.90	1.95	2.773 (3)	151
O10—H10O⋯O8vi	0.86	1.77	2.626 (3)	169

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .