Tetra-μ-acetato-κO:O'-bis-[(3,5-di-methyl-1H-pyrazole-κN)-copper(II)].

The dinuclear centrosymmetric title compound, [Cu(2)(CH(3)CO(2))(4)(C(5)H(8)N(2))(2)], has a distorted square-pyramidal coordination geometry around each Cu(II) atom in which four O atoms from the bridging acetate ligands form the basal plane while two N atoms from the pyrazole ligands occupy the apical positions. The crystal has two half mol-ecules in the asymmetric unit with a Cu⋯Cu distance of 2.6762 (4) Å. Disorder was found for two O atoms and two C atoms of one acetate ligand and refined with occupancies of 0.265 (7) and 0.735 (7). The crystal also features mol-ecules linked through two N-H⋯O hydrogen bonds resulting in one-dimensional chains extending along the crystallographic b axis.

Related literature

For the properties and applications of 1H-pyrazolyl-3,5-substituted ligands, see: Deka et al. (2006 ▶); Guzei et al. (2003 ▶); Mohlala et al. (2005 ▶); Nelana et al. (2008 ▶); Ojwach et al. (2005 ▶).

Experimental

Crystal data

[Cu2(C2H3O2)4(C5n class="Species">H8N2)2]

M = 555.52

Triclinic,

a = 8.1125 (4) Å

b = 13.6429 (7) Å

c = 13.7755 (7) Å

α = 61.571 (1)°

β = 87.449 (1)°

γ = 82.354 (1)°

V = 1328.55 (12) Å3

Z = 2

Mo Kα radiation

μ = 1.64 mm−1

T = 100 K

0.39 × 0.16 × 0.10 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.566, T max = 0.853

17190 measured reflections

6578 independent reflections

5934 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.089

S = 1.06

6578 reflections

310 parameters

17 restraints

H-atom parameters constrained

Δρmax = 1.28 e Å−3

Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶), ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811032600/hg5077sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032600/hg5077Isup2.hkl

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

[Cu2(C2H3O2)4(C5H8N2)2]	Z = 2
Mr = 555.52	F(000) = 572
Triclinic, P1	Dx = 1.389 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1125 (4) Å	Cell parameters from 17682 reflections
b = 13.6429 (7) Å	θ = 2.5–28.4°
c = 13.7755 (7) Å	µ = 1.64 mm−1
α = 61.571 (1)°	T = 100 K
β = 87.449 (1)°	Block, green
γ = 82.354 (1)°	0.39 × 0.16 × 0.1 mm
V = 1328.55 (12) Å3

Bruker X8 APEXII 4K Kappa CCD diffractometer	5934 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 28.4°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.566, Tmax = 0.853	k = −18→17
17190 measured reflections	l = −18→18
6578 independent 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0503P)2 + 0.7634P] where P = (Fo2 + 2Fc2)/3
6578 reflections	(Δ/σ)max = 0.012
310 parameters	Δρmax = 1.28 e Å−3
17 restraints	Δρmin = −0.59 e Å−3

Experimental. Diorder: Disorder was found for two O atoms and two C atoms of one acetate ligand in which is not an uncommon situation. The disorder was modelled for two O–, two C– and H-atoms using distance restraints and PART instructions and the total occupancy at each atom site was kept as 1 during the refinement. DELU and SIMU constraints and restraints were used on the disordered atoms. All carbon atoms involved in disorder were modelled with anisotropic thermal parameters and refined with occupancies of 0.265 (7) and 0.735 (7). The "solvent" molecule resided in a special position and looked disordered as well. Modelling the disorder only distabillized the refinement. As a result, the moleculed was removed using the SQUEEZE subroutine in PLATON giving an R factor of 3.0%. H-atom Placement: All H-atoms were placed in idealized locations and refined as riding with appropriate thermal displacement coefficients Uiso(H) = 1.2 or 1.5 times Ueq(bearing atom).

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.The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level.PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ···. 2.18The solvent molecule was excluded. The remaining electron density peaks are very close to other atoms and make no chemical sense. PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ···.. 3 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 33 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 39 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 1 PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 10 PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ···. 4 PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ·········. 0.00100 Deg.These are noted PLAT301_ALERT_3_G Note: Main Residue Disorder ··················. 13 Perc.See disorder explanation above. PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety C18 PLAT605_ALERT_4_G Structure Contains Solvent Accessible VOIDS of. 199 A**3 PLAT869_ALERT_4_G ALERTS Related to the use of SQUEEZE Suppressed ! Solvent molecule was excluded as it was grossly disordered. PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd). 1.17 Ratio PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ······. 17 PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ······. ! Noted.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.53478 (2)	0.494657 (16)	0.406632 (17)	0.01851 (7)
O1	0.40264 (18)	0.64415 (11)	0.33807 (11)	0.0291 (3)
O2	0.34793 (16)	0.65464 (11)	0.49368 (11)	0.0270 (3)
C1	0.3431 (2)	0.69462 (15)	0.39072 (16)	0.0237 (3)
C2	0.2597 (3)	0.81398 (16)	0.32348 (18)	0.0329 (4)
H2A	0.1426	0.8186	0.3437	0.049*
H2B	0.2666	0.8358	0.2447	0.049*
H2C	0.3159	0.8648	0.3385	0.049*
O3	0.32633 (15)	0.42403 (12)	0.43652 (12)	0.0264 (3)
O4	0.26852 (16)	0.43494 (12)	0.59184 (11)	0.0272 (3)
N1	0.59519 (19)	0.48564 (13)	0.25736 (13)	0.0227 (3)
N2	0.61058 (18)	0.38656 (13)	0.25468 (13)	0.0225 (3)
H2	0.602	0.3213	0.3131	0.027*
C3	0.2366 (2)	0.40998 (14)	0.51864 (16)	0.0226 (3)
C4	0.0775 (2)	0.35986 (17)	0.52824 (19)	0.0308 (4)
H4A	0.0222	0.3494	0.5966	0.046*
H4B	0.1034	0.2871	0.5294	0.046*
H4C	0.0036	0.4106	0.4649	0.046*
C5	0.6131 (3)	0.68424 (17)	0.12252 (19)	0.0398 (5)
H5A	0.5011	0.7136	0.134	0.06*
H5B	0.6415	0.7267	0.0447	0.06*
H5C	0.6935	0.692	0.1687	0.06*
C6	0.6178 (2)	0.56309 (16)	0.15334 (16)	0.0269 (4)
C7	0.6457 (3)	0.51248 (17)	0.08502 (16)	0.0303 (4)
H7	0.6644	0.5488	0.0079	0.036*
C8	0.6403 (2)	0.39916 (17)	0.15302 (16)	0.0272 (4)
C9	0.6625 (3)	0.30197 (19)	0.12979 (19)	0.0363 (5)
H9A	0.7677	0.2549	0.1634	0.055*
H9B	0.6644	0.3298	0.0498	0.055*
H9C	0.5701	0.2574	0.1609	0.055*
Cu2	0.40853 (2)	0.091442 (18)	0.42346 (2)	0.02307 (7)
O7A	0.338 (2)	0.1009 (10)	0.5625 (7)	0.0308 (6)	0.265 (7)
O8A	0.500 (3)	−0.0504 (12)	0.6844 (12)	0.0307 (7)	0.265 (7)
C12A	0.390 (2)	0.0326 (10)	0.6618 (7)	0.0265 (7)	0.265 (7)
C13A	0.3283 (13)	0.0421 (10)	0.7642 (8)	0.0357 (8)	0.265 (7)
H13A	0.4128	0.0705	0.7894	0.054*	0.265 (7)
H13B	0.308	−0.0321	0.8231	0.054*	0.265 (7)
H13C	0.2247	0.094	0.7457	0.054*	0.265 (7)
O7	0.3327 (7)	0.1281 (3)	0.5399 (3)	0.0308 (6)	0.735 (7)
O8	0.4827 (8)	−0.0262 (4)	0.6696 (4)	0.0307 (7)	0.735 (7)
C12	0.3826 (6)	0.0633 (3)	0.6357 (3)	0.0265 (7)	0.735 (7)
C13	0.3140 (4)	0.0927 (3)	0.7245 (3)	0.0357 (8)	0.735 (7)
H13D	0.3479	0.1646	0.7103	0.054*	0.735 (7)
H13E	0.3576	0.0338	0.797	0.054*	0.735 (7)
H13F	0.1923	0.0988	0.7234	0.054*	0.735 (7)
O5	0.61101 (16)	0.16201 (11)	0.41197 (12)	0.0290 (3)
O6	0.76410 (15)	0.00869 (11)	0.53847 (12)	0.0264 (3)
N3	0.23162 (18)	0.33734 (13)	0.29863 (14)	0.0241 (3)
H3	0.2743	0.3505	0.3483	0.029*
N4	0.26197 (18)	0.23761 (13)	0.29750 (14)	0.0248 (3)
C10	0.7459 (2)	0.10916 (14)	0.46471 (16)	0.0217 (3)
C11	0.8953 (2)	0.17237 (16)	0.43519 (18)	0.0283 (4)
H11A	0.9293	0.1893	0.3602	0.042*
H11B	0.9871	0.1262	0.4874	0.042*
H11C	0.8665	0.2427	0.4387	0.042*
C14	0.0769 (3)	0.52926 (18)	0.2005 (2)	0.0438 (5)
H14A	−0.0194	0.5283	0.2464	0.066*
H14B	0.0469	0.5806	0.1228	0.066*
H14C	0.1688	0.5548	0.2226	0.066*
C15	0.1293 (2)	0.41377 (17)	0.21551 (17)	0.0295 (4)
C16	0.0898 (3)	0.36072 (18)	0.15710 (17)	0.0325 (4)
H16	0.0191	0.3919	0.0935	0.039*
C17	0.1746 (2)	0.25240 (17)	0.21025 (17)	0.0291 (4)
C18	0.1723 (3)	0.1581 (2)	0.1831 (2)	0.0442 (5)
H18A	0.2449	0.0919	0.2356	0.066*
H18B	0.2121	0.1813	0.108	0.066*
H18C	0.0585	0.1397	0.1881	0.066*

	U11	U22	U33	U12	U13	U23
Cu1	0.01382 (10)	0.01959 (11)	0.02424 (11)	−0.00497 (7)	−0.00013 (7)	−0.01135 (9)
O1	0.0309 (7)	0.0250 (6)	0.0293 (7)	0.0015 (5)	−0.0050 (5)	−0.0119 (6)
O2	0.0234 (6)	0.0237 (6)	0.0323 (7)	0.0002 (5)	0.0000 (5)	−0.0127 (5)
C1	0.0167 (7)	0.0199 (8)	0.0342 (9)	−0.0051 (6)	−0.0024 (7)	−0.0115 (7)
C2	0.0340 (10)	0.0204 (8)	0.0389 (11)	0.0002 (7)	−0.0056 (8)	−0.0102 (8)
O3	0.0175 (6)	0.0336 (7)	0.0382 (7)	−0.0098 (5)	0.0029 (5)	−0.0238 (6)
O4	0.0212 (6)	0.0345 (7)	0.0314 (7)	−0.0143 (5)	0.0032 (5)	−0.0176 (6)
N1	0.0203 (7)	0.0227 (7)	0.0261 (7)	−0.0055 (5)	0.0016 (5)	−0.0118 (6)
N2	0.0194 (7)	0.0231 (7)	0.0270 (7)	−0.0055 (5)	0.0019 (6)	−0.0129 (6)
C3	0.0142 (7)	0.0206 (8)	0.0342 (9)	−0.0043 (6)	−0.0016 (6)	−0.0132 (7)
C4	0.0189 (8)	0.0351 (10)	0.0491 (12)	−0.0132 (7)	0.0053 (8)	−0.0267 (9)
C5	0.0529 (13)	0.0254 (10)	0.0361 (11)	−0.0120 (9)	0.0088 (10)	−0.0095 (8)
C6	0.0270 (9)	0.0265 (9)	0.0261 (9)	−0.0064 (7)	0.0011 (7)	−0.0108 (7)
C7	0.0313 (10)	0.0348 (10)	0.0241 (9)	−0.0050 (8)	0.0017 (7)	−0.0133 (8)
C8	0.0221 (8)	0.0339 (10)	0.0296 (9)	−0.0051 (7)	0.0004 (7)	−0.0178 (8)
C9	0.0376 (11)	0.0404 (11)	0.0410 (11)	−0.0042 (9)	0.0013 (9)	−0.0276 (10)
Cu2	0.01346 (11)	0.02278 (12)	0.03971 (14)	−0.00579 (8)	0.00376 (9)	−0.01966 (10)
O7A	0.0260 (8)	0.0252 (19)	0.0478 (14)	0.0024 (16)	0.0025 (14)	−0.0243 (13)
O8A	0.0267 (17)	0.029 (2)	0.0418 (16)	−0.0021 (15)	0.0072 (12)	−0.0219 (16)
C12A	0.0203 (10)	0.028 (2)	0.0427 (16)	−0.0108 (16)	0.0121 (15)	−0.0251 (15)
C13A	0.0362 (13)	0.040 (2)	0.0327 (19)	0.0104 (15)	0.0002 (13)	−0.0219 (17)
O7	0.0260 (8)	0.0252 (19)	0.0478 (14)	0.0024 (16)	0.0025 (14)	−0.0243 (13)
O8	0.0267 (17)	0.029 (2)	0.0418 (16)	−0.0021 (15)	0.0072 (12)	−0.0219 (16)
C12	0.0203 (10)	0.028 (2)	0.0427 (16)	−0.0108 (16)	0.0121 (15)	−0.0251 (15)
C13	0.0362 (13)	0.040 (2)	0.0327 (19)	0.0104 (15)	0.0002 (13)	−0.0219 (17)
O5	0.0178 (6)	0.0226 (6)	0.0441 (8)	−0.0066 (5)	−0.0034 (5)	−0.0127 (6)
O6	0.0147 (5)	0.0223 (6)	0.0437 (8)	−0.0053 (5)	0.0016 (5)	−0.0162 (6)
N3	0.0181 (7)	0.0247 (7)	0.0330 (8)	−0.0053 (5)	−0.0005 (6)	−0.0157 (6)
N4	0.0186 (7)	0.0278 (8)	0.0349 (8)	−0.0079 (6)	0.0034 (6)	−0.0194 (7)
C10	0.0153 (7)	0.0212 (8)	0.0353 (9)	−0.0058 (6)	0.0042 (6)	−0.0183 (7)
C11	0.0166 (8)	0.0245 (8)	0.0461 (11)	−0.0078 (6)	0.0045 (7)	−0.0175 (8)
C14	0.0451 (13)	0.0270 (10)	0.0538 (14)	0.0009 (9)	−0.0147 (11)	−0.0148 (10)
C15	0.0233 (9)	0.0293 (9)	0.0334 (10)	−0.0073 (7)	0.0005 (7)	−0.0120 (8)
C16	0.0305 (10)	0.0382 (11)	0.0282 (9)	−0.0103 (8)	−0.0002 (8)	−0.0138 (8)
C17	0.0258 (9)	0.0365 (10)	0.0313 (9)	−0.0118 (7)	0.0051 (7)	−0.0197 (8)
C18	0.0488 (13)	0.0505 (14)	0.0502 (13)	−0.0092 (11)	−0.0038 (11)	−0.0363 (12)

Cu1—O2i	1.9691 (13)	Cu2—O7A	2.032 (9)
Cu1—O1	1.9685 (13)	Cu2—N4	2.1585 (17)
Cu1—O4i	1.9747 (12)	Cu2—Cu2ii	2.6755 (5)
Cu1—O3	1.9879 (12)	O7A—C12A	1.283 (8)
Cu1—N1	2.1492 (16)	O8A—C12A	1.265 (9)
Cu1—Cu1i	2.6763 (4)	O8A—Cu2ii	1.912 (15)
O1—C1	1.261 (2)	C12A—C13A	1.534 (9)
O2—C1	1.254 (2)	C13A—H13A	0.98
O2—Cu1i	1.9691 (13)	C13A—H13B	0.98
C1—C2	1.515 (2)	C13A—H13C	0.98
C2—H2A	0.98	O7—C12	1.236 (4)
C2—H2B	0.98	O8—C12	1.263 (4)
C2—H2C	0.98	O8—Cu2ii	1.997 (5)
O3—C3	1.266 (2)	C12—C13	1.522 (4)
O4—C3	1.254 (2)	C13—H13D	0.98
O4—Cu1i	1.9747 (12)	C13—H13E	0.98
N1—C6	1.338 (2)	C13—H13F	0.98
N1—N2	1.359 (2)	O5—C10	1.268 (2)
N2—C8	1.342 (2)	O6—C10	1.252 (2)
N2—H2	0.88	O6—Cu2ii	1.9657 (12)
C3—C4	1.512 (2)	N3—C15	1.344 (2)
C4—H4A	0.98	N3—N4	1.357 (2)
C4—H4B	0.98	N3—H3	0.88
C4—H4C	0.98	N4—C17	1.340 (3)
C5—C6	1.493 (3)	C10—C11	1.509 (2)
C5—H5A	0.98	C11—H11A	0.98
C5—H5B	0.98	C11—H11B	0.98
C5—H5C	0.98	C11—H11C	0.98
C6—C7	1.404 (3)	C14—C15	1.492 (3)
C7—C8	1.380 (3)	C14—H14A	0.98
C7—H7	0.95	C14—H14B	0.98
C8—C9	1.493 (3)	C14—H14C	0.98
C9—H9A	0.98	C15—C16	1.383 (3)
C9—H9B	0.98	C16—C17	1.392 (3)
C9—H9C	0.98	C16—H16	0.95
Cu2—O8Aii	1.912 (15)	C17—C18	1.503 (3)
Cu2—O7	1.949 (3)	C18—H18A	0.98
Cu2—O6ii	1.9657 (12)	C18—H18B	0.98
Cu2—O5	1.9756 (13)	C18—H18C	0.98
Cu2—O8ii	1.997 (5)
O2i—Cu1—O1	167.13 (6)	O5—Cu2—O8ii	88.6 (2)
O2i—Cu1—O4i	90.21 (6)	O8Aii—Cu2—O7A	167.1 (4)
O1—Cu1—O4i	89.34 (6)	O7—Cu2—O7A	9.9 (3)
O2i—Cu1—O3	87.95 (6)	O6ii—Cu2—O7A	84.8 (5)
O1—Cu1—O3	89.68 (6)	O5—Cu2—O7A	92.1 (5)
O4i—Cu1—O3	167.33 (6)	O8ii—Cu2—O7A	158.3 (3)
O2i—Cu1—N1	95.41 (6)	O8Aii—Cu2—N4	90.8 (3)
O1—Cu1—N1	97.43 (6)	O7—Cu2—N4	93.06 (12)
O4i—Cu1—N1	95.81 (6)	O6ii—Cu2—N4	95.65 (6)
O3—Cu1—N1	96.84 (6)	O5—Cu2—N4	97.26 (6)
O2i—Cu1—Cu1i	84.06 (4)	O8ii—Cu2—N4	99.45 (13)
O1—Cu1—Cu1i	83.11 (4)	O7A—Cu2—N4	101.9 (3)
O4i—Cu1—Cu1i	83.34 (4)	O8Aii—Cu2—Cu2ii	88.0 (3)
O3—Cu1—Cu1i	83.99 (4)	O7—Cu2—Cu2ii	88.14 (11)
N1—Cu1—Cu1i	179.00 (4)	O6ii—Cu2—Cu2ii	84.11 (4)
C1—O1—Cu1	124.01 (12)	O5—Cu2—Cu2ii	82.99 (4)
C1—O2—Cu1i	123.04 (12)	O8ii—Cu2—Cu2ii	79.36 (12)
O2—C1—O1	125.59 (17)	O7A—Cu2—Cu2ii	79.3 (3)
O2—C1—C2	117.43 (17)	N4—Cu2—Cu2ii	178.78 (5)
O1—C1—C2	116.98 (17)	C12A—O7A—Cu2	127.1 (9)
C1—C2—H2A	109.5	C12A—O8A—Cu2ii	123.2 (10)
C1—C2—H2B	109.5	O8A—C12A—O7A	122.3 (10)
H2A—C2—H2B	109.5	O8A—C12A—C13A	112.9 (9)
C1—C2—H2C	109.5	O7A—C12A—C13A	124.8 (10)
H2A—C2—H2C	109.5	C12A—C13A—H13A	109.5
H2B—C2—H2C	109.5	C12A—C13A—H13B	109.5
C3—O3—Cu1	122.78 (11)	H13A—C13A—H13B	109.5
C3—O4—Cu1i	124.51 (12)	C12A—C13A—H13C	109.5
C6—N1—N2	105.07 (15)	H13A—C13A—H13C	109.5
C6—N1—Cu1	133.35 (13)	H13B—C13A—H13C	109.5
N2—N1—Cu1	121.51 (11)	C12—O7—Cu2	118.6 (3)
C8—N2—N1	112.54 (15)	C12—O8—Cu2ii	126.0 (3)
C8—N2—H2	123.7	O7—C12—O8	127.8 (4)
N1—N2—H2	123.7	O7—C12—C13	116.7 (3)
O4—C3—O3	125.35 (16)	O8—C12—C13	115.5 (4)
O4—C3—C4	117.62 (17)	C10—O5—Cu2	124.10 (12)
O3—C3—C4	117.03 (16)	C10—O6—Cu2ii	123.70 (11)
C3—C4—H4A	109.5	C15—N3—N4	112.53 (16)
C3—C4—H4B	109.5	C15—N3—H3	123.7
H4A—C4—H4B	109.5	N4—N3—H3	123.7
C3—C4—H4C	109.5	C17—N4—N3	104.94 (16)
H4A—C4—H4C	109.5	C17—N4—Cu2	131.64 (13)
H4B—C4—H4C	109.5	N3—N4—Cu2	123.27 (12)
C6—C5—H5A	109.5	O6—C10—O5	124.78 (16)
C6—C5—H5B	109.5	O6—C10—C11	117.99 (15)
H5A—C5—H5B	109.5	O5—C10—C11	117.23 (16)
C6—C5—H5C	109.5	C10—C11—H11A	109.5
H5A—C5—H5C	109.5	C10—C11—H11B	109.5
H5B—C5—H5C	109.5	H11A—C11—H11B	109.5
N1—C6—C7	110.27 (17)	C10—C11—H11C	109.5
N1—C6—C5	121.39 (18)	H11A—C11—H11C	109.5
C7—C6—C5	128.34 (18)	H11B—C11—H11C	109.5
C8—C7—C6	105.85 (17)	C15—C14—H14A	109.5
C8—C7—H7	127.1	C15—C14—H14B	109.5
C6—C7—H7	127.1	H14A—C14—H14B	109.5
N2—C8—C7	106.27 (17)	C15—C14—H14C	109.5
N2—C8—C9	122.23 (18)	H14A—C14—H14C	109.5
C7—C8—C9	131.49 (19)	H14B—C14—H14C	109.5
C8—C9—H9A	109.5	N3—C15—C16	105.90 (18)
C8—C9—H9B	109.5	N3—C15—C14	122.15 (19)
H9A—C9—H9B	109.5	C16—C15—C14	131.9 (2)
C8—C9—H9C	109.5	C15—C16—C17	106.16 (18)
H9A—C9—H9C	109.5	C15—C16—H16	126.9
H9B—C9—H9C	109.5	C17—C16—H16	126.9
O8Aii—Cu2—O7	175.4 (6)	N4—C17—C16	110.47 (18)
O8Aii—Cu2—O6ii	92.2 (7)	N4—C17—C18	120.98 (19)
O7—Cu2—O6ii	89.93 (17)	C16—C17—C18	128.53 (19)
O8Aii—Cu2—O5	88.0 (7)	C17—C18—H18A	109.5
O7—Cu2—O5	89.00 (18)	C17—C18—H18B	109.5
O6ii—Cu2—O5	167.08 (6)	H18A—C18—H18B	109.5
O8Aii—Cu2—O8ii	8.8 (4)	C17—C18—H18C	109.5
O7—Cu2—O8ii	167.47 (13)	H18A—C18—H18C	109.5
O6ii—Cu2—O8ii	89.6 (2)	H18B—C18—H18C	109.5
O2i—Cu1—O1—C1	8.2 (3)	Cu2—O7A—C12A—O8A	3(3)
O4i—Cu1—O1—C1	−79.85 (15)	Cu2—O7A—C12A—C13A	−178.1 (12)
O3—Cu1—O1—C1	87.51 (15)	O6ii—Cu2—O7—C12	82.6 (4)
N1—Cu1—O1—C1	−175.63 (14)	O5—Cu2—O7—C12	−84.5 (4)
Cu1i—Cu1—O1—C1	3.53 (14)	O8ii—Cu2—O7—C12	−5.3 (15)
Cu1i—O2—C1—O1	4.2 (3)	O7A—Cu2—O7—C12	24 (4)
Cu1i—O2—C1—C2	−175.42 (12)	N4—Cu2—O7—C12	178.3 (4)
Cu1—O1—C1—O2	−5.7 (3)	Cu2ii—Cu2—O7—C12	−1.5 (4)
Cu1—O1—C1—C2	173.89 (12)	Cu2—O7—C12—O8	1.6 (9)
O2i—Cu1—O3—C3	85.70 (14)	Cu2—O7—C12—C13	−177.4 (3)
O1—Cu1—O3—C3	−81.65 (14)	Cu2ii—O8—C12—O7	−0.5 (10)
O4i—Cu1—O3—C3	3.9 (3)	Cu2ii—O8—C12—C13	178.5 (4)
N1—Cu1—O3—C3	−179.09 (14)	O8Aii—Cu2—O5—C10	−84.2 (4)
Cu1i—Cu1—O3—C3	1.46 (13)	O7—Cu2—O5—C10	92.26 (18)
O2i—Cu1—N1—C6	−150.52 (17)	O6ii—Cu2—O5—C10	7.0 (4)
O1—Cu1—N1—C6	30.33 (18)	O8ii—Cu2—O5—C10	−75.43 (19)
O4i—Cu1—N1—C6	−59.76 (18)	O7A—Cu2—O5—C10	82.9 (4)
O3—Cu1—N1—C6	120.91 (17)	N4—Cu2—O5—C10	−174.79 (15)
O2i—Cu1—N1—N2	32.91 (13)	Cu2ii—Cu2—O5—C10	4.01 (15)
O1—Cu1—N1—N2	−146.24 (12)	C15—N3—N4—C17	−0.2 (2)
O4i—Cu1—N1—N2	123.67 (13)	C15—N3—N4—Cu2	−176.20 (12)
O3—Cu1—N1—N2	−55.66 (13)	O8Aii—Cu2—N4—C17	41.6 (7)
C6—N1—N2—C8	−0.6 (2)	O7—Cu2—N4—C17	−140.9 (2)
Cu1—N1—N2—C8	176.81 (12)	O6ii—Cu2—N4—C17	−50.68 (17)
Cu1i—O4—C3—O3	1.4 (3)	O5—Cu2—N4—C17	129.72 (17)
Cu1i—O4—C3—C4	−178.07 (13)	O8ii—Cu2—N4—C17	39.9 (3)
Cu1—O3—C3—O4	−2.1 (3)	O7A—Cu2—N4—C17	−136.6 (6)
Cu1—O3—C3—C4	177.33 (12)	O8Aii—Cu2—N4—N3	−143.5 (7)
N2—N1—C6—C7	0.6 (2)	O7—Cu2—N4—N3	34.0 (2)
Cu1—N1—C6—C7	−176.34 (13)	O6ii—Cu2—N4—N3	124.19 (13)
N2—N1—C6—C5	−178.95 (18)	O5—Cu2—N4—N3	−55.42 (14)
Cu1—N1—C6—C5	4.1 (3)	O8ii—Cu2—N4—N3	−145.3 (3)
N1—C6—C7—C8	−0.5 (2)	O7A—Cu2—N4—N3	38.3 (6)
C5—C6—C7—C8	179.1 (2)	Cu2ii—O6—C10—O5	6.4 (3)
N1—N2—C8—C7	0.3 (2)	Cu2ii—O6—C10—C11	−173.03 (13)
N1—N2—C8—C9	179.72 (17)	Cu2—O5—C10—O6	−7.4 (3)
C6—C7—C8—N2	0.1 (2)	Cu2—O5—C10—C11	172.06 (13)
C6—C7—C8—C9	−179.2 (2)	N4—N3—C15—C16	0.3 (2)
O8Aii—Cu2—O7A—C12A	8(5)	N4—N3—C15—C14	179.44 (19)
O7—Cu2—O7A—C12A	−154 (6)	N3—C15—C16—C17	−0.3 (2)
O6ii—Cu2—O7A—C12A	85.3 (17)	C14—C15—C16—C17	−179.3 (2)
O5—Cu2—O7A—C12A	−82.2 (17)	N3—N4—C17—C16	−0.1 (2)
O8ii—Cu2—O7A—C12A	10 (3)	Cu2—N4—C17—C16	175.49 (13)
N4—Cu2—O7A—C12A	180.0 (17)	N3—N4—C17—C18	−178.19 (18)
Cu2ii—Cu2—O7A—C12A	0.3 (17)	Cu2—N4—C17—C18	−2.6 (3)
Cu2ii—O8A—C12A—O7A	−5(3)	C15—C16—C17—N4	0.3 (2)
Cu2ii—O8A—C12A—C13A	175.6 (13)	C15—C16—C17—C18	178.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.88	1.93	2.785 (2)	163.
N3—H3···O3	0.88	2	2.847 (2)	163.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O5	0.88	1.93	2.785 (2)	163
N3—H3⋯O3	0.88	2	2.847 (2)	163