Bis(μ₂-benzoato-κ²O,O′)bis­(benzoato-κO)bis(ethanol-κO)bis­(μ₃-hydroxido)hexa­kis­(μ-pyrazol­ato-κ²N,N′)hexa­copper(II) ethanol disolvate

Trinuclear copper–pyrazolate entities are present in various Cu-based enzymes and nanojar supra­molecular arrangements. The reaction of copper(II) chloride with pyrazole (pzH) and sodium benzoate (benzNa) assisted by microwave radiation afforded a neutral centrosymmetric hexa­nuclear copper(II) complex, [Cu₆(C₇H₅O₂)₄(OH)₂(C₃H₃N₂)₆(C₂H₅OH)₂]·2C₂H₅OH. Half a mol­ecule is present in the asymmetric unit that comprises a [Cu₃(μ₃-OH)(pz)₃]²⁺ core with the copper(II) atoms arranged in an irregular triangle. The three copper(II) atoms are bridged by an O atom of the central hydroxyl group and by three bridging pyrazolate ligands on each of the sides. The carboxyl­ate groups show a chelating mode to one and a bridging syn,syn mode to the other two Cu^II atoms. The coordination environment of one Cu^II atom is square-planar while it is distorted square-pyramidal for the other two. Two ethanol mol­ecules are present in the asymmetric unit, one binding to one of the Cu^II atoms, one as a solvent mol­ecule. In the crystal, stabilization arises from inter­molecular O—H...O hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.020
• wR factor = 0.050
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of        C27 Check
PLAT480_ALERT_4_C Long H...A H-Bond Reported H27A     ..N5       .       2.68 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Theta(Min).          6 Note

Alert level G
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.001 Degree
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N1       .        5.8 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1      --N6       .        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu2      --N2       .        5.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu2      --N3       .        6.2 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu3      --N4       .        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu3      --N5       .        7.6 s.u.
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.14 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Cu3       (II)      .       2.17 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         43 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         17 Info
PLAT992_ALERT_5_G Repd & Actual _reflns_number_gt Values Differ by          1 Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

---

Computing details

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(µ₂-benzoato-κ²O,O')bis(benzoato-κO)bis(ethanol-κO)bis(µ₃-hydroxido)hexakis(µ-pyrazolato-κ²N,N')hexacopper(II) ethanol disolvate

Crystal data

[Cu6(C7H5O2)4(OH)2(C3H3N2)6(C2H6O)2]·2C2H6O	Z = 1
Mr = 1486.40	F(000) = 758
Triclinic, P1	Dx = 1.690 Mg m^−3
a = 10.4608 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4064 (5) Å	Cell parameters from 9612 reflections
c = 13.0357 (6) Å	θ = 3.0–27.6°
α = 85.061 (1)°	µ = 2.22 mm^−1
β = 72.520 (1)°	T = 100 K
γ = 80.044 (1)°	Block, clear light blue
V = 1460.29 (12) Å^3	0.35 × 0.25 × 0.15 mm

Data collection

Bruker D8 Venture diffractometer	6754 independent reflections
Radiation source: Incoatec microsource	6300 reflections with I > 2σ(I)
Mirrors monochromator	Rint = 0.022
Detector resolution: 10.4167 pixels mm^-1	θmax = 27.7°, θmin = 2.5°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −14→14
Tmin = 0.645, Tmax = 0.746	l = −16→16
64647 measured reflections

Refinement

Refinement on F^2	Primary atom site location: inferred from neighbouring sites
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0232P)^2 + 1.2646P] where P = (Fo^2 + 2Fc^2)/3
6754 reflections	(Δ/σ)max = 0.002
400 parameters	Δρmax = 1.00 e Å^−3
0 restraints	Δρmin = −0.72 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. All hydrogen atoms were placed geometrically and refined using a riding-atom model approximation, with C—H = 0.95–1.00 Å, with U_iso(H) = 1.2U_eq(C). A rotating model was used for the methyl groups. The H7 atom of the µ₃-OH group was located in the final Fourier difference map and refined freely.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.28967 (2)	0.73986 (2)	0.64822 (2)	0.00957 (4)
Cu2	0.57945 (2)	0.84981 (2)	0.60585 (2)	0.00910 (4)
Cu3	0.44372 (2)	0.84872 (2)	0.40022 (2)	0.00903 (4)
O1	0.71009 (10)	0.89817 (9)	0.67045 (8)	0.0126 (2)
O2	0.58170 (10)	1.06869 (9)	0.73631 (8)	0.0132 (2)
O3	0.13205 (10)	0.66939 (9)	0.74774 (8)	0.0126 (2)
O4	0.27501 (10)	0.51209 (9)	0.67280 (8)	0.0152 (2)
O7	0.45907 (10)	0.78176 (9)	0.54287 (8)	0.00978 (19)
N1	0.37824 (12)	0.72985 (11)	0.76044 (10)	0.0120 (2)
N2	0.49920 (12)	0.76972 (11)	0.74229 (10)	0.0117 (2)
N3	0.66477 (12)	0.91576 (10)	0.46482 (9)	0.0106 (2)
N4	0.60854 (12)	0.91744 (10)	0.38259 (9)	0.0109 (2)
N5	0.26458 (12)	0.80068 (10)	0.43446 (10)	0.0112 (2)
N6	0.20228 (12)	0.76028 (11)	0.53554 (10)	0.0117 (2)
C1	0.35158 (15)	0.67042 (13)	0.85560 (11)	0.0147 (3)
H1	0.2731	0.6339	0.8872	0.018*
C2	0.45569 (16)	0.67008 (13)	0.90129 (12)	0.0159 (3)
H2	0.4632	0.6343	0.9682	0.019*
C3	0.54640 (15)	0.73377 (13)	0.82703 (12)	0.0138 (3)
H3	0.6292	0.7495	0.8349	0.017*
C4	0.78133 (14)	0.96040 (12)	0.42651 (12)	0.0124 (3)
H4	0.8403	0.969	0.4674	0.015*
C5	0.80270 (15)	0.99204 (13)	0.31813 (12)	0.0141 (3)
H5	0.8766	1.0259	0.2709	0.017*
C6	0.69127 (15)	0.96284 (12)	0.29428 (11)	0.0129 (3)
H6	0.6761	0.9735	0.2256	0.015*
C7	0.18136 (15)	0.79900 (13)	0.37370 (12)	0.0134 (3)
H7	0.2006	0.8224	0.2996	0.016*
C8	0.06347 (15)	0.75804 (13)	0.43504 (12)	0.0154 (3)
H8	−0.0123	0.7481	0.4126	0.018*
O8	0.60791 (17)	0.57097 (14)	0.52992 (12)	0.0421 (4)
C9	0.08100 (15)	0.73499 (13)	0.53626 (12)	0.0143 (3)
H9	0.017	0.7057	0.5972	0.017*
C10	0.67100 (14)	0.97951 (12)	0.73796 (11)	0.0112 (3)
H10	0.644 (3)	0.546 (2)	0.477 (2)	0.048 (8)*
C11	0.73560 (14)	0.96907 (12)	0.82770 (11)	0.0114 (3)
H11	0.498 (2)	0.720 (2)	0.5324 (19)	0.033 (6)*
C12	0.85067 (15)	0.88498 (13)	0.82471 (12)	0.0139 (3)
H12	0.8886	0.8338	0.7657	0.017*
C13	0.90977 (15)	0.87607 (14)	0.90811 (12)	0.0165 (3)
H13	0.9883	0.8191	0.906	0.02*
C14	0.85389 (16)	0.95059 (14)	0.99447 (12)	0.0163 (3)
H14	0.894	0.9441	1.0516	0.02*
C15	0.73963 (16)	1.03462 (13)	0.99774 (12)	0.0169 (3)
H15	0.7019	1.0856	1.0568	0.02*
C16	0.68035 (15)	1.04405 (13)	0.91430 (12)	0.0147 (3)
H16	0.6023	1.1016	0.9164	0.018*
C17	0.16176 (14)	0.55833 (13)	0.73175 (11)	0.0124 (3)
C18	0.05533 (15)	0.48198 (13)	0.78522 (11)	0.0136 (3)
C19	0.07998 (16)	0.36048 (13)	0.76582 (12)	0.0157 (3)
H19	0.1649	0.3259	0.72	0.019*
C20	−0.01983 (17)	0.29002 (14)	0.81361 (13)	0.0185 (3)
H20	−0.0025	0.2071	0.8012	0.022*
C21	−0.14445 (18)	0.34064 (15)	0.87923 (14)	0.0236 (3)
H21	−0.213	0.2927	0.9108	0.028*
C22	−0.16933 (18)	0.46163 (16)	0.89891 (15)	0.0273 (4)
H22	−0.2547	0.4961	0.9442	0.033*
C23	−0.06960 (17)	0.53216 (14)	0.85243 (13)	0.0214 (3)
H23	−0.0865	0.6146	0.8664	0.026*
O5	0.54975 (12)	0.68595 (10)	0.29512 (9)	0.0171 (2)
H5A	0.601 (2)	0.6366 (18)	0.3077 (8)	0.026*
C24	0.64511 (17)	0.71837 (16)	0.10209 (13)	0.0223 (3)
H24A	0.6292	0.7106	0.0328	0.033*
H24B	0.734	0.6737	0.1019	0.033*
H24C	0.6429	0.8026	0.1135	0.033*
C25	0.53594 (16)	0.66945 (13)	0.19152 (12)	0.0167 (3)
H25A	0.4458	0.71	0.1876	0.02*
H25B	0.5413	0.5834	0.1818	0.02*
C27	0.67313 (16)	0.52015 (13)	0.60771 (13)	0.0170 (3)
H27A	0.6896	0.4324	0.6031	0.02*
H27B	0.6122	0.5401	0.6804	0.02*
C26	0.8050 (2)	0.56271 (18)	0.5932 (2)	0.0415 (5)
H26A	0.8668	0.5411	0.5222	0.062*
H26B	0.8454	0.5254	0.6491	0.062*
H26C	0.7893	0.6495	0.5988	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00918 (8)	0.01126 (8)	0.00869 (8)	−0.00253 (6)	−0.00274 (6)	−0.00020 (6)
Cu2	0.01051 (8)	0.00998 (8)	0.00809 (8)	−0.00296 (6)	−0.00396 (6)	0.00012 (6)
Cu3	0.00953 (8)	0.01005 (8)	0.00861 (8)	−0.00248 (6)	−0.00404 (6)	0.00070 (6)
O1	0.0131 (5)	0.0153 (5)	0.0117 (5)	−0.0038 (4)	−0.0056 (4)	−0.0016 (4)
O2	0.0143 (5)	0.0144 (5)	0.0118 (5)	−0.0017 (4)	−0.0061 (4)	0.0021 (4)
O3	0.0113 (5)	0.0131 (5)	0.0127 (5)	−0.0026 (4)	−0.0020 (4)	−0.0008 (4)
O4	0.0127 (5)	0.0166 (5)	0.0141 (5)	−0.0006 (4)	−0.0016 (4)	−0.0009 (4)
O7	0.0106 (5)	0.0099 (5)	0.0094 (5)	−0.0018 (4)	−0.0036 (4)	−0.0001 (4)
N1	0.0122 (6)	0.0129 (6)	0.0110 (6)	−0.0037 (4)	−0.0028 (4)	−0.0004 (4)
N2	0.0128 (6)	0.0121 (5)	0.0114 (6)	−0.0030 (4)	−0.0047 (5)	−0.0005 (4)
N3	0.0109 (5)	0.0111 (5)	0.0108 (5)	−0.0017 (4)	−0.0048 (4)	−0.0006 (4)
N4	0.0118 (6)	0.0124 (5)	0.0094 (5)	−0.0021 (4)	−0.0043 (4)	−0.0002 (4)
N5	0.0128 (6)	0.0108 (5)	0.0110 (5)	−0.0019 (4)	−0.0047 (5)	0.0001 (4)
N6	0.0114 (6)	0.0119 (5)	0.0121 (6)	−0.0028 (4)	−0.0032 (5)	−0.0001 (4)
C1	0.0176 (7)	0.0154 (7)	0.0108 (6)	−0.0053 (5)	−0.0026 (5)	0.0009 (5)
C2	0.0208 (7)	0.0170 (7)	0.0117 (7)	−0.0052 (6)	−0.0066 (6)	0.0018 (5)
C3	0.0166 (7)	0.0142 (7)	0.0128 (7)	−0.0040 (5)	−0.0068 (6)	0.0002 (5)
C4	0.0110 (6)	0.0111 (6)	0.0153 (7)	−0.0014 (5)	−0.0038 (5)	−0.0020 (5)
C5	0.0127 (7)	0.0140 (7)	0.0141 (7)	−0.0029 (5)	−0.0013 (5)	−0.0006 (5)
C6	0.0146 (7)	0.0127 (6)	0.0102 (6)	−0.0024 (5)	−0.0019 (5)	0.0001 (5)
C7	0.0147 (7)	0.0130 (6)	0.0147 (7)	−0.0025 (5)	−0.0077 (5)	0.0005 (5)
C8	0.0124 (7)	0.0165 (7)	0.0193 (7)	−0.0024 (5)	−0.0078 (6)	−0.0006 (6)
O8	0.0558 (10)	0.0408 (8)	0.0249 (7)	0.0325 (7)	−0.0222 (7)	−0.0175 (6)
C9	0.0108 (6)	0.0159 (7)	0.0166 (7)	−0.0030 (5)	−0.0038 (5)	−0.0009 (5)
C10	0.0116 (6)	0.0123 (6)	0.0109 (6)	−0.0063 (5)	−0.0035 (5)	0.0027 (5)
C11	0.0135 (7)	0.0112 (6)	0.0112 (6)	−0.0044 (5)	−0.0051 (5)	0.0020 (5)
C12	0.0139 (7)	0.0149 (7)	0.0137 (7)	−0.0027 (5)	−0.0046 (5)	−0.0009 (5)
C13	0.0136 (7)	0.0188 (7)	0.0181 (7)	−0.0022 (6)	−0.0069 (6)	0.0014 (6)
C14	0.0194 (7)	0.0207 (7)	0.0130 (7)	−0.0081 (6)	−0.0096 (6)	0.0036 (5)
C15	0.0251 (8)	0.0145 (7)	0.0125 (7)	−0.0037 (6)	−0.0069 (6)	−0.0015 (5)
C16	0.0181 (7)	0.0121 (6)	0.0143 (7)	−0.0009 (5)	−0.0064 (6)	0.0009 (5)
C17	0.0125 (6)	0.0156 (7)	0.0102 (6)	−0.0021 (5)	−0.0051 (5)	0.0005 (5)
C18	0.0148 (7)	0.0151 (7)	0.0119 (7)	−0.0038 (5)	−0.0047 (5)	0.0010 (5)
C19	0.0162 (7)	0.0162 (7)	0.0155 (7)	−0.0021 (5)	−0.0054 (6)	−0.0020 (5)
C20	0.0248 (8)	0.0144 (7)	0.0178 (7)	−0.0060 (6)	−0.0069 (6)	−0.0008 (6)
C21	0.0246 (8)	0.0217 (8)	0.0229 (8)	−0.0123 (7)	−0.0001 (7)	0.0010 (6)
C22	0.0214 (8)	0.0217 (8)	0.0296 (9)	−0.0064 (7)	0.0085 (7)	−0.0032 (7)
C23	0.0212 (8)	0.0147 (7)	0.0232 (8)	−0.0040 (6)	0.0019 (6)	−0.0012 (6)
O5	0.0203 (6)	0.0151 (5)	0.0155 (5)	0.0042 (4)	−0.0077 (4)	−0.0029 (4)
C24	0.0227 (8)	0.0292 (9)	0.0161 (7)	−0.0059 (7)	−0.0064 (6)	−0.0009 (6)
C25	0.0205 (7)	0.0152 (7)	0.0161 (7)	−0.0029 (6)	−0.0071 (6)	−0.0026 (5)
C27	0.0198 (7)	0.0130 (7)	0.0181 (7)	−0.0004 (6)	−0.0064 (6)	−0.0011 (5)
C26	0.0208 (9)	0.0276 (10)	0.0754 (16)	−0.0017 (7)	−0.0088 (10)	−0.0209 (10)

Geometric parameters (Å, º)

Cu1—N6	1.9291 (12)	C8—H8	0.95
Cu1—N1	1.9392 (12)	O8—C27	1.417 (2)
Cu1—O7	1.9932 (10)	O8—H10	0.73 (3)
Cu1—O3	2.0103 (10)	C9—H9	0.95
Cu1—O4	2.6155 (10)	C10—C11	1.5041 (19)
Cu2—N3	1.9366 (12)	C11—C16	1.394 (2)
Cu2—N2	1.9471 (12)	C11—C12	1.396 (2)
Cu2—O1	1.9781 (10)	C12—C13	1.392 (2)
Cu2—O7	1.9827 (10)	C12—H12	0.95
Cu3—N5	1.9550 (12)	C13—C14	1.389 (2)
Cu3—N4	1.9591 (12)	C13—H13	0.95
Cu3—O7	1.9899 (10)	C14—C15	1.389 (2)
Cu3—O2^i	2.0086 (10)	C14—H14	0.95
Cu3—O5	2.3168 (11)	C15—C16	1.393 (2)
O1—C10	1.2633 (17)	C15—H15	0.95
O2—C10	1.2600 (17)	C16—H16	0.95
O2—Cu3^i	2.0086 (10)	C17—C18	1.499 (2)
O3—C17	1.2709 (18)	C18—C23	1.394 (2)
O4—C17	1.2566 (18)	C18—C19	1.396 (2)
O7—H11	0.76 (2)	C19—C20	1.392 (2)
N1—C1	1.3374 (18)	C19—H19	0.95
N1—N2	1.3654 (16)	C20—C21	1.385 (2)
N2—C3	1.3460 (18)	C20—H20	0.95
N3—C4	1.3418 (18)	C21—C22	1.391 (2)
N3—N4	1.3663 (16)	C21—H21	0.95
N4—C6	1.3402 (18)	C22—C23	1.389 (2)
N5—C7	1.3446 (18)	C22—H22	0.95
N5—N6	1.3626 (17)	C23—H23	0.95
N6—C9	1.3461 (18)	O5—C25	1.4320 (18)
C1—C2	1.389 (2)	O5—H5A	0.75 (2)
C1—H1	0.95	C24—C25	1.511 (2)
C2—C3	1.389 (2)	C24—H24A	0.98
C2—H2	0.95	C24—H24B	0.98
C3—H3	0.95	C24—H24C	0.98
C4—C5	1.388 (2)	C25—H25A	0.99
C4—H4	0.95	C25—H25B	0.99
C5—C6	1.391 (2)	C27—C26	1.495 (2)
C5—H5	0.95	C27—H27A	0.99
C6—H6	0.95	C27—H27B	0.99
C7—C8	1.386 (2)	C26—H26A	0.98
C7—H7	0.95	C26—H26B	0.98
C8—C9	1.383 (2)	C26—H26C	0.98
N6—Cu1—N1	176.43 (5)	C27—O8—H10	110 (2)
N6—Cu1—O7	89.83 (5)	N6—C9—C8	109.81 (13)
N1—Cu1—O7	88.66 (5)	N6—C9—H9	125.1
N6—Cu1—O3	90.38 (5)	C8—C9—H9	125.1
N1—Cu1—O3	91.64 (5)	O2—C10—O1	125.14 (13)
O7—Cu1—O3	170.42 (4)	O2—C10—C11	117.31 (12)
N3—Cu2—N2	174.97 (5)	O1—C10—C11	117.55 (12)
N3—Cu2—O1	93.18 (5)	C16—C11—C12	119.80 (13)
N2—Cu2—O1	88.71 (5)	C16—C11—C10	119.76 (13)
N3—Cu2—O7	89.06 (5)	C12—C11—C10	120.44 (13)
N2—Cu2—O7	88.55 (5)	C13—C12—C11	120.01 (14)
O1—Cu2—O7	173.24 (4)	C13—C12—H12	120.0
N5—Cu3—N4	170.64 (5)	C11—C12—H12	120.0
N5—Cu3—O7	89.44 (4)	C14—C13—C12	119.95 (14)
N4—Cu3—O7	87.98 (4)	C14—C13—H13	120.0
N5—Cu3—O2^i	90.09 (5)	C12—C13—H13	120.0
N4—Cu3—O2^i	91.58 (5)	C13—C14—C15	120.29 (14)
O7—Cu3—O2^i	174.28 (4)	C13—C14—H14	119.9
N5—Cu3—O5	93.33 (5)	C15—C14—H14	119.9
N4—Cu3—O5	95.98 (5)	C14—C15—C16	119.95 (14)
O7—Cu3—O5	100.03 (4)	C14—C15—H15	120.0
O2^i—Cu3—O5	85.69 (4)	C16—C15—H15	120.0
C10—O1—Cu2	119.78 (9)	C15—C16—C11	120.00 (14)
C10—O2—Cu3^i	123.31 (9)	C15—C16—H16	120.0
C17—O3—Cu1	104.76 (9)	C11—C16—H16	120.0
Cu2—O7—Cu3	117.22 (5)	O4—C17—O3	122.41 (13)
Cu2—O7—Cu1	115.10 (5)	O4—C17—C18	119.97 (13)
Cu3—O7—Cu1	116.42 (5)	O3—C17—C18	117.62 (13)
Cu2—O7—H11	99.7 (18)	C23—C18—C19	119.67 (14)
Cu3—O7—H11	105.3 (18)	C23—C18—C17	120.34 (13)
Cu1—O7—H11	98.8 (18)	C19—C18—C17	119.97 (13)
C1—N1—N2	108.23 (12)	C20—C19—C18	120.01 (14)
C1—N1—Cu1	129.67 (10)	C20—C19—H19	120.0
N2—N1—Cu1	121.21 (9)	C18—C19—H19	120.0
C3—N2—N1	107.82 (12)	C21—C20—C19	120.08 (15)
C3—N2—Cu2	131.65 (10)	C21—C20—H20	120.0
N1—N2—Cu2	120.28 (9)	C19—C20—H20	120.0
C4—N3—N4	108.19 (11)	C20—C21—C22	120.08 (15)
C4—N3—Cu2	131.04 (10)	C20—C21—H21	120.0
N4—N3—Cu2	120.71 (9)	C22—C21—H21	120.0
C6—N4—N3	107.81 (11)	C23—C22—C21	120.12 (16)
C6—N4—Cu3	130.08 (10)	C23—C22—H22	119.9
N3—N4—Cu3	121.89 (9)	C21—C22—H22	119.9
C7—N5—N6	107.68 (12)	C22—C23—C18	120.03 (15)
C7—N5—Cu3	131.52 (10)	C22—C23—H23	120.0
N6—N5—Cu3	120.80 (9)	C18—C23—H23	120.0
C9—N6—N5	108.06 (12)	C25—O5—Cu3	124.88 (9)
C9—N6—Cu1	129.94 (10)	C25—O5—H5A	109.5
N5—N6—Cu1	121.93 (9)	Cu3—O5—H5A	125.5
N1—C1—C2	109.86 (13)	C25—C24—H24A	109.5
N1—C1—H1	125.1	C25—C24—H24B	109.5
C2—C1—H1	125.1	H24A—C24—H24B	109.5
C1—C2—C3	104.43 (13)	C25—C24—H24C	109.5
C1—C2—H2	127.8	H24A—C24—H24C	109.5
C3—C2—H2	127.8	H24B—C24—H24C	109.5
N2—C3—C2	109.66 (13)	O5—C25—C24	111.55 (13)
N2—C3—H3	125.2	O5—C25—H25A	109.3
C2—C3—H3	125.2	C24—C25—H25A	109.3
N3—C4—C5	109.74 (13)	O5—C25—H25B	109.3
N3—C4—H4	125.1	C24—C25—H25B	109.3
C5—C4—H4	125.1	H25A—C25—H25B	108.0
C4—C5—C6	104.31 (13)	O8—C27—C26	112.79 (17)
C4—C5—H5	127.8	O8—C27—H27A	109.0
C6—C5—H5	127.8	C26—C27—H27A	109.0
N4—C6—C5	109.95 (13)	O8—C27—H27B	109.0
N4—C6—H6	125.0	C26—C27—H27B	109.0
C5—C6—H6	125.0	H27A—C27—H27B	107.8
N5—C7—C8	110.03 (13)	C27—C26—H26A	109.5
N5—C7—H7	125.0	C27—C26—H26B	109.5
C8—C7—H7	125.0	H26A—C26—H26B	109.5
C9—C8—C7	104.41 (13)	C27—C26—H26C	109.5
C9—C8—H8	127.8	H26A—C26—H26C	109.5
C7—C8—H8	127.8	H26B—C26—H26C	109.5
C1—N1—N2—C3	0.21 (15)	Cu3^i—O2—C10—C11	145.05 (10)
Cu1—N1—N2—C3	−169.96 (9)	Cu2—O1—C10—O2	−33.95 (18)
C1—N1—N2—Cu2	175.10 (9)	Cu2—O1—C10—C11	145.80 (10)
Cu1—N1—N2—Cu2	4.94 (14)	O2—C10—C11—C16	11.01 (19)
C4—N3—N4—C6	0.16 (15)	O1—C10—C11—C16	−168.77 (13)
Cu2—N3—N4—C6	−177.39 (9)	O2—C10—C11—C12	−168.85 (13)
C4—N3—N4—Cu3	175.24 (9)	O1—C10—C11—C12	11.38 (19)
Cu2—N3—N4—Cu3	−2.31 (14)	C16—C11—C12—C13	0.1 (2)
C7—N5—N6—C9	−0.45 (15)	C10—C11—C12—C13	179.95 (13)
Cu3—N5—N6—C9	179.42 (9)	C11—C12—C13—C14	0.2 (2)
C7—N5—N6—Cu1	176.74 (9)	C12—C13—C14—C15	−0.4 (2)
Cu3—N5—N6—Cu1	−3.39 (14)	C13—C14—C15—C16	0.2 (2)
N2—N1—C1—C2	−0.25 (16)	C14—C15—C16—C11	0.1 (2)
Cu1—N1—C1—C2	168.82 (10)	C12—C11—C16—C15	−0.3 (2)
N1—C1—C2—C3	0.18 (17)	C10—C11—C16—C15	179.89 (13)
N1—N2—C3—C2	−0.09 (16)	Cu1—O3—C17—O4	6.52 (16)
Cu2—N2—C3—C2	−174.19 (10)	Cu1—O3—C17—C18	−172.80 (10)
C1—C2—C3—N2	−0.05 (17)	O4—C17—C18—C23	178.73 (14)
N4—N3—C4—C5	0.04 (16)	O3—C17—C18—C23	−1.9 (2)
Cu2—N3—C4—C5	177.25 (10)	O4—C17—C18—C19	−2.8 (2)
N3—C4—C5—C6	−0.22 (16)	O3—C17—C18—C19	176.59 (13)
N3—N4—C6—C5	−0.31 (16)	C23—C18—C19—C20	−0.1 (2)
Cu3—N4—C6—C5	−174.84 (10)	C17—C18—C19—C20	−178.63 (13)
C4—C5—C6—N4	0.32 (16)	C18—C19—C20—C21	0.9 (2)
N6—N5—C7—C8	0.35 (16)	C19—C20—C21—C22	−1.1 (3)
Cu3—N5—C7—C8	−179.50 (10)	C20—C21—C22—C23	0.3 (3)
N5—C7—C8—C9	−0.12 (17)	C21—C22—C23—C18	0.5 (3)
N5—N6—C9—C8	0.38 (16)	C19—C18—C23—C22	−0.6 (2)
Cu1—N6—C9—C8	−176.50 (10)	C17—C18—C23—C22	177.90 (16)
C7—C8—C9—N6	−0.16 (17)	Cu3—O5—C25—C24	92.04 (14)
Cu3^i—O2—C10—O1	−35.20 (19)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H10···O4^ii	0.73 (3)	2.00 (3)	2.7325 (18)	173 (3)
O7—H11···O8	0.76 (2)	1.87 (2)	2.6175 (17)	168 (2)
O5—H5A···O4^ii	0.75	2.0	2.7393 (16)	170
C27—H27A···N5^ii	0.99	2.68	3.6640 (19)	173

Symmetry code: (ii) −x+1, −y+1, −z+1.