A three-dimensional mixed-valence Cu^II/Cu^I coordination polymer constructed from biphenyl-3,4′,5-tri­carboxyl­ate and 1,4-bis­(1H-imidazol-1-yl)benzene ligands

Coordination polymers (CPs) built by coordination bonds between metal ions/clusters and multidentate organic ligands exhibit fascinating structural topologies and potential applications as functional solid materials. The title coordination polymer, poly[di­aqua­bis­(μ₄-biphenyl-3,4′,5-tri­carboxyl­ato-κ⁴O³:O^3′:O^4′:O⁵)tris­[μ₂-1,4-bis­(1H-imidazol-1-yl)benzene-κ²N³:N^3′]dicopper(II)dicopper(I)], [Cu^II₂Cu^I₂(C₁₅H₇O₆)₂(C₁₂H₁₀N₄)₃(H₂O)₂]_n, was crystallized from a mixture of bi­phenyl-3,4′,5-tri­carb­oxy­lic acid (H₃bpt), 1,4-bis­(1H-imidazol-1-yl)benzene (1,4-bib) and copper(II) chloride in a water–CH₃CN mixture under solvothermal reaction conditions. The asymmetric unit consists of two crystallographically independent Cu atoms, one of which is Cu^II, while the other has been reduced to the Cu^I ion. The Cu^II centre is penta­coordinated by three O atoms from three bpt³⁻ ligands, one N atom from a 1,4-bib ligand and one O atom from a coordinated water mol­ecule, and the coordination geometry can be described as distorted tri­gonal bipyramidal. The Cu^I atom exhibits a T-shaped geometry (CuN₂O) coordinated by one O atom from a bpt³⁻ ligand and two N atoms from two 1,4-bib ligands. The Cu^II atoms are extended by bpt³⁻ and 1,4-bib linkers to generate a two-dimensional network, while the Cu^I atoms are linked by 1,4-bib ligands, forming one-dimensional chains along the [20] direction. In addition, the completely deprotonated μ₄-η¹:η¹:η¹:η¹ bpt³⁻ ligands bridge one Cu^I and three Cu^II cations along the a (or [100]) direction to form a three-dimensional framework with a (10³)₂(10)₂(4².6.10².12)₂(4².6.8².10)₂(8) topology via a 2,2,3,4,4-connected net. An investigation of the magnetic properties indicated a very weak ferromagnetic behaviour.

Computing details

Data collection: mar165; cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL-2000 (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2015) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: pubCIF (Westrip, 2010).

Poly[diaquabis(µ₄-biphenyl-3,4',5-tricarboxylato-κ⁴O³:O^3':O⁵:O^4')tris[µ₂-1,4-bis(1H-imidazol-1-yl)benzene-κ²N³:N^3']dicopper(II)dicopper(I)]

Crystal data

[Cu4(C15H7O6)2(C12H10N4)3(H2O)2]	F(000) = 1512
Mr = 1487.32	Dx = 1.752 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.7200 Å
a = 11.898 (2) Å	Cell parameters from 61085 reflections
b = 28.663 (6) Å	θ = 1.9–25.0°
c = 8.343 (2) Å	µ = 1.58 mm^−1
β = 97.77 (3)°	T = 173 K
V = 2819.1 (10) Å^3	Block, blue
Z = 2	0.35 × 0.30 × 0.30 mm

Data collection

MARCCD 165 diffractometer	8578 independent reflections
Radiation source: synchrotron, 3W1A at BSRF	7418 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
oscillation mode scans	θmax = 31.0°, θmin = 2.3°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −16→16
Tmin = 0.609, Tmax = 0.649	k = −40→40
15528 measured reflections	l = 0→11

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0498P)^2 + 3.2291P] where P = (Fo^2 + 2Fc^2)/3
8578 reflections	(Δ/σ)max = 0.001
433 parameters	Δρmax = 1.87 e Å^−3
0 restraints	Δρmin = −1.72 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. 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 > 2sigma(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	−0.008038 (18)	0.029437 (8)	1.19733 (3)	0.01327 (6)
Cu2	0.533720 (19)	0.232675 (8)	0.41746 (3)	0.01309 (6)
N1	0.67173 (13)	0.26482 (6)	0.4145 (2)	0.0130 (3)
N2	0.83493 (12)	0.28504 (5)	0.33753 (18)	0.0105 (3)
N3	1.20853 (13)	0.29297 (5)	−0.00774 (19)	0.0110 (3)
N4	1.38054 (13)	0.28407 (5)	−0.0746 (2)	0.0127 (3)
N5	−0.12116 (12)	0.00106 (5)	1.31849 (19)	0.0110 (3)
N6	−0.27933 (12)	−0.01155 (5)	1.42067 (18)	0.0099 (3)
O1	0.12023 (12)	0.05542 (5)	1.1097 (2)	0.0203 (3)
O2	0.07539 (11)	0.13011 (5)	1.05023 (18)	0.0149 (3)
O3	0.58422 (11)	0.16484 (5)	0.31845 (16)	0.0138 (2)
O4	0.74867 (13)	0.12870 (5)	0.30346 (18)	0.0208 (3)
O5	0.91803 (11)	0.02848 (5)	0.76334 (17)	0.0137 (3)
O6	0.86199 (11)	0.04436 (5)	1.00504 (16)	0.0142 (2)
O7	−0.03726 (11)	0.09817 (5)	1.28832 (17)	0.0144 (3)
H7A	−0.1066	0.1015	1.2949	0.022*
H7B	−0.0139	0.1142	1.2109	0.022*
C1	0.13799 (14)	0.09517 (6)	1.0497 (2)	0.0111 (3)
C2	0.24752 (14)	0.09817 (6)	0.9777 (2)	0.0095 (3)
C3	0.31776 (14)	0.05901 (6)	0.9818 (2)	0.0104 (3)
H3	0.2960	0.0308	1.0287	0.013*
C4	0.41943 (14)	0.06124 (6)	0.9173 (2)	0.0105 (3)
H4	0.4670	0.0345	0.9226	0.013*
C5	0.45337 (14)	0.10207 (6)	0.8447 (2)	0.0091 (3)
C6	0.38271 (15)	0.14143 (6)	0.8418 (2)	0.0114 (3)
H6	0.4040	0.1696	0.7939	0.014*
C7	0.28132 (15)	0.13946 (6)	0.9089 (2)	0.0115 (3)
H7	0.2349	0.1665	0.9076	0.014*
C8	0.55976 (14)	0.10153 (6)	0.7698 (2)	0.0091 (3)
C9	0.65468 (14)	0.07752 (6)	0.8452 (2)	0.0098 (3)
H9	0.6532	0.0643	0.9494	0.012*
C10	0.75144 (14)	0.07269 (6)	0.7696 (2)	0.0094 (3)
C11	0.75467 (14)	0.09244 (6)	0.6175 (2)	0.0094 (3)
H11	0.8198	0.0883	0.5644	0.011*
C12	0.66259 (14)	0.11828 (6)	0.5427 (2)	0.0097 (3)
C13	0.56578 (14)	0.12273 (6)	0.6197 (2)	0.0101 (3)
H13	0.5031	0.1404	0.5695	0.012*
C14	0.85199 (14)	0.04619 (6)	0.8542 (2)	0.0105 (3)
C15	0.66563 (15)	0.13901 (6)	0.3757 (2)	0.0117 (3)
C16	0.70256 (16)	0.30819 (6)	0.4797 (2)	0.0133 (3)
H16	0.6598	0.3261	0.5459	0.016*
C17	0.75336 (15)	0.25179 (6)	0.3302 (2)	0.0122 (3)
H17	0.7545	0.2232	0.2729	0.015*
C18	0.80361 (15)	0.32108 (6)	0.4342 (2)	0.0126 (3)
H18	0.8445	0.3490	0.4627	0.015*
C19	0.92985 (14)	0.28560 (6)	0.2503 (2)	0.0107 (3)
C20	0.97863 (15)	0.24414 (6)	0.2044 (2)	0.0117 (3)
H20	0.9495	0.2149	0.2331	0.014*
C21	1.07026 (15)	0.24589 (6)	0.1165 (2)	0.0111 (3)
H21	1.1029	0.2179	0.0827	0.013*
C22	1.11322 (14)	0.28908 (6)	0.0789 (2)	0.0104 (3)
C23	1.06492 (15)	0.33038 (6)	0.1254 (2)	0.0144 (3)
H23	1.0953	0.3596	0.0994	0.017*
C24	0.97248 (15)	0.32858 (7)	0.2098 (2)	0.0146 (3)
H24	0.9383	0.3566	0.2399	0.017*
C25	1.32906 (15)	0.32151 (7)	−0.1601 (2)	0.0139 (3)
H25	1.3625	0.3401	−0.2350	0.017*
C26	1.22275 (15)	0.32740 (6)	−0.1197 (2)	0.0134 (3)
H26	1.1691	0.3505	−0.1603	0.016*
C27	1.30590 (15)	0.26771 (6)	0.0158 (2)	0.0120 (3)
H27	1.3188	0.2419	0.0873	0.014*
C28	−0.22366 (14)	0.01725 (6)	1.3295 (2)	0.0108 (3)
H28	−0.2542	0.0452	1.2803	0.013*
C29	−0.20707 (15)	−0.04820 (6)	1.4687 (2)	0.0139 (3)
H29	−0.2225	−0.0741	1.5334	0.017*
C30	−0.10960 (15)	−0.03994 (6)	1.4053 (2)	0.0130 (3)
H30	−0.0442	−0.0593	1.4187	0.016*
C31	−0.42129 (15)	−0.02730 (6)	1.5974 (2)	0.0116 (3)
H31	−0.3674	−0.0458	1.6639	0.014*
C32	−0.39096 (14)	−0.00537 (6)	1.4607 (2)	0.0101 (3)
C33	−0.46940 (15)	0.02215 (6)	1.3637 (2)	0.0118 (3)
H33	−0.4482	0.0374	1.2712	0.014*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00653 (10)	0.01228 (11)	0.02288 (13)	0.00311 (7)	0.00878 (8)	0.00795 (8)
Cu2	0.00892 (10)	0.01523 (11)	0.01637 (12)	−0.00001 (7)	0.00627 (8)	0.00116 (8)
N1	0.0100 (6)	0.0164 (7)	0.0136 (7)	−0.0008 (5)	0.0053 (5)	−0.0011 (5)
N2	0.0084 (6)	0.0118 (6)	0.0120 (7)	−0.0004 (5)	0.0035 (5)	−0.0002 (5)
N3	0.0084 (6)	0.0114 (6)	0.0136 (7)	−0.0010 (5)	0.0032 (5)	0.0009 (5)
N4	0.0095 (6)	0.0128 (7)	0.0167 (7)	−0.0006 (5)	0.0054 (5)	−0.0008 (6)
N5	0.0067 (6)	0.0117 (6)	0.0160 (7)	0.0008 (5)	0.0059 (5)	0.0029 (5)
N6	0.0071 (6)	0.0105 (6)	0.0130 (7)	−0.0003 (5)	0.0050 (5)	0.0009 (5)
O1	0.0129 (6)	0.0137 (6)	0.0385 (9)	0.0030 (5)	0.0185 (6)	0.0096 (6)
O2	0.0118 (6)	0.0126 (6)	0.0224 (7)	0.0028 (5)	0.0098 (5)	0.0031 (5)
O3	0.0122 (6)	0.0156 (6)	0.0144 (6)	0.0046 (5)	0.0051 (5)	0.0038 (5)
O4	0.0205 (7)	0.0251 (7)	0.0201 (7)	0.0134 (6)	0.0147 (6)	0.0114 (6)
O5	0.0122 (6)	0.0131 (6)	0.0180 (6)	0.0072 (5)	0.0096 (5)	0.0055 (5)
O6	0.0099 (6)	0.0216 (7)	0.0113 (6)	0.0019 (5)	0.0023 (4)	0.0017 (5)
O7	0.0109 (6)	0.0168 (6)	0.0170 (6)	0.0026 (5)	0.0072 (5)	0.0021 (5)
C1	0.0089 (7)	0.0109 (7)	0.0146 (8)	0.0005 (6)	0.0055 (6)	0.0014 (6)
C2	0.0069 (6)	0.0122 (7)	0.0102 (7)	−0.0002 (5)	0.0038 (5)	−0.0009 (6)
C3	0.0086 (7)	0.0113 (7)	0.0123 (7)	0.0002 (6)	0.0047 (6)	0.0014 (6)
C4	0.0086 (7)	0.0110 (7)	0.0128 (7)	0.0017 (5)	0.0052 (6)	0.0015 (6)
C5	0.0072 (6)	0.0111 (7)	0.0095 (7)	0.0003 (5)	0.0035 (5)	0.0015 (6)
C6	0.0102 (7)	0.0103 (7)	0.0150 (8)	0.0003 (6)	0.0061 (6)	0.0024 (6)
C7	0.0097 (7)	0.0110 (7)	0.0148 (8)	0.0007 (6)	0.0056 (6)	0.0002 (6)
C8	0.0065 (6)	0.0098 (7)	0.0120 (7)	−0.0010 (5)	0.0051 (5)	0.0001 (6)
C9	0.0083 (7)	0.0102 (7)	0.0116 (7)	0.0003 (5)	0.0042 (6)	0.0017 (6)
C10	0.0083 (7)	0.0079 (7)	0.0129 (7)	0.0002 (5)	0.0045 (6)	−0.0006 (6)
C11	0.0083 (7)	0.0092 (7)	0.0115 (7)	−0.0001 (5)	0.0043 (5)	−0.0007 (6)
C12	0.0088 (7)	0.0101 (7)	0.0111 (7)	−0.0003 (5)	0.0046 (6)	0.0004 (6)
C13	0.0091 (7)	0.0097 (7)	0.0123 (7)	0.0005 (5)	0.0040 (6)	0.0014 (6)
C14	0.0083 (7)	0.0100 (7)	0.0142 (8)	−0.0013 (5)	0.0050 (6)	0.0015 (6)
C15	0.0121 (7)	0.0100 (7)	0.0142 (8)	0.0011 (6)	0.0059 (6)	0.0022 (6)
C16	0.0146 (8)	0.0137 (8)	0.0122 (8)	0.0025 (6)	0.0042 (6)	−0.0007 (6)
C17	0.0099 (7)	0.0149 (8)	0.0127 (8)	−0.0016 (6)	0.0047 (6)	−0.0018 (6)
C18	0.0131 (7)	0.0116 (7)	0.0135 (8)	0.0012 (6)	0.0034 (6)	−0.0013 (6)
C19	0.0076 (7)	0.0140 (7)	0.0107 (7)	−0.0002 (6)	0.0023 (5)	0.0004 (6)
C20	0.0115 (7)	0.0112 (7)	0.0128 (8)	−0.0014 (6)	0.0034 (6)	0.0005 (6)
C21	0.0110 (7)	0.0104 (7)	0.0125 (8)	−0.0004 (6)	0.0037 (6)	−0.0004 (6)
C22	0.0076 (7)	0.0122 (7)	0.0118 (7)	−0.0014 (6)	0.0029 (6)	0.0014 (6)
C23	0.0121 (8)	0.0115 (7)	0.0207 (9)	0.0004 (6)	0.0061 (6)	0.0021 (6)
C24	0.0110 (7)	0.0130 (8)	0.0205 (9)	0.0023 (6)	0.0052 (6)	0.0023 (7)
C25	0.0133 (8)	0.0148 (8)	0.0140 (8)	−0.0028 (6)	0.0035 (6)	0.0002 (6)
C26	0.0115 (7)	0.0136 (8)	0.0151 (8)	−0.0010 (6)	0.0016 (6)	0.0038 (6)
C27	0.0093 (7)	0.0129 (7)	0.0146 (8)	0.0003 (6)	0.0041 (6)	0.0001 (6)
C28	0.0075 (7)	0.0117 (7)	0.0140 (8)	0.0003 (6)	0.0048 (6)	0.0022 (6)
C29	0.0115 (7)	0.0121 (7)	0.0197 (9)	0.0027 (6)	0.0074 (6)	0.0050 (6)
C30	0.0093 (7)	0.0128 (8)	0.0176 (8)	0.0016 (6)	0.0046 (6)	0.0036 (6)
C31	0.0092 (7)	0.0139 (8)	0.0125 (8)	0.0004 (6)	0.0041 (6)	0.0013 (6)
C32	0.0067 (7)	0.0116 (7)	0.0130 (7)	−0.0012 (5)	0.0050 (6)	−0.0011 (6)
C33	0.0097 (7)	0.0142 (8)	0.0125 (8)	−0.0006 (6)	0.0055 (6)	0.0020 (6)

Geometric parameters (Å, º)

Cu1—O1	1.9286 (14)	C6—C7	1.398 (2)
Cu1—N5	1.9654 (15)	C6—H6	0.9500
Cu1—O5^i	1.9786 (13)	C7—H7	0.9500
Cu1—O6^ii	2.1160 (15)	C8—C9	1.398 (2)
Cu1—O7	2.1563 (14)	C8—C13	1.403 (2)
Cu2—N1	1.8860 (16)	C9—C10	1.393 (2)
Cu2—N4^iii	1.8945 (16)	C9—H9	0.9500
Cu2—O3	2.2266 (14)	C10—C11	1.395 (2)
N1—C17	1.327 (2)	C10—C14	1.509 (2)
N1—C16	1.386 (2)	C11—C12	1.398 (2)
N2—C17	1.356 (2)	C11—H11	0.9500
N2—C18	1.392 (2)	C12—C13	1.398 (2)
N2—C19	1.424 (2)	C12—C15	1.520 (2)
N3—C27	1.358 (2)	C13—H13	0.9500
N3—C26	1.385 (2)	C16—C18	1.360 (2)
N3—C22	1.429 (2)	C16—H16	0.9500
N4—C27	1.326 (2)	C17—H17	0.9500
N4—C25	1.384 (2)	C18—H18	0.9500
N4—Cu2^iv	1.8945 (16)	C19—C24	1.391 (2)
N5—C28	1.320 (2)	C19—C20	1.398 (2)
N5—C30	1.378 (2)	C20—C21	1.395 (2)
N6—C28	1.355 (2)	C20—H20	0.9500
N6—C29	1.382 (2)	C21—C22	1.391 (2)
N6—C32	1.424 (2)	C21—H21	0.9500
O1—C1	1.274 (2)	C22—C23	1.394 (2)
O2—C1	1.249 (2)	C23—C24	1.384 (2)
O3—C15	1.261 (2)	C23—H23	0.9500
O4—C15	1.260 (2)	C24—H24	0.9500
O5—C14	1.269 (2)	C25—C26	1.363 (2)
O5—Cu1^i	1.9786 (13)	C25—H25	0.9500
O6—C14	1.249 (2)	C26—H26	0.9500
O6—Cu1^v	2.1160 (15)	C27—H27	0.9500
O7—H7A	0.8400	C28—H28	0.9500
O7—H7B	0.8688	C29—C30	1.359 (2)
C1—C2	1.509 (2)	C29—H29	0.9500
C2—C3	1.397 (2)	C30—H30	0.9500
C2—C7	1.398 (2)	C31—C33^vi	1.390 (2)
C3—C4	1.390 (2)	C31—C32	1.392 (2)
C3—H3	0.9500	C31—H31	0.9500
C4—C5	1.402 (2)	C32—C33	1.394 (2)
C4—H4	0.9500	C33—C31^vi	1.390 (2)
C5—C6	1.405 (2)	C33—H33	0.9500
C5—C8	1.486 (2)
O1—Cu1—N5	170.66 (7)	C10—C11—H11	119.8
O1—Cu1—O5^i	87.05 (6)	C12—C11—H11	119.8
N5—Cu1—O5^i	87.73 (6)	C11—C12—C13	119.22 (16)
O1—Cu1—O6^ii	99.74 (6)	C11—C12—C15	120.13 (15)
N5—Cu1—O6^ii	89.57 (6)	C13—C12—C15	120.57 (15)
O5^i—Cu1—O6^ii	128.25 (6)	C12—C13—C8	121.02 (16)
O1—Cu1—O7	87.37 (6)	C12—C13—H13	119.5
N5—Cu1—O7	92.46 (6)	C8—C13—H13	119.5
O5^i—Cu1—O7	144.84 (6)	O6—C14—O5	127.06 (17)
O6^ii—Cu1—O7	86.91 (5)	O6—C14—C10	116.96 (15)
N1—Cu2—N4^iii	165.39 (7)	O5—C14—C10	115.98 (16)
N1—Cu2—O3	98.20 (6)	O4—C15—O3	124.64 (17)
N4^iii—Cu2—O3	95.78 (6)	O4—C15—C12	117.66 (16)
C17—N1—C16	106.65 (15)	O3—C15—C12	117.69 (15)
C17—N1—Cu2	124.77 (13)	C18—C16—N1	109.32 (16)
C16—N1—Cu2	128.14 (13)	C18—C16—H16	125.3
C17—N2—C18	107.55 (15)	N1—C16—H16	125.3
C17—N2—C19	126.68 (15)	N1—C17—N2	110.43 (16)
C18—N2—C19	125.51 (15)	N1—C17—H17	124.8
C27—N3—C26	107.33 (15)	N2—C17—H17	124.8
C27—N3—C22	127.24 (15)	C16—C18—N2	106.04 (16)
C26—N3—C22	125.06 (15)	C16—C18—H18	127.0
C27—N4—C25	106.46 (15)	N2—C18—H18	127.0
C27—N4—Cu2^iv	130.66 (14)	C24—C19—C20	120.52 (16)
C25—N4—Cu2^iv	122.63 (12)	C24—C19—N2	118.32 (16)
C28—N5—C30	106.92 (14)	C20—C19—N2	121.15 (16)
C28—N5—Cu1	126.42 (12)	C21—C20—C19	119.73 (16)
C30—N5—Cu1	126.65 (12)	C21—C20—H20	120.1
C28—N6—C29	107.09 (14)	C19—C20—H20	120.1
C28—N6—C32	126.76 (15)	C22—C21—C20	119.20 (16)
C29—N6—C32	126.15 (15)	C22—C21—H21	120.4
C1—O1—Cu1	132.56 (12)	C20—C21—H21	120.4
C15—O3—Cu2	127.17 (13)	C21—C22—C23	120.99 (16)
C14—O5—Cu1^i	126.98 (12)	C21—C22—N3	121.62 (16)
C14—O6—Cu1^v	137.10 (12)	C23—C22—N3	117.38 (15)
Cu1—O7—H7A	109.5	C24—C23—C22	119.72 (17)
Cu1—O7—H7B	98.0	C24—C23—H23	120.1
H7A—O7—H7B	113.8	C22—C23—H23	120.1
O2—C1—O1	125.82 (16)	C23—C24—C19	119.82 (17)
O2—C1—C2	120.22 (15)	C23—C24—H24	120.1
O1—C1—C2	113.93 (15)	C19—C24—H24	120.1
C3—C2—C7	119.06 (15)	C26—C25—N4	109.24 (16)
C3—C2—C1	119.37 (15)	C26—C25—H25	125.4
C7—C2—C1	121.56 (15)	N4—C25—H25	125.4
C4—C3—C2	120.17 (16)	C25—C26—N3	106.30 (16)
C4—C3—H3	119.9	C25—C26—H26	126.9
C2—C3—H3	119.9	N3—C26—H26	126.9
C3—C4—C5	121.47 (16)	N4—C27—N3	110.67 (16)
C3—C4—H4	119.3	N4—C27—H27	124.7
C5—C4—H4	119.3	N3—C27—H27	124.7
C4—C5—C6	118.11 (15)	N5—C28—N6	110.56 (15)
C4—C5—C8	119.00 (15)	N5—C28—H28	124.7
C6—C5—C8	122.86 (15)	N6—C28—H28	124.7
C7—C6—C5	120.48 (16)	C30—C29—N6	106.55 (15)
C7—C6—H6	119.8	C30—C29—H29	126.7
C5—C6—H6	119.8	N6—C29—H29	126.7
C6—C7—C2	120.68 (16)	C29—C30—N5	108.87 (15)
C6—C7—H7	119.7	C29—C30—H30	125.6
C2—C7—H7	119.7	N5—C30—H30	125.6
C9—C8—C13	118.67 (15)	C33^vi—C31—C32	119.85 (16)
C9—C8—C5	119.87 (15)	C33^vi—C31—H31	120.1
C13—C8—C5	121.37 (15)	C32—C31—H31	120.1
C10—C9—C8	120.80 (16)	C31—C32—C33	120.25 (15)
C10—C9—H9	119.6	C31—C32—N6	119.31 (16)
C8—C9—H9	119.6	C33—C32—N6	120.44 (15)
C9—C10—C11	119.87 (16)	C31^vi—C33—C32	119.90 (16)
C9—C10—C14	119.34 (15)	C31^vi—C33—H33	120.1
C11—C10—C14	120.79 (15)	C32—C33—H33	120.1
C10—C11—C12	120.31 (15)
N4^iii—Cu2—N1—C17	−146.0 (2)	C11—C12—C15—O4	5.9 (3)
O3—Cu2—N1—C17	17.12 (17)	C13—C12—C15—O4	−170.78 (17)
N4^iii—Cu2—N1—C16	25.3 (4)	C11—C12—C15—O3	−174.94 (16)
O3—Cu2—N1—C16	−171.60 (16)	C13—C12—C15—O3	8.4 (3)
O5^i—Cu1—N5—C28	−169.93 (16)	C17—N1—C16—C18	−0.1 (2)
O6^ii—Cu1—N5—C28	−41.62 (16)	Cu2—N1—C16—C18	−172.67 (13)
O7—Cu1—N5—C28	45.27 (16)	C16—N1—C17—N2	−0.4 (2)
O5^i—Cu1—N5—C30	8.66 (16)	Cu2—N1—C17—N2	172.42 (12)
O6^ii—Cu1—N5—C30	136.97 (16)	C18—N2—C17—N1	0.8 (2)
O7—Cu1—N5—C30	−136.15 (16)	C19—N2—C17—N1	−173.54 (16)
O5^i—Cu1—O1—C1	180.0 (2)	N1—C16—C18—N2	0.6 (2)
O6^ii—Cu1—O1—C1	51.6 (2)	C17—N2—C18—C16	−0.9 (2)
O7—Cu1—O1—C1	−34.8 (2)	C19—N2—C18—C16	173.57 (16)
N1—Cu2—O3—C15	57.82 (15)	C17—N2—C19—C24	149.86 (18)
N4^iii—Cu2—O3—C15	−126.41 (15)	C18—N2—C19—C24	−23.5 (3)
Cu1—O1—C1—O2	8.6 (3)	C17—N2—C19—C20	−29.4 (3)
Cu1—O1—C1—C2	−173.20 (14)	C18—N2—C19—C20	157.17 (17)
O2—C1—C2—C3	178.45 (17)	C24—C19—C20—C21	−0.4 (3)
O1—C1—C2—C3	0.2 (2)	N2—C19—C20—C21	178.83 (16)
O2—C1—C2—C7	−0.7 (3)	C19—C20—C21—C22	1.4 (3)
O1—C1—C2—C7	−178.96 (17)	C20—C21—C22—C23	−1.1 (3)
C7—C2—C3—C4	−0.3 (3)	C20—C21—C22—N3	178.56 (16)
C1—C2—C3—C4	−179.44 (16)	C27—N3—C22—C21	−43.5 (3)
C2—C3—C4—C5	−1.1 (3)	C26—N3—C22—C21	144.46 (19)
C3—C4—C5—C6	1.4 (3)	C27—N3—C22—C23	136.17 (19)
C3—C4—C5—C8	−176.59 (16)	C26—N3—C22—C23	−35.9 (3)
C4—C5—C6—C7	−0.4 (3)	C21—C22—C23—C24	−0.3 (3)
C8—C5—C6—C7	177.56 (17)	N3—C22—C23—C24	−179.93 (17)
C5—C6—C7—C2	−1.0 (3)	C22—C23—C24—C19	1.3 (3)
C3—C2—C7—C6	1.3 (3)	C20—C19—C24—C23	−0.9 (3)
C1—C2—C7—C6	−179.54 (17)	N2—C19—C24—C23	179.78 (17)
C4—C5—C8—C9	−39.6 (2)	C27—N4—C25—C26	0.0 (2)
C6—C5—C8—C9	142.53 (18)	Cu2^iv—N4—C25—C26	−174.73 (13)
C4—C5—C8—C13	137.15 (18)	N4—C25—C26—N3	−0.1 (2)
C6—C5—C8—C13	−40.8 (3)	C27—N3—C26—C25	0.1 (2)
C13—C8—C9—C10	−3.1 (3)	C22—N3—C26—C25	173.52 (16)
C5—C8—C9—C10	173.64 (16)	C25—N4—C27—N3	0.0 (2)
C8—C9—C10—C11	0.7 (3)	Cu2^iv—N4—C27—N3	174.23 (13)
C8—C9—C10—C14	−179.51 (16)	C26—N3—C27—N4	−0.1 (2)
C9—C10—C11—C12	2.0 (3)	C22—N3—C27—N4	−173.32 (16)
C14—C10—C11—C12	−177.78 (16)	C30—N5—C28—N6	0.2 (2)
C10—C11—C12—C13	−2.2 (3)	Cu1—N5—C28—N6	179.01 (12)
C10—C11—C12—C15	−178.92 (16)	C29—N6—C28—N5	−0.4 (2)
C11—C12—C13—C8	−0.3 (3)	C32—N6—C28—N5	179.32 (16)
C15—C12—C13—C8	176.44 (16)	C28—N6—C29—C30	0.4 (2)
C9—C8—C13—C12	2.9 (3)	C32—N6—C29—C30	−179.29 (17)
C5—C8—C13—C12	−173.82 (16)	N6—C29—C30—N5	−0.3 (2)
Cu1^v—O6—C14—O5	17.6 (3)	C28—N5—C30—C29	0.1 (2)
Cu1^v—O6—C14—C10	−161.66 (13)	Cu1—N5—C30—C29	−178.73 (13)
Cu1^i—O5—C14—O6	32.0 (3)	C33^vi—C31—C32—C33	0.7 (3)
Cu1^i—O5—C14—C10	−148.66 (12)	C33^vi—C31—C32—N6	−178.97 (16)
C9—C10—C14—O6	−25.3 (2)	C28—N6—C32—C31	−157.00 (18)
C11—C10—C14—O6	154.48 (17)	C29—N6—C32—C31	22.7 (3)
C9—C10—C14—O5	155.36 (16)	C28—N6—C32—C33	23.3 (3)
C11—C10—C14—O5	−24.9 (2)	C29—N6—C32—C33	−157.00 (18)
Cu2—O3—C15—O4	−117.94 (19)	C31—C32—C33—C31^vi	−0.7 (3)
Cu2—O3—C15—C12	63.0 (2)	N6—C32—C33—C31^vi	178.96 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O2	0.87	1.88	2.702 (2)	158
O7—H7A···O4^vii	0.84	1.90	2.712 (2)	162

Symmetry code: (vii) x−1, y, z+1.