A two-dimensional mixed-valence Cu^II/Cu^I coordination polymer constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-di­carboxyl­ate

Coordination polymers are a thriving class of functional solid-state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self-assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro­(solvo)thermal conditions. 2-(Pyridin-3-yl)-1H-imidazole-4,5-di­carboxyl­ate (HPIDC²⁻) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aqua­bis­[μ₃-5-carb­oxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxyl­ato-κ⁵N¹,O⁵:N³,O⁴:N²]copper(II)dicopper(I)], [Cu^IICu^I₂(C₁₀H₅N₃O₄)₂(H₂O)]_n, (I), were obtained from 2-(pyridin-3-yl)-1H-imidazole-4,5-di­carb­oxy­lic acid (H₃PIDC) and copper(II) chloride under hydro­thermal conditions. The asymmetric unit consists of one independent Cu^II ion, two Cu^I ions, two HPIDC²⁻ ligands and one coordinated water mol­ecule. The Cu^II centre displays a square-pyramidal geometry (CuN₂O₃), with two N,O-chelating HPIDC²⁻ ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water mol­ecule in the axial position. The Cu^I atoms adopt three-coordinated Y-shaped coordinations. In each [CuN₂O] unit, deprotonated HPIDC²⁻ acts as an N,O-chelating ligand, and a symmetry-equivalent HPIDC²⁻ ligand acts as an N-atom donor via the pyridine group. The HPIDC²⁻ ligands in the polymer serve as T-shaped 3-connectors and adopt a μ₃-κ²N,O:κ²N′,O′:κN′′-coordination mode, linking one Cu^II and two Cu^I cations. The Cu cations are arranged in one-dimensional –Cu1–Cu2–Cu3– chains along the [001] direction. Further crosslinking of these chains by HPIDC²⁻ ligands along the b axis in a –Cu2–HPIDC²⁻–Cu3–HPIDC²⁻–Cu1– sequence results in a two-dimensional polymer in the (100) plane. The resulting (2,3)-connected net has a (12³)₂(12)₃ topology. Powder X-ray diffraction confirmed the phase purity for (I), and susceptibilty measurements indicated a very weak ferromagnetic behaviour. A thermogravimetric analysis shows the loss of the apical aqua ligand before decomposition of the title compound.

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: publCIF (Westrip, 2010).

Poly[aquabis[µ₃-5-carboxy-2-(pyridin-3-yl)-1H-imidazole-4-carboxylato-κ⁵N¹,O⁵:N³,O⁴:N²]copper(II)dicopper(I)]

Crystal data

[Cu3(C10H5N3O4)2(H2O)]	Dx = 2.151 Mg m^−3
Mr = 670.98	Synchrotron radiation, λ = 0.7200 Å
Orthorhombic, Pbca	Cell parameters from 23113 reflections
a = 23.095 (5) Å	θ = 2.5–30.9°
b = 6.8430 (14) Å	µ = 3.24 mm^−1
c = 26.222 (5) Å	T = 100 K
V = 4144.1 (14) Å^3	Block, clear light green
Z = 8	0.18 × 0.05 × 0.03 mm
F(000) = 2664

Data collection

Mar165 diffractometer	5684 reflections with I > 2σ(I)
Radiation source: synchrotron, 3W1A at BSRF	Rint = 0.038
oscillation mode scans	θmax = 31.0°, θmin = 3.1°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −32→33
Tmin = 0.603, Tmax = 0.912	k = 0→9
21854 measured reflections	l = −36→36
6232 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0677P)^2 + 2.5986P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.002
6232 reflections	Δρmax = 0.64 e Å^−3
343 parameters	Δρmin = −1.26 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	0.56251 (2)	0.80133 (3)	0.41648 (2)	0.01247 (7)
Cu2	0.64111 (2)	0.49080 (3)	0.62693 (2)	0.01100 (7)
Cu3	0.74170 (2)	0.46961 (4)	0.84484 (2)	0.01359 (7)
O1	0.46779 (6)	0.8393 (2)	0.46012 (6)	0.0155 (3)
O2	0.43454 (6)	0.7608 (2)	0.53744 (6)	0.0160 (3)
H2	0.4461	0.7340	0.5662	0.024*
O3	0.47374 (6)	0.6219 (2)	0.61767 (6)	0.0180 (3)
O4	0.56163 (6)	0.5510 (3)	0.64889 (6)	0.0172 (3)
O5	0.72071 (6)	0.4333 (2)	0.60544 (5)	0.0126 (2)
O6	0.81126 (6)	0.3916 (2)	0.63461 (5)	0.0128 (2)
O7	0.86255 (6)	0.4407 (2)	0.72245 (6)	0.0179 (3)
H7	0.8466	0.4214	0.6950	0.027*
O8	0.83360 (7)	0.4831 (2)	0.80257 (6)	0.0188 (3)
O9	0.61460 (6)	0.1856 (2)	0.61020 (6)	0.0182 (3)
H9A	0.5961	0.1750	0.5837	0.027*
H9B	0.6395	0.1002	0.6099	0.027*
N1	0.74627 (7)	0.5684 (2)	0.41534 (6)	0.0122 (3)
N2	0.57865 (7)	0.7101 (2)	0.48324 (6)	0.0102 (3)
N3	0.61344 (6)	0.6034 (2)	0.55839 (6)	0.0095 (3)
N4	0.55793 (7)	0.5979 (2)	0.84917 (6)	0.0124 (3)
N5	0.71801 (7)	0.4776 (2)	0.77589 (6)	0.0104 (3)
N6	0.67598 (6)	0.4616 (2)	0.69873 (6)	0.0092 (3)
C1	0.79262 (8)	0.6061 (3)	0.44525 (7)	0.0133 (3)
H1	0.8303	0.5936	0.4311	0.016*
C2	0.78725 (8)	0.6623 (3)	0.49588 (7)	0.0127 (3)
H2A	0.8206	0.6889	0.5160	0.015*
C3	0.73213 (8)	0.6788 (3)	0.51650 (7)	0.0110 (3)
H3	0.7273	0.7204	0.5508	0.013*
C4	0.68386 (7)	0.6345 (2)	0.48683 (7)	0.0093 (3)
C5	0.69261 (8)	0.5805 (3)	0.43597 (7)	0.0106 (3)
H5	0.6600	0.5516	0.4153	0.013*
C6	0.62557 (7)	0.6476 (2)	0.50908 (7)	0.0093 (3)
C7	0.53381 (8)	0.7048 (2)	0.51753 (7)	0.0105 (3)
C8	0.47555 (8)	0.7725 (3)	0.50334 (8)	0.0122 (3)
C9	0.55565 (7)	0.6387 (3)	0.56344 (7)	0.0097 (3)
C10	0.52815 (8)	0.6019 (3)	0.61306 (7)	0.0128 (3)
C11	0.50917 (8)	0.5241 (3)	0.82838 (8)	0.0139 (3)
H11	0.4737	0.5373	0.8464	0.017*
C12	0.50907 (8)	0.4294 (3)	0.78159 (7)	0.0148 (3)
H12	0.4740	0.3794	0.7679	0.018*
C13	0.56063 (8)	0.4082 (3)	0.75485 (7)	0.0124 (3)
H13	0.5616	0.3399	0.7233	0.015*
C14	0.61122 (8)	0.4898 (3)	0.77535 (7)	0.0100 (3)
C15	0.60753 (8)	0.5834 (3)	0.82245 (7)	0.0119 (3)
H15	0.6416	0.6396	0.8364	0.014*
C16	0.66755 (8)	0.4772 (2)	0.74958 (7)	0.0096 (3)
C17	0.76096 (7)	0.4602 (3)	0.74015 (7)	0.0099 (3)
C18	0.82173 (8)	0.4626 (3)	0.75732 (8)	0.0140 (3)
C19	0.73481 (7)	0.4490 (3)	0.69280 (7)	0.0092 (3)
C20	0.75777 (7)	0.4236 (3)	0.64109 (7)	0.0104 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01277 (12)	0.01642 (12)	0.00823 (13)	−0.00052 (7)	−0.00025 (7)	0.00401 (7)
Cu2	0.00931 (12)	0.01746 (12)	0.00623 (13)	0.00409 (7)	0.00026 (7)	0.00039 (7)
Cu3	0.01492 (13)	0.01833 (13)	0.00752 (13)	0.00102 (8)	−0.00294 (8)	0.00036 (8)
O1	0.0152 (6)	0.0171 (6)	0.0143 (7)	0.0002 (5)	−0.0047 (5)	0.0035 (5)
O2	0.0123 (6)	0.0177 (6)	0.0181 (7)	0.0014 (5)	−0.0011 (5)	0.0026 (5)
O3	0.0106 (6)	0.0273 (7)	0.0163 (7)	0.0042 (5)	0.0021 (5)	0.0032 (5)
O4	0.0123 (6)	0.0291 (8)	0.0101 (7)	0.0076 (5)	0.0018 (5)	0.0032 (5)
O5	0.0110 (6)	0.0177 (6)	0.0090 (6)	0.0039 (5)	0.0020 (5)	0.0002 (5)
O6	0.0094 (5)	0.0160 (6)	0.0130 (6)	0.0001 (5)	0.0028 (5)	−0.0002 (5)
O7	0.0106 (6)	0.0245 (7)	0.0185 (7)	0.0011 (5)	0.0000 (5)	−0.0013 (6)
O8	0.0151 (6)	0.0250 (7)	0.0162 (7)	0.0004 (5)	−0.0035 (5)	−0.0009 (5)
O9	0.0138 (6)	0.0196 (7)	0.0213 (8)	0.0024 (5)	−0.0058 (5)	0.0014 (5)
N1	0.0140 (7)	0.0125 (7)	0.0101 (7)	0.0010 (5)	0.0017 (5)	0.0000 (5)
N2	0.0123 (6)	0.0101 (6)	0.0083 (7)	0.0007 (5)	−0.0011 (5)	0.0015 (5)
N3	0.0106 (6)	0.0113 (6)	0.0066 (7)	0.0013 (5)	−0.0003 (5)	0.0005 (5)
N4	0.0127 (7)	0.0153 (7)	0.0092 (7)	0.0001 (5)	0.0010 (5)	−0.0021 (5)
N5	0.0101 (6)	0.0137 (6)	0.0074 (7)	0.0001 (5)	−0.0005 (5)	0.0010 (5)
N6	0.0094 (6)	0.0122 (6)	0.0060 (7)	0.0015 (5)	−0.0008 (5)	−0.0009 (5)
C1	0.0125 (7)	0.0128 (7)	0.0144 (9)	0.0004 (6)	0.0020 (6)	0.0012 (6)
C2	0.0134 (7)	0.0124 (7)	0.0124 (8)	−0.0013 (6)	−0.0019 (6)	0.0017 (6)
C3	0.0149 (7)	0.0094 (7)	0.0086 (8)	−0.0013 (6)	−0.0016 (6)	0.0009 (5)
C4	0.0115 (7)	0.0091 (7)	0.0074 (8)	−0.0002 (5)	0.0002 (5)	0.0008 (5)
C5	0.0128 (7)	0.0118 (7)	0.0072 (8)	0.0000 (6)	0.0007 (6)	−0.0003 (5)
C6	0.0112 (7)	0.0091 (7)	0.0077 (7)	−0.0007 (5)	−0.0010 (6)	0.0011 (5)
C7	0.0115 (7)	0.0096 (7)	0.0105 (8)	0.0002 (5)	−0.0017 (6)	0.0011 (5)
C8	0.0121 (7)	0.0106 (7)	0.0139 (9)	−0.0009 (6)	−0.0033 (6)	−0.0003 (6)
C9	0.0098 (7)	0.0101 (7)	0.0091 (8)	0.0012 (5)	−0.0005 (6)	−0.0001 (5)
C10	0.0108 (7)	0.0162 (8)	0.0113 (8)	0.0032 (6)	0.0003 (6)	0.0002 (6)
C11	0.0119 (8)	0.0189 (8)	0.0110 (9)	−0.0001 (6)	0.0021 (6)	−0.0005 (6)
C12	0.0114 (7)	0.0212 (8)	0.0119 (8)	−0.0024 (6)	−0.0005 (6)	−0.0023 (7)
C13	0.0122 (7)	0.0147 (8)	0.0101 (8)	−0.0009 (6)	−0.0009 (6)	−0.0007 (6)
C14	0.0094 (7)	0.0132 (7)	0.0075 (8)	0.0004 (5)	0.0009 (6)	−0.0004 (5)
C15	0.0116 (7)	0.0149 (8)	0.0094 (8)	−0.0001 (6)	0.0002 (6)	−0.0012 (6)
C16	0.0095 (7)	0.0111 (7)	0.0082 (8)	−0.0003 (5)	−0.0008 (6)	0.0000 (5)
C17	0.0092 (7)	0.0115 (7)	0.0092 (8)	0.0003 (5)	0.0005 (6)	0.0007 (6)
C18	0.0105 (7)	0.0133 (7)	0.0181 (9)	−0.0002 (6)	−0.0020 (6)	0.0015 (6)
C19	0.0088 (7)	0.0094 (7)	0.0095 (8)	0.0007 (5)	0.0004 (5)	0.0007 (6)
C20	0.0109 (7)	0.0081 (7)	0.0122 (8)	0.0003 (5)	0.0010 (6)	0.0005 (6)

Geometric parameters (Å, º)

Cu1—N2	1.8957 (16)	N4—C11	1.349 (2)
Cu1—N4^i	1.8981 (16)	N4—Cu1^iv	1.8980 (16)
Cu1—O1	2.4823 (15)	N5—C16	1.354 (2)
Cu2—O5	1.9627 (13)	N5—C17	1.370 (2)
Cu2—O4	1.9674 (14)	N6—C16	1.352 (2)
Cu2—N3	2.0572 (15)	N6—C19	1.370 (2)
Cu2—N6	2.0576 (16)	C1—C2	1.388 (3)
Cu2—O9	2.2200 (16)	C1—H1	0.9500
Cu3—N1^ii	1.8874 (17)	C2—C3	1.388 (3)
Cu3—N5	1.8897 (17)	C2—H2A	0.9500
Cu3—O8	2.3960 (17)	C3—C4	1.393 (2)
O1—C8	1.235 (2)	C3—H3	0.9500
O2—C8	1.305 (2)	C4—C5	1.398 (2)
O2—H2	0.8200	C4—C6	1.470 (2)
O3—C10	1.270 (2)	C5—H5	0.9500
O4—C10	1.266 (2)	C7—C9	1.381 (2)
O5—C20	1.269 (2)	C7—C8	1.471 (2)
O6—C20	1.266 (2)	C9—C10	1.470 (3)
O7—C18	1.322 (2)	C11—C12	1.387 (3)
O7—H7	0.8201	C11—H11	0.9500
O8—C18	1.226 (3)	C12—C13	1.389 (3)
O9—H9A	0.8201	C12—H12	0.9500
O9—H9B	0.8201	C13—C14	1.402 (2)
N1—C1	1.352 (2)	C13—H13	0.9500
N1—C5	1.355 (2)	C14—C15	1.394 (2)
N1—Cu3^iii	1.8874 (16)	C14—C16	1.469 (2)
N2—C6	1.348 (2)	C15—H15	0.9500
N2—C7	1.372 (2)	C17—C19	1.383 (3)
N3—C6	1.357 (2)	C17—C18	1.474 (3)
N3—C9	1.363 (2)	C19—C20	1.466 (2)
N4—C15	1.346 (2)
N2—Cu1—N4^i	171.68 (7)	C3—C4—C5	118.33 (16)
N2—Cu1—O1	77.41 (6)	C3—C4—C6	119.86 (16)
N4^i—Cu1—O1	109.97 (6)	C5—C4—C6	121.81 (16)
O5—Cu2—O4	179.35 (7)	N1—C5—C4	121.96 (16)
O5—Cu2—N3	96.62 (6)	N1—C5—H5	119.0
O4—Cu2—N3	83.54 (6)	C4—C5—H5	119.0
O5—Cu2—N6	82.91 (6)	N2—C6—N3	112.56 (15)
O4—Cu2—N6	96.76 (6)	N2—C6—C4	123.79 (16)
N3—Cu2—N6	163.22 (6)	N3—C6—C4	123.62 (15)
O5—Cu2—O9	90.75 (6)	N2—C7—C9	107.71 (15)
O4—Cu2—O9	89.86 (7)	N2—C7—C8	121.10 (16)
N3—Cu2—O9	95.39 (6)	C9—C7—C8	131.11 (17)
N6—Cu2—O9	101.38 (6)	O1—C8—O2	123.10 (17)
N1^ii—Cu3—N5	169.64 (7)	O1—C8—C7	118.77 (17)
N1^ii—Cu3—O8	109.15 (6)	O2—C8—C7	118.13 (17)
N5—Cu3—O8	79.21 (6)	N3—C9—C7	109.32 (15)
C8—O1—Cu1	104.86 (12)	N3—C9—C10	118.62 (15)
C8—O2—H2	114.0	C7—C9—C10	132.06 (16)
C10—O4—Cu2	114.23 (12)	O4—C10—O3	124.31 (18)
C20—O5—Cu2	115.51 (11)	O4—C10—C9	116.12 (16)
C18—O7—H7	107.9	O3—C10—C9	119.57 (17)
C18—O8—Cu3	104.20 (13)	N4—C11—C12	122.24 (17)
Cu2—O9—H9A	113.2	N4—C11—H11	118.9
Cu2—O9—H9B	118.6	C12—C11—H11	118.9
H9A—O9—H9B	107.3	C11—C12—C13	119.57 (17)
C1—N1—C5	118.74 (16)	C11—C12—H12	120.2
C1—N1—Cu3^iii	118.56 (13)	C13—C12—H12	120.2
C5—N1—Cu3^iii	122.29 (13)	C12—C13—C14	118.63 (17)
C6—N2—C7	105.61 (15)	C12—C13—H13	120.7
C6—N2—Cu1	136.62 (13)	C14—C13—H13	120.7
C7—N2—Cu1	117.74 (12)	C15—C14—C13	118.14 (17)
C6—N3—C9	104.79 (14)	C15—C14—C16	119.26 (16)
C6—N3—Cu2	148.40 (12)	C13—C14—C16	122.59 (17)
C9—N3—Cu2	106.60 (11)	N4—C15—C14	123.16 (16)
C15—N4—C11	118.17 (16)	N4—C15—H15	118.4
C15—N4—Cu1^iv	117.61 (13)	C14—C15—H15	118.4
C11—N4—Cu1^iv	123.93 (13)	N6—C16—N5	112.26 (16)
C16—N5—C17	105.93 (15)	N6—C16—C14	125.87 (16)
C16—N5—Cu3	137.44 (13)	N5—C16—C14	121.86 (17)
C17—N5—Cu3	116.25 (12)	N5—C17—C19	107.63 (15)
C16—N6—C19	105.05 (15)	N5—C17—C18	118.66 (17)
C16—N6—Cu2	146.99 (13)	C19—C17—C18	133.69 (17)
C19—N6—Cu2	106.88 (12)	O8—C18—O7	121.54 (18)
N1—C1—C2	122.48 (17)	O8—C18—C17	120.65 (18)
N1—C1—H1	118.8	O7—C18—C17	117.81 (18)
C2—C1—H1	118.8	N6—C19—C17	109.13 (15)
C1—C2—C3	118.52 (17)	N6—C19—C20	118.10 (15)
C1—C2—H2A	120.7	C17—C19—C20	132.76 (16)
C3—C2—H2A	120.7	O6—C20—O5	124.62 (17)
C2—C3—C4	119.92 (17)	O6—C20—C19	119.83 (16)
C2—C3—H3	120.0	O5—C20—C19	115.54 (15)
C4—C3—H3	120.0
O1—Cu1—N2—C6	−175.86 (19)	C7—C9—C10—O4	−176.18 (19)
O1—Cu1—N2—C7	2.30 (12)	N3—C9—C10—O3	−175.50 (17)
N1^ii—Cu3—N5—C16	35.3 (5)	C7—C9—C10—O3	3.9 (3)
O8—Cu3—N5—C16	179.93 (19)	C15—N4—C11—C12	2.1 (3)
N1^ii—Cu3—N5—C17	−136.3 (4)	Cu1^iv—N4—C11—C12	−171.65 (15)
O8—Cu3—N5—C17	8.33 (12)	N4—C11—C12—C13	0.2 (3)
C5—N1—C1—C2	−1.9 (3)	C11—C12—C13—C14	−2.2 (3)
Cu3^iii—N1—C1—C2	170.90 (14)	C12—C13—C14—C15	1.9 (3)
N1—C1—C2—C3	0.5 (3)	C12—C13—C14—C16	−179.20 (17)
C1—C2—C3—C4	1.6 (3)	C11—N4—C15—C14	−2.4 (3)
C2—C3—C4—C5	−2.2 (3)	Cu1^iv—N4—C15—C14	171.72 (14)
C2—C3—C4—C6	178.56 (15)	C13—C14—C15—N4	0.4 (3)
C1—N1—C5—C4	1.3 (3)	C16—C14—C15—N4	−178.55 (17)
Cu3^iii—N1—C5—C4	−171.27 (13)	C19—N6—C16—N5	0.8 (2)
C3—C4—C5—N1	0.8 (3)	Cu2—N6—C16—N5	−164.20 (17)
C6—C4—C5—N1	179.99 (16)	C19—N6—C16—C14	−178.35 (16)
C7—N2—C6—N3	−0.40 (19)	Cu2—N6—C16—C14	16.6 (3)
Cu1—N2—C6—N3	177.91 (13)	C17—N5—C16—N6	−0.4 (2)
C7—N2—C6—C4	−178.60 (15)	Cu3—N5—C16—N6	−172.55 (14)
Cu1—N2—C6—C4	−0.3 (3)	C17—N5—C16—C14	178.82 (16)
C9—N3—C6—N2	0.52 (19)	Cu3—N5—C16—C14	6.7 (3)
Cu2—N3—C6—N2	173.74 (17)	C15—C14—C16—N6	−153.51 (18)
C9—N3—C6—C4	178.73 (16)	C13—C14—C16—N6	27.6 (3)
Cu2—N3—C6—C4	−8.1 (3)	C15—C14—C16—N5	27.4 (2)
C3—C4—C6—N2	143.35 (18)	C13—C14—C16—N5	−151.52 (18)
C5—C4—C6—N2	−35.8 (3)	C16—N5—C17—C19	−0.21 (19)
C3—C4—C6—N3	−34.7 (2)	Cu3—N5—C17—C19	173.89 (12)
C5—C4—C6—N3	146.15 (17)	C16—N5—C17—C18	178.10 (16)
C6—N2—C7—C9	0.11 (19)	Cu3—N5—C17—C18	−7.8 (2)
Cu1—N2—C7—C9	−178.58 (12)	Cu3—O8—C18—O7	−172.39 (15)
C6—N2—C7—C8	177.13 (16)	Cu3—O8—C18—C17	7.1 (2)
Cu1—N2—C7—C8	−1.6 (2)	N5—C17—C18—O8	−1.2 (3)
Cu1—O1—C8—O2	−177.61 (15)	C19—C17—C18—O8	176.5 (2)
Cu1—O1—C8—C7	3.18 (19)	N5—C17—C18—O7	178.32 (16)
N2—C7—C8—O1	−1.8 (3)	C19—C17—C18—O7	−3.9 (3)
C9—C7—C8—O1	174.44 (18)	C16—N6—C19—C17	−0.92 (19)
N2—C7—C8—O2	178.96 (16)	Cu2—N6—C19—C17	170.62 (12)
C9—C7—C8—O2	−4.8 (3)	C16—N6—C19—C20	177.95 (15)
C6—N3—C9—C7	−0.43 (19)	Cu2—N6—C19—C20	−10.51 (19)
Cu2—N3—C9—C7	−176.72 (12)	N5—C17—C19—N6	0.7 (2)
C6—N3—C9—C10	179.11 (16)	C18—C17—C19—N6	−177.23 (19)
Cu2—N3—C9—C10	2.81 (19)	N5—C17—C19—C20	−177.93 (18)
N2—C7—C9—N3	0.2 (2)	C18—C17—C19—C20	4.1 (4)
C8—C7—C9—N3	−176.41 (17)	Cu2—O5—C20—O6	−178.67 (14)
N2—C7—C9—C10	−179.25 (18)	Cu2—O5—C20—C19	2.4 (2)
C8—C7—C9—C10	4.1 (3)	N6—C19—C20—O6	−172.84 (16)
Cu2—O4—C10—O3	170.26 (16)	C17—C19—C20—O6	5.7 (3)
Cu2—O4—C10—C9	−9.7 (2)	N6—C19—C20—O5	6.1 (2)
N3—C9—C10—O4	4.4 (3)	C17—C19—C20—O5	−175.32 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O6^v	0.82	1.94	2.718 (2)	159
O9—H9A···O1^vi	0.82	1.87	2.655 (2)	160
O7—H7···O6	0.82	1.79	2.612 (2)	177
O2—H2···O3	0.82	1.68	2.480 (2)	165

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