A one-dimensional coordination polymer of 5-[(imidazol-1-yl)methyl]benzene-1,3-dicarb­oxy­lic acid with Cu^II cations

5-[(Imidazol-1-yl)methyl]benzene-1,3-dicarb­oxy­lic acid (H₂L) was synthesized and the dimethyl­formamide- and dimethyl­acetamide-solvated structures of its adducts with Cu^II, namely catena-poly[[copper(II)-bis­[μ-3-carb­oxy-5-[(imidazol-1-yl)methyl]benzoato]] di­methyl­form­amide disolvate], {[Cu(C₁₂H₉N₂O₄)₂]·2C₃H₇NO}_n, (I), and catena-poly[[copper(II)-bis­[μ-3-carb­oxy-5-[(imid­azol-1-yl)methyl]benzoato]] dimethyl­acet­amide disolvate], {[Cu(C₁₂H₉N₂O₄)₂]·2C₄H₉NO}_n, (II), the formation of which are associated with mono-deprotonation of H₂L. The two structures are isomorphous and isometric. They consist of one-dimensional coordination polymers of the organic ligand with Cu^II in a 2:1 ratio, [Cu(μ-HL)₂]_n, crystallizing as the dimethyl­formamide (DMF) or dimethyl­acetamide (DMA) disolvates. The Cu^II cations are characterized by a coordination number of six, being located on centres of crystallographic inversion. In the polymeric chains, each Cu^II cation is linked to four neighbouring HL⁻ ligands, and the organic ligand is coordinated via Cu—O and Cu—N bonds to two Cu^II cations. In the corresponding crystal structures of (I) and (II), the coordination chains, aligned parallel to the c axis, are further inter­linked by strong hydrogen bonds between the noncoordinated carb­oxy groups in one array and the coordinated carboxyl­ate groups of neighbouring chains. Mol­ecules of DMF and DMA (disordered) are accommodated at the inter­face between adjacent polymeric assemblies. This report provides the first structural evidence for the formation of coordination polymers with H₂L via multiple metal–ligand bonds through both carboxyl­ate and imidazole groups.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2012 (Sheldrick, 2008).

(I) catena-poly[[copper(II)-bis[µ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylformamide disolvate]

Crystal data

[Cu(C12H9N2O4)2]·2C3H7NO	F(000) = 726
Mr = 700.17	Dx = 1.475 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.5555 (1) Å	Cell parameters from 3437 reflections
b = 21.9603 (5) Å	θ = 2.8–27.8°
c = 9.8497 (2) Å	µ = 0.76 mm^−1
β = 105.2590 (9)°	T = 110 K
V = 1576.66 (5) Å^3	Prism, green
Z = 2	0.30 × 0.25 × 0.25 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3689 independent reflections
Radiation source: sealed X-ray tube	2639 reflections with I > 2σ(I)
Detector resolution: 12.8 pixels mm^-1	Rint = 0.050
1° φ and ω scans	θmax = 27.8°, θmin = 2.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −9→9
Tmin = 0.804, Tmax = 0.833	k = −28→28
12428 measured reflections	l = −12→12

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0892P)^2 + 0.9016P], where P = (Fo^2 + 2Fc^2)/3
3689 reflections	(Δ/σ)max = 0.003
217 parameters	Δρmax = 0.89 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu1	1.0000	0.0000	1.0000	0.01997 (17)
O2	0.8865 (3)	0.01891 (9)	0.7991 (2)	0.0219 (4)
O3	1.0407 (3)	0.10340 (9)	0.8724 (2)	0.0265 (5)
C4	0.9250 (4)	0.07429 (13)	0.7813 (3)	0.0211 (6)
C5	0.8188 (4)	0.10403 (13)	0.6471 (3)	0.0223 (6)
C6	0.8110 (4)	0.16732 (13)	0.6368 (3)	0.0225 (6)
H6	0.8764	0.1915	0.7136	0.027*
C7	0.7084 (4)	0.19521 (13)	0.5149 (3)	0.0238 (6)
C8	0.7049 (4)	0.26335 (14)	0.5099 (3)	0.0274 (7)
O9	0.7652 (3)	0.29491 (10)	0.6109 (2)	0.0361 (6)
O10	0.6367 (4)	0.28468 (11)	0.3815 (2)	0.0452 (6)
H10	0.6062	0.3213	0.3859	0.068*
C11	0.6091 (4)	0.16024 (14)	0.4024 (3)	0.0240 (6)
H11	0.5391	0.1795	0.3191	0.029*
C12	0.6132 (4)	0.09634 (14)	0.4127 (3)	0.0229 (6)
C13	0.7189 (4)	0.06904 (14)	0.5341 (3)	0.0225 (6)
H13	0.7234	0.0259	0.5407	0.027*
C14	0.5056 (4)	0.05795 (15)	0.2918 (3)	0.0248 (6)
H14A	0.4991	0.0156	0.3247	0.030*
H14B	0.3788	0.0738	0.2599	0.030*
N15	0.5888 (3)	0.05786 (11)	0.1726 (2)	0.0221 (5)
C16	0.7474 (4)	0.03079 (14)	0.1726 (3)	0.0251 (6)
H16	0.8234	0.0099	0.2509	0.030*
N17	0.7851 (3)	0.03691 (11)	0.0488 (2)	0.0228 (5)
C18	0.6374 (4)	0.06878 (16)	−0.0345 (3)	0.0318 (7)
H18	0.6227	0.0796	−0.1302	0.038*
C19	0.5170 (4)	0.08215 (16)	0.0423 (3)	0.0313 (7)
H19	0.4052	0.1040	0.0114	0.038*
O20	0.2857 (5)	0.07385 (14)	0.6088 (3)	0.0649 (9)
C21	0.2918 (6)	0.1295 (2)	0.6124 (5)	0.0593 (12)
H21	0.3629	0.1481	0.6962	0.071*
N22	0.2068 (4)	0.16587 (16)	0.5085 (4)	0.0501 (9)
C23	0.2170 (7)	0.2311 (2)	0.5154 (8)	0.088 (2)
H23A	0.2934	0.2435	0.6079	0.132*
H23B	0.0934	0.2480	0.5012	0.132*
H23C	0.2713	0.2463	0.4419	0.132*
C24	0.0989 (6)	0.1401 (3)	0.3784 (6)	0.0689 (14)
H24A	0.1138	0.0958	0.3810	0.103*
H24B	0.1402	0.1568	0.2997	0.103*
H24C	−0.0307	0.1503	0.3662	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0217 (3)	0.0189 (3)	0.0178 (3)	0.00116 (18)	0.00244 (18)	0.00131 (19)
O2	0.0246 (10)	0.0196 (10)	0.0201 (10)	0.0016 (8)	0.0033 (8)	0.0029 (8)
O3	0.0288 (10)	0.0209 (10)	0.0248 (11)	−0.0021 (8)	−0.0017 (9)	0.0008 (9)
C4	0.0221 (13)	0.0200 (14)	0.0211 (14)	0.0025 (11)	0.0058 (11)	0.0003 (11)
C5	0.0224 (14)	0.0229 (15)	0.0206 (14)	0.0025 (11)	0.0038 (11)	0.0033 (12)
C6	0.0221 (14)	0.0217 (15)	0.0217 (14)	−0.0008 (11)	0.0020 (11)	−0.0006 (12)
C7	0.0250 (14)	0.0195 (15)	0.0256 (15)	0.0009 (11)	0.0044 (12)	−0.0004 (12)
C8	0.0292 (15)	0.0222 (16)	0.0267 (16)	0.0018 (12)	−0.0001 (13)	0.0013 (12)
O9	0.0477 (13)	0.0226 (12)	0.0291 (12)	0.0001 (10)	−0.0057 (10)	−0.0011 (10)
O10	0.0688 (17)	0.0216 (12)	0.0320 (13)	0.0061 (12)	−0.0099 (12)	0.0014 (10)
C11	0.0235 (14)	0.0242 (15)	0.0223 (14)	0.0018 (11)	0.0026 (11)	0.0011 (12)
C12	0.0211 (13)	0.0252 (15)	0.0225 (14)	0.0000 (11)	0.0059 (11)	−0.0010 (12)
C13	0.0230 (13)	0.0222 (15)	0.0225 (14)	0.0004 (11)	0.0062 (11)	0.0022 (12)
C14	0.0219 (14)	0.0312 (16)	0.0211 (14)	−0.0017 (12)	0.0054 (12)	−0.0012 (12)
N15	0.0224 (11)	0.0232 (12)	0.0193 (12)	−0.0004 (9)	0.0029 (9)	−0.0026 (9)
C16	0.0251 (14)	0.0268 (16)	0.0218 (15)	0.0026 (12)	0.0031 (12)	0.0006 (12)
N17	0.0242 (12)	0.0230 (13)	0.0192 (12)	0.0005 (10)	0.0024 (10)	0.0015 (10)
C18	0.0317 (16)	0.0380 (19)	0.0255 (16)	0.0092 (14)	0.0073 (13)	0.0074 (14)
C19	0.0314 (16)	0.0329 (18)	0.0273 (15)	0.0089 (13)	0.0037 (13)	0.0021 (13)
O20	0.092 (2)	0.0385 (17)	0.081 (2)	0.0115 (16)	0.0520 (19)	0.0138 (16)
C21	0.065 (3)	0.056 (3)	0.066 (3)	0.010 (2)	0.035 (2)	0.009 (2)
N22	0.0426 (17)	0.046 (2)	0.070 (2)	0.0083 (15)	0.0291 (17)	0.0170 (18)
C23	0.074 (3)	0.041 (3)	0.168 (6)	0.009 (2)	0.066 (4)	0.022 (3)
C24	0.053 (3)	0.084 (4)	0.079 (3)	0.012 (2)	0.033 (3)	0.018 (3)

Geometric parameters (Å, º)

Cu1—O2^i	1.9828 (19)	C14—N15	1.470 (4)
Cu1—O2	1.9828 (19)	C14—H14A	0.9900
Cu1—N17^ii	1.983 (2)	C14—H14B	0.9900
Cu1—N17^iii	1.983 (2)	N15—C16	1.338 (4)
Cu1—O3	2.652 (2)	N15—C19	1.364 (4)
Cu1—O3^i	2.652 (2)	C16—N17	1.330 (4)
O2—C4	1.273 (3)	C16—H16	0.9500
O3—C4	1.251 (3)	N17—C18	1.388 (4)
C4—C5	1.503 (4)	N17—Cu1^iv	1.983 (2)
C5—C6	1.394 (4)	C18—C19	1.359 (4)
C5—C13	1.399 (4)	C18—H18	0.9500
C6—C7	1.388 (4)	C19—H19	0.9500
C6—H6	0.9500	O20—C21	1.224 (5)
C7—C11	1.394 (4)	C21—N22	1.323 (6)
C7—C8	1.497 (4)	C21—H21	0.9500
C8—O9	1.200 (4)	N22—C23	1.435 (6)
C8—O10	1.319 (4)	N22—C24	1.441 (6)
O10—H10	0.8400	C23—H23A	0.9800
C11—C12	1.407 (4)	C23—H23B	0.9800
C11—H11	0.9500	C23—H23C	0.9800
C12—C13	1.387 (4)	C24—H24A	0.9800
C12—C14	1.510 (4)	C24—H24B	0.9800
C13—H13	0.9500	C24—H24C	0.9800
O2^i—Cu1—O2	180.00 (11)	C12—C14—H14B	109.2
O2^i—Cu1—N17^ii	89.40 (9)	H14A—C14—H14B	107.9
O2—Cu1—N17^ii	90.60 (9)	C16—N15—C19	107.9 (2)
O2^i—Cu1—N17^iii	90.60 (9)	C16—N15—C14	124.9 (2)
O2—Cu1—N17^iii	89.40 (9)	C19—N15—C14	127.1 (2)
N17^ii—Cu1—N17^iii	180.0	N17—C16—N15	111.3 (3)
C4—O2—Cu1	106.43 (17)	N17—C16—H16	124.3
O3—C4—O2	122.1 (3)	N15—C16—H16	124.3
O3—C4—C5	121.3 (3)	C16—N17—C18	105.1 (2)
O2—C4—C5	116.6 (2)	C16—N17—Cu1^iv	124.6 (2)
C6—C5—C13	119.1 (3)	C18—N17—Cu1^iv	130.2 (2)
C6—C5—C4	120.0 (3)	C19—C18—N17	109.4 (3)
C13—C5—C4	120.8 (3)	C19—C18—H18	125.3
C7—C6—C5	120.4 (3)	N17—C18—H18	125.3
C7—C6—H6	119.8	C18—C19—N15	106.3 (3)
C5—C6—H6	119.8	C18—C19—H19	126.8
C6—C7—C11	120.4 (3)	N15—C19—H19	126.8
C6—C7—C8	118.1 (3)	O20—C21—N22	125.0 (5)
C11—C7—C8	121.5 (3)	O20—C21—H21	117.5
O9—C8—O10	123.8 (3)	N22—C21—H21	117.5
O9—C8—C7	123.4 (3)	C21—N22—C23	123.8 (5)
O10—C8—C7	112.7 (3)	C21—N22—C24	119.8 (4)
C8—O10—H10	109.5	C23—N22—C24	116.4 (4)
C7—C11—C12	119.7 (3)	N22—C23—H23A	109.5
C7—C11—H11	120.2	N22—C23—H23B	109.5
C12—C11—H11	120.2	H23A—C23—H23B	109.5
C13—C12—C11	119.4 (3)	N22—C23—H23C	109.5
C13—C12—C14	120.5 (3)	H23A—C23—H23C	109.5
C11—C12—C14	120.2 (3)	H23B—C23—H23C	109.5
C12—C13—C5	121.1 (3)	N22—C24—H24A	109.5
C12—C13—H13	119.5	N22—C24—H24B	109.5
C5—C13—H13	119.5	H24A—C24—H24B	109.5
N15—C14—C12	112.1 (2)	N22—C24—H24C	109.5
N15—C14—H14A	109.2	H24A—C24—H24C	109.5
C12—C14—H14A	109.2	H24B—C24—H24C	109.5
N15—C14—H14B	109.2

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O3^v	0.84	1.72	2.557 (3)	173

Symmetry code: (v) x−1/2, −y+1/2, z−1/2.

(II) catena-poly[[copper(II)-bis[µ-3-carboxy-5-[(imidazol-1-yl)methyl]benzoato]] dimethylacetamide disolvate]

Crystal data

[Cu(C12H9N2O4)2]·2C4H9NO	F(000) = 758
Mr = 728.22	Dx = 1.483 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.7557 (2) Å	Cell parameters from 3589 reflections
b = 21.9826 (4) Å	θ = 2.8–27.8°
c = 9.8160 (3) Å	µ = 0.74 mm^−1
β = 102.9198 (9)°	T = 110 K
V = 1631.17 (7) Å^3	Prism, green
Z = 2	0.35 × 0.25 × 0.15 mm

Data collection

Nonius KappaCCD area-detector diffractometer	3856 independent reflections
Radiation source: fine-focussealed tube	2759 reflections with I > 2σ(I)
Detector resolution: 12.8 pixels mm^-1	Rint = 0.051
1° φ and ω scans	θmax = 27.8°, θmin = 2.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −10→10
Tmin = 0.737, Tmax = 0.897	k = −28→28
13044 measured reflections	l = −12→12

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0666P)^2 + 0.7243P], where P = (Fo^2 + 2Fc^2)/3
3856 reflections	(Δ/σ)max = 0.019
224 parameters	Δρmax = 0.45 e Å^−3
1 restraint	Δρmin = −0.43 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	1.0000	0.0000	1.0000	0.02180 (15)
O2	0.8896 (2)	0.01963 (7)	0.80335 (17)	0.0238 (4)
O3	1.0298 (2)	0.10518 (7)	0.87420 (19)	0.0290 (4)
C4	0.9232 (3)	0.07523 (10)	0.7846 (3)	0.0233 (5)
C5	0.8213 (3)	0.10380 (10)	0.6512 (3)	0.0228 (5)
C6	0.8126 (3)	0.16662 (11)	0.6372 (3)	0.0256 (5)
H6	0.8811	0.1918	0.7077	0.031*
C7	0.7035 (3)	0.19281 (11)	0.5198 (3)	0.0251 (5)
C8	0.6935 (4)	0.26077 (11)	0.5131 (3)	0.0280 (6)
O9	0.7857 (3)	0.29380 (8)	0.5971 (2)	0.0402 (5)
O10	0.5731 (3)	0.28024 (8)	0.4062 (2)	0.0445 (6)
H10	0.5673	0.3184	0.4090	0.067*
C11	0.6058 (3)	0.15605 (11)	0.4137 (3)	0.0247 (5)
H11	0.5312	0.1741	0.3339	0.030*
C12	0.6184 (3)	0.09252 (11)	0.4255 (3)	0.0237 (5)
C13	0.7262 (3)	0.06708 (11)	0.5443 (3)	0.0244 (5)
H13	0.7353	0.0241	0.5528	0.029*
C14	0.5177 (3)	0.05198 (11)	0.3112 (3)	0.0268 (6)
H14A	0.5166	0.0100	0.3472	0.032*
H14B	0.3937	0.0662	0.2831	0.032*
N15	0.5968 (3)	0.05183 (9)	0.1882 (2)	0.0249 (5)
C16	0.7446 (3)	0.02185 (12)	0.1787 (3)	0.0286 (6)
H16	0.8097	−0.0039	0.2497	0.034*
N17	0.7882 (3)	0.03271 (9)	0.0578 (2)	0.0250 (5)
C18	0.6573 (4)	0.07157 (14)	−0.0133 (3)	0.0420 (7)
H18	0.6508	0.0873	−0.1045	0.050*
C19	0.5407 (4)	0.08363 (13)	0.0671 (3)	0.0393 (7)
H19	0.4396	0.1092	0.0438	0.047*
O20	0.2637 (9)	0.0770 (3)	0.5737 (7)	0.053 (2)*	0.5
C21	0.3333 (12)	0.1585 (4)	0.6889 (9)	0.056 (2)*	0.5
H21A	0.3105	0.1378	0.7715	0.084*	0.5
H21B	0.2924	0.2007	0.6875	0.084*	0.5
H21C	0.4605	0.1579	0.6922	0.084*	0.5
C22	0.2389 (8)	0.1273 (3)	0.5631 (7)	0.0293 (13)*	0.5
N23	0.1612 (6)	0.1601 (2)	0.4477 (5)	0.0340 (11)*	0.5
C24	0.0641 (12)	0.1288 (4)	0.3219 (10)	0.045 (2)*	0.5
H24A	0.0565	0.0853	0.3416	0.068*	0.5
H24B	0.1263	0.1344	0.2462	0.068*	0.5
H24C	−0.0553	0.1459	0.2937	0.068*	0.5
C25	0.1624 (9)	0.2266 (3)	0.4381 (8)	0.0429 (15)*	0.5
H25A	0.0558	0.2430	0.4627	0.064*	0.5
H25B	0.1646	0.2387	0.3424	0.064*	0.5
H25C	0.2675	0.2427	0.5028	0.064*	0.5
O28	0.2206 (8)	0.0701 (2)	0.5518 (6)	0.0377 (15)*	0.5
C27	0.1988 (10)	0.1242 (3)	0.5056 (8)	0.0425 (17)*	0.5
C26	0.0858 (14)	0.1268 (4)	0.3636 (11)	0.057 (3)*	0.5
H26A	0.0803	0.0864	0.3204	0.085*	0.5
H26B	0.1354	0.1560	0.3073	0.085*	0.5
H26C	−0.0336	0.1397	0.3685	0.085*	0.5
N29	0.2419 (8)	0.1766 (3)	0.5720 (6)	0.0561 (15)*	0.5
C30	0.3559 (14)	0.1755 (5)	0.7143 (7)	0.074 (3)*	0.5
H30A	0.2904	0.1917	0.7807	0.110*	0.5
H30B	0.4613	0.2004	0.7167	0.110*	0.5
H30C	0.3919	0.1335	0.7398	0.110*	0.5
C31	0.1893 (11)	0.2358 (3)	0.5194 (9)	0.0565 (19)*	0.5
H31A	0.1415	0.2583	0.5888	0.085*	0.5
H31B	0.0982	0.2322	0.4327	0.085*	0.5
H31C	0.2918	0.2575	0.5006	0.085*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0270 (3)	0.0187 (2)	0.0180 (2)	0.00284 (16)	0.00143 (17)	0.00190 (16)
O2	0.0303 (10)	0.0178 (8)	0.0215 (9)	0.0009 (7)	0.0020 (8)	0.0011 (7)
O3	0.0337 (10)	0.0218 (9)	0.0271 (10)	−0.0010 (7)	−0.0029 (8)	0.0021 (7)
C4	0.0258 (13)	0.0216 (12)	0.0224 (13)	0.0033 (9)	0.0051 (11)	0.0008 (10)
C5	0.0247 (13)	0.0217 (12)	0.0216 (13)	0.0027 (9)	0.0041 (10)	0.0036 (9)
C6	0.0266 (14)	0.0247 (13)	0.0240 (13)	0.0008 (10)	0.0027 (11)	−0.0009 (10)
C7	0.0270 (14)	0.0214 (12)	0.0265 (14)	0.0032 (9)	0.0049 (11)	0.0016 (10)
C8	0.0309 (14)	0.0247 (13)	0.0274 (14)	0.0028 (10)	0.0043 (12)	0.0034 (10)
O9	0.0487 (13)	0.0232 (9)	0.0397 (12)	−0.0016 (8)	−0.0094 (10)	−0.0006 (8)
O10	0.0553 (14)	0.0203 (9)	0.0452 (13)	0.0024 (9)	−0.0159 (10)	0.0039 (8)
C11	0.0258 (14)	0.0247 (12)	0.0228 (13)	0.0009 (10)	0.0040 (11)	0.0031 (10)
C12	0.0248 (13)	0.0241 (12)	0.0224 (13)	0.0000 (9)	0.0061 (10)	0.0013 (10)
C13	0.0261 (13)	0.0197 (12)	0.0276 (14)	0.0009 (9)	0.0062 (11)	0.0005 (10)
C14	0.0277 (14)	0.0275 (13)	0.0243 (14)	−0.0017 (10)	0.0042 (11)	0.0008 (10)
N15	0.0277 (11)	0.0245 (11)	0.0215 (11)	0.0021 (8)	0.0032 (9)	−0.0015 (8)
C16	0.0309 (15)	0.0245 (12)	0.0280 (15)	0.0012 (10)	0.0016 (12)	−0.0001 (11)
N17	0.0292 (12)	0.0230 (11)	0.0209 (11)	0.0058 (8)	0.0018 (9)	0.0018 (8)
C18	0.0492 (19)	0.0497 (18)	0.0281 (16)	0.0196 (14)	0.0106 (14)	0.0132 (13)
C19	0.0417 (18)	0.0452 (17)	0.0306 (16)	0.0198 (13)	0.0071 (14)	0.0101 (13)

Geometric parameters (Å, º)

Cu1—O2	1.9764 (16)	C18—H18	0.9500
Cu1—O2^i	1.9765 (16)	C19—H19	0.9500
Cu1—N17^ii	1.989 (2)	O20—C22	1.123 (8)
Cu1—N17^iii	1.989 (2)	C21—C22	1.458 (11)
O2—C4	1.272 (3)	C21—H21A	0.9800
O3—C4	1.252 (3)	C21—H21B	0.9800
C4—C5	1.506 (3)	C21—H21C	0.9800
C5—C6	1.388 (3)	C22—N23	1.364 (8)
C5—C13	1.397 (3)	N23—C25	1.466 (8)
C6—C7	1.393 (3)	N23—C24	1.465 (10)
C6—H6	0.9500	C24—H24A	0.9800
C7—C11	1.399 (3)	C24—H24B	0.9800
C7—C8	1.497 (3)	C24—H24C	0.9800
C8—O9	1.206 (3)	C25—H25A	0.9800
C8—O10	1.311 (3)	C25—H25B	0.9800
O10—H10	0.8400	C25—H25C	0.9800
C11—C12	1.403 (3)	O28—C27	1.270 (9)
C11—H11	0.9500	C27—N29	1.329 (9)
C12—C13	1.391 (3)	C27—C26	1.473 (12)
C12—C14	1.507 (3)	C26—H26A	0.9800
C13—H13	0.9500	C26—H26B	0.9800
C14—N15	1.471 (3)	C26—H26C	0.9800
C14—H14A	0.9900	N29—C30	1.477 (2)
C14—H14B	0.9900	N29—C31	1.425 (9)
N15—C16	1.343 (3)	C30—H30A	0.9800
N15—C19	1.363 (3)	C30—H30B	0.9800
C16—N17	1.326 (3)	C30—H30C	0.9800
C16—H16	0.9500	C31—H31A	0.9800
N17—C18	1.389 (3)	C31—H31B	0.9800
N17—Cu1^iv	1.989 (2)	C31—H31C	0.9800
C18—C19	1.353 (4)
O2—Cu1—O2^i	180.0	C18—C19—H19	126.8
O2—Cu1—N17^ii	90.30 (8)	N15—C19—H19	126.8
O2^i—Cu1—N17^ii	89.71 (8)	C22—C21—H21A	109.5
O2—Cu1—N17^iii	89.70 (8)	C22—C21—H21B	109.5
O2^i—Cu1—N17^iii	90.29 (8)	H21A—C21—H21B	109.5
N17^ii—Cu1—N17^iii	180.0	C22—C21—H21C	109.5
C4—O2—Cu1	107.06 (15)	H21A—C21—H21C	109.5
O3—C4—O2	121.9 (2)	H21B—C21—H21C	109.5
O3—C4—C5	121.8 (2)	O20—C22—N23	129.2 (7)
O2—C4—C5	116.2 (2)	O20—C22—C21	109.9 (7)
C6—C5—C13	119.6 (2)	N23—C22—C21	120.0 (6)
C6—C5—C4	120.4 (2)	C22—N23—C25	124.9 (5)
C13—C5—C4	119.9 (2)	C22—N23—C24	120.0 (6)
C5—C6—C7	120.0 (2)	C25—N23—C24	115.0 (5)
C5—C6—H6	120.0	N23—C24—H24A	109.5
C7—C6—H6	120.0	N23—C24—H24B	109.5
C6—C7—C11	120.3 (2)	H24A—C24—H24B	109.5
C6—C7—C8	117.7 (2)	N23—C24—H24C	109.5
C11—C7—C8	122.0 (2)	H24A—C24—H24C	109.5
O9—C8—O10	123.9 (2)	H24B—C24—H24C	109.5
O9—C8—C7	123.6 (2)	N23—C25—H25A	109.5
O10—C8—C7	112.5 (2)	N23—C25—H25B	109.5
C8—O10—H10	109.5	H25A—C25—H25B	109.5
C7—C11—C12	119.8 (2)	N23—C25—H25C	109.5
C7—C11—H11	120.1	H25A—C25—H25C	109.5
C12—C11—H11	120.1	H25B—C25—H25C	109.5
C13—C12—C11	119.1 (2)	O28—C27—N29	129.6 (8)
C13—C12—C14	120.1 (2)	O28—C27—C26	112.2 (7)
C11—C12—C14	120.8 (2)	N29—C27—C26	117.5 (7)
C12—C13—C5	121.0 (2)	C27—C26—H26A	109.5
C12—C13—H13	119.5	C27—C26—H26B	109.5
C5—C13—H13	119.5	H26A—C26—H26B	109.5
N15—C14—C12	111.8 (2)	C27—C26—H26C	109.5
N15—C14—H14A	109.3	H26A—C26—H26C	109.5
C12—C14—H14A	109.3	H26B—C26—H26C	109.5
N15—C14—H14B	109.3	C27—N29—C30	118.7 (7)
C12—C14—H14B	109.3	C27—N29—C31	126.4 (6)
H14A—C14—H14B	107.9	C30—N29—C31	114.9 (7)
C16—N15—C19	107.6 (2)	N29—C30—H30A	109.5
C16—N15—C14	125.2 (2)	N29—C30—H30B	109.5
C19—N15—C14	127.1 (2)	H30A—C30—H30B	109.5
N17—C16—N15	111.4 (2)	N29—C30—H30C	109.5
N17—C16—H16	124.3	H30A—C30—H30C	109.5
N15—C16—H16	124.3	H30B—C30—H30C	109.5
C16—N17—C18	104.9 (2)	N29—C31—H31A	109.5
C16—N17—Cu1^iv	125.61 (17)	N29—C31—H31B	109.5
C18—N17—Cu1^iv	129.50 (18)	H31A—C31—H31B	109.5
C19—C18—N17	109.6 (2)	N29—C31—H31C	109.5
C19—C18—H18	125.2	H31A—C31—H31C	109.5
N17—C18—H18	125.2	H31B—C31—H31C	109.5
C18—C19—N15	106.4 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10···O3^v	0.84	1.73	2.551 (2)	166

Symmetry code: (v) x−1/2, −y+1/2, z−1/2.