Controlled inter­penetration of 4⁴ networks: syntheses and structures of two Cu₃-cluster coordination polymers

The reaction of copper nitrate and tri­ethano­lamine with benzene-1,4-di­car­boxy­lic acid (bdcH₂) or 4,4′-[1,4-phenyl­enebis(­oxy)]di­benzoic acid (podaH₂) leads to the formation of poly[bis­(μ₄-benzene-1,4-di­carboxyl­ato-κ⁴O¹:O^1′:O⁴:O⁴)bis­{μ₂-[bis­(2-hy­droxy­eth­yl)amino]­ethano­lato-κ⁴N,O,O′,O′′:κO}tricopper(II)], [Cu₃(C₈H₄O₄)₂(C₆H₁₄NO₃)₂] or [Cu₃(μ₄-bdc)₂(teaH₂)₂] (I), and poly[bis­{μ₄-4,4′-[1,4-phenyl­enebis(­oxy)]dibenzoato-κ⁴O:O′:O′′:O′′}bis­{μ₂-[bis­(2-hy­droxy­eth­yl)amino]­ethano­lato-κ⁴N,O,O′,O′′:κO}tricopper(II)], [Cu₃(C₂₀H₁₂O₆)₂(C₆H₁₄NO₃)₂] or [Cu₃(μ₄-poda)₂(teaH₂)₂], (II). The two representative compounds contain a well-established Cu₃ cluster supporting a given 4⁴ network. The ligand length is the underlying factor that controls the degree of inter­penetration. Controlled inter­penetration can be facile to realise by elongating protocols. Compound I shows a non-inter­penetrating 4⁴ network, whereas II features a threefold inter­penetrating network. Furthermore, similar hydrogen-bond inter­actions extend the different inter­penetrating 4⁴ networks into three-dimensional supra­molecular topologies. Variable-temperature magnetic studies showed a ferromagnetic coupling behaviour in the two complexes.

Computing details

For both structures, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: ShelXle (Hübschle et al., 2011).

Poly[bis(µ₄-benzene-1,4-dicarboxylato-κ⁴O¹:O^1':O⁴:O⁴)bis{µ₂-[bis(2-hydroxyethyl)amino]ethanolato-κ⁴N,O,O',O'':κO}tricopper(II)] (I)

Crystal data

[Cu3(C8H4O4)2(C6H14NO3)2]	F(000) = 834
Mr = 407.60	Dx = 1.775 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.1485 (12) Å	Cell parameters from 3030 reflections
b = 10.8671 (12) Å	θ = 2.1–26.1°
c = 13.2125 (14) Å	µ = 2.15 mm^−1
β = 107.631 (2)°	T = 293 K
V = 1525.5 (3) Å^3	Block, blue
Z = 4	0.30 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer	2150 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
ω scan	θmax = 26.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.255, Tmax = 0.448	k = −5→13
8072 measured reflections	l = −16→15
3030 independent reflections

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.5498P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3030 reflections	Δρmax = 0.72 e Å^−3
220 parameters	Δρmin = −0.50 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. Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement.

_reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences.

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

	x	y	z	Uiso*/Ueq
C1	0.7301 (4)	0.4266 (4)	1.5533 (3)	0.0179 (8)
C2	0.6942 (3)	0.3224 (4)	1.4765 (3)	0.0157 (8)
C3	0.7060 (3)	0.3385 (4)	1.3745 (3)	0.0180 (8)
H3	0.738267	0.411789	1.357245	0.022*
C4	0.6699 (4)	0.2467 (4)	1.3000 (3)	0.0195 (9)
H4	0.678836	0.258221	1.232927	0.023*
C5	0.6202 (4)	0.1365 (3)	1.3234 (3)	0.0157 (8)
C6	0.6120 (4)	0.1185 (4)	1.4258 (3)	0.0176 (8)
H6	0.581913	0.044204	1.443285	0.021*
C7	0.6484 (3)	0.2104 (4)	1.5016 (3)	0.0166 (8)
H7	0.642410	0.197478	1.569507	0.020*
C8	0.5674 (3)	0.0445 (4)	1.2373 (3)	0.0165 (8)
C9	0.4895 (4)	−0.2713 (4)	0.9978 (3)	0.0207 (9)
H9A	0.540855	−0.339407	1.034228	0.025*
H9B	0.508921	−0.256254	0.932076	0.025*
C10	0.3514 (4)	−0.3026 (4)	0.9741 (3)	0.0222 (9)
H10A	0.300291	−0.240612	0.927832	0.027*
H10B	0.333972	−0.381524	0.938377	0.027*
C11	0.3562 (4)	−0.4282 (3)	1.1314 (3)	0.0223 (9)
H11A	0.358936	−0.489897	1.079058	0.027*
H11B	0.291647	−0.452590	1.162777	0.027*
C12	0.4821 (4)	−0.4262 (4)	1.2173 (3)	0.0251 (10)
H12A	0.494261	−0.503374	1.255956	0.030*
H12B	0.548966	−0.417897	1.184896	0.030*
C13	0.1856 (4)	−0.2775 (4)	1.0615 (3)	0.0203 (9)
H13A	0.133786	−0.349324	1.035505	0.024*
H13B	0.158511	−0.212232	1.009469	0.024*
C14	0.1702 (4)	−0.2366 (3)	1.1671 (3)	0.0195 (9)
H14A	0.086781	−0.202328	1.155433	0.023*
H14B	0.179009	−0.307079	1.213832	0.023*
N1	0.3202 (3)	−0.3075 (3)	1.0765 (2)	0.0169 (7)
O1	0.8044 (2)	0.5057 (2)	1.53823 (19)	0.0200 (6)
O2	0.6824 (3)	0.4316 (2)	1.6294 (2)	0.0230 (7)
O3	0.5090 (3)	−0.0453 (2)	1.25975 (19)	0.0214 (6)
O4	0.5812 (3)	0.0659 (2)	1.14744 (19)	0.0195 (6)
O5	0.5159 (2)	−0.1644 (2)	1.06271 (18)	0.0167 (6)
O6	0.4891 (3)	−0.3273 (3)	1.2893 (2)	0.0243 (6)
O7	0.2635 (3)	−0.1458 (2)	1.21591 (19)	0.0177 (6)
Cu1	0.500000	0.000000	1.000000	0.01559 (18)
Cu2	0.41651 (4)	−0.16595 (4)	1.16115 (3)	0.01665 (14)
H01	0.442 (3)	−0.354 (4)	1.329 (3)	0.025*
H02	0.237 (4)	−0.072 (2)	1.188 (3)	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.023 (2)	0.014 (2)	0.0144 (19)	0.0006 (17)	0.0021 (17)	0.0003 (16)
C2	0.0166 (19)	0.015 (2)	0.0153 (18)	0.0010 (17)	0.0048 (15)	−0.0001 (16)
C3	0.022 (2)	0.017 (2)	0.0144 (18)	−0.0024 (18)	0.0036 (15)	−0.0001 (17)
C4	0.024 (2)	0.022 (2)	0.0113 (18)	−0.0055 (18)	0.0042 (16)	−0.0018 (17)
C5	0.020 (2)	0.011 (2)	0.0138 (18)	0.0013 (16)	0.0012 (15)	−0.0010 (15)
C6	0.021 (2)	0.0130 (19)	0.0163 (19)	−0.0013 (17)	0.0020 (16)	0.0018 (16)
C7	0.022 (2)	0.018 (2)	0.0096 (17)	−0.0004 (17)	0.0050 (15)	0.0004 (15)
C8	0.017 (2)	0.015 (2)	0.0166 (19)	0.0037 (17)	0.0032 (16)	0.0031 (16)
C9	0.030 (2)	0.018 (2)	0.0169 (19)	−0.0008 (19)	0.0116 (17)	−0.0005 (17)
C10	0.034 (2)	0.020 (2)	0.0128 (18)	−0.0052 (19)	0.0078 (17)	−0.0040 (17)
C11	0.033 (2)	0.014 (2)	0.024 (2)	0.0003 (18)	0.0137 (19)	−0.0018 (17)
C12	0.033 (3)	0.022 (2)	0.022 (2)	0.006 (2)	0.0116 (19)	0.0061 (18)
C13	0.021 (2)	0.018 (2)	0.019 (2)	−0.0028 (18)	0.0036 (17)	−0.0023 (17)
C14	0.023 (2)	0.012 (2)	0.026 (2)	−0.0031 (17)	0.0107 (17)	0.0006 (17)
N1	0.0231 (18)	0.0156 (18)	0.0134 (15)	−0.0026 (14)	0.0076 (13)	0.0012 (13)
O1	0.0267 (15)	0.0156 (15)	0.0189 (13)	−0.0059 (13)	0.0087 (12)	−0.0057 (12)
O2	0.0364 (17)	0.0182 (15)	0.0181 (14)	−0.0048 (13)	0.0138 (13)	−0.0033 (12)
O3	0.0306 (16)	0.0186 (15)	0.0144 (13)	−0.0095 (13)	0.0062 (12)	−0.0041 (12)
O4	0.0294 (16)	0.0176 (15)	0.0119 (12)	−0.0043 (12)	0.0068 (11)	−0.0022 (11)
O5	0.0227 (15)	0.0119 (13)	0.0162 (12)	−0.0010 (12)	0.0068 (11)	−0.0020 (11)
O6	0.0306 (17)	0.0224 (16)	0.0202 (14)	−0.0044 (14)	0.0082 (12)	0.0018 (13)
O7	0.0248 (15)	0.0131 (15)	0.0154 (13)	−0.0001 (12)	0.0063 (11)	−0.0008 (11)
Cu1	0.0235 (4)	0.0119 (3)	0.0113 (3)	−0.0013 (3)	0.0052 (3)	−0.0006 (3)
Cu2	0.0237 (3)	0.0134 (2)	0.0135 (2)	−0.0037 (2)	0.00664 (19)	−0.0022 (2)

Geometric parameters (Å, º)

C1—O1	1.250 (4)	C11—C12	1.515 (6)
C1—O2	1.273 (4)	C11—H11A	0.9700
C1—C2	1.492 (5)	C11—H11B	0.9700
C2—C7	1.399 (5)	C12—O6	1.421 (5)
C2—C3	1.404 (5)	C12—H12A	0.9700
C3—C4	1.374 (5)	C12—H12B	0.9700
C3—H3	0.9300	C13—N1	1.489 (5)
C4—C5	1.393 (5)	C13—C14	1.522 (5)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.398 (5)	C13—H13B	0.9700
C5—C8	1.495 (5)	C14—O7	1.437 (4)
C6—C7	1.385 (5)	C14—H14A	0.9700
C6—H6	0.9300	C14—H14B	0.9700
C7—H7	0.9300	N1—Cu2	2.011 (3)
C8—O3	1.257 (4)	O1—Cu1^i	2.384 (3)
C8—O4	1.264 (4)	O3—Cu2	1.914 (3)
C9—O5	1.421 (4)	O4—Cu1	2.015 (2)
C9—C10	1.514 (6)	O5—Cu2	1.948 (2)
C9—H9A	0.9700	O5—Cu1	1.954 (3)
C9—H9B	0.9700	O6—Cu2	2.401 (3)
C10—N1	1.496 (4)	O6—H01	0.898 (2)
C10—H10A	0.9700	O7—Cu2	2.057 (3)
C10—H10B	0.9700	O7—H02	0.895 (2)
C11—N1	1.494 (5)
O1—C1—O2	123.5 (3)	C14—C13—H13B	109.8
O1—C1—C2	117.9 (3)	H13A—C13—H13B	108.3
O2—C1—C2	118.6 (3)	O7—C14—C13	110.2 (3)
C7—C2—C3	118.9 (3)	O7—C14—H14A	109.6
C7—C2—C1	122.8 (3)	C13—C14—H14A	109.6
C3—C2—C1	118.3 (3)	O7—C14—H14B	109.6
C4—C3—C2	120.3 (4)	C13—C14—H14B	109.6
C4—C3—H3	119.8	H14A—C14—H14B	108.1
C2—C3—H3	119.8	C13—N1—C11	111.6 (3)
C3—C4—C5	121.1 (3)	C13—N1—C10	111.9 (3)
C3—C4—H4	119.5	C11—N1—C10	111.6 (3)
C5—C4—H4	119.5	C13—N1—Cu2	104.7 (2)
C4—C5—C6	118.8 (3)	C11—N1—Cu2	112.4 (2)
C4—C5—C8	119.9 (3)	C10—N1—Cu2	104.2 (2)
C6—C5—C8	121.2 (3)	C1—O1—Cu1^i	135.1 (2)
C7—C6—C5	120.6 (3)	C8—O3—Cu2	125.5 (2)
C7—C6—H6	119.7	C8—O4—Cu1	134.1 (3)
C5—C6—H6	119.7	C9—O5—Cu2	109.9 (2)
C6—C7—C2	120.3 (3)	C9—O5—Cu1	121.0 (2)
C6—C7—H7	119.9	Cu2—O5—Cu1	107.11 (12)
C2—C7—H7	119.9	C12—O6—Cu2	98.2 (2)
O3—C8—O4	125.7 (4)	C12—O6—H01	103 (3)
O3—C8—C5	116.9 (3)	Cu2—O6—H01	121 (3)
O4—C8—C5	117.4 (3)	C14—O7—Cu2	109.5 (2)
O5—C9—C10	108.7 (3)	C14—O7—H02	109 (3)
O5—C9—H9A	110.0	Cu2—O7—H02	99 (3)
C10—C9—H9A	110.0	O5—Cu1—O5^ii	180.0
O5—C9—H9B	110.0	O5—Cu1—O4	87.61 (1)
C10—C9—H9B	110.0	O5^ii—Cu1—O4	92.39 (1)
H9A—C9—H9B	108.3	O5—Cu1—O4^ii	92.39 (1)
N1—C10—C9	108.8 (3)	O5^ii—Cu1—O4^ii	87.61 (1)
N1—C10—H10A	109.9	O4—Cu1—O4^ii	180.0
C9—C10—H10A	109.9	O5—Cu1—O1^iii	98.17 (9)
N1—C10—H10B	109.9	O5^ii—Cu1—O1^iii	81.83 (9)
C9—C10—H10B	109.9	O4—Cu1—O1^iii	91.34 (1)
H10A—C10—H10B	108.3	O4^ii—Cu1—O1^iii	88.66 (1)
N1—C11—C12	113.7 (3)	O5—Cu1—O1^iv	81.83 (9)
N1—C11—H11A	108.8	O5^ii—Cu1—O1^iv	98.17 (9)
C12—C11—H11A	108.8	O4—Cu1—O1^iv	88.66 (1)
N1—C11—H11B	108.8	O4^ii—Cu1—O1^iv	91.34 (1)
C12—C11—H11B	108.8	O1^iii—Cu1—O1^iv	180.0
H11A—C11—H11B	107.7	O3—Cu2—O5	98.64 (1)
O6—C12—C11	111.3 (3)	O3—Cu2—N1	171.60 (1)
O6—C12—H12A	109.4	O5—Cu2—N1	87.20 (1)
C11—C12—H12A	109.4	O3—Cu2—O7	91.21 (1)
O6—C12—H12B	109.4	O5—Cu2—O7	159.14 (1)
C11—C12—H12B	109.4	N1—Cu2—O7	85.24 (1)
H12A—C12—H12B	108.0	O3—Cu2—O6	91.33 (1)
N1—C13—C14	109.3 (3)	O5—Cu2—O6	109.80 (1)
N1—C13—H13A	109.8	N1—Cu2—O6	80.96 (1)
C14—C13—H13A	109.8	O7—Cu2—O6	88.17 (1)
N1—C13—H13B	109.8
O1—C1—C2—C7	158.2 (4)	N1—C13—C14—O7	48.5 (4)
O2—C1—C2—C7	−22.9 (5)	C14—C13—N1—C11	75.3 (4)
O1—C1—C2—C3	−22.5 (5)	C14—C13—N1—C10	−158.8 (3)
O2—C1—C2—C3	156.4 (4)	C14—C13—N1—Cu2	−46.6 (3)
C7—C2—C3—C4	1.6 (6)	C12—C11—N1—C13	−136.3 (3)
C1—C2—C3—C4	−177.7 (4)	C12—C11—N1—C10	97.6 (4)
C2—C3—C4—C5	0.6 (6)	C12—C11—N1—Cu2	−19.1 (4)
C3—C4—C5—C6	−2.5 (6)	C9—C10—N1—C13	152.5 (3)
C3—C4—C5—C8	172.6 (3)	C9—C10—N1—C11	−81.6 (4)
C4—C5—C6—C7	2.3 (6)	C9—C10—N1—Cu2	39.9 (3)
C8—C5—C6—C7	−172.7 (3)	O2—C1—O1—Cu1^i	133.6 (3)
C5—C6—C7—C2	−0.2 (6)	C2—C1—O1—Cu1^i	−47.6 (5)
C3—C2—C7—C6	−1.8 (6)	O4—C8—O3—Cu2	−4.6 (6)
C1—C2—C7—C6	177.5 (3)	C5—C8—O3—Cu2	172.7 (2)
C4—C5—C8—O3	−170.8 (3)	O3—C8—O4—Cu1	13.7 (6)
C6—C5—C8—O3	4.2 (5)	C5—C8—O4—Cu1	−163.5 (3)
C4—C5—C8—O4	6.7 (5)	C10—C9—O5—Cu2	35.9 (3)
C6—C5—C8—O4	−178.3 (4)	C10—C9—O5—Cu1	−89.7 (3)
O5—C9—C10—N1	−51.6 (4)	C11—C12—O6—Cu2	−48.8 (3)
N1—C11—C12—O6	51.3 (4)	C13—C14—O7—Cu2	−24.7 (3)

Symmetry codes: (i) −x+3/2, y+1/2, −z+5/2; (ii) −x+1, −y, −z+2; (iii) −x+3/2, y−1/2, −z+5/2; (iv) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H01···O2^v	0.90 (1)	1.84 (2)	2.709 (4)	161 (4)
O7—H02···O2^iv	0.90 (1)	1.74 (1)	2.630 (4)	177 (4)

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

Poly[bis{µ₄-4,4'-[1,4-phenylenebis(oxy)]dibenzoato-κ⁴O:O':O'':O''}bis{µ₂-[bis(2-hydroxyethyl)amino]ethanolato-κ⁴N,O,O',O'':κO}tricopper(II)] (II)

Crystal data

[Cu3(C20H12O6)2(C6H14NO3)2]	F(000) = 1218
Mr = 591.79	Dx = 1.590 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 16.0209 (10) Å	Cell parameters from 5528 reflections
b = 9.3823 (5) Å	θ = 1.6–27.5°
c = 16.6801 (8) Å	µ = 1.36 mm^−1
β = 99.563 (4)°	T = 293 K
V = 2472.4 (2) Å^3	Block, blue
Z = 4	0.28 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer	4180 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
ω scan	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −20→10
Tmin = 0.218, Tmax = 0.324	k = −12→10
15743 measured reflections	l = −21→21
5528 independent reflections

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.4965P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
5528 reflections	Δρmax = 0.37 e Å^−3
346 parameters	Δρmin = −0.33 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
C1	1.18324 (15)	0.0774 (2)	1.01355 (14)	0.0287 (5)
C2	1.24690 (15)	0.1750 (2)	0.98602 (14)	0.0280 (5)
C3	1.33151 (15)	0.1716 (3)	1.02163 (15)	0.0346 (6)
H3	1.349863	0.104111	1.061489	0.041*
C4	1.38880 (16)	0.2668 (3)	0.99886 (17)	0.0424 (7)
H4	1.445253	0.264160	1.023595	0.051*
C5	1.36171 (17)	0.3662 (3)	0.93898 (18)	0.0412 (7)
C6	1.27904 (17)	0.3679 (3)	0.90058 (18)	0.0459 (7)
H6	1.261588	0.432148	0.858689	0.055*
C7	1.22201 (16)	0.2733 (3)	0.92469 (16)	0.0395 (6)
H7	1.165781	0.275602	0.899264	0.047*
C8	1.39593 (16)	0.5931 (3)	0.88995 (18)	0.0429 (7)
C9	1.3603 (2)	0.6854 (3)	0.93787 (19)	0.0553 (8)
H9	1.350099	0.656094	0.988632	0.066*
C10	1.3394 (2)	0.8218 (3)	0.9111 (2)	0.0576 (9)
H10	1.314534	0.884288	0.943440	0.069*
C11	1.35553 (18)	0.8648 (3)	0.8367 (2)	0.0469 (7)
C12	1.39126 (19)	0.7728 (3)	0.78954 (18)	0.0517 (8)
H12	1.402074	0.802444	0.739065	0.062*
C13	1.41185 (19)	0.6348 (3)	0.81586 (19)	0.0499 (8)
H13	1.436152	0.571843	0.783315	0.060*
C14	1.39051 (18)	1.0896 (3)	0.7847 (2)	0.0479 (7)
C15	1.47144 (19)	1.0964 (3)	0.82751 (19)	0.0495 (7)
H15	1.488225	1.035612	0.871242	0.059*
C16	1.52757 (18)	1.1942 (3)	0.80513 (17)	0.0439 (7)
H16	1.582172	1.199430	0.834475	0.053*
C17	1.50400 (16)	1.2851 (3)	0.73956 (16)	0.0350 (6)
C18	1.42259 (18)	1.2743 (3)	0.69608 (18)	0.0476 (7)
H18	1.406046	1.332402	0.651085	0.057*
C19	1.36588 (19)	1.1778 (3)	0.7191 (2)	0.0552 (8)
H19	1.311047	1.172473	0.690260	0.066*
C20	1.56334 (16)	1.3979 (3)	0.71788 (16)	0.0345 (6)
C21	1.01573 (16)	−0.3084 (3)	1.01918 (15)	0.0349 (6)
H21A	1.043568	−0.385311	0.995076	0.042*
H21B	0.958631	−0.298941	0.989357	0.042*
C22	1.01309 (15)	−0.3412 (3)	1.10755 (15)	0.0343 (6)
H22A	0.978822	−0.270899	1.129731	0.041*
H22B	0.988244	−0.434435	1.112373	0.041*
C23	1.20838 (18)	−0.4491 (3)	1.07865 (17)	0.0461 (7)
H23A	1.243545	−0.533173	1.078289	0.055*
H23B	1.175325	−0.438184	1.024753	0.055*
C24	1.14915 (17)	−0.4695 (3)	1.13979 (17)	0.0381 (6)
H24A	1.109409	−0.545132	1.120973	0.046*
H24B	1.181887	−0.499279	1.191279	0.046*
C25	1.19032 (17)	−0.2463 (3)	1.27490 (15)	0.0380 (6)
H25A	1.190165	−0.212264	1.329793	0.046*
H25B	1.233835	−0.318649	1.276820	0.046*
C26	1.10503 (17)	−0.3091 (3)	1.24084 (15)	0.0390 (6)
H26A	1.096602	−0.396901	1.269170	0.047*
H26B	1.060539	−0.242968	1.248636	0.047*
N1	1.10109 (12)	−0.3382 (2)	1.15290 (12)	0.0286 (4)
O1	1.54262 (12)	1.4729 (2)	0.65667 (11)	0.0476 (5)
O2	1.63265 (11)	1.4140 (2)	0.76686 (11)	0.0451 (5)
O3	1.21127 (11)	−0.00899 (19)	1.06932 (11)	0.0392 (4)
O4	1.10735 (10)	0.08938 (19)	0.98016 (11)	0.0375 (4)
O5	1.06080 (10)	−0.17947 (16)	1.01500 (9)	0.0288 (4)
O6	1.26060 (12)	−0.3283 (2)	1.09719 (11)	0.0424 (5)
O7	1.20793 (10)	−0.13027 (18)	1.22409 (10)	0.0317 (4)
O8	1.42226 (12)	0.4568 (2)	0.91758 (15)	0.0615 (6)
O9	1.32960 (13)	1.0002 (2)	0.80841 (17)	0.0684 (7)
Cu1	1.000000	0.000000	1.000000	0.02922 (12)
Cu2	1.14976 (2)	−0.16066 (3)	1.10911 (2)	0.02757 (10)
H02	1.1796 (15)	−0.0520 (18)	1.2343 (15)	0.041*
H01	1.2993 (13)	−0.347 (3)	1.1409 (11)	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0300 (12)	0.0223 (13)	0.0343 (13)	−0.0020 (10)	0.0072 (10)	0.0007 (10)
C2	0.0292 (12)	0.0231 (13)	0.0323 (13)	−0.0015 (10)	0.0065 (10)	0.0022 (10)
C3	0.0322 (13)	0.0350 (15)	0.0359 (14)	−0.0015 (12)	0.0038 (11)	0.0037 (11)
C4	0.0258 (13)	0.0434 (17)	0.0571 (17)	−0.0050 (12)	0.0042 (12)	0.0035 (14)
C5	0.0336 (14)	0.0332 (15)	0.0599 (18)	−0.0064 (12)	0.0170 (13)	0.0082 (13)
C6	0.0402 (16)	0.0409 (17)	0.0573 (18)	−0.0024 (13)	0.0098 (13)	0.0224 (14)
C7	0.0286 (13)	0.0393 (16)	0.0495 (16)	−0.0033 (12)	0.0033 (11)	0.0121 (13)
C8	0.0332 (14)	0.0333 (16)	0.0649 (19)	−0.0116 (12)	0.0160 (13)	0.0066 (14)
C9	0.064 (2)	0.057 (2)	0.0517 (18)	−0.0105 (17)	0.0299 (16)	0.0029 (15)
C10	0.064 (2)	0.046 (2)	0.072 (2)	−0.0106 (16)	0.0365 (18)	−0.0185 (16)
C11	0.0368 (15)	0.0331 (16)	0.075 (2)	−0.0093 (13)	0.0212 (15)	0.0024 (14)
C12	0.0560 (19)	0.055 (2)	0.0492 (17)	−0.0024 (16)	0.0234 (15)	0.0088 (15)
C13	0.0518 (18)	0.0440 (18)	0.0601 (19)	−0.0037 (14)	0.0271 (15)	−0.0108 (15)
C14	0.0383 (16)	0.0304 (16)	0.078 (2)	−0.0038 (13)	0.0199 (15)	0.0030 (15)
C15	0.0482 (17)	0.0372 (17)	0.0631 (19)	−0.0041 (14)	0.0090 (15)	0.0160 (14)
C16	0.0370 (15)	0.0374 (16)	0.0557 (18)	−0.0046 (13)	0.0031 (13)	0.0078 (13)
C17	0.0367 (14)	0.0259 (14)	0.0423 (15)	−0.0019 (11)	0.0067 (11)	0.0008 (11)
C18	0.0429 (16)	0.0386 (17)	0.0574 (18)	−0.0063 (14)	−0.0033 (13)	0.0094 (14)
C19	0.0352 (15)	0.0447 (19)	0.082 (2)	−0.0071 (14)	−0.0026 (15)	0.0089 (17)
C20	0.0356 (14)	0.0266 (14)	0.0409 (15)	0.0011 (11)	0.0054 (11)	0.0008 (11)
C21	0.0333 (13)	0.0203 (13)	0.0464 (15)	−0.0007 (11)	−0.0074 (11)	−0.0028 (11)
C22	0.0280 (12)	0.0253 (13)	0.0473 (15)	−0.0062 (11)	−0.0006 (11)	0.0029 (11)
C23	0.0475 (17)	0.0443 (17)	0.0439 (16)	0.0164 (14)	−0.0003 (13)	−0.0084 (13)
C24	0.0384 (14)	0.0249 (14)	0.0458 (15)	0.0039 (11)	−0.0083 (12)	−0.0003 (12)
C25	0.0472 (15)	0.0373 (16)	0.0270 (13)	−0.0021 (13)	−0.0012 (11)	0.0031 (11)
C26	0.0463 (16)	0.0395 (16)	0.0331 (14)	−0.0065 (13)	0.0121 (12)	0.0032 (12)
N1	0.0290 (10)	0.0228 (11)	0.0325 (11)	−0.0016 (9)	0.0003 (8)	0.0020 (8)
O1	0.0452 (11)	0.0478 (12)	0.0457 (11)	−0.0102 (9)	−0.0042 (9)	0.0162 (9)
O2	0.0385 (10)	0.0394 (12)	0.0529 (12)	−0.0102 (9)	−0.0059 (9)	0.0170 (9)
O3	0.0316 (9)	0.0393 (11)	0.0432 (10)	−0.0103 (8)	−0.0041 (8)	0.0166 (9)
O4	0.0257 (9)	0.0339 (10)	0.0515 (11)	−0.0027 (8)	0.0028 (8)	0.0156 (8)
O5	0.0290 (8)	0.0230 (9)	0.0317 (9)	−0.0019 (7)	−0.0034 (7)	0.0012 (7)
O6	0.0402 (11)	0.0487 (12)	0.0391 (11)	0.0081 (10)	0.0088 (8)	0.0065 (9)
O7	0.0305 (9)	0.0264 (9)	0.0356 (9)	−0.0006 (7)	−0.0022 (7)	−0.0023 (7)
O8	0.0351 (11)	0.0470 (13)	0.1058 (17)	−0.0071 (10)	0.0220 (11)	0.0256 (12)
O9	0.0406 (12)	0.0398 (13)	0.131 (2)	−0.0007 (10)	0.0307 (13)	0.0211 (13)
Cu1	0.0223 (2)	0.0239 (2)	0.0403 (3)	−0.00110 (17)	0.00192 (17)	0.00701 (18)
Cu2	0.02665 (16)	0.02465 (17)	0.02902 (17)	−0.00502 (12)	−0.00236 (11)	0.00485 (12)

Geometric parameters (Å, º)

C1—O4	1.255 (3)	C18—H18	0.9300
C1—O3	1.259 (3)	C19—H19	0.9300
C1—C2	1.498 (3)	C20—O1	1.239 (3)
C2—C7	1.386 (3)	C20—O2	1.273 (3)
C2—C3	1.387 (3)	C21—O5	1.416 (3)
C3—C4	1.378 (3)	C21—C22	1.513 (4)
C3—H3	0.9300	C21—H21A	0.9700
C4—C5	1.383 (4)	C21—H21B	0.9700
C4—H4	0.9300	C22—N1	1.485 (3)
C5—C6	1.372 (4)	C22—H22A	0.9700
C5—O8	1.380 (3)	C22—H22B	0.9700
C6—C7	1.381 (4)	C23—O6	1.412 (3)
C6—H6	0.9300	C23—C24	1.516 (4)
C7—H7	0.9300	C23—H23A	0.9700
C8—C13	1.360 (4)	C23—H23B	0.9700
C8—C9	1.366 (4)	C24—N1	1.488 (3)
C8—O8	1.400 (3)	C24—H24A	0.9700
C9—C10	1.378 (4)	C24—H24B	0.9700
C9—H9	0.9300	C25—O7	1.436 (3)
C10—C11	1.370 (4)	C25—C26	1.510 (4)
C10—H10	0.9300	C25—H25A	0.9700
C11—C12	1.357 (4)	C25—H25B	0.9700
C11—O9	1.395 (3)	C26—N1	1.483 (3)
C12—C13	1.389 (4)	C26—H26A	0.9700
C12—H12	0.9300	C26—H26B	0.9700
C13—H13	0.9300	N1—Cu2	2.027 (2)
C14—C15	1.374 (4)	O3—Cu2	1.912 (2)
C14—C19	1.376 (4)	O1—Cu1^i	2.601 (2)
C14—O9	1.393 (3)	O1—Cu2^i	2.671 (2)
C15—C16	1.379 (4)	O4—Cu1	1.990 (2)
C15—H15	0.9300	O5—Cu1	1.941 (2)
C16—C17	1.389 (4)	O5—Cu2	1.945 (2)
C16—H16	0.9300	O6—Cu2	2.405 (2)
C17—C18	1.387 (4)	O6—H01	0.893 (1)
C17—C20	1.506 (4)	O7—Cu2	2.009 (2)
C18—C19	1.381 (4)	O7—H02	0.895 (1)
O4—C1—O3	125.8 (2)	N1—C22—C21	108.3 (2)
O4—C1—C2	117.9 (2)	N1—C22—H22A	110.0
O3—C1—C2	116.3 (2)	C21—C22—H22A	110.0
C7—C2—C3	118.2 (2)	N1—C22—H22B	110.0
C7—C2—C1	120.4 (2)	C21—C22—H22B	110.0
C3—C2—C1	121.4 (2)	H22A—C22—H22B	108.4
C4—C3—C2	121.0 (2)	O6—C23—C24	111.6 (2)
C4—C3—H3	119.5	O6—C23—H23A	109.3
C2—C3—H3	119.5	C24—C23—H23A	109.3
C3—C4—C5	119.5 (2)	O6—C23—H23B	109.3
C3—C4—H4	120.2	C24—C23—H23B	109.3
C5—C4—H4	120.2	H23A—C23—H23B	108.0
C6—C5—O8	122.5 (2)	N1—C24—C23	113.0 (2)
C6—C5—C4	120.5 (2)	N1—C24—H24A	109.0
O8—C5—C4	116.9 (2)	C23—C24—H24A	109.0
C5—C6—C7	119.4 (3)	N1—C24—H24B	109.0
C5—C6—H6	120.3	C23—C24—H24B	109.0
C7—C6—H6	120.3	H24A—C24—H24B	107.8
C6—C7—C2	121.3 (2)	O7—C25—C26	109.2 (2)
C6—C7—H7	119.4	O7—C25—H25A	109.8
C2—C7—H7	119.4	C26—C25—H25A	109.8
C13—C8—C9	120.6 (3)	O7—C25—H25B	109.8
C13—C8—O8	118.0 (3)	C26—C25—H25B	109.8
C9—C8—O8	121.2 (3)	H25A—C25—H25B	108.3
C8—C9—C10	120.1 (3)	N1—C26—C25	109.3 (2)
C8—C9—H9	119.9	N1—C26—H26A	109.8
C10—C9—H9	119.9	C25—C26—H26A	109.8
C11—C10—C9	119.7 (3)	N1—C26—H26B	109.8
C11—C10—H10	120.2	C25—C26—H26B	109.8
C9—C10—H10	120.2	H26A—C26—H26B	108.3
C12—C11—C10	120.0 (3)	C26—N1—C22	112.8 (2)
C12—C11—O9	120.9 (3)	C26—N1—C24	111.09 (19)
C10—C11—O9	119.0 (3)	C22—N1—C24	112.35 (19)
C11—C12—C13	120.7 (3)	C26—N1—Cu2	104.44 (14)
C11—C12—H12	119.7	C22—N1—Cu2	102.78 (14)
C13—C12—H12	119.7	C24—N1—Cu2	112.84 (15)
C8—C13—C12	119.0 (3)	C1—O3—Cu2	126.49 (16)
C8—C13—H13	120.5	C1—O4—Cu1	133.54 (16)
C12—C13—H13	120.5	C21—O5—Cu1	119.89 (14)
C15—C14—C19	120.4 (3)	C21—O5—Cu2	110.42 (13)
C15—C14—O9	121.7 (3)	Cu1—O5—Cu2	108.06 (7)
C19—C14—O9	117.8 (3)	C23—O6—Cu2	97.14 (15)
C14—C15—C16	119.5 (3)	C23—O6—H01	108.9 (18)
C14—C15—H15	120.3	Cu2—O6—H01	119.0 (17)
C16—C15—H15	120.3	C25—O7—Cu2	110.52 (14)
C15—C16—C17	121.2 (3)	C25—O7—H02	110.7 (17)
C15—C16—H16	119.4	Cu2—O7—H02	97.4 (17)
C17—C16—H16	119.4	C5—O8—C8	117.5 (2)
C18—C17—C16	118.4 (2)	C14—O9—C11	117.5 (2)
C18—C17—C20	120.2 (2)	O5—Cu1—O5^ii	180.0
C16—C17—C20	121.4 (2)	O5—Cu1—O4^ii	92.41 (7)
C19—C18—C17	120.5 (3)	O5^ii—Cu1—O4^ii	87.59 (7)
C19—C18—H18	119.7	O5—Cu1—O4	87.59 (7)
C17—C18—H18	119.7	O5^ii—Cu1—O4	92.41 (7)
C14—C19—C18	120.0 (3)	O4^ii—Cu1—O4	180.00
C14—C19—H19	120.0	O3—Cu2—O5	97.95 (7)
C18—C19—H19	120.0	O3—Cu2—O7	92.39 (7)
O1—C20—O2	123.2 (2)	O5—Cu2—O7	160.92 (7)
O1—C20—C17	120.2 (2)	O3—Cu2—N1	171.35 (8)
O2—C20—C17	116.6 (2)	O5—Cu2—N1	86.68 (7)
O5—C21—C22	108.58 (19)	O7—Cu2—N1	85.28 (7)
O5—C21—H21A	110.0	O3—Cu2—O6	91.59 (7)
C22—C21—H21A	110.0	O5—Cu2—O6	109.03 (7)
O5—C21—H21B	110.0	O7—Cu2—O6	86.55 (7)
C22—C21—H21B	110.0	N1—Cu2—O6	79.97 (7)
H21A—C21—H21B	108.4
O4—C1—C2—C7	−1.0 (4)	C17—C18—C19—C14	−1.3 (5)
O3—C1—C2—C7	179.7 (2)	C18—C17—C20—O1	−6.7 (4)
O4—C1—C2—C3	177.9 (2)	C16—C17—C20—O1	176.3 (3)
O3—C1—C2—C3	−1.4 (3)	C18—C17—C20—O2	170.9 (3)
C7—C2—C3—C4	2.4 (4)	C16—C17—C20—O2	−6.2 (4)
C1—C2—C3—C4	−176.6 (2)	O5—C21—C22—N1	−53.1 (3)
C2—C3—C4—C5	−0.7 (4)	O6—C23—C24—N1	51.0 (3)
C3—C4—C5—C6	−1.9 (4)	O7—C25—C26—N1	50.0 (3)
C3—C4—C5—O8	−178.7 (2)	C25—C26—N1—C22	−155.8 (2)
O8—C5—C6—C7	179.4 (3)	C25—C26—N1—C24	77.0 (3)
C4—C5—C6—C7	2.8 (5)	C25—C26—N1—Cu2	−45.0 (2)
C5—C6—C7—C2	−1.1 (4)	C21—C22—N1—C26	156.2 (2)
C3—C2—C7—C6	−1.5 (4)	C21—C22—N1—C24	−77.3 (2)
C1—C2—C7—C6	177.5 (3)	C21—C22—N1—Cu2	44.3 (2)
C13—C8—C9—C10	0.5 (5)	C23—C24—N1—C26	−131.8 (2)
O8—C8—C9—C10	176.2 (3)	C23—C24—N1—C22	100.7 (3)
C8—C9—C10—C11	−0.8 (5)	C23—C24—N1—Cu2	−14.9 (3)
C9—C10—C11—C12	0.5 (5)	O4—C1—O3—Cu2	8.4 (4)
C9—C10—C11—O9	176.3 (3)	C2—C1—O3—Cu2	−172.39 (15)
C10—C11—C12—C13	0.0 (5)	O3—C1—O4—Cu1	5.2 (4)
O9—C11—C12—C13	−175.7 (3)	C2—C1—O4—Cu1	−174.09 (16)
C9—C8—C13—C12	0.0 (5)	C22—C21—O5—Cu1	−93.4 (2)
O8—C8—C13—C12	−175.8 (3)	C22—C21—O5—Cu2	33.2 (2)
C11—C12—C13—C8	−0.2 (5)	C24—C23—O6—Cu2	−51.7 (2)
C19—C14—C15—C16	1.1 (5)	C26—C25—O7—Cu2	−28.5 (2)
O9—C14—C15—C16	−175.1 (3)	C6—C5—O8—C8	33.1 (4)
C14—C15—C16—C17	−0.6 (5)	C4—C5—O8—C8	−150.1 (3)
C15—C16—C17—C18	−0.8 (4)	C13—C8—O8—C5	−124.3 (3)
C15—C16—C17—C20	176.4 (3)	C9—C8—O8—C5	59.9 (4)
C16—C17—C18—C19	1.7 (4)	C15—C14—O9—C11	−40.0 (4)
C20—C17—C18—C19	−175.5 (3)	C19—C14—O9—C11	143.7 (3)
C15—C14—C19—C18	−0.1 (5)	C12—C11—O9—C14	−58.1 (4)
O9—C14—C19—C18	176.2 (3)	C10—C11—O9—C14	126.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H01···O2^iii	0.89 (1)	1.84 (1)	2.725 (3)	170 (3)
O7—H02···O2^iv	0.90 (1)	1.63 (1)	2.523 (2)	172 (3)

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