Poly[[(μ₃-5,6-dicarboxy­bicyclo­[2.2.2]oct-7-ene-2,3-dicarboxyl­ato)(1,10-phenanthroline)copper(II)] monohydrate]

In the title compound, {[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O}_n, the Cu^II ion is five-coordinated by two N atoms from one phenanthroline ligand and three O atoms from three different H₂L²⁻ anions (H₄L is bicyclo­[2.2.2]oct-7-ene-2,3,5,6-tetra­carboxylic acid) in a distorted square-pyramidal geometry. Each H₂L²⁻ ion bridges three Cu^II atoms to form a zigzag sheet parallel to the ab plane. The crystal structure is consolidated by O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.026
• wR factor = 0.065
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  O7_c    ..       5.82 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.37
           From the CIF: _reflns_number_total               4555
           Count of symmetry unique reflns         2776
           Completeness (_total/calc)            164.09%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1779
           Fraction of Friedel pairs measured     0.641
           Are heavy atom types Z>Si present        yes
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C4     -C12           1.42 Ang.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2
PLAT791_ALERT_4_G The Model has Chirality at C13     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C14     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C15     (Verify) ....          S
PLAT791_ALERT_4_G The Model has Chirality at C16     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C17     (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C18     (Verify) ....          S
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............          2 Times

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
  14 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   9 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Coordination polymers based on poly(carboxylic acids) have been investigated in the area of solid state and material science (Yang et al., 2008). We selected bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid (H₄L) as a poly(carboxylic acid) ligand and phenanthroline (phen) as a secondary ligand, generating a new coordination polymer, [Cu(phen)(H₂L)]^.H₂O, which is reported here.

In the title compound, each Cu^II atom is five-coordinated by two N atoms from one phen ligand, and three O atoms from three different H₂L^2- anions in a distorted square-pyramidal geometry (Fig. 1 and Table 1). Each H₂L^2- bridges three Cu^II atoms to form a two-dimensional layer structure (Fig. 2). The O–H···O hydrogen bonds (Table 2) further consolidate the crystal structure.

Related literature

For general background, see: Yang et al. (2008).

S2. Experimental

A mixture of H₄L (0.5 mmol), phen (0.5 mmol), NaOH (1 mmol) and CuCl₂^.2H₂O (0.5 mmol) was suspended in deionized water (12 ml) and sealed in a 20-ml Teflon-lined autoclave. The mixture was heated at 373 K for 7 d and then the autoclave was slowly cooled to room temperature. The grown single crystals were collected, washed with deionized water and dried.

S3. Refinement

H atoms on C atoms were generated geometrically and refined as riding atoms with C—H = 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C). The H atoms of the water molecules were located in a difference Fourier map and refined with an O—H distance restraint of 0.85 (1) Å and with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures

	Fig. 1. Part of the polymeric structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) x - 1, y, z; (ii) 2 - x, y - 1/2, 2 - z.
	Fig. 2. View of a zigzag sheet structure in the title compound.

Poly[[(µ₃-5,6-dicarboxybicyclo[2.2.2]oct-7-ene-2,3-dicarboxylato)(1,10- phenanthroline)copper(II)] monohydrate]

Crystal data

[Cu(C12H10O8)(C12H8N2)]·H2O	F(000) = 558
Mr = 543.96	Dx = 1.689 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 4555 reflections
a = 6.5900 (4) Å	θ = 1.1–28.4°
b = 15.1650 (8) Å	µ = 1.08 mm^−1
c = 10.7490 (6) Å	T = 293 K
β = 95.244 (9)°	Block, blue
V = 1069.73 (10) Å^3	0.33 × 0.21 × 0.20 mm
Z = 2

Data collection

Bruker APEX CCD area-detector diffractometer	4555 independent reflections
Radiation source: fine-focus sealed tube	4343 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ and ω scans	θmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.696, Tmax = 0.803	k = −19→17
6580 measured reflections	l = −6→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0256P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
4555 reflections	Δρmax = 0.31 e Å^−3
333 parameters	Δρmin = −0.37 e Å^−3
2 restraints	Absolute structure: Flack (1983), 1914 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (8)

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.

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 > σ(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
C1	0.8692 (4)	0.81993 (17)	0.5050 (2)	0.0327 (5)
H1	0.9536	0.8445	0.5700	0.039*
C2	0.9222 (4)	0.82867 (19)	0.3826 (2)	0.0382 (6)
H2	1.0408	0.8583	0.3669	0.046*
C3	0.7992 (4)	0.79351 (17)	0.2862 (2)	0.0362 (6)
H3	0.8341	0.7990	0.2047	0.043*
C4	0.6199 (3)	0.74901 (17)	0.31010 (18)	0.0285 (5)
C5	0.4749 (4)	0.71054 (18)	0.2161 (2)	0.0352 (6)
H5A	0.4972	0.7156	0.1322	0.042*
C6	0.3084 (4)	0.66765 (18)	0.2479 (2)	0.0361 (6)
H6	0.2186	0.6434	0.1853	0.043*
C7	0.2660 (4)	0.65841 (16)	0.3763 (2)	0.0291 (5)
C8	0.1009 (4)	0.61105 (18)	0.4178 (2)	0.0364 (6)
H8B	0.0083	0.5828	0.3606	0.044*
C9	0.0779 (4)	0.60707 (19)	0.5428 (2)	0.0377 (6)
H9	−0.0301	0.5758	0.5711	0.045*
C10	0.2174 (4)	0.65023 (17)	0.6279 (2)	0.0329 (5)
H10	0.1995	0.6473	0.7127	0.039*
C11	0.4003 (3)	0.69806 (15)	0.46831 (19)	0.0240 (4)
C12	0.5789 (3)	0.74318 (14)	0.43543 (18)	0.0237 (5)
C13	1.0048 (3)	0.90548 (13)	0.94151 (18)	0.0192 (4)
H13	0.9289	0.8814	1.0080	0.023*
C14	1.0387 (3)	1.00356 (15)	0.97408 (18)	0.0223 (4)
H14	0.9159	1.0382	0.9497	0.027*
C15	1.0971 (3)	1.00950 (14)	1.11723 (18)	0.0220 (4)
H15	0.9782	0.9919	1.1598	0.026*
C16	1.2682 (3)	0.94109 (14)	1.14952 (18)	0.0211 (4)
H16	1.1993	0.8873	1.1736	0.025*
C17	1.3679 (3)	0.91758 (15)	1.02845 (19)	0.0229 (4)
H17	1.4990	0.8879	1.0479	0.027*
C18	1.2122 (3)	0.85576 (14)	0.95247 (18)	0.0203 (4)
H18	1.1978	0.8014	1.0002	0.024*
C19	1.3913 (3)	0.99816 (16)	0.94838 (19)	0.0288 (5)
H19	1.5166	1.0168	0.9246	0.035*
C20	1.2195 (4)	1.03987 (15)	0.91496 (19)	0.0268 (5)
H20	1.2108	1.0873	0.8600	0.032*
C21	0.8703 (3)	0.88961 (15)	0.82048 (19)	0.0208 (4)
C22	1.2984 (3)	0.83259 (15)	0.82983 (19)	0.0237 (4)
C23	1.4200 (4)	0.96369 (15)	1.2593 (2)	0.0265 (5)
C24	1.1515 (3)	1.10347 (15)	1.1550 (2)	0.0240 (5)
N1	0.7020 (3)	0.77771 (12)	0.53121 (15)	0.0253 (4)
N2	0.3738 (3)	0.69509 (13)	0.59172 (16)	0.0251 (4)
O1	0.7941 (3)	0.95074 (11)	0.75885 (15)	0.0331 (4)
O2	0.8349 (2)	0.80701 (10)	0.79532 (13)	0.0256 (3)
O1W	1.4570 (4)	0.98510 (18)	1.59374 (17)	0.0537 (6)
O3	1.4401 (2)	0.77476 (12)	0.84210 (14)	0.0323 (4)
O4	1.2381 (2)	0.86940 (12)	0.73066 (14)	0.0323 (4)
O5	1.3290 (3)	0.95633 (14)	1.36461 (15)	0.0406 (4)
H5	1.4105	0.9685	1.4244	0.061*
O6	1.5975 (3)	0.97879 (13)	1.25429 (17)	0.0402 (4)
O7	1.2819 (3)	1.12253 (12)	1.23587 (16)	0.0358 (4)
O8	1.0345 (3)	1.16299 (13)	1.09436 (17)	0.0443 (5)
H8	1.0703	1.2125	1.1181	0.066*
Cu1	0.59195 (3)	0.760541 (17)	0.697564 (19)	0.02264 (7)
HW11	1.378 (5)	0.952 (2)	1.625 (3)	0.050 (10)*
HW12	1.575 (4)	0.969 (3)	1.613 (4)	0.078 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0300 (12)	0.0339 (14)	0.0336 (12)	−0.0050 (11)	0.0001 (10)	0.0004 (10)
C2	0.0364 (14)	0.0379 (15)	0.0413 (13)	−0.0056 (12)	0.0101 (11)	0.0070 (11)
C3	0.0433 (15)	0.0387 (14)	0.0276 (11)	0.0050 (11)	0.0095 (10)	0.0068 (9)
C4	0.0351 (11)	0.0263 (13)	0.0238 (9)	0.0057 (11)	0.0014 (8)	0.0009 (9)
C5	0.0486 (16)	0.0344 (15)	0.0218 (10)	0.0106 (11)	−0.0018 (10)	−0.0044 (9)
C6	0.0425 (15)	0.0343 (14)	0.0292 (11)	0.0029 (12)	−0.0098 (10)	−0.0086 (10)
C7	0.0311 (12)	0.0253 (12)	0.0300 (11)	0.0023 (10)	−0.0023 (9)	−0.0075 (9)
C8	0.0286 (12)	0.0344 (14)	0.0446 (14)	−0.0020 (11)	−0.0059 (10)	−0.0113 (10)
C9	0.0314 (13)	0.0350 (15)	0.0465 (14)	−0.0084 (11)	0.0030 (11)	−0.0058 (11)
C10	0.0318 (13)	0.0335 (14)	0.0339 (12)	−0.0055 (11)	0.0066 (10)	−0.0044 (10)
C11	0.0260 (11)	0.0210 (11)	0.0244 (10)	0.0044 (9)	−0.0014 (8)	−0.0037 (8)
C12	0.0270 (10)	0.0196 (13)	0.0240 (9)	0.0042 (8)	−0.0003 (8)	−0.0017 (7)
C13	0.0199 (10)	0.0184 (11)	0.0194 (9)	−0.0018 (8)	0.0014 (8)	−0.0009 (7)
C14	0.0236 (11)	0.0192 (10)	0.0229 (10)	0.0006 (9)	−0.0049 (8)	−0.0024 (8)
C15	0.0198 (10)	0.0224 (11)	0.0236 (10)	−0.0003 (8)	−0.0002 (8)	−0.0015 (8)
C16	0.0233 (10)	0.0187 (10)	0.0208 (9)	−0.0020 (8)	−0.0007 (8)	−0.0015 (7)
C17	0.0175 (10)	0.0259 (12)	0.0247 (10)	0.0002 (9)	−0.0007 (8)	−0.0037 (8)
C18	0.0199 (10)	0.0215 (11)	0.0190 (9)	0.0006 (8)	−0.0004 (7)	−0.0012 (7)
C19	0.0284 (12)	0.0312 (13)	0.0276 (11)	−0.0119 (10)	0.0062 (9)	−0.0042 (9)
C20	0.0357 (12)	0.0215 (11)	0.0223 (10)	−0.0076 (10)	−0.0026 (9)	0.0017 (8)
C21	0.0182 (10)	0.0220 (12)	0.0216 (10)	−0.0008 (9)	−0.0006 (8)	−0.0013 (8)
C22	0.0212 (10)	0.0254 (12)	0.0248 (10)	−0.0034 (8)	0.0036 (8)	−0.0029 (8)
C23	0.0330 (13)	0.0197 (11)	0.0256 (10)	0.0030 (9)	−0.0043 (9)	0.0010 (8)
C24	0.0238 (11)	0.0221 (12)	0.0262 (11)	0.0028 (9)	0.0031 (9)	−0.0032 (8)
N1	0.0252 (9)	0.0254 (12)	0.0251 (8)	−0.0010 (8)	0.0008 (7)	−0.0022 (7)
N2	0.0242 (9)	0.0245 (10)	0.0264 (9)	0.0010 (8)	0.0006 (7)	−0.0030 (7)
O1	0.0381 (10)	0.0263 (9)	0.0323 (9)	0.0023 (8)	−0.0117 (7)	0.0020 (7)
O2	0.0265 (8)	0.0205 (8)	0.0283 (7)	−0.0040 (7)	−0.0051 (6)	−0.0019 (6)
O1W	0.0514 (14)	0.0778 (17)	0.0291 (9)	−0.0253 (13)	−0.0121 (9)	0.0156 (10)
O3	0.0290 (8)	0.0397 (12)	0.0282 (7)	0.0106 (8)	0.0033 (6)	−0.0084 (7)
O4	0.0349 (9)	0.0392 (10)	0.0225 (7)	0.0009 (8)	0.0016 (6)	0.0024 (7)
O5	0.0447 (10)	0.0543 (13)	0.0211 (7)	−0.0153 (9)	−0.0054 (7)	−0.0004 (7)
O6	0.0254 (9)	0.0509 (13)	0.0424 (10)	0.0001 (8)	−0.0069 (7)	−0.0105 (8)
O7	0.0387 (10)	0.0224 (9)	0.0427 (10)	0.0004 (7)	−0.0164 (8)	−0.0049 (7)
O8	0.0502 (11)	0.0249 (10)	0.0528 (11)	0.0103 (9)	−0.0222 (9)	−0.0094 (8)
Cu1	0.02218 (12)	0.02490 (13)	0.02043 (10)	−0.00053 (12)	−0.00032 (8)	−0.00387 (11)

Geometric parameters (Å, º)

C1—N1	1.326 (3)	C15—C16	1.548 (3)
C1—C2	1.398 (3)	C15—H15	0.98
C1—H1	0.93	C16—C23	1.515 (3)
C2—C3	1.364 (4)	C16—C17	1.552 (3)
C2—H2	0.93	C16—H16	0.98
C3—C4	1.405 (4)	C17—C19	1.511 (3)
C3—H3	0.93	C17—C18	1.564 (3)
C4—C12	1.401 (3)	C17—H17	0.98
C4—C5	1.448 (3)	C18—C22	1.523 (3)
C5—C6	1.346 (4)	C18—H18	0.98
C5—H5A	0.93	C19—C20	1.318 (3)
C6—C7	1.440 (3)	C19—H19	0.93
C6—H6	0.93	C20—H20	0.93
C7—C11	1.401 (3)	C21—O1	1.220 (3)
C7—C8	1.410 (3)	C21—O2	1.298 (3)
C8—C9	1.367 (3)	C22—O4	1.236 (3)
C8—H8B	0.93	C22—O3	1.279 (3)
C9—C10	1.399 (3)	C23—O6	1.198 (3)
C9—H9	0.93	C23—O5	1.334 (3)
C10—N2	1.323 (3)	C24—O7	1.200 (3)
C10—H10	0.93	C24—O8	1.320 (3)
C11—N2	1.354 (3)	N1—Cu1	2.0072 (17)
C11—C12	1.434 (3)	N2—Cu1	2.0119 (19)
C12—N1	1.356 (3)	O2—Cu1	1.9640 (15)
C13—C21	1.525 (3)	O1W—HW11	0.82 (3)
C13—C14	1.540 (3)	O1W—HW12	0.822 (19)
C13—C18	1.556 (3)	O3—Cu1^i	1.9355 (15)
C13—H13	0.98	O5—H5	0.82
C14—C20	1.505 (3)	O7—Cu1^ii	2.3398 (18)
C14—C15	1.554 (3)	O8—H8	0.82
C14—H14	0.98	Cu1—O3^iii	1.9355 (15)
C15—C24	1.516 (3)	Cu1—O7^iv	2.3398 (18)
N1—C1—C2	122.0 (2)	C15—C16—C17	108.75 (16)
N1—C1—H1	119.0	C23—C16—H16	105.8
C2—C1—H1	119.0	C15—C16—H16	105.8
C3—C2—C1	119.7 (2)	C17—C16—H16	105.8
C3—C2—H2	120.2	C19—C17—C16	111.41 (18)
C1—C2—H2	120.2	C19—C17—C18	106.48 (17)
C2—C3—C4	120.0 (2)	C16—C17—C18	105.53 (16)
C2—C3—H3	120.0	C19—C17—H17	111.1
C4—C3—H3	120.0	C16—C17—H17	111.1
C12—C4—C3	116.4 (2)	C18—C17—H17	111.1
C12—C4—C5	118.2 (2)	C22—C18—C13	116.14 (16)
C3—C4—C5	125.3 (2)	C22—C18—C17	108.15 (17)
C6—C5—C4	121.3 (2)	C13—C18—C17	106.20 (16)
C6—C5—H5A	119.4	C22—C18—H18	108.7
C4—C5—H5A	119.4	C13—C18—H18	108.7
C5—C6—C7	121.6 (2)	C17—C18—H18	108.7
C5—C6—H6	119.2	C20—C19—C17	114.4 (2)
C7—C6—H6	119.2	C20—C19—H19	122.8
C11—C7—C8	116.8 (2)	C17—C19—H19	122.8
C11—C7—C6	118.0 (2)	C19—C20—C14	113.8 (2)
C8—C7—C6	125.2 (2)	C19—C20—H20	123.1
C9—C8—C7	119.4 (2)	C14—C20—H20	123.1
C9—C8—H8B	120.3	O1—C21—O2	124.26 (19)
C7—C8—H8B	120.3	O1—C21—C13	121.4 (2)
C8—C9—C10	119.8 (2)	O2—C21—C13	114.15 (18)
C8—C9—H9	120.1	O4—C22—O3	124.92 (19)
C10—C9—H9	120.1	O4—C22—C18	121.8 (2)
N2—C10—C9	122.1 (2)	O3—C22—C18	113.28 (18)
N2—C10—H10	119.0	O6—C23—O5	124.8 (2)
C9—C10—H10	119.0	O6—C23—C16	125.9 (2)
N2—C11—C7	123.2 (2)	O5—C23—C16	109.01 (19)
N2—C11—C12	116.08 (19)	O7—C24—O8	122.7 (2)
C7—C11—C12	120.70 (19)	O7—C24—C15	123.8 (2)
N1—C12—C4	123.4 (2)	O8—C24—C15	113.40 (19)
N1—C12—C11	116.42 (17)	C1—N1—C12	118.41 (18)
C4—C12—C11	120.14 (19)	C1—N1—Cu1	128.81 (15)
C21—C13—C14	114.04 (17)	C12—N1—Cu1	112.72 (14)
C21—C13—C18	115.24 (16)	C10—N2—C11	118.6 (2)
C14—C13—C18	110.05 (17)	C10—N2—Cu1	128.54 (16)
C21—C13—H13	105.5	C11—N2—Cu1	112.83 (15)
C14—C13—H13	105.5	C21—O2—Cu1	125.43 (14)
C18—C13—H13	105.5	HW11—O1W—HW12	109 (4)
C20—C14—C13	111.19 (17)	C22—O3—Cu1^i	114.82 (14)
C20—C14—C15	105.24 (17)	C23—O5—H5	109.5
C13—C14—C15	107.38 (17)	C24—O7—Cu1^ii	130.37 (16)
C20—C14—H14	110.9	C24—O8—H8	109.5
C13—C14—H14	110.9	O3^iii—Cu1—O2	89.24 (7)
C15—C14—H14	110.9	O3^iii—Cu1—N1	162.98 (7)
C24—C15—C16	114.85 (17)	O2—Cu1—N1	94.97 (7)
C24—C15—C14	110.54 (18)	O3^iii—Cu1—N2	96.53 (7)
C16—C15—C14	107.01 (16)	O2—Cu1—N2	170.11 (7)
C24—C15—H15	108.1	N1—Cu1—N2	81.84 (7)
C16—C15—H15	108.1	O3^iii—Cu1—O7^iv	92.84 (7)
C14—C15—H15	108.1	O2—Cu1—O7^iv	84.71 (6)
C23—C16—C15	116.02 (18)	N1—Cu1—O7^iv	103.96 (7)
C23—C16—C17	113.89 (18)	N2—Cu1—O7^iv	86.97 (7)
N1—C1—C2—C3	0.4 (4)	C15—C14—C20—C19	57.3 (2)
C1—C2—C3—C4	0.2 (4)	C14—C13—C21—O1	−1.8 (3)
C2—C3—C4—C12	−0.3 (4)	C18—C13—C21—O1	−130.5 (2)
C2—C3—C4—C5	178.6 (2)	C14—C13—C21—O2	−177.45 (17)
C12—C4—C5—C6	−2.2 (4)	C18—C13—C21—O2	53.9 (2)
C3—C4—C5—C6	178.8 (3)	C13—C18—C22—O4	17.8 (3)
C4—C5—C6—C7	0.4 (4)	C17—C18—C22—O4	−101.4 (2)
C5—C6—C7—C11	2.0 (4)	C13—C18—C22—O3	−164.32 (18)
C5—C6—C7—C8	−176.8 (3)	C17—C18—C22—O3	76.5 (2)
C11—C7—C8—C9	0.9 (4)	C15—C16—C23—O6	−114.2 (3)
C6—C7—C8—C9	179.8 (2)	C17—C16—C23—O6	13.2 (3)
C7—C8—C9—C10	0.3 (4)	C15—C16—C23—O5	71.4 (2)
C8—C9—C10—N2	−0.4 (4)	C17—C16—C23—O5	−161.24 (19)
C8—C7—C11—N2	−2.3 (3)	C16—C15—C24—O7	−23.1 (3)
C6—C7—C11—N2	178.8 (2)	C14—C15—C24—O7	−144.3 (2)
C8—C7—C11—C12	176.3 (2)	C16—C15—C24—O8	160.03 (19)
C6—C7—C11—C12	−2.6 (3)	C14—C15—C24—O8	38.8 (2)
C3—C4—C12—N1	−0.1 (3)	C2—C1—N1—C12	−0.8 (4)
C5—C4—C12—N1	−179.1 (2)	C2—C1—N1—Cu1	−177.84 (18)
C3—C4—C12—C11	−179.3 (2)	C4—C12—N1—C1	0.6 (3)
C5—C4—C12—C11	1.6 (3)	C11—C12—N1—C1	179.9 (2)
N2—C11—C12—N1	0.2 (3)	C4—C12—N1—Cu1	178.13 (18)
C7—C11—C12—N1	−178.5 (2)	C11—C12—N1—Cu1	−2.6 (2)
N2—C11—C12—C4	179.5 (2)	C9—C10—N2—C11	−0.9 (4)
C7—C11—C12—C4	0.8 (3)	C9—C10—N2—Cu1	−179.39 (19)
C21—C13—C14—C20	−88.1 (2)	C7—C11—N2—C10	2.3 (3)
C18—C13—C14—C20	43.2 (2)	C12—C11—N2—C10	−176.4 (2)
C21—C13—C14—C15	157.29 (17)	C7—C11—N2—Cu1	−179.00 (18)
C18—C13—C14—C15	−71.42 (19)	C12—C11—N2—Cu1	2.3 (2)
C20—C14—C15—C24	56.4 (2)	O1—C21—O2—Cu1	−23.2 (3)
C13—C14—C15—C24	174.93 (17)	C13—C21—O2—Cu1	152.23 (14)
C20—C14—C15—C16	−69.3 (2)	O4—C22—O3—Cu1^i	9.8 (3)
C13—C14—C15—C16	49.2 (2)	C18—C22—O3—Cu1^i	−167.97 (14)
C24—C15—C16—C23	26.6 (3)	O8—C24—O7—Cu1^ii	−7.8 (4)
C14—C15—C16—C23	149.70 (18)	C15—C24—O7—Cu1^ii	175.59 (14)
C24—C15—C16—C17	−103.3 (2)	C21—O2—Cu1—O3^iii	−77.88 (17)
C14—C15—C16—C17	19.8 (2)	C21—O2—Cu1—N1	85.60 (17)
C23—C16—C17—C19	−91.2 (2)	C21—O2—Cu1—O7^iv	−170.81 (17)
C15—C16—C17—C19	39.8 (2)	C1—N1—Cu1—O3^iii	94.5 (3)
C23—C16—C17—C18	153.60 (18)	C12—N1—Cu1—O3^iii	−82.7 (3)
C15—C16—C17—C18	−75.3 (2)	C1—N1—Cu1—O2	−9.3 (2)
C21—C13—C18—C22	26.2 (3)	C12—N1—Cu1—O2	173.52 (15)
C14—C13—C18—C22	−104.5 (2)	C1—N1—Cu1—N2	−179.9 (2)
C21—C13—C18—C17	146.43 (17)	C12—N1—Cu1—N2	2.94 (15)
C14—C13—C18—C17	15.8 (2)	C1—N1—Cu1—O7^iv	−95.1 (2)
C19—C17—C18—C22	59.7 (2)	C12—N1—Cu1—O7^iv	87.74 (15)
C16—C17—C18—C22	178.16 (17)	C10—N2—Cu1—O3^iii	−21.4 (2)
C19—C17—C18—C13	−65.7 (2)	C11—N2—Cu1—O3^iii	160.06 (15)
C16—C17—C18—C13	52.9 (2)	C10—N2—Cu1—N1	175.7 (2)
C16—C17—C19—C20	−57.8 (2)	C11—N2—Cu1—N1	−2.86 (15)
C18—C17—C19—C20	56.8 (2)	C10—N2—Cu1—O7^iv	71.1 (2)
C17—C19—C20—C14	5.7 (3)	C11—N2—Cu1—O7^iv	−107.43 (15)
C13—C14—C20—C19	−58.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1W	0.82	1.84	2.567 (2)	148
O8—H8···O2^ii	0.82	1.79	2.594 (2)	166
O1W—HW11···O4^v	0.82 (3)	1.97 (3)	2.777 (3)	167 (3)
O1W—HW12···O1^vi	0.82 (2)	2.05 (3)	2.763 (3)	145 (4)

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