catena-Poly[[[bis­(1H-benzimidazole-κN³)copper(II)]-μ-3-(4-carboxyl­atophen­oxy)propionato-κ²O:O′] N,N-di­methyl­formamide solvate penta­hydrate]

In the crystal structure of the polymeric title compound, {[Cu(C₇H₅N₂)₂(C₁₀H₈O₅)]·C₃H₇NO·5H₂O}_n, the 3-(4-carb­oxyl­atophen­oxy)propionate dianion links the bis­(benz­imidazole)copper groups into a linear chain running along the a axis of the monoclinic unit cell, with the dianion binding through one O atom of each carboxylate end to confer a distorted square-planar environment on the copper center.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.071
• wR factor = 0.247
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H2W2   ..  H3W1    ..       2.03 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O2W    -   H2W2   ...          ?
PLAT420_ALERT_2_B D-H Without Acceptor       O3W    -   H3W1   ...          ?
PLAT420_ALERT_2_B D-H Without Acceptor       O4W    -   H4W2   ...          ?

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.590     0.880
            Tmin(prime) and Tmax expected:      0.742     0.877
            RR(prime) =      0.792
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.79
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        200 Ang.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O1      ..       5.13 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         N5
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2N    ..  H5W2    ..       2.13 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         10
PLAT733_ALERT_1_C Torsion Calc    -0.2(16), Rep     -0.2(3) ......       5.33 su-Ra
              C26 -N5  -C25 -O6     1.555   1.555   1.555   1.555

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C27 H37 Cu1 N5 O11
            Atom count from _chemical_formula_moiety:C3 H17 N1 O6
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         66

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The present report follows our studies on the transition metal derivatives of 3-(4-carboxylatophenoxy)propionic acid. Previous reports (Kong et al., 2007a,b) describe the crystal structures of isostrutural manganese(II) and cobalt(II) adducts with 2,2'-bipyridine. In the present work, DMF, which was used as a co-solvent, is incorporated into the crystal structure.

The 3-(4-carboxylatophenoxy)propionate dianion links the di(benzimidazole)copper groups into a linear chain running along the a axis of the monoclinic unit cell, with the dianion binding through one O atom each from both carboxylate ends to confer a distorted square-planar environment to the copper center.

Related literature

For the 2,2'-bipyridine chelated transition metal derivatives of 3-(4-carboxylatophenoxy)propionic acid, see: Kong et al. (2007a,b).

S2. Experimental

Copper nitrate hexahydrate (5 mmol), benzimidazole (10 mmol) and 3-(4-carboxylatophenoxy)propionic acid were dissolved in DMF-water (1:1, v/v) solution, and the pH was adjusted to 7 with 0.1 M sodium hydroxide. The solution was fltered and then set aside for the growth of crystals over a week.

S3. Refinement

The displacement parameters of the water and N,N-dimethylformamide (DMF) molecules were restrained to be nearly isotropic. The non-H atoms of the DMF molecule were restrained to lie in an approximately flat plane, and the C25—O6, C25—N5 and N5—C26 (= N5—C27) bond distances were restrained to 1.25 (1), 1.35 (1) and 1.45 (1) Å, respectively. C-bound H atoms were placed in calculated positions [C—H = 0.93–0.97 Å and U_iso(H) = 1.2–1.5U_eq(C)], and were included in the refinement in the riding-model approximation. The water H-atoms were placed in chemically sensible positions, however, not all of them form hydrogen bonds. Since the positions of the water H atoms cannot be unambiguously determined, a table of hydrogen bond is not included.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. Part of the polymeric structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius. Symmetry code: (i) x - 1, y, z.

catena-Poly[[[bis(1H-benzimidazole-κN³)copper(II)]-µ- 3-(4-carboxylatophenoxy)propionato-κ²O:O'] N,N-dimethylformamide solvate pentahydrate]

Crystal data

[Cu(C7H5N2)2(C10H8O5)]·C3H7NO·5H2O	F(000) = 1404
Mr = 671.16	Dx = 1.438 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 12961 reflections
a = 12.179 (2) Å	θ = 3.0–27.5°
b = 15.898 (2) Å	µ = 0.77 mm^−1
c = 16.420 (2) Å	T = 295 K
β = 102.834 (4)°	Block, blue
V = 3099.9 (8) Å^3	0.38 × 0.25 × 0.17 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	5460 independent reflections
Radiation source: fine-focus sealed tube	3293 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 10.000 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −14→13
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→18
Tmin = 0.590, Tmax = 0.880	l = −19→19
23434 measured reflections

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)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.247	w = 1/[σ^2(Fo^2) + (0.1404P)^2 + 1.2497P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
5460 reflections	Δρmax = 0.68 e Å^−3
399 parameters	Δρmin = −0.51 e Å^−3
66 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0080 (18)

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	0.42338 (5)	0.38523 (4)	0.21419 (4)	0.0554 (3)
O1	0.4755 (3)	0.2807 (3)	0.1671 (2)	0.0630 (10)
O2	0.5993 (4)	0.2998 (3)	0.2855 (3)	0.0785 (13)
O3	0.7685 (3)	0.2409 (3)	0.1683 (3)	0.0663 (11)
O4	1.2319 (4)	0.3954 (3)	0.1235 (3)	0.0865 (15)
O5	1.2925 (3)	0.3207 (3)	0.2359 (3)	0.0663 (11)
O6	0.4539 (7)	0.0029 (5)	0.2326 (6)	0.169 (3)
O1W	0.8142 (4)	0.3305 (3)	0.5698 (3)	0.0871 (14)
H1W1	0.8856	0.3333	0.5841	0.131*
H1W2	0.7928	0.2797	0.5711	0.131*
O2W	0.6657 (6)	0.2406 (4)	0.4455 (4)	0.124 (2)
H2W1	0.6472	0.2499	0.3933	0.186*
H2W2	0.6073	0.2235	0.4609	0.186*
O3W	0.3860 (6)	0.2179 (5)	0.3771 (5)	0.156 (3)
H3W1	0.4473	0.2443	0.3950	0.233*
H3W2	0.3542	0.2355	0.3288	0.233*
O4W	0.4405 (7)	0.0577 (5)	0.3838 (6)	0.180 (3)
H4W1	0.3869	0.0384	0.3462	0.270*
H4W2	0.4198	0.0559	0.4299	0.270*
O5W	0.6616 (4)	0.0497 (4)	0.4591 (3)	0.1076 (18)
H5W1	0.6344	0.0923	0.4303	0.161*
H5W2	0.7053	0.0653	0.5044	0.161*
N1	0.5139 (4)	0.4592 (3)	0.1570 (3)	0.0579 (12)
N2	0.6480 (4)	0.5091 (3)	0.0992 (3)	0.0628 (13)
H2N	0.7116	0.5125	0.0849	0.075*
N3	0.4082 (4)	0.4714 (3)	0.2970 (3)	0.0619 (12)
N4	0.3327 (4)	0.5670 (3)	0.3673 (3)	0.0685 (14)
H4N	0.2825	0.5977	0.3824	0.082*
N5	0.5337 (6)	−0.0769 (4)	0.1470 (5)	0.119 (2)
C1	0.5601 (5)	0.2565 (4)	0.2215 (4)	0.0602 (14)
C2	0.6158 (5)	0.1738 (4)	0.2072 (4)	0.0638 (15)
H2A	0.5943	0.1307	0.2425	0.077*
H2B	0.5892	0.1566	0.1495	0.077*
C3	0.7430 (5)	0.1814 (4)	0.2266 (4)	0.0646 (16)
H3A	0.7709	0.2010	0.2834	0.078*
H3B	0.7772	0.1274	0.2202	0.078*
C4	0.8798 (4)	0.2598 (4)	0.1730 (4)	0.0562 (14)
C5	0.8999 (5)	0.3188 (4)	0.1135 (4)	0.0636 (15)
H5	0.8399	0.3412	0.0744	0.076*
C6	1.0065 (5)	0.3428 (4)	0.1136 (4)	0.0622 (15)
H6	1.0191	0.3801	0.0731	0.075*
C7	1.0973 (4)	0.3128 (4)	0.1728 (3)	0.0538 (13)
C8	1.0759 (4)	0.2543 (4)	0.2300 (3)	0.0581 (14)
H8	1.1361	0.2331	0.2697	0.070*
C9	0.9696 (4)	0.2267 (4)	0.2302 (4)	0.0595 (14)
H9	0.9581	0.1862	0.2683	0.071*
C10	1.2128 (5)	0.3447 (4)	0.1763 (4)	0.0606 (14)
C11	0.6153 (5)	0.4466 (4)	0.1434 (4)	0.0604 (14)
H11	0.6592	0.3997	0.1623	0.072*
C12	0.4764 (5)	0.5357 (4)	0.1179 (3)	0.0552 (13)
C13	0.3774 (5)	0.5787 (4)	0.1105 (3)	0.0619 (14)
H13	0.3205	0.5588	0.1349	0.074*
C14	0.3653 (6)	0.6521 (4)	0.0657 (4)	0.0758 (18)
H14	0.2991	0.6828	0.0599	0.091*
C15	0.4500 (7)	0.6816 (4)	0.0286 (4)	0.0807 (19)
H15	0.4388	0.7315	−0.0016	0.097*
C16	0.5487 (6)	0.6396 (4)	0.0355 (4)	0.0727 (17)
H16	0.6050	0.6595	0.0104	0.087*
C17	0.5617 (5)	0.5667 (4)	0.0808 (3)	0.0582 (14)
C18	0.3140 (5)	0.5081 (4)	0.3077 (4)	0.0694 (16)
H18	0.2427	0.4941	0.2770	0.083*
C19	0.4946 (5)	0.5092 (4)	0.3561 (3)	0.0579 (14)
C20	0.6081 (5)	0.4948 (4)	0.3737 (4)	0.0706 (17)
H20	0.6400	0.4548	0.3447	0.085*
C21	0.6737 (6)	0.5429 (5)	0.4372 (5)	0.084 (2)
H21	0.7512	0.5343	0.4511	0.101*
C22	0.6276 (7)	0.6027 (4)	0.4801 (5)	0.083 (2)
H22	0.6747	0.6343	0.5212	0.100*
C23	0.5131 (7)	0.6168 (4)	0.4634 (4)	0.0771 (19)
H23	0.4815	0.6563	0.4933	0.093*
C24	0.4475 (6)	0.5696 (4)	0.4002 (4)	0.0640 (15)
C25	0.5381 (9)	−0.0393 (5)	0.2196 (7)	0.140 (4)
H25	0.6030	−0.0435	0.2617	0.168*
C26	0.4364 (13)	−0.0725 (14)	0.0809 (11)	0.336 (12)
H26A	0.4120	−0.0151	0.0727	0.504*
H26B	0.3773	−0.1058	0.0948	0.504*
H26C	0.4539	−0.0937	0.0306	0.504*
C27	0.6256 (8)	−0.1250 (6)	0.1309 (7)	0.134 (4)
H27A	0.6911	−0.1156	0.1747	0.201*
H27B	0.6409	−0.1081	0.0784	0.201*
H27C	0.6064	−0.1837	0.1287	0.201*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0417 (5)	0.0649 (5)	0.0626 (5)	−0.0028 (3)	0.0181 (3)	0.0022 (3)
O1	0.046 (2)	0.073 (3)	0.069 (2)	−0.0064 (19)	0.0104 (19)	0.001 (2)
O2	0.076 (3)	0.078 (3)	0.076 (3)	0.009 (2)	0.005 (2)	−0.008 (2)
O3	0.039 (2)	0.079 (3)	0.082 (3)	−0.0037 (19)	0.0169 (18)	0.017 (2)
O4	0.051 (3)	0.128 (4)	0.075 (3)	−0.027 (2)	0.004 (2)	0.030 (3)
O5	0.047 (2)	0.079 (3)	0.074 (3)	−0.002 (2)	0.015 (2)	0.008 (2)
O6	0.151 (6)	0.150 (6)	0.209 (7)	−0.001 (5)	0.044 (5)	0.004 (5)
O1W	0.084 (3)	0.089 (3)	0.086 (3)	0.026 (3)	0.015 (2)	0.000 (3)
O2W	0.154 (5)	0.127 (5)	0.087 (3)	0.010 (4)	0.018 (3)	0.001 (3)
O3W	0.136 (5)	0.181 (6)	0.149 (5)	−0.012 (5)	0.031 (4)	0.041 (5)
O4W	0.136 (5)	0.165 (6)	0.225 (7)	0.023 (5)	0.011 (5)	−0.010 (6)
O5W	0.078 (3)	0.148 (5)	0.102 (3)	0.019 (3)	0.032 (3)	−0.020 (3)
N1	0.051 (3)	0.065 (3)	0.062 (3)	−0.001 (2)	0.021 (2)	0.001 (2)
N2	0.052 (3)	0.074 (3)	0.069 (3)	−0.015 (2)	0.027 (2)	0.000 (3)
N3	0.043 (3)	0.073 (3)	0.073 (3)	0.001 (2)	0.020 (2)	0.007 (3)
N4	0.061 (3)	0.073 (3)	0.077 (3)	0.014 (3)	0.027 (3)	0.002 (3)
N5	0.104 (5)	0.116 (5)	0.126 (5)	0.014 (4)	0.000 (4)	−0.004 (5)
C1	0.047 (3)	0.065 (4)	0.072 (4)	−0.005 (3)	0.021 (3)	0.002 (3)
C2	0.047 (3)	0.058 (3)	0.091 (4)	−0.002 (3)	0.024 (3)	−0.001 (3)
C3	0.050 (3)	0.059 (3)	0.089 (4)	0.003 (3)	0.024 (3)	0.012 (3)
C4	0.041 (3)	0.063 (3)	0.068 (3)	−0.007 (2)	0.018 (3)	−0.001 (3)
C5	0.048 (3)	0.074 (4)	0.067 (3)	−0.001 (3)	0.010 (3)	0.014 (3)
C6	0.055 (4)	0.068 (4)	0.065 (3)	−0.004 (3)	0.017 (3)	0.013 (3)
C7	0.043 (3)	0.063 (3)	0.058 (3)	−0.003 (2)	0.015 (3)	0.004 (3)
C8	0.042 (3)	0.068 (4)	0.064 (3)	0.005 (3)	0.013 (3)	0.010 (3)
C9	0.040 (3)	0.072 (4)	0.069 (3)	0.005 (3)	0.017 (3)	0.019 (3)
C10	0.046 (3)	0.072 (4)	0.066 (4)	−0.004 (3)	0.016 (3)	0.006 (3)
C11	0.048 (3)	0.072 (4)	0.065 (3)	−0.003 (3)	0.018 (3)	−0.004 (3)
C12	0.055 (3)	0.061 (3)	0.051 (3)	−0.008 (3)	0.015 (2)	−0.009 (3)
C13	0.062 (4)	0.066 (4)	0.058 (3)	0.000 (3)	0.016 (3)	−0.003 (3)
C14	0.084 (5)	0.074 (4)	0.066 (4)	0.013 (4)	0.009 (3)	−0.011 (3)
C15	0.101 (6)	0.068 (4)	0.071 (4)	−0.008 (4)	0.015 (4)	0.009 (3)
C16	0.083 (5)	0.072 (4)	0.065 (4)	−0.016 (4)	0.021 (3)	−0.001 (3)
C17	0.062 (4)	0.060 (4)	0.054 (3)	−0.016 (3)	0.017 (3)	−0.004 (3)
C18	0.054 (4)	0.087 (4)	0.069 (4)	−0.001 (3)	0.018 (3)	0.005 (4)
C19	0.051 (3)	0.062 (3)	0.064 (3)	0.000 (3)	0.019 (3)	0.007 (3)
C20	0.059 (4)	0.075 (4)	0.080 (4)	−0.001 (3)	0.020 (3)	−0.010 (3)
C21	0.060 (4)	0.096 (5)	0.094 (5)	0.003 (4)	0.010 (4)	−0.008 (4)
C22	0.085 (5)	0.081 (5)	0.079 (5)	−0.006 (4)	0.012 (4)	−0.008 (4)
C23	0.095 (6)	0.066 (4)	0.071 (4)	0.003 (4)	0.021 (4)	−0.002 (3)
C24	0.077 (4)	0.051 (3)	0.070 (4)	0.006 (3)	0.031 (3)	0.003 (3)
C25	0.142 (7)	0.128 (7)	0.150 (7)	0.002 (6)	0.034 (6)	0.000 (6)
C26	0.327 (15)	0.329 (15)	0.330 (15)	0.029 (10)	0.028 (10)	−0.003 (10)
C27	0.119 (7)	0.136 (7)	0.156 (7)	0.005 (5)	0.048 (6)	0.009 (6)

Geometric parameters (Å, º)

Cu1—N3	1.967 (5)	C4—C9	1.378 (8)
Cu1—N1	1.984 (4)	C4—C5	1.415 (8)
Cu1—O5^i	1.993 (4)	C5—C6	1.353 (8)
Cu1—O1	1.995 (4)	C5—H5	0.93
O1—C1	1.264 (7)	C6—C7	1.385 (8)
O2—C1	1.259 (7)	C6—H6	0.93
O3—C4	1.374 (6)	C7—C8	1.386 (7)
O3—C3	1.428 (7)	C7—C10	1.485 (7)
O4—C10	1.242 (7)	C8—C9	1.369 (7)
O5—C10	1.275 (7)	C8—H8	0.93
O5—Cu1^ii	1.993 (4)	C9—H9	0.93
O6—C25	1.283 (8)	C11—H11	0.93
O1W—H1W1	0.85	C12—C13	1.366 (8)
O1W—H1W2	0.85	C12—C17	1.405 (7)
O2W—H2W1	0.85	C13—C14	1.370 (9)
O2W—H2W2	0.85	C13—H13	0.93
O3W—H3W1	0.85	C14—C15	1.390 (9)
O3W—H3W2	0.85	C14—H14	0.93
O4W—H4W1	0.85	C15—C16	1.358 (9)
O4W—H4W2	0.85	C15—H15	0.93
O5W—H5W1	0.85	C16—C17	1.368 (9)
O5W—H5W2	0.85	C16—H16	0.93
N1—C11	1.318 (7)	C18—H18	0.93
N1—C12	1.405 (7)	C19—C20	1.367 (8)
N2—C11	1.342 (7)	C19—C24	1.401 (8)
N2—C17	1.376 (7)	C20—C21	1.394 (9)
N2—H2N	0.86	C20—H20	0.93
N3—C18	1.333 (7)	C21—C22	1.375 (10)
N3—C19	1.399 (7)	C21—H21	0.93
N4—C18	1.337 (8)	C22—C23	1.379 (10)
N4—C24	1.383 (8)	C22—H22	0.93
N4—H4N	0.86	C23—C24	1.383 (9)
N5—C25	1.324 (8)	C23—H23	0.93
N5—C26	1.420 (10)	C25—H25	0.93
N5—C27	1.428 (8)	C26—H26A	0.96
C1—C2	1.521 (8)	C26—H26B	0.96
C2—C3	1.516 (8)	C26—H26C	0.96
C2—H2A	0.97	C27—H27A	0.96
C2—H2B	0.97	C27—H27B	0.96
C3—H3A	0.97	C27—H27C	0.96
C3—H3B	0.97
N3—Cu1—N1	93.53 (19)	C4—C9—H9	120.5
N3—Cu1—O5^i	91.88 (18)	O4—C10—O5	120.1 (5)
N1—Cu1—O5^i	160.05 (19)	O4—C10—C7	121.2 (5)
N3—Cu1—O1	159.18 (19)	O5—C10—C7	118.7 (5)
N1—Cu1—O1	92.98 (17)	N1—C11—N2	112.4 (5)
O5^i—Cu1—O1	88.67 (16)	N1—C11—H11	123.8
C1—O1—Cu1	105.0 (4)	N2—C11—H11	123.8
C4—O3—C3	117.7 (4)	C13—C12—N1	131.6 (5)
C10—O5—Cu1^ii	102.2 (3)	C13—C12—C17	120.6 (6)
H1W1—O1W—H1W2	110.2	N1—C12—C17	107.7 (5)
H2W1—O2W—H2W2	107.7	C12—C13—C14	117.5 (6)
H3W1—O3W—H3W2	110.2	C12—C13—H13	121.3
H4W1—O4W—H4W2	107.7	C14—C13—H13	121.3
H5W1—O5W—H5W2	110.2	C13—C14—C15	121.4 (7)
C11—N1—C12	106.0 (5)	C13—C14—H14	119.3
C11—N1—Cu1	129.1 (4)	C15—C14—H14	119.3
C12—N1—Cu1	124.8 (4)	C16—C15—C14	121.8 (6)
C11—N2—C17	107.9 (4)	C16—C15—H15	119.1
C11—N2—H2N	126.0	C14—C15—H15	119.1
C17—N2—H2N	126.0	C15—C16—C17	117.1 (6)
C18—N3—C19	104.9 (5)	C15—C16—H16	121.4
C18—N3—Cu1	127.8 (4)	C17—C16—H16	121.4
C19—N3—Cu1	127.3 (4)	C16—C17—N2	132.4 (6)
C18—N4—C24	107.4 (5)	C16—C17—C12	121.7 (6)
C18—N4—H4N	126.3	N2—C17—C12	105.9 (5)
C24—N4—H4N	126.3	N3—C18—N4	113.1 (6)
C25—N5—C26	121.7 (13)	N3—C18—H18	123.4
C25—N5—C27	122.2 (9)	N4—C18—H18	123.4
C26—N5—C27	116.1 (12)	C20—C19—N3	130.1 (6)
O2—C1—O1	121.5 (6)	C20—C19—C24	121.1 (6)
O2—C1—C2	120.1 (6)	N3—C19—C24	108.7 (5)
O1—C1—C2	118.4 (6)	C19—C20—C21	116.8 (6)
C3—C2—C1	111.6 (5)	C19—C20—H20	121.6
C3—C2—H2A	109.3	C21—C20—H20	121.6
C1—C2—H2A	109.3	C22—C21—C20	122.1 (7)
C3—C2—H2B	109.3	C22—C21—H21	119.0
C1—C2—H2B	109.3	C20—C21—H21	119.0
H2A—C2—H2B	108.0	C21—C22—C23	121.4 (7)
O3—C3—C2	106.1 (5)	C21—C22—H22	119.3
O3—C3—H3A	110.5	C23—C22—H22	119.3
C2—C3—H3A	110.5	C24—C23—C22	116.8 (6)
O3—C3—H3B	110.5	C24—C23—H23	121.6
C2—C3—H3B	110.5	C22—C23—H23	121.6
H3A—C3—H3B	108.7	C23—C24—N4	132.5 (6)
O3—C4—C9	125.4 (5)	C23—C24—C19	121.7 (6)
O3—C4—C5	115.2 (5)	N4—C24—C19	105.8 (5)
C9—C4—C5	119.4 (5)	O6—C25—N5	120.8 (11)
C6—C5—C4	120.0 (5)	O6—C25—H25	119.6
C6—C5—H5	120.0	N5—C25—H25	119.6
C4—C5—H5	120.0	N5—C26—H26A	109.5
C5—C6—C7	121.3 (5)	N5—C26—H26B	109.5
C5—C6—H6	119.3	H26A—C26—H26B	109.5
C7—C6—H6	119.3	N5—C26—H26C	109.5
C6—C7—C8	117.8 (5)	H26A—C26—H26C	109.5
C6—C7—C10	120.7 (5)	H26B—C26—H26C	109.5
C8—C7—C10	121.5 (5)	N5—C27—H27A	109.5
C9—C8—C7	122.5 (5)	N5—C27—H27B	109.5
C9—C8—H8	118.8	H27A—C27—H27B	109.5
C7—C8—H8	118.8	N5—C27—H27C	109.5
C8—C9—C4	119.0 (5)	H27A—C27—H27C	109.5
C8—C9—H9	120.5	H27B—C27—H27C	109.5
N3—Cu1—O1—C1	−15.1 (7)	C17—N2—C11—N1	−1.1 (7)
N1—Cu1—O1—C1	93.0 (4)	C11—N1—C12—C13	178.6 (6)
O5^i—Cu1—O1—C1	−106.9 (4)	Cu1—N1—C12—C13	1.9 (8)
N3—Cu1—N1—C11	122.8 (5)	C11—N1—C12—C17	0.0 (6)
O5^i—Cu1—N1—C11	−131.8 (6)	Cu1—N1—C12—C17	−176.7 (4)
O1—Cu1—N1—C11	−37.4 (5)	N1—C12—C13—C14	−178.3 (6)
N3—Cu1—N1—C12	−61.3 (4)	C17—C12—C13—C14	0.1 (8)
O5^i—Cu1—N1—C12	44.2 (8)	C12—C13—C14—C15	0.5 (9)
O1—Cu1—N1—C12	138.5 (4)	C13—C14—C15—C16	−0.4 (10)
N1—Cu1—N3—C18	116.4 (5)	C14—C15—C16—C17	−0.2 (10)
O5^i—Cu1—N3—C18	−44.4 (5)	C15—C16—C17—N2	179.0 (6)
O1—Cu1—N3—C18	−135.6 (5)	C15—C16—C17—C12	0.8 (9)
N1—Cu1—N3—C19	−61.8 (5)	C11—N2—C17—C16	−177.4 (6)
O5^i—Cu1—N3—C19	137.4 (5)	C11—N2—C17—C12	1.0 (6)
O1—Cu1—N3—C19	46.2 (7)	C13—C12—C17—C16	−0.8 (9)
Cu1—O1—C1—O2	−5.3 (6)	N1—C12—C17—C16	177.9 (5)
Cu1—O1—C1—C2	175.8 (4)	C13—C12—C17—N2	−179.4 (5)
O2—C1—C2—C3	−43.4 (8)	N1—C12—C17—N2	−0.7 (6)
O1—C1—C2—C3	135.4 (6)	C19—N3—C18—N4	1.2 (7)
C4—O3—C3—C2	179.5 (5)	Cu1—N3—C18—N4	−177.3 (4)
C1—C2—C3—O3	−63.4 (7)	C24—N4—C18—N3	−1.0 (7)
C3—O3—C4—C9	−0.7 (8)	C18—N3—C19—C20	178.8 (6)
C3—O3—C4—C5	179.8 (5)	Cu1—N3—C19—C20	−2.7 (9)
O3—C4—C5—C6	179.0 (5)	C18—N3—C19—C24	−0.9 (6)
C9—C4—C5—C6	−0.5 (9)	Cu1—N3—C19—C24	177.6 (4)
C4—C5—C6—C7	−2.2 (9)	N3—C19—C20—C21	−179.7 (6)
C5—C6—C7—C8	2.8 (9)	C24—C19—C20—C21	0.0 (9)
C5—C6—C7—C10	−175.1 (6)	C19—C20—C21—C22	−0.5 (11)
C6—C7—C8—C9	−0.8 (9)	C20—C21—C22—C23	1.4 (11)
C10—C7—C8—C9	177.1 (5)	C21—C22—C23—C24	−1.6 (10)
C7—C8—C9—C4	−1.9 (9)	C22—C23—C24—N4	179.9 (6)
O3—C4—C9—C8	−177.0 (5)	C22—C23—C24—C19	1.1 (9)
C5—C4—C9—C8	2.5 (9)	C18—N4—C24—C23	−178.6 (7)
Cu1^ii—O5—C10—O4	1.2 (7)	C18—N4—C24—C19	0.3 (6)
Cu1^ii—O5—C10—C7	−177.2 (4)	C20—C19—C24—C23	−0.3 (9)
C6—C7—C10—O4	−4.1 (9)	N3—C19—C24—C23	179.5 (5)
C8—C7—C10—O4	178.0 (6)	C20—C19—C24—N4	−179.4 (5)
C6—C7—C10—O5	174.3 (5)	N3—C19—C24—N4	0.4 (6)
C8—C7—C10—O5	−3.6 (9)	C26—N5—C25—O6	−0.2 (3)
C12—N1—C11—N2	0.6 (6)	C27—N5—C25—O6	−179.4 (3)
Cu1—N1—C11—N2	177.2 (4)

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