Poly[(μ₂-1,4-benzene­dicarboxyl­ato)aqua­dipyridine­copper(II) 0.25-hydrate]

The title compound, [Cu(C₈H₄O₄)(C₅H₅N)₂(H₂O)]_n·0.25nH₂O, was obtained unintentionally as the product of an attempted synthesis of a 4-cyano­benzoate-bridged network complex of copper(II) using pyridine as a base to deprotonate the organic acid. Its crystal structure is built up by one-dimensional helical chains along the c direction and uncoordinated water mol­ecules through inter­molecular O—H...O hydrogen bonds and van der Waals inter­actions. The investigated crystal was a partial inversion twin.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 97%
• Disorder in solvent or counterion
• R factor = 0.065
• wR factor = 0.141
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C24

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.310
           From the CIF: _refine_ls_abs_structure_Flack_su    0.020
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT033_ALERT_2_C Flack Parameter Value Deviates 2 * su from zero.       0.31
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.85
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.13
PLAT213_ALERT_2_C Atom O21     has ADP max/min Ratio .............       3.10 prola
PLAT213_ALERT_2_C Atom C23     has ADP max/min Ratio .............       3.50 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.48 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C27
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C34
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N11
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        N31
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C25
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      25.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O2W
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C25    -   C28    ...       1.53 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C18 H16.5 Cu1 N2 O5.25
            Atom count from the _atom_site data:  C18 H16 Cu1 N2 O5.25
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.853
            Tmax scaled      0.853 Tmin scaled      0.745
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C18 H16.50 Cu N2 O5.25
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         72.00     72.00    0.00
           H         66.00     64.00    2.00
           Cu         4.00      4.00    0.00
           N          8.00      8.00    0.00
           O         21.00     21.00    0.00
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.10
           From the CIF: _reflns_number_total               2927
           Count of symmetry unique reflns         2051
           Completeness (_total/calc)            142.71%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       876
           Fraction of Friedel pairs measured     0.427
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

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

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

---

S1. Comment

Many interesting in situ reactions such as hydrolysis (Lin et al., 1998; Evans et al., 1999; Lin et al., 2000; Sun et al., 2001), redox (Xiong et al., 1998; Ma et al., 1999; Evans et al., 2000; Tao et al., 2002), and dehydration (Gutschke et al., 2000) can occur under solvothermal environment. It has been found that cyano substituted aromatic compound can be hydrolyzed and the cyano group would be changed to carboxylic acid. For example, Lin's group reported that 3-cyanopyridine or 4-cyanopyridine undergoes a hydrolysis reaction to form 3-pyridinecarboxylic acid (Lin et al., 2000) and 4-pyridinecarboxylic acid (Evans et al., 1999), respectively; Hong's group revealed that the hydrolysis of 1,4-dicyanobenzene gives rise to 1,4-benzenedicarboxylate acid (Sun et al., 2001). The present example shows that 4-cyanobenzoic acid also undergoes a similar hydrolysis procedure.

The hydrothermal reaction of 4-cyanobenzoic acid, CuO, pyridine (py) and water under weak basified conditions gave rise to the title compound (1) as blue prismatic crystals, which were very easy to be efflorescent and become opaque when out of the mother liquid. The IR spectrum of (1) exhibits strong bands at 1605 and 1390 cm^-1, which are attributed to the Vas and Vas peaks of COO^- group, respectively. The absence of peaks in the range of 2240—2220 cm^-1 shows that there exists no cyano group in (1).

A single-crystal X-ray diffraction analysis revealed that compund (1) has a similar 1-D chain structure as that of CuL¹(py)₂(H₂O).py.H₂O (L¹ = 1,4-benzenedicarboxylate ligand; Ohmura et al., 2003). The crystallographically independent unit of (1) consists of one L¹ ligand, two py ligands, one copper(II) atom, one coordination water molecule and hemisemi lattice water molecule. As show in Fig. 1, each copper(II) atom is almost in a square-based pyramidal environment, of which the axial position is occupied by coordination water molecule O1w (Cu1—O1w = 2.243 (3) Å) and the square plane is defined by two nitrogen atoms from two py ligands (Cu—N = 1.996 (3) and 2.010 (3) Å), two oxygen atoms from two L¹ ligands (Cu—O = 1.931 (2) and 1.934 (2) Å) with an O24—Cu1—O22 bond angle of 178.3 (1) °. The bond angles of O1w—Cu1—X (X = the atoms in the square plane) vary from 89.4 (1) to 96.2 (1) °, which indicates that O1w is approximately perpendicular to the square plane. In this way, each L¹ ligand links two symmetry-related copper(II) atoms (Cu···Cu, ca 10.901 Å) into a 1-D chain along the c direction. Compound 1 crystallizes in space group P2₁2₁2₁, and the 1-D chain perfectly lies in the 2₁ axis. Hence, the 1-D chain is in a helical mode as the case found in the structure of [Cu(L²)(NO₃)₂]₈ (L² = 2,5-bis(2-pyridyl)-1,3,4-oxodiazole) (Bu et al., 2002). To the best of our knowledge, 1-D helical chiral compound with bridging L¹ ligands has only a reported example in the literature (Cutland et al., 2001).

Considering the short contacts shows that the neighboring parallel chains are interconnected by O—H···O hydrogen bonds [O1W···O21ⁱ = 2.735 (4) Å, O1w—Hw1···O21ⁱ = 133.7 (6) °; O1W···O23ⁱⁱ = 2.719 (3) Å, O1w—Hw2···O23ⁱⁱ = 165 (1)°; (i) x - 1, y, z; (ii) -0.5 - x, 1 - y, -1/2 + z. (Table 1)] to form a layer (Fig. 1). Each of these hydrogen bonds is established from an axially coordinated water molecule to one of the carboxylate group of a neighboring L¹ ligand. The distance of two adjacent chains agrees with the Cu1···Cu1a separation of ca 5.990 Å, which is shorter than the L¹-bridged Cu···Cu separation. However, considering the short contacts between two adjacent layers, only van der Waals interactions can be found (Fig. 2). The layers are crosswise arranged along the b direction to form a self-complementary structure (Seo et al., 2000) that apparently stabilizes the whole crystal structure. Uncoordinated water molecules locate in the channels along the a direction.

Related literature

For related literature, see: Bu et al. (2002); Cutland et al. (2001); Evans & Lin (2000); Evans et al. (1999); Gutschke et al. (2000); Lin et al. (1998, 2000); Ma et al. (1999); Ohmura et al. (2003); Seo et al. (2000); Sun et al. (2001); Tao et al. (2002); Xiong et al. (1998).

S2. Experimental

A mixture of 4-cyanobenzoic acid (147 mg, 1 mmol), CuO (40 mg, 0.5 mmol), pyrimidine (1 ml) and H₂O (9 ml) was loaded into a 25-ml sealed Teflon-lined autoclave, and heated at 160 °C for 5 d, after which it was cooled to room temperature. Blue pismatic crystals of 1 were obtained by filtration of the result solution, and washed by ethanol and diethyl ether successively. IR peaks (cm^-1): 3363 (m), 3273 (m), 1605 (versus), 1502 (m), 1448 (s), 1390 (versus), 1356 (versus), 1219 (m), 1147 (m), 1070 (m), 1024 (w), 889 (w), 849 (m), 754 (s), 698 (s), 652 (m), 571 (m), 509 (w).

S3. Refinement

H atoms of coordination water molecules (O1W) were located in a difference Fourier map and refined as riding in their as-found relative positions, with U_iso(H) = 1.5Ueq(O). The DFIX commands were used to restrain the O—H bond distances of water molecules (Table 1). The H atoms of uncoordinated water molecules (O2W) were not included. Other H atoms were allowed to ride on their respective parent atoms with C—H distances of 0.93 Å, and were included in the refinement with isotropic displacement parameters U_iso(H) = 1.2Ueq(C). ISOR was applied to O2W atom to avoid large adp.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP (Siemens, 1995); program(s) used to solve structure: SHELXTL (Siemens, 1995); program(s) used to refine structure: SHELXTL (Siemens, 1995); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL (Siemens, 1995).

Figures

	Fig. 1. 2-D hydrogen-bonding network in the ac plane built upon 1-D helical chains with green dash lines showing the O1w—H···O (O21 or O23) hydrogen bonds. Hydrogen atoms are omitted for clarity.
	Fig. 2. 3-D packing diagram viewed along the a direction. Hydrogen atoms are omitted for clarity.

Poly[(µ₂-1,4-benzenedicarboxylato)aquadipyridinecopper(II) 0.25-hydrate]

Crystal data

[Cu(C8H4O4)(C5H5N)2(H2O)]·0.25H2O	F(000) = 838
Mr = 408.37	Dx = 1.375 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1986 reflections
a = 5.9896 (7) Å	θ = 2.3–25.1°
b = 15.2593 (18) Å	µ = 1.14 mm^−1
c = 21.581 (2) Å	T = 293 K
V = 1972.4 (4) Å^3	Prismatic, blue
Z = 4	0.48 × 0.24 × 0.14 mm

Data collection

Siemens SMART CCD diffractometer	2927 independent reflections
Radiation source: fine-focus sealed tube	1689 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
ω scans	θmax = 25.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
Tmin = 0.874, Tmax = 1.000	k = −11→18
5908 measured reflections	l = −23→25

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)] = 0.065	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.141	w = 1/[σ^2(Fo^2) + (0.032P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
2927 reflections	Δρmax = 0.71 e Å^−3
191 parameters	Δρmin = −0.33 e Å^−3
9 restraints	Absolute structure: Flack (1983), 876 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.31 (2)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.16689 (10)	0.53883 (4)	0.34904 (2)	0.03936 (14)
O21	0.5303 (6)	0.5146 (3)	0.45248 (14)	0.0864 (16)
O22	0.1645 (6)	0.49792 (18)	0.43385 (11)	0.0459 (10)
O23	−0.0356 (5)	0.4486 (3)	0.74787 (12)	0.0625 (12)
O24	0.3310 (6)	0.42383 (19)	0.76355 (11)	0.0486 (10)
C21	0.1555 (9)	0.4372 (3)	0.72974 (17)	0.0406 (15)
C22	0.2054 (7)	0.4467 (3)	0.66137 (15)	0.0368 (14)
C23	0.4192 (7)	0.4528 (5)	0.63920 (18)	0.068 (2)
H23A	0.5386	0.4453	0.6662	0.082*
C24	0.4604 (9)	0.4698 (5)	0.5775 (2)	0.090 (2)
H24A	0.6068	0.4770	0.5640	0.107*
C25	0.2899 (8)	0.4763 (3)	0.53580 (16)	0.0410 (15)
C26	0.0789 (7)	0.4670 (4)	0.55662 (18)	0.0547 (17)
H26A	−0.0401	0.4706	0.5291	0.066*
C27	0.0384 (8)	0.4517 (4)	0.62017 (18)	0.0632 (19)
H27A	−0.1079	0.4449	0.6338	0.076*
C28	0.3415 (11)	0.4975 (3)	0.46790 (19)	0.0523 (17)
N11	0.1812 (5)	0.41556 (16)	0.31642 (10)	0.0500 (9)
C11	0.3632 (5)	0.3621 (2)	0.32926 (15)	0.0810 (16)
H11A	0.4814	0.3834	0.3528	0.097*
C12	0.3685 (8)	0.2766 (2)	0.3070 (2)	0.103 (2)
H12A	0.4903	0.2408	0.3156	0.124*
C13	0.1918 (9)	0.24467 (19)	0.27188 (19)	0.111 (2)
H13A	0.1953	0.1875	0.2570	0.133*
C14	0.0097 (8)	0.2982 (2)	0.25904 (18)	0.128 (2)
H14A	−0.1085	0.2768	0.2355	0.154*
C15	0.0044 (6)	0.3836 (2)	0.28131 (15)	0.0891 (17)
H15A	−0.1173	0.4194	0.2727	0.107*
N31	0.2070 (5)	0.66163 (17)	0.37881 (11)	0.0500 (9)
C31	0.3862 (5)	0.7127 (2)	0.35951 (16)	0.0810 (16)
H31A	0.4865	0.6908	0.3305	0.097*
C32	0.4155 (7)	0.7964 (2)	0.3836 (2)	0.103 (2)
H32A	0.5354	0.8305	0.3707	0.124*
C33	0.2655 (9)	0.8290 (2)	0.4270 (2)	0.111 (2)
H33A	0.2851	0.8850	0.4431	0.133*
C34	0.0863 (8)	0.7780 (2)	0.44630 (18)	0.128 (2)
H34A	−0.0140	0.7999	0.4753	0.154*
C35	0.0571 (6)	0.6943 (2)	0.42221 (15)	0.0891 (17)
H35A	−0.0628	0.6602	0.4351	0.107*
O1W	−0.2068 (4)	0.54786 (18)	0.35159 (9)	0.0553 (10)
H1WA	−0.2573 (15)	0.5095 (3)	0.37645 (16)	0.083*
H1WB	−0.2802 (11)	0.5393 (6)	0.31842 (15)	0.083*
O2W	0.026 (4)	0.2549 (17)	0.4836 (10)	0.178 (5)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0449 (3)	0.0560 (3)	0.01714 (19)	0.0003 (4)	−0.0009 (3)	0.0010 (3)
O21	0.040 (2)	0.178 (4)	0.0409 (18)	−0.022 (3)	0.0112 (19)	0.033 (2)
O22	0.050 (2)	0.068 (2)	0.0196 (13)	0.0003 (19)	0.0030 (19)	0.0028 (13)
O23	0.034 (2)	0.126 (3)	0.0277 (15)	−0.010 (3)	0.0127 (16)	0.005 (2)
O24	0.047 (2)	0.079 (2)	0.0201 (14)	0.000 (2)	−0.0019 (19)	0.0022 (14)
C21	0.042 (3)	0.053 (3)	0.027 (2)	−0.025 (3)	−0.007 (3)	−0.0031 (19)
C22	0.037 (3)	0.058 (3)	0.0153 (19)	0.004 (3)	−0.004 (2)	−0.004 (2)
C23	0.021 (3)	0.162 (5)	0.022 (2)	−0.006 (4)	−0.008 (2)	0.013 (3)
C24	0.034 (3)	0.206 (7)	0.029 (2)	0.004 (5)	0.004 (3)	0.028 (4)
C25	0.038 (3)	0.068 (3)	0.0175 (19)	0.006 (3)	−0.003 (2)	0.006 (2)
C26	0.028 (3)	0.117 (4)	0.019 (2)	−0.002 (3)	0.000 (2)	0.003 (3)
C27	0.026 (3)	0.133 (5)	0.030 (2)	−0.001 (4)	0.007 (2)	−0.005 (3)
C28	0.054 (3)	0.076 (4)	0.028 (2)	−0.006 (3)	0.001 (3)	0.005 (2)
N11	0.0537 (19)	0.0574 (18)	0.0388 (13)	0.0086 (17)	−0.0068 (17)	0.0085 (12)
C11	0.084 (3)	0.068 (3)	0.091 (3)	−0.009 (3)	−0.012 (3)	−0.002 (2)
C12	0.115 (5)	0.052 (3)	0.143 (4)	−0.015 (3)	0.010 (3)	−0.016 (3)
C13	0.144 (5)	0.071 (3)	0.118 (3)	−0.002 (3)	0.004 (4)	−0.040 (3)
C14	0.140 (5)	0.105 (4)	0.140 (4)	0.009 (4)	0.018 (4)	−0.062 (3)
C15	0.093 (4)	0.096 (4)	0.078 (3)	0.015 (3)	−0.004 (3)	−0.030 (2)
N31	0.0537 (19)	0.0574 (18)	0.0388 (13)	0.0086 (17)	−0.0068 (17)	0.0085 (12)
C31	0.084 (3)	0.068 (3)	0.091 (3)	−0.009 (3)	−0.012 (3)	−0.002 (2)
C32	0.115 (5)	0.052 (3)	0.143 (4)	−0.015 (3)	0.010 (3)	−0.016 (3)
C33	0.144 (5)	0.071 (3)	0.118 (3)	−0.002 (3)	0.004 (4)	−0.040 (3)
C34	0.140 (5)	0.105 (4)	0.140 (4)	0.009 (4)	0.018 (4)	−0.062 (3)
C35	0.093 (4)	0.096 (4)	0.078 (3)	0.015 (3)	−0.004 (3)	−0.030 (2)
O1W	0.051 (2)	0.086 (2)	0.0287 (13)	−0.003 (2)	−0.0029 (19)	0.008 (2)
O2W	0.193 (7)	0.164 (7)	0.178 (7)	−0.005 (6)	−0.013 (6)	−0.022 (6)

Geometric parameters (Å, º)

Cu1—O24^i	1.931 (2)	N11—C15	1.3900
Cu1—O22	1.934 (2)	C11—C12	1.3900
Cu1—N31	1.996 (3)	C11—H11A	0.9300
Cu1—N11	2.010 (3)	C12—C13	1.3900
Cu1—O1W	2.243 (3)	C12—H12A	0.9300
O21—C28	1.208 (7)	C13—C14	1.3900
O22—C28	1.290 (6)	C13—H13A	0.9300
O23—C21	1.222 (6)	C14—C15	1.3900
O24—C21	1.296 (6)	C14—H14A	0.9300
O24—Cu1^ii	1.931 (2)	C15—H15A	0.9300
C21—C22	1.513 (5)	N31—C31	1.3900
C22—C27	1.341 (6)	N31—C35	1.3900
C22—C23	1.370 (6)	C31—C32	1.3900
C23—C24	1.380 (6)	C31—H31A	0.9300
C23—H23A	0.9300	C32—C33	1.3900
C24—C25	1.364 (6)	C32—H32A	0.9300
C24—H24A	0.9300	C33—C34	1.3900
C25—C26	1.349 (6)	C33—H33A	0.9300
C25—C28	1.532 (6)	C34—C35	1.3900
C26—C27	1.412 (6)	C34—H34A	0.9300
C26—H26A	0.9300	C35—H35A	0.9300
C27—H27A	0.9300	O1W—H1WA	0.850 (4)
N11—C11	1.3900	O1W—H1WB	0.850 (4)
O24^i—Cu1—O22	178.33 (13)	C15—N11—Cu1	119.12 (15)
O24^i—Cu1—N31	91.70 (12)	C12—C11—N11	120.0
O22—Cu1—N31	89.96 (11)	C12—C11—H11A	120.0
O24^i—Cu1—N11	86.63 (11)	N11—C11—H11A	120.0
O22—Cu1—N11	91.70 (11)	C11—C12—C13	120.0
N31—Cu1—N11	170.51 (13)	C11—C12—H12A	120.0
O24^i—Cu1—O1W	90.68 (12)	C13—C12—H12A	120.0
O22—Cu1—O1W	89.38 (12)	C14—C13—C12	120.0
N31—Cu1—O1W	93.13 (11)	C14—C13—H13A	120.0
N11—Cu1—O1W	96.23 (12)	C12—C13—H13A	120.0
C28—O22—Cu1	122.3 (3)	C15—C14—C13	120.0
C21—O24—Cu1^ii	119.8 (3)	C15—C14—H14A	120.0
O23—C21—O24	127.0 (4)	C13—C14—H14A	120.0
O23—C21—C22	118.9 (4)	C14—C15—N11	120.0
O24—C21—C22	113.8 (4)	C14—C15—H15A	120.0
C27—C22—C23	117.5 (4)	N11—C15—H15A	120.0
C27—C22—C21	120.3 (4)	C31—N31—C35	120.0
C23—C22—C21	122.1 (4)	C31—N31—Cu1	121.51 (15)
C22—C23—C24	121.2 (4)	C35—N31—Cu1	118.41 (15)
C22—C23—H23A	119.4	C32—C31—N31	120.0
C24—C23—H23A	119.4	C32—C31—H31A	120.0
C25—C24—C23	121.1 (5)	N31—C31—H31A	120.0
C25—C24—H24A	119.5	C31—C32—C33	120.0
C23—C24—H24A	119.5	C31—C32—H32A	120.0
C26—C25—C24	118.3 (4)	C33—C32—H32A	120.0
C26—C25—C28	122.0 (4)	C32—C33—C34	120.0
C24—C25—C28	119.7 (4)	C32—C33—H33A	120.0
C25—C26—C27	120.1 (4)	C34—C33—H33A	120.0
C25—C26—H26A	119.9	C33—C34—C35	120.0
C27—C26—H26A	119.9	C33—C34—H34A	120.0
C22—C27—C26	121.7 (4)	C35—C34—H34A	120.0
C22—C27—H27A	119.2	C34—C35—N31	120.0
C26—C27—H27A	119.2	C34—C35—H35A	120.0
O21—C28—O22	127.7 (4)	N31—C35—H35A	120.0
O21—C28—C25	119.9 (5)	Cu1—O1W—H1WA	109.2 (7)
O22—C28—C25	112.4 (5)	Cu1—O1W—H1WB	119.1 (5)
C11—N11—C15	120.0	H1WA—O1W—H1WB	103.9 (6)
C11—N11—Cu1	120.88 (15)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O21^iii	0.85 (1)	2.08 (1)	2.735 (4)	134 (1)
O1W—H1WB···O23^iv	0.85 (1)	1.89 (1)	2.719 (3)	165 (1)

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