cis-Diaqua­[(E)-2-(2-oxidobenzyl­idene­amino-κ²N,O)­benzoato-κO]copper(II): tubes built from O—H...O hydrogen-bonding, π–π and C—H...π inter­actions

In the title compound, [Cu(C₁₄H₉NO₃)(H₂O)₂],pairs of complexes are linked into dimers by three O—H...O hydrogen bonds. Strong O—H...O hydrogen bonds link the dimers into one-dimensional chains that further assemble into tubes through π–π and C—H...π inter­actions.

S1. Comment

(E)-2-(2-Hydroxybenzylideneamino)benzoic acid is a tridentate ligand, many of whose metal complexes have been studied (Clague et al., 1993; Asgedom et al., 1997; Dey et al., 1999; Redshaw & Elsegood, 2001; Rosair et al., 2002; Shan et al., 2003). As the result of our interest in Schiff base metal complexes as model compounds for the study of the active sites of metalloenzymes, we have investigated the title compound, (I), and we report here its structure.

Compound (I) (Fig. 1) crystallizes with Z = 18 in space group R3, and consists of two independent Cu(C₁₄H₉NO₃) complexes. In each complex, the Cu atom is coordinated by one N atom and four O atoms from two water molecules and one E-2-(2-hydroxybenzylideneamino)benzoic acid molecule, adopting square-pyramidal geometry, similar to that in [Cu(C₁₄H₉NO₃)(C₅H₅N)₂]·H₂O (Li et al.,1995) but n contrast to [Cu(C₁₄H₉NO₃)(C₃H₄N₂)], in which the Cu atom is four-coordinate with a square geometry (Gao et al., 2000). Although the two complexes have the same coordination spheres, the corresponding bonds around atoms Cu1 and Cu2 are significantly different (Table 1), especially the Cu—O distances between the Cu atom and the apical water ligands. The two aryl rings in each complex make dihedral angles of 58.7 (2) and 58.4 (2)°, respectively. The two complexes are connected to each other by three strong O—H···O hydrogen bonds to form a dimer in which the Cu···Cu distance is 4.674 (1) Å.

The supramolecular interactions (Table 2) are illustrated in Figs. 2 and 3. Four intermolecular O—H···O hydrogen bonds, with two coordinated water molecules as hydrogen-bond donors and two carboxyl O atoms of the ligand as acceptors, link the dimers to one-dimensional chains along the c axis (Fig. 2). Because of the relatively strong intermolecular hydrogen bonding, neighbouring dimers are connected closely, the Cu1···Cu2(x, y, 1 + z) separation being 5.304 (1) Å, leaving atoms Cu1 and Cu2 arranged in a zigzag shape in the chains. Six such chains, related to each other by a rotation of 60° in the (001) plane, are connected through π–πstacking interactions between the C1–C6 and C15–C20 aryl rings, with Cg1···Cg2(y, −x + y, 1 − z) (Cg1 is the centroid of the C1–C6 ring and Cg2 is the centroid of the C15—C20 ring), Cg1···Cg2(y, −x + y, 2 − z), Cg2···Cg1(x-y, x, 1 − z) and Cg2···Cg1(x-y, x, 2 − z) distances of 3.677 (3), 3.548 (3), 3.677 (4) and 3.548 (4) Å, and interplanar spacings of 3.250, 3.263, 3.279 and 3.302 Å, respectively, assembling the six chains into a tube (Fig. 3). Additionally, a C—H···π interaction (Fig. 3a) between the C23/H23 group and the C9–C13 aryl ring (centroid Cg3) in a neighbouring chain, with a C23···Cg3(x − y, x, 2 − z) separation of 3.618 (9) Å, also takes part in the stabilization of the tubes.

Large voids in the structure were examined using PLATON (Spek, 2003). In the three-dimensional structure of (I), there are three channels along the c axis (Fig. 3), accounting in total for 1518.3 ų per unit cell, i.e. some 11.4% of the total volume. The channels lie along a threefold inversion centre with an average cross-sectional area of ca 70.6 Ų and an average diameter of ca 9.5 Å. The channels in (I) appear to be occupied by water molecules; their behaviour is intractable, possibly due to dynamic disorder.

S2. Experimental

Compound (I) was synthesized by adding an ethanol solution (15 ml) of E-2-(2-hydroxybenzylideneamino)benzoic acid (0.120 g) to an aqueous solution (5 ml) of Cu(C₂H₃O₂)₂·H₂O (0.102 g). The mixed solution was refluxed at 333 K for 2 h; the pH was then adjusted to 7 with 0.1 mol dm⁻³ NaOH and the solution was filtered while it cooled to room temperature. Dark-blue needle-shaped crystals of (I) were obtained from the filtrate at room temperature after two weeks.

S3. Refinement

H atoms attached to C atoms were placed in geometrically idealized positions, with C—H = 0.93 Å, and refined with U_iso(H) values of 1.2U_eq(C). H atoms attached to O atoms were located from difference Fourier maps and refined as riding in their as-found positions with U_iso(H) values of 1.2Ueq(O). The O—H distances are in the range 0.82–0.91 Å. Examination of the refined structure using PLATON (Spek, 2003) revealed the presence of voids having a total volume of 1518.3 ų per unit cell, arranged into three channels along the c axis with the centres at approximately (0, 0, 0), (1/3, 2/3, 4/5), and (2/3, 1/3, 1/2). No electron density greater than 0.63 e ų could be found in the area of the void, and so no definitive solvent molecule could be found. Since the electron count per void is 51 from SQUEEZE (Spek, 2003) results and, considering the symmetry of the voids, six water molecules per void may be reasonable; these voids are certainly large enough. The large voids also slightly increased the final Rvalue.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level for non-H atoms. Dotted lines indicate hydrogen bonds.
	Fig. 2. The one-dimensional chain along the c axis, constructed from O—H···O hydrogen bonding.
	Fig. 3. (a) The six-membered ring built from π–π stacking and C—H···π interactions(dashed lines), with centroid (0, 0, 0). Dotted lines indicate O—H···O interactions. H atoms not involved in hydogen bonding have been omitted. [Symmetry code: (i) y, −x + y, 2 − z]. (b) An ab projection of the crystal structure of (I), showing the [001] channels (color code for the online issue: Cu, green; N, blue; O, red; C and H, gray).

cis-Diaqua[(E)-2-(2-oxidobenzylideneamino-κO)benzoato-κO']copper(II)

Crystal data

[Cu(C14H9NO3)(H2O)2]	Dx = 1.517 Mg m^−3
Mr = 338.81	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1391 reflections
Hall symbol: -R 3	θ = 2.3–17.0°
a = 46.263 (2) Å	µ = 1.49 mm^−1
c = 7.2030 (7) Å	T = 298 K
V = 13350.9 (15) Å^3	Needles, dark-blue
Z = 36	0.24 × 0.09 × 0.01 mm
F(000) = 6228

Data collection

Bruker SMART 1K CCD area-detector diffractometer	5220 independent reflections
Radiation source: fine-focus sealed tube	3659 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −54→26
Tmin = 0.715, Tmax = 0.985	k = 0→55
5220 measured reflections	l = 0→8

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0697P)^2 + 7.9408P] where P = (Fo^2 + 2Fc^2)/3
5220 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 0.63 e Å^−3
0 restraints	Δρmin = −0.61 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.

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
Cu1	0.190904 (18)	0.222020 (19)	0.97110 (10)	0.0251 (2)
O1	0.16768 (10)	0.19144 (11)	0.7725 (5)	0.0314 (10)
O2	0.20649 (10)	0.24159 (10)	1.2173 (5)	0.0270 (10)
O3	0.24209 (11)	0.26156 (13)	1.4501 (6)	0.0452 (13)
O4	0.14922 (10)	0.22217 (11)	1.0221 (6)	0.0380 (12)
H4A	0.1359	0.2177	0.9311	0.046*
H4B	0.1484	0.2372	1.0862	0.046*
O5	0.21484 (11)	0.26883 (10)	0.7888 (6)	0.0380 (11)
H5A	0.2364	0.2791	0.7510	0.046*
H5B	0.2012	0.2604	0.6882	0.046*
N1	0.22883 (11)	0.21479 (12)	0.9458 (6)	0.0214 (11)
C1	0.16729 (16)	0.16270 (15)	0.7572 (8)	0.0277 (15)
C2	0.13990 (17)	0.13477 (18)	0.6774 (8)	0.0374 (17)
H2	0.1214	0.1362	0.6404	0.045*
C3	0.14000 (19)	0.10532 (17)	0.6530 (9)	0.0438 (19)
H3	0.1218	0.0873	0.5969	0.053*
C4	0.1666 (2)	0.10199 (17)	0.7100 (9)	0.0433 (19)
H4	0.1663	0.0819	0.6935	0.052*
C5	0.19330 (18)	0.12825 (16)	0.7903 (8)	0.0347 (17)
H5	0.2108	0.1255	0.8321	0.042*
C6	0.19551 (16)	0.15991 (16)	0.8131 (8)	0.0284 (15)
C7	0.22537 (16)	0.18693 (15)	0.8888 (8)	0.0271 (14)
H7	0.2439	0.1841	0.8975	0.033*
C8	0.26063 (14)	0.24078 (14)	1.0005 (8)	0.0235 (13)
C9	0.28862 (16)	0.24834 (16)	0.8928 (9)	0.0331 (16)
H9	0.2861	0.2362	0.7850	0.040*
C10	0.32002 (16)	0.27355 (17)	0.9435 (10)	0.0416 (18)
H10	0.3385	0.2782	0.8708	0.050*
C11	0.32391 (16)	0.29177 (17)	1.1018 (10)	0.0417 (18)
H11	0.3450	0.3086	1.1375	0.050*
C12	0.29639 (16)	0.28499 (17)	1.2072 (9)	0.0363 (16)
H12	0.2993	0.2975	1.3136	0.044*
C13	0.26453 (15)	0.26009 (15)	1.1598 (8)	0.0260 (14)
C14	0.23604 (16)	0.25394 (15)	1.2861 (8)	0.0274 (14)
Cu2	0.125236 (18)	0.237059 (19)	0.53174 (10)	0.0265 (2)
O6	0.10684 (10)	0.20564 (11)	0.7302 (5)	0.0344 (11)
O7	0.13891 (10)	0.25999 (10)	0.2926 (5)	0.0274 (10)
O8	0.13426 (14)	0.28805 (15)	0.0616 (6)	0.0645 (17)
O9	0.15570 (10)	0.22038 (11)	0.4856 (6)	0.0390 (12)
H9A	0.1603	0.2095	0.5632	0.047*
H9B	0.1700	0.2268	0.3992	0.047*
O10	0.16392 (12)	0.28662 (14)	0.7373 (6)	0.0585 (15)
H10A	0.1579	0.2912	0.8344	0.070*
H10B	0.1857	0.2986	0.7308	0.070*
N2	0.09147 (12)	0.24974 (13)	0.5646 (6)	0.0252 (12)
C15	0.07471 (16)	0.18645 (16)	0.7482 (8)	0.0294 (15)
C16	0.06151 (19)	0.15433 (17)	0.8259 (8)	0.0402 (18)
H16	0.0761	0.1469	0.8608	0.048*
C17	0.0279 (2)	0.13366 (17)	0.8517 (9)	0.0436 (19)
H17	0.0202	0.1126	0.9030	0.052*
C18	0.0051 (2)	0.14340 (18)	0.8032 (9)	0.047 (2)
H18	−0.0176	0.1291	0.8219	0.057*
C19	0.01661 (15)	0.17468 (17)	0.7265 (8)	0.0354 (17)
H19	0.0015	0.1816	0.6937	0.042*
C20	0.05135 (15)	0.19640 (16)	0.6975 (8)	0.0276 (15)
C21	0.06180 (15)	0.22910 (16)	0.6232 (7)	0.0255 (14)
H21	0.0459	0.2358	0.6170	0.031*
C22	0.09928 (15)	0.28254 (15)	0.5119 (8)	0.0265 (14)
C23	0.08879 (17)	0.30033 (18)	0.6227 (10)	0.0455 (19)
H23	0.0766	0.2906	0.7300	0.055*
C24	0.09639 (19)	0.3322 (2)	0.5743 (12)	0.060 (2)
H24	0.0892	0.3439	0.6478	0.072*
C25	0.11456 (18)	0.34640 (19)	0.4175 (13)	0.055 (2)
H25	0.1201	0.3680	0.3852	0.066*
C26	0.12476 (17)	0.32898 (18)	0.3072 (11)	0.0458 (19)
H26	0.1365	0.3388	0.1989	0.055*
C27	0.11800 (14)	0.29691 (15)	0.3530 (8)	0.0264 (14)
C28	0.13100 (15)	0.28052 (16)	0.2270 (8)	0.0306 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0258 (4)	0.0341 (5)	0.0223 (4)	0.0202 (4)	−0.0012 (3)	−0.0043 (3)
O1	0.040 (3)	0.038 (3)	0.024 (2)	0.025 (2)	−0.009 (2)	−0.010 (2)
O2	0.027 (2)	0.034 (3)	0.023 (2)	0.017 (2)	0.0033 (18)	−0.0045 (19)
O3	0.037 (3)	0.072 (4)	0.027 (3)	0.027 (3)	−0.005 (2)	−0.016 (2)
O4	0.032 (3)	0.059 (3)	0.035 (3)	0.032 (2)	−0.009 (2)	−0.016 (2)
O5	0.038 (3)	0.040 (3)	0.030 (3)	0.015 (2)	0.001 (2)	0.000 (2)
N1	0.021 (3)	0.026 (3)	0.021 (3)	0.015 (2)	0.003 (2)	−0.002 (2)
C1	0.039 (4)	0.031 (4)	0.012 (3)	0.016 (3)	0.006 (3)	−0.003 (3)
C2	0.043 (4)	0.049 (5)	0.018 (3)	0.021 (4)	−0.004 (3)	−0.005 (3)
C3	0.046 (5)	0.031 (4)	0.034 (4)	0.004 (4)	0.002 (3)	−0.012 (3)
C4	0.073 (6)	0.024 (4)	0.030 (4)	0.023 (4)	0.008 (4)	−0.002 (3)
C5	0.062 (5)	0.031 (4)	0.025 (3)	0.033 (4)	0.012 (3)	0.006 (3)
C6	0.035 (4)	0.035 (4)	0.016 (3)	0.019 (3)	0.003 (3)	−0.002 (3)
C7	0.033 (4)	0.036 (4)	0.020 (3)	0.023 (3)	0.006 (3)	0.002 (3)
C8	0.018 (3)	0.026 (3)	0.024 (3)	0.009 (3)	0.001 (3)	0.003 (3)
C9	0.033 (4)	0.038 (4)	0.033 (4)	0.022 (3)	0.007 (3)	0.003 (3)
C10	0.019 (4)	0.042 (4)	0.059 (5)	0.011 (3)	0.016 (3)	0.005 (4)
C11	0.023 (4)	0.029 (4)	0.062 (5)	0.005 (3)	0.000 (3)	−0.001 (4)
C12	0.033 (4)	0.041 (4)	0.040 (4)	0.021 (4)	−0.007 (3)	−0.013 (3)
C13	0.031 (4)	0.030 (4)	0.022 (3)	0.019 (3)	−0.001 (3)	0.006 (3)
C14	0.029 (4)	0.025 (4)	0.029 (4)	0.015 (3)	−0.003 (3)	−0.001 (3)
Cu2	0.0258 (4)	0.0380 (5)	0.0230 (4)	0.0214 (4)	0.0040 (3)	0.0041 (3)
O6	0.027 (3)	0.057 (3)	0.026 (2)	0.025 (2)	0.0041 (19)	0.013 (2)
O7	0.031 (2)	0.033 (3)	0.024 (2)	0.020 (2)	0.0059 (19)	0.0051 (19)
O8	0.092 (5)	0.111 (5)	0.032 (3)	0.082 (4)	0.021 (3)	0.026 (3)
O9	0.042 (3)	0.067 (3)	0.031 (3)	0.044 (3)	0.014 (2)	0.018 (2)
O10	0.052 (3)	0.105 (5)	0.032 (3)	0.049 (3)	0.014 (2)	0.008 (3)
N2	0.023 (3)	0.035 (3)	0.021 (3)	0.018 (3)	0.009 (2)	0.002 (2)
C15	0.033 (4)	0.039 (4)	0.016 (3)	0.019 (3)	0.004 (3)	−0.001 (3)
C16	0.054 (5)	0.040 (4)	0.027 (4)	0.023 (4)	0.002 (3)	0.007 (3)
C17	0.057 (5)	0.029 (4)	0.031 (4)	0.010 (4)	0.009 (4)	0.007 (3)
C18	0.050 (5)	0.040 (5)	0.031 (4)	0.007 (4)	0.004 (4)	−0.009 (3)
C19	0.023 (4)	0.049 (5)	0.019 (3)	0.006 (3)	0.002 (3)	−0.014 (3)
C20	0.031 (4)	0.041 (4)	0.013 (3)	0.020 (3)	0.000 (3)	−0.004 (3)
C21	0.026 (4)	0.043 (4)	0.017 (3)	0.024 (3)	−0.001 (3)	−0.004 (3)
C22	0.031 (4)	0.028 (4)	0.031 (4)	0.023 (3)	−0.010 (3)	−0.010 (3)
C23	0.040 (4)	0.038 (5)	0.052 (5)	0.015 (4)	0.011 (4)	−0.014 (4)
C24	0.051 (5)	0.046 (5)	0.089 (7)	0.028 (4)	0.008 (5)	−0.023 (5)
C25	0.038 (5)	0.031 (4)	0.103 (7)	0.022 (4)	0.005 (5)	0.004 (4)
C26	0.034 (4)	0.043 (5)	0.057 (5)	0.017 (4)	0.012 (4)	0.015 (4)
C27	0.018 (3)	0.031 (4)	0.032 (3)	0.014 (3)	0.003 (3)	0.003 (3)
C28	0.027 (4)	0.039 (4)	0.025 (4)	0.016 (3)	0.009 (3)	0.009 (3)

Geometric parameters (Å, º)

Cu1—O1	1.919 (4)	Cu2—O6	1.909 (4)
Cu1—N1	1.952 (4)	Cu2—N2	1.938 (5)
Cu1—O2	1.957 (4)	Cu2—O9	1.944 (4)
Cu1—O4	1.967 (4)	Cu2—O7	1.955 (4)
Cu1—O5	2.290 (4)	Cu2—O10	2.559 (5)
Cu1—Cu2	4.674 (1)	O6—C15	1.302 (7)
O1—C1	1.325 (7)	O7—C28	1.267 (7)
O2—C14	1.288 (7)	O8—C28	1.229 (7)
O3—C14	1.225 (7)	O9—H9A	0.8480
O4—H4A	0.8505	O9—H9B	0.8458
O4—H4B	0.8536	O10—H10A	0.8187
O5—H5A	0.9042	O10—H10B	0.8742
O5—H5B	0.9097	N2—C21	1.290 (7)
N1—C7	1.284 (7)	N2—C22	1.424 (7)
N1—C8	1.413 (7)	C15—C16	1.410 (9)
C1—C2	1.403 (9)	C15—C20	1.418 (8)
C1—C6	1.433 (9)	C16—C17	1.372 (10)
C2—C3	1.376 (9)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.382 (10)
C3—C4	1.379 (10)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.383 (9)
C4—C5	1.354 (9)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.422 (8)
C5—C6	1.426 (8)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.442 (8)
C6—C7	1.429 (9)	C21—H21	0.9300
C7—H7	0.9300	C22—C27	1.388 (8)
C8—C9	1.396 (8)	C22—C23	1.396 (8)
C8—C13	1.409 (8)	C23—C24	1.379 (10)
C9—C10	1.382 (9)	C23—H23	0.9300
C9—H9	0.9300	C24—C25	1.364 (11)
C10—C11	1.376 (9)	C24—H24	0.9300
C10—H10	0.9300	C25—C26	1.373 (10)
C11—C12	1.377 (9)	C25—H25	0.9300
C11—H11	0.9300	C26—C27	1.394 (9)
C12—C13	1.385 (8)	C26—H26	0.9300
C12—H12	0.9300	C27—C28	1.489 (8)
C13—C14	1.507 (8)
O1—Cu1—N1	91.36 (18)	O6—Cu2—N2	91.10 (19)
O1—Cu1—O2	163.21 (18)	O6—Cu2—O9	87.79 (17)
N1—Cu1—O2	90.52 (18)	N2—Cu2—O9	174.2 (2)
O1—Cu1—O4	87.33 (18)	O6—Cu2—O7	166.71 (19)
N1—Cu1—O4	170.10 (19)	N2—Cu2—O7	91.97 (18)
O2—Cu1—O4	87.96 (17)	O9—Cu2—O7	87.86 (17)
O1—Cu1—O5	95.59 (17)	O6—Cu2—O10	95.44 (17)
N1—Cu1—O5	93.28 (18)	N2—Cu2—O10	88.08 (18)
O2—Cu1—O5	100.96 (16)	O9—Cu2—O10	97.68 (17)
O4—Cu1—O5	96.62 (17)	O7—Cu2—O10	97.59 (16)
C1—O1—Cu1	121.6 (4)	C15—O6—Cu2	121.1 (4)
C14—O2—Cu1	128.1 (4)	C28—O7—Cu2	126.8 (4)
Cu1—O4—H4A	116.5	Cu2—O9—H9A	124.7
Cu1—O4—H4B	123.4	Cu2—O9—H9B	125.3
H4A—O4—H4B	107.0	H9A—O9—H9B	108.2
Cu1—O5—H5A	123.6	Cu2—O10—H10A	123.4
Cu1—O5—H5B	98.6	Cu2—O10—H10B	127.2
H5A—O5—H5B	109.2	H10A—O10—H10B	108.3
C7—N1—C8	119.8 (5)	C21—N2—C22	119.0 (5)
C7—N1—Cu1	122.0 (4)	C21—N2—Cu2	122.4 (4)
C8—N1—Cu1	118.1 (4)	C22—N2—Cu2	118.5 (4)
O1—C1—C2	120.7 (6)	O6—C15—C16	120.2 (6)
O1—C1—C6	120.8 (5)	O6—C15—C20	123.3 (6)
C2—C1—C6	118.4 (6)	C16—C15—C20	116.5 (6)
C3—C2—C1	121.0 (7)	C17—C16—C15	122.1 (7)
C3—C2—H2	119.5	C17—C16—H16	119.0
C1—C2—H2	119.5	C15—C16—H16	119.0
C2—C3—C4	121.2 (6)	C16—C17—C18	121.5 (7)
C2—C3—H3	119.4	C16—C17—H17	119.2
C4—C3—H3	119.4	C18—C17—H17	119.2
C5—C4—C3	119.4 (7)	C17—C18—C19	119.0 (7)
C5—C4—H4	120.3	C17—C18—H18	120.5
C3—C4—H4	120.3	C19—C18—H18	120.5
C4—C5—C6	122.4 (7)	C18—C19—C20	120.4 (7)
C4—C5—H5	118.8	C18—C19—H19	119.8
C6—C5—H5	118.8	C20—C19—H19	119.8
C5—C6—C7	119.0 (6)	C15—C20—C19	120.6 (6)
C5—C6—C1	117.4 (6)	C15—C20—C21	121.8 (6)
C7—C6—C1	123.7 (6)	C19—C20—C21	117.6 (6)
N1—C7—C6	125.5 (6)	N2—C21—C20	124.9 (5)
N1—C7—H7	117.2	N2—C21—H21	117.5
C6—C7—H7	117.2	C20—C21—H21	117.5
C9—C8—C13	119.0 (6)	C27—C22—C23	120.4 (6)
C9—C8—N1	119.9 (5)	C27—C22—N2	119.7 (5)
C13—C8—N1	121.0 (5)	C23—C22—N2	119.9 (6)
C10—C9—C8	121.1 (6)	C24—C23—C22	120.6 (7)
C10—C9—H9	119.4	C24—C23—H23	119.7
C8—C9—H9	119.4	C22—C23—H23	119.7
C11—C10—C9	119.8 (6)	C25—C24—C23	119.4 (7)
C11—C10—H10	120.1	C25—C24—H24	120.3
C9—C10—H10	120.1	C23—C24—H24	120.3
C10—C11—C12	119.7 (6)	C24—C25—C26	120.4 (7)
C10—C11—H11	120.2	C24—C25—H25	119.8
C12—C11—H11	120.2	C26—C25—H25	119.8
C11—C12—C13	122.1 (6)	C25—C26—C27	121.9 (7)
C11—C12—H12	118.9	C25—C26—H26	119.1
C13—C12—H12	118.9	C27—C26—H26	119.1
C12—C13—C8	118.3 (6)	C22—C27—C26	117.3 (6)
C12—C13—C14	118.3 (5)	C22—C27—C28	125.0 (5)
C8—C13—C14	123.3 (5)	C26—C27—C28	117.7 (6)
O3—C14—O2	122.5 (6)	O8—C28—O7	122.2 (6)
O3—C14—C13	118.4 (6)	O8—C28—C27	118.0 (6)
O2—C14—C13	119.0 (5)	O7—C28—C27	119.7 (5)
N1—Cu1—O1—C1	42.3 (4)	N2—Cu2—O6—C15	42.2 (5)
O2—Cu1—O1—C1	−54.0 (8)	O9—Cu2—O6—C15	−132.1 (5)
O4—Cu1—O1—C1	−127.8 (4)	O7—Cu2—O6—C15	−61.1 (9)
O5—Cu1—O1—C1	135.8 (4)	O10—Cu2—O6—C15	130.4 (4)
O1—Cu1—O2—C14	116.5 (7)	O6—Cu2—O7—C28	116.2 (8)
N1—Cu1—O2—C14	20.0 (5)	N2—Cu2—O7—C28	12.9 (5)
O4—Cu1—O2—C14	−169.8 (5)	O9—Cu2—O7—C28	−172.9 (5)
O5—Cu1—O2—C14	−73.4 (5)	O10—Cu2—O7—C28	−75.4 (5)
O1—Cu1—N1—C7	−30.0 (5)	O6—Cu2—N2—C21	−31.0 (5)
O2—Cu1—N1—C7	133.3 (5)	O7—Cu2—N2—C21	136.1 (5)
O5—Cu1—N1—C7	−125.7 (5)	O10—Cu2—N2—C21	−126.4 (5)
O1—Cu1—N1—C8	152.9 (4)	O6—Cu2—N2—C22	152.6 (4)
O2—Cu1—N1—C8	−43.8 (4)	O7—Cu2—N2—C22	−40.3 (4)
O5—Cu1—N1—C8	57.2 (4)	O10—Cu2—N2—C22	57.2 (4)
Cu1—O1—C1—C2	149.6 (4)	Cu2—O6—C15—C16	148.9 (5)
Cu1—O1—C1—C6	−33.6 (7)	Cu2—O6—C15—C20	−32.9 (7)
O1—C1—C2—C3	176.9 (6)	O6—C15—C16—C17	178.3 (6)
C6—C1—C2—C3	0.0 (9)	C20—C15—C16—C17	−0.1 (9)
C1—C2—C3—C4	1.6 (10)	C15—C16—C17—C18	−0.3 (10)
C2—C3—C4—C5	−0.5 (10)	C16—C17—C18—C19	0.2 (10)
C3—C4—C5—C6	−2.1 (10)	C17—C18—C19—C20	0.2 (9)
C4—C5—C6—C7	−176.2 (6)	O6—C15—C20—C19	−177.9 (5)
C4—C5—C6—C1	3.6 (9)	C16—C15—C20—C19	0.5 (8)
O1—C1—C6—C5	−179.3 (5)	O6—C15—C20—C21	−0.7 (9)
C2—C1—C6—C5	−2.4 (8)	C16—C15—C20—C21	177.6 (5)
O1—C1—C6—C7	0.4 (9)	C18—C19—C20—C15	−0.6 (9)
C2—C1—C6—C7	177.3 (6)	C18—C19—C20—C21	−177.8 (6)
C8—N1—C7—C6	−173.7 (5)	C22—N2—C21—C20	−173.7 (5)
Cu1—N1—C7—C6	9.3 (8)	Cu2—N2—C21—C20	9.9 (8)
C5—C6—C7—N1	−167.6 (6)	C15—C20—C21—N2	13.2 (9)
C1—C6—C7—N1	12.7 (9)	C19—C20—C21—N2	−169.6 (5)
C7—N1—C8—C9	44.1 (8)	C21—N2—C22—C27	−137.8 (6)
Cu1—N1—C8—C9	−138.7 (5)	Cu2—N2—C22—C27	38.8 (7)
C7—N1—C8—C13	−138.0 (6)	C21—N2—C22—C23	43.8 (8)
Cu1—N1—C8—C13	39.1 (7)	Cu2—N2—C22—C23	−139.7 (5)
C13—C8—C9—C10	2.3 (9)	C27—C22—C23—C24	1.0 (10)
N1—C8—C9—C10	−179.8 (6)	N2—C22—C23—C24	179.5 (6)
C8—C9—C10—C11	−0.5 (11)	C22—C23—C24—C25	−0.5 (12)
C9—C10—C11—C12	−0.8 (11)	C23—C24—C25—C26	1.0 (12)
C10—C11—C12—C13	0.3 (11)	C24—C25—C26—C27	−2.0 (12)
C11—C12—C13—C8	1.5 (10)	C23—C22—C27—C26	−1.9 (9)
C11—C12—C13—C14	178.5 (6)	N2—C22—C27—C26	179.6 (6)
C9—C8—C13—C12	−2.8 (9)	C23—C22—C27—C28	178.8 (6)
N1—C8—C13—C12	179.4 (5)	N2—C22—C27—C28	0.4 (9)
C9—C8—C13—C14	−179.7 (5)	C25—C26—C27—C22	2.5 (10)
N1—C8—C13—C14	2.5 (9)	C25—C26—C27—C28	−178.3 (6)
Cu1—O2—C14—O3	−170.2 (5)	Cu2—O7—C28—O8	−163.3 (5)
Cu1—O2—C14—C13	11.4 (8)	Cu2—O7—C28—C27	18.1 (8)
C12—C13—C14—O3	−25.6 (9)	C22—C27—C28—O8	149.7 (7)
C8—C13—C14—O3	151.3 (6)	C26—C27—C28—O8	−29.5 (9)
C12—C13—C14—O2	152.9 (6)	C22—C27—C28—O7	−31.7 (9)
C8—C13—C14—O2	−30.2 (9)	C26—C27—C28—O7	149.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10B···O5	0.87	2.40	2.882 (7)	115
O10—H10A···O8^i	0.82	1.93	2.727 (6)	163
O9—H9B···O2^ii	0.85	1.97	2.813 (5)	174
O9—H9A···O1	0.85	1.84	2.667 (6)	166
O5—H5A···O3^ii	0.90	2.37	2.842 (6)	112
O4—H4B···O7^i	0.85	1.99	2.814 (6)	161
O4—H4A···O6	0.85	1.86	2.711 (6)	177
C23—H23···Cg3^iii	0.93	2.87	3.618 (9)	139

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