catena-Poly[[μ-hexa­nedioato-1κO¹:2κO⁶-bis­[aqua­(5-carboxy­penta­noato-κO)copper(II)]]-di-μ-4,4′-bipyridine-1κN:1′κN′;2κN:2′κN′]

In the title compound, [Cu₂(C₆H₈O₄)(C₆H₉O₄)₂(C₁₀H₈N₂)₂(H₂O)₂]_n, the square-pyramidally coordinated Cu atoms are bridged by both 4,4-bipyridine and adipate ligands into ladder-­like chains, with exo-orientated 5-carboxypentan­oate ligands pendant from both side rails. Half of the adipate ligand is related to the other half by inversion symmetry. Inter­chain O—H...O hydrogen bonds from the aqua ligands to the carbonyl O atoms of the 5-carboxy­penta­noate ligands are responsible for the formation of two-dimensional grid-like (4,4)-networks, which complete a twofold inter­penetration.

S1. Comment

In recent years, interest in the utilization of aliphatic dicarboxylic acids for the rational design and synthesis of coordination polymers grown rapidly, due to their fascinating network topologies and specific properties (Rao et al., 2004; Kitagawa et al., 2004). The aliphatic α,ω-dicarboxylate ligands have been recognized as important flexible spacers due to their conformational and coordination versatility, and they tend to bridge transition metal cations to form coordination polymers with low dimensionality (Zheng & Xie, 2004; Zheng & Sun, 2003; Zheng & Kong, 2002). However, even the high-dimensional α,ω-dicarboxylate coordination polymers normally exhibit little porosity (Rao et al., 2004). To avoid such drawbacks, our recent research has been intensively focused on the construction of porous α,ω-dicarboxylate coordination polymers by the introduction of the rigid 4,4'-bipyridine molecule as an ancillary ligand to co-bridge metal atoms into supramolecular architectures (Zheng & Ying, 2005; Zheng et al., 2004; Zheng & Kong, 2003). Among these coordination polymers, the transition metal atoms are bridged by α,ω-dicarboxylate anions to generate square clusters (Li et al., 1997, 2000), polymeric chains (Zheng & Kong, 2003; Rather & Zaworotko, 2003), ribbon-like chains (Zheng & Ying, 2005; Zheng et al., 2004) and layers (Zheng & Ying, 2005; Zheng et al., 2004; Mukherjee et al., 2003), and these structural motifs are further linked by 4,4'-bipyridine ligands into layers and three-dimensional frameworks with aperture sizes dependent on the length of dicarboxylate ligand used. In the cases of the adipate compounds, the three-dimensional frameworks have so much larger apertures that they form a twofold interpenetration with a topology identical to that of the well known cluster compound Nb₆F₁₅ (Batten & Robson, 1998). In this paper, we present a the title novel coordination polymer, (I), where the Cu atoms are co-bridged by adipate anions and 4,4'-bipyridine ligands into one-dimensional ladder-like chains.

The asymmetric unit of (I) consists of one Cu^II cation, one 4,4'-bipyridine molecule (bpy), one aqua ligand, one 5-carboxypentanoate anion and one half of an adipate anion residing on a crystallographic inversion centre. As depicted in Fig. 1, the Cu atoms in the title compound are each square-pyramidally coordinated by two pyridyl N atoms, N1 and N2ⁱ [symmetry code: (i) x, y, z + 1] of different bpy ligands and by three O atoms (O7, O3 and O1) belonging to one aqua ligand, one 5-carboxypentanoate anion and an adipate anion, with the aqua ligand at the apical site. The Cu atom is shifted by 0.151 (1) Å toward the apical O7 atom from the equatorial plane defined by the atoms O1, N1, O3 and N2ⁱ. The two trans Cu—N bond lengths have the same value of 2.030 (2) Å (Table 1), slightly longer than either of the two trans Cu—O bonds, of 1.954 (2) and 1.987 (1) Å. The apical Cu—O bond length is 2.365 (2) Å.

Fig. 2 demonstrates that the pentacoordinated Cu atoms are bridged by the adipate anions into dimers, which are further linked by bpy ligands to generate ladder-like polymeric chains with the exo-orientated 5-carboxypentanoate ligands perpendicularly pendant on both side rails. These polymeric chains extend infinitely along the [001] direction. They approach one another and the aqua ligands of one chain form interchain hydrogen bonds, with an R₂²(22) graph set (Etter, 1991; Etter et al., 1990), to the carbonyl O atoms of neighbouring adipate anions, with O7···O5ⁱⁱ = 2.797 (2) Å and O7—H···O5ⁱⁱ = 171 (3)° [symmetry code: (ii) −x, −y + 1, −z + 1; Fig. 2, Table 2], resulting in two-dimensional grid-like (4,4) layers (Hagrman et al., 1999). The layers are orientated parallel to (110) and (110), respectively, and complete a twofold interpenetration, as illustrated in Fig. 3 (Batten & Robson, 1998), in such a way that the R₂²(22) hydrogen-bonded rings of one layer are clamped between the adipate rungs of the interpenetrating layers. The interpenetrating layers are held together by the relatively strong interlayer hydrogen bonds from the carboxyl O6 groups to the uncoordinating carboxylate O2 atoms, with O6···O2ⁱⁱⁱ = 2.593 (3) Å and O6—H···O2ⁱⁱⁱ = 168 (3)° [symmetry code: (iii) −x − 1/2, y − 1/2, −z + 1/2]. Additionally, the aqua ligand forms a relatively strong intrachain hydrogen bond to the uncoordinated carboxylate O4 atom of the pendant 5-carboxypentanoate anion [O7···O4 = 2.647 (2) Å and O7—H···O4 − 164 (3)°].

Both adipate and 5-carboxypenanoate anions exhibit normal geometry (Zheng & Ying, 2005; Zheng et al., 2004; Mukherjee et al., 2003; Ying et al., 2004) and, as expected, the C—O bond distances to the coordinated O atoms are significantly longer than those to the uncoordinated ones. The C19—O5 distance of 1.211 (3) Å is considerabley shorter than the C19—O6 distance of 1.305 (3) Å, corresponding to double-bond character. The bpy ligands are found to be twisted around the central C5—C6 bond, with a dihedral angle of 45.0 (1)° between the two pyridyl components. The N1-containing pyridyl rings are oriented so as to favour formation of weak C—H···O hydrogen bonds (Table 2) and the orientation of the N2-containing pyridyl plane may be due to steric effects from the aqua ligand (Fig. 1).

S2. Experimental

Dropwise addition of Na₂CO₃ (1.0 M, 0.50 ml) to an aqueous solution (5.0 ml) of CuSO₄·5H₂O (0.075 g, 0.30 mmol) yielded a pale-blue precipitate, which was centrifuged and washed several times with doubly distilled water until there were no SO₄²⁻ anions in supernatant. The fresh precipitate was then added to a solution of 4,4'-bipyridine dehydrate? (0.058 g, 0.30 mmol) and adipic acid (0.044 g, 0.30 mol) in a water–methanol mixture (20 ml, 1:1 v/v) and stirred vigorously for 30 min. The suspension which formed was filtered and slow evaporation afforded a small number of blue crystals of (I) in the nearly colourless filtrate (pH 4.56).

S3. Refinement

All H atoms associated with C atoms were positioned gemoetrically and refined using a riding model, with C—H = 0.93 and 0.97 Å, while the H atoms of the aqua ligands and the O6 carboxyl group were located in a difference Fourier synthesis, with O—H distances refined. All U_iso(H) were refined freely. [Please check added text]

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the coordination environment around the Cu atoms in (I). Displacement ellipsoids are drawn at the 45% probability level. H atoms bonded to C atoms have been omitted for clarity. [Symmetry codes: (i) x, y, 1 + z; (A) ? Please provide missing symmetry code]
	Fig. 2. The grid-like (4,4) layer generated from Cu^II ions co-bridged by 4,4-bipyridine, adipate anions and 5-carboxypentanoate anions in (I). Dashed lines indicate hydrogen bonds. H atoms bonded to C atoms have been omitted for clarity.
	Fig. 3. The topology of the twofold interpenetration of the grid-like (4,4) layers in (I). Dark and light grey rods represent adipate anions and 4,4-bipyridine ligands, respectively, and dashed grey rods represent the 5-carboxypentanoate pairs.

catena-Poly[µ-hexanedioato-1κO¹:2κO⁶-bis[[[aqua(5-carboxypentanoato- κO]-di-µ-4,4'-bipyridine-1κN:1'κN';2κN:2'κN']copper(II)]]

Crystal data

[Cu2(C6H8O4)(C6H9O4)2(C10H8N2)2(H2O)2]	F(000) = 944
Mr = 454.94	Dx = 1.550 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.885 (2) Å	θ = 5.0–12.5°
b = 16.216 (3) Å	µ = 1.17 mm^−1
c = 11.108 (2) Å	T = 296 K
β = 96.04 (3)°	Block, blue
V = 1949.8 (6) Å^3	0.49 × 0.31 × 0.22 mm
Z = 4

Data collection

Bruker P4 diffractometer	3906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 27.5°, θmin = 2.2°
θ/2θ scans	h = −1→14
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −21→1
Tmin = 0.651, Tmax = 0.776	l = −14→14
6298 measured reflections	3 standard reflections every 97 reflections
4483 independent reflections	intensity decay: no

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0547P)^2 + 0.5023P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.002
4483 reflections	Δρmax = 0.73 e Å^−3
296 parameters	Δρmin = −0.49 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0132 (9)

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
Cu	0.23581 (2)	0.711699 (14)	0.419064 (19)	0.02090 (10)
N1	0.24324 (16)	0.71467 (10)	0.23727 (15)	0.0238 (3)
N2	0.22480 (16)	0.71660 (9)	−0.39977 (15)	0.0228 (3)
C1	0.3200 (2)	0.66799 (14)	0.17995 (17)	0.0305 (4)
H1	0.3760	0.6342	0.2256	0.035 (6)*
C2	0.3191 (2)	0.66816 (14)	0.05521 (18)	0.0312 (4)
H2	0.3753	0.6360	0.0185	0.045 (7)*
C3	0.1641 (2)	0.76332 (15)	0.17032 (18)	0.0330 (5)
H3	0.1129	0.7977	0.2097	0.042 (7)*
C4	0.1548 (2)	0.76502 (15)	0.04541 (18)	0.0342 (5)
H4	0.0961	0.7982	0.0019	0.036 (7)*
C5	0.23435 (19)	0.71638 (12)	−0.01441 (17)	0.0246 (4)
C6	0.22908 (19)	0.71716 (12)	−0.14841 (17)	0.0239 (4)
C7	0.33771 (19)	0.72087 (13)	−0.20389 (18)	0.0277 (4)
H7	0.4139	0.7227	−0.1574	0.046 (8)*
C8	0.33119 (19)	0.72177 (13)	−0.32814 (18)	0.0269 (4)
H8	0.4043	0.7262	−0.3641	0.035 (7)*
C9	0.11799 (19)	0.71443 (12)	−0.22254 (18)	0.0272 (4)
H9	0.0433	0.7137	−0.1889	0.028 (6)*
C10	0.11966 (18)	0.71278 (12)	−0.34679 (18)	0.0268 (4)
H10	0.0450	0.7089	−0.3956	0.026 (6)*
O1	0.34800 (13)	0.80855 (9)	0.43679 (13)	0.0265 (3)
O2	0.16287 (14)	0.86529 (10)	0.42026 (15)	0.0368 (4)
C11	0.27789 (19)	0.87150 (12)	0.43483 (16)	0.0259 (4)
C12	0.3372 (2)	0.95559 (13)	0.4495 (2)	0.0351 (5)
H12A	0.2941	0.9870	0.5063	0.055 (8)*
H12B	0.3252	0.9838	0.3721	0.036 (7)*
C13	0.4741 (2)	0.95649 (12)	0.4930 (2)	0.0327 (5)
H13A	0.5186	0.9265	0.4357	0.047 (7)*
H13B	0.4874	0.9283	0.5703	0.040 (7)*
O3	0.09387 (14)	0.63738 (10)	0.39787 (13)	0.0332 (3)
O4	0.20253 (16)	0.52739 (12)	0.3534 (2)	0.0543 (5)
C14	0.1045 (2)	0.56247 (14)	0.36495 (19)	0.0323 (5)
C15	−0.0131 (2)	0.51281 (14)	0.3385 (2)	0.0338 (5)
H15A	−0.0091	0.4843	0.2622	0.045 (7)*
H15B	−0.0143	0.4710	0.4008	0.045 (7)*
C16	−0.1341 (2)	0.55865 (15)	0.3311 (2)	0.0399 (5)
H16A	−0.1349	0.6012	0.2696	0.053 (8)*
H16B	−0.1422	0.5853	0.4081	0.017 (5)*
C17	−0.2428 (2)	0.50080 (14)	0.3004 (2)	0.0371 (5)
H17A	−0.2320	0.4726	0.2252	0.058 (9)*
H17B	−0.2426	0.4594	0.3635	0.053 (8)*
C18	−0.3665 (2)	0.54383 (16)	0.2874 (3)	0.0510 (7)
H18A	−0.3799	0.5706	0.3630	0.079 (12)*
H18B	−0.3676	0.5859	0.2252	0.059 (9)*
C19	−0.4684 (2)	0.48228 (14)	0.2539 (2)	0.0368 (5)
O5	−0.50146 (17)	0.43173 (12)	0.32393 (16)	0.0473 (4)
O6	−0.5141 (2)	0.48663 (13)	0.14061 (19)	0.0534 (5)
H6	−0.563 (3)	0.457 (2)	0.127 (3)	0.062 (11)*
O7	0.39705 (16)	0.61344 (11)	0.44463 (15)	0.0338 (3)
H7A	0.345 (3)	0.5789 (19)	0.421 (3)	0.042 (8)*
H7B	0.421 (3)	0.596 (2)	0.508 (3)	0.052 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.02340 (15)	0.02547 (15)	0.01382 (14)	−0.00576 (8)	0.00191 (9)	−0.00156 (8)
N1	0.0250 (8)	0.0319 (9)	0.0144 (7)	−0.0013 (6)	0.0015 (6)	−0.0015 (6)
N2	0.0272 (8)	0.0251 (8)	0.0161 (7)	−0.0020 (6)	0.0026 (6)	−0.0005 (6)
C1	0.0353 (11)	0.0365 (11)	0.0198 (9)	0.0101 (9)	0.0035 (8)	0.0038 (8)
C2	0.0352 (11)	0.0380 (12)	0.0209 (9)	0.0100 (9)	0.0051 (8)	0.0004 (8)
C3	0.0343 (11)	0.0460 (12)	0.0193 (9)	0.0118 (9)	0.0049 (8)	−0.0016 (9)
C4	0.0366 (11)	0.0467 (12)	0.0190 (9)	0.0151 (10)	0.0022 (8)	0.0007 (9)
C5	0.0290 (10)	0.0284 (10)	0.0167 (9)	−0.0014 (7)	0.0042 (7)	−0.0006 (7)
C6	0.0293 (10)	0.0255 (10)	0.0168 (9)	0.0022 (7)	0.0027 (7)	−0.0009 (7)
C7	0.0273 (10)	0.0372 (11)	0.0185 (9)	−0.0023 (8)	0.0019 (7)	−0.0002 (7)
C8	0.0247 (9)	0.0356 (11)	0.0205 (9)	−0.0037 (8)	0.0032 (7)	−0.0011 (7)
C9	0.0253 (9)	0.0358 (11)	0.0209 (9)	0.0014 (8)	0.0052 (7)	0.0007 (7)
C10	0.0252 (9)	0.0345 (11)	0.0202 (9)	0.0006 (7)	0.0000 (7)	0.0003 (7)
O1	0.0296 (7)	0.0247 (7)	0.0252 (7)	−0.0056 (6)	0.0027 (5)	−0.0002 (6)
O2	0.0314 (8)	0.0348 (8)	0.0424 (9)	−0.0032 (6)	−0.0040 (6)	0.0013 (7)
C11	0.0334 (10)	0.0268 (10)	0.0170 (8)	−0.0042 (8)	−0.0002 (7)	0.0018 (7)
C12	0.0401 (12)	0.0244 (10)	0.0401 (12)	−0.0048 (9)	0.0010 (9)	−0.0006 (9)
C13	0.0410 (12)	0.0230 (10)	0.0333 (11)	−0.0077 (9)	0.0008 (9)	−0.0016 (8)
O3	0.0308 (7)	0.0407 (9)	0.0287 (7)	−0.0148 (6)	0.0062 (6)	−0.0085 (6)
O4	0.0335 (9)	0.0503 (11)	0.0779 (14)	−0.0063 (8)	0.0009 (9)	−0.0199 (10)
C14	0.0331 (11)	0.0381 (12)	0.0253 (10)	−0.0138 (9)	0.0012 (8)	−0.0039 (8)
C15	0.0338 (11)	0.0348 (11)	0.0324 (11)	−0.0130 (9)	0.0013 (8)	−0.0041 (9)
C16	0.0351 (12)	0.0331 (12)	0.0503 (14)	−0.0101 (9)	−0.0006 (10)	−0.0053 (10)
C17	0.0323 (11)	0.0300 (11)	0.0482 (13)	−0.0068 (9)	0.0002 (10)	−0.0023 (10)
C18	0.0330 (12)	0.0333 (13)	0.084 (2)	−0.0047 (10)	−0.0066 (12)	−0.0067 (13)
C19	0.0265 (10)	0.0290 (11)	0.0535 (14)	0.0020 (8)	−0.0029 (9)	−0.0005 (10)
O5	0.0452 (10)	0.0477 (10)	0.0457 (10)	−0.0117 (8)	−0.0100 (8)	0.0056 (8)
O6	0.0519 (12)	0.0509 (12)	0.0538 (12)	−0.0169 (10)	−0.0104 (9)	0.0141 (9)
O7	0.0350 (8)	0.0364 (9)	0.0294 (8)	−0.0020 (7)	0.0011 (6)	0.0019 (7)

Geometric parameters (Å, º)

Cu—O3	1.9541 (15)	O2—C11	1.249 (3)
Cu—O1	1.9865 (14)	C11—C12	1.510 (3)
Cu—N1	2.0300 (17)	C12—C13	1.518 (3)
Cu—N2^i	2.0300 (17)	C12—H12A	0.9700
Cu—O7	2.3653 (17)	C12—H12B	0.9700
N1—C3	1.335 (3)	C13—C13^iii	1.521 (4)
N1—C1	1.337 (3)	C13—H13A	0.9700
N2—C8	1.337 (3)	C13—H13B	0.9700
N2—C10	1.342 (3)	O3—C14	1.277 (3)
N2—Cu^ii	2.0300 (17)	O4—C14	1.228 (3)
C1—C2	1.385 (3)	C14—C15	1.515 (3)
C1—H1	0.9300	C15—C16	1.507 (3)
C2—C5	1.382 (3)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C4	1.381 (3)	C16—C17	1.520 (3)
C3—H3	0.9300	C16—H16A	0.9700
C4—C5	1.391 (3)	C16—H16B	0.9700
C4—H4	0.9300	C17—C18	1.511 (3)
C5—C6	1.484 (3)	C17—H17A	0.9700
C6—C9	1.390 (3)	C17—H17B	0.9700
C6—C7	1.391 (3)	C18—C19	1.509 (3)
C7—C8	1.375 (3)	C18—H18A	0.9700
C7—H7	0.9300	C18—H18B	0.9700
C8—H8	0.9300	C19—O5	1.211 (3)
C9—C10	1.383 (3)	C19—O6	1.305 (3)
C9—H9	0.9300	O6—H6	0.72 (4)
C10—H10	0.9300	O7—H7A	0.82 (3)
O1—C11	1.273 (3)	O7—H7B	0.78 (3)
O3—Cu—O1	165.83 (7)	O1—C11—C12	118.24 (18)
O3—Cu—N1	90.49 (7)	C11—C12—C13	115.94 (18)
O1—Cu—N1	89.51 (6)	C11—C12—H12A	108.3
O3—Cu—N2^i	90.87 (7)	C13—C12—H12A	108.3
O1—Cu—N2^i	88.31 (6)	C11—C12—H12B	108.3
N1—Cu—N2^i	176.23 (6)	C13—C12—H12B	108.3
O3—Cu—O7	99.57 (7)	H12A—C12—H12B	107.4
O1—Cu—O7	94.59 (6)	C12—C13—C13^iii	112.5 (2)
N1—Cu—O7	91.64 (7)	C12—C13—H13A	109.1
N2^i—Cu—O7	91.59 (7)	C13^iii—C13—H13A	109.1
C3—N1—C1	117.90 (17)	C12—C13—H13B	109.1
C3—N1—Cu	118.51 (14)	C13^iii—C13—H13B	109.1
C1—N1—Cu	123.54 (13)	H13A—C13—H13B	107.8
C8—N2—C10	117.85 (17)	C14—O3—Cu	121.78 (14)
C8—N2—Cu^ii	117.04 (14)	O4—C14—O3	125.2 (2)
C10—N2—Cu^ii	125.09 (13)	O4—C14—C15	117.4 (2)
N1—C1—C2	122.46 (19)	O3—C14—C15	117.4 (2)
N1—C1—H1	118.8	C16—C15—C14	117.7 (2)
C2—C1—H1	118.8	C16—C15—H15A	107.9
C5—C2—C1	119.65 (19)	C14—C15—H15A	107.9
C5—C2—H2	120.2	C16—C15—H15B	107.9
C1—C2—H2	120.2	C14—C15—H15B	107.9
N1—C3—C4	123.13 (19)	H15A—C15—H15B	107.2
N1—C3—H3	118.4	C15—C16—C17	111.26 (19)
C4—C3—H3	118.4	C15—C16—H16A	109.4
C3—C4—C5	119.0 (2)	C17—C16—H16A	109.4
C3—C4—H4	120.5	C15—C16—H16B	109.4
C5—C4—H4	120.5	C17—C16—H16B	109.4
C2—C5—C4	117.78 (19)	H16A—C16—H16B	108.0
C2—C5—C6	121.28 (18)	C18—C17—C16	113.7 (2)
C4—C5—C6	120.94 (19)	C18—C17—H17A	108.8
C9—C6—C7	117.77 (18)	C16—C17—H17A	108.8
C9—C6—C5	122.24 (19)	C18—C17—H17B	108.8
C7—C6—C5	120.00 (19)	C16—C17—H17B	108.8
C8—C7—C6	119.26 (19)	H17A—C17—H17B	107.7
C8—C7—H7	120.4	C19—C18—C17	110.0 (2)
C6—C7—H7	120.4	C19—C18—H18A	109.7
N2—C8—C7	123.15 (19)	C17—C18—H18A	109.7
N2—C8—H8	118.4	C19—C18—H18B	109.7
C7—C8—H8	118.4	C17—C18—H18B	109.7
C10—C9—C6	119.34 (19)	H18A—C18—H18B	108.2
C10—C9—H9	120.3	O5—C19—O6	123.2 (2)
C6—C9—H9	120.3	O5—C19—C18	123.3 (2)
N2—C10—C9	122.56 (18)	O6—C19—C18	113.4 (2)
N2—C10—H10	118.7	C19—O6—H6	112 (3)
C9—C10—H10	118.7	Cu—O7—H7A	87 (2)
C11—O1—Cu	105.72 (13)	Cu—O7—H7B	122 (2)
O2—C11—O1	121.89 (19)	H7A—O7—H7B	101 (3)
O2—C11—C12	119.87 (19)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O2^iv	0.72 (3)	1.88 (3)	2.593 (3)	168 (3)
O7—H7A···O4	0.82 (3)	1.85 (3)	2.647 (2)	164 (3)
O7—H7B···O5^v	0.78 (3)	2.03 (3)	2.797 (2)	171 (3)
C1—H1···07	0.93	2.44	3.100 (3)	127
C3—H3···O2	0.93	2.59	3.233 (3)	127
C3—H3···O5^vi	0.93	2.50	3.259 (3)	139
C12—H12B···O4^vii	0.97	2.59	3.544 (3)	168

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