Tetra­kis([mu]-benzoato-[kappa]²O:O)bis­{[4-(dimethyl­amino)pyridine-[kappa]N¹]copper(II)}

The title compound, [Cu₂(C₇H₅O₂)₄(C₇H₁₀N₂)₂], is a crystallographically centrosymmetric binuclear complex, with Cu atoms [Cu...Cu = 2.6982 (4) Å] bridged by four benzoate ligands. Each of the Cu atoms in this bunuclear copper(II) acetate hydrate analogue is present in an approximately square-pyramidal environment, with four O atoms in a plane and the pyridine N atom at the apical site. Selected geometric parameters are compared with values for related tetra­benzoate complexes of copper(II).

S1. Comment

The N-heteroaromatic ligand N,N-dimethyl-4-aminopyridine (DMAP) finds use as a homogeneous catalyst in cellulose acylation in the synthesis of biodegradable plastics (Satgé et al., 2004). DMAP is also known for its active participation with transition metal complexes to exhibit luminescence properties (Araki et al., 2005). Our interest in copper(II) carboxylates with DMAP evolves from their catalytic activity. Moreover, carboxylic acid complexes of copper(II) have properties of special interest in the fields of biology and magnetism (Cotton et al., 1999). In particular, the dimeric copper(II) carboxylates [Cu₂(RCOO)₄L₂] are found to be antiferromagnetic and their magneto–structural correlation has been studied extensively (Kawata et al., 1992).

The title compound, [Cu₂(µ-C₆H₅CO₂)₄(DMAP)₂], (I), was previously synthesized by reacting metallic copper with dibenzoyl peroxide and N,N-dimethyl-4-aminopyridine (Zhang et al., 2003). The molecular structure of (I) as determined by us is analogous to that of copper(II) acetate hydrate and very similar to the structure reported by Zhang et al. (2003). It has a paddle-wheel type dimeric structure (Fig. 1) with an inversion centre located between the Cu ions. Each Cu atom is five-coordinate: the four equatorial O atoms belong to four bridging carboxyl groups and the N atom at the apical position is the pyridyl N atom of the DMAP ligand. The Cu—O bond lengths are ca 1.97 Å, but the Cu1—N1 distance is longer [2.141 (1) Å]. The Cu···Cu distance of 2.6982 (4) Å in (I) is shorter than the corresponding distances of 2.711 (1) Å in [Cu₂(C₆H₅COO)₄(2,6-diaminopyridine)₂]·2CH₃CN (Lah et al., 2001) and 2.723 (1) Å in [Cu₂(C₆H₅COO)₄(2-amino-6-methylpyridine)₂] (Kozlevčar et al., 2004), but longer than those in [Cu₂(C₆H₅COO)₄(caffeine)]₂ [2.647 (1) Å; Kawata et al., 1992], [Cu₂(C₆H₅COO)₄(4-ethylpyridine)₂] [2.6714 (6) Å; Das et al., 2007], [Cu₂(C₆H₅COO)₄(N,N-diethylnicotinamide)₂] [2.613 (1) Å; Hökelek et al., 1995], [Cu₂(C₆H₅COO)₄(pyridine)₂] [2.681 (1) Å; Speier & Fulop, 1989] and [Cu₂(C₆H₅OO)₄(urea)₂] [2.633 (2) Å; Leban et al., 1997]. However, it is only marginally longer than the distance found previously for compound (I) [2.6976 (9) Å; Zhang et al., 2003].

Based on structural data available in the Cambridge Structural Database (CSD, Version?; Allen, 2002), it has previously been observed (Sundberg et al., 1996) that for dimeric copper(II) acetate-type complexes there is a relationship between the Cu···Cu separation and the distance by which the central Cu atom moves away from the least-squares plane of the four coordinated O atoms. On the basis of data available for 123 such complexes, the authors found that longer the Cu···Cu distance within the dimer, the greater would be the deviation of the Cu atom from the mean O₄ plane. We have tabulated some available data for complexes of the type [Cu₂(C₆H₅COO)₄L₂] (L = pyridine or a substituted pyridine) in Table 2, with a view to seeing how well the earlier conclusions hold true for the tetrabenzoates of copper(II). As can be seen from the data, there are several compounds for which there is no correlation of the above nature. On the other hand, it is observed from the tabulated data that whenever there are substituents on the 2- (and/or 6-) position of the axial pyridine ligand, the Cu—N distance is relatively long. Again, with the exception of [Cu₂(C₆H₅COO)₄(4,7-dichloroquinoline)₂], the Cu···Cu distances are also long in complexes having ligands of this type. This suggests that steric factors due to the axial ligand may influence the Cu···Cu as well as Cu—N distances.

The distorted nature of the CuO₄N square pyramid can be understood from the O—Cu—O and O—Cu—N angles. While the former are in the range 88.08 (6)–166.41 (5)°, the latter are in the range 89.88 (6)–103.85 (6)°. The deviations from linearity of the two O—Cu—O angles (≈ 166°) for the two pairs of trans O atoms are particularly notable. However, the angles and bonds in the copper coordination environment in (I) are of comparable magnitude vis á vis the corresponding values found for several [Cu₂(C₆H₅COO)₄L₂] compounds (Kawata et al., 1992).

The Cu atom is 0.1878 (6) Å away from the mean plane formed by the four equatorial O atoms. On the other hand, the coordinated N atom also lies in the same direction, at a distance of 2.312 (1) Å from the plane. The dihedral angle between the planes through Cu1/O2/C15/O3/Cu1ⁱ/O2ⁱ/C15ⁱ/O3ⁱ and Cu1/O1/C8/O4/Cu1ⁱ/O1ⁱ/C8ⁱ/O4ⁱ [symmetry code: (i) Please define] is 88.74 (3)°, which is close to the ideal value of 90°, the observed difference being attributable to packing effects in a crystal of low symmetry. The corresponding value for the complex [Cu₂(C₆H₅COO)₄(N,N-diethylnicotinamide)₂] (Hökelek et al., 1995) is 88.9 (1)°.

Following the method given by Kawata et al. (1992), the rotation angles of the phenyl group relative to the carboxyl (COO) moiety in the bridging benzoate ions, ϕ_rot, and the bending angles of the COO moiety relative to the Cu—O···O—Cu plane, ϕ_bend, can be calculated. For an isolated binuclear comlex, the ϕ_rot and ϕ_bend values are expected to be close to zero (with minimum strain energy). However, in the present structure, (I), the corresponding values are 3.85 (31) and 15.66 (21)°, and 3.71 (28) and 0.91 (25)°, respectively. The deviation of these values from zero is likely to be a consequence of molecular packing in the crystal lattice. The deviations lead to an improvement in packing effeciency. In such cases, the increased intermolecular strain is compensated for by favourable intermolecular interactions.

A comparison of bond lengths and angles observed here for compound (I) and those reported previously by Zhang et al. (2003) shows that, while the crystallographic and geometric parameters are very similar, the s.u. values and the residuals observed in the present work are much improved. This improvement is an outcome of the use of a greater number of reflections in the present work. Moreover, the intensity data used earlier were not corrected for absorption effects.

Related literature

For related literature, see: Allen (2002); Araki et al. (2005); Cotton et al. (1999); Das et al. (2007); Farrugia (1999); Hökelek et al. (1995); Kawata et al. (1992); Kozlevčar et al. (2004); Lah et al. (2001); Leban et al. (1997); Satgé et al. (2004); Speier & Fulop (1989); Sundberg et al. (1996); Zhang et al. (2003).

S2. Experimental

CuCl₂·2H₂O (0.34 g, 2 mM [mmol ?]) was dissolved in methanol (25 ml). To this methanolic solution, sodium benzoate (C₆H₅COONa; 0.576 g, 4 mM [mmol ?]) was added, and the mixture was stirred for ca 10 min to obtain a greenish-blue solution. N,N-Dimethyl-4-aminopyridine (0.488 g, 4 mM [mmol ?]) was added to the solution and the mixture was stirred for an additional 2 h. The resulting greenish product was filtered off, washed with small volumes of methanol and dried in a vacuum desiccator over fused CaCl₂ (yield 75%). Single crystals of (I) suitable for X-ray diffraction wrere obtained from a methanol solution of the title complex by slow evaporation.

S3. Refinement

Structure determination work was carried out using the WinGX platform (Farrugia, 1999). All H atoms belonging to the phenyl groups in the benzoate ligands and in the pyridyl ring of the DMAP ligand were placed in calculated positions, with C—H = 0.93–0.96 Å and U_iso(H) = 1.2 or 1.5 times U_eq(C). [Please check added text] No restraints were applied for any other parameter during structure refinement.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x, 1 - y, z.]

Tetrakis(µ-benzoato-κ²O:O)bis{[4-(dimethylamino)pyridine-κN¹]copper(II)}

Crystal data

[Cu2(C7H5O2)4(C7H10N2)2]	F(000) = 884
Mr = 855.86	Dx = 1.434 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9336 reflections
a = 10.4339 (3) Å	θ = 2.2–26.9°
b = 11.1284 (3) Å	µ = 1.13 mm^−1
c = 17.1616 (5) Å	T = 293 K
β = 96.0140 (1)°	Block, blue
V = 1981.71 (10) Å^3	0.33 × 0.30 × 0.22 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	4112 independent reflections
Radiation source: fine-focus sealed tube	3511 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 27.1°, θmin = 2.2°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −12→13
Tmin = 0.707, Tmax = 0.789	k = −14→14
19035 measured reflections	l = −21→21

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.7331P] where P = (Fo^2 + 2Fc^2)/3
4112 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.27 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 8.9195 (0.0026) x + 4.9515 (0.0048) y - 3.0186 (0.0082) z = 1.3196 (0.0025)

* -0.1878 (0.0006) Cu1 * 0.0461 (0.0007) O1 * 0.0481 (0.0007) O2 * 0.0481 (0.0007) O3_$1 * 0.0455 (0.0007) O4_$1 - 2.3125 (0.0015) N1

Rms deviation of fitted atoms = 0.0939

4.9643 (0.0048) x + 4.1294 (0.0046) y - 14.4658 (0.0038) z = 2.0647 (0.0023)

Angle to previous plane (with approximate e.s.d.) = 88.35 (0.04)

* 0.0136 (0.0007) Cu1 * -0.0058 (0.0009) O2 * 0.0109 (0.0009) O3 * -0.0038 (0.0011) C15 * 0.0058 (0.0009) O2_$1 * -0.0109 (0.0009) O3_$1 * 0.0038 (0.0011) C15_$1 * -0.0136 (0.0007) Cu1_$1

Rms deviation of fitted atoms = 0.0094

1.6944 (0.0051) x + 9.3609 (0.0028) y + 8.5113 (0.0061) z = 4.6805 (0.0014)

Angle to previous plane (with approximate e.s.d.) = 88.74 (0.03)

* -0.0167 (0.0007) Cu1 * -0.0029 (0.0009) O1 * -0.0229 (0.0009) O4 * 0.0199 (0.0012) C8 * 0.0029 (0.0009) O1_$1 * 0.0229 (0.0009) O4_$1 * -0.0199 (0.0012) C8_$1 * 0.0167 (0.0007) Cu1_$1

Rms deviation of fitted atoms = 0.0174

1.2126 (0.0102) x + 8.7123 (0.0065) y + 10.2228 (0.0128) z = 4.0041 (0.0077)

Angle to previous plane (with approximate e.s.d.) = 6.94 (0.10)

* 0.0041 (0.0014) C9 * -0.0019 (0.0016) C10 * -0.0015 (0.0018) C11 * 0.0028 (0.0019) C12 * -0.0006 (0.0018) C13 * -0.0029 (0.0015) C14

Rms deviation of fitted atoms = 0.0026

1.3310 (0.0193) x + 9.1331 (0.0172) y + 9.2759 (0.0476) z = 4.4424 (0.0159)

Angle to previous plane (with approximate e.s.d.) = 3.85 (0.31)

* 0.0000 (0.0000) O1 * 0.0000 (0.0000) C8 * 0.0000 (0.0000) O4

Rms deviation of fitted atoms = 0.0000

1.7605 (0.0042) x + 9.3743 (0.0028) y + 8.4315 (0.0078) z = 4.6872 (0.0014)

Angle to previous plane (with approximate e.s.d.) = 3.71 (0.28)

* -0.0117 (0.0005) Cu1 * 0.0142 (0.0006) O1 * -0.0142 (0.0006) O4 * 0.0117 (0.0005) Cu1_$1

Rms deviation of fitted atoms = 0.0130

7.3269 (0.0086) x + 3.3330 (0.0114) y - 12.2863 (0.0128) z = 1.9132 (0.0104)

Angle to previous plane (with approximate e.s.d.) = 87.70 (0.06)

* -0.0102 (0.0015) C16 * -0.0038 (0.0018) C17 * 0.0149 (0.0021) C18 * -0.0120 (0.0021) C19 * -0.0023 (0.0019) C20 * 0.0133 (0.0017) C21

Rms deviation of fitted atoms = 0.0106

5.0509 (0.0098) x + 4.2031 (0.0321) y - 14.3417 (0.0282) z = 2.1272 (0.0231)

Angle to previous plane (with approximate e.s.d.) = 15.66 (0.21)

* 0.0000 (0.0000) O2 * 0.0000 (0.0000) C15 * 0.0000 (0.0000) O3

Rms deviation of fitted atoms = 0.0000

4.9360 (0.0035) x + 4.1332 (0.0053) y - 14.4857 (0.0046) z = 2.0667 (0.0026)

Angle to previous plane (with approximate e.s.d.) = 0.91 (1/4)

* 0.0095 (0.0005) Cu1 * -0.0115 (0.0006) O2 * 0.0117 (0.0006) O3 * -0.0097 (0.0005) Cu1_$1

Rms deviation of fitted atoms = 0.0107

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	0.116281 (18)	0.453741 (17)	0.025762 (12)	0.03015 (8)
O1	0.16639 (13)	0.53301 (12)	−0.06977 (8)	0.0450 (3)
O2	0.15437 (13)	0.60512 (11)	0.08338 (8)	0.0477 (3)
O3	−0.03701 (13)	0.68028 (12)	0.03801 (8)	0.0469 (3)
O4	−0.02716 (12)	0.60598 (13)	−0.11384 (8)	0.0452 (3)
N1	0.28991 (14)	0.35146 (13)	0.04880 (9)	0.0370 (3)
N2	0.60034 (18)	0.11035 (17)	0.06700 (12)	0.0593 (5)
C1	0.2912 (2)	0.25076 (18)	0.09129 (13)	0.0503 (5)
H1	0.2192	0.2347	0.1173	0.060*
C2	0.3898 (2)	0.16948 (19)	0.09950 (13)	0.0538 (5)
H2	0.3836	0.1015	0.1304	0.065*
C3	0.50054 (18)	0.18875 (17)	0.06129 (12)	0.0433 (4)
C4	0.49975 (18)	0.29386 (17)	0.01616 (12)	0.0463 (5)
H4	0.5699	0.3125	−0.0109	0.056*
C5	0.39489 (18)	0.36926 (17)	0.01201 (12)	0.0429 (4)
H5	0.3973	0.4379	−0.0188	0.051*
C6	0.7115 (2)	0.1290 (2)	0.02444 (18)	0.0725 (7)
H6A	0.7718	0.0646	0.0358	0.109*
H6B	0.7518	0.2040	0.0401	0.109*
H6C	0.6845	0.1308	−0.0308	0.109*
C7	0.6032 (3)	0.0072 (2)	0.11850 (18)	0.0799 (8)
H7A	0.6810	−0.0376	0.1147	0.120*
H7B	0.5300	−0.0431	0.1035	0.120*
H7C	0.6005	0.0338	0.1715	0.120*
C8	0.09178 (17)	0.59222 (15)	−0.11735 (10)	0.0348 (4)
C9	0.14991 (18)	0.65406 (15)	−0.18311 (10)	0.0376 (4)
C10	0.2804 (2)	0.6435 (2)	−0.19019 (12)	0.0527 (5)
H10	0.3321	0.5952	−0.1556	0.063*
C11	0.3334 (3)	0.7053 (3)	−0.24911 (15)	0.0704 (7)
H11	0.4210	0.6984	−0.2538	0.084*
C12	0.2583 (3)	0.7765 (2)	−0.30048 (14)	0.0713 (7)
H12	0.2949	0.8180	−0.3397	0.086*
C13	0.1290 (3)	0.7864 (2)	−0.29391 (14)	0.0670 (7)
H13	0.0777	0.8345	−0.3289	0.080*
C14	0.0744 (2)	0.72517 (18)	−0.23544 (12)	0.0498 (5)
H14	−0.0135	0.7319	−0.2314	0.060*
C15	0.07040 (17)	0.68630 (15)	0.07760 (10)	0.0355 (4)
C16	0.09923 (17)	0.80114 (15)	0.12161 (10)	0.0370 (4)
C17	0.0243 (2)	0.90117 (18)	0.10356 (14)	0.0547 (5)
H17	−0.0427	0.8979	0.0634	0.066*
C18	0.0488 (3)	1.0059 (2)	0.14503 (19)	0.0764 (8)
H18	−0.0002	1.0741	0.1317	0.092*
C19	0.1445 (3)	1.0104 (2)	0.20552 (17)	0.0700 (7)
H19	0.1580	1.0806	0.2346	0.084*
C20	0.2209 (3)	0.9122 (2)	0.22365 (15)	0.0659 (6)
H20	0.2870	0.9157	0.2644	0.079*
C21	0.1984 (2)	0.80817 (18)	0.18077 (13)	0.0553 (5)
H21	0.2512	0.7418	0.1921	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03020 (12)	0.02952 (11)	0.03079 (12)	0.00354 (8)	0.00348 (9)	−0.00053 (8)
O1	0.0421 (7)	0.0521 (8)	0.0423 (8)	0.0084 (6)	0.0112 (6)	0.0136 (6)
O2	0.0485 (8)	0.0359 (7)	0.0561 (9)	0.0034 (6)	−0.0063 (7)	−0.0112 (6)
O3	0.0428 (8)	0.0402 (7)	0.0557 (8)	0.0018 (6)	−0.0038 (7)	−0.0148 (6)
O4	0.0402 (7)	0.0586 (8)	0.0377 (7)	0.0040 (6)	0.0082 (6)	0.0118 (6)
N1	0.0320 (7)	0.0372 (7)	0.0414 (8)	0.0058 (6)	0.0024 (7)	0.0036 (6)
N2	0.0493 (10)	0.0549 (11)	0.0746 (13)	0.0205 (8)	0.0098 (10)	0.0112 (9)
C1	0.0438 (11)	0.0521 (11)	0.0573 (13)	0.0100 (9)	0.0164 (10)	0.0151 (9)
C2	0.0531 (12)	0.0477 (11)	0.0625 (13)	0.0125 (9)	0.0149 (11)	0.0203 (10)
C3	0.0387 (10)	0.0451 (10)	0.0456 (11)	0.0096 (8)	0.0014 (9)	0.0017 (8)
C4	0.0359 (10)	0.0499 (11)	0.0543 (12)	0.0055 (8)	0.0104 (9)	0.0092 (9)
C5	0.0375 (10)	0.0400 (9)	0.0508 (12)	0.0011 (8)	0.0026 (9)	0.0108 (8)
C6	0.0499 (13)	0.0727 (16)	0.097 (2)	0.0208 (12)	0.0194 (14)	−0.0033 (14)
C7	0.0808 (19)	0.0623 (15)	0.096 (2)	0.0325 (14)	0.0057 (16)	0.0217 (15)
C8	0.0431 (10)	0.0313 (8)	0.0309 (9)	−0.0006 (7)	0.0074 (8)	−0.0038 (7)
C9	0.0478 (10)	0.0350 (9)	0.0310 (9)	−0.0045 (7)	0.0096 (8)	−0.0036 (7)
C10	0.0518 (12)	0.0644 (13)	0.0435 (11)	−0.0054 (10)	0.0127 (10)	0.0020 (10)
C11	0.0649 (15)	0.0912 (18)	0.0597 (15)	−0.0191 (14)	0.0286 (13)	−0.0003 (14)
C12	0.096 (2)	0.0696 (15)	0.0532 (14)	−0.0225 (14)	0.0316 (14)	0.0093 (12)
C13	0.097 (2)	0.0561 (13)	0.0493 (13)	0.0022 (12)	0.0167 (13)	0.0171 (11)
C14	0.0620 (13)	0.0452 (10)	0.0437 (11)	0.0033 (9)	0.0124 (10)	0.0067 (9)
C15	0.0415 (10)	0.0328 (8)	0.0330 (9)	−0.0026 (7)	0.0080 (8)	−0.0023 (7)
C16	0.0417 (10)	0.0341 (9)	0.0354 (9)	−0.0035 (7)	0.0050 (8)	−0.0047 (7)
C17	0.0522 (12)	0.0428 (11)	0.0658 (14)	0.0044 (9)	−0.0099 (11)	−0.0130 (10)
C18	0.0745 (17)	0.0416 (12)	0.108 (2)	0.0108 (12)	−0.0142 (17)	−0.0234 (14)
C19	0.0820 (18)	0.0449 (12)	0.0798 (18)	−0.0039 (12)	−0.0074 (15)	−0.0255 (12)
C20	0.0814 (17)	0.0534 (13)	0.0576 (14)	−0.0090 (12)	−0.0180 (13)	−0.0098 (11)
C21	0.0694 (14)	0.0392 (10)	0.0537 (13)	0.0021 (10)	−0.0106 (12)	−0.0016 (9)

Geometric parameters (Å, º)

Cu1—O4^i	1.9711 (12)	C7—H7A	0.9600
Cu1—O2	1.9726 (13)	C7—H7B	0.9600
Cu1—O3^i	1.9791 (13)	C7—H7C	0.9600
Cu1—O1	1.9796 (12)	C8—C9	1.503 (2)
Cu1—N1	2.1410 (14)	C9—C14	1.381 (3)
Cu1—Cu1^i	2.6982 (4)	C9—C10	1.384 (3)
O1—C8	1.255 (2)	C10—C11	1.385 (3)
O2—C15	1.255 (2)	C10—H10	0.9300
O3—C15	1.250 (2)	C11—C12	1.369 (4)
O3—Cu1^i	1.9791 (13)	C11—H11	0.9300
O4—C8	1.258 (2)	C12—C13	1.370 (4)
O4—Cu1^i	1.9711 (12)	C12—H12	0.9300
N1—C5	1.335 (2)	C13—C14	1.384 (3)
N1—C1	1.336 (2)	C13—H13	0.9300
N2—C3	1.354 (2)	C14—H14	0.9300
N2—C7	1.447 (3)	C15—C16	1.499 (2)
N2—C6	1.449 (3)	C16—C21	1.374 (3)
C1—C2	1.367 (3)	C16—C17	1.377 (3)
C1—H1	0.9300	C17—C18	1.375 (3)
C2—C3	1.403 (3)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.364 (4)
C3—C4	1.402 (3)	C18—H18	0.9300
C4—C5	1.375 (3)	C19—C20	1.369 (4)
C4—H4	0.9300	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.379 (3)
C6—H6A	0.9600	C20—H20	0.9300
C6—H6B	0.9600	C21—H21	0.9300
C6—H6C	0.9600
O4^i—Cu1—O2	89.42 (6)	O4^i—Cu1—O2	89.42 (6)
O4^i—Cu1—O3^i	88.08 (6)	O4^i—Cu1—O3^i	88.08 (6)
O2—Cu1—O3^i	166.26 (6)	O2—Cu1—O3^i	166.26 (6)
O4^i—Cu1—O1	166.41 (5)	O4^i—Cu1—O1	166.41 (5)
O2—Cu1—O1	88.73 (6)	O2—Cu1—O1	88.73 (6)
O3^i—Cu1—O1	90.53 (6)	O3^i—Cu1—O1	90.53 (6)
O4^i—Cu1—N1	97.89 (6)	O4^i—Cu1—N1	97.89 (6)
O2—Cu1—N1	103.85 (6)	O2—Cu1—N1	103.85 (6)
O3^i—Cu1—N1	89.88 (6)	O3^i—Cu1—N1	89.88 (6)
O1—Cu1—N1	95.62 (5)	O1—Cu1—N1	95.62 (5)
O4^i—Cu1—Cu1^i	84.24 (4)	O4^i—Cu1—Cu1^i	84.24 (4)
O2—Cu1—Cu1^i	88.02 (4)	O2—Cu1—Cu1^i	88.02 (4)
O3^i—Cu1—Cu1^i	78.28 (4)	O3^i—Cu1—Cu1^i	78.28 (4)
O1—Cu1—Cu1^i	82.24 (4)	O1—Cu1—Cu1^i	82.24 (4)
N1—Cu1—Cu1^i	167.93 (4)	N1—Cu1—Cu1^i	167.93 (4)
C8—O1—Cu1	124.99 (11)	C8—O1—Cu1	124.99 (11)
C15—O2—Cu1	118.22 (12)	C15—O2—Cu1	118.22 (12)
C15—O3—Cu1^i	129.78 (12)	C15—O3—Cu1^i	129.78 (12)
C8—O4—Cu1^i	122.87 (12)	C8—O4—Cu1^i	122.87 (12)
C5—N1—C1	114.89 (15)	C5—N1—C1	114.89 (15)
C5—N1—Cu1	123.65 (12)	C5—N1—Cu1	123.65 (12)
C1—N1—Cu1	120.41 (12)	C1—N1—Cu1	120.41 (12)
C3—N2—C7	121.46 (19)	C3—N2—C7	121.46 (19)
C3—N2—C6	121.41 (19)	C3—N2—C6	121.41 (19)
C7—N2—C6	117.08 (19)	C7—N2—C6	117.08 (19)
N1—C1—C2	125.13 (18)	N1—C1—C2	125.13 (18)
N1—C1—H1	117.4	N1—C1—H1	117.4
C2—C1—H1	117.4	C2—C1—H1	117.4
C1—C2—C3	119.92 (18)	C1—C2—C3	119.92 (18)
C1—C2—H2	120.0	C1—C2—H2	120.0
C3—C2—H2	120.0	C3—C2—H2	120.0
N2—C3—C4	122.50 (18)	N2—C3—C4	122.50 (18)
N2—C3—C2	122.15 (18)	N2—C3—C2	122.15 (18)
C4—C3—C2	115.34 (17)	C4—C3—C2	115.34 (17)
C5—C4—C3	119.76 (17)	C5—C4—C3	119.76 (17)
C5—C4—H4	120.1	C5—C4—H4	120.1
C3—C4—H4	120.1	C3—C4—H4	120.1
N1—C5—C4	124.95 (17)	N1—C5—C4	124.95 (17)
N1—C5—H5	117.5	N1—C5—H5	117.5
C4—C5—H5	117.5	C4—C5—H5	117.5
N2—C6—H6A	109.5	N2—C6—H6A	109.5
N2—C6—H6B	109.5	N2—C6—H6B	109.5
H6A—C6—H6B	109.5	H6A—C6—H6B	109.5
N2—C6—H6C	109.5	N2—C6—H6C	109.5
H6A—C6—H6C	109.5	H6A—C6—H6C	109.5
H6B—C6—H6C	109.5	H6B—C6—H6C	109.5
N2—C7—H7A	109.5	N2—C7—H7A	109.5
N2—C7—H7B	109.5	N2—C7—H7B	109.5
H7A—C7—H7B	109.5	H7A—C7—H7B	109.5
N2—C7—H7C	109.5	N2—C7—H7C	109.5
H7A—C7—H7C	109.5	H7A—C7—H7C	109.5
H7B—C7—H7C	109.5	H7B—C7—H7C	109.5
O1—C8—O4	125.49 (16)	O1—C8—O4	125.49 (16)
O1—C8—C9	117.23 (16)	O1—C8—C9	117.23 (16)
O4—C8—C9	117.26 (16)	O4—C8—C9	117.26 (16)
C14—C9—C10	119.43 (18)	C14—C9—C10	119.43 (18)
C14—C9—C8	120.21 (17)	C14—C9—C8	120.21 (17)
C10—C9—C8	120.33 (18)	C10—C9—C8	120.33 (18)
C9—C10—C11	119.6 (2)	C9—C10—C11	119.6 (2)
C9—C10—H10	120.2	C9—C10—H10	120.2
C11—C10—H10	120.2	C11—C10—H10	120.2
C12—C11—C10	120.8 (2)	C12—C11—C10	120.8 (2)
C12—C11—H11	119.6	C12—C11—H11	119.6
C10—C11—H11	119.6	C10—C11—H11	119.6
C11—C12—C13	119.7 (2)	C11—C12—C13	119.7 (2)
C11—C12—H12	120.1	C11—C12—H12	120.1
C13—C12—H12	120.1	C13—C12—H12	120.1
C12—C13—C14	120.2 (2)	C12—C13—C14	120.2 (2)
C12—C13—H13	119.9	C12—C13—H13	119.9
C14—C13—H13	119.9	C14—C13—H13	119.9
C9—C14—C13	120.2 (2)	C9—C14—C13	120.2 (2)
C9—C14—H14	119.9	C9—C14—H14	119.9
C13—C14—H14	119.9	C13—C14—H14	119.9
O3—C15—O2	125.66 (16)	O3—C15—O2	125.66 (16)
O3—C15—C16	116.15 (16)	O3—C15—C16	116.15 (16)
O2—C15—C16	118.19 (17)	O2—C15—C16	118.19 (17)
C21—C16—C17	119.09 (18)	C21—C16—C17	119.09 (18)
C21—C16—C15	121.11 (17)	C21—C16—C15	121.11 (17)
C17—C16—C15	119.79 (17)	C17—C16—C15	119.79 (17)
C18—C17—C16	119.9 (2)	C18—C17—C16	119.9 (2)
C18—C17—H17	120.1	C18—C17—H17	120.1
C16—C17—H17	120.1	C16—C17—H17	120.1
C19—C18—C17	120.4 (2)	C19—C18—C17	120.4 (2)
C19—C18—H18	119.8	C19—C18—H18	119.8
C17—C18—H18	119.8	C17—C18—H18	119.8
C18—C19—C20	120.4 (2)	C18—C19—C20	120.4 (2)
C18—C19—H19	119.8	C18—C19—H19	119.8
C20—C19—H19	119.8	C20—C19—H19	119.8
C19—C20—C21	119.1 (2)	C19—C20—C21	119.1 (2)
C19—C20—H20	120.4	C19—C20—H20	120.4
C21—C20—H20	120.4	C21—C20—H20	120.4
C16—C21—C20	121.0 (2)	C16—C21—C20	121.0 (2)
C16—C21—H21	119.5	C16—C21—H21	119.5
C20—C21—H21	119.5	C20—C21—H21	119.5

Symmetry code: (i) −x, −y+1, −z.