Di­aqua­bis(4,4′-bi­pyridine-N)­bis­(di­hydrogenphosphato-O)copper(II): blocking of extended metal–ligand coordination by hydrogen bonding

The title compound, [Cu(H₂PO₄)₂(C₁₀H₈N₂)₂(H₂O)₂], is a mononuclear complex in which the Cu atom is square-planar coordinated by two di­hydrogenphosphate anions and two monodentate 4,4′-bi­pyridine (4,4′-bipy) groups, and by two more distant aqua ligands to complete a distorted octahedral coordination. Metal–metal bridging by 4,4′-bipy is blocked by inter­molecular hydrogen bonding from the di­hydrogen­phosphate to the second N atom of 4,4′-bipy. The crystal packing is controlled both by additional hydrogen bonding between the aqua and phosphate ligands and by π-stacking. These hydrogen-bonding interactions create two-dimensional networks which are connected by the bi­pyridine ligands.

S1. Comment

There is widespread interest in achieving control of the aggregation of organic ligands and metal ions into oligo- or polynuclear coordination structures via covalent metal–ligand bonds and non-covalent interactions (Wu et al., 1999; Janiak et al., 1999). Recent years have seen an appreciable number of studies on the coordination of phosphate ions to transition metals (Choudhuy et al., 2000; Finn & Zubieta, 2000; Neeraji et al., 2000; Shi et al., 2000; Yan et al., 2000). Amine phosphates, for example, react with metal ions under hydrothermal conditions to give open-framework metal phosphates (Neeraj et al., 1999; Cheetham et al., 1999; Oliver et al., 1998). Mono- and dihydrogenphosphate ligands are good candidates for participation in structure-directing hydrogen-bonding interactions (Subramanian & Zaworotko, 1994). Moreover, 4,4'-bipyridine (4,4'-bipy) is an often used building block and excellent bridging ligand for the construction of coordination polymeric frameworks (Hagrman et al., 1999; Li et al., 2000; Janiak et al., 1999; Wu et al., 1999, and references therein). Little work has been carried out on the simultaneous coordination of 4,4'-bipy and phosphate with metals (Hagrman et al., 1999). Hydrothermal reaction of In(NO₃)₂^.5H₂O, H₃PO₄ and 4,4'-bipy in n-butanol produced [In₄(4,4'-bipy)₄(H₂PO₄)₄(HPO₄)₄]^.4H₄O (Lii & Huang, 1999). The extended inorganic–organic hybrid material [M(4,4'-bipy)₂(VO₂)₂(HPO₄)₄] (M = Co, Ni) was also obtained by a hydrothermal reaction (Shi et al., 2000).

We describe here the structure of the monomeric complex [Cu(4,4'-bipy)₂(H₂PO₄)₂(H₂O)₂], (I) (Fig. 1). The molecular symmetry is D_{2 h} when H₂PO₄ is treated as a point ligand and C_{2 h} when the latter is taken into account as a full group. The coordination geometry around the Cu^II atom is a Jahn–Teller-distorted elongated octahedron. The two bipy N atoms and the two phosphate O atoms form the equatorial plane around copper. The two aqua ligands comprise the elongated axial coordination. There are intramolecular hydrogen bonds between the aqua and phosphate ligands (Fig. 2). The in-plane distances for Cu—N1 [2.024 (3) Å], Cu—N3 [2.007 (3) Å], Cu—O4 [1.945 (2) Å] and Cu—O6 [1.944 (2) Å] are normal. For Cu—N_py, the expected range is 2.046±0.032 Å (Orpen et al., 1989). There are few examples of copper–phosphate bonds. Nevertheless, the copper–phosphate distances are comparable to those in [{Cu(2,2'-bipy)}₂(VO)₃(PO₄)₂(HPO₄)₂]^.2H₂O [average Cu—O_phosphate = 1.975 (4) Å], in [{Cu(terpy)}₂(VO₂)₃(PO₄)(HPO₄)₂] [Cu—O_phosphate = 1.921 (4) Å; Finn & Zubieta, 2000], and in [{Cu₂(HL)(H₂PO₄)₂}₂](NO₃)₂^.2H₂O [H₂L = bis(pyridine-2-aldehyde) thiocarbohydrazone; Cu—O_phosphate = 1.890 (3) and 1.933 (3) Å; Moubaraki et al., 1998]. The axial distances from Cu to the aqua ligands with O9 [2.690 (3) Å] and O10 [2.605 (2) Å] lie at the top end of the expected range. For the terminal Cu—OH₂ bonds, the range is 2.399±0.154 Å (Orpen et al., 1989).

The 4,4'-bipy group functions as a monodentate ligand towards a metal atom in (I). This appears to be a rare phenomenon. Two known examples of monodentate 4,4'-bipy binding involve coordination to manganese (Attia & Pierpont, 1995; Tong et al., 1999). Much more common for 4,4'-bipy is a bidentate bridging coordination between metal atoms, thereby usually giving rise to extended metal–ligand structures, such as chains or grids. This is normally also observed in copper compounds with 4,4'-bipy (Blake et al., 1999; Hagrman et al., 1998; You et al., 2000; Tong et al., 1998; Zhang et al., 1999). In (I), one of the N-donor atoms of 4,4'-bipy is, however, engaged in intermolecular hydrogen bonding to a dihydrogenphosphate ligand of an adjacent complex (cf. Fig. 1). Without the protonated phosphate group, an extended copper–4,4'-bipy chain could have been envisioned, as found in [Cu(4,4'-bipy)(SO₄)(H₂O)₃]^.2H₂O and compounds with related bipyridine ligands (Hagrman et al., 1998). Hydrogen bonding from metal–aqua ligands to both N atoms of uncoordinated 4,4'-bipy molecules has been observed in [Co(4,4'-bipy)(H₂O)₄](PF₆)₂^.(4,4'-bipy)₃ (Dong et al., 2000), in [Mn(4,4'-bipy)₂(H₂O)₄](ClO₄)₂^.(4,4'-bipy)₄ (Tong et al., 1999), and in a series of [M(4,4'-bipy)(H₂O)_m]X₂^.(4,4'-bipy)_n compounds (M = Fe, Zn; m = 3, 4; X = ClO₄, NO₃, O₃SCF₃; n = 1, 1.5, 2; Carlucci et al., 1997). An example with metal coordination to one end of 4,4'-bipy and hydrogen bonding from an aqua ligand to the other end is [Cd₂(4,4-bipy)₅(H₂O)₄(NO₃)₂(PF₆)₂] (Dong et al., 2000). The pyridyl rings of the 4,4'-bipy molecules are non-coplanar and are twisted by interplanar angles of 30.6 (1) (rings with N1 and N2) and 22.6 (1)° (rings with N3 and N4).

The crystal packing is further controlled by hydrogen bonding among the phosphate ligands and between the aqua and phosphate ligands, as shown in Fig. 2. Hydrogen bonding between the phosphate ligands gives rise to a ring with inversion symmetry. The sole hydrogen-bond acceptor is the formally P═O double-bonded O atom. It accepts three hydrogen bonds, one intra- and two intermolecular. These hydrogen-bonding interactions create two-dimensional networks parallel to the xz plane, which then are connected by the bipyridine ligands. The crystal packing seems also to be influenced by π-stacking between the 4,4'-bipy ligands. They feature offset or slipped π–π interactions, with an interplanar separation of about 3.64 Å (Janiak, 2000). These latter packing interactions can be seen in Fig. 1.

Related literature

For related literature, see: Attia & Pierpont (1995); Blake et al. (1999); Carlucci et al. (1997); Cheetham et al. (1999); Chippindale et al. (2000); Choudhuy et al. (2000); Dong et al. (2000); Finn & Zubieta (2000); Hagrman et al. (1998, 1999); Janiak (2000); Janiak et al. (1999); Li et al. (2000); Lii & Huang (1999); Moubaraki et al. (1998); Neeraj et al. (1999); Oliver et al. (1998); Orpen et al. (1989); Shi et al. (2000); Subramanian & Zaworotko (1994); Tong et al. (1998, 1999); Wu et al. (1999); Yan et al. (2000); You et al. (2000); Zhang et al. (1999).

S2. Experimental

Copper nitrate trihydrate (0.241 g, 1.00 mmol) and 4,4'-bipyridine (0.156 g, 1.00 mmol) were mixed in distilled water (25 ml). To this slurry was carefully added a 1 mol l^-1 solution of H₃PO₄ with constant stirring until all the 4,4'-bipy had completely dissolved. The pH was adjusted to 4.3 using tetra-n-butylammonium hydroxide. The mixture was then stirred for 6 h. The solution was left to stand for three days at room temperature and some of the solvent evaporated. After this time, blue crystals of the title compound were collected by filtration (yield 280 mg, 46%). Crystal analysis, IR (KBr): 3444 (br, OH), 1607 (C═C), 1416 (P═O), 963 (P—O); calculated for C₂₀H₂₄CuN₄O₁₀P₂: C 39.66, H 3.96, N 9.25%; found C 39.21, H 2.95, N 8.90%.

S3. Refinement

The H atoms on O atoms were found and refined. The O—H bond distances were restrained to a target value of 0.83±0.02 Å with DFIX. Isotropic displacement parameters of U(H) = 1.5U_eq(O) were used. The H atoms on C atoms could also be found and refined but it was preferred to place them at calculated positions and refine them using appropriate riding models (HFIX 43; C—H = 0.94 Å) and isotropic displacement parameters of U(H) = 1.2U_eq(C). The structure could also be solved in a smaller triclinic unit cell with a = 7.707 (1), b = 7.945 (1), c = 10.207 (2) Å, α = 90.839 (3), β = 93.589 (3) and γ = 112.72 (1)°. Solution and refinement in the smaller triclinic cell was succesful to R1 = 0.0405, wR = 0.1122 for 2306 reflections with I > 2σ(I), R1 = 0.0474 and wR = 0.1179 for all data. The superstructure reflections which give rise to the larger unit cell are clearly visible, however. Furthermore, the pyridyl ring C atoms have high displacement parameters perpendicular to the ring plane. This corresponds to an averaged structure of the two bipy ligands where the pyridyl groups are tilted differently. Another example of a 4,4'-bipy complex with pseudosymmetry has been reported recently with the polymeric structure [MnCl₂(4,4'-bipy)]_n (Chippindale et al., 2000).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) and SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) and SHELXTL-Plus; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) view of the title compound illustrating some of the intermolecular hydrogen bonding and π-interactions. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii. [Symmetry code: (ii) 1 + x, y - 1, z.]
	Fig. 2. The hydrogen-bonding network between the aqua and phosphate ligands in (I). The bipy ligands have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii. The symmetry codes are as given in Table 2.

Diaquabis(4,4'-bipyridine)bis(dihydrogenphosphato)copper(II)

Crystal data

[Cu(H2PO4)2(C10H8N2)2(H2O)2]	Z = 2
Mr = 605.91	F(000) = 622
Triclinic, P1	Dx = 1.750 Mg m^−3
a = 7.948 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.208 (2) Å	Cell parameters from 3065 reflections
c = 14.362 (3) Å	θ = 1.4–27.5°
α = 85.693 (5)°	µ = 1.16 mm^−1
β = 82.008 (5)°	T = 210 K
γ = 89.172 (5)°	Block, blue
V = 1150.6 (4) Å^3	0.15 × 0.14 × 0.05 mm

Data collection

Bruker AXS CCD diffractometer	3065 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 27.5°, θmin = 1.4°
ω scans	h = −10→10
10246 measured reflections	k = −13→13
5200 independent reflections	l = −18→18

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0348P)^2] where P = (Fo^2 + 2Fc^2)/3
5200 reflections	(Δ/σ)max < 0.001
358 parameters	Δρmax = 0.39 e Å^−3
8 restraints	Δρmin = −0.62 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.

Refinement was carried out by using an uncorrected and an absorption- corrected data set (SADABS). With absorption correction (Maximum and minimum effective transmission: 1.000000 0.778807) refinement converged to R-factor-all 0.0746 R-factor-gt 0.0393 wR-factor-ref 0.1101 wR-factor-gt 0.0939 goodness-of-fit-ref 0.996 restrained-S-all 0.996 residual electron density: density-max 0.666 density-min -0.827 density-r.m.s. 0.086 The R-factors and residual electron densities are even somewhat larger than those from the uncorrected data set (see below). Thus, the uncorrected data set was chosen for full refinement.

The structure could also be solved in a smaller triclinic unit cell with a = 7.707 (1), b = 7.945 (1), c = 10.207 (2) Å, α = 90.839 (3), β = 93.589 (3), γ = 112.72 (1) °. Solution and refinement in the smaller triclinic cell was succesful to R1 = 0.0405, wR = 0.1122 for 2306 reflections with I > σ(I), R1 = 0.0474, wR = 0.1179 for all data. The superstructure reflections which give rise to the larger unit cell are clearly visible, however. Furthermore, the pyridyl ring carbon atoms have high thermal parameters perpendicular to the ring plane. This corresponds to an averaged structure of the two bipy ligands where the pyridyl groups are tilted differently. Another example of a 4,4'-bipy complex with pseudosymmetry has recently reported with the polymeric structure of [MnCl₂(4,4'-bipy)]_n (Chippindale et al., 2000).

The hydrogen atoms on oxygen were found and refined. The O—H bond distances were restrained to a target value of 0.83±0.02 Å with DFIX. Isotropic temperature factors of U(H) = 1.5 U_eq(O) were used. The hydrogen atoms on carbon could also be found and refined but it was prefered to place them at calculated positions using appropriate riding models (HFIX 43) and isotropic temperature factors of U(H) = 1.2 U_eq(C).

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

	x	y	z	Uiso*/Ueq
Cu	0.24669 (6)	−0.00412 (4)	−0.25266 (3)	0.02267 (11)
O1	−0.0633 (3)	−0.1516 (2)	−0.43557 (16)	0.0275 (5)
H01	−0.105 (4)	−0.084 (2)	−0.457 (2)	0.041*
O2	0.2209 (3)	−0.0425 (2)	−0.49030 (15)	0.0258 (5)
O3	0.1871 (3)	−0.2874 (2)	−0.44940 (16)	0.0303 (6)
H03	0.271 (3)	−0.319 (3)	−0.427 (2)	0.046*
O4	0.1455 (3)	−0.13335 (19)	−0.32069 (14)	0.0247 (5)
O5	0.2842 (3)	0.0415 (2)	−0.01461 (15)	0.0255 (5)
O6	0.3490 (3)	0.12572 (19)	−0.18587 (14)	0.0254 (5)
O7	0.5707 (3)	0.1408 (2)	−0.07926 (16)	0.0276 (5)
H07	0.612 (4)	0.081 (3)	−0.047 (2)	0.041*
O8	0.3272 (3)	0.2852 (2)	−0.06202 (16)	0.0279 (5)
H08	0.233 (3)	0.309 (3)	−0.072 (3)	0.042*
O9	0.4469 (3)	0.0994 (2)	−0.40621 (16)	0.0312 (5)
H9A	0.388 (4)	0.063 (3)	−0.439 (2)	0.047*
H9B	0.545 (3)	0.098 (4)	−0.431 (2)	0.047*
O10	0.0402 (3)	−0.0799 (2)	−0.10176 (16)	0.0309 (6)
H10A	−0.058 (3)	−0.076 (4)	−0.076 (2)	0.046*
H10B	0.087 (4)	−0.037 (3)	−0.065 (2)	0.046*
P1	0.12817 (10)	−0.14690 (7)	−0.42277 (5)	0.01881 (18)
P2	0.37670 (10)	0.14133 (7)	−0.08597 (5)	0.01842 (18)
N1	0.4186 (3)	−0.1405 (2)	−0.21717 (17)	0.0219 (6)
N2	1.0355 (3)	−0.6089 (2)	−0.09874 (18)	0.0245 (6)
N3	0.0771 (3)	0.1324 (2)	−0.28698 (17)	0.0217 (6)
N4	−0.5286 (3)	0.6117 (2)	−0.40124 (19)	0.0268 (6)
C1	0.3787 (4)	−0.2359 (3)	−0.1480 (2)	0.0257 (7)
H1	0.2675	−0.2389	−0.1155	0.031*
C2	0.4943 (4)	−0.3295 (3)	−0.1230 (2)	0.0235 (7)
H2	0.4612	−0.3943	−0.0742	0.028*
C3	0.6587 (4)	−0.3284 (3)	−0.1695 (2)	0.0197 (7)
C4	0.6992 (4)	−0.2292 (3)	−0.2406 (2)	0.0261 (7)
H4	0.8097	−0.2232	−0.2739	0.031*
C5	0.5765 (4)	−0.1399 (3)	−0.2618 (2)	0.0282 (7)
H5	0.6061	−0.0746	−0.3108	0.034*
C6	0.7878 (4)	−0.4263 (3)	−0.1447 (2)	0.0197 (7)
C7	0.7444 (4)	−0.5545 (3)	−0.1103 (2)	0.0223 (7)
H7	0.6305	−0.5818	−0.1021	0.027*
C8	0.8714 (4)	−0.6411 (3)	−0.0885 (2)	0.0259 (7)
H8	0.8404	−0.7272	−0.0651	0.031*
C9	1.0756 (4)	−0.4863 (3)	−0.1329 (2)	0.0277 (7)
H9	1.1908	−0.4622	−0.1413	0.033*
C10	0.9592 (4)	−0.3933 (3)	−0.1565 (2)	0.0267 (7)
H10	0.9948	−0.3084	−0.1803	0.032*
C11	−0.0890 (4)	0.1073 (3)	−0.2754 (2)	0.0252 (7)
H11	−0.1254	0.0223	−0.2524	0.030*
C12	−0.2105 (4)	0.1991 (3)	−0.2953 (2)	0.0232 (7)
H12	−0.3263	0.1769	−0.2851	0.028*
C13	−0.1595 (4)	0.3246 (3)	−0.33077 (19)	0.0201 (7)
C14	0.0128 (4)	0.3509 (3)	−0.3432 (2)	0.0238 (7)
H14	0.0525	0.4348	−0.3670	0.029*
C15	0.1269 (4)	0.2538 (3)	−0.3206 (2)	0.0236 (7)
H15	0.2434	0.2738	−0.3291	0.028*
C16	−0.2864 (4)	0.4263 (3)	−0.3536 (2)	0.0201 (7)
C17	−0.4547 (4)	0.4163 (3)	−0.3125 (2)	0.0265 (7)
H17	−0.4900	0.3464	−0.2680	0.032*
C18	−0.5696 (4)	0.5104 (3)	−0.3378 (2)	0.0281 (7)
H18	−0.6830	0.5029	−0.3089	0.034*
C19	−0.3660 (4)	0.6228 (3)	−0.4387 (2)	0.0294 (8)
H19	−0.3342	0.6941	−0.4826	0.035*
C20	−0.2419 (4)	0.5347 (3)	−0.4160 (2)	0.0252 (7)
H20	−0.1281	0.5480	−0.4427	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0246 (2)	0.01727 (17)	0.0289 (2)	0.00607 (13)	−0.01192 (15)	−0.00526 (14)
O1	0.0210 (13)	0.0258 (12)	0.0360 (13)	0.0009 (10)	−0.0093 (10)	0.0064 (10)
O2	0.0166 (12)	0.0292 (12)	0.0311 (12)	0.0005 (9)	−0.0054 (9)	0.0039 (10)
O3	0.0337 (15)	0.0260 (12)	0.0355 (13)	0.0125 (10)	−0.0165 (11)	−0.0105 (10)
O4	0.0299 (13)	0.0195 (11)	0.0259 (11)	0.0011 (9)	−0.0077 (10)	−0.0030 (9)
O5	0.0165 (12)	0.0281 (12)	0.0314 (12)	0.0010 (9)	−0.0055 (9)	0.0054 (10)
O6	0.0349 (14)	0.0192 (11)	0.0241 (11)	−0.0019 (9)	−0.0102 (10)	−0.0028 (9)
O7	0.0178 (12)	0.0262 (12)	0.0380 (13)	0.0003 (10)	−0.0085 (10)	0.0116 (10)
O8	0.0297 (14)	0.0201 (11)	0.0372 (13)	0.0085 (10)	−0.0146 (11)	−0.0078 (10)
O9	0.0255 (14)	0.0385 (14)	0.0296 (13)	0.0025 (11)	−0.0022 (11)	−0.0064 (11)
O10	0.0257 (14)	0.0368 (14)	0.0305 (13)	0.0001 (11)	−0.0001 (11)	−0.0112 (11)
P1	0.0169 (4)	0.0171 (4)	0.0232 (4)	0.0026 (3)	−0.0066 (3)	−0.0006 (3)
P2	0.0168 (4)	0.0161 (4)	0.0232 (4)	0.0020 (3)	−0.0067 (3)	0.0001 (3)
N1	0.0220 (15)	0.0176 (13)	0.0272 (14)	0.0023 (11)	−0.0069 (11)	−0.0022 (11)
N2	0.0245 (16)	0.0213 (14)	0.0285 (14)	0.0062 (11)	−0.0065 (12)	−0.0022 (11)
N3	0.0231 (15)	0.0182 (13)	0.0250 (13)	0.0025 (11)	−0.0066 (11)	−0.0033 (11)
N4	0.0278 (17)	0.0198 (14)	0.0351 (16)	0.0072 (12)	−0.0104 (13)	−0.0062 (12)
C1	0.0206 (17)	0.0256 (17)	0.0297 (17)	0.0025 (13)	−0.0011 (14)	0.0005 (14)
C2	0.0220 (17)	0.0220 (16)	0.0251 (16)	0.0020 (13)	−0.0023 (13)	0.0045 (13)
C3	0.0202 (17)	0.0171 (15)	0.0228 (16)	0.0020 (13)	−0.0053 (13)	−0.0041 (13)
C4	0.0191 (17)	0.0270 (17)	0.0307 (18)	0.0035 (13)	−0.0018 (14)	0.0029 (14)
C5	0.0289 (19)	0.0234 (16)	0.0308 (18)	0.0016 (14)	−0.0038 (14)	0.0059 (14)
C6	0.0210 (17)	0.0182 (15)	0.0202 (15)	0.0029 (13)	−0.0038 (13)	−0.0024 (12)
C7	0.0196 (17)	0.0222 (15)	0.0248 (16)	0.0001 (12)	−0.0029 (13)	0.0004 (13)
C8	0.0280 (19)	0.0200 (16)	0.0299 (17)	0.0037 (13)	−0.0067 (14)	0.0008 (13)
C9	0.0187 (17)	0.0238 (17)	0.0410 (19)	0.0035 (13)	−0.0062 (14)	−0.0024 (15)
C10	0.0214 (17)	0.0186 (15)	0.0403 (19)	−0.0005 (13)	−0.0062 (14)	0.0003 (14)
C11	0.0244 (18)	0.0192 (15)	0.0327 (17)	−0.0010 (12)	−0.0073 (14)	−0.0002 (13)
C12	0.0209 (17)	0.0208 (15)	0.0288 (17)	0.0012 (12)	−0.0069 (13)	−0.0005 (13)
C13	0.0222 (17)	0.0222 (16)	0.0167 (15)	0.0043 (13)	−0.0048 (13)	−0.0034 (13)
C14	0.0233 (17)	0.0197 (15)	0.0281 (17)	−0.0012 (12)	−0.0046 (13)	0.0025 (13)
C15	0.0186 (16)	0.0235 (16)	0.0282 (17)	0.0001 (13)	−0.0025 (13)	−0.0007 (13)
C16	0.0228 (18)	0.0190 (16)	0.0203 (15)	0.0037 (13)	−0.0085 (13)	−0.0036 (13)
C17	0.0218 (18)	0.0238 (17)	0.0335 (18)	0.0025 (13)	−0.0055 (14)	0.0029 (14)
C18	0.0200 (17)	0.0271 (17)	0.0380 (19)	0.0023 (13)	−0.0064 (14)	−0.0028 (15)
C19	0.034 (2)	0.0225 (17)	0.0304 (18)	0.0052 (14)	−0.0027 (15)	0.0046 (14)
C20	0.0203 (17)	0.0250 (17)	0.0289 (17)	0.0049 (13)	0.0004 (13)	−0.0008 (14)

Geometric parameters (Å, º)

Cu—O6	1.9435 (19)	C1—H1	0.9400
Cu—O4	1.9452 (19)	C2—C3	1.381 (4)
Cu—N3	2.007 (3)	C2—H2	0.9400
Cu—N1	2.024 (3)	C3—C4	1.392 (4)
Cu—O10	2.605 (2)	C3—C6	1.482 (4)
Cu—O9	2.690 (3)	C4—C5	1.374 (4)
O1—P1	1.560 (2)	C4—H4	0.9400
O1—H01	0.822 (18)	C5—H5	0.9400
O2—P1	1.513 (2)	C6—C10	1.392 (4)
O3—P1	1.561 (2)	C6—C7	1.394 (4)
O3—H03	0.828 (18)	C7—C8	1.386 (4)
O4—P1	1.508 (2)	C7—H7	0.9400
O5—P2	1.511 (2)	C8—H8	0.9400
O6—P2	1.502 (2)	C9—C10	1.374 (4)
O7—P2	1.558 (2)	C9—H9	0.9400
O7—H07	0.827 (18)	C10—H10	0.9400
O8—P2	1.565 (2)	C11—C12	1.379 (4)
O8—H08	0.812 (18)	C11—H11	0.9400
O9—H9A	0.819 (18)	C12—C13	1.388 (4)
O9—H9B	0.809 (18)	C12—H12	0.9400
O10—H10A	0.815 (18)	C13—C14	1.384 (4)
O10—H10B	0.836 (18)	C13—C16	1.487 (4)
P1—O2	1.513 (2)	C14—C15	1.384 (4)
P2—O5	1.511 (2)	C14—H14	0.9400
N1—C5	1.327 (4)	C15—H15	0.9400
N1—C1	1.346 (4)	C16—C17	1.387 (4)
N2—C8	1.335 (4)	C16—C20	1.389 (4)
N2—C9	1.336 (4)	C17—C18	1.379 (4)
N3—C11	1.334 (4)	C17—H17	0.9400
N3—C15	1.341 (4)	C18—H18	0.9400
N4—C19	1.332 (4)	C19—C20	1.381 (4)
N4—C18	1.339 (4)	C19—H19	0.9400
C1—C2	1.379 (4)	C20—H20	0.9400
O6—Cu—O4	179.42 (10)	C1—C2—C3	120.3 (3)
O6—Cu—N3	88.77 (9)	C1—C2—H2	119.8
O4—Cu—N3	91.15 (9)	C3—C2—H2	119.8
O6—Cu—N1	90.65 (9)	C2—C3—C4	116.7 (3)
O4—Cu—N1	89.43 (9)	C2—C3—C6	122.3 (3)
N3—Cu—N1	179.41 (10)	C4—C3—C6	120.9 (3)
O6—Cu—O10	91.53 (8)	C5—C4—C3	119.5 (3)
O4—Cu—O10	89.04 (8)	C5—C4—H4	120.3
N3—Cu—O10	89.89 (9)	C3—C4—H4	120.3
N1—Cu—O10	90.05 (10)	N1—C5—C4	123.9 (3)
O6—Cu—O9	85.15 (8)	N1—C5—H5	118.0
O4—Cu—O9	94.28 (8)	C4—C5—H5	118.0
N3—Cu—O9	85.10 (9)	C10—C6—C7	117.4 (3)
N1—Cu—O9	94.93 (9)	C10—C6—C3	120.6 (3)
O10—Cu—O9	174.04 (8)	C7—C6—C3	122.0 (3)
P1—O1—H01	117 (2)	C8—C7—C6	119.1 (3)
P1—O3—H03	117 (3)	C8—C7—H7	120.5
P1—O4—Cu	134.82 (13)	C6—C7—H7	120.5
P2—O6—Cu	136.53 (13)	N2—C8—C7	123.5 (3)
P2—O7—H07	120 (2)	N2—C8—H8	118.2
P2—O8—H08	116 (3)	C7—C8—H8	118.2
Cu—O9—H9A	88 (3)	N2—C9—C10	124.1 (3)
Cu—O9—H9B	140 (3)	N2—C9—H9	117.9
H9A—O9—H9B	109 (3)	C10—C9—H9	117.9
Cu—O10—H10A	144 (3)	C9—C10—C6	119.1 (3)
Cu—O10—H10B	95 (3)	C9—C10—H10	120.4
H10A—O10—H10B	99 (3)	C6—C10—H10	120.4
O4—P1—O2	114.07 (12)	N3—C11—C12	123.7 (3)
O4—P1—O2	114.07 (12)	N3—C11—H11	118.1
O2—P1—O2	0.00 (18)	C12—C11—H11	118.1
O4—P1—O1	110.14 (13)	C11—C12—C13	119.1 (3)
O2—P1—O1	110.91 (12)	C11—C12—H12	120.4
O2—P1—O1	110.91 (12)	C13—C12—H12	120.4
O4—P1—O3	109.09 (12)	C14—C13—C12	117.3 (3)
O2—P1—O3	111.09 (13)	C14—C13—C16	121.9 (3)
O2—P1—O3	111.09 (13)	C12—C13—C16	120.8 (3)
O1—P1—O3	100.73 (12)	C13—C14—C15	120.1 (3)
O6—P2—O5	114.16 (12)	C13—C14—H14	119.9
O6—P2—O5	114.16 (12)	C15—C14—H14	119.9
O5—P2—O5	0.0 (3)	N3—C15—C14	122.3 (3)
O6—P2—O7	109.76 (13)	N3—C15—H15	118.8
O5—P2—O7	111.14 (12)	C14—C15—H15	118.8
O5—P2—O7	111.14 (12)	C17—C16—C20	117.4 (3)
O6—P2—O8	108.33 (12)	C17—C16—C13	120.9 (3)
O5—P2—O8	111.55 (13)	C20—C16—C13	121.8 (3)
O5—P2—O8	111.55 (13)	C18—C17—C16	119.1 (3)
O7—P2—O8	101.09 (12)	C18—C17—H17	120.5
C5—N1—C1	116.9 (3)	C16—C17—H17	120.5
C5—N1—Cu	121.1 (2)	N4—C18—C17	123.7 (3)
C1—N1—Cu	121.9 (2)	N4—C18—H18	118.2
C8—N2—C9	116.8 (3)	C17—C18—H18	118.2
C11—N3—C15	117.4 (3)	N4—C19—C20	123.1 (3)
C11—N3—Cu	121.7 (2)	N4—C19—H19	118.4
C15—N3—Cu	120.9 (2)	C20—C19—H19	118.4
C19—N4—C18	117.1 (3)	C19—C20—C16	119.6 (3)
N1—C1—C2	122.6 (3)	C19—C20—H20	120.2
N1—C1—H1	118.7	C16—C20—H20	120.2
C2—C1—H1	118.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H01···O2^i	0.82 (2)	1.76 (2)	2.570 (3)	170 (4)
O3—H03···N4^ii	0.83 (2)	1.81 (2)	2.627 (3)	170 (4)
O7—H07···O5^iii	0.83 (2)	1.74 (2)	2.570 (3)	175 (4)
O8—H08···N2^iv	0.81 (2)	1.84 (2)	2.646 (3)	170 (4)
O9—H9A···O2	0.82 (2)	1.97 (2)	2.780 (3)	168 (4)
O9—H9B···O2^v	0.81 (2)	2.13 (2)	2.918 (3)	163 (3)
O10—H10A···O5^vi	0.82 (2)	2.11 (2)	2.909 (3)	166 (3)
O10—H10B···O5	0.84 (2)	2.02 (2)	2.800 (3)	156 (3)

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