Comparative study of two chemically isostructural polymers: [Cu₂(VO₂)(HPO₄)₂(NO₃)(bpy)₂]·2H₂O/H₃PO₄ (bpy is 2,2′-bi­pyridine)

The title compounds, poly­[bis(2,2′-bi­pyridine)­bis(μ₃-hydrogen phosphato)­nitratodi-μ₂-oxo-dicopper(II)­vanadium dihydrate], [Cu₂(VO₂)(HPO₄)₂(NO₃)(C₁₀H₈N₂)₂]·2H₂O, (I), and poly­[bis(2,2′-bi­pyridine)­bis(μ₃-hydrogen phosphato)­nitratodi-μ₂-oxo-dicopper(II)­vanadium phospho­ric acid solvate], [Cu₂(VO₂)(HPO₄)₂(NO₃)(C₁₀H₈N₂)₂]·H₃PO₄, (II), were obtained by similar hydro­thermal methods but under different crystallization conditions. The trinuclear entity which serves as the basic unit in both structures presents two independent Cu^II ions immersed in similar square-pyramidal N₂O₃ environments plus an octahedral VO₆ core and is organized into a one-dimensional polymer, which is essentially identical in the two structures. The compounds are stabilized by different solvates, viz. two crystallization water mol­ecules in (I) and a phospho­ric acid mol­ecule in (II), which provide the main structural differences through the diversity of interchain interactions in which they serve as bridges.

S1. Comment

Vanadium phosphates have been extensively investigated in recent years due to their catalytic activity (Cheetham et al., 1999), physical properties (mainly magnetic; Moreno et al., 2003), ability as ionic interchangers, etc. Of particular interest is VO₂PO₄, a layered compound that can undergo intercalation reactions (Shi et al., 2000). A variety of guest species, including pyridine, aniline, amides, amines, carboxylic acid, alcohol and diols (Yang & Lu, 2002) have been inserted between the layers by displacement of a coordinated water molecule. Other guest species, such as alkyl ammonium ions and ferrocene, have been intercalated through partial or complete reduction of V^V to V^IV (or an even lower oxidation state) in the host structure (Shpeizer et al., 2001; Huang et al., 2001).

Our interest in vanadyl phosphates stems from the possibility of linking their polyhedra in order to create one-, two- or three-dimensional host structures with an organic or organometallic guest compound inside, to which the host can be bound either through strong covalent links or weaker hydrogen-bonded interactions.

Hydrothermal methods offer a feasible synthetic route to this type of compound through the chemical reaction of appropriate reagents in a sealed heated solution kept above ambient temperature and pressure (Feng & Xu, 2001). Under these conditions, the phosphate and vanadate polyhedra are prone to share vertices or edges in order to give rise to chains, planes or three-dimensional structures (Pivan et al., 2001).

In addition, this framework can bind to other systems, such as metal complexes, and thus give rise to compounds with a variety of interesting physical properties. In particular, magnetic coupling of metal centres can be achieved though this kind of architecture (Kahn, 1993; Kahn et al., 1982). For this to happen, it is necessary that the metal centres be coordinated in proximity to one another, and this implies that the ligands involved should have coordinating centres relatively close to one another so as to render this feasible. We present here structural results arising from these ideas for two compounds, [Cu₂(HPO₄)₂(VO₂)(NO₃)(bpy)₂]·Solvate, where bpy is 1,10-bipyridine and Solvate represents 2H₂O in (I) and H₃PO₄ in (II). These are two chemically isostructural systems obtained by hydrothermal methods, which only differ in the solvate molecules stabilizing the structures. \sch

Fig. 1 presents views of both structures, showing the common numbering scheme. The elemental unit is a trinuclear entity centred on two Cu^II ions and one vanadyl group, coordinated by two bpy, two phosphate and one nitrate ligand. The two structures are stabilized by different solvate units [water in (I) and phosphoric acid in (II)]. Each independent Cu atom (A and B) is surrounded by a five-coordinate environment provided by two N atoms from the chelating bpy unit and three O atoms coming from two symmetry-related phosphate units and the vanadyl group.

The Cu coordination polyhedron has the shape of a square pyramid, where the Cu—O_vanadyl bond occupies the apical position and the remainder establish the distorted square base.

The vanadyl group is immersed in an irregular octahedral environment, where the original geometry of the VO₂ entity is preserved, as shown by the extremely short V—O distances and the almost tetrahedral O1—V1—O2 angle. This is somewhat compensated by the chelating nitrate, with a small angle and two rather long V—O distances trans to atoms O1 and O2, in what could be considered the equatorial plane of the octahedron. Two phosphate atoms, O1A and O1B, complete the coordination, filling the apical positions at an intermediate distance from the cation. Besides the usual selected distances and angles provided by Tables 1 and 3, Table 5 gives additional information regarding the coordination polyhedra.

All the phosphate groups, as well as the phosphoric acid molecule in (II), have regular geometries. The former present a very clear distinction between P—O_coord and P—OH bond lengths, the non-coordinated one being longer by a percentage ranging from 5% to 9%. A similar situation arises with the solvate unit, in which the P═O bond is shorter than the mean of the P—OH bonds by a similar amount (ca 5%), as well as with the nitrate (N═O < N—O_coord by ca 2.5–3%) (See Tables 1 and 3 for details).

The PO₄H units act as active coordination agents, giving rise to strongly coupled chains of polyhedra. Their elemental constituents are the dimeric units (A and B) which build up around two independent symmetry centres in P1 [A at (1/2,1/2,0) and B at (1/2,-1,1/2) for (I), and A at (1,1,0) and B at (1,1,1/2) for (II)] and which result in very similar Cu—O—P—O-(Cu'-O'-P'-O') loops. The V atom, in turn, has a twofold binding to each of the independent Cu^II ions, through one of the vanadyl O atoms on one side, and through a longer O—P—O bridge on the other. The intercationic distances arising from this arrangement are rather large: Cu1A···Cu1A(−1 − x, −1 − y, −z) 5.077 (1) Å, Cu1B···Cu1B(−1 − x, −3 − y, −1 − z) 5.013 (1) Å, V1···Cu1A 3.634 (1) Å and V1···Cu1B(−1 − x, −3 − y, −1 − z) 3.578 (1) Å for (I), and Cu1A···Cu1A(2 − x, 2 − y, −z) 5.073 (1) Å, Cu1B···Cu1B(2 − x, 2 − y, 1 − z) 5.061 (1) Å, V1···Cu1A 3.688 (1) Å and V1···Cu1B(2 − x, 2 − y, 1 − z) 3.618 (1) Å for (II).

The resulting chains, flattened into the shape of strips with the aromatic groups protruding outward on the `wide' side, are fairly isostructural, as can be assessed by inspection of Fig. 2, where both structures have been superimposed, leading to a mean deviation of 0.32 (1) Å for all common atoms, which reduces to 0.05 (1) Å when only the cations are considered.

The main differences between the two structures are due to the inter-chain interactions, which arise from two well differentiated effects. On one hand, the stronger hydrogen-bonding interactions mediated by the active donor solvates [H₂O in (I) and PO₄H₃ in (II)] link the chains through their `narrow' dimension into hydrogen-bonded planes parallel to (011) in (I) and to (100) in (II) (see Tables 2 and 4, and Fig. 3). These hydrogen-bonded planes, in turn, interact with each other through weaker π–π contacts between interleaving bpy groups of neighbouring planes, at a graphitic distance (ca 3.4 Å) from each other (Table 6, Fig. 4). In spite of the strength of the forces involved, the second type of interaction leads to shorter intercationic distances (out-of-plane-Cu···Cu < 5.7 Å, versus in-plane-Cu···Cu > 9.5 Å).

Summarizing, we have generated two different, though basically isostructural, compounds from the same solution subject to hydrothermal treatment. They present the same polymeric one-dimensional motif and the structures differ only in the way in which the chains interact with each other through the different hydrogen-bonding schemes mediated by the different solvent molecules present.

S2. Experimental

Both compounds were obtained via hydrothermal synthesis, as follows. A mixture of V₂O₅ (0.84 mmol), 2,2'-bipyridine (0.85 mmol), Cu(NO₃)₂·3H₂O (1.68 mmol), zinc powder (1.62 mmol) and H₃PO₄ (5 ml, 1.48 M) was sealed in a Teflon-lined acid digestion bomb and heated at 390 K for 3 d under autogenous pressure, followed by slow cooling at 20 K h⁻¹ to room temperature. The immediate product of the reaction consisted of green prismatic crystals of (II). Left unattended for several weeks, the remaining mother liquor yielded a crop of similarly shaped and coloured crystals, corresponding to compound (I).

S3. Refinement

H atoms attached to C atoms and unambiguously defined by stereochemistry were placed in calculated positions (C—H = 0.93 Å) and allowed to ride, with U_iso(H) = 1.2U_eq(C). Please check added text. Those attached to O atoms were located in late-stage difference maps and refined with restrained distances O—H = 0.82 (1) and H···H = 1.36 (2) Å. Full use of the CCDC package was made for searching in the Cambridge Structural Database (Allen, 2002).

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. Molecular diagrams showing the numbering scheme used, as well as the way in which chains are formed, for (a) compound (I) and (b) compound (II). Full ellipsoids denote the independent unit, with full bonds corresponding to the backbone and empty bonds to the solvent molecules. Empty ellipsoids represent the symmetry-generated part of the structure. Displacement ellipsoids are drawn at the 40% level. H atoms attached to C atoms have been omitted for clarity.
	Fig. 2. Superimposed drawings of the two backbones of (I) and (II), showing their isostructural character.
	Fig. 3. Polyhedral diagram showing a lateral view of the chains, and the manner in which they attach to each other through a diversity of hydrogen-bonding interactions mediated by the different solvents. (a) Compound (I). (b) Compound (II).
	Fig. 4. Polyhedral diagrams showing the linking of the hydrogen-bonded planes through weaker π–π interactions between interleaved bpy groups of neighbouring planes. (a) Compound (I). (b) Compound (II).

(I) Poly[bis(2,2'-bipyridyl)bis(µ₃-hydrogen phosphato)nitrato-di-µ₂oxo-dicopper(II)vanadium dihydrate]

Crystal data

[Cu2V(HPO4)2(NO3)O2(C10H8N2)2]·2H2O	Z = 2
Mr = 812.39	F(000) = 816
Triclinic, P1	Dx = 1.978 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5927 (13) Å	Cell parameters from 2933 reflections
b = 12.0359 (15) Å	θ = 5.0–54.2°
c = 12.1655 (15) Å	µ = 2.08 mm^−1
α = 107.090 (2)°	T = 293 K
β = 110.399 (2)°	Prism, green
γ = 93.876 (2)°	0.28 × 0.24 × 0.16 mm
V = 1364.3 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4697 independent reflections
Radiation source: fine-focus sealed tube	3098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→12
Tmin = 0.57, Tmax = 0.72	k = −14→12
5669 measured reflections	l = −14→13

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0234P)^2] where P = (Fo^2 + 2Fc^2)/3
4697 reflections	(Δ/σ)max = 0.012
424 parameters	Δρmax = 0.53 e Å^−3
8 restraints	Δρmin = −0.45 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1A	−0.49668 (6)	−0.46008 (6)	−0.19268 (5)	0.02646 (17)
Cu1B	−0.46239 (6)	−0.95434 (6)	−0.67567 (5)	0.02608 (17)
V1	−0.38098 (8)	−0.73936 (8)	−0.20562 (8)	0.0266 (2)
P1A	−0.31099 (13)	−0.51393 (12)	0.04277 (12)	0.0250 (3)
P1B	−0.30809 (13)	−0.94874 (13)	−0.39950 (12)	0.0263 (3)
O1A	−0.3509 (3)	−0.6459 (3)	−0.0339 (3)	0.0295 (8)
O2A	−0.3615 (3)	−0.4863 (3)	0.1470 (3)	0.0330 (9)
O3A	−0.1481 (3)	−0.4825 (4)	0.1159 (3)	0.0391 (10)
H3A	−0.115 (5)	−0.460 (5)	0.073 (4)	0.047*
O4A	−0.3463 (3)	−0.4390 (3)	−0.0388 (3)	0.0273 (8)
O1B	−0.3303 (3)	−0.8246 (3)	−0.3426 (3)	0.0279 (8)
O2B	−0.3951 (3)	−1.0439 (3)	−0.3861 (3)	0.0292 (8)
O3B	−0.1556 (3)	−0.9567 (4)	−0.3253 (3)	0.0397 (10)
H3B	−0.098 (4)	−0.903 (3)	−0.315 (5)	0.048*
O4B	−0.3219 (3)	−0.9704 (3)	−0.5327 (3)	0.0299 (9)
O1D	−0.1652 (3)	−0.6367 (3)	−0.1450 (3)	0.0379 (9)
O2D	−0.1778 (4)	−0.7890 (3)	−0.0899 (3)	0.0389 (10)
O3D	0.0207 (4)	−0.6813 (4)	−0.0378 (4)	0.0613 (13)
N1A	−0.6332 (4)	−0.4173 (4)	−0.3305 (3)	0.0277 (10)
N2A	−0.3722 (4)	−0.4104 (4)	−0.2680 (3)	0.0265 (10)
N1B	−0.5802 (4)	−0.9081 (4)	−0.8175 (3)	0.0264 (10)
N2B	−0.3204 (4)	−0.9151 (4)	−0.7394 (3)	0.0257 (10)
N1D	−0.1042 (5)	−0.7019 (4)	−0.0892 (4)	0.0341 (11)
C1A	−0.7661 (5)	−0.4220 (5)	−0.3549 (4)	0.0342 (14)
H1AA	−0.8039	−0.4534	−0.3095	0.041*
C2A	−0.8505 (5)	−0.3825 (5)	−0.4446 (5)	0.0401 (15)
H2AA	−0.9429	−0.3858	−0.4583	0.048*
C3A	−0.7955 (6)	−0.3381 (5)	−0.5135 (5)	0.0436 (16)
H3AA	−0.8505	−0.3115	−0.5751	0.052*
C4A	−0.6579 (6)	−0.3334 (5)	−0.4901 (5)	0.0367 (14)
H4AA	−0.6186	−0.3041	−0.5358	0.044*
C5A	−0.5793 (5)	−0.3732 (4)	−0.3974 (4)	0.0286 (13)
C6A	−0.4308 (5)	−0.3708 (5)	−0.3635 (4)	0.0284 (13)
C7A	−0.3550 (5)	−0.3312 (5)	−0.4221 (5)	0.0356 (14)
H7AA	−0.3961	−0.3023	−0.4864	0.043*
C8A	−0.2175 (6)	−0.3357 (5)	−0.3828 (5)	0.0433 (16)
H8AA	−0.1647	−0.3106	−0.4212	0.052*
C9A	−0.1580 (5)	−0.3774 (5)	−0.2866 (5)	0.0375 (14)
H9AA	−0.0652	−0.3810	−0.2593	0.045*
C10A	−0.2391 (6)	−0.4136 (5)	−0.2320 (5)	0.0367 (14)
H10A	−0.1990	−0.4417	−0.1668	0.044*
C1B	−0.7147 (5)	−0.9104 (5)	−0.8540 (5)	0.0352 (14)
H1BA	−0.7617	−0.9385	−0.8128	0.042*
C2B	−0.7870 (6)	−0.8726 (5)	−0.9506 (5)	0.0393 (15)
H2BA	−0.8807	−0.8742	−0.9729	0.047*
C3B	−0.7191 (6)	−0.8328 (5)	−1.0129 (5)	0.0385 (15)
H3BA	−0.7661	−0.8072	−1.0783	0.046*
C4B	−0.5808 (5)	−0.8310 (5)	−0.9779 (4)	0.0336 (13)
H4BA	−0.5329	−0.8039	−1.0191	0.040*
C5B	−0.5134 (5)	−0.8701 (4)	−0.8805 (4)	0.0268 (12)
C6B	−0.3651 (5)	−0.8744 (4)	−0.8355 (4)	0.0238 (12)
C7B	−0.2774 (5)	−0.8427 (5)	−0.8879 (5)	0.0354 (14)
H7BA	−0.3096	−0.8144	−0.9540	0.042*
C8B	−0.1426 (6)	−0.8536 (5)	−0.8410 (5)	0.0387 (14)
H8BA	−0.0825	−0.8325	−0.8749	0.046*
C9B	−0.0973 (5)	−0.8959 (5)	−0.7440 (5)	0.0389 (15)
H9BA	−0.0065	−0.9047	−0.7118	0.047*
C10B	−0.1883 (5)	−0.9249 (5)	−0.6953 (5)	0.0351 (14)
H10B	−0.1570	−0.9527	−0.6288	0.042*
O1	−0.4734 (3)	−0.6575 (3)	−0.2753 (3)	0.0305 (9)
O2	−0.4872 (3)	−0.8489 (3)	−0.2158 (3)	0.0307 (9)
O1W	0.2404 (5)	−0.7931 (5)	−0.3923 (5)	0.0701 (14)
H1WA	0.303 (5)	−0.753 (4)	−0.325 (3)	0.084*
H1WB	0.263 (6)	−0.858 (3)	−0.414 (5)	0.084*
O2W	0.0369 (5)	−0.7826 (4)	−0.3052 (5)	0.0695 (14)
H2WA	0.088 (5)	−0.800 (5)	−0.343 (5)	0.083*
H2WB	0.063 (6)	−0.714 (2)	−0.259 (5)	0.083*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1A	0.0317 (4)	0.0288 (4)	0.0250 (3)	0.0077 (3)	0.0143 (3)	0.0134 (3)
Cu1B	0.0332 (4)	0.0272 (4)	0.0260 (4)	0.0087 (3)	0.0166 (3)	0.0136 (3)
V1	0.0318 (5)	0.0262 (5)	0.0261 (5)	0.0080 (4)	0.0139 (4)	0.0112 (4)
P1A	0.0261 (7)	0.0277 (8)	0.0236 (7)	0.0044 (6)	0.0108 (6)	0.0111 (6)
P1B	0.0287 (8)	0.0324 (9)	0.0252 (7)	0.0110 (6)	0.0142 (6)	0.0147 (7)
O1A	0.037 (2)	0.025 (2)	0.0262 (19)	0.0086 (16)	0.0109 (16)	0.0097 (17)
O2A	0.038 (2)	0.043 (3)	0.0233 (19)	0.0079 (18)	0.0170 (17)	0.0126 (18)
O3A	0.027 (2)	0.057 (3)	0.034 (2)	0.0054 (19)	0.0110 (17)	0.017 (2)
O4A	0.036 (2)	0.024 (2)	0.0233 (18)	0.0052 (16)	0.0099 (16)	0.0118 (16)
O1B	0.039 (2)	0.027 (2)	0.0268 (19)	0.0143 (16)	0.0184 (16)	0.0123 (17)
O2B	0.035 (2)	0.033 (2)	0.033 (2)	0.0123 (17)	0.0224 (17)	0.0187 (18)
O3B	0.033 (2)	0.054 (3)	0.045 (2)	0.0202 (19)	0.018 (2)	0.028 (2)
O4B	0.036 (2)	0.037 (2)	0.0233 (18)	0.0094 (17)	0.0167 (16)	0.0133 (17)
O1D	0.039 (2)	0.041 (3)	0.042 (2)	0.0104 (19)	0.0174 (19)	0.023 (2)
O2D	0.048 (2)	0.040 (3)	0.035 (2)	0.0052 (19)	0.0204 (19)	0.0165 (19)
O3D	0.028 (2)	0.076 (4)	0.069 (3)	0.008 (2)	0.006 (2)	0.026 (3)
N1A	0.035 (3)	0.028 (3)	0.024 (2)	0.011 (2)	0.013 (2)	0.012 (2)
N2A	0.026 (2)	0.025 (3)	0.026 (2)	0.0055 (19)	0.010 (2)	0.006 (2)
N1B	0.033 (3)	0.025 (3)	0.028 (2)	0.0086 (19)	0.017 (2)	0.012 (2)
N2B	0.035 (3)	0.025 (3)	0.022 (2)	0.009 (2)	0.015 (2)	0.011 (2)
N1D	0.033 (3)	0.038 (3)	0.031 (3)	0.007 (2)	0.013 (2)	0.008 (2)
C1A	0.036 (3)	0.038 (4)	0.026 (3)	0.007 (3)	0.012 (3)	0.008 (3)
C2A	0.037 (3)	0.043 (4)	0.039 (3)	0.015 (3)	0.012 (3)	0.015 (3)
C3A	0.048 (4)	0.041 (4)	0.035 (3)	0.012 (3)	0.006 (3)	0.016 (3)
C4A	0.053 (4)	0.029 (4)	0.030 (3)	0.011 (3)	0.015 (3)	0.013 (3)
C5A	0.043 (3)	0.022 (3)	0.023 (3)	0.010 (2)	0.015 (3)	0.008 (2)
C6A	0.038 (3)	0.025 (3)	0.020 (3)	0.006 (2)	0.009 (2)	0.008 (2)
C7A	0.046 (4)	0.036 (4)	0.035 (3)	0.010 (3)	0.021 (3)	0.020 (3)
C8A	0.054 (4)	0.039 (4)	0.045 (4)	0.001 (3)	0.033 (3)	0.012 (3)
C9A	0.037 (3)	0.037 (4)	0.041 (3)	0.003 (3)	0.018 (3)	0.013 (3)
C10A	0.051 (4)	0.028 (3)	0.030 (3)	0.006 (3)	0.015 (3)	0.008 (3)
C1B	0.043 (4)	0.032 (4)	0.034 (3)	0.009 (3)	0.020 (3)	0.010 (3)
C2B	0.047 (4)	0.038 (4)	0.035 (3)	0.016 (3)	0.014 (3)	0.016 (3)
C3B	0.057 (4)	0.032 (4)	0.027 (3)	0.018 (3)	0.011 (3)	0.016 (3)
C4B	0.041 (3)	0.035 (4)	0.032 (3)	0.014 (3)	0.016 (3)	0.019 (3)
C5B	0.046 (3)	0.018 (3)	0.024 (3)	0.010 (2)	0.019 (3)	0.011 (2)
C6B	0.031 (3)	0.019 (3)	0.026 (3)	0.006 (2)	0.018 (2)	0.007 (2)
C7B	0.046 (4)	0.039 (4)	0.032 (3)	0.013 (3)	0.022 (3)	0.018 (3)
C8B	0.048 (4)	0.033 (4)	0.046 (4)	0.009 (3)	0.028 (3)	0.017 (3)
C9B	0.037 (3)	0.039 (4)	0.050 (4)	0.009 (3)	0.021 (3)	0.022 (3)
C10B	0.038 (3)	0.037 (4)	0.037 (3)	0.010 (3)	0.016 (3)	0.019 (3)
O1	0.038 (2)	0.032 (2)	0.0261 (19)	0.0148 (17)	0.0130 (17)	0.0140 (17)
O2	0.036 (2)	0.029 (2)	0.032 (2)	0.0052 (16)	0.0196 (17)	0.0086 (17)
O1W	0.058 (3)	0.075 (4)	0.082 (4)	0.020 (3)	0.027 (3)	0.032 (3)
O2W	0.057 (3)	0.066 (4)	0.083 (4)	0.010 (3)	0.035 (3)	0.013 (3)

Geometric parameters (Å, º)

Cu1A—O2A^i	1.909 (3)	C1A—H1AA	0.9300
Cu1A—O4A	1.922 (3)	C2A—C3A	1.374 (7)
Cu1A—N2A	1.999 (4)	C2A—H2AA	0.9300
Cu1A—N1A	2.021 (4)	C3A—C4A	1.379 (7)
Cu1A—O1	2.360 (3)	C3A—H3AA	0.9300
Cu1B—O2B^ii	1.908 (3)	C4A—C5A	1.381 (6)
Cu1B—O4B	1.926 (3)	C4A—H4AA	0.9300
Cu1B—N1B	2.001 (4)	C5A—C6A	1.476 (7)
Cu1B—N2B	2.004 (4)	C6A—C7A	1.390 (6)
Cu1B—O2^ii	2.267 (3)	C7A—C8A	1.376 (7)
V1—O2	1.620 (3)	C7A—H7AA	0.9300
V1—O1	1.640 (3)	C8A—C9A	1.375 (7)
V1—O1B	1.952 (3)	C8A—H8AA	0.9300
V1—O1A	1.959 (3)	C9A—C10A	1.373 (7)
V1—O1D	2.281 (3)	C9A—H9AA	0.9300
V1—O2D	2.351 (4)	C10A—H10A	0.9300
P1A—O4A	1.500 (3)	C1B—C2B	1.381 (6)
P1A—O2A	1.501 (3)	C1B—H1BA	0.9300
P1A—O1A	1.528 (3)	C2B—C3B	1.367 (7)
P1A—O3A	1.599 (4)	C2B—H2BA	0.9300
P1B—O2B	1.503 (3)	C3B—C4B	1.373 (7)
P1B—O4B	1.515 (3)	C3B—H3BA	0.9300
P1B—O1B	1.523 (3)	C4B—C5B	1.385 (6)
P1B—O3B	1.577 (4)	C4B—H4BA	0.9300
O3A—H3A	0.82 (4)	C5B—C6B	1.483 (7)
O3B—H3B	0.81 (4)	C6B—C7B	1.386 (6)
O1D—N1D	1.253 (5)	C7B—C8B	1.372 (7)
O2D—N1D	1.259 (5)	C7B—H7BA	0.9300
O3D—N1D	1.221 (5)	C8B—C9B	1.368 (7)
N1A—C1A	1.327 (6)	C8B—H8BA	0.9300
N1A—C5A	1.344 (6)	C9B—C10B	1.370 (6)
N2A—C10A	1.330 (6)	C9B—H9BA	0.9300
N2A—C6A	1.350 (6)	C10B—H10B	0.9300
N1B—C1B	1.332 (6)	O2—Cu1B^ii	2.267 (3)
N1B—C5B	1.355 (6)	O1W—H1WA	0.83 (4)
N2B—C10B	1.341 (6)	O1W—H1WB	0.83 (4)
N2B—C6B	1.346 (5)	O2W—H2WA	0.83 (4)
C1A—C2A	1.378 (7)	O2W—H2WB	0.82 (4)
O2A^i—Cu1A—O4A	96.83 (13)	C6B—N2B—Cu1B	115.2 (3)
O2A^i—Cu1A—N2A	170.68 (14)	O3D—N1D—O1D	120.9 (5)
O4A—Cu1A—N2A	92.42 (14)	O3D—N1D—O2D	122.3 (5)
O2A^i—Cu1A—N1A	91.52 (15)	O1D—N1D—O2D	116.8 (4)
O4A—Cu1A—N1A	158.98 (16)	N1A—C1A—C2A	122.9 (5)
N2A—Cu1A—N1A	80.14 (16)	N1A—C1A—H1AA	118.5
O2A^i—Cu1A—O1	90.03 (13)	C2A—C1A—H1AA	118.5
O4A—Cu1A—O1	90.76 (12)	C3A—C2A—C1A	118.7 (5)
N2A—Cu1A—O1	88.72 (14)	C3A—C2A—H2AA	120.6
N1A—Cu1A—O1	108.56 (14)	C1A—C2A—H2AA	120.6
O2B^ii—Cu1B—O4B	95.86 (13)	C2A—C3A—C4A	119.1 (5)
O2B^ii—Cu1B—N1B	91.26 (15)	C2A—C3A—H3AA	120.4
O4B—Cu1B—N1B	168.04 (15)	C4A—C3A—H3AA	120.4
O2B^ii—Cu1B—N2B	166.80 (16)	C3A—C4A—C5A	118.8 (5)
O4B—Cu1B—N2B	90.38 (14)	C3A—C4A—H4AA	120.6
N1B—Cu1B—N2B	80.78 (16)	C5A—C4A—H4AA	120.6
O2B^ii—Cu1B—O2^ii	95.54 (13)	N1A—C5A—C4A	122.1 (5)
O4B—Cu1B—O2^ii	93.38 (13)	N1A—C5A—C6A	114.5 (4)
N1B—Cu1B—O2^ii	95.49 (14)	C4A—C5A—C6A	123.3 (5)
N2B—Cu1B—O2^ii	95.69 (14)	N2A—C6A—C7A	121.6 (5)
O2—V1—O1	106.87 (17)	N2A—C6A—C5A	114.1 (4)
O2—V1—O1B	97.03 (15)	C7A—C6A—C5A	124.2 (5)
O1—V1—O1B	97.37 (14)	C8A—C7A—C6A	118.4 (5)
O2—V1—O1A	95.48 (15)	C8A—C7A—H7AA	120.8
O1—V1—O1A	97.87 (15)	C6A—C7A—H7AA	120.8
O1B—V1—O1A	156.54 (13)	C7A—C8A—C9A	120.1 (5)
O2—V1—O1D	152.42 (15)	C7A—C8A—H8AA	120.0
O1—V1—O1D	100.71 (15)	C9A—C8A—H8AA	120.0
O1B—V1—O1D	78.85 (13)	C10A—C9A—C8A	118.3 (5)
O1A—V1—O1D	80.87 (13)	C10A—C9A—H9AA	120.8
O2—V1—O2D	97.45 (15)	C8A—C9A—H9AA	120.8
O1—V1—O2D	155.61 (15)	N2A—C10A—C9A	123.1 (5)
O1B—V1—O2D	81.07 (12)	N2A—C10A—H10A	118.5
O1A—V1—O2D	77.68 (13)	C9A—C10A—H10A	118.5
O1D—V1—O2D	55.00 (12)	N1B—C1B—C2B	122.6 (5)
O4A—P1A—O2A	115.7 (2)	N1B—C1B—H1BA	118.7
O4A—P1A—O1A	111.67 (18)	C2B—C1B—H1BA	118.7
O2A—P1A—O1A	111.39 (19)	C3B—C2B—C1B	119.1 (5)
O4A—P1A—O3A	106.84 (19)	C3B—C2B—H2BA	120.4
O2A—P1A—O3A	102.49 (19)	C1B—C2B—H2BA	120.4
O1A—P1A—O3A	108.0 (2)	C2B—C3B—C4B	119.3 (5)
O2B—P1B—O4B	113.38 (19)	C2B—C3B—H3BA	120.3
O2B—P1B—O1B	113.39 (19)	C4B—C3B—H3BA	120.3
O4B—P1B—O1B	110.29 (19)	C3B—C4B—C5B	119.1 (5)
O2B—P1B—O3B	104.8 (2)	C3B—C4B—H4BA	120.4
O4B—P1B—O3B	106.1 (2)	C5B—C4B—H4BA	120.4
O1B—P1B—O3B	108.3 (2)	N1B—C5B—C4B	121.7 (5)
P1A—O1A—V1	134.8 (2)	N1B—C5B—C6B	114.1 (4)
P1A—O2A—Cu1A^i	142.0 (2)	C4B—C5B—C6B	124.2 (4)
P1A—O3A—H3A	108 (4)	N2B—C6B—C7B	121.3 (4)
P1A—O4A—Cu1A	132.4 (2)	N2B—C6B—C5B	114.5 (4)
P1B—O1B—V1	138.0 (2)	C7B—C6B—C5B	124.2 (5)
P1B—O2B—Cu1B^ii	134.2 (2)	C8B—C7B—C6B	119.2 (5)
P1B—O3B—H3B	115 (4)	C8B—C7B—H7BA	120.4
P1B—O4B—Cu1B	133.0 (2)	C6B—C7B—H7BA	120.4
N1D—O1D—V1	95.8 (3)	C9B—C8B—C7B	119.6 (5)
N1D—O2D—V1	92.4 (3)	C9B—C8B—H8BA	120.2
C1A—N1A—C5A	118.3 (4)	C7B—C8B—H8BA	120.2
C1A—N1A—Cu1A	126.4 (3)	C8B—C9B—C10B	118.6 (5)
C5A—N1A—Cu1A	115.1 (3)	C8B—C9B—H9BA	120.7
C10A—N2A—C6A	118.6 (4)	C10B—C9B—H9BA	120.7
C10A—N2A—Cu1A	125.5 (4)	N2B—C10B—C9B	122.9 (5)
C6A—N2A—Cu1A	115.9 (3)	N2B—C10B—H10B	118.5
C1B—N1B—C5B	118.2 (4)	C9B—C10B—H10B	118.5
C1B—N1B—Cu1B	126.6 (3)	V1—O1—Cu1A	129.75 (16)
C5B—N1B—Cu1B	115.2 (3)	V1—O2—Cu1B^ii	133.36 (18)
C10B—N2B—C6B	118.3 (4)	H1WA—O1W—H1WB	106 (3)
C10B—N2B—Cu1B	126.4 (3)	H2WA—O2W—H2WB	109 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O3D^iii	0.82 (4)	2.14 (5)	2.871 (5)	150 (5)
O3B—H3B···O2W	0.81 (4)	1.91 (5)	2.718 (5)	175 (6)
O1W—H1WA···O1^iv	0.83 (4)	2.35 (5)	2.973 (6)	132 (6)
O1W—H1WB···O4B^v	0.83 (4)	2.18 (5)	3.006 (6)	179 (7)
O2W—H2WA···O1W	0.83 (4)	1.91 (5)	2.708 (7)	162 (5)
O2W—H2WB···O3A^iii	0.82 (4)	2.37 (5)	3.186 (6)	177 (7)

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

(II) Poly[bis(2,2'-bipyridyl)bis(µ₃-hydrogen phosphato)nitrato-di-µ₂oxo-dicopper(II)vanadium phosphoric acid solvate]

Crystal data

[Cu2V(HPO4)2(NO3)O2(C10H8N2)2]·H3PO4	Z = 2
Mr = 874.35	F(000) = 876
Triclinic, P1	Dx = 2.102 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8343 (13) Å	Cell parameters from 2467 reflections
b = 10.4632 (14) Å	θ = 5.8–51.3°
c = 14.3210 (19) Å	µ = 2.13 mm^−1
α = 72.070 (2)°	T = 299 K
β = 89.900 (2)°	Prism, green
γ = 80.651 (2)°	0.32 × 0.24 × 0.18 mm
V = 1381.6 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4812 independent reflections
Radiation source: fine-focus sealed tube	2471 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.55, Tmax = 0.68	k = −12→11
8625 measured reflections	l = −17→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0666P)^2] where P = (Fo^2 + 2Fc^2)/3
4812 reflections	(Δ/σ)max = 0.016
448 parameters	Δρmax = 0.76 e Å^−3
11 restraints	Δρmin = −0.83 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1A	1.23190 (11)	1.01432 (11)	0.06983 (8)	0.0192 (3)
Cu1B	1.23268 (11)	1.01758 (11)	0.56558 (8)	0.0189 (3)
V1	0.96825 (15)	1.12069 (16)	0.22687 (11)	0.0177 (4)
P1A	0.9375 (2)	1.1882 (2)	−0.00838 (17)	0.0160 (5)
P1B	0.9657 (2)	1.1911 (2)	0.43429 (17)	0.0170 (6)
P1C	1.0903 (3)	0.6371 (3)	0.33084 (18)	0.0235 (6)
O1A	0.8878 (6)	1.1447 (6)	0.0944 (4)	0.0208 (15)
O2A	0.8521 (6)	1.1419 (6)	−0.0767 (4)	0.0205 (14)
O3A	0.8994 (6)	1.3483 (6)	−0.0487 (5)	0.0276 (16)
H3A	0.969 (2)	1.3789 (15)	−0.074 (5)	0.033*
O4A	1.0910 (5)	1.1477 (6)	−0.0139 (4)	0.0202 (15)
O1B	1.0205 (6)	1.1752 (6)	0.3391 (4)	0.0217 (15)
O2B	0.8478 (6)	1.1172 (6)	0.4704 (4)	0.0243 (15)
O3B	0.9062 (6)	1.3513 (6)	0.4090 (4)	0.0220 (15)
H3B	0.887 (8)	1.364 (2)	0.4614 (14)	0.026*
O4B	1.0811 (6)	1.1637 (6)	0.5124 (4)	0.0236 (15)
O1C	0.9545 (6)	0.7397 (7)	0.3121 (6)	0.0379 (18)
H1C	0.966 (2)	0.816 (3)	0.310 (7)	0.045*
O2C	1.1502 (7)	0.5888 (6)	0.4324 (4)	0.0334 (17)
O3C	1.0526 (7)	0.5233 (7)	0.2948 (5)	0.0335 (17)
H3C	1.001 (8)	0.479 (6)	0.332 (4)	0.040*
O4C	1.1983 (6)	0.6978 (7)	0.2599 (5)	0.0317 (17)
H4C	1.164 (2)	0.764 (6)	0.215 (4)	0.038*
O1D	1.0136 (6)	1.3273 (6)	0.1528 (4)	0.0246 (15)
O2D	0.8063 (6)	1.3278 (7)	0.1988 (5)	0.0319 (17)
O3D	0.8722 (7)	1.5213 (7)	0.1215 (5)	0.0394 (19)
O1	1.1138 (6)	1.0292 (6)	0.2165 (4)	0.0260 (16)
O2	0.8658 (6)	1.0153 (6)	0.2843 (4)	0.0252 (16)
N1A	1.4170 (7)	0.8949 (7)	0.1153 (5)	0.0187 (17)
N2A	1.3409 (7)	1.1513 (7)	0.0804 (5)	0.0199 (18)
N1B	1.4109 (7)	0.8881 (7)	0.6153 (5)	0.0187 (18)
N2B	1.3517 (7)	1.1535 (7)	0.5794 (5)	0.0174 (17)
N1D	0.8962 (8)	1.3960 (9)	0.1570 (6)	0.027 (2)
C1A	1.4493 (9)	0.7623 (9)	0.1296 (6)	0.022 (2)
H1AA	1.3811	0.7160	0.1184	0.027*
C2A	1.5790 (10)	0.6905 (10)	0.1603 (7)	0.029 (2)
H2AA	1.5976	0.5971	0.1703	0.035*
C3A	1.6808 (9)	0.7571 (10)	0.1762 (7)	0.027 (2)
H3AA	1.7694	0.7098	0.1975	0.033*
C4A	1.6506 (9)	0.8923 (10)	0.1605 (7)	0.025 (2)
H4AA	1.7186	0.9400	0.1700	0.030*
C5A	1.5181 (9)	0.9597 (9)	0.1302 (6)	0.018 (2)
C6A	1.4730 (8)	1.1061 (9)	0.1114 (6)	0.020 (2)
C7A	1.5569 (10)	1.1934 (10)	0.1213 (7)	0.030 (2)
H7AA	1.6494	1.1606	0.1410	0.036*
C8A	1.5053 (10)	1.3300 (10)	0.1025 (7)	0.031 (3)
H8AA	1.5626	1.3893	0.1096	0.037*
C9A	1.3698 (10)	1.3774 (10)	0.0734 (7)	0.032 (3)
H9AA	1.3314	1.4686	0.0617	0.039*
C10A	1.2912 (9)	1.2832 (10)	0.0620 (6)	0.024 (2)
H10B	1.1991	1.3142	0.0403	0.029*
C1B	1.4298 (10)	0.7514 (10)	0.6316 (7)	0.028 (2)
H1BA	1.3554	0.7125	0.6201	0.034*
C2B	1.5566 (10)	0.6668 (11)	0.6649 (7)	0.034 (3)
H2BA	1.5678	0.5732	0.6766	0.040*
C3B	1.6642 (11)	0.7289 (11)	0.6797 (7)	0.036 (3)
H3BA	1.7509	0.6765	0.7005	0.043*
C4B	1.6451 (10)	0.8707 (11)	0.6638 (7)	0.033 (3)
H4BA	1.7184	0.9111	0.6751	0.040*
C5B	1.5173 (9)	0.9491 (10)	0.6313 (6)	0.021 (2)
C6B	1.4841 (9)	1.0995 (9)	0.6135 (6)	0.021 (2)
C7B	1.5735 (9)	1.1812 (11)	0.6269 (7)	0.029 (2)
H7BA	1.6636	1.1427	0.6507	0.035*
C8B	1.5315 (10)	1.3168 (10)	0.6060 (7)	0.029 (2)
H8BA	1.5920	1.3727	0.6141	0.035*
C9B	1.4011 (10)	1.3688 (10)	0.5734 (7)	0.029 (2)
H9BA	1.3698	1.4618	0.5597	0.035*
C10B	1.3140 (10)	1.2881 (9)	0.5602 (6)	0.024 (2)
H10A	1.2239	1.3276	0.5367	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1A	0.0125 (6)	0.0231 (7)	0.0225 (7)	−0.0049 (5)	−0.0025 (5)	−0.0071 (5)
Cu1B	0.0138 (6)	0.0232 (7)	0.0215 (6)	−0.0067 (5)	−0.0018 (5)	−0.0075 (5)
V1	0.0151 (8)	0.0212 (9)	0.0184 (9)	−0.0046 (7)	0.0010 (7)	−0.0077 (7)
P1A	0.0140 (12)	0.0180 (13)	0.0167 (13)	−0.0036 (10)	−0.0011 (10)	−0.0058 (11)
P1B	0.0168 (13)	0.0177 (13)	0.0165 (13)	−0.0042 (10)	−0.0028 (10)	−0.0048 (11)
P1C	0.0254 (14)	0.0231 (15)	0.0243 (15)	−0.0063 (12)	0.0028 (11)	−0.0096 (12)
O1A	0.018 (3)	0.029 (4)	0.021 (4)	−0.010 (3)	0.002 (3)	−0.012 (3)
O2A	0.019 (3)	0.026 (4)	0.017 (3)	−0.007 (3)	−0.007 (3)	−0.006 (3)
O3A	0.021 (4)	0.022 (4)	0.033 (4)	−0.005 (3)	−0.001 (3)	0.001 (3)
O4A	0.008 (3)	0.026 (4)	0.025 (4)	−0.002 (3)	0.000 (3)	−0.007 (3)
O1B	0.021 (3)	0.027 (4)	0.022 (4)	−0.007 (3)	0.002 (3)	−0.012 (3)
O2B	0.019 (3)	0.027 (4)	0.034 (4)	−0.014 (3)	0.001 (3)	−0.015 (3)
O3B	0.029 (4)	0.019 (4)	0.016 (3)	0.000 (3)	−0.004 (3)	−0.005 (3)
O4B	0.023 (4)	0.025 (4)	0.024 (4)	−0.006 (3)	−0.010 (3)	−0.008 (3)
O1C	0.027 (4)	0.027 (4)	0.063 (5)	0.000 (3)	0.003 (4)	−0.022 (4)
O2C	0.045 (4)	0.039 (4)	0.018 (4)	−0.007 (3)	0.005 (3)	−0.012 (3)
O3C	0.043 (5)	0.027 (4)	0.038 (4)	−0.011 (3)	0.010 (3)	−0.019 (4)
O4C	0.026 (4)	0.039 (5)	0.021 (4)	−0.009 (3)	−0.002 (3)	0.005 (3)
O1D	0.022 (4)	0.023 (4)	0.029 (4)	0.000 (3)	−0.002 (3)	−0.009 (3)
O2D	0.021 (4)	0.037 (4)	0.039 (4)	−0.008 (3)	0.004 (3)	−0.013 (4)
O3D	0.042 (5)	0.020 (4)	0.047 (5)	0.004 (3)	−0.011 (4)	−0.002 (4)
O1	0.020 (3)	0.034 (4)	0.026 (4)	−0.002 (3)	0.001 (3)	−0.014 (3)
O2	0.028 (4)	0.039 (4)	0.015 (4)	−0.018 (3)	0.004 (3)	−0.011 (3)
N1A	0.015 (4)	0.014 (4)	0.029 (5)	−0.006 (3)	0.000 (3)	−0.007 (4)
N2A	0.015 (4)	0.020 (5)	0.021 (4)	−0.003 (3)	0.004 (3)	−0.001 (4)
N1B	0.016 (4)	0.022 (5)	0.015 (4)	−0.002 (3)	−0.003 (3)	−0.003 (4)
N2B	0.019 (4)	0.024 (5)	0.013 (4)	−0.012 (4)	0.000 (3)	−0.006 (4)
N1D	0.024 (5)	0.041 (6)	0.018 (5)	−0.005 (4)	−0.004 (4)	−0.010 (4)
C1A	0.013 (5)	0.027 (6)	0.030 (6)	−0.006 (4)	0.003 (4)	−0.013 (5)
C2A	0.030 (6)	0.027 (6)	0.032 (6)	−0.001 (5)	0.007 (5)	−0.013 (5)
C3A	0.016 (5)	0.040 (7)	0.024 (6)	0.003 (5)	−0.002 (4)	−0.010 (5)
C4A	0.012 (5)	0.034 (6)	0.033 (6)	−0.003 (4)	−0.006 (4)	−0.017 (5)
C5A	0.022 (5)	0.020 (5)	0.013 (5)	−0.005 (4)	0.002 (4)	−0.006 (4)
C6A	0.008 (4)	0.036 (6)	0.018 (5)	−0.005 (4)	0.001 (4)	−0.011 (4)
C7A	0.017 (5)	0.039 (7)	0.031 (6)	0.001 (5)	−0.002 (4)	−0.011 (5)
C8A	0.023 (6)	0.041 (7)	0.032 (6)	−0.020 (5)	0.003 (5)	−0.012 (5)
C9A	0.028 (6)	0.031 (6)	0.035 (6)	−0.002 (5)	0.005 (5)	−0.007 (5)
C10A	0.008 (5)	0.042 (7)	0.022 (6)	−0.009 (5)	−0.003 (4)	−0.007 (5)
C1B	0.033 (6)	0.025 (6)	0.028 (6)	−0.002 (5)	0.004 (5)	−0.013 (5)
C2B	0.027 (6)	0.036 (7)	0.032 (6)	0.006 (5)	−0.003 (5)	−0.008 (5)
C3B	0.031 (6)	0.042 (7)	0.030 (6)	0.008 (5)	−0.002 (5)	−0.013 (6)
C4B	0.016 (5)	0.053 (8)	0.027 (6)	−0.004 (5)	−0.002 (4)	−0.009 (6)
C5B	0.016 (5)	0.035 (6)	0.014 (5)	−0.012 (4)	0.001 (4)	−0.009 (5)
C6B	0.021 (5)	0.032 (6)	0.009 (5)	−0.003 (4)	0.000 (4)	−0.005 (4)
C7B	0.017 (5)	0.046 (6)	0.029 (5)	−0.015 (4)	−0.003 (4)	−0.013 (5)
C8B	0.027 (6)	0.029 (6)	0.033 (6)	−0.009 (5)	0.000 (5)	−0.008 (5)
C9B	0.036 (6)	0.029 (6)	0.034 (6)	−0.017 (5)	0.006 (5)	−0.019 (5)
C10B	0.033 (6)	0.019 (6)	0.018 (5)	−0.003 (5)	0.003 (4)	−0.002 (4)

Geometric parameters (Å, º)

Cu1A—O4A	1.911 (5)	N2A—C6A	1.334 (10)
Cu1A—O2A^i	1.925 (6)	N1B—C1B	1.358 (11)
Cu1A—N2A	1.965 (7)	N1B—C5B	1.365 (10)
Cu1A—N1A	2.016 (7)	N2B—C10B	1.338 (10)
Cu1A—O1	2.432 (6)	N2B—C6B	1.358 (10)
Cu1B—O4B	1.920 (6)	C1A—C2A	1.368 (12)
Cu1B—O2B^ii	1.921 (6)	C1A—H1AA	0.9300
Cu1B—N1B	2.013 (7)	C2A—C3A	1.366 (12)
Cu1B—N2B	2.036 (7)	C2A—H2AA	0.9300
Cu1B—O2^ii	2.307 (6)	C3A—C4A	1.345 (12)
V1—O1	1.622 (6)	C3A—H3AA	0.9300
V1—O2	1.645 (6)	C4A—C5A	1.378 (11)
V1—O1B	1.958 (6)	C4A—H4AA	0.9300
V1—O1A	1.983 (6)	C5A—C6A	1.463 (12)
V1—O1D	2.213 (6)	C6A—C7A	1.364 (12)
V1—O2D	2.395 (7)	C7A—C8A	1.378 (13)
P1A—O4A	1.509 (6)	C7A—H7AA	0.9300
P1A—O1A	1.507 (6)	C8A—C9A	1.362 (12)
P1A—O2A	1.524 (6)	C8A—H8AA	0.9300
P1A—O3A	1.575 (6)	C9A—C10A	1.394 (12)
P1B—O2B	1.501 (6)	C9A—H9AA	0.9300
P1B—O1B	1.512 (6)	C10A—H10B	0.9300
P1B—O4B	1.524 (6)	C1B—C2B	1.396 (12)
P1B—O3B	1.609 (6)	C1B—H1BA	0.9300
P1C—O2C	1.473 (6)	C2B—C3B	1.377 (13)
P1C—O3C	1.531 (6)	C2B—H2BA	0.9300
P1C—O1C	1.539 (7)	C3B—C4B	1.410 (13)
P1C—O4C	1.543 (6)	C3B—H3BA	0.9300
O3A—H3A	0.84 (4)	C4B—C5B	1.379 (12)
O3B—H3B	0.82 (4)	C4B—H4BA	0.9300
O1C—H1C	0.81 (4)	C5B—C6B	1.495 (12)
O3C—H3C	0.82 (4)	C6B—C7B	1.373 (12)
O4C—H4C	0.82 (4)	C7B—C8B	1.350 (13)
O1D—N1D	1.269 (9)	C7B—H7BA	0.9300
O2D—N1D	1.260 (9)	C8B—C9B	1.333 (12)
O3D—N1D	1.234 (9)	C8B—H8BA	0.9300
N1A—C1A	1.322 (11)	C9B—C10B	1.348 (12)
N1A—C5A	1.343 (10)	C9B—H9BA	0.9300
N2A—C10A	1.331 (11)	C10B—H10A	0.9300
O4A—Cu1A—O2A^i	96.7 (2)	C10A—N2A—Cu1A	124.7 (6)
O4A—Cu1A—N2A	93.2 (3)	C6A—N2A—Cu1A	116.7 (6)
O2A^i—Cu1A—N2A	170.0 (3)	C1B—N1B—C5B	120.6 (8)
O4A—Cu1A—N1A	159.9 (3)	C1B—N1B—Cu1B	125.1 (6)
O2A^i—Cu1A—N1A	91.2 (3)	C5B—N1B—Cu1B	114.3 (6)
N2A—Cu1A—N1A	79.9 (3)	C10B—N2B—C6B	116.9 (8)
O4A—Cu1A—O1	91.8 (2)	C10B—N2B—Cu1B	127.6 (6)
O2A^i—Cu1A—O1	88.2 (2)	C6B—N2B—Cu1B	115.5 (6)
N2A—Cu1A—O1	90.1 (2)	O3D—N1D—O2D	122.6 (8)
N1A—Cu1A—O1	107.0 (2)	O3D—N1D—O1D	121.7 (8)
O4B—Cu1B—O2B^ii	95.4 (2)	O2D—N1D—O1D	115.7 (8)
O4B—Cu1B—N1B	170.7 (3)	N1A—C1A—C2A	122.7 (9)
O2B^ii—Cu1B—N1B	92.5 (3)	N1A—C1A—H1AA	118.6
O4B—Cu1B—N2B	90.3 (3)	C2A—C1A—H1AA	118.6
O2B^ii—Cu1B—N2B	166.1 (3)	C1A—C2A—C3A	119.4 (9)
N1B—Cu1B—N2B	81.0 (3)	C1A—C2A—H2AA	120.3
O4B—Cu1B—O2^ii	87.3 (2)	C3A—C2A—H2AA	120.3
O2B^ii—Cu1B—O2^ii	96.1 (2)	C4A—C3A—C2A	118.8 (9)
N1B—Cu1B—O2^ii	96.8 (2)	C4A—C3A—H3AA	120.6
N2B—Cu1B—O2^ii	96.9 (2)	C2A—C3A—H3AA	120.6
O1—V1—O2	107.4 (3)	C3A—C4A—C5A	119.5 (9)
O1—V1—O1B	98.9 (3)	C3A—C4A—H4AA	120.3
O2—V1—O1B	97.3 (3)	C5A—C4A—H4AA	120.3
O1—V1—O1A	96.5 (3)	N1A—C5A—C4A	122.1 (8)
O2—V1—O1A	94.1 (3)	N1A—C5A—C6A	113.5 (8)
O1B—V1—O1A	157.0 (2)	C4A—C5A—C6A	124.4 (8)
O1—V1—O1D	100.1 (3)	N2A—C6A—C7A	121.0 (9)
O2—V1—O1D	152.5 (3)	N2A—C6A—C5A	114.7 (8)
O1B—V1—O1D	78.5 (2)	C7A—C6A—C5A	124.3 (8)
O1A—V1—O1D	82.2 (2)	C6A—C7A—C8A	120.4 (9)
O1—V1—O2D	155.1 (3)	C6A—C7A—H7AA	119.8
O2—V1—O2D	97.3 (3)	C8A—C7A—H7AA	119.8
O1B—V1—O2D	80.2 (2)	C9A—C8A—C7A	119.5 (9)
O1A—V1—O2D	78.7 (2)	C9A—C8A—H8AA	120.3
O1D—V1—O2D	55.2 (2)	C7A—C8A—H8AA	120.3
O4A—P1A—O1A	113.7 (3)	C8A—C9A—C10A	117.0 (9)
O4A—P1A—O2A	113.3 (3)	C8A—C9A—H9AA	121.5
O1A—P1A—O2A	110.2 (3)	C10A—C9A—H9AA	121.5
O4A—P1A—O3A	108.7 (3)	N2A—C10A—C9A	123.5 (8)
O1A—P1A—O3A	107.0 (3)	N2A—C10A—H10B	118.3
O2A—P1A—O3A	103.2 (3)	C9A—C10A—H10B	118.3
O2B—P1B—O1B	114.4 (3)	N1B—C1B—C2B	122.5 (9)
O2B—P1B—O4B	113.7 (3)	N1B—C1B—H1BA	118.7
O1B—P1B—O4B	111.9 (3)	C2B—C1B—H1BA	118.7
O2B—P1B—O3B	106.7 (3)	C3B—C2B—C1B	116.7 (10)
O1B—P1B—O3B	104.8 (3)	C3B—C2B—H2BA	121.6
O4B—P1B—O3B	104.3 (3)	C1B—C2B—H2BA	121.6
O2C—P1C—O3C	113.7 (4)	C2B—C3B—C4B	121.1 (10)
O2C—P1C—O1C	115.8 (4)	C2B—C3B—H3BA	119.5
O3C—P1C—O1C	102.8 (4)	C4B—C3B—H3BA	119.5
O2C—P1C—O4C	109.4 (4)	C5B—C4B—C3B	119.7 (9)
O3C—P1C—O4C	104.7 (4)	C5B—C4B—H4BA	120.2
O1C—P1C—O4C	109.7 (4)	C3B—C4B—H4BA	120.2
P1A—O1A—V1	134.7 (3)	N1B—C5B—C4B	119.4 (9)
P1A—O2A—Cu1A^i	137.3 (4)	N1B—C5B—C6B	116.1 (8)
P1A—O3A—H3A	108 (3)	C4B—C5B—C6B	124.5 (8)
P1A—O4A—Cu1A	134.8 (4)	N2B—C6B—C7B	120.7 (9)
P1B—O1B—V1	140.8 (4)	N2B—C6B—C5B	113.1 (8)
P1B—O2B—Cu1B^ii	134.1 (4)	C7B—C6B—C5B	126.2 (9)
P1B—O3B—H3B	106 (3)	C8B—C7B—C6B	120.5 (9)
P1B—O4B—Cu1B	134.2 (4)	C8B—C7B—H7BA	119.7
P1C—O1C—H1C	113 (3)	C6B—C7B—H7BA	119.7
P1C—O3C—H3C	112 (3)	C7B—C8B—C9B	118.4 (9)
P1C—O4C—H4C	113 (3)	C7B—C8B—H8BA	120.8
N1D—O1D—V1	98.8 (5)	C9B—C8B—H8BA	120.8
N1D—O2D—V1	90.4 (5)	C8B—C9B—C10B	120.7 (10)
V1—O1—Cu1A	129.9 (3)	C8B—C9B—H9BA	119.6
V1—O2—Cu1B^ii	131.9 (3)	C10B—C9B—H9BA	119.6
C1A—N1A—C5A	117.4 (8)	N2B—C10B—C9B	122.7 (9)
C1A—N1A—Cu1A	127.3 (6)	N2B—C10B—H10A	118.6
C5A—N1A—Cu1A	115.3 (6)	C9B—C10B—H10A	118.6
C10A—N2A—C6A	118.6 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O3D^iii	0.84 (4)	2.02 (4)	2.848 (8)	169 (6)
O3B—H3B···O2C^ii	0.82 (4)	1.76 (4)	2.573 (8)	174 (5)
O1C—H1C···O2	0.81 (4)	2.08 (4)	2.777 (9)	144 (2)
O3C—H3C···O3B^iv	0.82 (4)	1.83 (4)	2.647 (9)	169 (7)
O4C—H4C···O2A^i	0.82 (4)	1.91 (4)	2.640 (8)	149 (7)

Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+2, −y+2, −z+1; (iii) −x+2, −y+3, −z; (iv) x, y−1, z.