Cd2Cu(PO4)2

Stojanović, J.; Đorđević, T.; Karanović, L.

doi:10.1107/S0108270108032332

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Cd₂Cu(PO₄)₂

J. Stojanovic, T. Đordevic and L. Karanovic

During an investigation of the insufficiently known system M1O-M2O-X₂O₅-H₂O (M1 = Cd²⁺, Sr²⁺ and Ba²⁺; M2 = Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺ and Mg²⁺; X = P⁵⁺, As⁵⁺ and V⁵⁺), single crystals of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd₂Cu(PO₄)₂, were obtained. This compound belongs to a small group of compounds adopting a Cu₃(PO₄)₂-type structure and having the general formula M1₂M2(XO₄)₂ (M1/M2 = Cd²⁺, Cu²⁺, Mg²⁺ and Zn²⁺; X = As⁵⁺, P⁵⁺ and V⁵⁺). The crystal structure is characterized by the interconnection of infinite [Cu(PO₄)₂]_n chains and [Cd₂O₁₀]_n double chains, both extending along the a axis. Exceptional characteristics of this structure are its novel chemical composition and the occurrence of double chains of CdO₆ polyhedra that were not found in related structures. In contrast to the isomorphous compounds, where the M1 cations are coordinated by five O atoms, the Cd atom is coordinated by six. The dissimilarity in the geometry of M1 coordination between Cd₂Cu(PO₄)₂ and the isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with the Cu, Mg and Zn cations. Sharing a common edge, two CdO₆ polyhedra form Cd₂O₁₀ dimers. Each such dimer is bonded to another dimer sharing common vertices, forming [Cd₂O₁₀]_n double chains in the [100] direction. The Cu atoms, located on an inversion centre (site symmetry $\overline{1}$ ), form isolated CuO₄ squares interconnected by PO₄ tetrahedra, forming [Cu(PO₄)₂]_n chains similar to those found in related structures. Conversely, the [Cd₂O₁₀]_n double chains, which were not found in related structures, are an exclusive feature of this structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108032332/ku3001sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108270108032332/ku3001Isup2.hkl Contains datablock I

Comment top

Natural and synthetic metal phosphates, arsenates and vanadates often form tetrahedral–octahedral framework structures with potentially interesting properties (e.g. ion conductivity, ion exchange and catalytic activities). An ongoing comprehensive study of the hydrothermal synthesis, crystallography and properties of phosphate(V), arsenate(V) and vanadate(V) compounds in the insufficiently known system M1O–M2O–X₂O₅–H₂O (M1 = Sr²⁺, Cd²⁺ and Ba²⁺; M2 = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺; and X = P⁵⁺, As⁵⁺ and V⁵⁺) yielded a large number of new M1²⁺–, M2²⁺– and M1–M2–(H–) phosphates, arsenates and vanadates (Mihajlović & Effenberger, 2004, 2006; Mihajlović, Libowitzky & Effenberger, 2004; Mihajlović, Kolitsch & Effenberger, 2004; Đorđević, Šutović et al., 2008; Đorđević, Karanović, & Tillmanns, 2008; Đorđević & Karanović, 2008; Đordević, 2008a,b), which were characterized structurally and, in part, also by spectroscopic techniques. The present contribution reports the hydrothermal synthesis and crystal structure of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd₂Cu(PO₄)₂.

Cd₂Cu(PO₄)₂ is isomorphous with only five compounds, namely two phosphates, two arsenates and one vanadate [structure prototype Cu₃(PO₄)₂ (Forsyth et al., 1990; Shoemaker et al., 1977), (Mg_0.21,Cu_0.79)₃(PO₄)₂ (Moqine et al., 1994), Cu₃(AsO₄)₂ (Effenberger, 1988), Zn₂Cu(AsO₄)₂ (mineral stranskiite; Plieth & Sänger, 1967; Calvo & Leung, 1969; Keller, et al., 1979) and Cu₃(VO₄)₂ (mineral mcbirneyite; (Coing-Boyat, 1982)]. All compounds crystallize in the space group P1 and have the general formula M1₂M2(XO₄)₂ (M1/M2 = Cd²⁺, Cu²⁺, Mg²⁺ and Zn²⁺, and X = As⁵⁺, P⁵⁺ and V⁵⁺; Table 1). It is interesting that the crystal structure of Cd₂Cu(PO₄)₂ is different from that of monoclinic Cd_1.35Cu_1.65(PO₄)₂, which has a very similar chemical composition (Müller-Buschbaum & Münchau, 1996). The crystal structure of Cd₂Cu(PO₄)₂ consists of [Cu(PO₄)₂]_n chains, running along the [100] direction, interconnected by double chains of CdO₆ polyhedra extending in the same direction (Fig. 1). Very similar [Cu(PO₄)₂]_n chains have been described in the crystal structures of Ba₂Cu(PO₄)₂.H₂O (Effenberger, 1999), Ba₂Cu(PO₄)₂ (Etheredge & Hwu, 1996) and Sr₂Cu(PO₄)₂ (Johannes et al., 2006).

The Cu atom, located on an inversion centre (M2 position), is coordinated by four O atoms with an average Cu1—O bond distance of 1.941 (3) Å, forming a slightly distorted square-planar coordination [the O2ⁱⁱ—Cu1—O3 and O2ⁱⁱ—Cu1—O3ⁱ bond angles are 88.42 (10) and 91.58 (10)°; symmetry codes: (i) -x, -y, -z; (ii) -x, -y + 1, -z]. All four O atoms (O2 × 2 and O3 × 2) of the CuO₄ squares are triply coordinated, bridging Cd1, Cu1 and P1 atoms. The P atom exhibits the usual tetrahedral coordination, with a mean P1—O distance of 1.541 (3) Å. The CuO₄ squares and PO₄ tetrahedra generate [Cu(PO₄)₂]_n chains along the a axis (Fig. 1a).

Similar to other isomorphous compounds, the M1 cation (M1 = Cd) is situated in the general position. However, it is surrounded by six not five O atoms, forming a (5+1)-coordination polyhedron, which can be described as an extremely distorted octahedron. Pairs of CdO₆ polyhedra sharing an O4—O4ⁱ edge form Cd₂O₁₀ dimers (Fig. 1b) similar to the isolated M1O₈ dimers in related structures. The exceptional characteristic of this structure is that the Cd₂O₁₀ dimers are further polymerized, sharing common vertices (O1 and its symmetry equivalents) in double chains [Cd₂O₁₀]_n running along the a axis. In this way, every Cd polyhedron shares additionally two vertices with neighboring polyhedra. The neighboring [Cd₂O₁₀]_n double chains are interconnected by PO₄ tetrahedra, which are linked to both CdO₆ and CuO₄ polyhedra. In addition to atom P1, atoms O1 and O4 are bonded to two Cd1 atoms, and O2 and O3 to one Cd1 and one Cu1 atoms (Fig. 2).

Excluding the sixth O atom [O1^vi; symmetry code: (vi) x+1, y, z] of the CdO₆ polyhedron, the average Cd1—O bond length is 2.259 (2) Å. The sixth O atom, located at a Cd1—O1^vi distance of 2.716 (2) Å, contributes to the bond valence by approximately 5.5%. Taking into account the contribution of the five O atoms only, atom Cd1is undersaturated, i.e. ν_ij(Cd1) is 1.92 valence units (v.u.). Including the sixth O atom, O1^viν_ij(Cd1) increase to 2.02 v.u. The bond valence calculated according to the formula suggested by Brown and Altermatt (1985) for O1 shows that O1 is also undersaturated, i.e. ν_ij(O1) is 1.80 v.u. This could indicate that vacancies exist at the O1 position, but the refinement showed that no such significant vacancies are present at this site [the refined occupancy was 1.05 (1)]. Therefore, the refinement was completed with a fixed atom site occupancy value of 1. Very probably, the undersaturation of O1 is due to the unusually long distance of 2.716 (2) Å. Hypothetically, if it is assumed that both the Cd1—O1 and the Cd1—O1^vi distances are equal to 2.242 (2) Å, the calculated ν_ij(O1) was becomes 2.09 v.u.

The dissimilarity in the geometry of M1 coordination between Cd₂Cu(PO₄)₂ and the other isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with that of Cu, Mg and Zn. The increase in the polymerization of the CdO₆ polyhedra is accompanied by a decrease of the M1···M1 distances along the a axis. The Cd1···Cd1 distance along the chain extension is 4.7982 (3) Å, which is identical to the unit-cell parameter a and is shorter than the Cu···Cu distances in Cu₃(PO₄)₂, Cu(AsO₄)₂ and Cu₃(VO₄)₂, as well as the Zn···Zn distance in Zn₂Cu(AsO₄)₂. Therefore, the unit-cell parameter a in Cd₂Cu(PO₄)₂ achieves the shortest value amongst the isomorphous compounds, although it has the largest M1 cation and unit-cell volume (Table 1). In contrast, the b parameter has the largest value, while c is longer than those obtained for Cu₃(PO₄)₂, Cu₃(AsO₄)₂ and Cu₃(VO₄)₂, but similar to c in Zn₂Cu(AsO₄)₂.

An interesting aspect of the crystal structure is that it can also be described as PO₄ tetrahedra sandwiched between two metal layers, which are situated near the (101) plane (Fig. 3). The two Cd1 cations in the dimer are located in the same (101) plane and separated from each other by 3.5198 (8) Å, and the Cd1—O4—Cd1^v [symmetry code: (v) -x + 1, -y, -z + 1] angle is 102.33 (10)°. As mentioned above the Cd1···Cd1 distances between neighbours along the chain direction are 4.7982 (3) Å, and the shortest Cd1···Cd1 distance between neighbouring dimers positioned in the adjacent (101) plane is 4.2599 (5) Å. The shortest Cu1···Cd1 distances in the (101) plane are 3.5270 (3) and 3.7977 (4), and between two (101) planes is 3.9408 (4) Å. Because the Cu1 atoms are situated at the origin of the unit cell, the Cu1—Cu1 distances are equal to the lengths of unit-cell parameters a, b and c. All metal–metal distances are longer than the sum of the van der Waals radii [3.16 Å (2 × r_Cd), 2.98 Å (r_Cd + r_Cu = 1.58 + 1.40 = 2.98 Å) and 2.80 Å (2 × r_Cu), respectively (Bondi, 1964)].

Related literature top

For related literature, see: Bondi (1964); Brown & Altermatt (1985); Calvo & Leung (1969); Coing-Boyat (1982); Effenberger (1988, 1999); Etheredge & Hwu (1996); Forsyth et al. (1990); Johannes et al. (2006); Keller et al. (1979); Müller-Buschbaum & Münchau (1996); Mihajlović & Effenberger (2004, 2006); Mihajlović, Kolitsch & Effenberger (2004); Mihajlović, Libowitzky & Effenberger (2004); Moqine et al. (1994); Plieth & Sänger (1967); Shoemaker et al. (1977); Đordević (2008a, 2008b); Đorđević & Karanović (2008); Đorđević, Karanović & Tillmanns (2008); Đorđević, Šutović, Stojanović & Karanović (2008).

Experimental top

A mixture of Cd(OH)₂ (Alfa Products, > 99%), (NH₄)₂HPO₄( Loba Chemie, > 99%) and CuCl₂.2H₂O (Merck, > 99%) was transferred into teflon vessels and filled to approximately 70% of the inner volume with distilled water [quantities of reagents?]. The pH of the mixture was 5. The vessel was enclosed in a stainless steel autoclave and heated from room temperature to 493 K (4h), held at 493 K for 192 h, and finally spontaneously cooled to room temperature. At the end of the reaction the pH of the solvent was 6.

The title compound crystallized as blue prismatic crystals (yield ca 55%) of up to 100 µm in length together with green prismatic crystals of Cu₂(PO₄)OH (yield ca 35 %) and colourless crystals of NH₄Cl (yield ca 10 %). All the reaction products were filtered off, washed thoroughly with distilled water and dried in air at room temperature.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. (a) The infinite [Cu(PO₄)₂]_n chain and (b) the double [Cd₂O₁₀]_n chain with the atomic numbering scheme (displacement ellipsoids are shown at the 91% probability level). The longest Cd1—O1 bond distance is shown as a fine line. [Symmetry codes: (i) -x, -y, -z; (ii) -x, -y+1, -z; (iii) x, y-1, z; (v) -x+1, -y, -z+1; (vi) x+1, y, z; (viii) x, y, z-1; (ix) -x+1, -y+1, -z].
	Fig. 2. A perspective view of the crystal structure of Cd₂Cu(PO₄)₂, projected along [100] (b axis horizontal). Large grey spheres represent Cd1 and smaller spheres Cu1 atoms. PO₄tetrahedra and CuO₄coordination squares are shaded.
	Fig. 3. Perspective views of the crystal structure of Cd₂Cu(PO₄)₂, projected approximately along (a) [111] and (b) [010], showing PO₄ tetrahedra sandwiched between metal layers situated near the (101) plane. Larger grey spheres represent Cd1 and smaller spheres Cu1 atoms. PO₄tetrahedra are shaded.

dicadmium copper(II) bis[phosphate(V)] top

Crystal data top

Cd₂Cu(PO₄)₂	Z = 1
M_r = 478.31	F(000) = 219
Triclinic, P1	D_x = 4.884 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.7982 (3) Å	Cell parameters from 3683 reflections
b = 5.5801 (3) Å	θ = 1.0–30.0°
c = 6.7217 (3) Å	µ = 10.22 mm⁻¹
α = 74.266 (3)°	T = 295 K
β = 86.330 (3)°	Prism, blue
γ = 69.924 (3)°	0.09 × 0.04 × 0.02 mm
V = 162.62 (2) Å³

Data collection top

Nonius KappaCCD diffractomer	805 independent reflections
Radiation source: fine-focus sealed X-ray tube	747 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ + ω scans	θ_max = 28.3°, θ_min = 4.0°
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	h = −6→6
T_min = 0.460, T_max = 0.822	k = −7→7
1596 measured reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	w = 1/[σ²(F_o²) + (0.0187P)² + 0.3359P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.043	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.79 e Å⁻³
805 reflections	Δρ_min = −0.59 e Å⁻³
63 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0054 (15)

Crystal data top

Cd₂Cu(PO₄)₂	γ = 69.924 (3)°
M_r = 478.31	V = 162.62 (2) Å³
Triclinic, P1	Z = 1
a = 4.7982 (3) Å	Mo Kα radiation
b = 5.5801 (3) Å	µ = 10.22 mm⁻¹
c = 6.7217 (3) Å	T = 295 K
α = 74.266 (3)°	0.09 × 0.04 × 0.02 mm
β = 86.330 (3)°

Data collection top

Nonius KappaCCD diffractomer	805 independent reflections
Absorption correction: multi-scan (Otwinowski & Minor, 1997)	747 reflections with I > 2σ(I)
T_min = 0.460, T_max = 0.822	R_int = 0.016
1596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	63 parameters
wR(F²) = 0.043	0 restraints
S = 1.09	Δρ_max = 0.79 e Å⁻³
805 reflections	Δρ_min = −0.59 e Å⁻³

Special details top

Experimental. Qualitative chemical analyses were performed using a JEOL JSM-6400LV and JSM-6460LV scanning electron microscopes (SEM) connected with a LINK energy-dispersive X-ray analysis (EDX) unit. The presence of Cd, Cu and P was confirmed in all investigated samples.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.0000	0.0000	0.00974 (14)
Cd1	0.29320 (5)	0.28014 (5)	0.31066 (4)	0.01168 (11)
P1	0.37203 (18)	0.31990 (16)	0.78682 (13)	0.00803 (18)
O1	−0.2020 (5)	0.3928 (5)	0.3243 (4)	0.0135 (5)
O2	0.3110 (5)	0.6921 (5)	0.1636 (4)	0.0126 (5)
O3	0.2297 (5)	0.2256 (5)	−0.0068 (4)	0.0099 (5)
O4	0.3801 (5)	0.1346 (5)	0.6523 (4)	0.0124 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0070 (3)	0.0087 (3)	0.0127 (3)	−0.0027 (2)	−0.0016 (2)	−0.0010 (2)
Cd1	0.01194 (15)	0.01009 (15)	0.01117 (16)	−0.00144 (10)	−0.00111 (9)	−0.00252 (9)
P1	0.0067 (4)	0.0079 (4)	0.0087 (4)	−0.0014 (3)	−0.0001 (3)	−0.0022 (3)
O1	0.0108 (12)	0.0074 (11)	0.0175 (13)	−0.0001 (9)	−0.0013 (9)	0.0009 (9)
O2	0.0080 (11)	0.0131 (12)	0.0160 (13)	−0.0038 (9)	−0.0011 (9)	−0.0019 (10)
O3	0.0102 (11)	0.0115 (12)	0.0090 (11)	−0.0043 (10)	0.0001 (9)	−0.0032 (9)
O4	0.0139 (12)	0.0110 (12)	0.0120 (12)	−0.0018 (10)	0.0005 (9)	−0.0057 (9)

Geometric parameters (Å, º) top

Cu1—O3	1.928 (2)	P1—O2^xiv	1.553 (2)
Cu1—O3ⁱ	1.928 (2)	O1—P1^xi	1.525 (3)
Cu1—O2ⁱⁱ	1.952 (3)	O1—Cd1^vii	2.716 (2)
Cu1—O2ⁱⁱⁱ	1.952 (3)	O1—Cd1^xi	3.359 (3)
Cu1—O4^iv	2.966 (3)	O1—Cu1^xiii	3.892 (3)
Cu1—O4^v	2.966 (3)	O1—Cd1^v	4.038 (3)
Cu1—O1	3.370 (3)	O1—Cd1ⁱⁱ	4.148 (3)
Cu1—O1ⁱ	3.370 (3)	O1—Cu1^xvii	4.365 (3)
Cu1—O3^vi	3.470 (2)	O1—Cu1^xv	4.480 (3)
Cu1—O3^vii	3.470 (2)	O1—Cd1^xvii	4.684 (3)
Cu1—Cd1ⁱ	3.5270 (3)	O1—Cd1^ix	4.926 (3)
Cu1—Cd1	3.5270 (3)	O1—Cd1^xviii	5.567 (3)
Cu1—O4^viii	3.644 (3)	O1—Cu1^vii	5.800 (3)
Cu1—O4^ix	3.644 (3)	O1—Cd1ⁱⁱⁱ	5.861 (3)
Cu1—Cd1ⁱⁱ	3.7977 (4)	O2—P1^xiv	1.553 (2)
Cu1—Cd1ⁱⁱⁱ	3.7977 (4)	O2—Cu1^xiii	1.952 (3)
Cu1—O1ⁱⁱ	3.892 (3)	O2—Cd1^xii	3.599 (3)
Cu1—O1ⁱⁱⁱ	3.892 (3)	O2—Cd1^xiii	3.648 (3)
Cu1—Cd1^vi	3.9408 (4)	O2—Cd1^xiv	4.181 (3)
Cu1—Cd1^vii	3.9408 (4)	O2—Cu1^xix	4.184 (3)
Cu1—O3ⁱⁱ	4.089 (3)	O2—Cd1ⁱⁱ	4.381 (3)
Cd1—O4	2.232 (3)	O2—Cd1^xi	4.426 (3)
Cd1—O1	2.242 (2)	O2—Cu1^x	4.486 (3)
Cd1—O4^ix	2.263 (3)	O2—Cd1^x	4.517 (3)
Cd1—O2	2.271 (2)	O2—Cd1^xvii	5.072 (3)
Cd1—O3	2.288 (2)	O2—Cd1^ix	5.377 (3)
Cd1—O1^x	2.716 (2)	O2—Cd1^xx	5.772 (3)
Cd1—O3ⁱⁱ	3.306 (3)	O3—P1^iv	1.548 (2)
Cd1—O1^xi	3.359 (3)	O3—Cd1ⁱⁱ	3.306 (3)
Cd1—Cd1^ix	3.5019 (8)	O3—Cu1^x	3.470 (2)
Cd1—O2^xii	3.599 (3)	O3—Cd1^vi	3.933 (3)
Cd1—O2ⁱⁱⁱ	3.648 (3)	O3—Cu1^xiii	4.089 (3)
Cd1—O4^xi	3.776 (3)	O3—Cd1^xii	4.207 (3)
Cd1—Cu1^xiii	3.7977 (4)	O3—Cd1^iv	4.513 (2)
Cd1—O3^vi	3.933 (3)	O3—Cd1^vii	4.798 (3)
Cd1—Cu1^x	3.9408 (4)	O3—Cd1^ix	4.987 (3)
Cd1—O1^v	4.038 (3)	O3—Cd1ⁱⁱⁱ	5.035 (3)
Cd1—O4^xiv	4.146 (3)	O3—Cd1ⁱ	5.203 (3)
Cd1—O1ⁱⁱ	4.148 (3)	O3—Cd1^v	5.688 (3)
Cd1—O2^xiv	4.181 (3)	O3—Cd1^x	5.787 (3)
Cd1—O3^xii	4.207 (3)	O4—Cd1^ix	2.263 (3)
Cd1—Cd1^xi	4.2599 (5)	O4—Cu1^xv	2.966 (3)
Cd1—O2ⁱⁱ	4.381 (3)	O4—Cu1^xxi	3.644 (3)
Cd1—O2^xi	4.426 (3)	O4—Cd1^xi	3.776 (3)
Cd1—O3^xv	4.513 (2)	O4—Cd1^xiv	4.146 (3)
Cd1—O2^vii	4.517 (3)	O4—Cd1^v	4.536 (3)
Cd1—O4^v	4.536 (3)	O4—Cd1^xv	4.680 (3)
Cd1—O4^iv	4.680 (3)	O4—Cd1^x	5.027 (3)
Cd1—O1^xvi	4.684 (3)	O4—Cu1^x	5.217 (3)
Cd1—Cd1ⁱⁱ	4.7525 (5)	O4—Cu1^xiii	5.418 (3)
P1—O1^xi	1.525 (3)	O4—Cd1^vii	5.545 (3)
P1—O4	1.538 (3)	O4—Cu1^xxii	5.625 (3)
P1—O3^xv	1.548 (3)

O3—Cu1—O3ⁱ	180.00 (8)	O2^xii—Cd1—O4^v	112.59 (5)
O3—Cu1—O2ⁱⁱ	88.42 (10)	O2ⁱⁱⁱ—Cd1—O4^v	47.17 (5)
O3ⁱ—Cu1—O2ⁱⁱ	91.58 (10)	O4^xi—Cd1—O4^v	83.81 (5)
O3—Cu1—O2ⁱⁱⁱ	91.58 (10)	O3^vi—Cd1—O4^v	85.22 (5)
O3ⁱ—Cu1—O2ⁱⁱⁱ	88.42 (10)	O1^v—Cd1—O4^v	45.13 (5)
O2ⁱⁱ—Cu1—O2ⁱⁱⁱ	180.0	O4^xiv—Cd1—O4^v	157.62 (6)
O3—Cu1—O4^iv	56.49 (8)	O1ⁱⁱ—Cd1—O4^v	95.71 (5)
O3ⁱ—Cu1—O4^iv	123.51 (8)	O2^xiv—Cd1—O4^v	122.55 (5)
O2ⁱⁱ—Cu1—O4^iv	83.92 (9)	O3^xii—Cd1—O4^v	154.60 (5)
O2ⁱⁱⁱ—Cu1—O4^iv	96.08 (9)	O2ⁱⁱ—Cd1—O4^v	49.27 (5)
O3ⁱ—Cu1—O4^v	56.49 (8)	O2^xi—Cd1—O4^v	63.26 (5)
O2ⁱⁱ—Cu1—O4^v	96.08 (9)	O3^xv—Cd1—O4^v	91.23 (5)
O2ⁱⁱⁱ—Cu1—O4^v	83.92 (9)	O2^vii—Cd1—O4^v	54.97 (5)
O4^iv—Cu1—O4^v	180.00 (10)	O4—Cd1—O4^iv	151.12 (9)
O3—Cu1—O1	63.73 (8)	O1—Cd1—O4^iv	96.87 (8)
O3ⁱ—Cu1—O1	116.27 (8)	O4^ix—Cd1—O4^iv	73.86 (8)
O2ⁱⁱ—Cu1—O1	78.23 (9)	O2—Cd1—O4^iv	88.61 (8)
O2ⁱⁱⁱ—Cu1—O1	101.77 (9)	O3—Cd1—O4^iv	12.16 (6)
O4^iv—Cu1—O1	117.66 (6)	O1^x—Cd1—O4^iv	98.83 (7)
O4^v—Cu1—O1	62.34 (6)	O1^v—Cd1—O4^iv	103.00 (5)
O3—Cu1—O1ⁱ	116.27 (8)	O4^xiv—Cd1—O4^iv	112.69 (4)
O3ⁱ—Cu1—O1ⁱ	63.73 (8)	O1ⁱⁱ—Cd1—O4^iv	32.52 (4)
O2ⁱⁱⁱ—Cu1—O1ⁱ	78.23 (9)	O2^xiv—Cd1—O4^iv	149.68 (5)
O4^iv—Cu1—O1ⁱ	62.34 (6)	O3^xii—Cd1—O4^iv	78.43 (5)
O1—Cu1—O1ⁱ	180.00 (9)	O2ⁱⁱ—Cd1—O4^iv	43.57 (5)
O3—Cu1—O3^vi	57.12 (10)	O2^xi—Cd1—O4^iv	141.42 (5)
O3ⁱ—Cu1—O3^vi	122.88 (10)	O3^xv—Cd1—O4^iv	167.04 (4)
O2ⁱⁱ—Cu1—O3^vi	134.74 (8)	O2^vii—Cd1—O4^iv	87.41 (5)
O2ⁱⁱⁱ—Cu1—O3^vi	45.26 (8)	O4^v—Cd1—O4^iv	80.12 (5)
O4^iv—Cu1—O3^vi	53.56 (7)	O4—Cd1—O1^xvi	83.89 (8)
O4^v—Cu1—O3^vi	126.44 (7)	O1—Cd1—O1^xvi	114.80 (8)
O1—Cu1—O3^vi	106.11 (6)	O2—Cd1—O1^xvi	141.00 (7)
O1ⁱ—Cu1—O3^vi	73.89 (6)	O3—Cd1—O1^xvi	71.71 (7)
O3ⁱ—Cu1—O3^vii	57.12 (10)	O1^x—Cd1—O1^xvi	94.10 (6)
O2ⁱⁱ—Cu1—O3^vii	45.26 (8)	O3ⁱⁱ—Cd1—O1^xvi	134.67 (5)
O4^v—Cu1—O3^vii	53.56 (7)	O1^xi—Cd1—O1^xvi	131.77 (4)
O3^vi—Cu1—O3^vii	180.0	O2^xii—Cd1—O1^xvi	75.43 (6)
O3—Cu1—O4^viii	126.63 (8)	O2ⁱⁱⁱ—Cd1—O1^xvi	31.42 (5)
O3ⁱ—Cu1—O4^viii	53.37 (8)	O4^xi—Cd1—O1^xvi	154.77 (5)
O2ⁱⁱ—Cu1—O4^viii	42.11 (8)	O3^vi—Cd1—O1^xvi	32.94 (5)
O2ⁱⁱⁱ—Cu1—O4^viii	137.89 (8)	O1^v—Cd1—O1^xvi	49.16 (6)
O4^iv—Cu1—O4^viii	92.50 (7)	O4^xiv—Cd1—O1^xvi	130.08 (5)
O4^v—Cu1—O4^viii	87.50 (7)	O1ⁱⁱ—Cd1—O1^xvi	99.23 (5)
O1—Cu1—O4^viii	110.35 (6)	O2^xiv—Cd1—O1^xvi	99.17 (6)
O1ⁱ—Cu1—O4^viii	69.65 (6)	O3^xii—Cd1—O1^xvi	112.02 (5)
O3^vi—Cu1—O4^viii	139.12 (6)	O2ⁱⁱ—Cd1—O1^xvi	87.92 (6)
O3^vii—Cu1—O4^viii	40.88 (6)	O2^xi—Cd1—O1^xvi	108.62 (5)
O3—Cu1—O4^ix	53.37 (8)	O3^xv—Cd1—O1^xvi	100.91 (6)
O3ⁱ—Cu1—O4^ix	126.63 (8)	O2^vii—Cd1—O1^xvi	123.78 (5)
O2ⁱⁱⁱ—Cu1—O4^ix	42.11 (8)	O4^v—Cd1—O1^xvi	71.19 (5)
O4^v—Cu1—O4^ix	92.50 (7)	O4^iv—Cd1—O1^xvi	67.25 (5)
O1—Cu1—O4^ix	69.65 (6)	O1^xi—P1—O4	111.01 (14)
O1ⁱ—Cu1—O4^ix	110.35 (6)	O1^xi—P1—O3^xv	111.94 (14)
O4^viii—Cu1—O4^ix	180.00 (8)	O4—P1—O3^xv	107.58 (14)
O3—Cu1—O1ⁱⁱ	34.42 (8)	O1^xi—P1—O2^xiv	106.53 (14)
O3ⁱ—Cu1—O1ⁱⁱ	145.58 (8)	O4—P1—O2^xiv	111.58 (14)
O2ⁱⁱ—Cu1—O1ⁱⁱ	60.66 (8)	O3^xv—P1—O2^xiv	108.22 (14)
O2ⁱⁱⁱ—Cu1—O1ⁱⁱ	119.34 (8)	Cd1^xi—O1—Cu1^xiii	81.65 (5)
O4^iv—Cu1—O1ⁱⁱ	40.43 (6)	Cu1—O1—Cu1^xiii	100.16 (6)
O4^v—Cu1—O1ⁱⁱ	139.57 (6)	Cd1—O1—Cd1^v	101.62 (8)
O1—Cu1—O1ⁱⁱ	79.84 (6)	Cd1^vii—O1—Cd1^v	58.63 (5)
O1ⁱ—Cu1—O1ⁱⁱ	100.16 (6)	Cd1^xi—O1—Cd1^v	97.51 (6)
O3^vi—Cu1—O1ⁱⁱ	75.55 (6)	Cd1—O1—Cd1ⁱⁱ	91.09 (8)
O3^vii—Cu1—O1ⁱⁱ	104.45 (6)	Cd1^vii—O1—Cd1ⁱⁱ	88.83 (7)
O4^viii—Cu1—O1ⁱⁱ	93.12 (6)	Cd1^xi—O1—Cd1ⁱⁱ	126.78 (7)
O4^ix—Cu1—O1ⁱⁱ	86.88 (6)	Cd1^v—O1—Cd1ⁱⁱ	132.11 (7)
O3—Cu1—O1ⁱⁱⁱ	145.58 (8)	Cd1—O1—Cu1^xvii	139.66 (9)
O2ⁱⁱ—Cu1—O1ⁱⁱⁱ	119.34 (8)	Cd1^vii—O1—Cu1^xvii	59.57 (5)
O4^v—Cu1—O1ⁱⁱⁱ	40.43 (6)	Cd1^xi—O1—Cu1^xvii	89.06 (6)
O1—Cu1—O1ⁱⁱⁱ	100.16 (6)	Cu1—O1—Cu1^xvii	100.51 (6)
O3^vi—Cu1—O1ⁱⁱⁱ	104.45 (6)	Cu1^xiii—O1—Cu1^xvii	70.79 (5)
O3^vii—Cu1—O1ⁱⁱⁱ	75.55 (6)	Cd1^v—O1—Cu1^xvii	117.12 (6)
O4^ix—Cu1—O1ⁱⁱⁱ	93.12 (6)	Cd1ⁱⁱ—O1—Cu1^xvii	55.08 (4)
O1ⁱⁱ—Cu1—O1ⁱⁱⁱ	180.00 (9)	Cd1^vii—O1—Cd1^ix	121.44 (7)
O3—Cu1—O3ⁱⁱ	47.27 (9)	Cd1^xi—O1—Cd1^ix	90.40 (6)
O3ⁱ—Cu1—O3ⁱⁱ	132.73 (9)	Cd1^v—O1—Cd1^ix	63.83 (4)
O2ⁱⁱ—Cu1—O3ⁱⁱ	51.57 (8)	Cd1ⁱⁱ—O1—Cd1^ix	124.73 (6)
O2ⁱⁱⁱ—Cu1—O3ⁱⁱ	128.43 (8)	Cd1—O1—Cd1^xviii	154.39 (9)
O4^iv—Cu1—O3ⁱⁱ	85.32 (6)	Cd1^vii—O1—Cd1^xviii	48.03 (4)
O4^v—Cu1—O3ⁱⁱ	94.68 (6)	Cd1^xi—O1—Cd1^xviii	59.02 (4)
O1—Cu1—O3ⁱⁱ	38.43 (5)	Cd1^v—O1—Cd1^xviii	75.16 (5)
O1ⁱ—Cu1—O3ⁱⁱ	141.57 (5)	Cd1ⁱⁱ—O1—Cd1^xviii	110.10 (6)
O3^vi—Cu1—O3ⁱⁱ	104.31 (6)	Cd1^xvii—O1—Cd1^xviii	57.58 (4)
O3^vii—Cu1—O3ⁱⁱ	75.69 (6)	Cd1^ix—O1—Cd1^xviii	124.69 (5)
O4^viii—Cu1—O3ⁱⁱ	93.27 (6)	Cu1—O1—Cu1^vii	55.79 (4)
O4^ix—Cu1—O3ⁱⁱ	86.73 (6)	Cu1^xiii—O1—Cu1^vii	121.73 (6)
O1ⁱⁱ—Cu1—O3ⁱⁱ	44.90 (5)	Cd1—O1—Cd1ⁱⁱⁱ	71.72 (6)
O1ⁱⁱⁱ—Cu1—O3ⁱⁱ	135.10 (5)	Cd1^vii—O1—Cd1ⁱⁱⁱ	79.23 (6)
O4—Cd1—O1	95.88 (9)	Cd1^xi—O1—Cd1ⁱⁱⁱ	135.23 (6)
O4—Cd1—O4^ix	77.67 (10)	Cd1—O2—Cd1^xiv	93.55 (8)
O1—Cd1—O4^ix	125.88 (9)	Cd1^xii—O2—Cd1^xiv	119.34 (6)
O4—Cd1—O2	115.22 (9)	Cd1^xiii—O2—Cd1^xiv	52.60 (4)
O1—Cd1—O2	97.50 (9)	Cu1^xiii—O2—Cu1^xix	96.00 (8)
O4^ix—Cd1—O2	134.24 (9)	Cd1—O2—Cd1ⁱⁱ	84.90 (7)
O4—Cd1—O3	153.16 (9)	Cd1^xii—O2—Cd1ⁱⁱ	73.18 (5)
O1—Cd1—O3	84.75 (9)	Cd1^xiii—O2—Cd1ⁱⁱ	122.67 (7)
O4^ix—Cd1—O3	80.30 (9)	Cd1^xiv—O2—Cd1ⁱⁱ	166.75 (7)
O2—Cd1—O3	91.18 (9)	Cu1^xix—O2—Cd1ⁱⁱ	120.66 (6)
O4—Cd1—O1^x	81.89 (9)	Cd1ⁱⁱ—O2—Cd1^xi	99.49 (5)
O1—Cd1—O1^x	150.70 (11)	Cu1^xiii—O2—Cu1^x	132.51 (10)
O4^ix—Cd1—O1^x	82.40 (8)	Cd1—O2—Cd1^x	82.89 (7)
O2—Cd1—O1^x	58.48 (8)	Cd1^xii—O2—Cd1^x	70.66 (5)
O3—Cd1—O1^x	110.22 (8)	Cd1^xiii—O2—Cd1^x	93.60 (6)
O4—Cd1—O3ⁱⁱ	134.13 (8)	Cd1^xiv—O2—Cd1^x	58.50 (4)
O1—Cd1—O3ⁱⁱ	50.31 (8)	Cu1^xix—O2—Cd1^x	51.59 (3)
O4^ix—Cd1—O3ⁱⁱ	144.97 (8)	Cd1ⁱⁱ—O2—Cd1^x	134.00 (6)
O2—Cd1—O3ⁱⁱ	54.29 (7)	Cd1^xi—O2—Cd1^x	117.61 (6)
O3—Cd1—O3ⁱⁱ	64.88 (9)	Cu1^xiii—O2—Cu1	97.41 (8)
O1^x—Cd1—O3ⁱⁱ	112.20 (7)	Cu1^xix—O2—Cu1	136.47 (6)
O4—Cd1—O1^xi	48.71 (7)	Cd1—O2—Cd1^xvii	102.25 (8)
O1—Cd1—O1^xi	82.99 (9)	Cd1^xii—O2—Cd1^xvii	129.93 (7)
O4^ix—Cd1—O1^xi	123.05 (8)	Cd1^xiii—O2—Cd1^xvii	64.36 (4)
O2—Cd1—O1^xi	70.70 (8)	Cd1^xiv—O2—Cd1^xvii	93.22 (5)
O3—Cd1—O1^xi	156.48 (7)	Cu1^xix—O2—Cd1^xvii	120.33 (5)
O1^x—Cd1—O1^xi	73.60 (8)	Cd1ⁱⁱ—O2—Cd1^xvii	74.32 (4)
O4—Cd1—O2^xii	140.14 (8)	Cu1^x—O2—Cd1^xvii	158.46 (6)
O1—Cd1—O2^xii	123.63 (8)	Cd1^x—O2—Cd1^xvii	151.66 (6)
O4^ix—Cd1—O2^xii	74.92 (8)	Cu1—O2—Cd1^xvii	97.84 (5)
O2—Cd1—O2^xii	68.43 (9)	Cd1^xii—O2—Cd1^ix	111.38 (6)
O3—Cd1—O2^xii	43.87 (7)	Cd1^xiii—O2—Cd1^ix	121.95 (6)
O1^x—Cd1—O2^xii	66.35 (7)	Cd1^xiv—O2—Cd1^ix	70.16 (4)
O3ⁱⁱ—Cd1—O2^xii	82.12 (6)	Cu1^xix—O2—Cd1^ix	111.06 (5)
O1^xi—Cd1—O2^xii	133.29 (6)	Cd1ⁱⁱ—O2—Cd1^ix	110.68 (5)
O4—Cd1—O2ⁱⁱⁱ	103.51 (8)	Cd1^xi—O2—Cd1^ix	74.49 (5)
O1—Cd1—O2ⁱⁱⁱ	88.32 (8)	Cd1^x—O2—Cd1^ix	59.93 (4)
O4^ix—Cd1—O2ⁱⁱⁱ	43.91 (7)	Cu1—O2—Cd1^ix	63.54 (3)
O2—Cd1—O2ⁱⁱⁱ	139.86 (10)	Cd1^xvii—O2—Cd1^ix	115.27 (5)
O3—Cd1—O2ⁱⁱⁱ	49.66 (7)	Cu1^xiii—O2—Cd1^xx	50.01 (7)
O1^x—Cd1—O2ⁱⁱⁱ	120.71 (7)	Cd1—O2—Cd1^xx	131.88 (9)
O3ⁱⁱ—Cd1—O2ⁱⁱⁱ	104.95 (6)	Cd1^xiii—O2—Cd1^xx	88.04 (5)
O1^xi—Cd1—O2ⁱⁱⁱ	149.29 (6)	Cd1^xiv—O2—Cd1^xx	130.25 (5)
O2^xii—Cd1—O2ⁱⁱⁱ	75.33 (6)	Cu1^xix—O2—Cd1^xx	64.28 (4)
O4—Cd1—O4^xi	93.73 (8)	Cd1ⁱⁱ—O2—Cd1^xx	57.02 (4)
O1—Cd1—O4^xi	40.29 (7)	Cd1^xi—O2—Cd1^xx	137.47 (5)
O4^ix—Cd1—O4^xi	163.60 (10)	Cu1^x—O2—Cd1^xx	87.77 (5)
O2—Cd1—O4^xi	62.07 (7)	Cd1^x—O2—Cd1^xx	102.22 (6)
O3—Cd1—O4^xi	103.53 (8)	Cu1—O2—Cd1^xx	94.45 (5)
O1^x—Cd1—O4^xi	110.48 (7)	Cd1^xvii—O2—Cd1^xx	94.93 (5)
O3ⁱⁱ—Cd1—O4^xi	40.49 (6)	Cd1^ix—O2—Cd1^xx	143.86 (5)
O1^xi—Cd1—O4^xi	55.11 (6)	Cu1—O3—Cd1ⁱⁱ	89.01 (8)
O2^xii—Cd1—O4^xi	119.01 (6)	Cd1—O3—Cd1ⁱⁱ	115.12 (9)
O2ⁱⁱⁱ—Cd1—O4^xi	127.54 (6)	Cu1—O3—Cu1^x	122.88 (10)
O4—Cd1—Cu1^xiii	125.95 (7)	Cd1—O3—Cu1^x	83.68 (7)
O1—Cd1—Cu1^xiii	75.38 (7)	Cd1ⁱⁱ—O3—Cu1^x	134.32 (8)
O4^ix—Cd1—Cu1^xiii	149.34 (6)	Cu1—O3—Cd1^vi	76.05 (7)
O2—Cd1—Cu1^xiii	23.93 (6)	Cd1—O3—Cd1^vi	132.72 (9)
O3—Cd1—Cu1^xiii	80.27 (6)	Cd1ⁱⁱ—O3—Cd1^vi	111.16 (7)
O1^x—Cd1—Cu1^xiii	82.35 (6)	Cu1^x—O3—Cd1^vi	56.49 (4)
O3ⁱⁱ—Cd1—Cu1^xiii	30.50 (4)	Cu1—O3—Cu1^xiii	132.73 (9)
O1^xi—Cd1—Cu1^xiii	77.24 (5)	Cd1—O3—Cu1^xiii	66.25 (6)
O4—Cd1—O3^vi	113.58 (8)	Cd1ⁱⁱ—O3—Cu1^xiii	55.76 (4)
O1—Cd1—O3^vi	122.20 (8)	Cu1^x—O3—Cu1^xiii	104.31 (6)
O4^ix—Cd1—O3^vi	36.07 (7)	Cd1^vi—O3—Cu1^xiii	141.72 (7)
O2—Cd1—O3^vi	111.14 (8)	Cu1—O3—Cd1^xii	153.18 (10)
O3—Cd1—O3^vi	47.28 (9)	Cd1—O3—Cd1^xii	93.54 (7)
O1^x—Cd1—O3^vi	84.58 (7)	Cd1ⁱⁱ—O3—Cd1^xii	78.38 (5)
O1^xi—Cd1—O3^vi	153.06 (5)	Cu1^x—O3—Cd1^xii	58.36 (4)
O2^xii—Cd1—O3^vi	43.06 (5)	Cd1^vi—O3—Cd1^xii	86.48 (5)
O2ⁱⁱⁱ—Cd1—O3^vi	38.49 (5)	Cu1^xiii—O3—Cd1^xii	56.70 (4)
O4^xi—Cd1—O3^vi	150.81 (5)	Cu1—O3—Cd1^iv	85.25 (8)
O4—Cd1—O1^v	54.71 (8)	Cd1—O3—Cd1^iv	161.46 (9)
O1—Cd1—O1^v	78.38 (8)	Cd1ⁱⁱ—O3—Cd1^iv	63.86 (5)
O4^ix—Cd1—O1^v	53.87 (7)	Cu1^x—O3—Cd1^iv	85.34 (6)
O2—Cd1—O1^v	168.01 (7)	Cd1^vi—O3—Cd1^iv	48.39 (4)
O3—Cd1—O1^v	99.58 (7)	Cu1^xiii—O3—Cd1^iv	102.33 (6)
O1^x—Cd1—O1^v	121.37 (5)	Cd1^xii—O3—Cd1^iv	67.96 (4)
O3ⁱⁱ—Cd1—O1^v	126.14 (6)	Cu1—O3—Cd1^vii	52.70 (6)
O1^xi—Cd1—O1^v	97.51 (6)	Cd1—O3—Cd1^vii	76.20 (6)
O2^xii—Cd1—O1^v	123.26 (6)	Cd1ⁱⁱ—O3—Cd1^vii	71.96 (5)
O2ⁱⁱⁱ—Cd1—O1^v	51.81 (5)	Cu1^x—O3—Cd1^vii	152.72 (6)
O4^xi—Cd1—O1^v	109.77 (6)	Cd1^vi—O3—Cd1^vii	128.75 (6)
O3^vi—Cd1—O1^v	80.31 (5)	Cu1^xiii—O3—Cd1^vii	84.37 (5)
O4—Cd1—O4^xiv	84.91 (8)	Cd1^xii—O3—Cd1^vii	140.12 (6)
O1—Cd1—O4^xiv	114.66 (7)	Cd1^iv—O3—Cd1^vii	118.53 (5)
O4^ix—Cd1—O4^xiv	118.05 (9)	Cu1—O3—Cd1^ix	93.79 (8)
O2—Cd1—O4^xiv	32.90 (7)	Cd1ⁱⁱ—O3—Cd1^ix	151.41 (7)
O3—Cd1—O4^xiv	119.27 (7)	Cu1^x—O3—Cd1^ix	65.65 (5)
O1^x—Cd1—O4^xiv	36.11 (6)	Cd1^vi—O3—Cd1^ix	97.09 (5)
O3ⁱⁱ—Cd1—O4^xiv	84.27 (6)	Cu1^xiii—O3—Cd1^ix	103.95 (6)
O1^xi—Cd1—O4^xiv	50.21 (6)	Cd1^xii—O3—Cd1^ix	108.63 (5)
O2^xii—Cd1—O4^xiv	83.08 (6)	Cd1^iv—O3—Cd1^ix	144.71 (6)
O2ⁱⁱⁱ—Cd1—O4^xiv	154.88 (5)	Cd1^vii—O3—Cd1^ix	87.24 (5)
O4^xi—Cd1—O4^xiv	74.38 (5)	Cd1—O3—Cd1ⁱⁱⁱ	91.36 (7)
O3^vi—Cd1—O4^xiv	116.43 (5)	Cd1ⁱⁱ—O3—Cd1ⁱⁱⁱ	130.03 (6)
O1^v—Cd1—O4^xiv	139.29 (5)	Cu1^x—O3—Cd1ⁱⁱⁱ	87.54 (6)
O4—Cd1—O1ⁱⁱ	172.61 (7)	Cd1^vi—O3—Cd1ⁱⁱⁱ	65.07 (4)
O1—Cd1—O1ⁱⁱ	88.91 (8)	Cu1^xiii—O3—Cd1ⁱⁱⁱ	152.74 (6)
O4^ix—Cd1—O1ⁱⁱ	104.05 (8)	Cd1^xii—O3—Cd1ⁱⁱⁱ	144.66 (6)
O2—Cd1—O1ⁱⁱ	58.38 (8)	Cd1^iv—O3—Cd1ⁱⁱⁱ	103.05 (5)
O3—Cd1—O1ⁱⁱ	32.81 (7)	Cd1^vii—O3—Cd1ⁱⁱⁱ	74.89 (5)
O1^x—Cd1—O1ⁱⁱ	91.17 (7)	Cd1^ix—O3—Cd1ⁱⁱⁱ	58.28 (4)
O3ⁱⁱ—Cd1—O1ⁱⁱ	46.69 (6)	Cd1—O3—Cd1ⁱ	137.10 (8)
O1^xi—Cd1—O1ⁱⁱ	126.78 (7)	Cd1ⁱⁱ—O3—Cd1ⁱ	78.49 (5)
O2^xii—Cd1—O1ⁱⁱ	36.27 (5)	Cu1^x—O3—Cd1ⁱ	116.79 (6)
O2ⁱⁱⁱ—Cd1—O1ⁱⁱ	82.21 (6)	Cd1^vi—O3—Cd1ⁱ	61.51 (4)
O4^xi—Cd1—O1ⁱⁱ	86.28 (6)	Cu1^xiii—O3—Cd1ⁱ	132.83 (6)
O3^vi—Cd1—O1ⁱⁱ	68.00 (6)	Cd1^xii—O3—Cd1ⁱ	129.36 (5)
O1^v—Cd1—O1ⁱⁱ	132.11 (7)	Cd1^iv—O3—Cd1ⁱ	61.42 (4)
O4^xiv—Cd1—O1ⁱⁱ	87.97 (5)	Cd1^vii—O3—Cd1ⁱ	69.87 (4)
O4—Cd1—O2^xiv	31.43 (7)	Cd1^ix—O3—Cd1ⁱ	113.13 (5)
O1—Cd1—O2^xiv	113.43 (8)	Cd1ⁱⁱⁱ—O3—Cd1ⁱ	55.28 (3)
O4^ix—Cd1—O2^xiv	88.47 (8)	Cu1—O3—Cd1^v	52.25 (6)
O2—Cd1—O2^xiv	86.45 (8)	Cd1—O3—Cd1^v	61.03 (5)
O3—Cd1—O2^xiv	161.82 (7)	Cd1ⁱⁱ—O3—Cd1^v	109.74 (6)
O1^x—Cd1—O2^xiv	53.66 (7)	Cu1^x—O3—Cd1^v	115.63 (6)
O3ⁱⁱ—Cd1—O2^xiv	126.15 (6)	Cd1^vi—O3—Cd1^v	111.31 (5)
O1^xi—Cd1—O2^xiv	36.16 (6)	Cu1^xiii—O3—Cd1^v	106.89 (5)
O2^xii—Cd1—O2^xiv	119.34 (6)	Cd1^xii—O3—Cd1^v	154.52 (5)
O2ⁱⁱⁱ—Cd1—O2^xiv	127.40 (4)	Cd1^iv—O3—Cd1^v	137.50 (5)
O4^xi—Cd1—O2^xiv	91.28 (6)	Cd1^ix—O3—Cd1^v	52.93 (3)
O3^vi—Cd1—O2^xiv	117.32 (5)	Cd1ⁱⁱⁱ—O3—Cd1^v	46.32 (3)
O1^v—Cd1—O2^xiv	84.94 (6)	Cd1ⁱ—O3—Cd1^v	76.08 (4)
O4^xiv—Cd1—O2^xiv	54.35 (5)	Cu1—O3—Cd1^x	144.58 (9)
O1ⁱⁱ—Cd1—O2^xiv	141.19 (5)	Cd1—O3—Cd1^x	53.63 (5)
O4—Cd1—O3^xii	113.67 (8)	Cd1ⁱⁱ—O3—Cd1^x	126.34 (6)
O1—Cd1—O3^xii	126.45 (7)	Cd1^vi—O3—Cd1^x	91.00 (5)
O4^ix—Cd1—O3^xii	104.22 (7)	Cu1^xiii—O3—Cd1^x	76.29 (5)
O2—Cd1—O3^xii	30.05 (7)	Cd1^xii—O3—Cd1^x	54.02 (3)
O3—Cd1—O3^xii	86.46 (7)	Cd1^iv—O3—Cd1^x	110.71 (5)
O1^x—Cd1—O3^xii	35.57 (6)	Cd1^vii—O3—Cd1^x	129.83 (5)
O3ⁱⁱ—Cd1—O3^xii	78.38 (5)	Cd1^ix—O3—Cd1^x	54.66 (3)
O1^xi—Cd1—O3^xii	84.80 (5)	Cd1ⁱⁱⁱ—O3—Cd1^x	103.59 (5)
O2^xii—Cd1—O3^xii	48.56 (5)	Cd1ⁱ—O3—Cd1^x	149.84 (5)
O2ⁱⁱⁱ—Cd1—O3^xii	123.24 (5)	Cd1^v—O3—Cd1^x	105.77 (4)
O4^xi—Cd1—O3^xii	91.99 (5)	Cd1—O4—Cu1^xv	131.99 (10)
O3^vi—Cd1—O3^xii	86.48 (5)	Cd1^ix—O4—Cu1^xv	96.89 (9)
O1^v—Cd1—O3^xii	155.06 (5)	Cd1—O4—Cu1^xxi	135.45 (10)
O4^xiv—Cd1—O3^xii	34.68 (5)	Cd1^ix—O4—Cu1^xxi	68.81 (7)
O1ⁱⁱ—Cd1—O3^xii	58.96 (5)	Cu1^xv—O4—Cu1^xxi	92.50 (7)
O2^xiv—Cd1—O3^xii	82.47 (5)	Cd1—O4—Cd1^xi	86.27 (8)
O4—Cd1—O2ⁱⁱ	140.40 (7)	Cd1^ix—O4—Cd1^xi	163.60 (10)
O1—Cd1—O2ⁱⁱ	53.32 (7)	Cu1^xv—O4—Cd1^xi	67.33 (5)
O4^ix—Cd1—O2ⁱⁱ	99.68 (8)	Cu1^xxi—O4—Cd1^xi	114.60 (7)
O2—Cd1—O2ⁱⁱ	95.10 (7)	Cd1—O4—Cd1^xiv	95.09 (8)
O3—Cd1—O2ⁱⁱ	31.43 (7)	Cd1^ix—O4—Cd1^xiv	118.05 (9)
O1^x—Cd1—O2ⁱⁱ	137.44 (6)	Cu1^xv—O4—Cd1^xiv	113.75 (7)
O3ⁱⁱ—Cd1—O2ⁱⁱ	47.65 (5)	Cu1^xxi—O4—Cd1^xiv	57.92 (4)
O1^xi—Cd1—O2ⁱⁱ	132.53 (5)	Cd1—O4—Cd1^xiv	95.09 (8)
O2^xii—Cd1—O2ⁱⁱ	73.18 (5)	Cd1^ix—O4—Cd1^xiv	118.05 (9)
O2ⁱⁱⁱ—Cd1—O2ⁱⁱ	57.33 (7)	Cu1^xv—O4—Cd1^xiv	113.75 (7)
O4^xi—Cd1—O2ⁱⁱ	77.95 (6)	Cu1^xxi—O4—Cd1^xiv	57.92 (4)
O3^vi—Cd1—O2ⁱⁱ	74.40 (5)	Cd1^xi—O4—Cd1^xiv	74.38 (5)
O1^v—Cd1—O2ⁱⁱ	91.42 (6)	Cd1—O4—Cd1^v	88.36 (8)
O4^xiv—Cd1—O2ⁱⁱ	127.98 (5)	Cd1^ix—O4—Cd1^v	82.52 (7)
O1ⁱⁱ—Cd1—O2ⁱⁱ	46.79 (5)	Cu1^xv—O4—Cd1^v	51.01 (4)
O2^xiv—Cd1—O2ⁱⁱ	166.75 (7)	Cu1^xxi—O4—Cd1^v	130.67 (7)
O3^xii—Cd1—O2ⁱⁱ	105.34 (5)	Cd1^xi—O4—Cd1^v	83.81 (5)
O4—Cd1—O2^xi	48.12 (7)	Cd1^xiv—O4—Cd1^v	157.62 (6)
O1—Cd1—O2^xi	48.24 (7)	Cd1—O4—Cd1^xv	151.12 (9)
O4^ix—Cd1—O2^xi	110.65 (8)	Cd1^ix—O4—Cd1^xv	106.14 (8)
O2—Cd1—O2^xi	109.17 (7)	Cu1^xv—O4—Cd1^xv	48.87 (4)
O3—Cd1—O2^xi	129.72 (7)	Cu1^xxi—O4—Cd1^xv	54.82 (4)
O1^x—Cd1—O2^xi	119.71 (6)	Cd1^xi—O4—Cd1^xv	67.41 (5)
O3ⁱⁱ—Cd1—O2^xi	90.11 (6)	Cd1^xiv—O4—Cd1^xv	67.31 (4)
O1^xi—Cd1—O2^xi	49.38 (5)	Cd1^v—O4—Cd1^xv	99.88 (5)
O2^xii—Cd1—O2^xi	171.73 (7)	Cd1—O4—Cd1^x	71.21 (7)
O2ⁱⁱⁱ—Cd1—O2^xi	104.20 (5)	Cd1^ix—O4—Cd1^x	76.23 (7)
O4^xi—Cd1—O2^xi	54.55 (6)	Cu1^xv—O4—Cd1^x	156.75 (7)
O3^vi—Cd1—O2^xi	139.59 (5)	Cu1^xxi—O4—Cd1^x	64.26 (4)
O1^v—Cd1—O2^xi	59.69 (5)	Cd1^xi—O4—Cd1^x	120.02 (6)
O4^xiv—Cd1—O2^xi	99.01 (5)	Cd1^xiv—O4—Cd1^x	54.32 (4)
O1ⁱⁱ—Cd1—O2^xi	135.55 (5)	Cd1^v—O4—Cd1^x	146.20 (6)
O2^xiv—Cd1—O2^xi	67.69 (4)	Cd1^xv—O4—Cd1^x	111.05 (5)
O3^xii—Cd1—O2^xi	132.56 (5)	Cd1^ix—O4—Cu1	84.81 (7)
O2ⁱⁱ—Cd1—O2^xi	99.49 (5)	Cu1^xv—O4—Cu1	108.05 (6)
O4—Cd1—O3^xv	18.13 (7)	Cu1^xxi—O4—Cu1	148.46 (6)
O1—Cd1—O3^xv	83.12 (8)	Cd1^xi—O4—Cu1	95.64 (6)
O4^ix—Cd1—O3^xv	95.58 (8)	Cd1^xiv—O4—Cu1	128.09 (6)
O2—Cd1—O3^xv	104.26 (8)	Cd1^v—O4—Cu1	58.17 (4)
O3—Cd1—O3^xv	161.46 (9)	Cd1^xv—O4—Cu1	154.65 (6)
O1^x—Cd1—O3^xv	86.92 (7)	Cd1^x—O4—Cu1	93.59 (5)
O3ⁱⁱ—Cd1—O3^xv	116.14 (5)	Cd1^ix—O4—Cu1^x	65.76 (6)
O2^xii—Cd1—O3^xv	152.38 (5)	Cu1^xv—O4—Cu1^x	155.08 (7)
O2ⁱⁱⁱ—Cd1—O3^xv	115.88 (6)	Cu1^xxi—O4—Cu1^x	97.08 (5)
O4^xi—Cd1—O3^xv	75.66 (6)	Cd1^xi—O4—Cu1^x	127.41 (6)
O3^vi—Cd1—O3^xv	131.61 (4)	Cd1^xiv—O4—Cu1^x	90.74 (5)
O1^v—Cd1—O3^xv	64.23 (5)	Cd1^v—O4—Cu1^x	106.80 (5)
O4^xiv—Cd1—O3^xv	78.70 (5)	Cd1^xv—O4—Cu1^x	150.38 (6)
O1ⁱⁱ—Cd1—O3^xv	159.85 (5)	Cu1—O4—Cu1^x	54.95 (3)
O2^xiv—Cd1—O3^xv	33.33 (4)	Cd1^ix—O4—Cu1^xiii	133.70 (8)
O3^xii—Cd1—O3^xv	112.04 (4)	Cu1^xv—O4—Cu1^xiii	123.67 (7)
O2ⁱⁱ—Cd1—O3^xv	134.42 (5)	Cu1^xxi—O4—Cu1^xiii	124.04 (6)
O2^xi—Cd1—O3^xv	35.22 (4)	Cd1^xi—O4—Cu1^xiii	59.16 (4)
O4—Cd1—O2^vii	110.48 (8)	Cd1^xiv—O4—Cu1^xiii	68.19 (4)
O4^ix—Cd1—O2^vii	136.15 (7)	Cd1^v—O4—Cu1^xiii	104.92 (5)
O2—Cd1—O2^vii	82.89 (7)	Cd1^xv—O4—Cu1^xiii	116.94 (5)
O3—Cd1—O2^vii	75.94 (7)	Cd1^x—O4—Cu1^xiii	73.32 (4)
O1^x—Cd1—O2^vii	140.47 (6)	Cu1—O4—Cu1^xiii	63.48 (3)
O3ⁱⁱ—Cd1—O2^vii	33.11 (5)	Cu1^x—O4—Cu1^xiii	68.42 (4)
O1^xi—Cd1—O2^vii	86.73 (6)	Cd1—O4—Cd1^vii	59.13 (6)
O2^xii—Cd1—O2^vii	109.34 (5)	Cd1^ix—O4—Cd1^vii	112.81 (8)
O2ⁱⁱⁱ—Cd1—O2^vii	93.60 (6)	Cu1^xv—O4—Cd1^vii	72.88 (5)
O4^xi—Cd1—O2^vii	34.46 (5)	Cu1^xxi—O4—Cd1^vii	165.37 (6)
O3^vi—Cd1—O2^vii	120.18 (5)	Cd1^xi—O4—Cd1^vii	59.61 (4)
O1^v—Cd1—O2^vii	94.52 (6)	Cd1^xiv—O4—Cd1^vii	126.88 (6)
O4^xiv—Cd1—O2^vii	105.70 (5)	Cd1^xv—O4—Cd1^vii	112.30 (5)
O1ⁱⁱ—Cd1—O2^vii	73.42 (6)	Cd1^x—O4—Cd1^vii	130.33 (5)
O2^xiv—Cd1—O2^vii	121.50 (4)	Cu1^x—O4—Cd1^vii	96.66 (4)
O3^xii—Cd1—O2^vii	110.41 (5)	Cu1^xiii—O4—Cd1^vii	66.24 (4)
O2ⁱⁱ—Cd1—O2^vii	46.00 (6)	Cd1—O4—Cu1^xxii	109.40 (8)
O2^xi—Cd1—O2^vii	62.39 (6)	Cd1^ix—O4—Cu1^xxii	144.31 (8)
O3^xv—Cd1—O2^vii	95.55 (6)	Cu1^xv—O4—Cu1^xxii	73.82 (5)
O4—Cd1—O4^v	91.64 (8)	Cu1^xxi—O4—Cu1^xxii	77.12 (5)
O1—Cd1—O4^v	43.61 (7)	Cd1^v—O4—Cu1^xxii	113.71 (5)
O4^ix—Cd1—O4^v	82.52 (7)	Cd1^x—O4—Cu1^xxii	98.65 (5)
O2—Cd1—O4^v	136.52 (7)	Cu1—O4—Cu1^xxii	130.88 (5)
O3—Cd1—O4^v	70.35 (7)	Cu1^x—O4—Cu1^xxii	130.76 (5)
O1^x—Cd1—O4^v	164.56 (6)	Cu1^xiii—O4—Cu1^xxii	74.96 (4)
O3ⁱⁱ—Cd1—O4^v	82.34 (5)	Cd1^vii—O4—Cu1^xxii	97.54 (5)
O1^xi—Cd1—O4^v	112.39 (5)

Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) x, y−1, z; (iv) x, y, z−1; (v) −x, −y, −z+1; (vi) −x+1, −y, −z; (vii) x−1, y, z; (viii) x−1, y, z−1; (ix) −x+1, −y, −z+1; (x) x+1, y, z; (xi) −x, −y+1, −z+1; (xii) −x+1, −y+1, −z; (xiii) x, y+1, z; (xiv) −x+1, −y+1, −z+1; (xv) x, y, z+1; (xvi) x+1, y−1, z; (xvii) x−1, y+1, z; (xviii) −x−1, −y+1, −z+1; (xix) x+1, y+1, z; (xx) x, y+1, z−1; (xxi) x+1, y, z+1; (xxii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula	Cd₂Cu(PO₄)₂
M_r	478.31
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	4.7982 (3), 5.5801 (3), 6.7217 (3)
α, β, γ (°)	74.266 (3), 86.330 (3), 69.924 (3)
V (Å³)	162.62 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	10.22
Crystal size (mm)	0.09 × 0.04 × 0.02

Data collection
Diffractometer	Nonius KappaCCD diffractomer
Absorption correction	Multi-scan (Otwinowski & Minor, 1997)
T_min, T_max	0.460, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	1596, 805, 747
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.043, 1.09
No. of reflections	805
No. of parameters	63
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.59

Computer programs: COLLECT (Nonius, 2002), HKL SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski et al., 2003), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999), ATOMS (Dowty, 2000), publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

Cu1—O3	1.928 (2)	Cd1—O1	2.242 (2)
Cu1—O3ⁱ	1.928 (2)	Cd1—O4^v	2.263 (3)
Cu1—O2ⁱⁱ	1.952 (3)	Cd1—O2	2.271 (2)
Cu1—O2ⁱⁱⁱ	1.952 (3)	Cd1—O3	2.288 (2)
Cu1—Cd1ⁱ	3.5270 (3)	Cd1—O1^vi	2.716 (2)
Cu1—Cd1ⁱⁱ	3.7977 (4)	Cd1—Cd1^v	3.5019 (8)
Cu1—Cd1^iv	3.9408 (4)	Cd1—Cd1^vii	4.2599 (5)
Cd1—O4	2.232 (3)	Cd1—Cd1ⁱⁱ	4.7525 (5)

O3—Cu1—O2ⁱⁱ	88.42 (10)	O3ⁱ—Cu1—O2ⁱⁱ	91.58 (10)

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

Table 1. Unit-cell parameters of the M1₂M2(XO₄)₂ (M1, M2 = Cd²⁺, Cu²⁺, Mg²⁺ and Zn²⁺, and X = As⁵⁺, P⁵⁺ and V⁵⁺) family of compounds top

Compound	a(Å)	b(Å)	c(Å)	α(^o)	β(^o)	γ(^o)	V(Å³)
Cu₃(PO₄)₂¹	4.855 (1)	5.288 (1)	6.184 (1)	72.34 (1)	86.99 (1)	68.54 (1)	140.49
Cu₃(PO₄)₂¹	4.848 (1)	5.280 (1)	6.183 (1)	72.30 (1)	86.90 (1)	68.59 (1)	140.08
Cu₃(PO₄)₂²	4.8537 (7)	5.2855 (6)	6.1821 (8)	72.35 (1)	86.99 (1)	68.54 (1)	140.35
Mg_0.63Cu_2.37(PO₄)₂³	4.845 (3)	5.265 (3)	6.246 (2)	71.98 (4)	93.04 (4)	111.42 (4)	140.72
Red. Cell^#	4.845 (3)	5.265 (3)	6.246 (2)	71.98 (4)	86.959	68.579
Cd₂Cu(PO₄)₂⁴	4.7982 (3)	5.5801 (3)	6.7217 (3)	74.266 (3)	86.330 (3)	69.924 (3)	162.62
Cu₃(VO₄)₂⁵	5.196 (4)	5.355 (1)	6.505 (4)	69.22 (3)	88.69 (4)	68.08 (3)	155.73
Cu₃(AsO₄)₂⁶	5.046 (2)	5.417 (2)	6.354 (2)	70.61 (2)	86.52 (2)	68.43 (2)	151.98
Zn₂Cu(AsO₄)₂⁷	5.092 (2)	6.695 (2)	5.304 (2)	110.16 (2)	112.09 (2)	86.74 (2)	156.73
Red. Cell^*	5.092 (2)	5.304 (2)	6.695 (2)	69.84	86.74	67.91
Zn₂Cu(AsO₄)₂⁸	5.094 (1)	6.752 (1)	5.304 (1)	111.0 (1)	112.5 (1)	86.0 (1)	156.87
Red. Cell^*	5.094 (1)	5.304 (1)	6.752 (1)	69	86	67.5
Zn₂Cu(AsO₄)₂⁹	5.094 (5)	6.752 (5)	5.304 (5)	111	112	86	157.47
Red. Cell^*	5.094 (5)	5.304 (5)	6.752 (5)	69	86	68

Notes: (a) Transformation matrix 1: 1 0 0 / 0 -1 0 / 0 0 -1; (b) transformation matrix 2: 1 0 0 / 0 0 -1 / 0 1 0. References: (1) Forsyth et al. (1990); (2) Shoemaker et al. (1977); (3) Moqine et al. (1994); (4) this work; (5) Coing-Boyat (1982); (6) Effenberger (1988); (7) Keller et al. (1979); (8) Plieth & Sänger (1967); (9) Calvo & Leung (1969).

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