A new polymorph of Cu₃B₂O₆

A new polymorph of nona­copper(II) bis­(orthoborate) bis­(hexa­oxodiborate), Cu₉(BO₃)₂(B₂O₆)₂, or Cu₃B₂O₆ with Z' = 3, has a pseudo-layered monoclinic structure containing BO₃ triangles and B₂O₆ units consisting of corner-sharing BO₃ triangles and BO₄ tetra­hedra. The compound was obtained during an investigation of the Li-Cu-B-O system. In contrast to the triclinic form of Cu₃B₂O₆, the layers are linked to one another by BO₄ tetra­hedra.

S1. Comment

The copper(II) boron oxides CuB₂O₄ and Cu₃B₂O₆ attract great interest owing to the combination of their structural and unusual physical properties (Sakurai et al., 2002; Saito et al., 2008; Martinez-Ripoll et al., 1971; Behm, 1982). The noncentrosymmetric (I42d) canted antiferromagnet CuB₂O₄ becomes chiral by application of a static magnetic field (Saito et al., 2008). Its crystal structure consists exclusively of BO₄ tetrahedra and CuO₄ squares. Antiferromagnetic triclinic Cu₃B₂O₆ can be considered as a two-dimensional spin system because of the pronounced layered character of the crystal structure (Sakurai et al., 2002). Recently, a high-pressure modification of CuB₄O₇ (Knyrim et al., 2008) with Cu^II, isotypic with β-ZnB₄O₇, has been reported, showing BO₄ tetrahedra and CuO₅ square pyramids. The common feature of all these systems is Jahn–Teller distortion of the Cu coordination polyhedra, due to the electronic configuration of the d⁹ ion, which can lead to anisotropic character of the crystal structure.

During an investigation of the Li–Cu–B–O system we prepared a new polymorphic modification of Cu₃B₂O₆. A monoclinic crystal structure of Cu₃B₂O₆ was obtained, which can be considered as pseudo-layered with much shorter distances between neighbouring layers (1.505 Å; Fig. 1) than in the triclinic polymorph (2.7 Å; Behm, 1982). The monoclinic structure contains six-layered packing; the layers are parallel to the [402] plane and offset with respect to one another.

There are isolated BO₃ triangles and B₂O₆ units, consisting of corner-shared BO₃ triangles and BO₄ tetrahedra, in the structure, giving the formula Cu₉(BO₃)₂(B₂O₆)₂, while the other polymorph has only B₂O₅^4- and BO₃^3- species and a separate O^2- anion, resulting in the composition Cu₁₅[(B₂O₅)₂(BO₃)₆O₂]. The shortest distance between neighbouring layers is 1.506 (6) Å for the B—O bond in the BO₄ tetrahedra (Fig. 1). The average B—O length is 1.366 (7) Å in the triangles and 1.483 (6) Å in the tetrahedra. This form of borate anion is quite unusual, but a report on the presence of tetrahedrally and triangularly bonded B atoms in one formation already exists (Rowsell et al., 2002). Almost all of the Cu atoms have nearly planar square coordination environments, with one or two longer contacts to O atoms from neighbouring layers, forming distorted square-pyramidal or octahedral coordination environments. Atoms Cu1 and Cu2 are exceptions, having no additional contacts shorter than 3.1 Å. Each layer contains CuO₄ squares and Cu₂O₆ dimers sharing the corners, and BO₃ triangles and B₂O₅ units, which are surrounded on both sides by infinite CuO₂ chains from edge-sharing CuO₄ squares (Fig. 2). The CuO₂ chains extend parallel to the b axis. The Cu—O bond lengths in the layer vary from 1.868 (3) to 2.088 (4) Å and those between neighbouring layers vary from 2.333 (3) to 2.738 (3) Å, forming CuO₅ and CuO₆ polyhedra.

It has already been shown (Behm, 1982; Pardo et al., 1974) that other borates (M₃B₂O₆, with M²⁺ = Mg, Ni and Co) crystallize in a completely different structure type, with only isolated BO₃ triangles and practically undistorted MO₆ octahedra, which form a three-dimensional network. The peculiarity of Cu₃B₂O₆ structures is probably based on the ability of Cu²⁺ to adopt different coordination environments as a result of Jahn–Teller distortion.

S2. Experimental

Single crystals of a new monoclinic polymorph of Cu₃B₂O₆ were obtained by melting a mixture of LiBO₂ and CuO at 1273 K in air and then cooling it slowly to room temperature. All attempts to obtain the monoclinic form by quenching of a stoichiometric mixture of CuO and B₂O₃ from 1273 K in air led to the formation of the triclinic form of Cu₃B₂O₆. High-temperature powder X-ray diffraction data of triclinic Cu₃B₂O₆ from room temperature up to 1073 K yielded no phase transformation.

S3. Refinement

There is some positional disordering in the location of one O atom.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of the new Cu3B2O6 pseudo-layered monoclinic modification. Solid lines show the closest interlayer Cu—O bonds.
	Fig. 2. The pseudo-layer packing of Cu3B2O6. Each layer consists of isolated CuO4 squares, Cu2O6 dimers of edge-sharing CuO4 squares, infinite CuO2 chains, and BO3 and corner-sharing B2O5 units. B—O bonds are shown with thicker lines. Displacement ellipsoids are plotted at the 70% probability level.

Nonacopper(II) bis(hexaoxodiborate) bisorthoborate

Crystal data

Cu9B6O18	F(000) = 1740
Mr = 924.81	Dx = 4.433 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2562 reflections
a = 17.820 (2) Å	θ = 2.7–31.8°
b = 8.5232 (12) Å	µ = 13.64 mm^−1
c = 9.1706 (12) Å	T = 296 K
β = 95.913 (6)°	Prism, green
V = 1385.4 (3) Å^3	0.20 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	3410 independent reflections
Radiation source: fine-focus sealed tube	2542 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: 25 pixels mm^-1	θmax = 28.3°, θmin = 1.2°
ϕ scans	h = −14→23
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −11→11
Tmin = 0.101, Tmax = 0.153	l = −8→12
9748 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.030	Secondary atom site location: difference Fourier map
wR(F^2) = 0.063	w = 1/[σ^2(Fo^2) + (0.0316P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.001
3410 reflections	Δρmax = 1.11 e Å^−3
301 parameters	Δρmin = −0.91 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.05596 (3)	0.32007 (7)	0.66267 (7)	0.01518 (15)
Cu2	0.14770 (3)	1.08020 (7)	0.52540 (6)	0.00941 (13)
Cu3	0.09805 (4)	0.70984 (7)	0.66138 (8)	0.01764 (15)
Cu4	0.26208 (3)	0.25771 (7)	0.28273 (6)	0.00880 (13)
Cu5	0.25274 (3)	0.59337 (7)	0.25439 (6)	0.00897 (13)
Cu6	0.26838 (3)	0.92391 (7)	0.27160 (6)	0.00941 (13)
Cu7	0.36673 (3)	0.76126 (7)	0.00016 (6)	0.00842 (13)
Cu8	0.43525 (3)	0.39597 (7)	−0.08558 (6)	0.00916 (13)
Cu9	0.43942 (3)	1.01033 (7)	−0.16993 (7)	0.01316 (14)
B1	−0.0131 (3)	0.5000 (7)	0.7998 (7)	0.0148 (12)
O11A	0.0572 (3)	0.5301 (6)	0.7488 (6)	0.0200 (13)	0.80
O11B	0.0329 (13)	0.537 (3)	0.690 (3)	0.0200 (13)	0.20
O12	−0.05446 (19)	0.5998 (4)	0.8738 (4)	0.0156 (8)
O13	−0.0292 (2)	0.3457 (4)	0.7684 (5)	0.0297 (10)
B21	0.2070 (3)	0.7422 (6)	0.5130 (6)	0.0088 (11)
B22	0.1715 (3)	0.4394 (7)	0.4847 (6)	0.0113 (11)
O21	0.15759 (17)	0.8592 (4)	0.5667 (3)	0.0087 (7)
O22	0.16421 (18)	0.5886 (4)	0.5438 (4)	0.0107 (7)
O23	0.21858 (18)	0.7596 (4)	0.3627 (3)	0.0101 (7)
O24	0.27939 (18)	0.7356 (4)	0.6133 (4)	0.0091 (7)
O25	0.21256 (19)	0.4261 (4)	0.3697 (4)	0.0133 (7)
O26	0.13875 (19)	0.3143 (4)	0.5437 (4)	0.0174 (8)
B31	0.3116 (3)	0.4163 (6)	0.0241 (6)	0.0091 (11)
B32	0.3488 (3)	0.1150 (6)	0.0580 (6)	0.0094 (11)
O31	0.35989 (17)	0.5374 (4)	−0.0307 (3)	0.0087 (7)
O32	0.35636 (18)	0.2651 (4)	−0.0047 (3)	0.0097 (7)
O33	0.30315 (18)	0.4254 (4)	0.1756 (3)	0.0099 (7)
O34	0.23944 (17)	0.4097 (4)	−0.0764 (4)	0.0090 (7)
O35	0.30901 (19)	0.0989 (4)	0.1753 (4)	0.0124 (7)
O36	0.38450 (18)	−0.0077 (4)	0.0005 (3)	0.0101 (7)
B4	0.4777 (3)	0.6897 (6)	−0.2246 (6)	0.0086 (10)
O41	0.42753 (19)	0.7857 (4)	−0.1693 (4)	0.0122 (7)
O42	0.49875 (18)	0.5434 (4)	−0.1678 (4)	0.0117 (7)
O43	0.51419 (19)	0.7201 (4)	−0.3474 (4)	0.0150 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0176 (3)	0.0049 (3)	0.0260 (4)	−0.0004 (2)	0.0165 (3)	−0.0009 (3)
Cu2	0.0104 (3)	0.0045 (3)	0.0146 (3)	0.0006 (2)	0.0072 (2)	0.0006 (2)
Cu3	0.0187 (3)	0.0046 (3)	0.0333 (4)	−0.0010 (2)	0.0204 (3)	−0.0005 (3)
Cu4	0.0138 (3)	0.0042 (3)	0.0094 (3)	0.0011 (2)	0.0065 (2)	0.0008 (2)
Cu5	0.0147 (3)	0.0040 (3)	0.0092 (3)	0.0009 (2)	0.0062 (2)	−0.0003 (2)
Cu6	0.0160 (3)	0.0041 (3)	0.0091 (3)	−0.0022 (2)	0.0060 (2)	−0.0003 (2)
Cu7	0.0115 (3)	0.0037 (3)	0.0111 (3)	−0.0005 (2)	0.0066 (2)	−0.0001 (2)
Cu8	0.0107 (3)	0.0044 (3)	0.0137 (3)	0.0005 (2)	0.0075 (2)	0.0003 (2)
Cu9	0.0194 (3)	0.0044 (3)	0.0182 (3)	−0.0011 (2)	0.0144 (3)	−0.0008 (2)
B1	0.013 (3)	0.007 (3)	0.027 (3)	0.000 (2)	0.010 (2)	0.002 (2)
O11A	0.018 (3)	0.007 (2)	0.039 (4)	−0.006 (2)	0.019 (2)	−0.009 (3)
O11B	0.018 (3)	0.007 (2)	0.039 (4)	−0.006 (2)	0.019 (2)	−0.009 (3)
O12	0.0165 (18)	0.0064 (18)	0.027 (2)	−0.0011 (14)	0.0164 (15)	0.0015 (15)
O13	0.033 (2)	0.0079 (19)	0.054 (3)	−0.0040 (17)	0.034 (2)	−0.0088 (19)
B21	0.011 (2)	0.004 (2)	0.013 (3)	0.000 (2)	0.007 (2)	0.000 (2)
B22	0.015 (3)	0.009 (3)	0.011 (3)	0.000 (2)	0.008 (2)	0.001 (2)
O21	0.0104 (16)	0.0038 (16)	0.0130 (17)	0.0001 (13)	0.0061 (13)	−0.0006 (13)
O22	0.0160 (17)	0.0043 (16)	0.0136 (18)	−0.0009 (13)	0.0097 (14)	−0.0015 (13)
O23	0.0173 (17)	0.0068 (16)	0.0069 (17)	0.0009 (14)	0.0057 (13)	0.0017 (13)
O24	0.0114 (16)	0.0071 (17)	0.0092 (16)	−0.0014 (13)	0.0039 (13)	0.0037 (13)
O25	0.0209 (18)	0.0026 (16)	0.0185 (19)	0.0017 (14)	0.0120 (14)	0.0021 (14)
O26	0.0218 (19)	0.0042 (17)	0.029 (2)	−0.0002 (15)	0.0180 (16)	−0.0022 (16)
B31	0.015 (3)	0.004 (2)	0.009 (3)	0.003 (2)	0.006 (2)	0.000 (2)
B32	0.009 (2)	0.006 (3)	0.013 (3)	−0.001 (2)	0.004 (2)	0.000 (2)
O31	0.0112 (16)	0.0048 (16)	0.0111 (18)	−0.0008 (13)	0.0063 (13)	−0.0014 (13)
O32	0.0128 (16)	0.0081 (17)	0.0096 (17)	0.0016 (14)	0.0071 (13)	0.0001 (13)
O33	0.0158 (17)	0.0046 (16)	0.0107 (17)	0.0016 (13)	0.0075 (13)	−0.0001 (13)
O34	0.0102 (16)	0.0066 (17)	0.0113 (17)	−0.0009 (13)	0.0063 (13)	−0.0013 (13)
O35	0.0200 (18)	0.0055 (17)	0.0134 (18)	0.0017 (14)	0.0093 (14)	0.0017 (14)
O36	0.0170 (17)	0.0033 (16)	0.0122 (17)	0.0007 (14)	0.0111 (14)	0.0020 (13)
B4	0.007 (2)	0.007 (3)	0.013 (3)	−0.002 (2)	0.006 (2)	0.003 (2)
O41	0.0179 (18)	0.0047 (17)	0.0161 (19)	−0.0006 (14)	0.0122 (14)	0.0024 (14)
O42	0.0111 (16)	0.0114 (18)	0.0141 (18)	0.0014 (14)	0.0090 (14)	0.0032 (14)
O43	0.0222 (19)	0.0048 (17)	0.021 (2)	0.0008 (14)	0.0141 (15)	−0.0011 (14)

Geometric parameters (Å, º)

Cu1—O11A	1.956 (5)	Cu6—Cu4^iii	2.8494 (9)
Cu1—O11B	1.92 (2)	Cu6—Cu7^iv	3.0329 (8)
Cu1—O12^i	1.906 (3)	Cu7—Cu6^vi	3.0329 (8)
Cu1—O13	1.896 (4)	B1—O12	1.354 (7)
Cu1—O26	1.924 (4)	B1—O13	1.370 (7)
Cu2—O12^ii	1.990 (3)	B1—O11B	1.40 (3)
Cu2—O21	1.925 (3)	B1—O11A	1.405 (8)
Cu2—O26^iii	2.010 (3)	O12—Cu1^ii	1.906 (3)
Cu2—O34^iv	1.967 (3)	O12—Cu2^i	1.990 (3)
Cu3—O11A	1.908 (5)	O13—Cu3^i	1.850 (4)
Cu3—O11B	1.91 (2)	O21—Cu5^iv	2.324 (3)
Cu3—O13^ii	1.850 (4)	B21—O21	1.451 (6)
Cu3—O21	1.921 (3)	B21—O22	1.555 (6)
Cu3—O22	1.970 (3)	B21—O23	1.422 (6)
Cu4—O25	1.903 (3)	B21—O24	1.506 (6)
Cu4—O33	1.921 (3)	B22—O22	1.394 (6)
Cu4—O34^v	1.994 (3)	B22—O25	1.348 (7)
Cu4—O35	1.916 (3)	B22—O26	1.355 (6)
Cu5—O21^vi	2.324 (3)	O24—Cu7^iv	1.958 (3)
Cu5—O23	1.868 (3)	O24—Cu6^iv	2.013 (3)
Cu5—O24^vi	2.037 (3)	O24—Cu5^iv	2.037 (3)
Cu5—O25	1.954 (3)	O26—Cu2^ix	2.010 (3)
Cu5—O33	1.874 (3)	O31—Cu6^vi	2.333 (3)
Cu6—O23	1.897 (3)	B31—O31	1.465 (6)
Cu6—O24^vi	2.013 (3)	B31—O32	1.552 (6)
Cu6—O31^iv	2.333 (3)	B31—O33	1.415 (6)
Cu6—O34^iv	2.090 (3)	B31—O34	1.505 (6)
Cu6—O35^iii	1.913 (3)	B32—O32	1.415 (6)
Cu7—O24^vi	1.958 (3)	B32—O35	1.355 (6)
Cu7—O31	1.931 (3)	B32—O36	1.359 (6)
Cu7—O36^iii	1.994 (3)	O34—Cu2^vi	1.967 (3)
Cu7—O41	1.995 (3)	O34—Cu4^x	1.994 (3)
Cu8—O31	1.910 (3)	O34—Cu6^vi	2.090 (3)
Cu8—O32	1.996 (3)	O35—Cu6^ix	1.913 (3)
Cu8—O42	1.898 (3)	O36—Cu9^ix	1.934 (3)
Cu8—O43^vii	1.885 (3)	O36—Cu7^ix	1.994 (3)
Cu9—O36^iii	1.934 (3)	B4—O41	1.349 (6)
Cu9—O41	1.926 (3)	B4—O42	1.389 (6)
Cu9—O42^viii	1.961 (3)	B4—O43	1.381 (6)
Cu9—O43^viii	1.969 (3)	O42—Cu9^vii	1.961 (3)
Cu2—Cu1^iii	2.9767 (9)	O43—Cu8^viii	1.885 (3)
Cu2—Cu5^iv	3.0484 (9)	O43—Cu9^vii	1.969 (3)
Cu4—Cu6^ix	2.8494 (9)	O11A—O11B	0.66 (2)
Cu5—Cu2^vi	3.0484 (9)	B4—Cu9^vii	2.397 (6)
O13—Cu1—O12^i	101.87 (16)	O43^viii—Cu9—B4^viii	35.17 (16)
O13—Cu1—O11B	68.2 (8)	B1—O12—Cu1^ii	122.0 (3)
O12^i—Cu1—O11B	166.8 (7)	B1—O12—Cu2^i	134.8 (3)
O13—Cu1—O26	173.75 (17)	Cu1^ii—O12—Cu2^i	99.62 (16)
O12^i—Cu1—O26	82.70 (15)	B1—O13—Cu3^i	131.3 (4)
O11B—Cu1—O26	106.6 (8)	B1—O13—Cu1	93.2 (3)
O13—Cu1—O11A	70.39 (19)	Cu3^i—O13—Cu1	134.5 (2)
O12^i—Cu1—O11A	166.3 (2)	B21—O21—Cu3	94.6 (3)
O11B—Cu1—O11A	19.6 (6)	B21—O21—Cu2	130.7 (3)
O26—Cu1—O11A	105.97 (19)	Cu3—O21—Cu2	133.92 (18)
O21—Cu2—O34^iv	94.15 (13)	B21—O21—Cu5^iv	87.1 (2)
O21—Cu2—O12^ii	93.14 (14)	Cu3—O21—Cu5^iv	100.09 (13)
O34^iv—Cu2—O12^ii	172.65 (14)	Cu2—O21—Cu5^iv	91.19 (12)
O21—Cu2—O26^iii	163.92 (15)	B22—O22—B21	129.0 (4)
O34^iv—Cu2—O26^iii	94.21 (14)	B22—O22—Cu3	140.9 (3)
O12^ii—Cu2—O26^iii	78.49 (14)	B21—O22—Cu3	89.5 (2)
O21—Cu2—Cu1^iii	129.18 (10)	B21—O23—Cu5	121.6 (3)
O34^iv—Cu2—Cu1^iii	133.67 (10)	B21—O23—Cu6	128.7 (3)
O12^ii—Cu2—Cu1^iii	39.16 (10)	Cu5—O23—Cu6	97.65 (15)
O26^iii—Cu2—Cu1^iii	39.75 (10)	B21—O24—Cu7^iv	110.7 (3)
O21—Cu2—Cu5^iv	49.65 (9)	B21—O24—Cu6^iv	109.0 (3)
O34^iv—Cu2—Cu5^iv	82.35 (9)	Cu7^iv—O24—Cu6^iv	122.24 (16)
O12^ii—Cu2—Cu5^iv	101.76 (10)	B21—O24—Cu5^iv	96.9 (3)
O26^iii—Cu2—Cu5^iv	118.20 (11)	Cu7^iv—O24—Cu5^iv	125.21 (16)
Cu1^iii—Cu2—Cu5^iv	111.53 (3)	Cu6^iv—O24—Cu5^iv	88.80 (13)
O13^ii—Cu3—O11A	93.5 (2)	B22—O25—Cu4	134.7 (3)
O13^ii—Cu3—O11B	90.1 (8)	B22—O25—Cu5	128.3 (3)
O11A—Cu3—O11B	19.9 (7)	Cu4—O25—Cu5	96.42 (16)
O13^ii—Cu3—O21	99.16 (15)	B22—O26—Cu1	126.4 (3)
O11A—Cu3—O21	167.06 (18)	B22—O26—Cu2^ix	135.0 (3)
O11B—Cu3—O21	160.8 (8)	Cu1—O26—Cu2^ix	98.33 (15)
O13^ii—Cu3—O22	166.97 (16)	B31—O31—Cu8	95.7 (3)
O11A—Cu3—O22	94.87 (19)	B31—O31—Cu7	132.5 (3)
O11B—Cu3—O22	94.4 (8)	Cu8—O31—Cu7	128.82 (17)
O21—Cu3—O22	73.19 (13)	B31—O31—Cu6^vi	88.8 (2)
O25—Cu4—O35	173.84 (14)	Cu8—O31—Cu6^vi	109.78 (14)
O25—Cu4—O33	82.57 (14)	Cu7—O31—Cu6^vi	90.17 (12)
O35—Cu4—O33	93.05 (14)	B32—O32—B31	127.6 (4)
O25—Cu4—O34^v	97.75 (14)	B32—O32—Cu8	139.1 (3)
O35—Cu4—O34^v	87.46 (14)	B31—O32—Cu8	89.6 (3)
O33—Cu4—O34^v	167.64 (13)	B31—O33—Cu5	121.6 (3)
O25—Cu4—Cu6^ix	142.18 (11)	B31—O33—Cu4	123.1 (3)
O35—Cu4—Cu6^ix	41.88 (10)	Cu5—O33—Cu4	98.53 (15)
O33—Cu4—Cu6^ix	134.91 (10)	B31—O34—Cu2^vi	114.0 (3)
O34^v—Cu4—Cu6^ix	47.15 (9)	B31—O34—Cu4^x	101.9 (3)
O23—Cu5—O33	168.47 (14)	Cu2^vi—O34—Cu4^x	124.93 (16)
O23—Cu5—O25	96.20 (14)	B31—O34—Cu6^vi	97.4 (3)
O33—Cu5—O25	82.42 (14)	Cu2^vi—O34—Cu6^vi	124.16 (16)
O23—Cu5—O24^vi	84.53 (14)	Cu4^x—O34—Cu6^vi	88.48 (13)
O33—Cu5—O24^vi	98.62 (14)	B32—O35—Cu6^ix	134.4 (3)
O25—Cu5—O24^vi	171.08 (14)	B32—O35—Cu4	128.9 (3)
O23—Cu5—O21^vi	90.52 (13)	Cu6^ix—O35—Cu4	96.16 (15)
O33—Cu5—O21^vi	100.93 (13)	B32—O36—Cu9^ix	123.3 (3)
O25—Cu5—O21^vi	104.33 (13)	B32—O36—Cu7^ix	132.9 (3)
O24^vi—Cu5—O21^vi	66.76 (12)	Cu9^ix—O36—Cu7^ix	99.84 (14)
O23—Cu5—Cu2^vi	121.59 (10)	B4—O41—Cu9	121.6 (3)
O33—Cu5—Cu2^vi	69.42 (10)	B4—O41—Cu7	131.6 (3)
O25—Cu5—Cu2^vi	77.62 (10)	Cu9—O41—Cu7	100.08 (15)
O24^vi—Cu5—Cu2^vi	94.40 (9)	B4—O42—Cu8	126.5 (3)
O21^vi—Cu5—Cu2^vi	39.16 (8)	B4—O42—Cu9^vii	89.7 (3)
O23—Cu6—O35^iii	174.33 (14)	Cu8—O42—Cu9^vii	127.65 (18)
O23—Cu6—O24^vi	84.48 (14)	B4—O43—Cu8^viii	134.1 (3)
O35^iii—Cu6—O24^vi	97.12 (14)	B4—O43—Cu9^vii	89.6 (3)
O23—Cu6—O34^iv	92.78 (14)	Cu8^viii—O43—Cu9^vii	122.53 (18)
O35^iii—Cu6—O34^iv	84.83 (13)	O12—B1—O13	126.6 (5)
O24^vi—Cu6—O34^iv	171.19 (13)	O12—B1—O11B	127.5 (11)
O23—Cu6—O31^iv	94.78 (12)	O13—B1—O11B	101.0 (11)
O35^iii—Cu6—O31^iv	88.92 (13)	O12—B1—O11A	127.0 (5)
O24^vi—Cu6—O31^iv	122.91 (12)	O13—B1—O11A	106.3 (5)
O34^iv—Cu6—O31^iv	65.60 (11)	O11B—B1—O11A	27.3 (9)
O23—Cu6—Cu4^iii	134.37 (10)	O23—B21—O21	114.3 (4)
O35^iii—Cu6—Cu4^iii	41.96 (10)	O23—B21—O24	113.3 (4)
O24^vi—Cu6—Cu4^iii	135.01 (10)	O21—B21—O24	109.3 (4)
O34^iv—Cu6—Cu4^iii	44.38 (9)	O23—B21—O22	112.8 (4)
O31^iv—Cu6—Cu4^iii	81.85 (8)	O21—B21—O22	101.0 (4)
O23—Cu6—Cu7^iv	64.84 (10)	O24—B21—O22	105.2 (4)
O35^iii—Cu6—Cu7^iv	120.37 (10)	O25—B22—O26	122.5 (5)
O24^vi—Cu6—Cu7^iv	93.13 (9)	O25—B22—O22	117.4 (4)
O34^iv—Cu6—Cu7^iv	93.27 (9)	O26—B22—O22	120.1 (5)
O31^iv—Cu6—Cu7^iv	39.54 (8)	O33—B31—O31	115.1 (4)
Cu4^iii—Cu6—Cu7^iv	121.13 (2)	O33—B31—O34	115.6 (4)
O31—Cu7—O24^vi	92.86 (13)	O31—B31—O34	108.1 (4)
O31—Cu7—O36^iii	169.56 (14)	O33—B31—O32	108.7 (4)
O24^vi—Cu7—O36^iii	96.91 (13)	O31—B31—O32	101.3 (4)
O31—Cu7—O41	91.16 (13)	O34—B31—O32	106.6 (4)
O24^vi—Cu7—O41	159.51 (14)	O35—B32—O36	122.3 (4)
O36^iii—Cu7—O41	78.40 (13)	O35—B32—O32	119.6 (4)
O31—Cu7—Cu6^vi	50.29 (9)	O36—B32—O32	118.1 (5)
O24^vi—Cu7—Cu6^vi	86.52 (9)	O11B—O11A—B1	76 (2)
O36^iii—Cu7—Cu6^vi	126.53 (9)	O11B—O11A—Cu3	80 (2)
O41—Cu7—Cu6^vi	80.65 (10)	B1—O11A—Cu3	132.8 (4)
O43^vii—Cu8—O42	94.16 (15)	O11B—O11A—Cu1	77 (2)
O43^vii—Cu8—O31	163.88 (14)	B1—O11A—Cu1	89.6 (3)
O42—Cu8—O31	98.67 (14)	Cu3—O11A—Cu1	123.6 (3)
O43^vii—Cu8—O32	93.18 (14)	O41—B4—O43	125.4 (4)
O42—Cu8—O32	171.42 (13)	O41—B4—O42	124.5 (4)
O31—Cu8—O32	73.36 (13)	O43—B4—O42	110.1 (4)
O41—Cu9—O36^iii	81.57 (14)	O41—B4—Cu9^vii	176.5 (4)
O41—Cu9—O42^viii	102.45 (14)	O43—B4—Cu9^vii	55.2 (2)
O36^iii—Cu9—O42^viii	174.54 (14)	O42—B4—Cu9^vii	54.9 (2)
O41—Cu9—O43^viii	161.35 (15)	O11A—O11B—B1	77 (3)
O36^iii—Cu9—O43^viii	104.50 (14)	O11A—O11B—Cu3	80 (2)
O42^viii—Cu9—O43^viii	70.54 (14)	B1—O11B—Cu3	132.9 (16)
O41—Cu9—B4^viii	135.05 (17)	O11A—O11B—Cu1	84 (2)
O36^iii—Cu9—B4^viii	139.53 (16)	B1—O11B—Cu1	91.4 (13)
O42^viii—Cu9—B4^viii	35.40 (15)	Cu3—O11B—Cu1	125.8 (13)

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) x, −y+3/2, z+1/2; (v) x, −y+1/2, z+1/2; (vi) x, −y+3/2, z−1/2; (vii) −x+1, y−1/2, −z−1/2; (viii) −x+1, y+1/2, −z−1/2; (ix) x, y−1, z; (x) x, −y+1/2, z−1/2.