Structural and Raman spectroscopic characterization of pyroxene-type compounds in the CaCu_1−xZn_xGe₂O₆ solid-solution series

Pyroxene-type germanate compounds with the composition CaCuGe₂O₆–CaZnGe₂O₆ have been synthesized via a solid-state ceramic sintering route. Phase-pure polycrystalline and small single-crystal material was obtained all over the series, representing a complete solid-solution series. Differential thermal analysis, single-crystal X-ray diffraction and Raman spectroscopy were used to characterize phase stability, phase changes and structural alterations induced by the substitution of Cu²⁺ with Zn²⁺. Whereas pure CaCuGe₂O₆ exhibits P2₁/c symmetry with a strong distortion of the M1 octahedra and two different Ge sites, one of them with an unusual fivefold coordination, the replacement of Cu²⁺ by Zn²⁺ induces a chemically driven phase change to the C2/c symmetry. The phase change takes place around Zn²⁺ contents of 0.12 formula units and is associated with large changes in the unit-cell parameters. Here, the increase of c by as much as 3.2% is remarkable and it is mainly controlled by an expansion of the tetrahedral chains. Further differences between the P2₁/c and C2/c structures are a more regular chain of edge-sharing M1 octahedra as a consequence of more and more reduced Jahn–Teller distortion and a less kinked, symmetry-equivalent tetrahedral chain. The coordination of the Ca site increases from sevenfold to eightfold with large changes in the Ca—O bond lengths during the phase change. Raman spectroscopy was mainly used to monitor the P2₁/c to C2/c phase change as a function of composition, but also as a function of temperature and to follow changes in specific Raman modes throughout the solid-solution series.

Computing details

For all compounds, data collection: Bruker APEX2 (Bruker, 2012); cell refinement: Bruker APEX2 (Bruker, 2012); data reduction: Bruker APEX2 (Bruker, 2012); program(s) used to solve structure: SHELXL2014/7 (Sheldrick, 2014); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014); molecular graphics: Diamonds 3.2g (Brandenburg,2006); software used to prepare material for publication: WinGX v1.70.01 (Farrugia 2012).

(CaCu_1)

Crystal data

CaCuGe2O6	F(000) = 644
Mr = 344.80	Dx = 4.860 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1958 (5) Å	Cell parameters from 6243 reflections
b = 9.2140 (6) Å	θ = 2.1–30.0°
c = 5.2101 (3) Å	µ = 18.19 mm^−1
β = 105.682 (2)°	T = 293 K
V = 471.24 (5) Å^3	Prismatic, pale green
Z = 4	0.12 × 0.08 × 0.07 mm

Data collection

SMART APEX diffractometer	1214 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
rotation, ω–scans at 4 different φ positions	θmax = 30.0°, θmin = 2.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −13→13
Tmin = 0.359, Tmax = 0.746	k = −12→12
6243 measured reflections	l = −6→7
1310 independent reflections

Refinement

Refinement on F^2	91 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.019	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 1.0882P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.043	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.61 e Å^−3
1310 reflections	Δρmin = −0.83 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ca1	0.28336 (6)	0.45273 (6)	0.80910 (12)	0.00832 (12)
Cu1	0.22735 (4)	0.66145 (4)	0.25606 (7)	0.00712 (9)
GeA	0.04908 (3)	0.34919 (3)	0.20950 (6)	0.00527 (8)
GeB	0.49117 (3)	0.35080 (3)	0.40131 (6)	0.00568 (8)
O1A	−0.1268 (2)	0.3612 (2)	0.1154 (4)	0.0078 (4)
O1B	0.6582 (2)	0.3205 (2)	0.3789 (4)	0.0070 (4)
O2A	0.1458 (2)	0.4889 (2)	0.3757 (4)	0.0104 (4)
O2B	0.4323 (2)	0.5217 (2)	0.2602 (4)	0.0098 (4)
O3A	0.1029 (2)	0.1945 (2)	0.4202 (4)	0.0085 (4)
O3B	0.4001 (2)	0.2516 (2)	0.5900 (4)	0.0073 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0091 (3)	0.0078 (3)	0.0077 (3)	0.0003 (2)	0.0019 (2)	0.0009 (2)
Cu1	0.00781 (17)	0.00667 (17)	0.00574 (16)	−0.00152 (12)	−0.00015 (13)	−0.00006 (12)
GeA	0.00461 (14)	0.00557 (14)	0.00517 (14)	−0.00055 (10)	0.00054 (11)	−0.00026 (10)
GeB	0.00534 (14)	0.00487 (14)	0.00729 (15)	0.00017 (10)	0.00247 (11)	0.00085 (10)
O1A	0.0038 (9)	0.0099 (10)	0.0093 (10)	−0.0006 (7)	0.0009 (8)	−0.0005 (8)
O1B	0.0063 (9)	0.0062 (9)	0.0087 (10)	0.0005 (7)	0.0024 (8)	−0.0007 (7)
O2A	0.0122 (10)	0.0081 (10)	0.0082 (10)	−0.0052 (8)	−0.0018 (8)	−0.0005 (8)
O2B	0.0146 (10)	0.0060 (9)	0.0079 (10)	0.0020 (8)	0.0014 (8)	0.0005 (7)
O3A	0.0097 (10)	0.0082 (9)	0.0092 (10)	0.0028 (8)	0.0054 (8)	0.0031 (8)
O3B	0.0068 (9)	0.0083 (10)	0.0065 (9)	−0.0026 (7)	0.0014 (8)	0.0011 (7)

Geometric parameters (Å, º)

Ca1—O2A	2.338 (2)	Cu1—O1A^vii	2.294 (2)
Ca1—O1A^i	2.446 (2)	Cu1—O2B	2.450 (2)
Ca1—O1B^ii	2.448 (2)	GeA—O2A	1.708 (2)
Ca1—O3A^iii	2.477 (2)	GeA—O1A	1.730 (2)
Ca1—O3B^iii	2.482 (2)	GeA—O3A^viii	1.784 (2)
Ca1—O2B^iv	2.511 (2)	GeA—O3A	1.792 (2)
Ca1—O3B	2.624 (2)	GeB—O1B	1.761 (2)
Ca1—O2B^ii	3.026 (2)	GeB—O2B	1.772 (2)
Cu1—O1A^v	1.941 (2)	GeB—O3B	1.777 (2)
Cu1—O1B^ii	1.951 (2)	GeB—O3B^viii	1.890 (2)
Cu1—O2A	1.972 (2)	GeB—O2B^ii	2.087 (2)
Cu1—O1B^vi	2.109 (2)
O2A—Ca1—O1A^i	78.94 (7)	Ca1—Cu1—Ca1^x	120.63 (2)
O2A—Ca1—O1B^ii	68.86 (7)	O2A—GeA—O1A	120.49 (10)
O1A^i—Ca1—O1B^ii	72.93 (7)	O2A—GeA—O3A^viii	109.35 (10)
O2A—Ca1—O3A^iii	90.80 (7)	O1A—GeA—O3A^viii	107.87 (10)
O1A^i—Ca1—O3A^iii	77.75 (7)	O2A—GeA—O3A	104.46 (10)
O1B^ii—Ca1—O3A^iii	146.84 (7)	O1A—GeA—O3A	110.30 (9)
O2A—Ca1—O3B^iii	138.10 (7)	O3A^viii—GeA—O3A	103.00 (7)
O1A^i—Ca1—O3B^iii	131.80 (7)	O2A—GeA—Ca1	35.31 (7)
O1B^ii—Ca1—O3B^iii	138.89 (7)	O1A—GeA—Ca1	129.66 (7)
O3A^iii—Ca1—O3B^iii	73.43 (7)	O3A^viii—GeA—Ca1	121.49 (7)
O2A—Ca1—O2B^iv	157.12 (7)	O3A—GeA—Ca1	69.47 (7)
O1A^i—Ca1—O2B^iv	85.87 (7)	O2A—GeA—Ca1^viii	103.82 (7)
O1B^ii—Ca1—O2B^iv	90.44 (7)	O1A—GeA—Ca1^viii	133.22 (7)
O3A^iii—Ca1—O2B^iv	102.66 (7)	O3A^viii—GeA—Ca1^viii	66.74 (7)
O3B^iii—Ca1—O2B^iv	64.39 (7)	O3A—GeA—Ca1^viii	38.58 (6)
O2A—Ca1—O3B	84.53 (7)	Ca1—GeA—Ca1^viii	79.461 (18)
O1A^i—Ca1—O3B	163.20 (7)	O1B—GeB—O2B	109.80 (10)
O1B^ii—Ca1—O3B	103.91 (7)	O1B—GeB—O3B	127.94 (9)
O3A^iii—Ca1—O3B	99.66 (7)	O2B—GeB—O3B	121.13 (10)
O3B^iii—Ca1—O3B	61.27 (3)	O1B—GeB—O3B^viii	97.11 (9)
O2B^iv—Ca1—O3B	110.81 (7)	O2B—GeB—O3B^viii	93.14 (9)
O2A—Ca1—O2B^ii	102.57 (7)	O3B—GeB—O3B^viii	90.51 (6)
O1A^i—Ca1—O2B^ii	130.75 (6)	O1B—GeB—O2B^ii	89.86 (9)
O1B^ii—Ca1—O2B^ii	62.69 (6)	O2B—GeB—O2B^ii	81.82 (9)
O3A^iii—Ca1—O2B^ii	150.07 (6)	O3B—GeB—O2B^ii	87.38 (9)
O3B^iii—Ca1—O2B^ii	78.90 (6)	O3B^viii—GeB—O2B^ii	172.49 (8)
O2B^iv—Ca1—O2B^ii	74.67 (7)	O1B—GeB—GeB^ii	101.75 (7)
O3B—Ca1—O2B^ii	56.04 (6)	O2B—GeB—GeB^ii	44.96 (7)
O2A—Ca1—Cu1^iv	116.13 (6)	O3B—GeB—GeB^ii	106.30 (7)
O1A^i—Ca1—Cu1^iv	37.46 (5)	O3B^viii—GeB—GeB^ii	137.81 (6)
O1B^ii—Ca1—Cu1^iv	83.60 (5)	O2B^ii—GeB—GeB^ii	36.86 (6)
O3A^iii—Ca1—Cu1^iv	82.46 (5)	O1B—GeB—Cu1^ii	39.84 (7)
O3B^iii—Ca1—Cu1^iv	100.31 (5)	O2B—GeB—Cu1^ii	116.82 (7)
O2B^iv—Ca1—Cu1^iv	49.16 (5)	O3B—GeB—Cu1^ii	102.39 (7)
O3B—Ca1—Cu1^iv	159.29 (5)	O3B^viii—GeB—Cu1^ii	132.36 (6)
O2B^ii—Ca1—Cu1^iv	113.99 (4)	O2B^ii—GeB—Cu1^ii	55.15 (6)
O2A—Ca1—GeB^ii	83.81 (5)	GeB^ii—GeB—Cu1^ii	82.271 (14)
O1A^i—Ca1—GeB^ii	102.15 (5)	O1B—GeB—Ca1^ii	45.51 (7)
O1B^ii—Ca1—GeB^ii	30.86 (5)	O2B—GeB—Ca1^ii	64.41 (7)
O3A^iii—Ca1—GeB^ii	174.51 (5)	O3B—GeB—Ca1^ii	166.08 (7)
O3B^iii—Ca1—GeB^ii	110.02 (5)	O3B^viii—GeB—Ca1^ii	102.21 (6)
O2B^iv—Ca1—GeB^ii	82.78 (5)	O2B^ii—GeB—Ca1^ii	80.70 (6)
O3B—Ca1—GeB^ii	78.83 (5)	GeB^ii—GeB—Ca1^ii	67.845 (15)
O2B^ii—Ca1—GeB^ii	31.88 (4)	Cu1^ii—GeB—Ca1^ii	64.822 (14)
Cu1^iv—Ca1—GeB^ii	100.843 (18)	O1B—GeB—Ca1^ix	111.32 (7)
O2A—Ca1—GeB^iv	171.36 (6)	O2B—GeB—Ca1^ix	46.68 (7)
O1A^i—Ca1—GeB^iv	108.92 (5)	O3B—GeB—Ca1^ix	110.88 (7)
O1B^ii—Ca1—GeB^iv	116.32 (5)	O3B^viii—GeB—Ca1^ix	46.50 (6)
O3A^iii—Ca1—GeB^iv	87.50 (5)	O2B^ii—GeB—Ca1^ix	128.00 (6)
O3B^iii—Ca1—GeB^iv	33.52 (5)	GeB^ii—GeB—Ca1^ix	91.357 (16)
O2B^iv—Ca1—GeB^iv	30.90 (5)	Cu1^ii—GeB—Ca1^ix	146.562 (16)
O3B—Ca1—GeB^iv	87.41 (5)	Ca1^ii—GeB—Ca1^ix	82.326 (17)
O2B^ii—Ca1—GeB^iv	75.25 (4)	O1B—GeB—Ca1^viii	115.43 (7)
Cu1^iv—Ca1—GeB^iv	72.050 (15)	O2B—GeB—Ca1^viii	122.26 (7)
GeB^ii—Ca1—GeB^iv	97.674 (17)	O3B—GeB—Ca1^viii	43.09 (7)
O2A—Ca1—Cu1	34.61 (5)	O3B^viii—GeB—Ca1^viii	48.48 (6)
O1A^i—Ca1—Cu1	76.78 (5)	O2B^ii—GeB—Ca1^viii	130.32 (6)
O1B^ii—Ca1—Cu1	34.64 (5)	GeB^ii—GeB—Ca1^viii	141.763 (18)
O3A^iii—Ca1—Cu1	123.05 (5)	Cu1^ii—GeB—Ca1^viii	120.849 (15)
O3B^iii—Ca1—Cu1	151.31 (5)	Ca1^ii—GeB—Ca1^viii	147.448 (14)
O2B^iv—Ca1—Cu1	125.02 (5)	Ca1^ix—GeB—Ca1^viii	83.592 (19)
O3B—Ca1—Cu1	91.31 (5)	O1B—GeB—Ca1	146.68 (7)
O2B^ii—Ca1—Cu1	78.50 (4)	O2B—GeB—Ca1	79.69 (7)
Cu1^iv—Ca1—Cu1	104.889 (19)	O3B—GeB—Ca1	46.48 (7)
GeB^ii—Ca1—Cu1	51.978 (12)	O3B^viii—GeB—Ca1	114.60 (6)
GeB^iv—Ca1—Cu1	149.10 (2)	O2B^ii—GeB—Ca1	59.14 (6)
O1A^v—Cu1—O1B^ii	175.31 (8)	GeB^ii—GeB—Ca1	61.664 (14)
O1A^v—Cu1—O2A	94.24 (8)	Cu1^ii—GeB—Ca1	106.994 (15)
O1B^ii—Cu1—O2A	87.29 (8)	Ca1^ii—GeB—Ca1	129.509 (12)
O1A^v—Cu1—O1B^vi	86.18 (8)	Ca1^ix—GeB—Ca1	98.432 (17)
O1B^ii—Cu1—O1B^vi	91.54 (8)	Ca1^viii—GeB—Ca1	81.562 (18)
O2A—Cu1—O1B^vi	169.86 (8)	GeA—O1A—Cu1^v	120.24 (11)
O1A^v—Cu1—O1A^vii	102.72 (8)	GeA—O1A—Cu1^xi	112.13 (10)
O1B^ii—Cu1—O1A^vii	81.01 (8)	Cu1^v—O1A—Cu1^xi	92.71 (8)
O2A—Cu1—O1A^vii	107.15 (8)	GeA—O1A—Ca1^i	132.15 (10)
O1B^vi—Cu1—O1A^vii	82.58 (7)	Cu1^v—O1A—Ca1^i	92.52 (8)
O1A^v—Cu1—GeB^ii	140.01 (6)	Cu1^xi—O1A—Ca1^i	98.78 (7)
O1B^ii—Cu1—GeB^ii	35.32 (6)	GeB—O1B—Cu1^ii	104.85 (10)
O2A—Cu1—GeB^ii	101.69 (6)	GeB—O1B—Cu1^xii	139.87 (11)
O1B^vi—Cu1—GeB^ii	72.08 (6)	Cu1^ii—O1B—Cu1^xii	98.35 (9)
O1A^vii—Cu1—GeB^ii	107.05 (5)	GeB—O1B—Ca1^ii	103.63 (9)
O1A^v—Cu1—Ca1^ix	50.02 (6)	Cu1^ii—O1B—Ca1^ii	99.86 (8)
O1B^ii—Cu1—Ca1^ix	125.83 (6)	Cu1^xii—O1B—Ca1^ii	104.08 (8)
O2A—Cu1—Ca1^ix	85.33 (6)	GeA—O2A—Cu1	133.03 (12)
O1B^vi—Cu1—Ca1^ix	87.20 (6)	GeA—O2A—Ca1	119.72 (10)
O1A^vii—Cu1—Ca1^ix	151.63 (5)	Cu1—O2A—Ca1	103.06 (9)
GeB^ii—Cu1—Ca1^ix	94.706 (16)	GeB—O2B—GeB^ii	98.18 (9)
O1A^v—Cu1—Ca1	135.25 (6)	GeB—O2B—Ca1^ix	102.42 (9)
O1B^ii—Cu1—Ca1	45.50 (6)	GeB^ii—O2B—Ca1^ix	157.95 (10)
O2A—Cu1—Ca1	42.33 (6)	GeB—O2B—Ca1^ii	83.72 (8)
O1B^vi—Cu1—Ca1	134.27 (6)	GeB^ii—O2B—Ca1^ii	84.56 (7)
O1A^vii—Cu1—Ca1	101.15 (5)	Ca1^ix—O2B—Ca1^ii	105.33 (7)
GeB^ii—Cu1—Ca1	63.199 (13)	GeA^iii—O3A—GeA	125.72 (11)
Ca1^ix—Cu1—Ca1	104.889 (19)	GeA^iii—O3A—Ca1^viii	119.42 (10)
O1A^v—Cu1—Ca1^x	102.30 (6)	GeA—O3A—Ca1^viii	114.60 (9)
O1B^ii—Cu1—Ca1^x	78.48 (6)	GeB—O3B—GeB^iii	121.51 (11)
O2A—Cu1—Ca1^x	147.55 (7)	GeB—O3B—Ca1^viii	107.64 (9)
O1B^vi—Cu1—Ca1^x	41.29 (6)	GeB^iii—O3B—Ca1^viii	99.97 (8)
O1A^vii—Cu1—Ca1^x	42.18 (5)	GeB—O3B—Ca1	104.11 (9)
GeB^ii—Cu1—Ca1^x	83.275 (14)	GeB^iii—O3B—Ca1	98.90 (8)
Ca1^ix—Cu1—Ca1^x	126.57 (2)	Ca1^viii—O3B—Ca1	126.20 (8)

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

(Cu95_2)

Crystal data

CaCu0.95Ge2O6Zn0.05	F(000) = 644
Mr = 344.89	Dx = 4.855 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2081 (7) Å	Cell parameters from 5299 reflections
b = 9.2091 (7) Å	θ = 2.1–29.9°
c = 5.2142 (4) Å	µ = 18.19 mm^−1
β = 105.726 (3)°	T = 293 K
V = 471.83 (6) Å^3	Prismatic, pale green
Z = 4	0.14 × 0.09 × 0.07 mm

Data collection

SMART APEX diffractometer	1239 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
rotation, ω–scans at 4 different φ positions	θmax = 29.9°, θmin = 2.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −13→13
Tmin = 0.15, Tmax = 0.28	k = −12→12
5299 measured reflections	l = −7→7
1298 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0174P)^2 + 0.5542P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max < 0.001
wR(F^2) = 0.039	Δρmax = 0.41 e Å^−3
S = 1.15	Δρmin = −0.78 e Å^−3
1298 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
92 parameters	Extinction coefficient: 0.0060 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.28269 (5)	0.45246 (5)	0.80890 (9)	0.00910 (10)
Cu1	0.22749 (3)	0.66153 (3)	0.25715 (6)	0.00787 (8)	0.95
Zn1	0.22749 (3)	0.66153 (3)	0.25715 (6)	0.00787 (8)	0.05
GeA	0.04867 (2)	0.34912 (2)	0.21047 (5)	0.00586 (7)
GeB	0.49093 (2)	0.35083 (2)	0.40057 (5)	0.00628 (7)
O1A	−0.12743 (17)	0.36066 (17)	0.1154 (3)	0.0086 (3)
O1B	0.65814 (17)	0.32099 (17)	0.3774 (3)	0.0079 (3)
O2A	0.14462 (18)	0.48928 (18)	0.3760 (3)	0.0118 (3)
O2B	0.43104 (18)	0.52171 (17)	0.2609 (3)	0.0104 (3)
O3A	0.10279 (17)	0.19476 (18)	0.4215 (3)	0.0091 (3)
O3B	0.39974 (16)	0.25188 (17)	0.5890 (3)	0.0080 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0107 (2)	0.0082 (2)	0.0084 (2)	0.00029 (16)	0.00258 (17)	0.00119 (15)
Cu1	0.00843 (15)	0.00777 (14)	0.00648 (13)	−0.00156 (10)	0.00046 (10)	−0.00005 (10)
Zn1	0.00843 (15)	0.00777 (14)	0.00648 (13)	−0.00156 (10)	0.00046 (10)	−0.00005 (10)
GeA	0.00559 (12)	0.00609 (12)	0.00575 (11)	−0.00042 (8)	0.00130 (9)	−0.00026 (8)
GeB	0.00627 (13)	0.00555 (12)	0.00781 (12)	0.00033 (8)	0.00328 (9)	0.00090 (8)
O1A	0.0069 (8)	0.0108 (8)	0.0081 (7)	0.0008 (6)	0.0023 (6)	−0.0006 (6)
O1B	0.0066 (8)	0.0085 (7)	0.0089 (7)	−0.0001 (6)	0.0026 (6)	−0.0010 (6)
O2A	0.0148 (9)	0.0101 (8)	0.0088 (7)	−0.0045 (6)	0.0005 (6)	−0.0005 (6)
O2B	0.0165 (9)	0.0055 (7)	0.0083 (7)	0.0011 (6)	0.0016 (6)	0.0008 (6)
O3A	0.0106 (8)	0.0100 (8)	0.0078 (7)	0.0027 (6)	0.0042 (6)	0.0028 (6)
O3B	0.0069 (7)	0.0105 (8)	0.0068 (7)	−0.0012 (6)	0.0023 (6)	0.0013 (6)

Geometric parameters (Å, º)

Ca1—O2A	2.3391 (18)	Cu1—O1A^vii	2.2838 (16)
Ca1—O1A^i	2.4432 (16)	Cu1—O2B	2.4400 (19)
Ca1—O1B^ii	2.4451 (17)	GeA—O2A	1.7065 (17)
Ca1—O3A^iii	2.4778 (17)	GeA—O1A	1.7336 (17)
Ca1—O3B^iii	2.4812 (17)	GeA—O3A^viii	1.7863 (15)
Ca1—O2B^iv	2.5139 (17)	GeA—O3A	1.7907 (16)
Ca1—O3B	2.6261 (16)	GeB—O1B	1.7651 (16)
Ca1—O2B^ii	3.0503 (18)	GeB—O2B	1.7718 (16)
Cu1—O1A^v	1.9450 (17)	GeB—O3B	1.7771 (15)
Cu1—O1B^ii	1.9531 (17)	GeB—O3B^viii	1.8922 (16)
Cu1—O2A	1.9750 (17)	GeB—O2B^ii	2.0895 (16)
Cu1—O1B^vi	2.1108 (16)
O2A—Ca1—O1A^i	78.82 (6)	O3B—Ca1—O2B^ii	55.86 (5)
O2A—Ca1—O1B^ii	69.03 (6)	O1A^v—Cu1—O1B^ii	175.13 (7)
O1A^i—Ca1—O1B^ii	72.79 (5)	O1A^v—Cu1—O2A	94.32 (7)
O2A—Ca1—O3A^iii	90.94 (6)	O1B^ii—Cu1—O2A	87.34 (7)
O1A^i—Ca1—O3A^iii	78.01 (6)	O1A^v—Cu1—O1B^vi	85.95 (7)
O1B^ii—Ca1—O3A^iii	147.11 (6)	O1B^ii—Cu1—O1B^vi	91.64 (6)
O2A—Ca1—O3B^iii	138.25 (6)	O2A—Cu1—O1B^vi	170.28 (7)
O1A^i—Ca1—O3B^iii	132.00 (6)	O1A^v—Cu1—O1A^vii	102.70 (7)
O1B^ii—Ca1—O3B^iii	138.55 (6)	O1B^ii—Cu1—O1A^vii	81.15 (6)
O3A^iii—Ca1—O3B^iii	73.45 (5)	O2A—Cu1—O1A^vii	106.87 (7)
O2A—Ca1—O2B^iv	156.95 (6)	O1B^vi—Cu1—O1A^vii	82.50 (6)
O1A^i—Ca1—O2B^iv	85.54 (6)	O2A—GeA—O1A	120.45 (8)
O1B^ii—Ca1—O2B^iv	90.29 (5)	O2A—GeA—O3A^viii	109.36 (8)
O3A^iii—Ca1—O2B^iv	102.33 (5)	O1A—GeA—O3A^viii	107.84 (8)
O3B^iii—Ca1—O2B^iv	64.46 (5)	O2A—GeA—O3A	104.50 (8)
O2A—Ca1—O3B	84.67 (6)	O1A—GeA—O3A	110.34 (7)
O1A^i—Ca1—O3B	163.31 (6)	O3A^viii—GeA—O3A	102.96 (5)
O1B^ii—Ca1—O3B	103.66 (5)	O1B—GeB—O2B	110.02 (8)
O3A^iii—Ca1—O3B	99.94 (5)	O1B—GeB—O3B	128.26 (7)
O3B^iii—Ca1—O3B	61.32 (2)	O2B—GeB—O3B	120.58 (8)
O2B^iv—Ca1—O3B	110.97 (6)	O1B—GeB—O3B^viii	97.07 (7)
O2A—Ca1—O2B^ii	102.70 (5)	O2B—GeB—O3B^viii	93.23 (7)
O1A^i—Ca1—O2B^ii	130.45 (5)	O3B—GeB—O3B^viii	90.51 (5)
O1B^ii—Ca1—O2B^ii	62.50 (5)	O1B—GeB—O2B^ii	89.49 (7)
O3A^iii—Ca1—O2B^ii	150.04 (5)	O2B—GeB—O2B^ii	81.86 (7)
O3B^iii—Ca1—O2B^ii	78.77 (5)	O3B—GeB—O2B^ii	87.58 (7)
O2B^iv—Ca1—O2B^ii	74.86 (5)	O3B^viii—GeB—O2B^ii	172.87 (7)

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

(shelx_Cu90_7)

Crystal data

CaCu0.90Ge2O6Zn0.10	F(000) = 644
Mr = 344.98	Dx = 4.851 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2193 (4) Å	Cell parameters from 6214 reflections
b = 9.2041 (4) Å	θ = 2.1–29.9°
c = 5.2187 (2) Å	µ = 18.20 mm^−1
β = 105.771 (2)°	T = 293 K
V = 472.39 (3) Å^3	Prismatic, pale green
Z = 4	0.14 × 0.07 × 0.06 mm

Data collection

SMART APEX diffractometer	1254 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
rotation, ω–scans at 4 different φ positions	θmax = 29.9°, θmin = 2.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −14→13
Tmin = 0.24, Tmax = 0.34	k = −12→12
6214 measured reflections	l = −7→7
1317 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0125P)^2 + 0.9589P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max = 0.001
wR(F^2) = 0.037	Δρmax = 0.43 e Å^−3
S = 1.16	Δρmin = −0.89 e Å^−3
1317 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
92 parameters	Extinction coefficient: 0.0065 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.28221 (5)	0.45221 (5)	0.80867 (10)	0.00911 (10)
Cu1	0.22775 (3)	0.66169 (3)	0.25832 (6)	0.00794 (8)	0.9
Zn1	0.22775 (3)	0.66169 (3)	0.25832 (6)	0.00794 (8)	0.1
GeA	0.04824 (2)	0.34906 (3)	0.21142 (5)	0.00582 (7)
GeB	0.49064 (2)	0.35085 (3)	0.39950 (5)	0.00639 (7)
O1A	−0.12776 (17)	0.35984 (18)	0.1160 (3)	0.0087 (3)
O1B	0.65719 (17)	0.32141 (18)	0.3756 (3)	0.0079 (3)
O2A	0.14356 (18)	0.48959 (19)	0.3765 (4)	0.0116 (3)
O2B	0.42990 (19)	0.52174 (18)	0.2604 (3)	0.0107 (3)
O3A	0.10286 (17)	0.19477 (19)	0.4233 (3)	0.0092 (3)
O3B	0.39960 (17)	0.25219 (19)	0.5884 (3)	0.0083 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0106 (2)	0.0082 (2)	0.0084 (2)	0.00028 (17)	0.00247 (17)	0.00114 (16)
Cu1	0.00875 (14)	0.00774 (14)	0.00624 (14)	−0.00167 (10)	0.00015 (10)	0.00003 (10)
Zn1	0.00875 (14)	0.00774 (14)	0.00624 (14)	−0.00167 (10)	0.00015 (10)	0.00003 (10)
GeA	0.00545 (12)	0.00619 (12)	0.00543 (12)	−0.00035 (8)	0.00077 (9)	−0.00025 (8)
GeB	0.00643 (12)	0.00565 (12)	0.00783 (12)	0.00021 (8)	0.00323 (9)	0.00103 (8)
O1A	0.0069 (7)	0.0118 (8)	0.0074 (8)	0.0007 (6)	0.0019 (6)	−0.0003 (6)
O1B	0.0068 (7)	0.0091 (8)	0.0084 (8)	−0.0011 (6)	0.0031 (6)	−0.0009 (6)
O2A	0.0138 (8)	0.0108 (8)	0.0083 (8)	−0.0043 (7)	−0.0003 (7)	−0.0014 (6)
O2B	0.0169 (9)	0.0057 (7)	0.0087 (8)	0.0008 (7)	0.0021 (7)	0.0004 (6)
O3A	0.0097 (8)	0.0103 (8)	0.0085 (8)	0.0026 (6)	0.0042 (6)	0.0028 (6)
O3B	0.0081 (8)	0.0107 (8)	0.0067 (7)	−0.0010 (6)	0.0030 (6)	0.0012 (6)

Geometric parameters (Å, º)

Ca1—O2A	2.3401 (18)	Cu1—O1A^vii	2.2726 (17)
Ca1—O1B^i	2.4441 (18)	Cu1—O2B	2.4321 (18)
Ca1—O1A^ii	2.4445 (17)	GeA—O2A	1.7052 (18)
Ca1—O3A^iii	2.4785 (18)	GeA—O1A	1.7338 (17)
Ca1—O3B^iii	2.4815 (18)	GeA—O3A^viii	1.7866 (17)
Ca1—O2B^iv	2.5121 (18)	GeA—O3A	1.7930 (17)
Ca1—O3B	2.6266 (18)	GeB—O1B	1.7610 (17)
Ca1—O2B^i	3.0690 (19)	GeB—O2B	1.7725 (17)
Cu1—O1A^v	1.9531 (17)	GeB—O3B	1.7779 (17)
Cu1—O1B^i	1.9583 (17)	GeB—O3B^viii	1.8919 (17)
Cu1—O2A	1.9794 (18)	GeB—O2B^i	2.0980 (18)
Cu1—O1B^vi	2.1164 (17)
O2A—Ca1—O1B^i	69.34 (6)	O1B^i—Cu1—O2A	87.49 (7)
O2A—Ca1—O1A^ii	78.62 (6)	O1A^v—Cu1—O1B^vi	85.80 (7)
O1B^i—Ca1—O1A^ii	72.77 (6)	O1B^i—Cu1—O1B^vi	91.54 (6)
O2A—Ca1—O3A^iii	91.09 (6)	O2A—Cu1—O1B^vi	170.51 (7)
O1B^i—Ca1—O3A^iii	147.49 (6)	O1A^v—Cu1—O1A^vii	102.48 (7)
O1A^ii—Ca1—O3A^iii	78.19 (6)	O1B^i—Cu1—O1A^vii	81.52 (7)
O2A—Ca1—O3B^iii	138.40 (6)	O2A—Cu1—O1A^vii	106.54 (7)
O1B^i—Ca1—O3B^iii	138.09 (6)	O1B^vi—Cu1—O1A^vii	82.62 (6)
O1A^ii—Ca1—O3B^iii	132.21 (6)	O1A^v—Cu1—O2B	99.41 (6)
O3A^iii—Ca1—O3B^iii	73.45 (6)	O1B^i—Cu1—O2B	75.74 (6)
O2A—Ca1—O2B^iv	156.78 (6)	O2A—Cu1—O2B	90.88 (7)
O1B^i—Ca1—O2B^iv	90.01 (6)	O1B^vi—Cu1—O2B	79.74 (6)
O1A^ii—Ca1—O2B^iv	85.31 (6)	O1A^vii—Cu1—O2B	150.66 (6)
O3A^iii—Ca1—O2B^iv	101.99 (6)	O2A—GeA—O1A	120.48 (8)
O3B^iii—Ca1—O2B^iv	64.53 (6)	O2A—GeA—O3A^viii	109.28 (8)
O2A—Ca1—O3B	84.85 (6)	O1A—GeA—O3A^viii	107.95 (8)
O1B^i—Ca1—O3B	103.33 (6)	O2A—GeA—O3A	104.48 (9)
O1A^ii—Ca1—O3B	163.34 (6)	O1A—GeA—O3A	110.32 (8)
O3A^iii—Ca1—O3B	100.29 (6)	O3A^viii—GeA—O3A	102.95 (6)
O3B^iii—Ca1—O3B	61.37 (2)	O1B—GeB—O2B	110.19 (8)
O2B^iv—Ca1—O3B	111.09 (6)	O1B—GeB—O3B	128.47 (8)
O2A—Ca1—O2B^i	102.94 (6)	O2B—GeB—O3B	120.17 (8)
O1B^i—Ca1—O2B^i	62.21 (5)	O1B—GeB—O3B^viii	96.98 (7)
O1A^ii—Ca1—O2B^i	130.17 (5)	O2B—GeB—O3B^viii	93.30 (8)
O3A^iii—Ca1—O2B^i	150.03 (5)	O3B—GeB—O3B^viii	90.60 (5)
O3B^iii—Ca1—O2B^i	78.62 (5)	O1B—GeB—O2B^i	89.23 (7)
O2B^iv—Ca1—O2B^i	74.91 (6)	O2B—GeB—O2B^i	82.09 (8)
O3B—Ca1—O2B^i	55.73 (5)	O3B—GeB—O2B^i	87.53 (7)
O1A^v—Cu1—O1B^i	174.84 (7)	O3B^viii—GeB—O2B^i	173.28 (7)
O1A^v—Cu1—O2A	94.41 (7)

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

(shelx_Cu88_3)

Crystal data

CaCu0.88Ge2O6Zn0.12	F(000) = 644
Mr = 345.02	Dx = 4.778 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2118 (8) Å	Cell parameters from 3163 reflections
b = 9.0969 (7) Å	θ = 3.1–30.0°
c = 5.3914 (4) Å	µ = 17.94 mm^−1
β = 106.7232 (9)°	T = 293 K
V = 479.66 (6) Å^3	Isometric, colourless
Z = 4	0.12 × 0.11 × 0.11 mm

Data collection

SMART APEX diffractometer	625 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
rotation, ω–scans at 4 different φ positions	θmax = 30.0°, θmin = 3.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −14→14
Tmin = 0.14, Tmax = 0.15	k = −12→12
3163 measured reflections	l = −7→7
669 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0214P)^2 + 0.5434P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.017	(Δ/σ)max < 0.001
wR(F^2) = 0.043	Δρmax = 0.48 e Å^−3
S = 1.13	Δρmin = −0.64 e Å^−3
669 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0042 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca	0.0000	0.30203 (7)	0.2500	0.01211 (15)
Zn	0.0000	0.90681 (4)	0.2500	0.01077 (11)	0.12
Cu	0.0000	0.90681 (4)	0.2500	0.01077 (11)	0.88
Ge	0.28324 (3)	0.09780 (3)	0.21646 (5)	0.01057 (10)
O1	0.10666 (18)	0.09273 (19)	0.1225 (3)	0.0144 (4)
O2	0.3591 (2)	0.2601 (2)	0.3377 (4)	0.0184 (4)
O3	0.35724 (16)	0.0279 (2)	0.9788 (3)	0.0132 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0119 (3)	0.0147 (3)	0.0090 (3)	0.000	0.0017 (2)	0.000
Zn	0.0079 (2)	0.0164 (2)	0.0068 (2)	0.000	0.00028 (15)	0.000
Cu	0.0079 (2)	0.0164 (2)	0.0068 (2)	0.000	0.00028 (15)	0.000
Ge	0.00653 (15)	0.01788 (16)	0.00667 (14)	0.00088 (9)	0.00089 (9)	−0.00163 (9)
O1	0.0071 (8)	0.0248 (10)	0.0099 (8)	0.0017 (6)	0.0001 (7)	−0.0033 (7)
O2	0.0199 (10)	0.0179 (9)	0.0144 (9)	0.0000 (7)	0.0002 (7)	−0.0037 (7)
O3	0.0088 (8)	0.0223 (9)	0.0086 (8)	0.0008 (6)	0.0027 (6)	−0.0028 (7)

Geometric parameters (Å, º)

Ca—O2^i	2.3432 (19)	Zn—O1^vi	2.2249 (18)
Ca—O1	2.3906 (18)	Ge—O2	1.7074 (18)
Ca—O3^ii	2.6599 (18)	Ge—O1	1.7276 (18)
Ca—O3^iii	2.6941 (18)	Ge—O3^vii	1.7818 (17)
Zn—O1^iv	1.9900 (17)	Ge—O3^viii	1.8065 (17)
Zn—O2^v	2.114 (2)
O2^i—Ca—O2^ii	152.10 (9)	O3^ii—Ca—O3^x	65.66 (6)
O2^i—Ca—O1	75.01 (6)	O3^i—Ca—O3^x	61.63 (3)
O2^ii—Ca—O1	82.80 (6)	O3^iii—Ca—O3^x	80.60 (8)
O2^i—Ca—O1^ix	82.80 (6)	O1^iv—Zn—O1^xi	179.76 (10)
O2^ii—Ca—O1^ix	75.01 (6)	O1^iv—Zn—O2^v	89.19 (7)
O1—Ca—O1^ix	74.42 (9)	O1^xi—Zn—O2^v	90.97 (7)
O2^i—Ca—O3^ii	88.24 (6)	O1^iv—Zn—O2^xii	90.97 (7)
O2^ii—Ca—O3^ii	108.14 (6)	O1^xi—Zn—O2^xii	89.19 (7)
O1—Ca—O3^ii	88.51 (6)	O2^v—Zn—O2^xii	101.67 (10)
O1^ix—Ca—O3^ii	162.27 (6)	O1^iv—Zn—O1^vi	97.80 (7)
O2^i—Ca—O3^i	108.14 (6)	O1^xi—Zn—O1^vi	82.01 (7)
O2^ii—Ca—O3^i	88.24 (6)	O2^v—Zn—O1^vi	167.03 (7)
O1—Ca—O3^i	162.27 (6)	O2^xii—Zn—O1^vi	89.18 (7)
O1^ix—Ca—O3^i	88.51 (6)	O1^iv—Zn—O1^xiii	82.01 (7)
O3^ii—Ca—O3^i	108.86 (8)	O1^xi—Zn—O1^xiii	97.80 (7)
O2^i—Ca—O3^iii	141.95 (6)	O2^v—Zn—O1^xiii	89.18 (7)
O2^ii—Ca—O3^iii	65.18 (6)	O2^xii—Zn—O1^xiii	167.03 (7)
O1—Ca—O3^iii	122.91 (5)	O1^vi—Zn—O1^xiii	81.05 (9)
O1^ix—Ca—O3^iii	132.18 (6)	O2—Ge—O1	117.10 (9)
O3^ii—Ca—O3^iii	61.63 (3)	O2—Ge—O3^vii	110.14 (9)
O3^i—Ca—O3^iii	65.66 (6)	O1—Ge—O3^vii	113.73 (8)
O2^i—Ca—O3^x	65.18 (6)	O2—Ge—O3^viii	101.89 (9)
O2^ii—Ca—O3^x	141.95 (6)	O1—Ge—O3^viii	112.27 (8)
O1—Ca—O3^x	132.18 (6)	O3^vii—Ge—O3^viii	99.71 (5)
O1^ix—Ca—O3^x	122.91 (5)

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

(Cu80_1)

Crystal data

CaCu0.80Ge2O6Zn0.20	F(000) = 645
Mr = 345.17	Dx = 4.779 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2079 (7) Å	Cell parameters from 3131 reflections
b = 9.0872 (6) Å	θ = 3.1–29.8°
c = 5.3962 (4) Å	µ = 17.98 mm^−1
β = 106.5988 (7)°	T = 293 K
V = 479.70 (6) Å^3	Isometric, colourless
Z = 4	0.08 × 0.07 × 0.07 mm

Data collection

SMART APEX diffractometer	654 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
rotation, ω–scans at 4 different φ positions	θmax = 29.8°, θmin = 3.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −14→13
Tmin = 0.25, Tmax = 0.29	k = −12→12
3131 measured reflections	l = −7→7
665 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0191P)^2 + 0.7323P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max = 0.001
wR(F^2) = 0.040	Δρmax = 0.54 e Å^−3
S = 1.24	Δρmin = −0.82 e Å^−3
665 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0055 (4)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca	0.0000	0.30209 (6)	0.2500	0.01207 (12)
Zn	0.0000	0.90685 (3)	0.2500	0.01002 (10)	0.2
Cu	0.0000	0.90685 (3)	0.2500	0.01002 (10)	0.8
Ge	0.28344 (2)	0.09781 (2)	0.21714 (4)	0.00976 (9)
O1	0.10688 (15)	0.09263 (15)	0.1240 (3)	0.0137 (3)
O2	0.35961 (16)	0.26056 (16)	0.3378 (3)	0.0179 (3)
O3	0.35749 (13)	0.02788 (16)	0.9792 (2)	0.0126 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0122 (3)	0.0136 (2)	0.0099 (2)	0.000	0.00221 (19)	0.000
Zn	0.00825 (18)	0.01351 (18)	0.00745 (17)	0.000	0.00085 (12)	0.000
Cu	0.00825 (18)	0.01351 (18)	0.00745 (17)	0.000	0.00085 (12)	0.000
Ge	0.00679 (13)	0.01410 (13)	0.00806 (12)	0.00079 (6)	0.00156 (8)	−0.00127 (6)
O1	0.0075 (6)	0.0211 (7)	0.0117 (7)	0.0027 (5)	0.0013 (5)	−0.0026 (5)
O2	0.0192 (7)	0.0156 (7)	0.0168 (7)	−0.0010 (5)	0.0018 (5)	−0.0033 (5)
O3	0.0089 (6)	0.0190 (7)	0.0099 (6)	−0.0001 (5)	0.0029 (5)	−0.0031 (5)

Geometric parameters (Å, º)

Ca—O2^i	2.3461 (15)	Zn—O1^vi	2.2196 (14)
Ca—O1	2.3874 (14)	Ge—O2	1.7108 (15)
Ca—O3^ii	2.6572 (14)	Ge—O1	1.7278 (15)
Ca—O3^iii	2.6921 (14)	Ge—O3^vii	1.7829 (13)
Zn—O1^iv	2.0014 (14)	Ge—O3^viii	1.8068 (13)
Zn—O2^v	2.1055 (15)
O2^i—Ca—O2^ii	151.91 (7)	O3^ii—Ca—O3^x	65.60 (5)
O2^i—Ca—O1	75.02 (5)	O3^i—Ca—O3^x	61.75 (2)
O2^ii—Ca—O1	82.61 (5)	O3^iii—Ca—O3^x	80.69 (6)
O2^i—Ca—O1^ix	82.61 (5)	O1^iv—Zn—O1^xi	179.73 (8)
O2^ii—Ca—O1^ix	75.02 (5)	O1^iv—Zn—O2^xii	89.12 (6)
O1—Ca—O1^ix	74.26 (7)	O1^xi—Zn—O2^xii	91.05 (6)
O2^i—Ca—O3^ii	88.12 (5)	O1^iv—Zn—O2^v	91.05 (6)
O2^ii—Ca—O3^ii	108.36 (5)	O1^xi—Zn—O2^v	89.12 (5)
O1—Ca—O3^ii	88.60 (5)	O2^xii—Zn—O2^v	101.70 (8)
O1^ix—Ca—O3^ii	162.11 (5)	O1^iv—Zn—O1^vi	97.64 (5)
O2^i—Ca—O3^i	108.36 (5)	O1^xi—Zn—O1^vi	82.15 (6)
O2^ii—Ca—O3^i	88.12 (5)	O2^xii—Zn—O1^vi	167.13 (6)
O1—Ca—O3^i	162.11 (5)	O2^v—Zn—O1^vi	89.17 (5)
O1^ix—Ca—O3^i	88.60 (5)	O1^iv—Zn—O1^xiii	82.15 (6)
O3^ii—Ca—O3^i	108.89 (6)	O1^xi—Zn—O1^xiii	97.64 (5)
O2^i—Ca—O3^iii	142.06 (5)	O2^xii—Zn—O1^xiii	89.17 (5)
O2^ii—Ca—O3^iii	65.24 (5)	O2^v—Zn—O1^xiii	167.13 (6)
O1—Ca—O3^iii	122.84 (4)	O1^vi—Zn—O1^xiii	80.97 (7)
O1^ix—Ca—O3^iii	132.31 (4)	O2—Ge—O1	117.20 (7)
O3^ii—Ca—O3^iii	61.75 (2)	O2—Ge—O3^vii	110.01 (7)
O3^i—Ca—O3^iii	65.60 (5)	O1—Ge—O3^vii	113.73 (6)
O2^i—Ca—O3^x	65.24 (5)	O2—Ge—O3^viii	101.86 (7)
O2^ii—Ca—O3^x	142.06 (5)	O1—Ge—O3^viii	112.26 (6)
O1—Ca—O3^x	132.31 (4)	O3^vii—Ge—O3^viii	99.77 (4)
O1^ix—Ca—O3^x	122.83 (4)

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

(Cu60_2)

Crystal data

CaCu0.60Ge2O6Zn0.40	F(000) = 646
Mr = 345.53	Dx = 4.785 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1962 (8) Å	Cell parameters from 3137 reflections
b = 9.0653 (7) Å	θ = 3.1–29.9°
c = 5.4050 (4) Å	µ = 18.09 mm^−1
β = 106.2287 (9)°	T = 293 K
V = 479.69 (6) Å^3	Isometric, colourless
Z = 4	0.11 × 0.09 × 0.08 mm

Data collection

SMART APEX diffractometer	643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
rotation, ω–scans at 4 different φ positions	θmax = 29.9°, θmin = 3.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −14→14
Tmin = 0.19, Tmax = 0.23	k = −12→12
3137 measured reflections	l = −7→7
664 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.022P)^2 + 0.6443P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max = 0.001
wR(F^2) = 0.043	Δρmax = 0.68 e Å^−3
S = 1.19	Δρmin = −0.64 e Å^−3
664 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0009 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca	0.0000	0.30264 (7)	0.2500	0.01067 (14)
Zn	0.0000	0.90721 (4)	0.2500	0.00901 (11)	0.4
Cu	0.0000	0.90721 (4)	0.2500	0.00901 (11)	0.6
Ge	0.28381 (2)	0.09787 (2)	0.21943 (4)	0.00796 (10)
O1	0.10763 (16)	0.09272 (16)	0.1271 (3)	0.0119 (3)
O2	0.36031 (17)	0.26067 (17)	0.3388 (3)	0.0147 (3)
O3	0.35770 (14)	0.02831 (17)	0.9804 (3)	0.0112 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0115 (3)	0.0108 (3)	0.0094 (3)	0.000	0.0023 (2)	0.000
Zn	0.00849 (19)	0.01086 (19)	0.00706 (19)	0.000	0.00115 (14)	0.000
Cu	0.00849 (19)	0.01086 (19)	0.00706 (19)	0.000	0.00115 (14)	0.000
Ge	0.00681 (14)	0.00968 (14)	0.00733 (14)	0.00045 (6)	0.00187 (9)	−0.00075 (7)
O1	0.0083 (7)	0.0159 (8)	0.0112 (8)	0.0016 (5)	0.0022 (6)	−0.0020 (5)
O2	0.0177 (8)	0.0115 (7)	0.0138 (8)	−0.0030 (6)	0.0026 (6)	−0.0021 (6)
O3	0.0089 (7)	0.0150 (7)	0.0100 (7)	−0.0007 (5)	0.0030 (5)	−0.0036 (6)

Geometric parameters (Å, º)

Ca—O2^i	2.3511 (17)	Zn—O1^vii	2.0269 (16)
Ca—O2^ii	2.3511 (17)	Zn—O2^viii	2.0990 (16)
Ca—O1^iii	2.3821 (15)	Zn—O2^ix	2.0990 (16)
Ca—O1	2.3822 (15)	Zn—O1^x	2.2093 (16)
Ca—O3^ii	2.6486 (15)	Zn—O1^xi	2.2093 (16)
Ca—O3^i	2.6486 (15)	Ge—O2	1.7093 (16)
Ca—O3^iv	2.6892 (16)	Ge—O1	1.7254 (16)
Ca—O3^v	2.6892 (16)	Ge—O3^xii	1.7827 (15)
Zn—O1^vi	2.0269 (16)	Ge—O3^xiii	1.8089 (15)
O2^i—Ca—O2^ii	151.74 (8)	O3^ii—Ca—O3^v	65.71 (5)
O2^i—Ca—O1^iii	82.18 (6)	O3^i—Ca—O3^v	62.04 (2)
O2^ii—Ca—O1^iii	75.28 (6)	O3^iv—Ca—O3^v	80.94 (7)
O2^i—Ca—O1	75.28 (6)	O1^vi—Zn—O1^vii	179.96 (8)
O2^ii—Ca—O1	82.18 (6)	O1^vi—Zn—O2^viii	88.94 (6)
O1^iii—Ca—O1	73.96 (8)	O1^vii—Zn—O2^viii	91.08 (7)
O2^i—Ca—O3^ii	87.91 (5)	O1^vi—Zn—O2^ix	91.08 (7)
O2^ii—Ca—O3^ii	108.60 (5)	O1^vii—Zn—O2^ix	88.94 (6)
O1^iii—Ca—O3^ii	161.62 (5)	O2^viii—Zn—O2^ix	101.48 (9)
O1—Ca—O3^ii	88.59 (5)	O1^vi—Zn—O1^x	97.31 (6)
O2^i—Ca—O3^i	108.60 (5)	O1^vii—Zn—O1^x	82.66 (6)
O2^ii—Ca—O3^i	87.91 (5)	O2^viii—Zn—O1^x	167.50 (6)
O1^iii—Ca—O3^i	88.59 (5)	O2^ix—Zn—O1^x	89.26 (6)
O1—Ca—O3^i	161.62 (5)	O1^vi—Zn—O1^xi	82.66 (6)
O3^ii—Ca—O3^i	109.29 (7)	O1^vii—Zn—O1^xi	97.31 (6)
O2^i—Ca—O3^iv	142.23 (5)	O2^viii—Zn—O1^xi	89.26 (6)
O2^ii—Ca—O3^iv	65.23 (5)	O2^ix—Zn—O1^xi	167.50 (6)
O1^iii—Ca—O3^iv	132.65 (5)	O1^x—Zn—O1^xi	80.87 (8)
O1—Ca—O3^iv	122.55 (5)	O2—Ge—O1	117.45 (8)
O3^ii—Ca—O3^iv	62.04 (2)	O2—Ge—O3^xii	109.77 (7)
O3^i—Ca—O3^iv	65.71 (5)	O1—Ge—O3^xii	113.42 (7)
O2^i—Ca—O3^v	65.23 (5)	O2—Ge—O3^xiii	101.82 (7)
O2^ii—Ca—O3^v	142.23 (5)	O1—Ge—O3^xiii	112.43 (7)
O1^iii—Ca—O3^v	122.55 (5)	O3^xii—Ge—O3^xiii	99.98 (5)
O1—Ca—O3^v	132.65 (5)

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

(Cu40_3)

Crystal data

CaCu0.31Ge2O6Zn0.69	F(000) = 647
Mr = 346.06	Dx = 4.789 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1811 (7) Å	Cell parameters from 3178 reflections
b = 9.0368 (6) Å	θ = 3.1–29.9°
c = 5.4196 (4) Å	µ = 18.25 mm^−1
β = 105.7255 (8)°	T = 293 K
V = 479.96 (6) Å^3	Isometric, colourless
Z = 4	0.10 × 0.08 × 0.08 mm

Data collection

SMART APEX diffractometer	656 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
rotation, ω–scans at 4 different φ positions	θmax = 29.9°, θmin = 3.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −14→13
Tmin = 0.20, Tmax = 0.27	k = −12→12
3178 measured reflections	l = −7→7
671 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 0.5591P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max = 0.001
wR(F^2) = 0.040	Δρmax = 0.34 e Å^−3
S = 1.20	Δρmin = −0.69 e Å^−3
671 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0051 (4)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca	0.0000	0.30353 (6)	0.2500	0.00890 (13)
Zn	0.0000	0.90793 (4)	0.2500	0.00814 (10)	0.69
Cu	0.0000	0.90793 (4)	0.2500	0.00814 (10)	0.31
Ge	0.28445 (2)	0.09786 (2)	0.22406 (4)	0.00611 (9)
O1	0.10887 (15)	0.09274 (14)	0.1329 (3)	0.0089 (3)
O2	0.36182 (15)	0.26093 (16)	0.3414 (3)	0.0116 (3)
O3	0.35804 (14)	0.02871 (16)	0.9828 (3)	0.0092 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0099 (3)	0.0080 (3)	0.0084 (2)	0.000	0.0017 (2)	0.000
Zn	0.00808 (18)	0.00897 (18)	0.00693 (17)	0.000	0.00129 (13)	0.000
Cu	0.00808 (18)	0.00897 (18)	0.00693 (17)	0.000	0.00129 (13)	0.000
Ge	0.00534 (13)	0.00669 (13)	0.00609 (13)	0.00014 (6)	0.00118 (8)	−0.00049 (6)
O1	0.0063 (7)	0.0104 (7)	0.0095 (7)	0.0010 (5)	0.0014 (5)	−0.0007 (5)
O2	0.0142 (7)	0.0085 (7)	0.0116 (7)	−0.0031 (5)	0.0027 (5)	−0.0021 (5)
O3	0.0082 (7)	0.0113 (7)	0.0087 (6)	−0.0011 (5)	0.0031 (5)	−0.0031 (5)

Geometric parameters (Å, º)

Ca—O2^i	2.3525 (15)	Zn—O1^v	2.1913 (14)
Ca—O1	2.3750 (14)	Ge—O2	1.7102 (14)
Ca—O3^i	2.6396 (14)	Ge—O1	1.7213 (15)
Ca—O3^ii	2.6818 (15)	Ge—O3^vi	1.7868 (14)
Zn—O1^iii	2.0710 (15)	Ge—O3^vii	1.8073 (14)
Zn—O2^iv	2.0896 (15)
O2^viii—Ca—O2^i	151.33 (7)	O3^i—Ca—O3^x	65.85 (5)
O2^viii—Ca—O1^ix	81.35 (5)	O3^viii—Ca—O3^x	62.45 (2)
O2^i—Ca—O1^ix	75.72 (5)	O3^ii—Ca—O3^x	81.29 (6)
O2^viii—Ca—O1	75.72 (5)	O1^iii—Zn—O1^xi	179.66 (8)
O2^i—Ca—O1	81.35 (5)	O1^iii—Zn—O2^iv	88.43 (5)
O1^ix—Ca—O1	73.35 (7)	O1^xi—Zn—O2^iv	91.36 (6)
O2^viii—Ca—O3^i	87.56 (5)	O1^iii—Zn—O2^xii	91.36 (6)
O2^i—Ca—O3^i	109.08 (5)	O1^xi—Zn—O2^xii	88.43 (5)
O1^ix—Ca—O3^i	160.73 (5)	O2^iv—Zn—O2^xii	101.06 (8)
O1—Ca—O3^i	88.70 (5)	O1^iii—Zn—O1^v	96.72 (5)
O2^viii—Ca—O3^viii	109.08 (5)	O1^xi—Zn—O1^v	83.54 (6)
O2^i—Ca—O3^viii	87.56 (5)	O2^iv—Zn—O1^v	168.23 (6)
O1^ix—Ca—O3^viii	88.70 (5)	O2^xii—Zn—O1^v	89.43 (5)
O1—Ca—O3^viii	160.73 (5)	O1^iii—Zn—O1^xiii	83.54 (6)
O3^i—Ca—O3^viii	109.89 (6)	O1^xi—Zn—O1^xiii	96.72 (5)
O2^viii—Ca—O3^ii	142.51 (5)	O2^iv—Zn—O1^xiii	89.43 (5)
O2^i—Ca—O3^ii	65.31 (5)	O2^xii—Zn—O1^xiii	168.23 (6)
O1^ix—Ca—O3^ii	133.36 (5)	O1^v—Zn—O1^xiii	80.68 (7)
O1—Ca—O3^ii	122.04 (4)	O2—Ge—O1	117.88 (7)
O3^i—Ca—O3^ii	62.45 (2)	O2—Ge—O3^vi	109.34 (7)
O3^viii—Ca—O3^ii	65.85 (5)	O1—Ge—O3^vi	112.92 (7)
O2^viii—Ca—O3^x	65.31 (5)	O2—Ge—O3^vii	101.81 (7)
O2^i—Ca—O3^x	142.51 (5)	O1—Ge—O3^vii	112.67 (6)
O1^ix—Ca—O3^x	122.04 (5)	O3^vi—Ge—O3^vii	100.29 (5)
O1—Ca—O3^x	133.36 (5)

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

(Cu10_9)

Crystal data

CaCu0.10Ge2O6Zn0.90	F(000) = 648
Mr = 346.45	Dx = 4.785 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1706 (7) Å	Cell parameters from 3154 reflections
b = 9.0196 (6) Å	θ = 3.1–29.7°
c = 5.4346 (3) Å	µ = 18.33 mm^−1
β = 105.2776 (7)°	T = 293 K
V = 480.92 (5) Å^3	Isometric, colourless
Z = 4	0.13 × 0.12 × 0.10 mm

Data collection

SMART APEX diffractometer	649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
rotation, ω–scans at 4 different φ positions	θmax = 29.7°, θmin = 3.1°
Absorption correction: multi-scan multiscan correction with APEX2 software (Bruker 2012)	h = −13→13
Tmin = 0.10, Tmax = 0.16	k = −12→12
3154 measured reflections	l = −7→7
660 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.021P)^2 + 0.5946P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.015	(Δ/σ)max < 0.001
wR(F^2) = 0.039	Δρmax = 0.49 e Å^−3
S = 1.24	Δρmin = −0.90 e Å^−3
660 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick 2014, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0047 (4)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca	0.0000	0.30373 (6)	0.2500	0.00894 (12)
Zn	0.0000	0.90820 (3)	0.2500	0.00820 (10)	0.9
Cu	0.0000	0.90820 (3)	0.2500	0.00820 (10)	0.1
Ge	0.28472 (2)	0.09788 (2)	0.22574 (4)	0.00594 (9)
O1	0.10914 (14)	0.09220 (13)	0.1348 (3)	0.0085 (3)
O2	0.36238 (13)	0.26132 (14)	0.3412 (3)	0.0111 (3)
O3	0.35818 (12)	0.02864 (15)	0.9839 (2)	0.0093 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0098 (2)	0.0083 (2)	0.0082 (2)	0.000	0.00141 (18)	0.000
Zn	0.00833 (17)	0.00888 (17)	0.00707 (17)	0.000	0.00146 (12)	0.000
Cu	0.00833 (17)	0.00888 (17)	0.00707 (17)	0.000	0.00146 (12)	0.000
Ge	0.00526 (13)	0.00668 (12)	0.00575 (12)	−0.00007 (5)	0.00120 (8)	−0.00041 (6)
O1	0.0068 (6)	0.0100 (6)	0.0083 (6)	0.0001 (4)	0.0012 (5)	−0.0001 (4)
O2	0.0129 (6)	0.0089 (6)	0.0112 (6)	−0.0032 (5)	0.0027 (5)	−0.0014 (5)
O3	0.0082 (6)	0.0120 (6)	0.0080 (6)	−0.0009 (4)	0.0028 (5)	−0.0031 (4)

Geometric parameters (Å, º)

Ca—O2^i	2.3663 (13)	Zn—O2^vii	2.0798 (13)
Ca—O2^ii	2.3663 (13)	Zn—O1^viii	2.0936 (14)
Ca—O1^iii	2.3728 (13)	Zn—O1^ix	2.0936 (14)
Ca—O1	2.3728 (13)	Zn—O1^x	2.1781 (13)
Ca—O3^i	2.6362 (13)	Zn—O1^xi	2.1781 (13)
Ca—O3^ii	2.6362 (13)	Ge—O2	1.7117 (13)
Ca—O3^iv	2.6809 (14)	Ge—O1	1.7236 (14)
Ca—O3^v	2.6809 (14)	Ge—O3^xii	1.7868 (12)
Zn—O2^vi	2.0798 (13)	Ge—O3^xiii	1.8101 (13)
O2^i—Ca—O2^ii	151.29 (7)	O3^i—Ca—O3^v	62.68 (2)
O2^i—Ca—O1^iii	81.15 (5)	O3^ii—Ca—O3^v	65.85 (4)
O2^ii—Ca—O1^iii	75.83 (5)	O3^iv—Ca—O3^v	81.66 (6)
O2^i—Ca—O1	75.83 (5)	O2^vi—Zn—O2^vii	100.87 (8)
O2^ii—Ca—O1	81.15 (5)	O2^vi—Zn—O1^viii	88.49 (5)
O1^iii—Ca—O1	72.95 (6)	O2^vii—Zn—O1^viii	91.38 (5)
O2^i—Ca—O3^i	109.36 (4)	O2^vi—Zn—O1^ix	91.38 (5)
O2^ii—Ca—O3^i	87.30 (4)	O2^vii—Zn—O1^ix	88.49 (5)
O1^iii—Ca—O3^i	88.89 (4)	O1^viii—Zn—O1^ix	179.81 (7)
O1—Ca—O3^i	160.36 (4)	O2^vi—Zn—O1^x	168.45 (5)
O2^i—Ca—O3^ii	87.30 (4)	O2^vii—Zn—O1^x	89.48 (5)
O2^ii—Ca—O3^ii	109.36 (4)	O1^viii—Zn—O1^x	96.44 (5)
O1^iii—Ca—O3^ii	160.36 (4)	O1^ix—Zn—O1^x	83.71 (5)
O1—Ca—O3^ii	88.89 (4)	O2^vi—Zn—O1^xi	89.48 (5)
O3^i—Ca—O3^ii	110.00 (6)	O2^vii—Zn—O1^xi	168.45 (5)
O2^i—Ca—O3^iv	142.66 (5)	O1^viii—Zn—O1^xi	83.71 (5)
O2^ii—Ca—O3^iv	65.18 (4)	O1^ix—Zn—O1^xi	96.44 (5)
O1^iii—Ca—O3^iv	133.53 (4)	O1^x—Zn—O1^xi	80.73 (7)
O1—Ca—O3^iv	121.88 (4)	O2—Ge—O1	118.28 (6)
O3^i—Ca—O3^iv	65.85 (4)	O2—Ge—O3^xii	109.20 (6)
O3^ii—Ca—O3^iv	62.68 (2)	O1—Ge—O3^xii	112.41 (6)
O2^i—Ca—O3^v	65.18 (4)	O2—Ge—O3^xiii	101.68 (6)
O2^ii—Ca—O3^v	142.66 (5)	O1—Ge—O3^xiii	112.84 (6)
O1^iii—Ca—O3^v	121.88 (4)	O3^xii—Ge—O3^xiii	100.52 (4)
O1—Ca—O3^v	133.53 (4)

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