On the crystal chemistry of olivine-type germanate compounds, Ca_1 + xM_1 - xGeO₄ (M²⁺ = Ca, Mg, Co, Mn)

Germanate compounds, CaMGeO₄ with M²⁺ = Ca, Mg, Co and Mn, were synthesized as single crystals by slow cooling from the melt or by flux growth techniques. All the compositions investigated exhibit Pnma symmetry at 298 K and adopt the olivine structure. The M2 site is exclusively occupied by Ca²⁺, while on M1 both Ca²⁺ and M²⁺ cations are found. The amount of Ca²⁺ on M1 increases with the size of the M1 cation, with the smallest amount in the Mg compound (0.1 atoms per formula unit) and the largest in the Mn compound (0.20 atoms per formula unit), while in Ca₂GeO₄, also with olivine structure, both sites are completely filled with Ca²⁺. When compared with those of Ca silicate olivine, the lattice parameters a and c are distinctly larger in the analogous germanate compounds, while b has essentially the same values, regardless of the tetrahedral cation, meaning that b is independent of the tetrahedral cation. Structural variations on the octahedrally coordinated M1 site are largely determined by the size of the M1 cation, the average M1-O bond lengths being identical in Ca silicate and Ca germanate olivine. Increasing the size of the M1 cation induces an increasing polyhedral distortion, expressed by the parameters bond-length distortion, octahedral angle variance and octahedral quadratic elongation. However, the Ca germanate olivine compounds generally have more regular octahedra than the analogous silicates. The octahedrally coordinated M2 site does not exhibit large variations in structural parameters as a consequence of the constant chemical composition; the same is valid for the tetrahedral site.

S1. Comment

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Computing details

Data collection: Bruker SMART+ (Bruker, 2001) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1. Cell refinement: Bruker SAINT+ (Bruker, 2001) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1. Data reduction: Bruker SAINT+ (Bruker, 2001) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: Diamonds 3.0 (Pennington,1999) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1. Software used to prepare material for publication: WinGX v1.70.01 (Farrugia 1999) for Ca2Co_2, cazn_b, camn_a5, camn_a2, camg_a1, caco_a2, caco_a1, ca2mn_1, ca2mg_1, ca2ge_1.

Figures

Figure 1. View of (I) (50% probability displacement ellipsoids)

(Ca2Co_2)

Crystal data

Ca1.17Co0.83GeO4	Dx = 4.188 Mg m^−3
Mr = 232.4	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1351 reflections
a = 11.3021 (7) Å	θ = 3.6–28.7°
b = 6.4657 (4) Å	µ = 13.40 mm^−1
c = 5.0435 (3) Å	T = 295 K
V = 368.56 (4) Å^3	Cuboid, pink
Z = 4	0.18 × 0.16 × 0.13 mm
F(000) = 439.2

Data collection

SMART APEX diffractometer	504 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.062
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 28.7°, θmin = 3.6°
Tmin = 0.10, Tmax = 0.18	h = −14→14
4087 measured reflections	k = −8→8
507 independent reflections	l = −6→6

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0368P)^2 + 0.3685P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.029	(Δ/σ)max < 0.001
wR(F^2) = 0.070	Δρmax = 0.98 e Å^−3
S = 1.36	Δρmin = −1.68 e Å^−3
507 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
45 parameters	Extinction coefficient: 0.066 (5)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.41693 (4)	0.25	0.07614 (9)	0.0109 (2)
Co1	0.5	0	0.5	0.0108 (2)	0.81
Ca1	0.5	0	0.5	0.0108 (2)	0.19
Ca2	0.22504 (7)	0.25	0.51158 (18)	0.0115 (3)	0.98
Co2	0.22504 (7)	0.25	0.51158 (18)	0.0115 (3)	0.02
O1	0.4176 (3)	0.25	−0.2700 (7)	0.0144 (6)
O2	0.5554 (3)	0.25	0.2437 (7)	0.0145 (6)
O3	0.34885 (18)	0.0354 (3)	0.2281 (5)	0.0141 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0094 (3)	0.0145 (3)	0.0087 (3)	0	0.00037 (14)	0
Co1	0.0097 (4)	0.0126 (4)	0.0101 (4)	0.0019 (2)	−0.0005 (2)	0.0018 (2)
Ca1	0.0097 (4)	0.0126 (4)	0.0101 (4)	0.0019 (2)	−0.0005 (2)	0.0018 (2)
Ca2	0.0088 (4)	0.0131 (4)	0.0125 (5)	0	0.0001 (3)	0
Co2	0.0088 (4)	0.0131 (4)	0.0125 (5)	0	0.0001 (3)	0
O1	0.0131 (14)	0.0231 (16)	0.0070 (14)	0	−0.0007 (10)	0
O2	0.0091 (12)	0.0220 (15)	0.0125 (14)	0	0.0004 (11)	0
O3	0.0140 (9)	0.0135 (9)	0.0147 (11)	−0.0023 (8)	0.0016 (8)	−0.0003 (8)

Geometric parameters (Å, º)

Ge1—O1	1.746 (4)	Ca2—O3^v	2.301 (2)
Ge1—O3^i	1.762 (2)	Ca2—O3^vi	2.301 (2)
Ge1—O3	1.762 (2)	Ca2—O2^vii	2.310 (3)
Ge1—O2	1.778 (3)	Ca2—O3	2.435 (2)
Co1—O2^ii	2.162 (2)	Ca2—O3^i	2.435 (2)
Co1—O2	2.162 (2)	Ca2—O1^iii	2.439 (3)
Co1—O1^iii	2.197 (2)	Ca2—Ca1^viii	3.5033 (7)
Co1—O1^iv	2.197 (2)	Ca2—Co1^viii	3.5033 (7)
Co1—O3	2.203 (2)	Ca2—Ge1^vii	3.5104 (10)
Co1—O3^ii	2.203 (2)
O1—Ge1—O3^i	115.90 (9)	O1^iii—Co1—O3^ii	94.39 (10)
O1—Ge1—O3	115.90 (9)	O1^iv—Co1—O3^ii	85.61 (10)
O3^i—Ge1—O3	103.91 (14)	O3—Co1—O3^ii	180
O1—Ge1—O2	118.13 (14)	O3^v—Ca2—O3^vi	106.62 (12)
O3^i—Ge1—O2	100.22 (9)	O3^v—Ca2—O2^vii	87.89 (7)
O3—Ge1—O2	100.22 (9)	O3^vi—Ca2—O2^vii	87.89 (7)
O2^ii—Co1—O2	180	O3^v—Ca2—O3	91.73 (5)
O2^ii—Co1—O1^iii	96.41 (9)	O3^vi—Ca2—O3	160.79 (9)
O2—Co1—O1^iii	83.59 (9)	O2^vii—Ca2—O3	98.61 (9)
O2^ii—Co1—O1^iv	83.59 (9)	O3^v—Ca2—O3^i	160.79 (9)
O2—Co1—O1^iv	96.41 (9)	O3^vi—Ca2—O3^i	91.73 (5)
O1^iii—Co1—O1^iv	180	O2^vii—Ca2—O3^i	98.61 (9)
O2^ii—Co1—O3	103.02 (10)	O3—Ca2—O3^i	69.50 (10)
O2—Co1—O3	76.98 (10)	O3^v—Ca2—O1^iii	96.29 (8)
O1^iii—Co1—O3	85.61 (10)	O3^vi—Ca2—O1^iii	96.29 (8)
O1^iv—Co1—O3	94.39 (10)	O2^vii—Ca2—O1^iii	172.97 (12)
O2^ii—Co1—O3^ii	76.98 (10)	O3—Ca2—O1^iii	75.67 (9)
O2—Co1—O3^ii	103.02 (10)	O3^i—Ca2—O1^iii	75.67 (9)

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

(cfg_rot)

Crystal data

Ca2GeO4	F(000) = 416
Mr = 216.75	Dx = 3.556 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
a = 11.3919 (7) Å	µ = 9.97 mm^−1
b = 6.7800 (4) Å	T = 293 K
c = 5.2424 (3) Å	Cuboid, colourless
V = 404.91 (4) Å^3	0.16 × 0.14 × 0.13 mm
Z = 4

Data collection

4592 measured reflections	θmax = 28.7°, θmin = 3.6°
551 independent reflections	h = −15→15
544 reflections with I > 2σ(I)	k = −9→9
Rint = 0.057	l = −7→7

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0136P)^2 + 0.4447P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.019	(Δ/σ)max < 0.001
wR(F^2) = 0.042	Δρmax = 0.83 e Å^−3
S = 1.25	Δρmin = −0.39 e Å^−3
551 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
41 parameters	Extinction coefficient: 0.063 (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.

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

	x	y	z	Uiso*/Ueq
Ge1	0.40390 (3)	0.25	0.06928 (5)	0.00632 (14)
Ca1	0.5	0	0.5	0.00852 (16)
Ca2	0.22011 (5)	0.25	0.50770 (11)	0.00785 (16)
O1	0.40739 (17)	0.25	−0.2630 (4)	0.0090 (4)
O2	0.54566 (17)	0.25	0.2119 (4)	0.0084 (4)
O3	0.33625 (12)	0.0447 (2)	0.2146 (3)	0.0093 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0064 (2)	0.00650 (18)	0.00606 (19)	0	0.00010 (10)	0
Ca1	0.0102 (3)	0.0069 (3)	0.0084 (3)	0.0018 (2)	−0.0002 (2)	0.00047 (19)
Ca2	0.0062 (3)	0.0078 (3)	0.0096 (3)	0	−0.0002 (2)	0
O1	0.0120 (10)	0.0092 (9)	0.0059 (9)	0	0.0002 (7)	0
O2	0.0066 (9)	0.0092 (9)	0.0095 (9)	0	−0.0002 (7)	0
O3	0.0093 (6)	0.0083 (6)	0.0102 (7)	−0.0017 (5)	0.0004 (5)	0.0003 (5)

Geometric parameters (Å, º)

Ge1—O1	1.742 (2)	Ca1—Ca1^ii	3.3900 (2)
Ge1—O3	1.7642 (14)	Ca1—Ge1^viii	3.6025 (3)
Ge1—O3^i	1.7642 (14)	Ca1—Ge1^ix	3.6025 (3)
Ge1—O2	1.780 (2)	Ca2—O2^xi	2.297 (2)
Ge1—Ca1^ii	3.0282 (3)	Ca2—O3^xii	2.3621 (15)
Ge1—Ca1	3.0282 (3)	Ca2—O3^xiii	2.3621 (15)
Ge1—Ca2	3.1090 (6)	Ca2—O1^ix	2.449 (2)
Ge1—Ca1^iii	3.6025 (3)	Ca2—O3^i	2.4597 (15)
Ge1—Ca1^iv	3.6025 (3)	Ca2—O3	2.4597 (15)
Ge1—Ca2^iii	3.6125 (7)	Ca2—Ca1^ii	3.6112 (5)
Ge1—Ca2^v	3.6248 (7)	Ca2—Ge1^ix	3.6125 (7)
Ge1—Ca2^vi	3.6868 (3)	Ca2—Ge1^xi	3.6248 (7)
Ca1—O2	2.3293 (14)	Ca2—Ge1^xiii	3.6868 (3)
Ca1—O2^vii	2.3293 (14)	O1—Ca1^iii	2.3515 (14)
Ca1—O1^viii	2.3515 (14)	O1—Ca1^iv	2.3515 (14)
Ca1—O1^ix	2.3515 (14)	O1—Ca2^iii	2.449 (2)
Ca1—O3^vii	2.4105 (14)	O2—Ca2^v	2.297 (2)
Ca1—O3	2.4105 (14)	O2—Ca1^ii	2.3293 (14)
Ca1—Ge1^vii	3.0282 (3)	O3—Ca2^vi	2.3621 (15)
Ca1—Ca1^x	3.3900 (2)
O1—Ge1—O3	116.21 (6)	Ge1—Ca1—Ca1^ii	55.963 (4)
O1—Ge1—O3^i	116.21 (6)	Ge1^vii—Ca1—Ca1^ii	124.037 (4)
O3—Ge1—O3^i	104.21 (9)	Ca1^x—Ca1—Ca1^ii	180
O1—Ge1—O2	113.53 (9)	O2—Ca1—Ge1^viii	74.77 (4)
O3—Ge1—O2	102.42 (6)	O2^vii—Ca1—Ge1^viii	105.23 (4)
O3^i—Ge1—O2	102.42 (6)	O1^viii—Ca1—Ge1^viii	24.05 (5)
O1—Ge1—Ca1^ii	137.49 (4)	O1^ix—Ca1—Ge1^viii	155.95 (5)
O3—Ge1—Ca1^ii	106.12 (5)	O3^vii—Ca1—Ge1^viii	102.71 (3)
O3^i—Ge1—Ca1^ii	52.72 (5)	O3—Ca1—Ge1^viii	77.29 (3)
O2—Ge1—Ca1^ii	50.11 (4)	Ge1—Ca1—Ge1^viii	75.848 (6)
O1—Ge1—Ca1	137.49 (4)	Ge1^vii—Ca1—Ge1^viii	104.152 (6)
O3—Ge1—Ca1	52.72 (5)	Ca1^x—Ca1—Ge1^viii	61.933 (3)
O3^i—Ge1—Ca1	106.12 (5)	Ca1^ii—Ca1—Ge1^viii	118.067 (3)
O2—Ge1—Ca1	50.11 (4)	O2—Ca1—Ge1^ix	105.23 (4)
Ca1^ii—Ge1—Ca1	68.074 (7)	O2^vii—Ca1—Ge1^ix	74.77 (4)
O1—Ge1—Ca2	138.98 (7)	O1^viii—Ca1—Ge1^ix	155.95 (5)
O3—Ge1—Ca2	52.17 (5)	O1^ix—Ca1—Ge1^ix	24.05 (5)
O3^i—Ge1—Ca2	52.17 (5)	O3^vii—Ca1—Ge1^ix	77.29 (3)
O2—Ge1—Ca2	107.49 (7)	O3—Ca1—Ge1^ix	102.71 (3)
Ca1^ii—Ge1—Ca2	72.074 (11)	Ge1—Ca1—Ge1^ix	104.152 (6)
Ca1—Ge1—Ca2	72.074 (11)	Ge1^vii—Ca1—Ge1^ix	75.848 (6)
O1—Ge1—Ca1^iii	33.37 (3)	Ca1^x—Ca1—Ge1^ix	118.067 (3)
O3—Ge1—Ca1^iii	96.84 (5)	Ca1^ii—Ca1—Ge1^ix	61.933 (3)
O3^i—Ge1—Ca1^iii	149.51 (5)	Ge1^viii—Ca1—Ge1^ix	180.000 (10)
O2—Ge1—Ca1^iii	94.14 (6)	O2^xi—Ca2—O3^xii	89.71 (5)
Ca1^ii—Ge1—Ca1^iii	140.463 (10)	O2^xi—Ca2—O3^xiii	89.71 (5)
Ca1—Ge1—Ca1^iii	104.152 (6)	O3^xii—Ca2—O3^xiii	115.51 (8)
Ca2—Ge1—Ca1^iii	144.792 (9)	O2^xi—Ca2—O1^ix	179.32 (7)
O1—Ge1—Ca1^iv	33.37 (3)	O3^xii—Ca2—O1^ix	90.66 (5)
O3—Ge1—Ca1^iv	149.51 (5)	O3^xiii—Ca2—O1^ix	90.66 (5)
O3^i—Ge1—Ca1^iv	96.84 (5)	O2^xi—Ca2—O3^i	98.76 (6)
O2—Ge1—Ca1^iv	94.14 (6)	O3^xii—Ca2—O3^i	87.38 (3)
Ca1^ii—Ge1—Ca1^iv	104.152 (6)	O3^xiii—Ca2—O3^i	155.75 (6)
Ca1—Ge1—Ca1^iv	140.463 (10)	O1^ix—Ca2—O3^i	80.68 (5)
Ca2—Ge1—Ca1^iv	144.792 (9)	O2^xi—Ca2—O3	98.76 (6)
Ca1^iii—Ge1—Ca1^iv	56.134 (6)	O3^xii—Ca2—O3	155.75 (6)
O1—Ge1—Ca2^iii	36.73 (7)	O3^xiii—Ca2—O3	87.38 (3)
O3—Ge1—Ca2^iii	95.66 (5)	O1^ix—Ca2—O3	80.68 (5)
O3^i—Ge1—Ca2^iii	95.66 (5)	O3^i—Ca2—O3	68.94 (7)
O2—Ge1—Ca2^iii	150.26 (7)	O2^xi—Ca2—Ge1	102.25 (5)
Ca1^ii—Ge1—Ca2^iii	144.804 (5)	O3^xii—Ca2—Ge1	121.50 (4)
Ca1—Ge1—Ca2^iii	144.804 (5)	O3^xiii—Ca2—Ge1	121.50 (4)
Ca2—Ge1—Ca2^iii	102.250 (18)	O1^ix—Ca2—Ge1	77.07 (5)
Ca1^iii—Ge1—Ca2^iii	60.067 (9)	O3^i—Ca2—Ge1	34.50 (3)
Ca1^iv—Ge1—Ca2^iii	60.067 (9)	O3—Ca2—Ge1	34.50 (3)
O1—Ge1—Ca2^v	82.30 (7)	O2^xi—Ca2—Ca1^ii	139.33 (4)
O3—Ge1—Ca2^v	118.83 (5)	O3^xii—Ca2—Ca1^ii	81.27 (4)
O3^i—Ge1—Ca2^v	118.83 (5)	O3^xiii—Ca2—Ca1^ii	129.95 (4)
O2—Ge1—Ca2^v	31.23 (7)	O1^ix—Ca2—Ca1^ii	40.21 (3)
Ca1^ii—Ge1—Ca2^v	73.963 (9)	O3^i—Ca2—Ca1^ii	41.62 (3)
Ca1—Ge1—Ca2^v	73.963 (9)	O3—Ca2—Ca1^ii	77.51 (4)
Ca2—Ge1—Ca2^v	138.723 (13)	Ge1—Ca2—Ca1^ii	52.926 (10)
Ca1^iii—Ge1—Ca2^v	66.782 (9)	O2^xi—Ca2—Ca1	139.33 (4)
Ca1^iv—Ge1—Ca2^v	66.782 (9)	O3^xii—Ca2—Ca1	129.95 (4)
Ca2^iii—Ge1—Ca2^v	119.027 (11)	O3^xiii—Ca2—Ca1	81.27 (4)
O1—Ge1—Ca2^vi	85.48 (3)	O1^ix—Ca2—Ca1	40.21 (3)
O3—Ge1—Ca2^vi	31.21 (5)	O3^i—Ca2—Ca1	77.51 (4)
O3^i—Ge1—Ca2^vi	126.59 (5)	O3—Ca2—Ca1	41.62 (3)
O2—Ge1—Ca2^vi	112.615 (11)	Ge1—Ca2—Ca1	52.926 (9)
Ca1^ii—Ge1—Ca2^vi	135.930 (12)	Ca1^ii—Ca2—Ca1	55.987 (9)
Ca1—Ge1—Ca2^vi	71.889 (9)	O2^xi—Ca2—Ge1^ix	155.50 (5)
Ca2—Ge1—Ca2^vi	78.853 (7)	O3^xii—Ca2—Ge1^ix	77.49 (4)
Ca1^iii—Ge1—Ca2^vi	67.126 (9)	O3^xiii—Ca2—Ge1^ix	77.49 (4)
Ca1^iv—Ge1—Ca2^vi	118.461 (11)	O1^ix—Ca2—Ge1^ix	25.18 (5)
Ca2^iii—Ge1—Ca2^vi	72.937 (8)	O3^i—Ca2—Ge1^ix	101.39 (4)
Ca2^v—Ge1—Ca2^vi	111.781 (9)	O3—Ca2—Ge1^ix	101.39 (4)
O2—Ca1—O2^vii	180	Ge1—Ca2—Ge1^ix	102.250 (18)
O2—Ca1—O1^viii	94.69 (5)	Ca1^ii—Ca2—Ge1^ix	59.828 (10)
O2^vii—Ca1—O1^viii	85.31 (5)	Ca1—Ca2—Ge1^ix	59.828 (10)
O2—Ca1—O1^ix	85.31 (5)	O2^xi—Ca2—Ge1^xi	23.69 (5)
O2^vii—Ca1—O1^ix	94.69 (5)	O3^xii—Ca2—Ge1^xi	77.35 (4)
O1^viii—Ca1—O1^ix	180.00 (12)	O3^xiii—Ca2—Ge1^xi	77.35 (4)
O2—Ca1—O3^vii	108.73 (6)	O1^ix—Ca2—Ge1^xi	156.99 (5)
O2^vii—Ca1—O3^vii	71.27 (6)	O3^i—Ca2—Ge1^xi	117.71 (4)
O1^viii—Ca1—O3^vii	83.70 (6)	O3—Ca2—Ge1^xi	117.71 (4)
O1^ix—Ca1—O3^vii	96.30 (6)	Ge1—Ca2—Ge1^xi	125.939 (18)
O2—Ca1—O3	71.27 (6)	Ca1^ii—Ca2—Ge1^xi	151.187 (6)
O2^vii—Ca1—O3	108.73 (6)	Ca1—Ca2—Ge1^xi	151.187 (6)
O1^viii—Ca1—O3	96.30 (6)	Ge1^ix—Ca2—Ge1^xi	131.811 (17)
O1^ix—Ca1—O3	83.70 (6)	O2^xi—Ca2—Ge1^xiii	73.279 (17)
O3^vii—Ca1—O3	180	O3^xii—Ca2—Ge1^xiii	129.30 (4)
O2—Ca1—Ge1	35.89 (5)	O3^xiii—Ca2—Ge1^xiii	22.77 (3)
O2^vii—Ca1—Ge1	144.11 (5)	O1^ix—Ca2—Ge1^xiii	106.910 (17)
O1^viii—Ca1—Ge1	99.89 (5)	O3^i—Ca2—Ge1^xiii	141.38 (4)
O1^ix—Ca1—Ge1	80.11 (5)	O3—Ca2—Ge1^xiii	74.95 (3)
O3^vii—Ca1—Ge1	144.39 (3)	Ge1—Ca2—Ge1^xiii	108.831 (11)
O3—Ca1—Ge1	35.61 (3)	Ca1^ii—Ca2—Ge1^xiii	140.435 (13)
O2—Ca1—Ge1^vii	144.11 (5)	Ca1—Ca2—Ge1^xiii	84.705 (7)
O2^vii—Ca1—Ge1^vii	35.89 (5)	Ge1^ix—Ca2—Ge1^xiii	98.670 (11)
O1^viii—Ca1—Ge1^vii	80.11 (5)	Ge1^xi—Ca2—Ge1^xiii	68.219 (9)
O1^ix—Ca1—Ge1^vii	99.89 (5)	Ge1—O1—Ca1^iii	122.58 (6)
O3^vii—Ca1—Ge1^vii	35.61 (3)	Ge1—O1—Ca1^iv	122.58 (6)
O3—Ca1—Ge1^vii	144.39 (3)	Ca1^iii—O1—Ca1^iv	92.24 (7)
Ge1—Ca1—Ge1^vii	180	Ge1—O1—Ca2^iii	118.09 (10)
O2—Ca1—Ca1^x	136.69 (4)	Ca1^iii—O1—Ca2^iii	97.56 (6)
O2^vii—Ca1—Ca1^x	43.31 (4)	Ca1^iv—O1—Ca2^iii	97.56 (6)
O1^viii—Ca1—Ca1^x	43.88 (4)	Ge1—O2—Ca2^v	125.09 (10)
O1^ix—Ca1—Ca1^x	136.12 (4)	Ge1—O2—Ca1^ii	94.00 (7)
O3^vii—Ca1—Ca1^x	82.78 (3)	Ca2^v—O2—Ca1^ii	121.22 (6)
O3—Ca1—Ca1^x	97.22 (3)	Ge1—O2—Ca1	94.00 (7)
Ge1—Ca1—Ca1^x	124.037 (4)	Ca2^v—O2—Ca1	121.22 (6)
Ge1^vii—Ca1—Ca1^x	55.963 (4)	Ca1^ii—O2—Ca1	93.39 (7)
O2—Ca1—Ca1^ii	43.31 (4)	Ge1—O3—Ca2^vi	126.01 (7)
O2^vii—Ca1—Ca1^ii	136.69 (4)	Ge1—O3—Ca1	91.67 (6)
O1^viii—Ca1—Ca1^ii	136.12 (4)	Ca2^vi—O3—Ca1	112.90 (6)
O1^ix—Ca1—Ca1^ii	43.88 (4)	Ge1—O3—Ca2	93.33 (6)
O3^vii—Ca1—Ca1^ii	97.22 (3)	Ca2^vi—O3—Ca2	128.27 (6)
O3—Ca1—Ca1^ii	82.78 (3)	Ca1—O3—Ca2	95.71 (5)

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

(cazn_b)

Crystal data

GeO4·1.99(Ca)	Dx = 3.55 Mg m^−3
Mr = 216.37	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1351 reflections
a = 11.3919 (7) Å	θ = 3.6–28.7°
b = 6.7800 (4) Å	µ = 9.96 mm^−1
c = 5.2424 (3) Å	T = 295 K
V = 404.91 (4) Å^3	Cuboid, colourless
Z = 4	0.13 × 0.12 × 0.09 mm
F(000) = 415.2

Data collection

SMART APEX diffractometer	588 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.039
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.4°, θmin = 3.6°
Tmin = 0.29, Tmax = 0.42	h = −15→15
4870 measured reflections	k = −9→9
595 independent reflections	l = −7→7

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.019P)^2 + 0.4001P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.018	(Δ/σ)max < 0.001
wR(F^2) = 0.044	Δρmax = 0.69 e Å^−3
S = 1.24	Δρmin = −0.45 e Å^−3
595 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
41 parameters	Extinction coefficient: 0.0145 (14)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.40389 (2)	0.25	0.06933 (5)	0.00810 (12)
Ca1	0.5	0	0.5	0.01047 (15)
Ca2	0.22012 (5)	0.25	0.50770 (11)	0.00935 (15)	0.99
O1	0.40727 (17)	0.25	−0.2635 (4)	0.0109 (4)
O2	0.54569 (16)	0.25	0.2118 (4)	0.0101 (4)
O3	0.33646 (12)	0.0446 (2)	0.2145 (3)	0.0112 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.00906 (17)	0.00883 (17)	0.00643 (17)	0	0.00004 (10)	0
Ca1	0.0132 (3)	0.0092 (3)	0.0091 (3)	0.0019 (2)	−0.00049 (19)	0.0006 (2)
Ca2	0.0089 (3)	0.0096 (3)	0.0095 (3)	0	0.00007 (19)	0
O1	0.0132 (9)	0.0134 (9)	0.0061 (9)	0	0.0001 (7)	0
O2	0.0082 (9)	0.0125 (9)	0.0097 (9)	0	−0.0008 (7)	0
O3	0.0127 (6)	0.0101 (6)	0.0108 (6)	−0.0019 (5)	0.0004 (5)	0.0006 (5)

Geometric parameters (Å, º)

Ge1—O1	1.745 (2)	Ca1—O3^ii	2.4088 (14)
Ge1—O3^i	1.7634 (14)	Ca1—O3	2.4088 (14)
Ge1—O3	1.7634 (14)	Ca2—O2^v	2.296 (2)
Ge1—O2	1.7796 (19)	Ca2—O3^vi	2.3621 (15)
Ca1—O2^ii	2.3297 (14)	Ca2—O3^vii	2.3621 (15)
Ca1—O2	2.3297 (14)	Ca2—O1^iv	2.446 (2)
Ca1—O1^iii	2.3509 (14)	Ca2—O3^i	2.4615 (15)
Ca1—O1^iv	2.3509 (14)	Ca2—O3	2.4615 (15)
O1—Ge1—O3^i	116.17 (6)	O1^iii—Ca1—O3	96.33 (6)
O1—Ge1—O3	116.17 (6)	O1^iv—Ca1—O3	83.67 (6)
O3^i—Ge1—O3	104.35 (9)	O3^ii—Ca1—O3	180
O1—Ge1—O2	113.54 (9)	O2^v—Ca2—O3^vi	89.65 (5)
O3^i—Ge1—O2	102.38 (6)	O2^v—Ca2—O3^vii	89.65 (5)
O3—Ge1—O2	102.38 (6)	O3^vi—Ca2—O3^vii	115.45 (7)
O2^ii—Ca1—O2	180	O2^v—Ca2—O1^iv	179.30 (7)
O2^ii—Ca1—O1^iii	85.29 (5)	O3^vi—Ca2—O1^iv	90.73 (4)
O2—Ca1—O1^iii	94.71 (5)	O3^vii—Ca2—O1^iv	90.73 (4)
O2^ii—Ca1—O1^iv	94.71 (5)	O2^v—Ca2—O3^i	98.81 (6)
O2—Ca1—O1^iv	85.29 (5)	O3^vi—Ca2—O3^i	87.43 (3)
O1^iii—Ca1—O1^iv	180.00 (8)	O3^vii—Ca2—O3^i	155.78 (6)
O2^ii—Ca1—O3^ii	71.25 (6)	O1^iv—Ca2—O3^i	80.62 (5)
O2—Ca1—O3^ii	108.75 (6)	O2^v—Ca2—O3	98.81 (6)
O1^iii—Ca1—O3^ii	83.67 (6)	O3^vi—Ca2—O3	155.78 (6)
O1^iv—Ca1—O3^ii	96.33 (6)	O3^vii—Ca2—O3	87.43 (3)
O2^ii—Ca1—O3	108.75 (6)	O1^iv—Ca2—O3	80.62 (5)
O2—Ca1—O3	71.25 (6)	O3^i—Ca2—O3	68.93 (7)

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

(camn_a5)

Crystal data

Ca1.14GeMn0.86O4	Dx = 4.018 Mg m^−3
Mr = 229.6	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1351 reflections
a = 11.3260 (7) Å	θ = 3.6–28.7°
b = 6.5604 (4) Å	µ = 12.21 mm^−1
c = 5.1069 (3) Å	T = 295 K
V = 379.46 (4) Å^3	Cuboid, brown
Z = 4	0.17 × 0.15 × 0.14 mm
F(000) = 433.2

Data collection

SMART APEX diffractometer	551 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.063
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.5°, θmin = 3.6°
Tmin = 0.15, Tmax = 0.18	h = −15→15
4621 measured reflections	k = −9→8
558 independent reflections	l = −7→6

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 0.2826P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.023	(Δ/σ)max < 0.001
wR(F^2) = 0.058	Δρmax = 0.68 e Å^−3
S = 1.16	Δρmin = −0.67 e Å^−3
558 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
45 parameters	Extinction coefficient: 0.0099 (15)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.41128 (3)	0.25	0.07481 (7)	0.00950 (16)
Mn1	0.5	0	0.5	0.01158 (18)	0.8
Ca1	0.5	0	0.5	0.01158 (18)	0.2
Ca2	0.22287 (6)	0.25	0.51094 (14)	0.01073 (19)	0.94
Mn2	0.22287 (6)	0.25	0.51094 (14)	0.01073 (19)	0.06
O1	0.4130 (2)	0.25	−0.2661 (5)	0.0130 (5)
O2	0.5512 (2)	0.25	0.2316 (5)	0.0131 (5)
O3	0.34395 (14)	0.0384 (3)	0.2242 (3)	0.0128 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0098 (2)	0.0105 (2)	0.0082 (2)	0	0.00012 (11)	0
Mn1	0.0131 (3)	0.0109 (3)	0.0107 (3)	0.00223 (19)	−0.0003 (2)	0.00163 (19)
Ca1	0.0131 (3)	0.0109 (3)	0.0107 (3)	0.00223 (19)	−0.0003 (2)	0.00163 (19)
Ca2	0.0097 (3)	0.0105 (3)	0.0121 (3)	0	0.0007 (2)	0
Mn2	0.0097 (3)	0.0105 (3)	0.0121 (3)	0	0.0007 (2)	0
O1	0.0156 (12)	0.0172 (12)	0.0063 (11)	0	0.0005 (8)	0
O2	0.0101 (10)	0.0165 (12)	0.0126 (12)	0	−0.0005 (9)	0
O3	0.0140 (8)	0.0117 (8)	0.0127 (9)	−0.0020 (6)	0.0017 (7)	−0.0003 (6)

Geometric parameters (Å, º)

Ge1—O1	1.741 (3)	Mn1—O3	2.2740 (17)
Ge1—O3^i	1.7582 (17)	Ca2—O2^v	2.305 (3)
Ge1—O3	1.7582 (17)	Ca2—O3^vi	2.3104 (18)
Ge1—O2	1.776 (2)	Ca2—O3^vii	2.3104 (18)
Mn1—O2^ii	2.2148 (17)	Ca2—O1^iii	2.436 (3)
Mn1—O2	2.2148 (17)	Ca2—O3	2.4397 (18)
Mn1—O1^iii	2.2553 (18)	Ca2—O3^i	2.4397 (18)
Mn1—O1^iv	2.2553 (18)	Ca2—Ca1^viii	3.5419 (6)
Mn1—O3^ii	2.2740 (17)
O1—Ge1—O3^i	116.03 (7)	O1^iii—Mn1—O3	84.73 (8)
O1—Ge1—O3	116.03 (7)	O1^iv—Mn1—O3	95.27 (8)
O3^i—Ge1—O3	104.31 (11)	O3^ii—Mn1—O3	180
O1—Ge1—O2	116.14 (11)	O2^v—Ca2—O3^vi	88.68 (6)
O3^i—Ge1—O2	101.04 (7)	O2^v—Ca2—O3^vii	88.68 (6)
O3—Ge1—O2	101.04 (7)	O3^vi—Ca2—O3^vii	109.93 (9)
O2^ii—Mn1—O2	180	O2^v—Ca2—O1^iii	175.36 (9)
O2^ii—Mn1—O1^iii	95.53 (7)	O3^vi—Ca2—O1^iii	93.97 (6)
O2—Mn1—O1^iii	84.47 (7)	O3^vii—Ca2—O1^iii	93.97 (6)
O2^ii—Mn1—O1^iv	84.47 (7)	O2^v—Ca2—O3	98.72 (7)
O2—Mn1—O1^iv	95.53 (7)	O3^vi—Ca2—O3	158.91 (7)
O1^iii—Mn1—O1^iv	180	O3^vii—Ca2—O3	90.06 (4)
O2^ii—Mn1—O3^ii	74.83 (8)	O1^iii—Ca2—O3	77.50 (7)
O2—Mn1—O3^ii	105.17 (8)	O2^v—Ca2—O3^i	98.72 (7)
O1^iii—Mn1—O3^ii	95.27 (8)	O3^vi—Ca2—O3^i	90.06 (4)
O1^iv—Mn1—O3^ii	84.73 (8)	O3^vii—Ca2—O3^i	158.91 (7)
O2^ii—Mn1—O3	105.17 (8)	O1^iii—Ca2—O3^i	77.50 (7)
O2—Mn1—O3	74.83 (8)	O3—Ca2—O3^i	69.37 (8)

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

(camn_a2)

Crystal data

Ca1.17GeMn0.83O4	Dx = 4.007 Mg m^−3
Mr = 229.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1351 reflections
a = 11.3256 (7) Å	θ = 3.6–28.7°
b = 6.5643 (4) Å	µ = 12.14 mm^−1
c = 5.1098 (3) Å	T = 295 K
V = 379.89 (4) Å^3	Cuboid, brown
Z = 4	0.18 × 0.15 × 0.14 mm
F(000) = 432.6

Data collection

SMART APEX diffractometer	548 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.058
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.5°, θmin = 3.6°
Tmin = 0.23, Tmax = 0.34	h = −15→15
4624 measured reflections	k = −8→8
555 independent reflections	l = −7→7

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0218P)^2 + 0.2627P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.021	(Δ/σ)max < 0.001
wR(F^2) = 0.050	Δρmax = 0.8 e Å^−3
S = 1.22	Δρmin = −0.65 e Å^−3
555 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
45 parameters	Extinction coefficient: 0.0288 (18)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.41100 (3)	0.25	0.07458 (6)	0.00812 (15)
Mn1	0.5	0	0.5	0.01045 (17)	0.8
Ca1	0.5	0	0.5	0.01045 (17)	0.2
Ca2	0.22281 (6)	0.25	0.51088 (13)	0.00887 (17)	0.97
Mn2	0.22281 (6)	0.25	0.51088 (13)	0.00887 (17)	0.03
O1	0.4126 (2)	0.25	−0.2649 (5)	0.0116 (5)
O2	0.5510 (2)	0.25	0.2311 (5)	0.0117 (5)
O3	0.34371 (14)	0.0381 (3)	0.2243 (3)	0.0112 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0071 (2)	0.0100 (2)	0.0073 (2)	0	0.00024 (11)	0
Mn1	0.0109 (3)	0.0105 (3)	0.0099 (3)	0.0025 (2)	−0.00007 (19)	0.00141 (18)
Ca1	0.0109 (3)	0.0105 (3)	0.0099 (3)	0.0025 (2)	−0.00007 (19)	0.00141 (18)
Ca2	0.0061 (3)	0.0096 (3)	0.0109 (3)	0	0.0008 (2)	0
Mn2	0.0061 (3)	0.0096 (3)	0.0109 (3)	0	0.0008 (2)	0
O1	0.0116 (11)	0.0174 (12)	0.0059 (10)	0	−0.0006 (8)	0
O2	0.0077 (11)	0.0149 (12)	0.0126 (11)	0	−0.0003 (9)	0
O3	0.0109 (8)	0.0112 (8)	0.0115 (8)	−0.0020 (6)	0.0007 (6)	−0.0006 (6)

Geometric parameters (Å, º)

Ge1—O1	1.735 (3)	Mn1—O3^ii	2.2760 (16)
Ge1—O3	1.7611 (17)	Mn1—O3	2.2760 (16)
Ge1—O3^i	1.7611 (17)	Ca2—O2^v	2.305 (2)
Ge1—O2	1.776 (2)	Ca2—O3^vi	2.3094 (17)
Mn1—O2	2.2169 (16)	Ca2—O3^vii	2.3094 (17)
Mn1—O2^ii	2.2169 (16)	Ca2—O1^iv	2.436 (2)
Mn1—O1^iii	2.2617 (17)	Ca2—O3	2.4401 (17)
Mn1—O1^iv	2.2617 (17)	Ca2—O3^i	2.4401 (17)
O1—Ge1—O3	116.04 (6)	O1^iii—Mn1—O3	95.24 (7)
O1—Ge1—O3^i	116.04 (6)	O1^iv—Mn1—O3	84.76 (7)
O3—Ge1—O3^i	104.36 (11)	O3^ii—Mn1—O3	180
O1—Ge1—O2	116.16 (11)	O2^v—Ca2—O3^vi	88.74 (6)
O3—Ge1—O2	100.99 (7)	O2^v—Ca2—O3^vii	88.74 (6)
O3^i—Ge1—O2	100.99 (7)	O3^vi—Ca2—O3^vii	109.94 (9)
O2—Mn1—O2^ii	180.00 (11)	O2^v—Ca2—O1^iv	175.61 (9)
O2—Mn1—O1^iii	95.39 (7)	O3^vi—Ca2—O1^iv	93.77 (5)
O2^ii—Mn1—O1^iii	84.61 (7)	O3^vii—Ca2—O1^iv	93.77 (5)
O2—Mn1—O1^iv	84.61 (7)	O2^v—Ca2—O3	98.72 (7)
O2^ii—Mn1—O1^iv	95.39 (7)	O3^vi—Ca2—O3	158.96 (7)
O1^iii—Mn1—O1^iv	180.00 (10)	O3^vii—Ca2—O3	89.98 (4)
O2—Mn1—O3^ii	105.19 (7)	O1^iv—Ca2—O3	77.70 (6)
O2^ii—Mn1—O3^ii	74.81 (7)	O2^v—Ca2—O3^i	98.72 (7)
O1^iii—Mn1—O3^ii	84.76 (7)	O3^vi—Ca2—O3^i	89.98 (4)
O1^iv—Mn1—O3^ii	95.24 (7)	O3^vii—Ca2—O3^i	158.96 (7)
O2—Mn1—O3	74.81 (7)	O1^iv—Ca2—O3^i	77.70 (6)
O2^ii—Mn1—O3	105.19 (7)	O3—Ca2—O3^i	69.52 (8)

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

(camg_a1)

Crystal data

Ca1.16GeMg0.83O4	Dx = 3.7 Mg m^−3
Mr = 203.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3945 reflections
a = 11.2916 (7) Å	θ = 3.6–28.7°
b = 6.4405 (4) Å	µ = 10.01 mm^−1
c = 5.0251 (3) Å	T = 295 K
V = 365.44 (4) Å^3	Cuboid, colourless
Z = 4	0.07 × 0.05 × 0.04 mm
F(000) = 389.1

Data collection

SMART APEX diffractometer	536 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.036
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.7°, θmin = 3.6°
Tmin = 0.55, Tmax = 0.67	h = −15→15
4411 measured reflections	k = −8→8
542 independent reflections	l = −6→7

Refinement

Refinement on F^2	43 parameters
Least-squares matrix: full	1 restraint
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0229P)^2 + 0.4844P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max < 0.001
S = 1.22	Δρmax = 0.77 e Å^−3
542 reflections	Δρmin = −0.61 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	−0.41683 (3)	0.25	0.07827 (7)	0.01143 (15)
Mg1	−0.5	0	0.5	0.0119 (2)	0.84
Ca1	−0.5	0	0.5	0.0119 (2)	0.16
Ca2	−0.22417 (6)	0.25	0.51236 (14)	0.01142 (18)
O1	−0.4184 (2)	0.25	−0.2679 (5)	0.0155 (5)
O2	−0.5548 (2)	0.25	0.2480 (5)	0.0151 (5)
O3	−0.34974 (14)	0.0350 (3)	0.2315 (3)	0.0146 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0114 (2)	0.0139 (2)	0.0090 (2)	0	−0.00049 (12)	0
Mg1	0.0131 (5)	0.0123 (5)	0.0103 (5)	−0.0022 (4)	0.0006 (4)	0.0019 (4)
Ca1	0.0131 (5)	0.0123 (5)	0.0103 (5)	−0.0022 (4)	0.0006 (4)	0.0019 (4)
Ca2	0.0101 (3)	0.0124 (3)	0.0118 (3)	0	−0.0005 (2)	0
O1	0.0173 (12)	0.0220 (13)	0.0073 (11)	0	0.0000 (9)	0
O2	0.0092 (10)	0.0209 (13)	0.0152 (11)	0	−0.0005 (9)	0
O3	0.0153 (8)	0.0139 (8)	0.0145 (8)	0.0023 (7)	−0.0022 (7)	−0.0016 (7)

Geometric parameters (Å, º)

Ge1—O1	1.740 (3)	Mg1—O1^iii	2.1914 (17)
Ge1—O3^i	1.7563 (18)	Mg1—O1^iv	2.1914 (17)
Ge1—O3	1.7563 (18)	Ca2—O3^v	2.2975 (18)
Ge1—O2	1.776 (2)	Ca2—O3^vi	2.2975 (18)
Mg1—O2^ii	2.1399 (17)	Ca2—O2^vii	2.317 (2)
Mg1—O2	2.1399 (17)	Ca2—O3	2.4330 (18)
Mg1—O3^ii	2.1793 (17)	Ca2—O3^i	2.4330 (18)
Mg1—O3	2.1793 (17)	Ca2—O1^iii	2.455 (2)
O1—Ge1—O3^i	116.28 (7)	O3^ii—Mg1—O1^iv	85.75 (8)
O1—Ge1—O3	116.28 (7)	O3—Mg1—O1^iv	94.25 (8)
O3^i—Ge1—O3	104.09 (11)	O1^iii—Mg1—O1^iv	180
O1—Ge1—O2	118.13 (11)	O3^v—Ca2—O3^vi	106.05 (9)
O3^i—Ge1—O2	99.66 (7)	O3^v—Ca2—O2^vii	88.33 (6)
O3—Ge1—O2	99.66 (7)	O3^vi—Ca2—O2^vii	88.33 (6)
O2^ii—Mg1—O2	180	O3^v—Ca2—O3	160.82 (7)
O2^ii—Mg1—O3^ii	77.35 (8)	O3^vi—Ca2—O3	92.01 (4)
O2—Mg1—O3^ii	102.65 (8)	O2^vii—Ca2—O3	98.83 (7)
O2^ii—Mg1—O3	102.65 (8)	O3^v—Ca2—O3^i	92.01 (4)
O2—Mg1—O3	77.35 (8)	O3^vi—Ca2—O3^i	160.82 (7)
O3^ii—Mg1—O3	180	O2^vii—Ca2—O3^i	98.83 (7)
O2^ii—Mg1—O1^iii	96.68 (7)	O3—Ca2—O3^i	69.39 (8)
O2—Mg1—O1^iii	83.32 (7)	O3^v—Ca2—O1^iii	96.25 (6)
O3^ii—Mg1—O1^iii	94.25 (8)	O3^vi—Ca2—O1^iii	96.25 (6)
O3—Mg1—O1^iii	85.75 (8)	O2^vii—Ca2—O1^iii	172.35 (9)
O2^ii—Mg1—O1^iv	83.32 (7)	O3—Ca2—O1^iii	74.95 (6)
O2—Mg1—O1^iv	96.68 (7)	O3^i—Ca2—O1^iii	74.95 (6)

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

(caco_a2)

Crystal data

Ca1.11Co0.89GeO4	Dx = 4.247 Mg m^−3
Mr = 233.55	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3980 reflections
a = 11.2923 (7) Å	θ = 3.6–28.7°
b = 6.4369 (4) Å	µ = 13.70 mm^−1
c = 5.0246 (3) Å	T = 295 K
V = 365.23 (4) Å^3	Cuboid, pink
Z = 4	0.14 × 0.14 × 0.10 mm
F(000) = 440.9

Data collection

SMART APEX diffractometer	516 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.038
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.6°, θmin = 3.6°
Tmin = 0.13, Tmax = 0.25	h = −15→15
4343 measured reflections	k = −8→8
530 independent reflections	l = −6→6

Refinement

Refinement on F^2	43 parameters
Least-squares matrix: full	1 restraint
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.2316P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.047	(Δ/σ)max < 0.001
S = 1.15	Δρmax = 0.70 e Å^−3
530 reflections	Δρmin = −0.62 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	−0.41832 (3)	0.25	0.07672 (7)	0.01088 (14)
Co1	−0.5	0	0.5	0.01129 (15)	0.89
Ca1	−0.5	0	0.5	0.01129 (15)	0.11
Ca2	−0.22571 (6)	0.25	0.51182 (13)	0.01147 (17)
O1	−0.41872 (19)	0.25	−0.2705 (5)	0.0145 (5)
O2	−0.55598 (19)	0.25	0.2472 (5)	0.0141 (5)
O3	−0.35015 (14)	0.0347 (3)	0.2283 (3)	0.0140 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0120 (2)	0.0120 (2)	0.0087 (2)	0	−0.00003 (11)	0
Co1	0.0125 (2)	0.0114 (2)	0.0099 (3)	−0.00141 (16)	0.00046 (16)	0.00137 (16)
Ca1	0.0125 (2)	0.0114 (2)	0.0099 (3)	−0.00141 (16)	0.00046 (16)	0.00137 (16)
Ca2	0.0109 (3)	0.0114 (3)	0.0121 (3)	0	−0.0003 (2)	0
O1	0.0164 (11)	0.0185 (12)	0.0085 (11)	0	0.0008 (8)	0
O2	0.0115 (10)	0.0180 (12)	0.0128 (11)	0	−0.0003 (9)	0
O3	0.0157 (8)	0.0124 (8)	0.0138 (8)	0.0022 (6)	−0.0010 (6)	0.0003 (6)

Geometric parameters (Å, º)

Ge1—O1	1.745 (3)	Co1—O3	2.1857 (16)
Ge1—O3^i	1.7589 (17)	Co1—O3^ii	2.1857 (16)
Ge1—O3	1.7589 (17)	Ca2—O3^v	2.2965 (17)
Ge1—O2	1.775 (2)	Ca2—O3^vi	2.2965 (17)
Co1—O2^ii	2.1453 (16)	Ca2—O2^vii	2.317 (2)
Co1—O2	2.1453 (16)	Ca2—O3	2.4344 (18)
Co1—O1^iii	2.1822 (16)	Ca2—O3^i	2.4344 (18)
Co1—O1^iv	2.1822 (16)	Ca2—O1^iii	2.439 (2)
O1—Ge1—O3^i	115.72 (7)	O1^iii—Co1—O3^ii	94.06 (7)
O1—Ge1—O3	115.72 (7)	O1^iv—Co1—O3^ii	85.94 (7)
O3^i—Ge1—O3	104.02 (11)	O3—Co1—O3^ii	180.00 (5)
O1—Ge1—O2	118.71 (10)	O3^v—Ca2—O3^vi	105.85 (9)
O3^i—Ge1—O2	100.04 (7)	O3^v—Ca2—O2^vii	87.56 (6)
O3—Ge1—O2	100.04 (7)	O3^vi—Ca2—O2^vii	87.56 (6)
O2^ii—Co1—O2	180	O3^v—Ca2—O3	161.23 (7)
O2^ii—Co1—O1^iii	96.68 (7)	O3^vi—Ca2—O3	92.19 (4)
O2—Co1—O1^iii	83.32 (7)	O2^vii—Ca2—O3	98.56 (7)
O2^ii—Co1—O1^iv	83.32 (7)	O3^v—Ca2—O3^i	92.19 (4)
O2—Co1—O1^iv	96.68 (7)	O3^vi—Ca2—O3^i	161.23 (7)
O1^iii—Co1—O1^iv	180.00 (10)	O2^vii—Ca2—O3^i	98.56 (7)
O2^ii—Co1—O3	102.61 (8)	O3—Ca2—O3^i	69.42 (8)
O2—Co1—O3	77.39 (8)	O3^v—Ca2—O1^iii	96.95 (6)
O1^iii—Co1—O3	85.94 (8)	O3^vi—Ca2—O1^iii	96.95 (6)
O1^iv—Co1—O3	94.06 (7)	O2^vii—Ca2—O1^iii	172.47 (9)
O2^ii—Co1—O3^ii	77.39 (8)	O3—Ca2—O1^iii	75.32 (6)
O2—Co1—O3^ii	102.61 (8)	O3^i—Ca2—O1^iii	75.32 (6)

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

(caco_a1)

Crystal data

Ca1.11Co0.89GeO4	Dx = 4.249 Mg m^−3
Mr = 233.55	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4315 reflections
a = 11.2873 (7) Å	θ = 3.6–28.7°
b = 6.4369 (4) Å	µ = 13.71 mm^−1
c = 5.0245 (3) Å	T = 295 K
V = 365.06 (4) Å^3	Cuboid, pink
Z = 4	0.13 × 0.12 × 0.09 mm
F(000) = 441

Data collection

SMART APEX diffractometer	528 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.040
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 29.3°, θmin = 3.6°
Tmin = 0.19, Tmax = 0.30	h = −15→15
4315 measured reflections	k = −8→8
531 independent reflections	l = −6→6

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0183P)^2 + 1.0355P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.021	(Δ/σ)max < 0.001
wR(F^2) = 0.049	Δρmax = 0.66 e Å^−3
S = 1.20	Δρmin = −0.58 e Å^−3
531 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.0090 (10)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	−0.41844 (3)	0.25	0.07673 (8)	0.01049 (15)
Co1	−0.5	0	0.5	0.01082 (16)	0.89
Ca1	−0.5	0	0.5	0.01082 (16)	0.11
Ca2	−0.22573 (7)	0.25	0.51180 (15)	0.01130 (18)
O1	−0.4189 (2)	0.25	−0.2707 (5)	0.0138 (5)
O2	−0.5563 (2)	0.25	0.2470 (6)	0.0136 (5)
O3	−0.35020 (16)	0.0345 (3)	0.2283 (4)	0.0138 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0122 (2)	0.0102 (2)	0.0091 (2)	0	−0.00011 (13)	0
Co1	0.0129 (3)	0.0095 (3)	0.0101 (3)	−0.00137 (19)	0.00060 (17)	0.00125 (18)
Ca1	0.0129 (3)	0.0095 (3)	0.0101 (3)	−0.00137 (19)	0.00060 (17)	0.00125 (18)
Ca2	0.0114 (3)	0.0101 (3)	0.0124 (4)	0	−0.0004 (3)	0
O1	0.0167 (13)	0.0181 (13)	0.0066 (11)	0	0.0005 (10)	0
O2	0.0120 (11)	0.0160 (13)	0.0128 (12)	0	0.0000 (10)	0
O3	0.0163 (8)	0.0106 (8)	0.0145 (9)	0.0025 (7)	−0.0009 (7)	−0.0002 (7)

Geometric parameters (Å, º)

Ge1—O1	1.746 (3)	Co1—O3	2.1845 (19)
Ge1—O3^i	1.7599 (19)	Co1—O3^ii	2.1845 (19)
Ge1—O3	1.7599 (19)	Ca2—O3^v	2.2962 (19)
Ge1—O2	1.775 (3)	Ca2—O3^vi	2.2962 (19)
Co1—O2	2.1467 (19)	Ca2—O2^vii	2.313 (3)
Co1—O2^ii	2.1467 (19)	Ca2—O3	2.434 (2)
Co1—O1^iii	2.1804 (18)	Ca2—O3^i	2.434 (2)
Co1—O1^iv	2.1804 (18)	Ca2—O1^iv	2.439 (3)
O1—Ge1—O3^i	115.73 (8)	O1^iii—Co1—O3^ii	86.01 (9)
O1—Ge1—O3	115.73 (8)	O1^iv—Co1—O3^ii	93.99 (9)
O3^i—Ge1—O3	104.02 (13)	O3—Co1—O3^ii	180.00 (6)
O1—Ge1—O2	118.63 (13)	O3^v—Ca2—O3^vi	105.81 (10)
O3^i—Ge1—O2	100.07 (8)	O3^v—Ca2—O2^vii	87.58 (7)
O3—Ge1—O2	100.07 (8)	O3^vi—Ca2—O2^vii	87.58 (7)
O2—Co1—O2^ii	180	O3^v—Ca2—O3	161.27 (8)
O2—Co1—O1^iii	96.68 (8)	O3^vi—Ca2—O3	92.19 (4)
O2^ii—Co1—O1^iii	83.32 (8)	O2^vii—Ca2—O3	98.53 (8)
O2—Co1—O1^iv	83.32 (8)	O3^v—Ca2—O3^i	92.19 (4)
O2^ii—Co1—O1^iv	96.68 (8)	O3^vi—Ca2—O3^i	161.27 (8)
O1^iii—Co1—O1^iv	180.00 (12)	O2^vii—Ca2—O3^i	98.53 (8)
O2—Co1—O3	77.45 (9)	O3—Ca2—O3^i	69.46 (9)
O2^ii—Co1—O3	102.55 (9)	O3^v—Ca2—O1^iv	96.98 (7)
O1^iii—Co1—O3	93.99 (9)	O3^vi—Ca2—O1^iv	96.98 (7)
O1^iv—Co1—O3	86.01 (9)	O2^vii—Ca2—O1^iv	172.40 (10)
O2—Co1—O3^ii	102.55 (9)	O3—Ca2—O1^iv	75.30 (7)
O2^ii—Co1—O3^ii	77.45 (9)	O3^i—Ca2—O1^iv	75.30 (7)

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

(ca2mn_1)

Crystal data

Ca1.31GeMn0.69O4	Dx = 3.924 Mg m^−3
Mr = 227.02	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4305 reflections
a = 11.3391 (7) Å	θ = 3.6–28.7°
b = 6.6035 (4) Å	µ = 11.74 mm^−1
c = 5.1326 (3) Å	T = 295 K
V = 384.32 (4) Å^3	Cuboid, brown
Z = 4	0.14 × 0.12 × 0.11 mm
F(000) = 429.8

Data collection

SMART APEX diffractometer	510 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.054
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 28.4°, θmin = 3.6°
Tmin = 0.21, Tmax = 0.27	h = −14→15
4316 measured reflections	k = −8→8
517 independent reflections	l = −6→6

Refinement

Refinement on F^2	44 parameters
Least-squares matrix: full	2 restraints
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0157P)^2 + 0.6189P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.045	(Δ/σ)max < 0.001
S = 1.24	Δρmax = 0.78 e Å^−3
517 reflections	Δρmin = −0.96 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.41000 (3)	0.25	0.07392 (7)	0.01007 (14)
Mn1	0.5	0	0.5	0.01205 (17)	0.67
Ca1	0.5	0	0.5	0.01205 (17)	0.33
Ca2	0.22236 (6)	0.25	0.51037 (14)	0.01080 (18)	0.98
Mn2	0.22236 (6)	0.25	0.51037 (14)	0.01080 (18)	0.02
O1	0.4122 (2)	0.25	−0.2640 (5)	0.0132 (5)
O2	0.5499 (2)	0.25	0.2284 (5)	0.0139 (5)
O3	0.34278 (15)	0.0396 (3)	0.2232 (3)	0.0135 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0105 (2)	0.0119 (2)	0.0079 (2)	0	0.00037 (13)	0
Mn1	0.0139 (3)	0.0120 (3)	0.0103 (3)	0.0027 (2)	0.0000 (2)	0.0015 (2)
Ca1	0.0139 (3)	0.0120 (3)	0.0103 (3)	0.0027 (2)	0.0000 (2)	0.0015 (2)
Ca2	0.0097 (3)	0.0113 (3)	0.0113 (3)	0	0.0006 (3)	0
Mn2	0.0097 (3)	0.0113 (3)	0.0113 (3)	0	0.0006 (3)	0
O1	0.0134 (12)	0.0190 (13)	0.0072 (11)	0	−0.0006 (9)	0
O2	0.0101 (11)	0.0196 (12)	0.0121 (12)	0	−0.0004 (10)	0
O3	0.0139 (8)	0.0132 (8)	0.0132 (9)	−0.0019 (7)	0.0015 (7)	−0.0005 (7)

Geometric parameters (Å, º)

Ge1—O1	1.735 (3)	Mn1—O3^ii	2.2945 (18)
Ge1—O3	1.7605 (18)	Mn1—O3	2.2945 (18)
Ge1—O3^i	1.7605 (18)	Ca2—O2^v	2.308 (3)
Ge1—O2	1.773 (3)	Ca2—O3^vi	2.3227 (18)
Mn1—O2^ii	2.2335 (17)	Ca2—O3^vii	2.3227 (18)
Mn1—O2	2.2335 (17)	Ca2—O3	2.4430 (18)
Mn1—O1^iii	2.2770 (17)	Ca2—O3^i	2.4430 (18)
Mn1—O1^iv	2.2770 (17)	Ca2—O1^iv	2.444 (3)
O1—Ge1—O3	116.19 (7)	O1^iii—Mn1—O3	95.34 (8)
O1—Ge1—O3^i	116.19 (7)	O1^iv—Mn1—O3	84.66 (8)
O3—Ge1—O3^i	104.26 (11)	O3^ii—Mn1—O3	180
O1—Ge1—O2	115.75 (12)	O2^v—Ca2—O3^vi	88.87 (6)
O3—Ge1—O2	101.11 (8)	O2^v—Ca2—O3^vii	88.87 (6)
O3^i—Ge1—O2	101.11 (8)	O3^vi—Ca2—O3^vii	110.82 (9)
O2^ii—Mn1—O2	180	O2^v—Ca2—O3	98.82 (7)
O2^ii—Mn1—O1^iii	84.66 (7)	O3^vi—Ca2—O3	158.40 (7)
O2—Mn1—O1^iii	95.34 (7)	O3^vii—Ca2—O3	89.61 (4)
O2^ii—Mn1—O1^iv	95.34 (7)	O2^v—Ca2—O3^i	98.82 (7)
O2—Mn1—O1^iv	84.66 (7)	O3^vi—Ca2—O3^i	89.61 (4)
O1^iii—Mn1—O1^iv	180.00 (11)	O3^vii—Ca2—O3^i	158.40 (7)
O2^ii—Mn1—O3^ii	74.11 (8)	O3—Ca2—O3^i	69.34 (9)
O2—Mn1—O3^ii	105.89 (8)	O2^v—Ca2—O1^iv	176.21 (9)
O1^iii—Mn1—O3^ii	84.66 (8)	O3^vi—Ca2—O1^iv	93.28 (6)
O1^iv—Mn1—O3^ii	95.34 (8)	O3^vii—Ca2—O1^iv	93.28 (6)
O2^ii—Mn1—O3	105.89 (8)	O3—Ca2—O1^iv	78.09 (7)
O2—Mn1—O3	74.11 (8)	O3^i—Ca2—O1^iv	78.09 (7)

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

(ca2mg_1)

Crystal data

GeO4·1.07(Ca)0.93(Mg)	Dx = 3.682 Mg m^−3
Mr = 202.04	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3967 reflections
a = 11.2882 (7) Å	θ = 3.6–28.7°
b = 6.4309 (4) Å	µ = 9.92 mm^−1
c = 5.0223 (3) Å	T = 295 K
V = 364.59 (4) Å^3	Cube, colourless
Z = 4	0.08 × 0.07 × 0.07 mm
F(000) = 386.2

Data collection

SMART APEX diffractometer	476 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.097
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 28.3°, θmin = 3.6°
Tmin = 0.46, Tmax = 0.50	h = −14→15
3967 measured reflections	k = −8→8
487 independent reflections	l = −6→6

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0238P)^2 + 0.2954P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.026	(Δ/σ)max < 0.001
wR(F^2) = 0.054	Δρmax = 0.74 e Å^−3
S = 1.16	Δρmin = −1.37 e Å^−3
487 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
45 parameters	Extinction coefficient: 0.0044 (15)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.41756 (3)	0.25	0.07864 (7)	0.01020 (17)
Mg1	0.5	0	0.5	0.0105 (3)	0.91
Ca1	0.5	0	0.5	0.0105 (3)	0.09
Ca2	0.22438 (6)	0.25	0.51245 (14)	0.0100 (2)	0.98
Mg2	0.22438 (6)	0.25	0.51245 (14)	0.0100 (2)	0.02
O1	0.41885 (19)	0.25	−0.2675 (5)	0.0138 (6)
O2	0.5554 (2)	0.25	0.2497 (5)	0.0141 (5)
O3	0.35056 (14)	0.0347 (3)	0.2323 (3)	0.0134 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0099 (2)	0.0126 (3)	0.0081 (2)	0	0.00034 (11)	0
Mg1	0.0111 (5)	0.0115 (6)	0.0088 (5)	0.0018 (4)	−0.0004 (4)	0.0023 (4)
Ca1	0.0111 (5)	0.0115 (6)	0.0088 (5)	0.0018 (4)	−0.0004 (4)	0.0023 (4)
Ca2	0.0081 (3)	0.0112 (4)	0.0108 (4)	0	0.0002 (2)	0
Mg2	0.0081 (3)	0.0112 (4)	0.0108 (4)	0	0.0002 (2)	0
O1	0.0136 (12)	0.0192 (15)	0.0085 (10)	0	0.0003 (8)	0
O2	0.0100 (10)	0.0200 (14)	0.0124 (11)	0	0.0011 (9)	0
O3	0.0136 (8)	0.0125 (9)	0.0140 (8)	−0.0019 (7)	0.0016 (6)	−0.0010 (7)

Geometric parameters (Å, º)

Ge1—O1	1.739 (3)	Mg1—O1^iii	2.1879 (16)
Ge1—O3^i	1.7561 (19)	Mg1—O1^iv	2.1879 (16)
Ge1—O3	1.7561 (19)	Ca2—O3^v	2.2996 (19)
Ge1—O2	1.778 (2)	Ca2—O3^vi	2.2996 (19)
Mg1—O2^ii	2.1347 (16)	Ca2—O2^vii	2.317 (2)
Mg1—O2	2.1347 (16)	Ca2—O3	2.4340 (18)
Mg1—O3	2.1686 (16)	Ca2—O3^i	2.4340 (18)
Mg1—O3^ii	2.1686 (16)	Ca2—O1^iii	2.458 (2)
O1—Ge1—O3^i	116.30 (7)	O3—Mg1—O1^iv	94.05 (8)
O1—Ge1—O3	116.30 (7)	O3^ii—Mg1—O1^iv	85.95 (8)
O3^i—Ge1—O3	104.05 (12)	O1^iii—Mg1—O1^iv	180
O1—Ge1—O2	118.41 (11)	O3^v—Ca2—O3^vi	105.55 (9)
O3^i—Ge1—O2	99.48 (7)	O3^v—Ca2—O2^vii	88.28 (6)
O3—Ge1—O2	99.48 (7)	O3^vi—Ca2—O2^vii	88.28 (6)
O2^ii—Mg1—O2	180	O3^v—Ca2—O3	161.04 (7)
O2^ii—Mg1—O3	102.40 (8)	O3^vi—Ca2—O3	92.29 (4)
O2—Mg1—O3	77.60 (8)	O2^vii—Ca2—O3	98.82 (7)
O2^ii—Mg1—O3^ii	77.60 (8)	O3^v—Ca2—O3^i	92.29 (4)
O2—Mg1—O3^ii	102.40 (8)	O3^vi—Ca2—O3^i	161.04 (7)
O3—Mg1—O3^ii	180	O2^vii—Ca2—O3^i	98.82 (7)
O2^ii—Mg1—O1^iii	96.69 (7)	O3—Ca2—O3^i	69.32 (9)
O2—Mg1—O1^iii	83.31 (7)	O3^v—Ca2—O1^iii	96.47 (6)
O3—Mg1—O1^iii	85.95 (8)	O3^vi—Ca2—O1^iii	96.47 (6)
O3^ii—Mg1—O1^iii	94.05 (8)	O2^vii—Ca2—O1^iii	172.11 (9)
O2^ii—Mg1—O1^iv	83.31 (7)	O3—Ca2—O1^iii	74.76 (6)
O2—Mg1—O1^iv	96.69 (7)	O3^i—Ca2—O1^iii	74.76 (6)

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

(ca2ge_1)

Crystal data

GeO4·2.00(Ca)	Dx = 3.555 Mg m^−3
Mr = 216.69	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4351 reflections
a = 11.3923 (8) Å	θ = 3.6–28.7°
b = 6.7854 (8) Å	µ = 9.97 mm^−1
c = 5.2388 (4) Å	T = 295 K
V = 404.97 (6) Å^3	Cuboid, colourless
Z = 4	0.16 × 0.15 × 0.13 mm
F(000) = 416

Data collection

SMART APEX diffractometer	533 reflections with I > 2σ(I)
rotation, ω–scans at 4 different ϕ positions	Rint = 0.084
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996)	θmax = 28.3°, θmin = 3.6°
Tmin = 0.22, Tmax = 0.28	h = −15→15
4496 measured reflections	k = −8→9
536 independent reflections	l = −6→6

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.8056P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.024	(Δ/σ)max < 0.001
wR(F^2) = 0.063	Δρmax = 0.92 e Å^−3
S = 1.21	Δρmin = −0.94 e Å^−3
536 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
43 parameters	Extinction coefficient: 0.55 (2)

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ge1	0.40386 (4)	0.25	0.06914 (8)	0.0074 (3)
Ca1	0.5	0	0.5	0.0096 (4)	0.999 (5)
Ca2	0.22020 (7)	0.25	0.50764 (16)	0.0092 (4)	1.00 (5)
O1	0.4071 (2)	0.25	−0.2640 (6)	0.0098 (6)
O2	0.5459 (2)	0.25	0.2119 (6)	0.0099 (6)
O3	0.33635 (17)	0.0444 (3)	0.2152 (4)	0.0102 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge1	0.0057 (3)	0.0080 (3)	0.0084 (3)	0	0.00006 (14)	0
Ca1	0.0099 (5)	0.0079 (5)	0.0110 (5)	0.0017 (3)	−0.0004 (3)	0.0006 (3)
Ca2	0.0059 (5)	0.0094 (5)	0.0124 (5)	0	0.0002 (3)	0
O1	0.0103 (14)	0.0119 (14)	0.0070 (14)	0	0.0007 (10)	0
O2	0.0069 (13)	0.0116 (14)	0.0111 (13)	0	0.0004 (11)	0
O3	0.0096 (9)	0.0095 (9)	0.0116 (9)	−0.0019 (7)	0.0008 (8)	0.0013 (8)

Geometric parameters (Å, º)

Ge1—O1	1.746 (3)	Ca1—O3^ii	2.407 (2)
Ge1—O3	1.767 (2)	Ca1—O3	2.407 (2)
Ge1—O3^i	1.767 (2)	Ca2—O2^v	2.295 (3)
Ge1—O2	1.782 (3)	Ca2—O3^vi	2.364 (2)
Ca1—O2	2.330 (2)	Ca2—O3^vii	2.364 (2)
Ca1—O2^ii	2.330 (2)	Ca2—O1^iv	2.443 (3)
Ca1—O1^iii	2.351 (2)	Ca2—O3	2.458 (2)
Ca1—O1^iv	2.351 (2)	Ca2—O3^i	2.458 (2)
O1—Ge1—O3	116.25 (8)	O1^iii—Ca1—O3	96.49 (9)
O1—Ge1—O3^i	116.25 (8)	O1^iv—Ca1—O3	83.51 (9)
O3—Ge1—O3^i	104.25 (14)	O3^ii—Ca1—O3	180
O1—Ge1—O2	113.59 (13)	O2^v—Ca2—O3^vi	89.69 (7)
O3—Ge1—O2	102.32 (9)	O2^v—Ca2—O3^vii	89.69 (7)
O3^i—Ge1—O2	102.32 (9)	O3^vi—Ca2—O3^vii	115.36 (11)
O2—Ca1—O2^ii	180	O2^v—Ca2—O1^iv	179.26 (11)
O2—Ca1—O1^iii	94.80 (8)	O3^vi—Ca2—O1^iv	90.70 (7)
O2^ii—Ca1—O1^iii	85.20 (8)	O3^vii—Ca2—O1^iv	90.70 (7)
O2—Ca1—O1^iv	85.20 (8)	O2^v—Ca2—O3	98.83 (8)
O2^ii—Ca1—O1^iv	94.80 (8)	O3^vi—Ca2—O3	155.89 (8)
O1^iii—Ca1—O1^iv	180.00 (12)	O3^vii—Ca2—O3	87.36 (4)
O2—Ca1—O3^ii	108.61 (9)	O1^iv—Ca2—O3	80.56 (8)
O2^ii—Ca1—O3^ii	71.39 (9)	O2^v—Ca2—O3^i	98.83 (8)
O1^iii—Ca1—O3^ii	83.51 (9)	O3^vi—Ca2—O3^i	87.36 (4)
O1^iv—Ca1—O3^ii	96.49 (9)	O3^vii—Ca2—O3^i	155.89 (8)
O2—Ca1—O3	71.39 (9)	O1^iv—Ca2—O3^i	80.56 (8)
O2^ii—Ca1—O3	108.61 (9)	O3—Ca2—O3^i	69.13 (10)

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