Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108010434/ws5059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059Ca2Co_2sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059cfg_rotsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059cazn_bsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059camn_a5sup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059camn_a2sup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059camg_a1sup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059caco_a2sup8.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059caco_a1sup9.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059ca2mn_1sup10.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059ca2mg_1sup11.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108768108010434/ws5059ca2ge_1sup12.hkl |
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.
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) Å3 | Cuboid, pink |
Z = 4 | 0.18 × 0.16 × 0.13 mm |
F(000) = 439.2 |
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 on F2 | 2 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.3685P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.029 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
45 parameters | Extinction coefficient: 0.066 (5) |
Ca1.17Co0.83GeO4 | V = 368.56 (4) Å3 |
Mr = 232.4 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3021 (7) Å | µ = 13.40 mm−1 |
b = 6.4657 (4) Å | T = 295 K |
c = 5.0435 (3) Å | 0.18 × 0.16 × 0.13 mm |
SMART APEX diffractometer | 507 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 504 reflections with I > 2σ(I) |
Tmin = 0.10, Tmax = 0.18 | Rint = 0.062 |
4087 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 45 parameters |
wR(F2) = 0.070 | 2 restraints |
S = 1.36 | Δρmax = 0.98 e Å−3 |
507 reflections | Δρmin = −1.68 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.746 (4) | Ca2—O3v | 2.301 (2) |
Ge1—O3i | 1.762 (2) | Ca2—O3vi | 2.301 (2) |
Ge1—O3 | 1.762 (2) | Ca2—O2vii | 2.310 (3) |
Ge1—O2 | 1.778 (3) | Ca2—O3 | 2.435 (2) |
Co1—O2ii | 2.162 (2) | Ca2—O3i | 2.435 (2) |
Co1—O2 | 2.162 (2) | Ca2—O1iii | 2.439 (3) |
Co1—O1iii | 2.197 (2) | Ca2—Ca1viii | 3.5033 (7) |
Co1—O1iv | 2.197 (2) | Ca2—Co1viii | 3.5033 (7) |
Co1—O3 | 2.203 (2) | Ca2—Ge1vii | 3.5104 (10) |
Co1—O3ii | 2.203 (2) | ||
O1—Ge1—O3i | 115.90 (9) | O1iii—Co1—O3ii | 94.39 (10) |
O1—Ge1—O3 | 115.90 (9) | O1iv—Co1—O3ii | 85.61 (10) |
O3i—Ge1—O3 | 103.91 (14) | O3—Co1—O3ii | 180 |
O1—Ge1—O2 | 118.13 (14) | O3v—Ca2—O3vi | 106.62 (12) |
O3i—Ge1—O2 | 100.22 (9) | O3v—Ca2—O2vii | 87.89 (7) |
O3—Ge1—O2 | 100.22 (9) | O3vi—Ca2—O2vii | 87.89 (7) |
O2ii—Co1—O2 | 180 | O3v—Ca2—O3 | 91.73 (5) |
O2ii—Co1—O1iii | 96.41 (9) | O3vi—Ca2—O3 | 160.79 (9) |
O2—Co1—O1iii | 83.59 (9) | O2vii—Ca2—O3 | 98.61 (9) |
O2ii—Co1—O1iv | 83.59 (9) | O3v—Ca2—O3i | 160.79 (9) |
O2—Co1—O1iv | 96.41 (9) | O3vi—Ca2—O3i | 91.73 (5) |
O1iii—Co1—O1iv | 180 | O2vii—Ca2—O3i | 98.61 (9) |
O2ii—Co1—O3 | 103.02 (10) | O3—Ca2—O3i | 69.50 (10) |
O2—Co1—O3 | 76.98 (10) | O3v—Ca2—O1iii | 96.29 (8) |
O1iii—Co1—O3 | 85.61 (10) | O3vi—Ca2—O1iii | 96.29 (8) |
O1iv—Co1—O3 | 94.39 (10) | O2vii—Ca2—O1iii | 172.97 (12) |
O2ii—Co1—O3ii | 76.98 (10) | O3—Ca2—O1iii | 75.67 (9) |
O2—Co1—O3ii | 103.02 (10) | O3i—Ca2—O1iii | 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. |
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) Å3 | 0.16 × 0.14 × 0.13 mm |
Z = 4 |
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 on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0136P)2 + 0.4447P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.019 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
41 parameters | Extinction coefficient: 0.063 (3) |
Ca2GeO4 | V = 404.91 (4) Å3 |
Mr = 216.75 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3919 (7) Å | µ = 9.97 mm−1 |
b = 6.7800 (4) Å | T = 293 K |
c = 5.2424 (3) Å | 0.16 × 0.14 × 0.13 mm |
4592 measured reflections | 544 reflections with I > 2σ(I) |
551 independent reflections | Rint = 0.057 |
R[F2 > 2σ(F2)] = 0.019 | 41 parameters |
wR(F2) = 0.042 | 0 restraints |
S = 1.25 | Δρmax = 0.83 e Å−3 |
551 reflections | Δρmin = −0.39 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.742 (2) | Ca1—Ca1ii | 3.3900 (2) |
Ge1—O3 | 1.7642 (14) | Ca1—Ge1viii | 3.6025 (3) |
Ge1—O3i | 1.7642 (14) | Ca1—Ge1ix | 3.6025 (3) |
Ge1—O2 | 1.780 (2) | Ca2—O2xi | 2.297 (2) |
Ge1—Ca1ii | 3.0282 (3) | Ca2—O3xii | 2.3621 (15) |
Ge1—Ca1 | 3.0282 (3) | Ca2—O3xiii | 2.3621 (15) |
Ge1—Ca2 | 3.1090 (6) | Ca2—O1ix | 2.449 (2) |
Ge1—Ca1iii | 3.6025 (3) | Ca2—O3i | 2.4597 (15) |
Ge1—Ca1iv | 3.6025 (3) | Ca2—O3 | 2.4597 (15) |
Ge1—Ca2iii | 3.6125 (7) | Ca2—Ca1ii | 3.6112 (5) |
Ge1—Ca2v | 3.6248 (7) | Ca2—Ge1ix | 3.6125 (7) |
Ge1—Ca2vi | 3.6868 (3) | Ca2—Ge1xi | 3.6248 (7) |
Ca1—O2 | 2.3293 (14) | Ca2—Ge1xiii | 3.6868 (3) |
Ca1—O2vii | 2.3293 (14) | O1—Ca1iii | 2.3515 (14) |
Ca1—O1viii | 2.3515 (14) | O1—Ca1iv | 2.3515 (14) |
Ca1—O1ix | 2.3515 (14) | O1—Ca2iii | 2.449 (2) |
Ca1—O3vii | 2.4105 (14) | O2—Ca2v | 2.297 (2) |
Ca1—O3 | 2.4105 (14) | O2—Ca1ii | 2.3293 (14) |
Ca1—Ge1vii | 3.0282 (3) | O3—Ca2vi | 2.3621 (15) |
Ca1—Ca1x | 3.3900 (2) | ||
O1—Ge1—O3 | 116.21 (6) | Ge1—Ca1—Ca1ii | 55.963 (4) |
O1—Ge1—O3i | 116.21 (6) | Ge1vii—Ca1—Ca1ii | 124.037 (4) |
O3—Ge1—O3i | 104.21 (9) | Ca1x—Ca1—Ca1ii | 180 |
O1—Ge1—O2 | 113.53 (9) | O2—Ca1—Ge1viii | 74.77 (4) |
O3—Ge1—O2 | 102.42 (6) | O2vii—Ca1—Ge1viii | 105.23 (4) |
O3i—Ge1—O2 | 102.42 (6) | O1viii—Ca1—Ge1viii | 24.05 (5) |
O1—Ge1—Ca1ii | 137.49 (4) | O1ix—Ca1—Ge1viii | 155.95 (5) |
O3—Ge1—Ca1ii | 106.12 (5) | O3vii—Ca1—Ge1viii | 102.71 (3) |
O3i—Ge1—Ca1ii | 52.72 (5) | O3—Ca1—Ge1viii | 77.29 (3) |
O2—Ge1—Ca1ii | 50.11 (4) | Ge1—Ca1—Ge1viii | 75.848 (6) |
O1—Ge1—Ca1 | 137.49 (4) | Ge1vii—Ca1—Ge1viii | 104.152 (6) |
O3—Ge1—Ca1 | 52.72 (5) | Ca1x—Ca1—Ge1viii | 61.933 (3) |
O3i—Ge1—Ca1 | 106.12 (5) | Ca1ii—Ca1—Ge1viii | 118.067 (3) |
O2—Ge1—Ca1 | 50.11 (4) | O2—Ca1—Ge1ix | 105.23 (4) |
Ca1ii—Ge1—Ca1 | 68.074 (7) | O2vii—Ca1—Ge1ix | 74.77 (4) |
O1—Ge1—Ca2 | 138.98 (7) | O1viii—Ca1—Ge1ix | 155.95 (5) |
O3—Ge1—Ca2 | 52.17 (5) | O1ix—Ca1—Ge1ix | 24.05 (5) |
O3i—Ge1—Ca2 | 52.17 (5) | O3vii—Ca1—Ge1ix | 77.29 (3) |
O2—Ge1—Ca2 | 107.49 (7) | O3—Ca1—Ge1ix | 102.71 (3) |
Ca1ii—Ge1—Ca2 | 72.074 (11) | Ge1—Ca1—Ge1ix | 104.152 (6) |
Ca1—Ge1—Ca2 | 72.074 (11) | Ge1vii—Ca1—Ge1ix | 75.848 (6) |
O1—Ge1—Ca1iii | 33.37 (3) | Ca1x—Ca1—Ge1ix | 118.067 (3) |
O3—Ge1—Ca1iii | 96.84 (5) | Ca1ii—Ca1—Ge1ix | 61.933 (3) |
O3i—Ge1—Ca1iii | 149.51 (5) | Ge1viii—Ca1—Ge1ix | 180.000 (10) |
O2—Ge1—Ca1iii | 94.14 (6) | O2xi—Ca2—O3xii | 89.71 (5) |
Ca1ii—Ge1—Ca1iii | 140.463 (10) | O2xi—Ca2—O3xiii | 89.71 (5) |
Ca1—Ge1—Ca1iii | 104.152 (6) | O3xii—Ca2—O3xiii | 115.51 (8) |
Ca2—Ge1—Ca1iii | 144.792 (9) | O2xi—Ca2—O1ix | 179.32 (7) |
O1—Ge1—Ca1iv | 33.37 (3) | O3xii—Ca2—O1ix | 90.66 (5) |
O3—Ge1—Ca1iv | 149.51 (5) | O3xiii—Ca2—O1ix | 90.66 (5) |
O3i—Ge1—Ca1iv | 96.84 (5) | O2xi—Ca2—O3i | 98.76 (6) |
O2—Ge1—Ca1iv | 94.14 (6) | O3xii—Ca2—O3i | 87.38 (3) |
Ca1ii—Ge1—Ca1iv | 104.152 (6) | O3xiii—Ca2—O3i | 155.75 (6) |
Ca1—Ge1—Ca1iv | 140.463 (10) | O1ix—Ca2—O3i | 80.68 (5) |
Ca2—Ge1—Ca1iv | 144.792 (9) | O2xi—Ca2—O3 | 98.76 (6) |
Ca1iii—Ge1—Ca1iv | 56.134 (6) | O3xii—Ca2—O3 | 155.75 (6) |
O1—Ge1—Ca2iii | 36.73 (7) | O3xiii—Ca2—O3 | 87.38 (3) |
O3—Ge1—Ca2iii | 95.66 (5) | O1ix—Ca2—O3 | 80.68 (5) |
O3i—Ge1—Ca2iii | 95.66 (5) | O3i—Ca2—O3 | 68.94 (7) |
O2—Ge1—Ca2iii | 150.26 (7) | O2xi—Ca2—Ge1 | 102.25 (5) |
Ca1ii—Ge1—Ca2iii | 144.804 (5) | O3xii—Ca2—Ge1 | 121.50 (4) |
Ca1—Ge1—Ca2iii | 144.804 (5) | O3xiii—Ca2—Ge1 | 121.50 (4) |
Ca2—Ge1—Ca2iii | 102.250 (18) | O1ix—Ca2—Ge1 | 77.07 (5) |
Ca1iii—Ge1—Ca2iii | 60.067 (9) | O3i—Ca2—Ge1 | 34.50 (3) |
Ca1iv—Ge1—Ca2iii | 60.067 (9) | O3—Ca2—Ge1 | 34.50 (3) |
O1—Ge1—Ca2v | 82.30 (7) | O2xi—Ca2—Ca1ii | 139.33 (4) |
O3—Ge1—Ca2v | 118.83 (5) | O3xii—Ca2—Ca1ii | 81.27 (4) |
O3i—Ge1—Ca2v | 118.83 (5) | O3xiii—Ca2—Ca1ii | 129.95 (4) |
O2—Ge1—Ca2v | 31.23 (7) | O1ix—Ca2—Ca1ii | 40.21 (3) |
Ca1ii—Ge1—Ca2v | 73.963 (9) | O3i—Ca2—Ca1ii | 41.62 (3) |
Ca1—Ge1—Ca2v | 73.963 (9) | O3—Ca2—Ca1ii | 77.51 (4) |
Ca2—Ge1—Ca2v | 138.723 (13) | Ge1—Ca2—Ca1ii | 52.926 (10) |
Ca1iii—Ge1—Ca2v | 66.782 (9) | O2xi—Ca2—Ca1 | 139.33 (4) |
Ca1iv—Ge1—Ca2v | 66.782 (9) | O3xii—Ca2—Ca1 | 129.95 (4) |
Ca2iii—Ge1—Ca2v | 119.027 (11) | O3xiii—Ca2—Ca1 | 81.27 (4) |
O1—Ge1—Ca2vi | 85.48 (3) | O1ix—Ca2—Ca1 | 40.21 (3) |
O3—Ge1—Ca2vi | 31.21 (5) | O3i—Ca2—Ca1 | 77.51 (4) |
O3i—Ge1—Ca2vi | 126.59 (5) | O3—Ca2—Ca1 | 41.62 (3) |
O2—Ge1—Ca2vi | 112.615 (11) | Ge1—Ca2—Ca1 | 52.926 (9) |
Ca1ii—Ge1—Ca2vi | 135.930 (12) | Ca1ii—Ca2—Ca1 | 55.987 (9) |
Ca1—Ge1—Ca2vi | 71.889 (9) | O2xi—Ca2—Ge1ix | 155.50 (5) |
Ca2—Ge1—Ca2vi | 78.853 (7) | O3xii—Ca2—Ge1ix | 77.49 (4) |
Ca1iii—Ge1—Ca2vi | 67.126 (9) | O3xiii—Ca2—Ge1ix | 77.49 (4) |
Ca1iv—Ge1—Ca2vi | 118.461 (11) | O1ix—Ca2—Ge1ix | 25.18 (5) |
Ca2iii—Ge1—Ca2vi | 72.937 (8) | O3i—Ca2—Ge1ix | 101.39 (4) |
Ca2v—Ge1—Ca2vi | 111.781 (9) | O3—Ca2—Ge1ix | 101.39 (4) |
O2—Ca1—O2vii | 180 | Ge1—Ca2—Ge1ix | 102.250 (18) |
O2—Ca1—O1viii | 94.69 (5) | Ca1ii—Ca2—Ge1ix | 59.828 (10) |
O2vii—Ca1—O1viii | 85.31 (5) | Ca1—Ca2—Ge1ix | 59.828 (10) |
O2—Ca1—O1ix | 85.31 (5) | O2xi—Ca2—Ge1xi | 23.69 (5) |
O2vii—Ca1—O1ix | 94.69 (5) | O3xii—Ca2—Ge1xi | 77.35 (4) |
O1viii—Ca1—O1ix | 180.00 (12) | O3xiii—Ca2—Ge1xi | 77.35 (4) |
O2—Ca1—O3vii | 108.73 (6) | O1ix—Ca2—Ge1xi | 156.99 (5) |
O2vii—Ca1—O3vii | 71.27 (6) | O3i—Ca2—Ge1xi | 117.71 (4) |
O1viii—Ca1—O3vii | 83.70 (6) | O3—Ca2—Ge1xi | 117.71 (4) |
O1ix—Ca1—O3vii | 96.30 (6) | Ge1—Ca2—Ge1xi | 125.939 (18) |
O2—Ca1—O3 | 71.27 (6) | Ca1ii—Ca2—Ge1xi | 151.187 (6) |
O2vii—Ca1—O3 | 108.73 (6) | Ca1—Ca2—Ge1xi | 151.187 (6) |
O1viii—Ca1—O3 | 96.30 (6) | Ge1ix—Ca2—Ge1xi | 131.811 (17) |
O1ix—Ca1—O3 | 83.70 (6) | O2xi—Ca2—Ge1xiii | 73.279 (17) |
O3vii—Ca1—O3 | 180 | O3xii—Ca2—Ge1xiii | 129.30 (4) |
O2—Ca1—Ge1 | 35.89 (5) | O3xiii—Ca2—Ge1xiii | 22.77 (3) |
O2vii—Ca1—Ge1 | 144.11 (5) | O1ix—Ca2—Ge1xiii | 106.910 (17) |
O1viii—Ca1—Ge1 | 99.89 (5) | O3i—Ca2—Ge1xiii | 141.38 (4) |
O1ix—Ca1—Ge1 | 80.11 (5) | O3—Ca2—Ge1xiii | 74.95 (3) |
O3vii—Ca1—Ge1 | 144.39 (3) | Ge1—Ca2—Ge1xiii | 108.831 (11) |
O3—Ca1—Ge1 | 35.61 (3) | Ca1ii—Ca2—Ge1xiii | 140.435 (13) |
O2—Ca1—Ge1vii | 144.11 (5) | Ca1—Ca2—Ge1xiii | 84.705 (7) |
O2vii—Ca1—Ge1vii | 35.89 (5) | Ge1ix—Ca2—Ge1xiii | 98.670 (11) |
O1viii—Ca1—Ge1vii | 80.11 (5) | Ge1xi—Ca2—Ge1xiii | 68.219 (9) |
O1ix—Ca1—Ge1vii | 99.89 (5) | Ge1—O1—Ca1iii | 122.58 (6) |
O3vii—Ca1—Ge1vii | 35.61 (3) | Ge1—O1—Ca1iv | 122.58 (6) |
O3—Ca1—Ge1vii | 144.39 (3) | Ca1iii—O1—Ca1iv | 92.24 (7) |
Ge1—Ca1—Ge1vii | 180 | Ge1—O1—Ca2iii | 118.09 (10) |
O2—Ca1—Ca1x | 136.69 (4) | Ca1iii—O1—Ca2iii | 97.56 (6) |
O2vii—Ca1—Ca1x | 43.31 (4) | Ca1iv—O1—Ca2iii | 97.56 (6) |
O1viii—Ca1—Ca1x | 43.88 (4) | Ge1—O2—Ca2v | 125.09 (10) |
O1ix—Ca1—Ca1x | 136.12 (4) | Ge1—O2—Ca1ii | 94.00 (7) |
O3vii—Ca1—Ca1x | 82.78 (3) | Ca2v—O2—Ca1ii | 121.22 (6) |
O3—Ca1—Ca1x | 97.22 (3) | Ge1—O2—Ca1 | 94.00 (7) |
Ge1—Ca1—Ca1x | 124.037 (4) | Ca2v—O2—Ca1 | 121.22 (6) |
Ge1vii—Ca1—Ca1x | 55.963 (4) | Ca1ii—O2—Ca1 | 93.39 (7) |
O2—Ca1—Ca1ii | 43.31 (4) | Ge1—O3—Ca2vi | 126.01 (7) |
O2vii—Ca1—Ca1ii | 136.69 (4) | Ge1—O3—Ca1 | 91.67 (6) |
O1viii—Ca1—Ca1ii | 136.12 (4) | Ca2vi—O3—Ca1 | 112.90 (6) |
O1ix—Ca1—Ca1ii | 43.88 (4) | Ge1—O3—Ca2 | 93.33 (6) |
O3vii—Ca1—Ca1ii | 97.22 (3) | Ca2vi—O3—Ca2 | 128.27 (6) |
O3—Ca1—Ca1ii | 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. |
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) Å3 | Cuboid, colourless |
Z = 4 | 0.13 × 0.12 × 0.09 mm |
F(000) = 415.2 |
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 on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.019P)2 + 0.4001P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.018 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
41 parameters | Extinction coefficient: 0.0145 (14) |
GeO4·1.99(Ca) | V = 404.91 (4) Å3 |
Mr = 216.37 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3919 (7) Å | µ = 9.96 mm−1 |
b = 6.7800 (4) Å | T = 295 K |
c = 5.2424 (3) Å | 0.13 × 0.12 × 0.09 mm |
SMART APEX diffractometer | 595 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 588 reflections with I > 2σ(I) |
Tmin = 0.29, Tmax = 0.42 | Rint = 0.039 |
4870 measured reflections |
R[F2 > 2σ(F2)] = 0.018 | 41 parameters |
wR(F2) = 0.044 | 0 restraints |
S = 1.24 | Δρmax = 0.69 e Å−3 |
595 reflections | Δρmin = −0.45 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.745 (2) | Ca1—O3ii | 2.4088 (14) |
Ge1—O3i | 1.7634 (14) | Ca1—O3 | 2.4088 (14) |
Ge1—O3 | 1.7634 (14) | Ca2—O2v | 2.296 (2) |
Ge1—O2 | 1.7796 (19) | Ca2—O3vi | 2.3621 (15) |
Ca1—O2ii | 2.3297 (14) | Ca2—O3vii | 2.3621 (15) |
Ca1—O2 | 2.3297 (14) | Ca2—O1iv | 2.446 (2) |
Ca1—O1iii | 2.3509 (14) | Ca2—O3i | 2.4615 (15) |
Ca1—O1iv | 2.3509 (14) | Ca2—O3 | 2.4615 (15) |
O1—Ge1—O3i | 116.17 (6) | O1iii—Ca1—O3 | 96.33 (6) |
O1—Ge1—O3 | 116.17 (6) | O1iv—Ca1—O3 | 83.67 (6) |
O3i—Ge1—O3 | 104.35 (9) | O3ii—Ca1—O3 | 180 |
O1—Ge1—O2 | 113.54 (9) | O2v—Ca2—O3vi | 89.65 (5) |
O3i—Ge1—O2 | 102.38 (6) | O2v—Ca2—O3vii | 89.65 (5) |
O3—Ge1—O2 | 102.38 (6) | O3vi—Ca2—O3vii | 115.45 (7) |
O2ii—Ca1—O2 | 180 | O2v—Ca2—O1iv | 179.30 (7) |
O2ii—Ca1—O1iii | 85.29 (5) | O3vi—Ca2—O1iv | 90.73 (4) |
O2—Ca1—O1iii | 94.71 (5) | O3vii—Ca2—O1iv | 90.73 (4) |
O2ii—Ca1—O1iv | 94.71 (5) | O2v—Ca2—O3i | 98.81 (6) |
O2—Ca1—O1iv | 85.29 (5) | O3vi—Ca2—O3i | 87.43 (3) |
O1iii—Ca1—O1iv | 180.00 (8) | O3vii—Ca2—O3i | 155.78 (6) |
O2ii—Ca1—O3ii | 71.25 (6) | O1iv—Ca2—O3i | 80.62 (5) |
O2—Ca1—O3ii | 108.75 (6) | O2v—Ca2—O3 | 98.81 (6) |
O1iii—Ca1—O3ii | 83.67 (6) | O3vi—Ca2—O3 | 155.78 (6) |
O1iv—Ca1—O3ii | 96.33 (6) | O3vii—Ca2—O3 | 87.43 (3) |
O2ii—Ca1—O3 | 108.75 (6) | O1iv—Ca2—O3 | 80.62 (5) |
O2—Ca1—O3 | 71.25 (6) | O3i—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. |
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) Å3 | Cuboid, brown |
Z = 4 | 0.17 × 0.15 × 0.14 mm |
F(000) = 433.2 |
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 on F2 | 2 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.2826P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.023 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
45 parameters | Extinction coefficient: 0.0099 (15) |
Ca1.14GeMn0.86O4 | V = 379.46 (4) Å3 |
Mr = 229.6 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3260 (7) Å | µ = 12.21 mm−1 |
b = 6.5604 (4) Å | T = 295 K |
c = 5.1069 (3) Å | 0.17 × 0.15 × 0.14 mm |
SMART APEX diffractometer | 558 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 551 reflections with I > 2σ(I) |
Tmin = 0.15, Tmax = 0.18 | Rint = 0.063 |
4621 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 45 parameters |
wR(F2) = 0.058 | 2 restraints |
S = 1.16 | Δρmax = 0.68 e Å−3 |
558 reflections | Δρmin = −0.67 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.741 (3) | Mn1—O3 | 2.2740 (17) |
Ge1—O3i | 1.7582 (17) | Ca2—O2v | 2.305 (3) |
Ge1—O3 | 1.7582 (17) | Ca2—O3vi | 2.3104 (18) |
Ge1—O2 | 1.776 (2) | Ca2—O3vii | 2.3104 (18) |
Mn1—O2ii | 2.2148 (17) | Ca2—O1iii | 2.436 (3) |
Mn1—O2 | 2.2148 (17) | Ca2—O3 | 2.4397 (18) |
Mn1—O1iii | 2.2553 (18) | Ca2—O3i | 2.4397 (18) |
Mn1—O1iv | 2.2553 (18) | Ca2—Ca1viii | 3.5419 (6) |
Mn1—O3ii | 2.2740 (17) | ||
O1—Ge1—O3i | 116.03 (7) | O1iii—Mn1—O3 | 84.73 (8) |
O1—Ge1—O3 | 116.03 (7) | O1iv—Mn1—O3 | 95.27 (8) |
O3i—Ge1—O3 | 104.31 (11) | O3ii—Mn1—O3 | 180 |
O1—Ge1—O2 | 116.14 (11) | O2v—Ca2—O3vi | 88.68 (6) |
O3i—Ge1—O2 | 101.04 (7) | O2v—Ca2—O3vii | 88.68 (6) |
O3—Ge1—O2 | 101.04 (7) | O3vi—Ca2—O3vii | 109.93 (9) |
O2ii—Mn1—O2 | 180 | O2v—Ca2—O1iii | 175.36 (9) |
O2ii—Mn1—O1iii | 95.53 (7) | O3vi—Ca2—O1iii | 93.97 (6) |
O2—Mn1—O1iii | 84.47 (7) | O3vii—Ca2—O1iii | 93.97 (6) |
O2ii—Mn1—O1iv | 84.47 (7) | O2v—Ca2—O3 | 98.72 (7) |
O2—Mn1—O1iv | 95.53 (7) | O3vi—Ca2—O3 | 158.91 (7) |
O1iii—Mn1—O1iv | 180 | O3vii—Ca2—O3 | 90.06 (4) |
O2ii—Mn1—O3ii | 74.83 (8) | O1iii—Ca2—O3 | 77.50 (7) |
O2—Mn1—O3ii | 105.17 (8) | O2v—Ca2—O3i | 98.72 (7) |
O1iii—Mn1—O3ii | 95.27 (8) | O3vi—Ca2—O3i | 90.06 (4) |
O1iv—Mn1—O3ii | 84.73 (8) | O3vii—Ca2—O3i | 158.91 (7) |
O2ii—Mn1—O3 | 105.17 (8) | O1iii—Ca2—O3i | 77.50 (7) |
O2—Mn1—O3 | 74.83 (8) | O3—Ca2—O3i | 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. |
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) Å3 | Cuboid, brown |
Z = 4 | 0.18 × 0.15 × 0.14 mm |
F(000) = 432.6 |
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 on F2 | 2 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0218P)2 + 0.2627P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.021 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
45 parameters | Extinction coefficient: 0.0288 (18) |
Ca1.17GeMn0.83O4 | V = 379.89 (4) Å3 |
Mr = 229.16 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3256 (7) Å | µ = 12.14 mm−1 |
b = 6.5643 (4) Å | T = 295 K |
c = 5.1098 (3) Å | 0.18 × 0.15 × 0.14 mm |
SMART APEX diffractometer | 555 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 548 reflections with I > 2σ(I) |
Tmin = 0.23, Tmax = 0.34 | Rint = 0.058 |
4624 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 45 parameters |
wR(F2) = 0.050 | 2 restraints |
S = 1.22 | Δρmax = 0.8 e Å−3 |
555 reflections | Δρmin = −0.65 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.735 (3) | Mn1—O3ii | 2.2760 (16) |
Ge1—O3 | 1.7611 (17) | Mn1—O3 | 2.2760 (16) |
Ge1—O3i | 1.7611 (17) | Ca2—O2v | 2.305 (2) |
Ge1—O2 | 1.776 (2) | Ca2—O3vi | 2.3094 (17) |
Mn1—O2 | 2.2169 (16) | Ca2—O3vii | 2.3094 (17) |
Mn1—O2ii | 2.2169 (16) | Ca2—O1iv | 2.436 (2) |
Mn1—O1iii | 2.2617 (17) | Ca2—O3 | 2.4401 (17) |
Mn1—O1iv | 2.2617 (17) | Ca2—O3i | 2.4401 (17) |
O1—Ge1—O3 | 116.04 (6) | O1iii—Mn1—O3 | 95.24 (7) |
O1—Ge1—O3i | 116.04 (6) | O1iv—Mn1—O3 | 84.76 (7) |
O3—Ge1—O3i | 104.36 (11) | O3ii—Mn1—O3 | 180 |
O1—Ge1—O2 | 116.16 (11) | O2v—Ca2—O3vi | 88.74 (6) |
O3—Ge1—O2 | 100.99 (7) | O2v—Ca2—O3vii | 88.74 (6) |
O3i—Ge1—O2 | 100.99 (7) | O3vi—Ca2—O3vii | 109.94 (9) |
O2—Mn1—O2ii | 180.00 (11) | O2v—Ca2—O1iv | 175.61 (9) |
O2—Mn1—O1iii | 95.39 (7) | O3vi—Ca2—O1iv | 93.77 (5) |
O2ii—Mn1—O1iii | 84.61 (7) | O3vii—Ca2—O1iv | 93.77 (5) |
O2—Mn1—O1iv | 84.61 (7) | O2v—Ca2—O3 | 98.72 (7) |
O2ii—Mn1—O1iv | 95.39 (7) | O3vi—Ca2—O3 | 158.96 (7) |
O1iii—Mn1—O1iv | 180.00 (10) | O3vii—Ca2—O3 | 89.98 (4) |
O2—Mn1—O3ii | 105.19 (7) | O1iv—Ca2—O3 | 77.70 (6) |
O2ii—Mn1—O3ii | 74.81 (7) | O2v—Ca2—O3i | 98.72 (7) |
O1iii—Mn1—O3ii | 84.76 (7) | O3vi—Ca2—O3i | 89.98 (4) |
O1iv—Mn1—O3ii | 95.24 (7) | O3vii—Ca2—O3i | 158.96 (7) |
O2—Mn1—O3 | 74.81 (7) | O1iv—Ca2—O3i | 77.70 (6) |
O2ii—Mn1—O3 | 105.19 (7) | O3—Ca2—O3i | 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. |
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) Å3 | Cuboid, colourless |
Z = 4 | 0.07 × 0.05 × 0.04 mm |
F(000) = 389.1 |
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 on F2 | 43 parameters |
Least-squares matrix: full | 1 restraint |
R[F2 > 2σ(F2)] = 0.022 | w = 1/[σ2(Fo2) + (0.0229P)2 + 0.4844P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.051 | (Δ/σ)max < 0.001 |
S = 1.22 | Δρmax = 0.77 e Å−3 |
542 reflections | Δρmin = −0.61 e Å−3 |
Ca1.16GeMg0.83O4 | V = 365.44 (4) Å3 |
Mr = 203.52 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.2916 (7) Å | µ = 10.01 mm−1 |
b = 6.4405 (4) Å | T = 295 K |
c = 5.0251 (3) Å | 0.07 × 0.05 × 0.04 mm |
SMART APEX diffractometer | 542 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 536 reflections with I > 2σ(I) |
Tmin = 0.55, Tmax = 0.67 | Rint = 0.036 |
4411 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 43 parameters |
wR(F2) = 0.051 | 1 restraint |
S = 1.22 | Δρmax = 0.77 e Å−3 |
542 reflections | Δρmin = −0.61 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.740 (3) | Mg1—O1iii | 2.1914 (17) |
Ge1—O3i | 1.7563 (18) | Mg1—O1iv | 2.1914 (17) |
Ge1—O3 | 1.7563 (18) | Ca2—O3v | 2.2975 (18) |
Ge1—O2 | 1.776 (2) | Ca2—O3vi | 2.2975 (18) |
Mg1—O2ii | 2.1399 (17) | Ca2—O2vii | 2.317 (2) |
Mg1—O2 | 2.1399 (17) | Ca2—O3 | 2.4330 (18) |
Mg1—O3ii | 2.1793 (17) | Ca2—O3i | 2.4330 (18) |
Mg1—O3 | 2.1793 (17) | Ca2—O1iii | 2.455 (2) |
O1—Ge1—O3i | 116.28 (7) | O3ii—Mg1—O1iv | 85.75 (8) |
O1—Ge1—O3 | 116.28 (7) | O3—Mg1—O1iv | 94.25 (8) |
O3i—Ge1—O3 | 104.09 (11) | O1iii—Mg1—O1iv | 180 |
O1—Ge1—O2 | 118.13 (11) | O3v—Ca2—O3vi | 106.05 (9) |
O3i—Ge1—O2 | 99.66 (7) | O3v—Ca2—O2vii | 88.33 (6) |
O3—Ge1—O2 | 99.66 (7) | O3vi—Ca2—O2vii | 88.33 (6) |
O2ii—Mg1—O2 | 180 | O3v—Ca2—O3 | 160.82 (7) |
O2ii—Mg1—O3ii | 77.35 (8) | O3vi—Ca2—O3 | 92.01 (4) |
O2—Mg1—O3ii | 102.65 (8) | O2vii—Ca2—O3 | 98.83 (7) |
O2ii—Mg1—O3 | 102.65 (8) | O3v—Ca2—O3i | 92.01 (4) |
O2—Mg1—O3 | 77.35 (8) | O3vi—Ca2—O3i | 160.82 (7) |
O3ii—Mg1—O3 | 180 | O2vii—Ca2—O3i | 98.83 (7) |
O2ii—Mg1—O1iii | 96.68 (7) | O3—Ca2—O3i | 69.39 (8) |
O2—Mg1—O1iii | 83.32 (7) | O3v—Ca2—O1iii | 96.25 (6) |
O3ii—Mg1—O1iii | 94.25 (8) | O3vi—Ca2—O1iii | 96.25 (6) |
O3—Mg1—O1iii | 85.75 (8) | O2vii—Ca2—O1iii | 172.35 (9) |
O2ii—Mg1—O1iv | 83.32 (7) | O3—Ca2—O1iii | 74.95 (6) |
O2—Mg1—O1iv | 96.68 (7) | O3i—Ca2—O1iii | 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. |
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) Å3 | Cuboid, pink |
Z = 4 | 0.14 × 0.14 × 0.10 mm |
F(000) = 440.9 |
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 on F2 | 43 parameters |
Least-squares matrix: full | 1 restraint |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.026P)2 + 0.2316P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.047 | (Δ/σ)max < 0.001 |
S = 1.15 | Δρmax = 0.70 e Å−3 |
530 reflections | Δρmin = −0.62 e Å−3 |
Ca1.11Co0.89GeO4 | V = 365.23 (4) Å3 |
Mr = 233.55 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.2923 (7) Å | µ = 13.70 mm−1 |
b = 6.4369 (4) Å | T = 295 K |
c = 5.0246 (3) Å | 0.14 × 0.14 × 0.10 mm |
SMART APEX diffractometer | 530 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 516 reflections with I > 2σ(I) |
Tmin = 0.13, Tmax = 0.25 | Rint = 0.038 |
4343 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 43 parameters |
wR(F2) = 0.047 | 1 restraint |
S = 1.15 | Δρmax = 0.70 e Å−3 |
530 reflections | Δρmin = −0.62 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.745 (3) | Co1—O3 | 2.1857 (16) |
Ge1—O3i | 1.7589 (17) | Co1—O3ii | 2.1857 (16) |
Ge1—O3 | 1.7589 (17) | Ca2—O3v | 2.2965 (17) |
Ge1—O2 | 1.775 (2) | Ca2—O3vi | 2.2965 (17) |
Co1—O2ii | 2.1453 (16) | Ca2—O2vii | 2.317 (2) |
Co1—O2 | 2.1453 (16) | Ca2—O3 | 2.4344 (18) |
Co1—O1iii | 2.1822 (16) | Ca2—O3i | 2.4344 (18) |
Co1—O1iv | 2.1822 (16) | Ca2—O1iii | 2.439 (2) |
O1—Ge1—O3i | 115.72 (7) | O1iii—Co1—O3ii | 94.06 (7) |
O1—Ge1—O3 | 115.72 (7) | O1iv—Co1—O3ii | 85.94 (7) |
O3i—Ge1—O3 | 104.02 (11) | O3—Co1—O3ii | 180.00 (5) |
O1—Ge1—O2 | 118.71 (10) | O3v—Ca2—O3vi | 105.85 (9) |
O3i—Ge1—O2 | 100.04 (7) | O3v—Ca2—O2vii | 87.56 (6) |
O3—Ge1—O2 | 100.04 (7) | O3vi—Ca2—O2vii | 87.56 (6) |
O2ii—Co1—O2 | 180 | O3v—Ca2—O3 | 161.23 (7) |
O2ii—Co1—O1iii | 96.68 (7) | O3vi—Ca2—O3 | 92.19 (4) |
O2—Co1—O1iii | 83.32 (7) | O2vii—Ca2—O3 | 98.56 (7) |
O2ii—Co1—O1iv | 83.32 (7) | O3v—Ca2—O3i | 92.19 (4) |
O2—Co1—O1iv | 96.68 (7) | O3vi—Ca2—O3i | 161.23 (7) |
O1iii—Co1—O1iv | 180.00 (10) | O2vii—Ca2—O3i | 98.56 (7) |
O2ii—Co1—O3 | 102.61 (8) | O3—Ca2—O3i | 69.42 (8) |
O2—Co1—O3 | 77.39 (8) | O3v—Ca2—O1iii | 96.95 (6) |
O1iii—Co1—O3 | 85.94 (8) | O3vi—Ca2—O1iii | 96.95 (6) |
O1iv—Co1—O3 | 94.06 (7) | O2vii—Ca2—O1iii | 172.47 (9) |
O2ii—Co1—O3ii | 77.39 (8) | O3—Ca2—O1iii | 75.32 (6) |
O2—Co1—O3ii | 102.61 (8) | O3i—Ca2—O1iii | 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. |
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) Å3 | Cuboid, pink |
Z = 4 | 0.13 × 0.12 × 0.09 mm |
F(000) = 441 |
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 on F2 | 1 restraint |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0183P)2 + 1.0355P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.021 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
43 parameters | Extinction coefficient: 0.0090 (10) |
Ca1.11Co0.89GeO4 | V = 365.06 (4) Å3 |
Mr = 233.55 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.2873 (7) Å | µ = 13.71 mm−1 |
b = 6.4369 (4) Å | T = 295 K |
c = 5.0245 (3) Å | 0.13 × 0.12 × 0.09 mm |
SMART APEX diffractometer | 531 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 528 reflections with I > 2σ(I) |
Tmin = 0.19, Tmax = 0.30 | Rint = 0.040 |
4315 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 43 parameters |
wR(F2) = 0.049 | 1 restraint |
S = 1.20 | Δρmax = 0.66 e Å−3 |
531 reflections | Δρmin = −0.58 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.746 (3) | Co1—O3 | 2.1845 (19) |
Ge1—O3i | 1.7599 (19) | Co1—O3ii | 2.1845 (19) |
Ge1—O3 | 1.7599 (19) | Ca2—O3v | 2.2962 (19) |
Ge1—O2 | 1.775 (3) | Ca2—O3vi | 2.2962 (19) |
Co1—O2 | 2.1467 (19) | Ca2—O2vii | 2.313 (3) |
Co1—O2ii | 2.1467 (19) | Ca2—O3 | 2.434 (2) |
Co1—O1iii | 2.1804 (18) | Ca2—O3i | 2.434 (2) |
Co1—O1iv | 2.1804 (18) | Ca2—O1iv | 2.439 (3) |
O1—Ge1—O3i | 115.73 (8) | O1iii—Co1—O3ii | 86.01 (9) |
O1—Ge1—O3 | 115.73 (8) | O1iv—Co1—O3ii | 93.99 (9) |
O3i—Ge1—O3 | 104.02 (13) | O3—Co1—O3ii | 180.00 (6) |
O1—Ge1—O2 | 118.63 (13) | O3v—Ca2—O3vi | 105.81 (10) |
O3i—Ge1—O2 | 100.07 (8) | O3v—Ca2—O2vii | 87.58 (7) |
O3—Ge1—O2 | 100.07 (8) | O3vi—Ca2—O2vii | 87.58 (7) |
O2—Co1—O2ii | 180 | O3v—Ca2—O3 | 161.27 (8) |
O2—Co1—O1iii | 96.68 (8) | O3vi—Ca2—O3 | 92.19 (4) |
O2ii—Co1—O1iii | 83.32 (8) | O2vii—Ca2—O3 | 98.53 (8) |
O2—Co1—O1iv | 83.32 (8) | O3v—Ca2—O3i | 92.19 (4) |
O2ii—Co1—O1iv | 96.68 (8) | O3vi—Ca2—O3i | 161.27 (8) |
O1iii—Co1—O1iv | 180.00 (12) | O2vii—Ca2—O3i | 98.53 (8) |
O2—Co1—O3 | 77.45 (9) | O3—Ca2—O3i | 69.46 (9) |
O2ii—Co1—O3 | 102.55 (9) | O3v—Ca2—O1iv | 96.98 (7) |
O1iii—Co1—O3 | 93.99 (9) | O3vi—Ca2—O1iv | 96.98 (7) |
O1iv—Co1—O3 | 86.01 (9) | O2vii—Ca2—O1iv | 172.40 (10) |
O2—Co1—O3ii | 102.55 (9) | O3—Ca2—O1iv | 75.30 (7) |
O2ii—Co1—O3ii | 77.45 (9) | O3i—Ca2—O1iv | 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. |
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) Å3 | Cuboid, brown |
Z = 4 | 0.14 × 0.12 × 0.11 mm |
F(000) = 429.8 |
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 on F2 | 44 parameters |
Least-squares matrix: full | 2 restraints |
R[F2 > 2σ(F2)] = 0.020 | w = 1/[σ2(Fo2) + (0.0157P)2 + 0.6189P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.045 | (Δ/σ)max < 0.001 |
S = 1.24 | Δρmax = 0.78 e Å−3 |
517 reflections | Δρmin = −0.96 e Å−3 |
Ca1.31GeMn0.69O4 | V = 384.32 (4) Å3 |
Mr = 227.02 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3391 (7) Å | µ = 11.74 mm−1 |
b = 6.6035 (4) Å | T = 295 K |
c = 5.1326 (3) Å | 0.14 × 0.12 × 0.11 mm |
SMART APEX diffractometer | 517 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 510 reflections with I > 2σ(I) |
Tmin = 0.21, Tmax = 0.27 | Rint = 0.054 |
4316 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 44 parameters |
wR(F2) = 0.045 | 2 restraints |
S = 1.24 | Δρmax = 0.78 e Å−3 |
517 reflections | Δρmin = −0.96 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.735 (3) | Mn1—O3ii | 2.2945 (18) |
Ge1—O3 | 1.7605 (18) | Mn1—O3 | 2.2945 (18) |
Ge1—O3i | 1.7605 (18) | Ca2—O2v | 2.308 (3) |
Ge1—O2 | 1.773 (3) | Ca2—O3vi | 2.3227 (18) |
Mn1—O2ii | 2.2335 (17) | Ca2—O3vii | 2.3227 (18) |
Mn1—O2 | 2.2335 (17) | Ca2—O3 | 2.4430 (18) |
Mn1—O1iii | 2.2770 (17) | Ca2—O3i | 2.4430 (18) |
Mn1—O1iv | 2.2770 (17) | Ca2—O1iv | 2.444 (3) |
O1—Ge1—O3 | 116.19 (7) | O1iii—Mn1—O3 | 95.34 (8) |
O1—Ge1—O3i | 116.19 (7) | O1iv—Mn1—O3 | 84.66 (8) |
O3—Ge1—O3i | 104.26 (11) | O3ii—Mn1—O3 | 180 |
O1—Ge1—O2 | 115.75 (12) | O2v—Ca2—O3vi | 88.87 (6) |
O3—Ge1—O2 | 101.11 (8) | O2v—Ca2—O3vii | 88.87 (6) |
O3i—Ge1—O2 | 101.11 (8) | O3vi—Ca2—O3vii | 110.82 (9) |
O2ii—Mn1—O2 | 180 | O2v—Ca2—O3 | 98.82 (7) |
O2ii—Mn1—O1iii | 84.66 (7) | O3vi—Ca2—O3 | 158.40 (7) |
O2—Mn1—O1iii | 95.34 (7) | O3vii—Ca2—O3 | 89.61 (4) |
O2ii—Mn1—O1iv | 95.34 (7) | O2v—Ca2—O3i | 98.82 (7) |
O2—Mn1—O1iv | 84.66 (7) | O3vi—Ca2—O3i | 89.61 (4) |
O1iii—Mn1—O1iv | 180.00 (11) | O3vii—Ca2—O3i | 158.40 (7) |
O2ii—Mn1—O3ii | 74.11 (8) | O3—Ca2—O3i | 69.34 (9) |
O2—Mn1—O3ii | 105.89 (8) | O2v—Ca2—O1iv | 176.21 (9) |
O1iii—Mn1—O3ii | 84.66 (8) | O3vi—Ca2—O1iv | 93.28 (6) |
O1iv—Mn1—O3ii | 95.34 (8) | O3vii—Ca2—O1iv | 93.28 (6) |
O2ii—Mn1—O3 | 105.89 (8) | O3—Ca2—O1iv | 78.09 (7) |
O2—Mn1—O3 | 74.11 (8) | O3i—Ca2—O1iv | 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. |
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) Å3 | Cube, colourless |
Z = 4 | 0.08 × 0.07 × 0.07 mm |
F(000) = 386.2 |
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 on F2 | 2 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0238P)2 + 0.2954P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.026 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
45 parameters | Extinction coefficient: 0.0044 (15) |
GeO4·1.07(Ca)0.93(Mg) | V = 364.59 (4) Å3 |
Mr = 202.04 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.2882 (7) Å | µ = 9.92 mm−1 |
b = 6.4309 (4) Å | T = 295 K |
c = 5.0223 (3) Å | 0.08 × 0.07 × 0.07 mm |
SMART APEX diffractometer | 487 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 476 reflections with I > 2σ(I) |
Tmin = 0.46, Tmax = 0.50 | Rint = 0.097 |
3967 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 45 parameters |
wR(F2) = 0.054 | 2 restraints |
S = 1.16 | Δρmax = 0.74 e Å−3 |
487 reflections | Δρmin = −1.37 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.739 (3) | Mg1—O1iii | 2.1879 (16) |
Ge1—O3i | 1.7561 (19) | Mg1—O1iv | 2.1879 (16) |
Ge1—O3 | 1.7561 (19) | Ca2—O3v | 2.2996 (19) |
Ge1—O2 | 1.778 (2) | Ca2—O3vi | 2.2996 (19) |
Mg1—O2ii | 2.1347 (16) | Ca2—O2vii | 2.317 (2) |
Mg1—O2 | 2.1347 (16) | Ca2—O3 | 2.4340 (18) |
Mg1—O3 | 2.1686 (16) | Ca2—O3i | 2.4340 (18) |
Mg1—O3ii | 2.1686 (16) | Ca2—O1iii | 2.458 (2) |
O1—Ge1—O3i | 116.30 (7) | O3—Mg1—O1iv | 94.05 (8) |
O1—Ge1—O3 | 116.30 (7) | O3ii—Mg1—O1iv | 85.95 (8) |
O3i—Ge1—O3 | 104.05 (12) | O1iii—Mg1—O1iv | 180 |
O1—Ge1—O2 | 118.41 (11) | O3v—Ca2—O3vi | 105.55 (9) |
O3i—Ge1—O2 | 99.48 (7) | O3v—Ca2—O2vii | 88.28 (6) |
O3—Ge1—O2 | 99.48 (7) | O3vi—Ca2—O2vii | 88.28 (6) |
O2ii—Mg1—O2 | 180 | O3v—Ca2—O3 | 161.04 (7) |
O2ii—Mg1—O3 | 102.40 (8) | O3vi—Ca2—O3 | 92.29 (4) |
O2—Mg1—O3 | 77.60 (8) | O2vii—Ca2—O3 | 98.82 (7) |
O2ii—Mg1—O3ii | 77.60 (8) | O3v—Ca2—O3i | 92.29 (4) |
O2—Mg1—O3ii | 102.40 (8) | O3vi—Ca2—O3i | 161.04 (7) |
O3—Mg1—O3ii | 180 | O2vii—Ca2—O3i | 98.82 (7) |
O2ii—Mg1—O1iii | 96.69 (7) | O3—Ca2—O3i | 69.32 (9) |
O2—Mg1—O1iii | 83.31 (7) | O3v—Ca2—O1iii | 96.47 (6) |
O3—Mg1—O1iii | 85.95 (8) | O3vi—Ca2—O1iii | 96.47 (6) |
O3ii—Mg1—O1iii | 94.05 (8) | O2vii—Ca2—O1iii | 172.11 (9) |
O2ii—Mg1—O1iv | 83.31 (7) | O3—Ca2—O1iii | 74.76 (6) |
O2—Mg1—O1iv | 96.69 (7) | O3i—Ca2—O1iii | 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. |
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) Å3 | Cuboid, colourless |
Z = 4 | 0.16 × 0.15 × 0.13 mm |
F(000) = 416 |
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 on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.026P)2 + 0.8056P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.024 | (Δ/σ)max < 0.001 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
43 parameters | Extinction coefficient: 0.55 (2) |
GeO4·2.00(Ca) | V = 404.97 (6) Å3 |
Mr = 216.69 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.3923 (8) Å | µ = 9.97 mm−1 |
b = 6.7854 (8) Å | T = 295 K |
c = 5.2388 (4) Å | 0.16 × 0.15 × 0.13 mm |
SMART APEX diffractometer | 536 independent reflections |
Absorption correction: numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | 533 reflections with I > 2σ(I) |
Tmin = 0.22, Tmax = 0.28 | Rint = 0.084 |
4496 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 43 parameters |
wR(F2) = 0.063 | 0 restraints |
S = 1.21 | Δρmax = 0.92 e Å−3 |
536 reflections | Δρmin = −0.94 e Å−3 |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ge1—O1 | 1.746 (3) | Ca1—O3ii | 2.407 (2) |
Ge1—O3 | 1.767 (2) | Ca1—O3 | 2.407 (2) |
Ge1—O3i | 1.767 (2) | Ca2—O2v | 2.295 (3) |
Ge1—O2 | 1.782 (3) | Ca2—O3vi | 2.364 (2) |
Ca1—O2 | 2.330 (2) | Ca2—O3vii | 2.364 (2) |
Ca1—O2ii | 2.330 (2) | Ca2—O1iv | 2.443 (3) |
Ca1—O1iii | 2.351 (2) | Ca2—O3 | 2.458 (2) |
Ca1—O1iv | 2.351 (2) | Ca2—O3i | 2.458 (2) |
O1—Ge1—O3 | 116.25 (8) | O1iii—Ca1—O3 | 96.49 (9) |
O1—Ge1—O3i | 116.25 (8) | O1iv—Ca1—O3 | 83.51 (9) |
O3—Ge1—O3i | 104.25 (14) | O3ii—Ca1—O3 | 180 |
O1—Ge1—O2 | 113.59 (13) | O2v—Ca2—O3vi | 89.69 (7) |
O3—Ge1—O2 | 102.32 (9) | O2v—Ca2—O3vii | 89.69 (7) |
O3i—Ge1—O2 | 102.32 (9) | O3vi—Ca2—O3vii | 115.36 (11) |
O2—Ca1—O2ii | 180 | O2v—Ca2—O1iv | 179.26 (11) |
O2—Ca1—O1iii | 94.80 (8) | O3vi—Ca2—O1iv | 90.70 (7) |
O2ii—Ca1—O1iii | 85.20 (8) | O3vii—Ca2—O1iv | 90.70 (7) |
O2—Ca1—O1iv | 85.20 (8) | O2v—Ca2—O3 | 98.83 (8) |
O2ii—Ca1—O1iv | 94.80 (8) | O3vi—Ca2—O3 | 155.89 (8) |
O1iii—Ca1—O1iv | 180.00 (12) | O3vii—Ca2—O3 | 87.36 (4) |
O2—Ca1—O3ii | 108.61 (9) | O1iv—Ca2—O3 | 80.56 (8) |
O2ii—Ca1—O3ii | 71.39 (9) | O2v—Ca2—O3i | 98.83 (8) |
O1iii—Ca1—O3ii | 83.51 (9) | O3vi—Ca2—O3i | 87.36 (4) |
O1iv—Ca1—O3ii | 96.49 (9) | O3vii—Ca2—O3i | 155.89 (8) |
O2—Ca1—O3 | 71.39 (9) | O1iv—Ca2—O3i | 80.56 (8) |
O2ii—Ca1—O3 | 108.61 (9) | O3—Ca2—O3i | 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. |
Experimental details
(Ca2Co_2) | (cfg_rot) | (cazn_b) | (camn_a5) | |
Crystal data | ||||
Chemical formula | Ca1.17Co0.83GeO4 | Ca2GeO4 | GeO4·1.99(Ca) | Ca1.14GeMn0.86O4 |
Mr | 232.4 | 216.75 | 216.37 | 229.6 |
Crystal system, space group | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma |
Temperature (K) | 295 | 293 | 295 | 295 |
a, b, c (Å) | 11.3021 (7), 6.4657 (4), 5.0435 (3) | 11.3919 (7), 6.7800 (4), 5.2424 (3) | 11.3919 (7), 6.7800 (4), 5.2424 (3) | 11.3260 (7), 6.5604 (4), 5.1069 (3) |
V (Å3) | 368.56 (4) | 404.91 (4) | 404.91 (4) | 379.46 (4) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 13.40 | 9.97 | 9.96 | 12.21 |
Crystal size (mm) | 0.18 × 0.16 × 0.13 | 0.16 × 0.14 × 0.13 | 0.13 × 0.12 × 0.09 | 0.17 × 0.15 × 0.14 |
Data collection | ||||
Diffractometer | SMART APEX diffractometer | ? | SMART APEX diffractometer | SMART APEX diffractometer |
Absorption correction | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | – | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) |
Tmin, Tmax | 0.10, 0.18 | – | 0.29, 0.42 | 0.15, 0.18 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4087, 507, 504 | 4592, 551, 544 | 4870, 595, 588 | 4621, 558, 551 |
Rint | 0.062 | 0.057 | 0.039 | 0.063 |
(sin θ/λ)max (Å−1) | 0.676 | 0.676 | 0.690 | 0.693 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.070, 1.36 | 0.019, 0.042, 1.25 | 0.018, 0.044, 1.24 | 0.023, 0.058, 1.16 |
No. of reflections | 507 | 551 | 595 | 558 |
No. of parameters | 45 | 41 | 41 | 45 |
No. of restraints | 2 | 0 | 0 | 2 |
Δρmax, Δρmin (e Å−3) | 0.98, −1.68 | 0.83, −0.39 | 0.69, −0.45 | 0.68, −0.67 |
(camn_a2) | (camg_a1) | (caco_a2) | (caco_a1) | |
Crystal data | ||||
Chemical formula | Ca1.17GeMn0.83O4 | Ca1.16GeMg0.83O4 | Ca1.11Co0.89GeO4 | Ca1.11Co0.89GeO4 |
Mr | 229.16 | 203.52 | 233.55 | 233.55 |
Crystal system, space group | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma |
Temperature (K) | 295 | 295 | 295 | 295 |
a, b, c (Å) | 11.3256 (7), 6.5643 (4), 5.1098 (3) | 11.2916 (7), 6.4405 (4), 5.0251 (3) | 11.2923 (7), 6.4369 (4), 5.0246 (3) | 11.2873 (7), 6.4369 (4), 5.0245 (3) |
V (Å3) | 379.89 (4) | 365.44 (4) | 365.23 (4) | 365.06 (4) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 12.14 | 10.01 | 13.70 | 13.71 |
Crystal size (mm) | 0.18 × 0.15 × 0.14 | 0.07 × 0.05 × 0.04 | 0.14 × 0.14 × 0.10 | 0.13 × 0.12 × 0.09 |
Data collection | ||||
Diffractometer | SMART APEX diffractometer | SMART APEX diffractometer | SMART APEX diffractometer | SMART APEX diffractometer |
Absorption correction | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) |
Tmin, Tmax | 0.23, 0.34 | 0.55, 0.67 | 0.13, 0.25 | 0.19, 0.30 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4624, 555, 548 | 4411, 542, 536 | 4343, 530, 516 | 4315, 531, 528 |
Rint | 0.058 | 0.036 | 0.038 | 0.040 |
(sin θ/λ)max (Å−1) | 0.692 | 0.696 | 0.694 | 0.687 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.050, 1.22 | 0.022, 0.051, 1.22 | 0.020, 0.047, 1.15 | 0.021, 0.049, 1.20 |
No. of reflections | 555 | 542 | 530 | 531 |
No. of parameters | 45 | 43 | 43 | 43 |
No. of restraints | 2 | 1 | 1 | 1 |
Δρmax, Δρmin (e Å−3) | 0.8, −0.65 | 0.77, −0.61 | 0.70, −0.62 | 0.66, −0.58 |
(ca2mn_1) | (ca2mg_1) | (ca2ge_1) | |
Crystal data | |||
Chemical formula | Ca1.31GeMn0.69O4 | GeO4·1.07(Ca)0.93(Mg) | GeO4·2.00(Ca) |
Mr | 227.02 | 202.04 | 216.69 |
Crystal system, space group | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 11.3391 (7), 6.6035 (4), 5.1326 (3) | 11.2882 (7), 6.4309 (4), 5.0223 (3) | 11.3923 (8), 6.7854 (8), 5.2388 (4) |
V (Å3) | 384.32 (4) | 364.59 (4) | 404.97 (6) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 11.74 | 9.92 | 9.97 |
Crystal size (mm) | 0.14 × 0.12 × 0.11 | 0.08 × 0.07 × 0.07 | 0.16 × 0.15 × 0.13 |
Data collection | |||
Diffractometer | SMART APEX diffractometer | SMART APEX diffractometer | SMART APEX diffractometer |
Absorption correction | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) | Numerical via equivalents using X-SHAPE (Stoe & Cie 1996) |
Tmin, Tmax | 0.21, 0.27 | 0.46, 0.50 | 0.22, 0.28 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4316, 517, 510 | 3967, 487, 476 | 4496, 536, 533 |
Rint | 0.054 | 0.097 | 0.084 |
(sin θ/λ)max (Å−1) | 0.668 | 0.667 | 0.668 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.045, 1.24 | 0.026, 0.054, 1.16 | 0.024, 0.063, 1.21 |
No. of reflections | 517 | 487 | 536 |
No. of parameters | 44 | 45 | 43 |
No. of restraints | 2 | 2 | 0 |
Δρmax, Δρmin (e Å−3) | 0.78, −0.96 | 0.74, −1.37 | 0.92, −0.94 |
Computer programs: Bruker SMART+ (Bruker, 2001), Bruker SAINT+ (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Diamonds 3.0 (Pennington,1999), WinGX v1.70.01 (Farrugia 1999).
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