Crystals of germanium-doped rubidium titanyl phosphate, Rb2(Ti)(Ge0.121Ti0.879)O2(PO4)2 (GeRTP#1) and Rb2(Ge0.125Ti0.875)(Ge0.225Ti0.775)O2(PO4)2 (GeRTP#2), have been structurally characterized from X-ray diffraction data at room temperature. In addition, a third structure, Rb2(TiO)2(PO4)2 (RTP), has been reinvestigated. The exchange of titanium for germanium results in a less distorted octahedral coordination around the two crystallographically independent titanium sites. Additionally, rubidium split-cation positions have been found in these doped RTP crystals. Dielectric measurements show that the phase-transition temperature, Tc, decreases with increasing germanium concentration, and a direct correlation between the room-temperature split of the rubidium cations and Tc has been discovered. General trends regarding the relationship between the room-temperature structures of KTP-like compounds and their Tc values are discussed.
Supporting information
For all compounds, data collection: SMART (Siemens, 1995); cell refinement: CAD-4 Software (Enraf-Nonius, 1989); data reduction: SAINT (Siemens, 1995) and SADABS (Sheldrick, 2001); program(s) used to solve structure: Atomic parameters from Norberg et al. (2000); program(s) used to refine structure: Xtal3.71 (Hall et al., 2000) program: CRYLSQ; molecular graphics: ORTEPIII for Windows (Farrugia, 1997); software used to prepare material for publication: Xtal3.71 (Hall et al., 2000) programs: BONDLA; ATABLE; CIFIO.
Crystal data top
O10P2Rb2Ti2 | F(000) = 912 |
Mr = 488.64 | Dx = 3.645 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2c -2n | Cell parameters from 18 reflections |
a = 12.9625 (15) Å | θ = 17.9–23.9° |
b = 6.5031 (3) Å | µ = 13.06 mm−1 |
c = 10.5615 (3) Å | T = 293 K |
V = 890.30 (11) Å3 | Rectangular, colourless |
Z = 4 | 0.14 × 0.12 × 0.08 mm |
Data collection top
Siemens SMART CCD diffractometer | 2054 independent reflections |
Radiation source: normal-focus sealed tube | 2054 reflections with F > 0σ(F) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −16→16 |
Tmin = 0.175, Tmax = 0.353 | k = −8→8 |
10947 measured reflections | l = −13→13 |
Refinement top
Refinement on F | w = 1/[σ2(F) + 0.0020(F)2] |
Least-squares matrix: full | (Δ/σ)max = 0.001 |
R[F2 > 2σ(F2)] = 0.024 | Δρmax = 1.11 e Å−3 |
wR(F2) = 0.037 | Δρmin = −0.71 e Å−3 |
S = 1.13 | Extinction correction: Isotropic Gaussian, Zachariasen, 1967; Larson (1970), Eq22 p292 "Cryst. Comp." Munksgaard 1970 |
2054 reflections | Extinction coefficient: 117E2 (5) |
146 parameters | Absolute structure: Flack (1983) parameter refined |
0 restraints | Absolute structure parameter: 0.497 (9) |
0 constraints | |
Crystal data top
O10P2Rb2Ti2 | V = 890.30 (11) Å3 |
Mr = 488.64 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.9625 (15) Å | µ = 13.06 mm−1 |
b = 6.5031 (3) Å | T = 293 K |
c = 10.5615 (3) Å | 0.14 × 0.12 × 0.08 mm |
Data collection top
Siemens SMART CCD diffractometer | 2054 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2054 reflections with F > 0σ(F) |
Tmin = 0.175, Tmax = 0.353 | Rint = 0.052 |
10947 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.037 | Δρmax = 1.11 e Å−3 |
S = 1.13 | Δρmin = −0.71 e Å−3 |
2054 reflections | Absolute structure: Flack (1983) parameter refined |
146 parameters | Absolute structure parameter: 0.497 (9) |
Special details top
Refinement. No constraints or restraints were used. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Rb1 | 0.61502 (4) | 0.78353 (9) | 0.70080 (11) | 0.0171 (3) | |
Rb2 | 0.89447 (4) | 0.69214 (9) | 0.95204 (11) | 0.0151 (3) | |
Ti1 | 0.62713 (6) | 0.49974 (12) | 1.02650 (12) | 0.0048 (4) | |
Ti2 | 0.75173 (6) | 0.26802 (12) | 0.77515 (13) | 0.0043 (4) | |
P1 | 0.50027 (9) | 0.3331 (2) | 0.76890 (16) | 0.0045 (6) | |
P2 | 0.82010 (9) | 0.50192 (16) | 0.51433 (14) | 0.0048 (5) | |
O1 | 0.5145 (3) | 0.4791 (6) | 0.8806 (3) | 0.0069 (18) | |
O2 | 0.4864 (3) | 0.4611 (6) | 0.6463 (3) | 0.0100 (18) | |
O3 | 0.5981 (3) | 0.2018 (6) | 0.7472 (4) | 0.0081 (18) | |
O4 | 0.4055 (3) | 0.1938 (6) | 0.7896 (4) | 0.0072 (17) | |
O11 | 0.7220 (3) | 0.4607 (6) | 0.8835 (3) | 0.0077 (17) | |
O12 | 0.7774 (3) | 0.0451 (6) | 0.6365 (3) | 0.0096 (18) | |
O5 | 0.8862 (3) | 0.3115 (7) | 0.4842 (4) | 0.008 (2) | |
O6 | 0.8871 (3) | 0.6904 (6) | 0.5421 (4) | 0.010 (2) | |
O7 | 0.7490 (3) | 0.5437 (6) | 0.3994 (3) | 0.0089 (17) | |
O8 | 0.7479 (3) | 0.4579 (6) | 0.6263 (11) | 0.0096 (17) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1 | 0.0176 (3) | 0.0092 (3) | 0.0244 (3) | −0.00395 (16) | 0.0058 (2) | −0.0021 (2) |
Rb2 | 0.0099 (3) | 0.0150 (3) | 0.0203 (3) | −0.00427 (16) | 0.0008 (2) | −0.0014 (2) |
Ti1 | 0.0043 (4) | 0.0054 (4) | 0.0047 (4) | 0.0003 (3) | −0.0005 (3) | −0.0008 (3) |
Ti2 | 0.0036 (4) | 0.0060 (4) | 0.0033 (4) | 0.0002 (3) | 0.0001 (3) | 0.0001 (3) |
P1 | 0.0031 (6) | 0.0065 (6) | 0.0040 (5) | −0.0000 (4) | −0.0009 (4) | −0.0009 (5) |
P2 | 0.0058 (5) | 0.0058 (6) | 0.0029 (5) | 0.0001 (4) | −0.0002 (4) | 0.0002 (4) |
O1 | 0.0065 (18) | 0.0107 (19) | 0.0037 (16) | 0.0021 (13) | −0.0021 (12) | −0.0045 (14) |
O2 | 0.0080 (19) | 0.0101 (18) | 0.0118 (18) | −0.0004 (15) | −0.0009 (13) | 0.0029 (15) |
O3 | 0.0082 (19) | 0.0068 (17) | 0.0092 (19) | −0.0002 (12) | −0.0006 (13) | 0.0023 (13) |
O4 | 0.0049 (16) | 0.0085 (16) | 0.0083 (17) | −0.0014 (12) | 0.0022 (14) | 0.0001 (13) |
O11 | 0.0088 (19) | 0.0101 (17) | 0.0041 (16) | −0.0009 (14) | 0.0028 (12) | −0.0020 (13) |
O12 | 0.007 (2) | 0.0090 (16) | 0.0124 (17) | −0.0018 (14) | 0.0031 (13) | −0.0002 (15) |
O5 | 0.011 (2) | 0.008 (2) | 0.006 (2) | 0.0007 (12) | 0.0008 (12) | 0.0010 (13) |
O6 | 0.012 (2) | 0.0042 (16) | 0.014 (2) | −0.0006 (11) | −0.0053 (14) | 0.0001 (15) |
O7 | 0.0101 (18) | 0.0122 (17) | 0.0043 (15) | −0.0019 (14) | 0.0006 (12) | 0.0040 (15) |
O8 | 0.0078 (17) | 0.0118 (18) | 0.0092 (17) | 0.0023 (13) | 0.0062 (14) | 0.0009 (15) |
Geometric parameters (Å, º) top
Rb1—O1 | 3.037 (4) | Ti1—O2 | 1.957 (4) |
Rb1—O2 | 2.740 (4) | Ti1—O11 | 1.964 (4) |
Rb1—O3 | 2.773 (4) | Ti1—O12 | 1.723 (4) |
Rb1—O11 | 3.171 (4) | Ti1—O5 | 2.083 (4) |
Rb1—O12 | 2.790 (4) | Ti1—O6 | 2.027 (4) |
Rb1—O5 | 2.998 (4) | Ti2—O3 | 2.059 (4) |
Rb1—O6 | 3.400 (4) | Ti2—O4i | 2.015 (4) |
Rb1—O7 | 3.220 (4) | Ti2—O11 | 1.740 (4) |
Rb1—O8 | 2.841 (5) | Ti2—O12 | 2.087 (4) |
Rb2—O1 | 2.749 (4) | Ti2—O7 | 1.962 (4) |
Rb2—O2 | 3.107 (4) | Ti2—O8 | 2.000 (10) |
Rb2—O3 | 3.120 (4) | P1—O1 | 1.526 (4) |
Rb2—O4i | 3.043 (4) | P1—O2 | 1.550 (4) |
Rb2—O11 | 2.791 (4) | P1—O3 | 1.545 (4) |
Rb2—O12 | 3.110 (4) | P1—O4 | 1.542 (4) |
Rb2—O5 | 2.863 (4) | P2—O5 | 1.539 (4) |
Rb2—O7 | 3.000 (4) | P2—O6 | 1.531 (4) |
Rb2—O8 | 3.127 (8) | P2—O7 | 1.548 (4) |
Ti1—O1 | 2.127 (4) | P2—O8 | 1.535 (9) |
| | | |
O1—Rb1—O2 | 51.06 (10) | O3—Rb2—O12 | 53.30 (10) |
O1—Rb1—O11 | 51.35 (10) | O3—Rb2—O7 | 100.91 (10) |
O1—Rb1—O8 | 87.00 (18) | O3—Rb2—O8 | 54.5 (2) |
O1—Rb1—O3 | 119.66 (11) | O3—Rb2—O4i | 125.35 (10) |
O1—Rb1—O12 | 150.85 (11) | O3—Rb2—O1 | 103.94 (10) |
O1—Rb1—O5 | 54.06 (11) | O12—Rb2—O7 | 84.63 (10) |
O1—Rb1—O7 | 99.79 (10) | O12—Rb2—O8 | 51.59 (12) |
O1—Rb1—O6 | 88.16 (10) | O12—Rb2—O4i | 97.67 (10) |
O2—Rb1—O11 | 83.53 (11) | O12—Rb2—O1 | 144.71 (11) |
O2—Rb1—O8 | 74.95 (13) | O7—Rb2—O8 | 47.30 (19) |
O2—Rb1—O3 | 137.70 (12) | O7—Rb2—O4i | 123.59 (11) |
O2—Rb1—O12 | 150.98 (12) | O7—Rb2—O1 | 72.99 (12) |
O2—Rb1—O5 | 104.65 (11) | O8—Rb2—O4i | 144.62 (11) |
O2—Rb1—O7 | 150.70 (11) | O8—Rb2—O1 | 93.76 (12) |
O2—Rb1—O6 | 53.56 (11) | O4i—Rb2—O1 | 117.37 (11) |
O11—Rb1—O8 | 53.8 (2) | O1—Ti1—O11 | 82.21 (15) |
O11—Rb1—O3 | 125.21 (11) | O1—Ti1—O2 | 87.73 (16) |
O11—Rb1—O12 | 102.83 (11) | O1—Ti1—O6 | 86.21 (17) |
O11—Rb1—O5 | 55.59 (10) | O1—Ti1—O12 | 172.91 (18) |
O11—Rb1—O7 | 73.28 (10) | O1—Ti1—O5 | 81.31 (16) |
O11—Rb1—O6 | 135.46 (10) | O11—Ti1—O2 | 169.92 (17) |
O8—Rb1—O3 | 145.93 (12) | O11—Ti1—O6 | 89.51 (17) |
O8—Rb1—O12 | 85.97 (13) | O11—Ti1—O12 | 95.20 (17) |
O8—Rb1—O5 | 109.0 (2) | O11—Ti1—O5 | 90.72 (16) |
O8—Rb1—O7 | 103.91 (18) | O2—Ti1—O6 | 90.45 (17) |
O8—Rb1—O6 | 115.30 (19) | O2—Ti1—O12 | 94.71 (18) |
O3—Rb1—O12 | 60.31 (11) | O2—Ti1—O5 | 87.13 (16) |
O3—Rb1—O5 | 76.33 (12) | O6—Ti1—O12 | 100.40 (18) |
O3—Rb1—O7 | 54.03 (11) | O6—Ti1—O5 | 167.37 (17) |
O3—Rb1—O6 | 88.25 (10) | O12—Ti1—O5 | 92.15 (17) |
O12—Rb1—O5 | 102.13 (11) | O3—Ti2—O11 | 91.74 (17) |
O12—Rb1—O7 | 54.92 (10) | O3—Ti2—O12 | 84.74 (15) |
O12—Rb1—O6 | 120.32 (11) | O3—Ti2—O8 | 89.57 (17) |
O5—Rb1—O7 | 47.23 (10) | O3—Ti2—O7 | 86.29 (17) |
O5—Rb1—O6 | 118.97 (10) | O3—Ti2—O4i | 173.61 (16) |
O7—Rb1—O6 | 140.38 (10) | O11—Ti2—O12 | 175.38 (17) |
O11—Rb2—O5 | 145.27 (12) | O11—Ti2—O8 | 93.8 (3) |
O11—Rb2—O2 | 150.82 (11) | O11—Ti2—O7 | 95.42 (17) |
O11—Rb2—O3 | 107.15 (10) | O11—Ti2—O4i | 94.63 (17) |
O11—Rb2—O12 | 54.75 (10) | O12—Ti2—O8 | 83.2 (3) |
O11—Rb2—O7 | 82.30 (11) | O12—Ti2—O7 | 87.34 (15) |
O11—Rb2—O8 | 88.73 (12) | O12—Ti2—O4i | 88.92 (16) |
O11—Rb2—O4i | 56.42 (11) | O8—Ti2—O7 | 170.0 (3) |
O11—Rb2—O1 | 143.27 (11) | O8—Ti2—O4i | 90.45 (17) |
O5—Rb2—O2 | 55.45 (12) | O7—Ti2—O4i | 92.65 (17) |
O5—Rb2—O3 | 81.42 (11) | O1—P1—O2 | 109.0 (2) |
O5—Rb2—O12 | 129.38 (11) | O1—P1—O3 | 111.1 (2) |
O5—Rb2—O7 | 130.09 (12) | O1—P1—O4 | 110.6 (2) |
O5—Rb2—O8 | 121.38 (15) | O2—P1—O3 | 105.6 (2) |
O5—Rb2—O4i | 90.76 (11) | O2—P1—O4 | 110.0 (2) |
O5—Rb2—O1 | 58.47 (12) | O3—P1—O4 | 110.4 (2) |
O2—Rb2—O3 | 46.64 (10) | O5—P2—O6 | 111.6 (2) |
O2—Rb2—O12 | 96.63 (11) | O5—P2—O7 | 108.1 (2) |
O2—Rb2—O7 | 90.09 (11) | O5—P2—O8 | 110.4 (2) |
O2—Rb2—O8 | 66.02 (15) | O6—P2—O7 | 110.3 (2) |
O2—Rb2—O4i | 144.40 (11) | O6—P2—O8 | 110.3 (3) |
O2—Rb2—O1 | 57.47 (10) | O7—P2—O8 | 105.9 (3) |
Symmetry code: (i) x+1/2, −y+1/2, z. |
Crystal data top
Ge0.121O10P2Rb2Ti1.879 | F(000) = 916.8 |
Mr = 491.62 | Dx = 3.714 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2c -2n | Cell parameters from 23 reflections |
a = 12.9386 (18) Å | θ = 19.6–27.3° |
b = 6.5085 (8) Å | µ = 13.53 mm−1 |
c = 10.4408 (10) Å | T = 293 K |
V = 879.23 (18) Å3 | Rectangular, colourless |
Z = 4 | 0.60 × 0.10 × 0.04 mm |
Data collection top
Siemens SMART CCD diffractometer | 2513 independent reflections |
Radiation source: normal-focus sealed tube | 2513 reflections with F > 0σ(F) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 29.8°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −18→18 |
Tmin = 0.207, Tmax = 0.578 | k = −9→9 |
12286 measured reflections | l = −14→14 |
Refinement top
Refinement on F | w = 1/[σ2(F) + 0.0015(F)2] |
Least-squares matrix: full | (Δ/σ)max = 0.00039 |
R[F2 > 2σ(F2)] = 0.021 | Δρmax = 0.61 e Å−3 |
wR(F2) = 0.032 | Δρmin = −0.60 e Å−3 |
S = 1.05 | Extinction correction: Isotropic Gaussian, Zachariasen, 1967; Larson (1970), Eq22 p292 "Cryst. Comp." Munksgaard 1970 |
2513 reflections | Extinction coefficient: 4E2 (1) |
158 parameters | Absolute structure: Flack (1983) parameter refined |
0 restraints | Absolute structure parameter: 0.429 (8) |
21 constraints | |
Crystal data top
Ge0.121O10P2Rb2Ti1.879 | V = 879.23 (18) Å3 |
Mr = 491.62 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.9386 (18) Å | µ = 13.53 mm−1 |
b = 6.5085 (8) Å | T = 293 K |
c = 10.4408 (10) Å | 0.60 × 0.10 × 0.04 mm |
Data collection top
Siemens SMART CCD diffractometer | 2513 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2513 reflections with F > 0σ(F) |
Tmin = 0.207, Tmax = 0.578 | Rint = 0.031 |
12286 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.032 | Δρmax = 0.61 e Å−3 |
S = 1.05 | Δρmin = −0.60 e Å−3 |
2513 reflections | Absolute structure: Flack (1983) parameter refined |
158 parameters | Absolute structure parameter: 0.429 (8) |
Special details top
Refinement. The following constraints were used during the refinement: H-atom parameters constrained pop(Rb1b)=1.0–1.0*pop(Rb1a) H-atom parameters constrained U11(Rb1b)=0.0 + 1.0*U11(Rb1a) H-atom parameters constrained U22(Rb1b)=0.0 + 1.0*U22(Rb1a) H-atom parameters constrained U33(Rb1b)=0.0 + 1.0*U33(Rb1a) H-atom parameters constrained U12(Rb1b)=0.0 + 1.0*U12(Rb1a) H-atom parameters constrained U13(Rb1b)=0.0 + 1.0*U13(Rb1a) H-atom parameters constrained U23(Rb1b)=0.0 + 1.0*U23(Rb1a) H-atom parameters constrained pop(Rb2b)=1.0–1.0*pop(Rb2a) H-atom parameters constrained U11(Rb2b)=0.0 + 1.0*U11(Rb2a) H-atom parameters constrained U22(Rb2b)=0.0 + 1.0*U22(Rb2a) H-atom parameters constrained U33(Rb2b)=0.0 + 1.0*U33(Rb2a) H-atom parameters constrained U12(Rb2b)=0.0 + 1.0*U12(Rb2a) H-atom parameters constrained U13(Rb2b)=0.0 + 1.0*U13(Rb2a) H-atom parameters constrained U23(Rb2b)=0.0 + 1.0*U23(Rb2a) H-atom parameters constrained pop(Ge2)=1.0–1.0*pop(Ti2) H-atom parameters constrained U11(Ge2)=0.0 + 1.0*U11(Ti2) H-atom parameters constrained U22(Ge2)=0.0 + 1.0*U22(Ti2) H-atom parameters constrained U33(Ge2)=0.0 + 1.0*U33(Ti2) H-atom parameters constrained U12(Ge2)=0.0 + 1.0*U12(Ti2) H-atom parameters constrained U13(Ge2)=0.0 + 1.0*U13(Ti2) H-atom parameters constrained U23(Ge2)=0.0 + 1.0*U23(Ti2) No restraints used. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rb1a | 0.61417 (4) | 0.78418 (8) | 0.6950 (2) | 0.0186 (4) | 0.927 (5) |
Rb1b | 0.6075 (7) | 0.7936 (12) | 0.6430 (17) | 0.0186 (4) | 0.073 (5) |
Rb2a | 0.89399 (4) | 0.69389 (9) | 0.94809 (19) | 0.0164 (5) | 0.945 (11) |
Rb2b | 0.8911 (9) | 0.699 (2) | 0.905 (4) | 0.0164 (5) | 0.055 (11) |
Ti1 | 0.62797 (5) | 0.49940 (9) | 1.0236 (3) | 0.0058 (3) | |
Ti2 | 0.7536 (4) | 0.2656 (7) | 0.7738 (6) | 0.0049 (9) | 0.879 (6) |
Ge2 | 0.7464 (19) | 0.245 (3) | 0.766 (2) | 0.0049 (9) | 0.121 (6) |
P1 | 0.50047 (7) | 0.33234 (15) | 0.7685 (3) | 0.0060 (4) | |
P2 | 0.82052 (7) | 0.50249 (13) | 0.5159 (3) | 0.0059 (4) | |
O1 | 0.5140 (3) | 0.4766 (5) | 0.8819 (4) | 0.0118 (14) | |
O2 | 0.4859 (3) | 0.4611 (5) | 0.6455 (4) | 0.0108 (14) | |
O3 | 0.5981 (2) | 0.2009 (5) | 0.7464 (4) | 0.0106 (14) | |
O4 | 0.4049 (2) | 0.1936 (5) | 0.7895 (4) | 0.0104 (14) | |
O11 | 0.7219 (2) | 0.4582 (5) | 0.8860 (4) | 0.0109 (13) | |
O12 | 0.7771 (2) | 0.0490 (5) | 0.6396 (4) | 0.0102 (13) | |
O5 | 0.8869 (2) | 0.3134 (5) | 0.4837 (4) | 0.0111 (14) | |
O6 | 0.8873 (2) | 0.6918 (5) | 0.5457 (4) | 0.0117 (14) | |
O7 | 0.7485 (3) | 0.5443 (5) | 0.4004 (4) | 0.0118 (13) | |
O8 | 0.7480 (3) | 0.4570 (5) | 0.630 (5) | 0.0117 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1a | 0.0199 (2) | 0.0093 (2) | 0.0266 (7) | −0.00422 (14) | 0.0062 (2) | −0.0018 (2) |
Rb1b | 0.0199 (2) | 0.0093 (2) | 0.0266 (7) | −0.00422 (14) | 0.0062 (2) | −0.0018 (2) |
Rb2a | 0.0119 (2) | 0.0152 (2) | 0.0219 (9) | −0.00397 (13) | 0.0011 (2) | −0.0019 (2) |
Rb2b | 0.0119 (2) | 0.0152 (2) | 0.0219 (9) | −0.00397 (13) | 0.0011 (2) | −0.0019 (2) |
Ti1 | 0.0060 (3) | 0.0048 (3) | 0.0065 (3) | 0.0007 (2) | −0.0012 (3) | −0.0007 (2) |
Ti2 | 0.0052 (9) | 0.0045 (11) | 0.0050 (8) | −0.0022 (6) | −0.0006 (6) | 0.0006 (7) |
Ge2 | 0.0052 (9) | 0.0045 (11) | 0.0050 (8) | −0.0022 (6) | −0.0006 (6) | 0.0006 (7) |
P1 | 0.0051 (4) | 0.0057 (4) | 0.0073 (4) | −0.0007 (3) | −0.0011 (3) | −0.0007 (4) |
P2 | 0.0067 (4) | 0.0049 (4) | 0.0062 (4) | −0.0001 (3) | −0.0001 (3) | 0.0007 (3) |
O1 | 0.0098 (14) | 0.0115 (15) | 0.0142 (14) | 0.0023 (11) | −0.0038 (11) | −0.0053 (12) |
O2 | 0.0092 (14) | 0.0101 (14) | 0.0132 (13) | −0.0037 (11) | −0.0030 (10) | 0.0055 (11) |
O3 | 0.0078 (14) | 0.0090 (14) | 0.0152 (14) | −0.0017 (9) | 0.0008 (10) | −0.0047 (11) |
O4 | 0.0068 (13) | 0.0091 (14) | 0.0153 (15) | −0.0022 (9) | 0.0002 (10) | 0.0015 (11) |
O11 | 0.0092 (13) | 0.0113 (13) | 0.0122 (13) | −0.0017 (11) | 0.0012 (10) | −0.0035 (11) |
O12 | 0.0103 (14) | 0.0093 (13) | 0.0109 (12) | −0.0014 (11) | 0.0035 (10) | 0.0008 (11) |
O5 | 0.0128 (14) | 0.0070 (14) | 0.0134 (14) | −0.0011 (10) | 0.0030 (9) | 0.0028 (11) |
O6 | 0.0157 (15) | 0.0073 (14) | 0.0122 (15) | −0.0003 (9) | −0.0034 (10) | −0.0009 (10) |
O7 | 0.0151 (14) | 0.0100 (13) | 0.0103 (12) | −0.0029 (12) | −0.0030 (10) | 0.0032 (11) |
O8 | 0.0110 (14) | 0.0113 (14) | 0.0127 (14) | 0.0041 (10) | 0.0049 (11) | 0.0026 (11) |
Geometric parameters (Å, º) top
Rb1a—O1 | 3.082 (4) | Rb2b—O7 | 2.882 (13) |
Rb1a—O2 | 2.728 (4) | Ti1—O1 | 2.094 (4) |
Rb1a—O3 | 2.773 (3) | Ti1—O2 | 1.964 (4) |
Rb1a—O11 | 3.228 (4) | Ti1—O11 | 1.902 (4) |
Rb1a—O12 | 2.783 (3) | Ti1—O12 | 1.755 (4) |
Rb1a—O5 | 3.021 (5) | Ti1—O5 | 2.095 (4) |
Rb1a—O6 | 3.327 (4) | Ti1—O6 | 2.025 (3) |
Rb1a—O7 | 3.260 (4) | Ti2—O3 | 2.077 (6) |
Rb1a—O8 | 2.828 (13) | Ti2—O4i | 1.982 (6) |
Rb1a—Rb1b | 0.553 (17) | Ti2—O11 | 1.764 (7) |
Rb1b—O2 | 2.675 (9) | Ti2—O12 | 2.011 (7) |
Rb1b—O3 | 2.865 (10) | Ti2—O7 | 1.956 (7) |
Rb1b—O12 | 2.753 (9) | Ti2—O8 | 1.95 (4) |
Rb1b—O6 | 3.026 (10) | Ti2—Ge2 | 0.18 (2) |
Rb1b—O8 | 2.850 (9) | Ge2—O3 | 1.95 (2) |
Rb2a—O1 | 2.737 (4) | Ge2—O4i | 2.10 (2) |
Rb2a—O2 | 3.113 (4) | Ge2—O11 | 1.89 (2) |
Rb2a—O3 | 3.116 (5) | Ge2—O12 | 1.88 (2) |
Rb2a—O4i | 3.020 (4) | Ge2—O7 | 1.92 (2) |
Rb2a—O11 | 2.780 (3) | Ge2—O8 | 1.98 (4) |
Rb2a—O12 | 3.128 (4) | P1—O1 | 1.521 (5) |
Rb2a—O5 | 2.859 (3) | P1—O2 | 1.545 (5) |
Rb2a—O7 | 2.974 (4) | P1—O3 | 1.542 (3) |
Rb2a—O8 | 3.15 (3) | P1—O4 | 1.546 (3) |
Rb2a—Rb2b | 0.45 (4) | P2—O5 | 1.538 (3) |
Rb2b—O1 | 2.652 (13) | P2—O6 | 1.536 (3) |
Rb2b—O4i | 2.83 (2) | P2—O7 | 1.548 (5) |
Rb2b—O11 | 2.701 (13) | P2—O8 | 1.54 (4) |
Rb2b—O5 | 2.988 (16) | | |
| | | |
O1—Rb1a—O2 | 50.46 (11) | O12—Rb2a—O1 | 143.05 (11) |
O1—Rb1a—O11 | 50.47 (9) | O7—Rb2a—O8 | 47.3 (7) |
O1—Rb1a—O8 | 85.4 (7) | O7—Rb2a—O4i | 125.28 (11) |
O1—Rb1a—O3 | 118.76 (13) | O7—Rb2a—O1 | 73.05 (10) |
O1—Rb1a—O12 | 148.47 (13) | O8—Rb2a—O4i | 144.30 (13) |
O1—Rb1a—O5 | 53.62 (10) | O8—Rb2a—O1 | 93.3 (2) |
O1—Rb1a—O7 | 98.62 (12) | O4i—Rb2a—O1 | 119.31 (12) |
O1—Rb1a—O6 | 87.48 (10) | O11—Rb2b—O5 | 141.6 (6) |
O2—Rb1a—O11 | 82.72 (10) | O11—Rb2b—O7 | 86.8 (4) |
O2—Rb1a—O8 | 75.32 (17) | O11—Rb2b—O4i | 59.7 (4) |
O2—Rb1a—O3 | 138.15 (10) | O11—Rb2b—O1 | 160.2 (9) |
O2—Rb1a—O12 | 153.97 (14) | O5—Rb2b—O7 | 129.0 (6) |
O2—Rb1a—O5 | 103.57 (12) | O5—Rb2b—O4i | 91.8 (4) |
O2—Rb1a—O7 | 148.93 (14) | O5—Rb2b—O1 | 58.1 (3) |
O2—Rb1a—O6 | 53.90 (10) | O7—Rb2b—O4i | 137.3 (9) |
O11—Rb1a—O8 | 52.4 (10) | O7—Rb2b—O1 | 75.8 (3) |
O11—Rb1a—O3 | 123.76 (13) | O4i—Rb2b—O1 | 129.9 (10) |
O11—Rb1a—O12 | 102.02 (10) | O1—Ti1—O11 | 84.62 (19) |
O11—Rb1a—O5 | 55.03 (10) | O1—Ti1—O2 | 86.49 (15) |
O11—Rb1a—O7 | 72.50 (10) | O1—Ti1—O6 | 86.66 (15) |
O11—Rb1a—O6 | 134.53 (8) | O1—Ti1—O12 | 173.45 (15) |
O8—Rb1a—O3 | 146.03 (10) | O1—Ti1—O5 | 82.17 (16) |
O8—Rb1a—O12 | 87.3 (2) | O11—Ti1—O2 | 171.1 (2) |
O8—Rb1a—O5 | 106.9 (10) | O11—Ti1—O6 | 90.51 (16) |
O8—Rb1a—O7 | 102.5 (6) | O11—Ti1—O12 | 95.71 (16) |
O8—Rb1a—O6 | 117.6 (7) | O11—Ti1—O5 | 92.62 (17) |
O3—Rb1a—O12 | 59.44 (10) | O2—Ti1—O6 | 89.00 (16) |
O3—Rb1a—O5 | 75.22 (12) | O2—Ti1—O12 | 93.1 (2) |
O3—Rb1a—O7 | 53.53 (10) | O2—Ti1—O5 | 86.12 (15) |
O3—Rb1a—O6 | 88.76 (9) | O6—Ti1—O12 | 99.87 (17) |
O12—Rb1a—O5 | 99.90 (11) | O6—Ti1—O5 | 168.06 (15) |
O12—Rb1a—O7 | 53.30 (11) | O12—Ti1—O5 | 91.28 (15) |
O12—Rb1a—O6 | 122.80 (11) | O3—Ti2—O11 | 90.6 (3) |
O5—Rb1a—O7 | 46.61 (9) | O3—Ti2—O12 | 84.7 (2) |
O5—Rb1a—O6 | 117.41 (10) | O3—Ti2—O8 | 89.2 (3) |
O7—Rb1a—O6 | 139.89 (9) | O3—Ti2—O7 | 86.0 (2) |
O2—Rb1b—O8 | 75.8 (2) | O3—Ti2—O4i | 174.8 (3) |
O2—Rb1b—O3 | 136.0 (5) | O11—Ti2—O12 | 174.9 (4) |
O2—Rb1b—O12 | 163.2 (4) | O11—Ti2—O8 | 92.8 (10) |
O2—Rb1b—O6 | 58.3 (2) | O11—Ti2—O7 | 94.1 (3) |
O8—Rb1b—O3 | 139.2 (7) | O11—Ti2—O4i | 94.6 (3) |
O8—Rb1b—O12 | 87.4 (3) | O12—Ti2—O8 | 85.2 (10) |
O8—Rb1b—O6 | 127.5 (6) | O12—Ti2—O7 | 87.5 (2) |
O3—Rb1b—O12 | 58.7 (2) | O12—Ti2—O4i | 90.2 (3) |
O3—Rb1b—O6 | 93.3 (3) | O8—Ti2—O7 | 171.6 (9) |
O12—Rb1b—O6 | 136.6 (4) | O8—Ti2—O4i | 90.9 (3) |
O11—Rb2a—O5 | 144.59 (10) | O7—Ti2—O4i | 93.2 (3) |
O11—Rb2a—O2 | 149.60 (12) | O3—Ge2—O11 | 90.8 (10) |
O11—Rb2a—O3 | 105.53 (11) | O3—Ge2—O12 | 91.9 (10) |
O11—Rb2a—O12 | 54.28 (10) | O3—Ge2—O8 | 92.1 (10) |
O11—Rb2a—O7 | 83.55 (10) | O3—Ge2—O7 | 90.7 (10) |
O11—Rb2a—O8 | 88.5 (3) | O3—Ge2—O4i | 177.5 (13) |
O11—Rb2a—O4i | 56.56 (9) | O11—Ge2—O12 | 175.3 (14) |
O11—Rb2a—O1 | 145.88 (13) | O11—Ge2—O8 | 88.1 (14) |
O5—Rb2a—O2 | 55.13 (10) | O11—Ge2—O7 | 91.3 (11) |
O5—Rb2a—O3 | 80.65 (11) | O11—Ge2—O4i | 87.0 (9) |
O5—Rb2a—O12 | 127.83 (12) | O12—Ge2—O8 | 88.0 (14) |
O5—Rb2a—O7 | 130.46 (10) | O12—Ge2—O7 | 92.5 (10) |
O5—Rb2a—O8 | 120.6 (5) | O12—Ge2—O4i | 90.2 (10) |
O5—Rb2a—O4i | 90.63 (10) | O8—Ge2—O7 | 177.2 (15) |
O5—Rb2a—O1 | 58.89 (10) | O8—Ge2—O4i | 86.6 (9) |
O2—Rb2a—O3 | 46.65 (9) | O7—Ge2—O4i | 90.6 (10) |
O2—Rb2a—O12 | 95.65 (11) | O1—P1—O2 | 109.0 (2) |
O2—Rb2a—O7 | 89.53 (10) | O1—P1—O3 | 111.4 (2) |
O2—Rb2a—O8 | 65.7 (4) | O1—P1—O4 | 110.0 (3) |
O2—Rb2a—O4i | 143.73 (9) | O2—P1—O3 | 106.0 (3) |
O2—Rb2a—O1 | 56.35 (11) | O2—P1—O4 | 109.7 (2) |
O3—Rb2a—O12 | 52.35 (9) | O3—P1—O4 | 110.61 (17) |
O3—Rb2a—O7 | 100.16 (10) | O5—P2—O6 | 111.83 (17) |
O3—Rb2a—O8 | 53.8 (7) | O5—P2—O7 | 107.8 (3) |
O3—Rb2a—O4i | 123.95 (10) | O5—P2—O8 | 110.8 (2) |
O3—Rb2a—O1 | 102.83 (11) | O6—P2—O7 | 110.8 (2) |
O12—Rb2a—O7 | 84.24 (10) | O6—P2—O8 | 109.9 (10) |
O12—Rb2a—O8 | 50.6 (3) | O7—P2—O8 | 105.5 (11) |
O12—Rb2a—O4i | 97.56 (9) | | |
Symmetry code: (i) x+1/2, −y+1/2, z. |
Crystal data top
Ge0.35O10P2Rb2Ti1.65 | F(000) = 925.6 |
Mr = 497.28 | Dx = 3.785 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2c -2n | Cell parameters from 19 reflections |
a = 12.9179 (12) Å | θ = 16.3–29.6° |
b = 6.5189 (8) Å | µ = 14.21 mm−1 |
c = 10.3633 (14) Å | T = 293 K |
V = 872.70 (18) Å3 | Rectangular, colourless |
Z = 4 | 0.10 × 0.05 × 0.04 mm |
Data collection top
Siemens SMART CCD diffractometer | 2497 independent reflections |
Radiation source: normal-focus sealed tube | 2497 reflections with F > 0σ(F) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 29.8°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −18→18 |
Tmin = 0.421, Tmax = 0.564 | k = −9→9 |
12604 measured reflections | l = −14→14 |
Refinement top
Refinement on F | 34 constraints |
Least-squares matrix: full | w = 1/[σ2(F) + 0.0020(F)2] |
R[F2 > 2σ(F2)] = 0.025 | (Δ/σ)max = 0.001 |
wR(F2) = 0.039 | Δρmax = 0.73 e Å−3 |
S = 1.04 | Δρmin = −0.91 e Å−3 |
2497 reflections | Absolute structure: Flack (1983) parameter refined |
156 parameters | Absolute structure parameter: 0.487 (11) |
0 restraints | |
Crystal data top
Ge0.35O10P2Rb2Ti1.65 | V = 872.70 (18) Å3 |
Mr = 497.28 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.9179 (12) Å | µ = 14.21 mm−1 |
b = 6.5189 (8) Å | T = 293 K |
c = 10.3633 (14) Å | 0.10 × 0.05 × 0.04 mm |
Data collection top
Siemens SMART CCD diffractometer | 2497 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2497 reflections with F > 0σ(F) |
Tmin = 0.421, Tmax = 0.564 | Rint = 0.039 |
12604 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.039 | Δρmax = 0.73 e Å−3 |
S = 1.04 | Δρmin = −0.91 e Å−3 |
2497 reflections | Absolute structure: Flack (1983) parameter refined |
156 parameters | Absolute structure parameter: 0.487 (11) |
Special details top
Refinement. The following constraints were used during the refinement: H-atom parameters constrained pop(Rb1b)=1.0–1.0*pop(Rb1a) H-atom parameters constrained U11(Rb1b)=0.0 + 1.0*U11(Rb1a) H-atom parameters constrained U22(Rb1b)=0.0 + 1.0*U22(Rb1a) H-atom parameters constrained U33(Rb1b)=0.0 + 1.0*U33(Rb1a) H-atom parameters constrained U12(Rb1b)=0.0 + 1.0*U12(Rb1a) H-atom parameters constrained U13(Rb1b)=0.0 + 1.0*U13(Rb1a) H-atom parameters constrained U23(Rb1b)=0.0 + 1.0*U23(Rb1a) H-atom parameters constrained pop(Rb2b)=1.0–1.0*pop(Rb2a) H-atom parameters constrained U11(Rb2b)=0.0 + 1.0*U11(Rb2a) H-atom parameters constrained U22(Rb2b)=0.0 + 1.0*U22(Rb2a) H-atom parameters constrained U33(Rb2b)=0.0 + 1.0*U33(Rb2a) H-atom parameters constrained U12(Rb2b)=0.0 + 1.0*U12(Rb2a) H-atom parameters constrained U13(Rb2b)=0.0 + 1.0*U13(Rb2a) H-atom parameters constrained U23(Rb2b)=0.0 + 1.0*U23(Rb2a) H-atom parameters constrained pop(Ge1)=1.0–1.0*pop(Ti1) H-atom parameters constrained x(Ge1)=0.0 + 1.0*x(Ti1) H-atom parameters constrained y(Ge1)=0.0 + 1.0*y(Ti1) H-atom parameters constrained z(Ge1)=0.0 + 1.0*z(Ti1) H-atom parameters constrained U11(Ge1)=0.0 + 1.0*U11(Ti1) H-atom parameters constrained U22(Ge1)=0.0 + 1.0*U22(Ti1) H-atom parameters constrained U33(Ge1)=0.0 + 1.0*U33(Ti1) H-atom parameters constrained U12(Ge1)=0.0 + 1.0*U12(Ti1) H-atom parameters constrained U13(Ge1)=0.0 + 1.0*U13(Ti1) H-atom parameters constrained U23(Ge1)=0.0 + 1.0*U23(Ti1) H-atom parameters constrained pop(Ge2)=1.0–1.0*pop(Ti2) H-atom parameters constrained x(Ge2)=0.0 + 1.0*x(Ti2) H-atom parameters constrained y(Ge2)=0.0 + 1.0*y(Ti2) H-atom parameters constrained z(Ge2)=0.0 + 1.0*z(Ti2) H-atom parameters constrained U11(Ge2)=0.0 + 1.0*U11(Ti2) H-atom parameters constrained U22(Ge2)=0.0 + 1.0*U22(Ti2) H-atom parameters constrained U33(Ge2)=0.0 + 1.0*U33(Ti2) H-atom parameters constrained U12(Ge2)=0.0 + 1.0*U12(Ti2) H-atom parameters constrained U13(Ge2)=0.0 + 1.0*U13(Ti2) H-atom parameters constrained U23(Ge2)=0.0 + 1.0*U23(Ti2) No restraints used. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Rb1a | 0.61351 (7) | 0.78509 (13) | 0.6842 (3) | 0.0204 (6) | 0.883 (8) |
Rb1b | 0.6079 (7) | 0.7937 (13) | 0.6302 (19) | 0.0204 (6) | 0.117 (8) |
Rb2a | 0.89346 (7) | 0.69529 (14) | 0.9373 (3) | 0.0183 (6) | 0.939 (6) |
Rb2b | 0.8892 (11) | 0.705 (2) | 0.880 (3) | 0.0183 (6) | 0.061 (6) |
Ti1 | 0.62817 (7) | 0.49922 (13) | 1.0151 (2) | 0.0078 (5) | 0.875 (10) |
Ge1 | 0.62817 (7) | 0.49922 (13) | 1.0151 (2) | 0.0078 (5) | 0.125 (10) |
Ti2 | 0.75268 (6) | 0.25812 (12) | 0.7649 (3) | 0.0078 (4) | 0.775 (8) |
Ge2 | 0.75268 (6) | 0.25812 (12) | 0.7649 (3) | 0.0078 (4) | 0.225 (8) |
P1 | 0.50068 (10) | 0.3321 (2) | 0.7620 (4) | 0.0070 (6) | |
P2 | 0.82103 (11) | 0.5026 (2) | 0.5103 (3) | 0.0064 (6) | |
O1 | 0.5150 (5) | 0.4773 (10) | 0.8759 (7) | 0.015 (3) | |
O2 | 0.4860 (5) | 0.4610 (10) | 0.6390 (7) | 0.013 (3) | |
O3 | 0.5979 (3) | 0.1994 (7) | 0.7407 (7) | 0.011 (2) | |
O4 | 0.4050 (3) | 0.1940 (7) | 0.7845 (5) | 0.011 (2) | |
O11 | 0.7216 (4) | 0.4563 (10) | 0.8817 (6) | 0.011 (2) | |
O12 | 0.7765 (5) | 0.0514 (9) | 0.6353 (6) | 0.012 (2) | |
O5 | 0.8872 (3) | 0.3131 (8) | 0.4784 (6) | 0.013 (2) | |
O6 | 0.8875 (4) | 0.6919 (9) | 0.5404 (7) | 0.012 (3) | |
O7 | 0.7479 (5) | 0.5444 (11) | 0.3955 (6) | 0.014 (2) | |
O8 | 0.7487 (5) | 0.4587 (10) | 0.6258 (6) | 0.013 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Rb1a | 0.0195 (4) | 0.0107 (3) | 0.0310 (12) | −0.0042 (2) | 0.0076 (4) | −0.0028 (4) |
Rb1b | 0.0195 (4) | 0.0107 (3) | 0.0310 (12) | −0.0042 (2) | 0.0076 (4) | −0.0028 (4) |
Rb2a | 0.0120 (3) | 0.0157 (4) | 0.0271 (9) | −0.0043 (2) | 0.0016 (4) | −0.0023 (4) |
Rb2b | 0.0120 (3) | 0.0157 (4) | 0.0271 (9) | −0.0043 (2) | 0.0016 (4) | −0.0023 (4) |
Ti1 | 0.0073 (5) | 0.0073 (5) | 0.0089 (5) | −0.0002 (3) | −0.0007 (4) | −0.0002 (3) |
Ge1 | 0.0073 (5) | 0.0073 (5) | 0.0089 (5) | −0.0002 (3) | −0.0007 (4) | −0.0002 (3) |
Ti2 | 0.0059 (4) | 0.0099 (4) | 0.0075 (6) | −0.0001 (3) | 0.0004 (4) | 0.0026 (4) |
Ge2 | 0.0059 (4) | 0.0099 (4) | 0.0075 (6) | −0.0001 (3) | 0.0004 (4) | 0.0026 (4) |
P1 | 0.0057 (5) | 0.0063 (5) | 0.0089 (7) | −0.0006 (4) | −0.0005 (6) | −0.0003 (8) |
P2 | 0.0060 (6) | 0.0064 (6) | 0.0069 (6) | 0.0001 (5) | −0.0004 (6) | 0.0005 (5) |
O1 | 0.010 (3) | 0.008 (2) | 0.025 (3) | 0.0028 (19) | −0.002 (2) | −0.006 (2) |
O2 | 0.009 (3) | 0.015 (3) | 0.015 (2) | −0.003 (2) | −0.004 (2) | 0.006 (2) |
O3 | 0.0059 (17) | 0.0100 (19) | 0.016 (3) | −0.0027 (11) | 0.001 (2) | −0.005 (2) |
O4 | 0.007 (2) | 0.013 (2) | 0.012 (3) | −0.0011 (13) | 0.0012 (15) | 0.0007 (16) |
O11 | 0.008 (2) | 0.014 (2) | 0.012 (2) | −0.004 (2) | 0.0017 (18) | −0.004 (2) |
O12 | 0.013 (3) | 0.009 (2) | 0.014 (2) | −0.000 (2) | 0.002 (2) | −0.0022 (18) |
O5 | 0.011 (2) | 0.008 (2) | 0.021 (3) | 0.0009 (16) | 0.0020 (17) | 0.0015 (19) |
O6 | 0.016 (3) | 0.010 (2) | 0.011 (3) | −0.0013 (18) | −0.0041 (19) | 0.0001 (19) |
O7 | 0.014 (3) | 0.016 (2) | 0.012 (2) | −0.004 (2) | −0.0050 (19) | 0.004 (2) |
O8 | 0.015 (3) | 0.010 (2) | 0.015 (2) | 0.007 (2) | 0.006 (2) | 0.004 (2) |
Geometric parameters (Å, º) top
Rb1a—O1 | 3.098 (7) | Ti1—O2 | 1.973 (7) |
Rb1a—O2 | 2.720 (7) | Ti1—O11 | 1.856 (6) |
Rb1a—O3 | 2.771 (5) | Ti1—O12 | 1.785 (6) |
Rb1a—O11 | 3.277 (7) | Ti1—O5 | 2.090 (5) |
Rb1a—O12 | 2.776 (6) | Ti1—O6 | 2.030 (6) |
Rb1a—O5 | 3.055 (7) | Ge1—O1 | 2.058 (7) |
Rb1a—O6 | 3.281 (6) | Ge1—O2 | 1.973 (7) |
Rb1a—O7 | 3.295 (7) | Ge1—O11 | 1.856 (6) |
Rb1a—O8 | 2.818 (6) | Ge1—O12 | 1.785 (6) |
Rb1a—Rb1b | 0.57 (2) | Ge1—O5 | 2.090 (5) |
Rb1b—O2 | 2.682 (11) | Ge1—O6 | 2.030 (6) |
Rb1b—O3 | 2.886 (12) | Ti2—O3 | 2.051 (4) |
Rb1b—O12 | 2.751 (10) | Ti2—O4i | 2.003 (4) |
Rb1b—O6 | 2.996 (12) | Ti2—O11 | 1.816 (7) |
Rb1b—O8 | 2.842 (11) | Ti2—O12 | 1.927 (7) |
Rb2a—O1 | 2.725 (6) | Ti2—O7 | 1.942 (7) |
Rb2a—O2 | 3.130 (7) | Ti2—O8 | 1.947 (7) |
Rb2a—O3 | 3.147 (8) | Ge2—O3 | 2.051 (4) |
Rb2a—O4i | 2.995 (5) | Ge2—O4i | 2.003 (4) |
Rb2a—O11 | 2.773 (6) | Ge2—O11 | 1.816 (7) |
Rb2a—O12 | 3.149 (6) | Ge2—O12 | 1.927 (7) |
Rb2a—O5 | 2.866 (5) | Ge2—O7 | 1.942 (7) |
Rb2a—O7 | 2.950 (7) | Ge2—O8 | 1.947 (7) |
Rb2a—O8 | 3.184 (7) | P1—O1 | 1.525 (8) |
Rb2a—Rb2b | 0.60 (3) | P1—O2 | 1.538 (8) |
Rb2b—O1 | 2.632 (16) | P1—O3 | 1.540 (4) |
Rb2b—O4i | 2.792 (19) | P1—O4 | 1.546 (5) |
Rb2b—O11 | 2.706 (16) | P2—O5 | 1.538 (5) |
Rb2b—O5 | 3.067 (18) | P2—O6 | 1.536 (6) |
Rb2b—O7 | 2.837 (16) | P2—O7 | 1.544 (7) |
Ti1—O1 | 2.058 (7) | P2—O8 | 1.545 (7) |
| | | |
O1—Rb1a—O2 | 50.1 (2) | O11—Rb2b—O5 | 136.7 (8) |
O1—Rb1a—O11 | 49.49 (16) | O11—Rb2b—O7 | 88.1 (4) |
O1—Rb1a—O8 | 84.44 (18) | O11—Rb2b—O4i | 60.1 (4) |
O1—Rb1a—O3 | 117.8 (2) | O11—Rb2b—O1 | 165.0 (6) |
O1—Rb1a—O12 | 146.5 (2) | O5—Rb2b—O7 | 126.8 (7) |
O1—Rb1a—O5 | 52.92 (17) | O5—Rb2b—O4i | 90.7 (4) |
O1—Rb1a—O7 | 97.4 (2) | O5—Rb2b—O1 | 56.9 (3) |
O1—Rb1a—O6 | 87.45 (16) | O7—Rb2b—O4i | 142.4 (8) |
O2—Rb1a—O11 | 81.80 (18) | O7—Rb2b—O1 | 76.9 (4) |
O2—Rb1a—O8 | 75.63 (19) | O4i—Rb2b—O1 | 133.0 (8) |
O2—Rb1a—O3 | 138.54 (16) | O1—Ti1—O11 | 86.0 (3) |
O2—Rb1a—O12 | 156.1 (2) | O1—Ti1—O2 | 86.2 (3) |
O2—Rb1a—O5 | 102.49 (19) | O1—Ti1—O6 | 87.2 (3) |
O2—Rb1a—O7 | 147.3 (2) | O1—Ti1—O12 | 173.0 (3) |
O2—Rb1a—O6 | 54.44 (17) | O1—Ti1—O5 | 82.7 (2) |
O11—Rb1a—O8 | 51.40 (17) | O11—Ti1—O2 | 172.2 (3) |
O11—Rb1a—O3 | 122.4 (2) | O11—Ti1—O6 | 90.7 (3) |
O11—Rb1a—O12 | 101.52 (17) | O11—Ti1—O12 | 95.8 (3) |
O11—Rb1a—O5 | 54.30 (15) | O11—Ti1—O5 | 94.2 (3) |
O11—Rb1a—O7 | 71.87 (17) | O2—Ti1—O6 | 88.3 (3) |
O11—Rb1a—O6 | 133.85 (15) | O2—Ti1—O12 | 92.0 (3) |
O8—Rb1a—O3 | 145.73 (16) | O2—Ti1—O5 | 85.3 (2) |
O8—Rb1a—O12 | 87.88 (18) | O6—Ti1—O12 | 99.6 (3) |
O8—Rb1a—O5 | 105.13 (17) | O6—Ti1—O5 | 168.4 (2) |
O8—Rb1a—O7 | 101.14 (18) | O12—Ti1—O5 | 90.3 (3) |
O8—Rb1a—O6 | 119.23 (19) | O1—Ge1—O11 | 86.0 (3) |
O3—Rb1a—O12 | 58.95 (15) | O1—Ge1—O2 | 86.2 (3) |
O3—Rb1a—O5 | 74.4 (2) | O1—Ge1—O6 | 87.2 (3) |
O3—Rb1a—O7 | 53.05 (17) | O1—Ge1—O12 | 173.0 (3) |
O3—Rb1a—O6 | 89.24 (15) | O1—Ge1—O5 | 82.7 (2) |
O12—Rb1a—O5 | 98.44 (17) | O11—Ge1—O2 | 172.2 (3) |
O12—Rb1a—O7 | 52.27 (17) | O11—Ge1—O6 | 90.7 (3) |
O12—Rb1a—O6 | 124.31 (19) | O11—Ge1—O12 | 95.8 (3) |
O5—Rb1a—O7 | 46.18 (15) | O11—Ge1—O5 | 94.2 (3) |
O5—Rb1a—O6 | 116.62 (16) | O2—Ge1—O6 | 88.3 (3) |
O7—Rb1a—O6 | 139.62 (16) | O2—Ge1—O12 | 92.0 (3) |
O2—Rb1b—O8 | 75.8 (3) | O2—Ge1—O5 | 85.3 (2) |
O2—Rb1b—O3 | 134.5 (5) | O6—Ge1—O12 | 99.6 (3) |
O2—Rb1b—O12 | 163.4 (4) | O6—Ge1—O5 | 168.4 (2) |
O2—Rb1b—O6 | 58.5 (3) | O12—Ge1—O5 | 90.3 (3) |
O8—Rb1b—O3 | 137.7 (5) | O3—Ti2—O11 | 89.9 (3) |
O8—Rb1b—O12 | 87.9 (3) | O3—Ti2—O12 | 86.6 (3) |
O8—Rb1b—O6 | 128.8 (4) | O3—Ti2—O8 | 90.5 (3) |
O3—Rb1b—O12 | 57.9 (2) | O3—Ti2—O7 | 87.0 (3) |
O3—Rb1b—O6 | 93.0 (3) | O3—Ti2—O4i | 177.8 (2) |
O12—Rb1b—O6 | 137.6 (4) | O11—Ti2—O12 | 176.0 (3) |
O11—Rb2a—O5 | 144.28 (17) | O11—Ti2—O8 | 90.6 (3) |
O11—Rb2a—O2 | 148.0 (2) | O11—Ti2—O7 | 92.6 (3) |
O11—Rb2a—O3 | 103.93 (16) | O11—Ti2—O4i | 92.2 (2) |
O11—Rb2a—O12 | 53.81 (17) | O12—Ti2—O8 | 87.6 (3) |
O11—Rb2a—O7 | 84.69 (18) | O12—Ti2—O7 | 89.1 (3) |
O11—Rb2a—O8 | 88.20 (18) | O12—Ti2—O4i | 91.3 (2) |
O11—Rb2a—O4i | 56.91 (16) | O8—Ti2—O7 | 176.0 (3) |
O11—Rb2a—O1 | 148.5 (2) | O8—Ti2—O4i | 89.8 (2) |
O5—Rb2a—O2 | 54.50 (17) | O7—Ti2—O4i | 92.6 (2) |
O5—Rb2a—O3 | 79.42 (16) | O3—Ge2—O11 | 89.9 (3) |
O5—Rb2a—O12 | 125.9 (2) | O3—Ge2—O12 | 86.6 (3) |
O5—Rb2a—O7 | 130.43 (16) | O3—Ge2—O8 | 90.5 (3) |
O5—Rb2a—O8 | 119.29 (18) | O3—Ge2—O7 | 87.0 (3) |
O5—Rb2a—O4i | 90.76 (14) | O3—Ge2—O4i | 177.8 (2) |
O5—Rb2a—O1 | 58.66 (17) | O11—Ge2—O12 | 176.0 (3) |
O2—Rb2a—O3 | 46.37 (15) | O11—Ge2—O8 | 90.6 (3) |
O2—Rb2a—O12 | 94.38 (18) | O11—Ge2—O7 | 92.6 (3) |
O2—Rb2a—O7 | 88.81 (18) | O11—Ge2—O4i | 92.2 (2) |
O2—Rb2a—O8 | 65.08 (17) | O12—Ge2—O8 | 87.6 (3) |
O2—Rb2a—O4i | 142.86 (15) | O12—Ge2—O7 | 89.1 (3) |
O2—Rb2a—O1 | 55.7 (2) | O12—Ge2—O4i | 91.3 (2) |
O3—Rb2a—O12 | 51.38 (14) | O8—Ge2—O7 | 176.0 (3) |
O3—Rb2a—O7 | 99.33 (16) | O8—Ge2—O4i | 89.8 (2) |
O3—Rb2a—O8 | 53.32 (14) | O7—Ge2—O4i | 92.6 (2) |
O3—Rb2a—O4i | 122.26 (14) | O1—P1—O2 | 108.5 (4) |
O3—Rb2a—O1 | 101.89 (18) | O1—P1—O3 | 111.1 (4) |
O12—Rb2a—O7 | 83.91 (17) | O1—P1—O4 | 110.0 (4) |
O12—Rb2a—O8 | 50.09 (16) | O2—P1—O3 | 106.8 (4) |
O12—Rb2a—O4i | 97.30 (14) | O2—P1—O4 | 110.1 (3) |
O12—Rb2a—O1 | 141.9 (2) | O3—P1—O4 | 110.3 (2) |
O7—Rb2a—O8 | 46.92 (17) | O5—P2—O6 | 112.2 (3) |
O7—Rb2a—O4i | 127.38 (18) | O5—P2—O7 | 108.4 (4) |
O7—Rb2a—O1 | 73.62 (18) | O5—P2—O8 | 110.7 (3) |
O8—Rb2a—O4i | 144.11 (15) | O6—P2—O7 | 110.9 (4) |
O8—Rb2a—O1 | 93.05 (18) | O6—P2—O8 | 109.3 (4) |
O4i—Rb2a—O1 | 120.8 (2) | O7—P2—O8 | 105.1 (3) |
Symmetry code: (i) x+1/2, −y+1/2, z. |
Experimental details
| (RTP) | (GeRTP1) | (GeRTP2) |
Crystal data |
Chemical formula | O10P2Rb2Ti2 | Ge0.121O10P2Rb2Ti1.879 | Ge0.35O10P2Rb2Ti1.65 |
Mr | 488.64 | 491.62 | 497.28 |
Crystal system, space group | Orthorhombic, Pna21 | Orthorhombic, Pna21 | Orthorhombic, Pna21 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 12.9625 (15), 6.5031 (3), 10.5615 (3) | 12.9386 (18), 6.5085 (8), 10.4408 (10) | 12.9179 (12), 6.5189 (8), 10.3633 (14) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 890.30 (11) | 879.23 (18) | 872.70 (18) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 13.06 | 13.53 | 14.21 |
Crystal size (mm) | 0.14 × 0.12 × 0.08 | 0.60 × 0.10 × 0.04 | 0.10 × 0.05 × 0.04 |
|
Data collection |
Diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) | Multi-scan (SADABS; Sheldrick, 2001) | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.175, 0.353 | 0.207, 0.578 | 0.421, 0.564 |
No. of measured, independent and observed [F > 0σ(F)] reflections | 10947, 2054, 2054 | 12286, 2513, 2513 | 12604, 2497, 2497 |
Rint | 0.052 | 0.031 | 0.039 |
(sin θ/λ)max (Å−1) | 0.650 | 0.700 | 0.700 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.037, 1.13 | 0.021, 0.032, 1.05 | 0.025, 0.039, 1.04 |
No. of reflections | 2054 | 2513 | 2497 |
No. of parameters | 146 | 158 | 156 |
Δρmax, Δρmin (e Å−3) | 1.11, −0.71 | 0.61, −0.60 | 0.73, −0.91 |
Absolute structure | Flack (1983) parameter refined | Flack (1983) parameter refined | Flack (1983) parameter refined |
Absolute structure parameter | 0.497 (9) | 0.429 (8) | 0.487 (11) |