Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614017768/eg3165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017768/eg3165NGaGsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017768/eg3165NMnGsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017768/eg3165NScGsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614017768/eg3165NInGsup5.hkl |
CCDC references: 1017578; 1017579; 1017580; 1017581
The pyroxene family shows a wide range of chemical compositions, in both naturally occurring and synthetic systems. The general formula is given as M2M1T2O6, in which M2 stands for divalent or monovalent cations such as, among others, Ca2+, Na+ and Li+, M1 stands for Mg2+, Al3+ and di- and trivalent transition metal cations, and T stands for Si4+ and Ge4+, the latter in the synthetic system only. The variety in composition is also reflected in the different space-group symmetries, with C2/c, P21/c, P2/n and Pbca being the most frequently occurring (Cameron & Papike 1981), P1 being found for the low-temperature phase of NaTiSi2O6 (Redhammer et al., 2003) and P21/n being recently reported for a new pyroxene structure type in LiAlGe2O6 (Redhammer et al., 2012).
For the sodium–silicate pyroxenes with space-group symmetry C2/c, M1 can be Al3+, Ga3+, Fe3+, Mn3+, V3+, Ti3+, Sc3+ or In3+, as summarized, for example, by Redhammer et al. (2003). In pyroxene research, Si4+ is frequently replaced by Ge4+ to tune the M1 chain distances, with the aim of studying magnetic properties at low temperature (Redhammer et al., 2011, 2013), but also of shifting structural phase transitions, e.g. from P21/c to C2/c, to higher temperatures or lower pressures, as demonstrated e.g. for LiFeGe2O6 (Redhammer et al., 2010; Nestola et al., 2009). For the NaM3+Ge2O6 system, the structures of NaFeGe2O6 (Redhammer et al., 2011), NaCrGe2O6 (Redhammer, Roth, Topa & Amthauer, 2008; Nenert et al., 2009), NaVGe2O6 (Emirdag-Eanes & Kolis, 2004), NaMnGe2O6 (synthesized at high pressure; Chen et al., 2013) and NaScGe2O6 (Genkina et al., 1985) have been reported. For the last compound, only isotropic atomic displacement parameters were given. In this contribution, we present the structure determinations of NaGaGe2O6 and NaInGe2O6, and also a redetermination and refinement of the structure of NaScGe2O6. Together with new data on NaMnGe2O6, synthesized at ambient pressure, a crystal chemical comparison among the NaM3+Ge2O6 compounds and with the corresponding sodium–silicate pyroxenes is provided. The synthesis of NaMnGe2O6 at ambient pressure has not been reported previously.
NaScGe2O6 and NaInGe2O6 were grown from stoichiometric mixtures of Na2CO3, GeO2 and Sc2O3 or In2O3 using a flux-growth synthesis route, with Na2MoO4 (eight parts) and NaVO3 (two parts) as the high-temperature solvent. The nutrient–flux ratio was 1:10. Oxide mixtures and flux were ground together, placed in platinum crucibles, covered with lids, heated to 1473 K at a rate of 3 K min-1 and held at this temperature for 24 h to allow the melt to homogenize. Afterwards, the temperature was lowered at a rate of 0.03 K min-1 to 973 K. Cooling to room temperature was accelerated by shutting down the furnace. After dissolving the flux in hot distilled water, transparent colourless idiomorphic crystals up to 2 mm in size were found for both compounds.
NaGaGe2O6 could not be grown using flux methods, but was synthesized from a stoichiometric mixture of Na2CO3, Ga2O3 and GeO2 at 20 GPa and 1473 K over a period of 70 h in a piston cylinder apparatus at the Institute of Crystallography, RWTH Aachen, Germany. Small single crystals up to 100 µm in size were obtained.
NaMnGe2O6 was obtained by chance during attempts to synthesize the pyroxene compound SrMn2+Ge2O6 using the Na2MoO4/NaVO3 flux. One part of a stoichiometric mixture of SrCO3, MnO and GeO2 was mixed with ten parts of the flux, heated to 1473 K and cooled slowly to 1128 K at a rate of 0.02 K min-1. After dissolving the flux, brown needle-like [Prismatic given in CIF tables - please clarify] single crystals of NaMnGe2O6, plates of an as yet unidentified and unknown Na–Mn–Ge phase and crystals of transparent SrWO3 were obtained. Semi-quantitative energy dispersive X-ray (EDX) analysis on the pyroxene phase yielded a low content of vanadium, besides dominating Na, Mn and Ge. Electron microprobe analysis of the single crystals, among them those used for the X-ray diffraction work, yielded an average chemical composition of Na1.02Mn0.95V0.10Ge1.95O6 (based on seven grains, with five to six points per grain), with an Na content varying in the range 1.00–1.04, Mn 0.94–0.97, Ge 1.93–1.97 and V 0.07–0.13.
When the synthesis was repeated starting with a stoichiometric mixture of Na2CO3, Mn2O3 and GeO2 with the Na2WO4 flux (1:10), but without the addition of NaVO3, a Ge-rich aenigmatite type compound (Redhammer, Roth & Amthauer, 2008) and NaGe9O20, but no pyroxene phase, were obtained. In contrast, addition of NaVO3 to the flux gave plate-to-needle-shaped NaMnGe2O6 upon cooling from 1373 to 1223 K; these crystals were not sufficiently large for intensity data collection. These results prove that NaMnGe2O6 can also be synthesized at ambient pressure; small amounts of vanadium and, associated with this, reduction of Mn3+ to Mn2+, are obviously necessary to stabilize the pyroxene structure.
Crystal data, data collection parameters and structure refinement details are summarized in Table 1, while Table 2 contains selected geometric and distortion parameters of the title compounds. Initial structure determinations were carried out using direct methods; after confirming the C2/c pyroxene structure, the atomic coordinates of NaCrGe2O6 (Redhammer, Roth & Amthauer, 2008 OR Redhammer, Roth, Topa & Amthauer, 2008 ?) were used as the starting point for further structure refinements. Structural data for NaScGe2O6 obtained in this study agree to within four standard uncertainties with those reported by Genkina et al. (1985); our data generally exhibit smaller standard uncertainties. However, our data for NaMnGe2O6 differ significantly from those given by Chen et al. (2013); this difference may arise from the different pressures used during the syntheses (ambient versus high pressure) and from the small content of vanadium in our sample, as discussed above. Based on the results of microprobe analysis for this NaMnGe2O6 crystal, a fractional occupancy of vanadium was introduced at the Ge site and the occupancy was allowed to vary with the restraint Ge + V = 1.00. Refinement based on intensity data sets for five different crystals yielded V contents of 0.08–0.11 atoms per formula unit (apfu) at the tetrahedral sites, in good agreement with the microprobe results. In the final refinement, the V content at the tetrahedral site was constrained to 0.1 apfu; the valence state is most likely V5+. Due to their similar scattering factors, our laboratory X-ray data do not allow a meaningful site-occupancy refinement of V versus Mn at the M1 position; full occupancy with Mn was assumed for simplicity.
The title compounds are all monoclinic, space group C2/c, and adopt the so-called high-temperature form of the two possible but distinct C2/c polymorphs of pyroxene topology (the second is the high-pressure C2/c structure; compare with, for example, Nestola et al., 2009). The asymmetric unit contains one Na position on 4e, one M3+ position, also on 4e, and one Ge and three O atoms, all on general position 8f. The transition metal cations occupy the hexacoordinated M1 site and share edges with their neighbours, thus forming infinite zigzag chains of octahedra parallel to the crystallographic c axis. The corner-sharing GeO4 tetrahedra also make up infinite chains parallel to the c axis, giving rise to the name `chain germanates' for this group of materials. The tetrahedral chains are related to each other by the twofold axis. Sodium occupies the 6+2-fold coordinated M2 position, filling the interstitial space between the M1O6 and GeO4 chains. Figs. 1 and 2 give representations of the NaGaGe2O6 structure.
Structural variations across the NaM3+Ge2O6 series are largely controlled by the size of the metal cation at the M1 site. The unit-cell volume increases from NaGaGe2O6 [r(Ga3+) = 0.62 Å; Shannon & Prewitt, 1969] to NaInGe2O6 [r(In3+) = 0.79 Å; Shannon & Prewitt, 1969]. The substitution of Si4+ by Ge4+ causes an increase in volume of 9%. Similar to the silicates, an almost linear variation of volume with ionic radius is observed from Ga3+- to Sc3+-bearing pyroxenes. It is evident that our data for NaMnGe2O6 deviate much less from this linear variation than those of Chen et al. (2013), whose sample was synthesized at high pressure, similar to the NaMnSi2O6 sample (Ohashi et al., 1987). The latter [Could refer to either of two, or even three. Would be clearer to give explicit compound name here] also deviates significantly from the linear trend defined by the silicates. The unit-cell volume of NaInGe2O6 is smaller than expected from the linear variation, but the observation is consistent with results for the silicates (see Fig. 3) and was also reported for LiM3+Si2O6 by Redhammer & Roth (2004a). The lattice parameters a, b, c and β show similar trends, again with the data for NaMn(Si,Ge)2O6, synthesized at high pressure, deviating more than the other pyroxenes. However, the lattice parameters of the V-containing ambient-pressure NaMnGe2O6 are once again closer to the common trend defined by the other pyroxenes.
The mean <M1—O> distance increases almost linearly with ionic radius in both Na–silicate and Na–germanate pyroxenes, with <M1—O> generally being somewhat larger in the germanate pyroxenes. The data for NaMn3+Ge2O6 obtained in this study again match the general trend more closely than those from Chen et al. (2013). This is also reflected by the individual Mn—O bond lengths, which are distinctly different in the sample of Chen et al. (2013) and those of this study, especially for the Mn—O1vi bonds within the equatorial plane of the octahedron (for symmetry codes in the following discussion, see Table 2). These are larger in the ambient-pressure NaMnGe2O6 by 0.061 Å, while the Mn—O1v bond to the apex O atoms of the octahedra is smaller by 0.046 Å, giving rise to a more regular and less elongated octahedron at ambient pressure compared with the high-pressure Mn pyroxene. Within the complete NaM3+Ge2O6 series, the individual M1—O bond lengths all increase to the same extent from Ga3+ to In3+.
Generally, the M1 octahedra are slightly elongated along the c axis, with ratios of <M1—Oequ>/M1—Oapex \sim 0.98–0.99, except for NaMnGe2O6. Here, values of 0.93 are calculated for ambient-pressure NaMnGe2O6 in this study and 0.88 for the high-pressure NaMnGe2O6 of Chen et al. (2013). This exceptional case is also expressed by the bond-length distortion (BLD; Table 2), which is distinctly more pronounced in high-pressure NaMnGe2O6 compared with the other compounds (Fig. 4). Here, again, data for ambient-pressure NaMnGe2O6 behave differently and are closer to the values of NaFeGe2O6, while the BLD is generally similar in silicates and germanates, especially for Ga3+, Sc3+ and In3+. Chen et al. (2013) suggested that the large BLD in high-pressure NaMnGe2O6 might be the result of the strong Jahn–Teller effect of Mn3+, and that high pressure could be mandatory to overcome it during the synthesis of NaMnGe2O6. To some extent, this contrasts with the results of this study. Obviously, the incorporation of small amounts of vanadium reduces the Jahn–Teller distortion and stabilizes the Mn-bearing pyroxene at ambient pressure. Additionally, the incorporation of V5+ on the tetrahedral site requires some reduction of Mn3+ to Mn2+ to maintain charge balance. The low content of Mn2+, which has a fully symmetric 3d5 electron-shell configuration, could then be seen as a possible reason for the less pronounced polyhedral distortion. As Mn2+ is distinctly larger (r = 0.82 Å) than Mn3+ (r = 0.65 Å; Shannon & Prewitt, 1969), this explains to some extent the differences between ambient- and high-pressure NaMnGe2O6. When compared with the data of Chen et al. (2013), the increase in the Mn—O1vi bond lengths within the equatorial plane of the octahedron in the ambient-pressure NaMnGe2O6 sample may be an indicator of the substitution of Mn3+ by Mn2+. The shorter Mn—O1v bond length to the apex atom is probably due to a smaller Jahn–Teller distortion. Also, the volume of the M1 site is slightly larger in the Mn pyroxene of this study compared with the high-pressure structure of Chen et al. (2013), again an indication of small amounts of larger Mn2+ on the M1 site due to the V5+ substitution on the tetrahedral sites.
Generally, the germanate pyroxenes display larger angular distortions of the octahedra than the comparable silicate compounds, and the angles O1vapex—M1—O1xiapex at the same point are closer to the ideal value of 180°. This is related to the larger space requirement and altered kinking state of the tetrahedral chain. The O1apex atom common to the octahedral and tetrahedral chains plays a pivotal role in maintaining the connection between these two building units of the pyroxene structure. It was noted by Redhammer & Roth (2004a) and Redhammer et al. (2003) that the octahedral angle variance (OAV) and the O1v—M1—O1xi angle behave differently for compounds having a spherical outer electron shell (Ga3+, Fe3+, Sc3+, In3+) than for those with a nonspherical electron configuration (Cr3+, V3+, Mn3+, Ti3+). This also holds true for the structures of the Na–germanates reported here, with NaGaGe2O6 having the most distorted octahedra in terms of the angular distortion (largest OAV; Table 2). The O1v—M1—O1xi angle here is 173.206 (16)°, deviating significantly from the ideal value of 180°, whereas NaCrGe2O6, with a comparable ionic radius, has an O1v—M1—O1xi angle of 178.752 (18)° (Redhammer, Roth & Amthauer, 2008 OR Redhammer, Roth, Topa & Amthauer, 2008 ?). Pyroxenes containing transition metals with nonspherical electron configurations have more stretched O1v—M1—O1xi geometries closer to 180° and thus lower angular distortions.
Similar observations are made for the variation in the M1—O1v—M1xiv angle, an important structural parameter with respect to magnetic superexchange (Fig. 5 and Table 2). The M1—O1v—M1xiv angles deviate distinctly from the ideal value of 90° in the Na–germanate series, but they follow a linear trend for the transition metals with spherical electron configurations, for both silicates and germanates. Thus, the M1—O1v—M1xiv values are larger by ~1.5° compared with the analogous silicates. The Cr, V, Ti and Mn members deviate from these trends. Also, the M1—M1xiv distances are smaller for the latter compounds [The analogue silicates or the Cr, V, Ti and Mn members?]. As the sum of the M1—O1v—M1xiv and the O1v—M1—O1xi angles is 180° (Ohashi et al., 1987), smaller M1—O1v—M1xiv angles correspond to larger O1v—M1—O1xi angles. These larger values may then be due to repulsion between the O1 atoms and the unpaired electrons of the above-mentioned transition metals. These observations underline the fact that not only steric considerations but also electronic configurations represent important factors for controlling the M1 site geometry.
Within a coordination sphere of 3.0 Å, the Na atom is surrounded by eight O atoms, six of them associated with Na—O bonds in the range 2.4–2.6 Å and the other two more distant, in the range 2.75–2.92 Å. The Na+ cation can thus be regarded as 6+2 coordinated. In particular, the long M2—O3iii bonds show a large variation with the radius of the M1 cation, which is a consequence of the altered kinking state of the tetrahedral chain. The O3 atoms not only belong to the coordination of the M2 cation, but also represent the bridging O atoms in the tetrahedral chain. The longest M2—O3iii bond is found in NaScGe2O6 [2.9124 (14) Å]. In NaInGe2O6 with an even larger M1 cation, this value is reduced, while the smaller Na—O3i is increased. This is a direct consequence of the kinking of the tetrahedra. The shortest Na—O bond is that to the O1 atom, giving a connection of the M1 and M2 polyhedra along a common edge perpendicular to the b axis (with the bond thus being parallel to b). The average <Na—O> bond length increases from Ga3+ to the Sc3+ member, with some deviations observed for the V3+- and Mn-bearing pyroxenes. However, these deviations from the general Na pyroxene trends are much less pronounced for the M2 than for the M1 site. Generally, the Na germanates show larger individual and average Na—O bond lengths in the germanates compared with the silicates, a direct consequence of the replacement of the smaller Si4+ by the larger Ge4+ cation.
In all members of the Na–germanate pyroxenes, the tetrahedral chains display an `opposite' (O) rotation sense of the chains (cf. Redhammer & Roth, 2004a). This kinking of the tetrahedral chains is one of the effective mechanisms to overcome geometric differences between octahedral and tetrahedral chains in pyroxenes. The kinking state, defined by the O3—O3vii—O3xv bridging angle, is 172.747 (14)° in NaGaGe2O6 and decreases with increasing size of the M1 cation to 166.21 (5)° in NaInGe2O6 (Table 2). The most stretched tetrahedral chains are found in NaFeGe2O6, with O3—O3vii—O3xv = 175.17 (7)°. However, not only does the kinking state change, but also a stretching of the Ge—O bond lengths takes place, with increasing size of the M1 cation. Here, especially, the two Ge1—O3 bonds running in the c direction become elongated, while the Ge1—O1 and Ge1—O2 bonds remain constant or are slightly shortened. Most prominent are the alterations in O—O edge lengths and O—Ge—O bond angles. Here, the O3—O3vii edge increases from 2.7395 (13) Å in NaGaGe2O6 to 2.8167 (17) Å in NaInGe2O6 and the corresponding O3—Ge1—O3vii angle opens up from 102.782 (11) to 105.54 (5)°. Also, the Ge1—O3—Ge1xiii angle changes by nearly 1° from 133.1 (2) to 133.96 (7)°. This all increases the size of the tetrahedral chain, especially along the c axis, and maintains the fit with the octahedral chain.
The BLD increases slightly from the Ga3+ to the In3+ member, whereas the angular distortion decreases. For the latter, the GeO4 tetrahedron exhibits a more distorted geometry than the SiO4 tetrahedron in the pyroxenes. However, the slopes of the variation are very similar and of the same order of magnitude.
The most significant deviation from the ideal geometry of a tetrahedron is observed for NaGaGe2O6. The substantial angular distortion is mainly a consequence of a large O1—Ge1—O2 angle, which is 116.88 (19)°; the O1—O2 edge opposite this angle is the longest of the tetrahedron, at 2.9613 (12) Å. The tetrahedral chain is laterally connected to the octahedral chain via the O1 atom (see Fig. 2). The fit of the large GeO4 tetrahedron to the small GaO6 octahedron can only be maintained by distortion and elongation of the tetrahedra. Replacing Ga3+ by the smaller Al3+ needs even larger distortions and causes higher structural strain, so the syntheses of both NaAlGe2O6 and NaGaGe2O6 are thus only possible at high pressures. The incorporation of larger M1 cations reduces the structural strain along the b axis, the O1—Ge1—O2 angle and O1—O2 edge length decreasing from 114.89 (6)° and 2.9193 (17) Å in NaInGe2O6, respectively. Generally, the tetrahedra are stretched along the c axis.
The average of the three O—Ge—O bonds involving the apex O1 atom is 112.81 (6)° in the Ga3+ member and decreases slightly to 112.00 (6)° in In3+. The basal planes of the tetrahedra within a chain are almost coplanar to each other, the tilt being 1.66° in the Ga3+ sample and 1.26° in the In3+ end member.
The data for the Mn-bearing pyroxenes, both ambient- and high-pressure synthesized samples, do not deviate much from each other and fit well into the trend defined by the whole NaM3+Ge2O6 series.
For all compounds, data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: APEX2 (Bruker, 2012); program(s) used to solve structure: SHELXS2012 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008). Molecular graphics: DIAMOND (Brandenburg,2006) for NGaG; DIAMOND (Brandenburg, 2006) for NMnG, NScG, NInG. For all compounds, software used to prepare material for publication: WinGX (Farrugia, 2012).
NaGaGe2O6 | F(000) = 616 |
Mr = 333.93 | Dx = 4.839 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9279 (9) Å | Cell parameters from 2544 reflections |
b = 8.8550 (8) Å | θ = 3.2–26.6° |
c = 5.4680 (6) Å | µ = 18.91 mm−1 |
β = 107.5419 (11)° | T = 293 K |
V = 458.35 (8) Å3 | Isometric, colourless |
Z = 4 | 0.11 × 0.09 × 0.08 mm |
Bruker SMART APEX diffractometer | 382 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
rotation, ω scans at four different φ positions | θmax = 26.6°, θmin = 3.2° |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | h = −12→12 |
Tmin = 0.359, Tmax = 0.746 | k = −11→11 |
2544 measured reflections | l = −6→6 |
489 independent reflections |
Refinement on F2 | 47 parameters |
Least-squares matrix: full | 0 restraints |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0237P)2 + 0.9355P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.056 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.85 e Å−3 |
489 reflections | Δρmin = −0.81 e Å−3 |
NaGaGe2O6 | V = 458.35 (8) Å3 |
Mr = 333.93 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.9279 (9) Å | µ = 18.91 mm−1 |
b = 8.8550 (8) Å | T = 293 K |
c = 5.4680 (6) Å | 0.11 × 0.09 × 0.08 mm |
β = 107.5419 (11)° |
Bruker SMART APEX diffractometer | 489 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | 382 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 0.746 | Rint = 0.048 |
2544 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 47 parameters |
wR(F2) = 0.056 | 0 restraints |
S = 1.03 | Δρmax = 0.85 e Å−3 |
489 reflections | Δρmin = −0.81 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 | ||
Na1 | 0 | 0.3016 (4) | 0.25 | 0.0150 (8) | |
Ga1 | 0 | 0.90672 (11) | 0.25 | 0.0061 (2) | |
Ge1 | 0.28868 (6) | 0.09561 (7) | 0.22575 (12) | 0.00600 (19) | |
O2 | 0.3580 (4) | 0.2737 (5) | 0.3025 (8) | 0.0105 (9) | |
O1 | 0.1039 (4) | 0.0798 (5) | 0.1262 (8) | 0.0062 (9) | |
O3 | 0.3617 (4) | 0.0098 (5) | 0.0076 (8) | 0.0089 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.018 (2) | 0.011 (2) | 0.0131 (19) | 0 | 0.0000 (16) | 0 |
Ga1 | 0.0061 (5) | 0.0063 (5) | 0.0060 (5) | 0 | 0.0019 (4) | 0 |
Ge1 | 0.0052 (3) | 0.0067 (3) | 0.0063 (3) | −0.0003 (3) | 0.0020 (2) | 0.0000 (3) |
O2 | 0.011 (2) | 0.008 (2) | 0.012 (2) | −0.0050 (19) | 0.0030 (18) | −0.0009 (18) |
O1 | 0.007 (2) | 0.007 (2) | 0.005 (2) | −0.0013 (18) | 0.0025 (17) | 0.0000 (18) |
O3 | 0.005 (2) | 0.015 (2) | 0.006 (2) | 0.0003 (19) | 0.0002 (16) | −0.004 (2) |
Na1—O1 | 2.409 (5) | Ga1—O1vi | 2.072 (4) |
Na1—O3i | 2.438 (5) | Ge1—O2 | 1.721 (4) |
Na1—O2ii | 2.518 (4) | Ge1—O3 | 1.746 (4) |
Na1—O3iii | 2.797 (5) | Ge1—O1 | 1.754 (4) |
Ga1—O2iv | 1.924 (4) | Ge1—O3vii | 1.760 (4) |
Ga1—O1v | 2.008 (4) | ||
O1viii—Na1—O1 | 70.8 (2) | O2ii—Na1—O3x | 115.55 (13) |
O1viii—Na1—O3i | 133.04 (14) | O2ix—Na1—O3x | 83.39 (13) |
O1—Na1—O3i | 123.40 (13) | O3iii—Na1—O3x | 106.7 (2) |
O1viii—Na1—O3iv | 123.40 (13) | O2iv—Ga1—O2i | 104.5 (3) |
O1—Na1—O3iv | 133.04 (14) | O2iv—Ga1—O1v | 93.27 (17) |
O3i—Na1—O3iv | 81.8 (2) | O2i—Ga1—O1v | 90.89 (16) |
O1viii—Na1—O2ii | 83.99 (16) | O2iv—Ga1—O1xi | 90.89 (16) |
O1—Na1—O2ii | 70.90 (15) | O2i—Ga1—O1xi | 93.27 (17) |
O3i—Na1—O2ii | 141.93 (18) | O1v—Ga1—O1xi | 173.2 (2) |
O3iv—Na1—O2ii | 67.24 (14) | O2iv—Ga1—O1vi | 163.96 (17) |
O1viii—Na1—O2ix | 70.90 (15) | O2i—Ga1—O1vi | 86.83 (18) |
O1—Na1—O2ix | 83.99 (16) | O1v—Ga1—O1vi | 97.94 (15) |
O3i—Na1—O2ix | 67.24 (14) | O1xi—Ga1—O1vi | 76.96 (17) |
O3iv—Na1—O2ix | 141.93 (18) | O2iv—Ga1—O1xii | 86.83 (18) |
O2ii—Na1—O2ix | 149.3 (3) | O2i—Ga1—O1xii | 163.96 (17) |
O1viii—Na1—O3iii | 160.96 (16) | O1v—Ga1—O1xii | 76.96 (17) |
O1—Na1—O3iii | 91.62 (12) | O1xi—Ga1—O1xii | 97.94 (15) |
O3i—Na1—O3iii | 62.67 (9) | O1vi—Ga1—O1xii | 84.6 (2) |
O3iv—Na1—O3iii | 63.66 (16) | O2—Ge1—O3 | 110.3 (2) |
O2ii—Na1—O3iii | 83.39 (13) | O2—Ge1—O1 | 116.88 (19) |
O2ix—Na1—O3iii | 115.55 (13) | O3—Ge1—O1 | 111.34 (19) |
O1viii—Na1—O3x | 91.62 (12) | O2—Ge1—O3vii | 104.10 (19) |
O1—Na1—O3x | 160.96 (16) | O3—Ge1—O3vii | 102.78 (13) |
O3i—Na1—O3x | 63.66 (16) | O1—Ge1—O3vii | 110.22 (18) |
O3iv—Na1—O3x | 62.67 (9) | Ge1—O3—Ge1xiii | 133.1 (2) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1/2, −y+1/2, −z; (iv) x−1/2, y+1/2, z; (v) x, −y+1, z+1/2; (vi) x, y+1, z; (vii) x, −y, z+1/2; (viii) −x, y, −z+1/2; (ix) −x+1/2, −y+1/2, −z+1; (x) x−1/2, −y+1/2, z+1/2; (xi) −x, −y+1, −z; (xii) −x, y+1, −z+1/2; (xiii) x, −y, z−1/2. |
NaMnV0.1Ge1.9O6 | F(000) = 588 |
Mr = 316.95 | Dx = 4.471 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9611 (13) Å | Cell parameters from 2505 reflections |
b = 8.8630 (11) Å | θ = 3.1–28.2° |
c = 5.5598 (7) Å | µ = 14.93 mm−1 |
β = 106.3818 (13)° | T = 293 K |
V = 470.92 (10) Å3 | Prismatic, brown |
Z = 4 | 0.17 × 0.09 × 0.07 mm |
Bruker SMART APEX diffractometer | 558 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
rotation, ω scans at four different φ positions | θmax = 28.7°, θmin = 3.1° |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | h = −12→13 |
Tmin = 0.359, Tmax = 0.746 | k = −11→11 |
2505 measured reflections | l = −7→7 |
585 independent reflections |
Refinement on F2 | 47 parameters |
Least-squares matrix: full | 0 restraints |
R[F2 > 2σ(F2)] = 0.021 | w = 1/[σ2(Fo2) + (0.0288P)2 + 2.9044P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.058 | (Δ/σ)max < 0.001 |
S = 1.12 | Δρmax = 0.84 e Å−3 |
585 reflections | Δρmin = −0.75 e Å−3 |
NaMnV0.1Ge1.9O6 | V = 470.92 (10) Å3 |
Mr = 316.95 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 9.9611 (13) Å | µ = 14.93 mm−1 |
b = 8.8630 (11) Å | T = 293 K |
c = 5.5598 (7) Å | 0.17 × 0.09 × 0.07 mm |
β = 106.3818 (13)° |
Bruker SMART APEX diffractometer | 585 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | 558 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 0.746 | Rint = 0.019 |
2505 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 47 parameters |
wR(F2) = 0.058 | 0 restraints |
S = 1.12 | Δρmax = 0.84 e Å−3 |
585 reflections | Δρmin = −0.75 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) | |
Na1 | 0 | 0.30110 (18) | 0.25 | 0.0111 (3) | |
Mn1 | 0 | 0.90765 (7) | 0.25 | 0.00847 (16) | |
Ge1 | 0.28982 (3) | 0.09350 (3) | 0.23556 (6) | 0.01186 (14) | 0.95 |
V1 | 0.28982 (3) | 0.09350 (3) | 0.23556 (6) | 0.01186 (14) | 0.05 |
O2 | 0.3585 (3) | 0.2713 (3) | 0.3065 (5) | 0.0233 (5) | |
O1 | 0.1080 (3) | 0.0806 (3) | 0.1442 (5) | 0.0188 (5) | |
O3 | 0.3622 (2) | 0.0100 (3) | 0.0145 (4) | 0.0183 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0156 (8) | 0.0057 (7) | 0.0095 (7) | 0 | −0.0006 (6) | 0 |
Mn1 | 0.0100 (3) | 0.0081 (3) | 0.0072 (3) | 0 | 0.0023 (2) | 0 |
Ge1 | 0.0118 (2) | 0.0114 (2) | 0.0124 (2) | −0.00043 (11) | 0.00355 (14) | −0.00162 (11) |
V1 | 0.0118 (2) | 0.0114 (2) | 0.0124 (2) | −0.00043 (11) | 0.00355 (14) | −0.00162 (11) |
O2 | 0.0318 (15) | 0.0142 (11) | 0.0249 (12) | −0.0040 (10) | 0.0096 (11) | −0.0022 (10) |
O1 | 0.0137 (11) | 0.0216 (12) | 0.0207 (12) | 0.0027 (9) | 0.0044 (9) | −0.0050 (9) |
O3 | 0.0164 (12) | 0.0247 (13) | 0.0140 (11) | 0.0010 (9) | 0.0045 (9) | −0.0047 (8) |
Na1—O1 | 2.383 (3) | Mn1—O1vi | 2.154 (3) |
Na1—O3i | 2.452 (3) | Ge1—O2 | 1.719 (2) |
Na1—O2ii | 2.553 (3) | Ge1—O1 | 1.742 (3) |
Na1—O3iii | 2.826 (3) | Ge1—O3 | 1.754 (2) |
Mn1—O2iv | 1.948 (3) | Ge1—O3vii | 1.771 (2) |
Mn1—O1v | 2.052 (3) | ||
O1—Na1—O1viii | 69.81 (13) | O2ii—Na1—O3x | 82.13 (8) |
O1—Na1—O3i | 121.84 (8) | O2ix—Na1—O3x | 115.77 (8) |
O1viii—Na1—O3i | 135.32 (8) | O3iii—Na1—O3x | 107.35 (11) |
O1—Na1—O3iv | 135.32 (8) | O2iv—Mn1—O2i | 103.31 (15) |
O1viii—Na1—O3iv | 121.84 (8) | O2iv—Mn1—O1v | 166.24 (11) |
O3i—Na1—O3iv | 81.93 (12) | O2i—Mn1—O1v | 87.46 (10) |
O1—Na1—O2ii | 73.74 (9) | O2iv—Mn1—O1xi | 87.46 (10) |
O1viii—Na1—O2ii | 82.40 (9) | O2i—Mn1—O1xi | 166.24 (11) |
O3i—Na1—O2ii | 141.16 (9) | O1v—Mn1—O1xi | 83.32 (13) |
O3iv—Na1—O2ii | 66.47 (8) | O2iv—Mn1—O1vi | 92.42 (10) |
O1—Na1—O2ix | 82.40 (9) | O2i—Mn1—O1vi | 91.02 (11) |
O1viii—Na1—O2ix | 73.74 (9) | O1v—Mn1—O1vi | 95.97 (9) |
O3i—Na1—O2ix | 66.47 (8) | O1xi—Mn1—O1vi | 79.85 (10) |
O3iv—Na1—O2ix | 141.16 (9) | O2iv—Mn1—O1xii | 91.02 (11) |
O2ii—Na1—O2ix | 150.88 (13) | O2i—Mn1—O1xii | 92.42 (10) |
O1—Na1—O3iii | 158.98 (9) | O1v—Mn1—O1xii | 79.85 (10) |
O1viii—Na1—O3iii | 92.19 (8) | O1xi—Mn1—O1xii | 95.97 (9) |
O3i—Na1—O3iii | 63.62 (9) | O1vi—Mn1—O1xii | 174.46 (13) |
O3iv—Na1—O3iii | 63.24 (5) | O2—Ge1—O1 | 116.18 (12) |
O2ii—Na1—O3iii | 115.77 (8) | O2—Ge1—O3 | 109.36 (12) |
O2ix—Na1—O3iii | 82.13 (8) | O1—Ge1—O3 | 111.54 (11) |
O1—Na1—O3x | 92.19 (8) | O2—Ge1—O3vii | 103.69 (12) |
O1viii—Na1—O3x | 158.98 (9) | O1—Ge1—O3vii | 110.76 (11) |
O3i—Na1—O3x | 63.24 (5) | O3—Ge1—O3vii | 104.40 (8) |
O3iv—Na1—O3x | 63.62 (9) | Ge1—O3—Ge1xiii | 133.29 (14) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x−1/2, y+1/2, z; (v) x, y+1, z; (vi) x, −y+1, z+1/2; (vii) x, −y, z+1/2; (viii) −x, y, −z+1/2; (ix) −x+1/2, −y+1/2, −z+1; (x) −x+1/2, −y+1/2, −z; (xi) −x, y+1, −z+1/2; (xii) −x, −y+1, −z; (xiii) x, −y, z−1/2. |
NaScGe2O6 | F(000) = 576 |
Mr = 309.13 | Dx = 4.146 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.1705 (7) Å | Cell parameters from 3175 reflections |
b = 9.1545 (7) Å | θ = 3.1–29.9° |
c = 5.5715 (4) Å | µ = 13.43 mm−1 |
β = 107.3051 (7)° | T = 293 K |
V = 495.26 (6) Å3 | Prismatic, colourless |
Z = 4 | 0.22 × 0.21 × 0.13 mm |
Bruker SMART APEX diffractometer | 672 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
rotation, ω scans at four different φ positions | θmax = 29.9°, θmin = 3.1° |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | h = −13→14 |
Tmin = 0.359, Tmax = 0.746 | k = −12→12 |
3175 measured reflections | l = −7→7 |
680 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0135P)2 + 0.7625P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.014 | (Δ/σ)max = 0.001 |
wR(F2) = 0.037 | Δρmax = 0.52 e Å−3 |
S = 1.20 | Δρmin = −0.69 e Å−3 |
680 reflections | Extinction correction: SHELXL2012 (Sheldrick, 2008) |
48 parameters | Extinction coefficient: 0.0561 (13) |
NaScGe2O6 | V = 495.26 (6) Å3 |
Mr = 309.13 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.1705 (7) Å | µ = 13.43 mm−1 |
b = 9.1545 (7) Å | T = 293 K |
c = 5.5715 (4) Å | 0.22 × 0.21 × 0.13 mm |
β = 107.3051 (7)° |
Bruker SMART APEX diffractometer | 680 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | 672 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 0.746 | Rint = 0.028 |
3175 measured reflections |
R[F2 > 2σ(F2)] = 0.014 | 48 parameters |
wR(F2) = 0.037 | 0 restraints |
S = 1.20 | Δρmax = 0.52 e Å−3 |
680 reflections | Δρmin = −0.69 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 | ||
Na1 | 0 | 0.30340 (12) | 0.25 | 0.0164 (2) | |
Sc1 | 0 | 0.90134 (4) | 0.25 | 0.00433 (11) | |
Ge1 | 0.28988 (2) | 0.09154 (2) | 0.24018 (3) | 0.00447 (10) | |
O2 | 0.35888 (13) | 0.26275 (13) | 0.3104 (2) | 0.0099 (2) | |
O1 | 0.11062 (13) | 0.07983 (12) | 0.1369 (2) | 0.0056 (2) | |
O3 | 0.35954 (12) | 0.00987 (15) | 0.0190 (2) | 0.0097 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0203 (6) | 0.0122 (5) | 0.0123 (5) | 0 | −0.0021 (4) | 0 |
Sc1 | 0.0044 (2) | 0.0041 (2) | 0.0044 (2) | 0 | 0.00121 (16) | 0 |
Ge1 | 0.00404 (13) | 0.00478 (13) | 0.00464 (13) | −0.00096 (5) | 0.00137 (8) | −0.00026 (5) |
O2 | 0.0113 (6) | 0.0064 (5) | 0.0127 (6) | −0.0048 (4) | 0.0048 (5) | −0.0022 (4) |
O1 | 0.0035 (5) | 0.0066 (5) | 0.0058 (6) | −0.0010 (4) | 0.0001 (4) | 0.0002 (4) |
O3 | 0.0073 (6) | 0.0141 (6) | 0.0075 (5) | −0.0001 (4) | 0.0020 (4) | −0.0049 (4) |
Na1—O3i | 2.4852 (16) | Sc1—O1vi | 2.1804 (12) |
Na1—O1 | 2.5046 (15) | Ge1—O2 | 1.7144 (12) |
Na1—O2ii | 2.5165 (13) | Ge1—O1 | 1.7442 (13) |
Na1—O3iii | 2.9124 (14) | Ge1—O3 | 1.7605 (11) |
Sc1—O2iv | 2.0176 (12) | Ge1—O3vii | 1.7669 (12) |
Sc1—O1v | 2.1214 (12) | ||
O3i—Na1—O3iv | 80.97 (7) | O2ii—Na1—O3x | 82.27 (4) |
O3i—Na1—O1viii | 136.32 (4) | O2ix—Na1—O3x | 114.64 (4) |
O3iv—Na1—O1viii | 121.32 (4) | O3iii—Na1—O3x | 108.12 (6) |
O3i—Na1—O1 | 121.32 (4) | O2iv—Sc1—O2i | 102.07 (7) |
O3iv—Na1—O1 | 136.32 (4) | O2iv—Sc1—O1v | 94.02 (5) |
O1viii—Na1—O1 | 70.40 (6) | O2i—Sc1—O1v | 91.84 (5) |
O3i—Na1—O2ii | 139.52 (5) | O2iv—Sc1—O1xi | 91.84 (5) |
O3iv—Na1—O2ii | 66.76 (4) | O2i—Sc1—O1xi | 94.02 (5) |
O1viii—Na1—O2ii | 83.07 (5) | O1v—Sc1—O1xi | 170.68 (6) |
O1—Na1—O2ii | 74.18 (4) | O2iv—Sc1—O1vi | 166.73 (5) |
O3i—Na1—O2ix | 66.76 (4) | O2i—Sc1—O1vi | 88.24 (5) |
O3iv—Na1—O2ix | 139.52 (5) | O1v—Sc1—O1vi | 93.98 (4) |
O1viii—Na1—O2ix | 74.19 (4) | O1xi—Sc1—O1vi | 78.98 (5) |
O1—Na1—O2ix | 83.07 (5) | O2iv—Sc1—O1xii | 88.24 (5) |
O2ii—Na1—O2ix | 152.15 (7) | O2i—Sc1—O1xii | 166.73 (5) |
O3i—Na1—O3iii | 65.26 (5) | O1v—Sc1—O1xii | 78.98 (5) |
O3iv—Na1—O3iii | 61.69 (3) | O1xi—Sc1—O1xii | 93.98 (4) |
O1viii—Na1—O3iii | 91.40 (4) | O1vi—Sc1—O1xii | 82.92 (6) |
O1—Na1—O3iii | 159.20 (5) | O2—Ge1—O1 | 116.63 (6) |
O2ii—Na1—O3iii | 114.64 (4) | O2—Ge1—O3 | 108.99 (6) |
O2ix—Na1—O3iii | 82.27 (4) | O1—Ge1—O3 | 109.99 (5) |
O3i—Na1—O3x | 61.69 (3) | O2—Ge1—O3vii | 104.46 (6) |
O3iv—Na1—O3x | 65.26 (5) | O1—Ge1—O3vii | 111.35 (5) |
O1viii—Na1—O3x | 159.20 (5) | O3—Ge1—O3vii | 104.63 (4) |
O1—Na1—O3x | 91.40 (4) | Ge1—O3—Ge1xiii | 134.34 (7) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x−1/2, y+1/2, z; (v) x, −y+1, z+1/2; (vi) x, y+1, z; (vii) x, −y, z+1/2; (viii) −x, y, −z+1/2; (ix) −x+1/2, −y+1/2, −z+1; (x) −x+1/2, −y+1/2, −z; (xi) −x, −y+1, −z; (xii) −x, y+1, −z+1/2; (xiii) x, −y, z−1/2. |
NaInGe2O6 | Z = 4 |
Mr = 378.99 | F(000) = 688 |
Monoclinic, C2/c | Dx = 5.019 Mg m−3 |
a = 10.2215 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.1814 (6) Å | µ = 16.65 mm−1 |
c = 5.5931 (4) Å | T = 293 K |
β = 107.1333 (7)° | Prismatic, colourless |
V = 501.61 (6) Å3 | 0.19 × 0.10 × 0.09 mm |
Bruker SMART APEX diffractometer | 679 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
rotation, ω scans at four different φ positions | θmax = 29.9°, θmin = 3.1° |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | h = −13→14 |
Tmin = 0.359, Tmax = 0.746 | k = −12→12 |
3250 measured reflections | l = −7→7 |
687 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0143P)2 + 0.2607P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.012 | (Δ/σ)max = 0.001 |
wR(F2) = 0.033 | Δρmax = 0.41 e Å−3 |
S = 1.2 | Δρmin = −0.52 e Å−3 |
687 reflections | Extinction correction: SHELXL2012 (Sheldrick, 2008) |
48 parameters | Extinction coefficient: 0.0159 (4) |
NaInGe2O6 | V = 501.61 (6) Å3 |
Mr = 378.99 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.2215 (7) Å | µ = 16.65 mm−1 |
b = 9.1814 (6) Å | T = 293 K |
c = 5.5931 (4) Å | 0.19 × 0.10 × 0.09 mm |
β = 107.1333 (7)° |
Bruker SMART APEX diffractometer | 687 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2012) | 679 reflections with I > 2σ(I) |
Tmin = 0.359, Tmax = 0.746 | Rint = 0.023 |
3250 measured reflections |
R[F2 > 2σ(F2)] = 0.012 | 48 parameters |
wR(F2) = 0.033 | 0 restraints |
S = 1.2 | Δρmax = 0.41 e Å−3 |
687 reflections | Δρmin = −0.52 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 | ||
Na1 | 0 | 0.30410 (12) | 0.25 | 0.0174 (2) | |
In1 | 0 | 0.89946 (2) | 0.25 | 0.00576 (8) | |
Ge1 | 0.29111 (2) | 0.09083 (2) | 0.24432 (4) | 0.00570 (8) | |
O2 | 0.35674 (13) | 0.26117 (14) | 0.3295 (2) | 0.0112 (3) | |
O1 | 0.11216 (13) | 0.08163 (13) | 0.1420 (2) | 0.0075 (3) | |
O3 | 0.35909 (12) | 0.01841 (17) | 0.0138 (2) | 0.0107 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0218 (6) | 0.0135 (5) | 0.0125 (5) | 0 | −0.0020 (4) | 0 |
In1 | 0.00537 (12) | 0.00618 (11) | 0.00548 (12) | 0 | 0.00121 (8) | 0 |
Ge1 | 0.00481 (12) | 0.00645 (12) | 0.00549 (12) | −0.00085 (5) | 0.00099 (8) | −0.00023 (5) |
O2 | 0.0131 (6) | 0.0088 (6) | 0.0131 (6) | −0.0052 (5) | 0.0061 (5) | −0.0023 (5) |
O1 | 0.0050 (6) | 0.0094 (6) | 0.0069 (6) | −0.0017 (4) | −0.0001 (5) | −0.0003 (4) |
O3 | 0.0085 (6) | 0.0151 (7) | 0.0082 (7) | −0.0006 (4) | 0.0023 (5) | −0.0042 (4) |
Na1—O2i | 2.4505 (14) | In1—O1vi | 2.2102 (12) |
Na1—O1 | 2.5019 (16) | Ge1—O2 | 1.7131 (13) |
Na1—O3ii | 2.5633 (17) | Ge1—O1 | 1.7503 (13) |
Na1—O3iii | 2.8565 (14) | Ge1—O3 | 1.7649 (12) |
In1—O2iv | 2.0829 (12) | Ge1—O3vii | 1.7731 (13) |
In1—O1v | 2.1610 (13) | ||
O2i—Na1—O2viii | 151.69 (8) | O3ii—Na1—O3x | 62.35 (3) |
O2i—Na1—O1 | 75.84 (5) | O3iv—Na1—O3x | 65.68 (5) |
O2viii—Na1—O1 | 81.10 (5) | O3iii—Na1—O3x | 110.43 (7) |
O2i—Na1—O1ix | 81.10 (5) | O2iv—In1—O2ii | 104.88 (7) |
O2viii—Na1—O1ix | 75.84 (5) | O2iv—In1—O1v | 91.64 (5) |
O1—Na1—O1ix | 70.55 (6) | O2ii—In1—O1v | 93.98 (5) |
O2i—Na1—O3ii | 140.22 (5) | O2iv—In1—O1xi | 93.98 (5) |
O2viii—Na1—O3ii | 66.86 (4) | O2ii—In1—O1xi | 91.64 (5) |
O1—Na1—O3ii | 121.55 (4) | O1v—In1—O1xi | 170.78 (6) |
O1ix—Na1—O3ii | 136.90 (4) | O2iv—In1—O1vi | 166.82 (5) |
O2i—Na1—O3iv | 66.86 (4) | O2ii—In1—O1vi | 87.07 (5) |
O2viii—Na1—O3iv | 140.22 (5) | O1v—In1—O1vi | 93.08 (4) |
O1—Na1—O3iv | 136.90 (4) | O1xi—In1—O1vi | 79.90 (5) |
O1ix—Na1—O3iv | 121.55 (4) | O2iv—In1—O1xii | 87.07 (5) |
O3ii—Na1—O3iv | 79.71 (7) | O2ii—In1—O1xii | 166.82 (5) |
O2i—Na1—O3iii | 112.68 (4) | O1v—In1—O1xii | 79.90 (5) |
O2viii—Na1—O3iii | 83.89 (4) | O1xi—In1—O1xii | 93.08 (4) |
O1—Na1—O3iii | 158.00 (5) | O1vi—In1—O1xii | 81.65 (7) |
O1ix—Na1—O3iii | 90.25 (4) | O2—Ge1—O1 | 114.89 (6) |
O3ii—Na1—O3iii | 65.68 (5) | O2—Ge1—O3 | 109.94 (6) |
O3iv—Na1—O3iii | 62.35 (3) | O1—Ge1—O3 | 109.95 (6) |
O2i—Na1—O3x | 83.89 (4) | O2—Ge1—O3vii | 104.87 (7) |
O2viii—Na1—O3x | 112.68 (4) | O1—Ge1—O3vii | 111.15 (6) |
O1—Na1—O3x | 90.25 (4) | O3—Ge1—O3vii | 105.54 (4) |
O1ix—Na1—O3x | 158.00 (5) | Ge1—O3—Ge1xiii | 133.96 (7) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z+1/2; (iv) x−1/2, y+1/2, z; (v) x, −y+1, z+1/2; (vi) x, y+1, z; (vii) x, −y, z+1/2; (viii) −x+1/2, −y+1/2, −z+1; (ix) −x, y, −z+1/2; (x) −x+1/2, −y+1/2, −z; (xi) −x, −y+1, −z; (xii) −x, y+1, −z+1/2; (xiii) x, −y, z−1/2. |
Experimental details
(NGaG) | (NMnG) | (NScG) | (NInG) | |
Crystal data | ||||
Chemical formula | NaGaGe2O6 | NaMnV0.1Ge1.9O6 | NaScGe2O6 | NaInGe2O6 |
Mr | 333.93 | 316.95 | 309.13 | 378.99 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 293 | 293 | 293 | 293 |
a, b, c (Å) | 9.9279 (9), 8.8550 (8), 5.4680 (6) | 9.9611 (13), 8.8630 (11), 5.5598 (7) | 10.1705 (7), 9.1545 (7), 5.5715 (4) | 10.2215 (7), 9.1814 (6), 5.5931 (4) |
β (°) | 107.5419 (11) | 106.3818 (13) | 107.3051 (7) | 107.1333 (7) |
V (Å3) | 458.35 (8) | 470.92 (10) | 495.26 (6) | 501.61 (6) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 18.91 | 14.93 | 13.43 | 16.65 |
Crystal size (mm) | 0.11 × 0.09 × 0.08 | 0.17 × 0.09 × 0.07 | 0.22 × 0.21 × 0.13 | 0.19 × 0.10 × 0.09 |
Data collection | ||||
Diffractometer | Bruker SMART APEX diffractometer | Bruker SMART APEX diffractometer | Bruker SMART APEX diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (APEX2; Bruker, 2012) | Multi-scan (APEX2; Bruker, 2012) | Multi-scan (APEX2; Bruker, 2012) | Multi-scan (APEX2; Bruker, 2012) |
Tmin, Tmax | 0.359, 0.746 | 0.359, 0.746 | 0.359, 0.746 | 0.359, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2544, 489, 382 | 2505, 585, 558 | 3175, 680, 672 | 3250, 687, 679 |
Rint | 0.048 | 0.019 | 0.028 | 0.023 |
(sin θ/λ)max (Å−1) | 0.631 | 0.677 | 0.701 | 0.700 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.056, 1.03 | 0.021, 0.058, 1.12 | 0.014, 0.037, 1.20 | 0.012, 0.033, 1.2 |
No. of reflections | 489 | 585 | 680 | 687 |
No. of parameters | 47 | 47 | 48 | 48 |
Δρmax, Δρmin (e Å−3) | 0.85, −0.81 | 0.84, −0.75 | 0.52, −0.69 | 0.41, −0.52 |
Computer programs: APEX2 (Bruker, 2012), SHELXS2012 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008), DIAMOND (Brandenburg,2006), DIAMOND (Brandenburg, 2006), WinGX (Farrugia, 2012).
NGaG | NMnG | NMnGf | NScG | NScGg | NInG | |
r (ionic) (Å) | 0.62 | 0.65 | 0.65 | 0.73 | 0.73 | 0.79 |
a (Å) | 9.9279 (9) | 9.9611 (13) | 9.859 (2) | 10.1705 (7) | 10.162 (2) | 10.2215 (7) |
b (Å) | 8.8550 (8) | 8.8630 (11) | 8.7507 (18) | 9.1545 (7) | 9.154 (1) | 9.1814 (6) |
c (Å) | 5.4680 (6) | 5.5598 (7) | 5.5724 (11) | 5.5715 (4) | 5.571 (1) | 5.5931 (4) |
β (°) | 107.5419 (11) | 106.3818 (13) | 105.64 (3) | 107.3051 (7) | 107.26 (2) | 107.1333 (7) |
Na1—O1 (Å) | 2.409 (5) | 2.383 (3) | 2.341 (4) | 2.5046 (15) | 2.509 (4) | 2.5019 (16) |
Na1—O2ii (Å) | 2.518 (4) | 2.553 (3) | 2.561 (3) | 2.5165 (13) | 2.513 (4) | 2.4505 (14) |
Na1—O3i (Å) | 2.438 (5) | 2.452 (3) | 2.429 (3) | 2.4852 (16) | 2.485 (4) | 2.5633 (17) |
Na1—O3iii (Å) | 2.797 (5) | 2.826 (3) | 2.805 (3) | 2.9124 (14) | 2.908 (5) | 2.8565 (14) |
<Na—O>8 | 2.540 | 2.554 | 2.534 | 2.605 | 2.604 | 2.593 |
M1—O2iv (Å) | 1.924 (4) | 1.948 (3) | 1.991 (3) | 2.0176 (12) | 2.021 (4) | 2.0829 (12) |
M1—O1v (Å) | 2.008 (4) | 2.154 (3) | 2.198 (3) | 2.1214 (12) | 2.118 (3) | 2.1610 (13) |
M1—O1vi (Å) | 2.072 (4) | 2.052 (3) | 1.918 (3) | 2.1804 (12) | 2.179 (3) | 2.2102 (12) |
<M1—O> (Å) | 2.001 | 2.051 | 2.036 | 2.107 | 2.106 | 2.151 |
BLDa (%) | 2.57 | 3.35 | 5.31 | 2.81 | 2.69 | 2.12 |
V (Å3) | 10.37 | 11.24 | 10.98 | 12.21 | 12.19 | 12.98 |
OAVb (°2) | 68.08 | 48.07 | 44.07 | 46.83 | 48.01 | 51.63 |
OQEc | 1.0213 | 1.0171 | 1.0195 | 1.0149 | 1.0152 | 1.0156 |
M1—M1xiv (Å) | 3.1943 (3) | 3.2263 (5) | 3.1691 (8) | 3.3201 (12) | 3.3193 (18) | 3.3510 (12) |
O1v—M1—O1xi (°) | 173.206 (16) | 174.39 (8) | 175.67 (12) | 170.682 (12) | 170.58 (12) | 170.878 (13) |
M1—O1v—M1xiv (°) | 103.046 (15) | 100.19 (8) | 99.35 (13) | 101.023 (12) | 101.15 (12) | 100.09 (5) |
Ge1—O2 (Å) | 1.721 (4) | 1.719 (2) | 1.725 (3) | 1.7144 (12) | 1.716 (3) | 1.7131 (13) |
Ge1—O1 (Å) | 1.754 (4) | 1.742 (3) | 1.743 (3) | 1.7442 (13) | 1.745 (4) | 1.7503 (13) |
Ge1—O3 (Å) | 1.746 (4) | 1.754 (2) | 1.750 (3) | 1.7605 (11) | 1.754 (4) | 1.7649 (12) |
Ge1—O3vii (Å) | 1.760 (4) | 1.771 (2) | 1.767 (3) | 1.7669 (12) | 1.773 (4) | 1.7731 (13) |
<Ge—O> (Å) | 1.745 | 1.747 | 1.747 | 1.746 | 1.747 | 1.750 |
BLDa (%) | 0.70 | 0.93 | 0.69 | 0.98 | 0.95 | 1.07 |
V T (Å3) | 2.701 | 2.713 | 2.714 | 2.714 | 2.717 | 2.739 |
TAVd (°2) | 26.67 | 22.13 | 20.28 | 20.34 | 20.70 | 13.85 |
TQEe | 1.0067 | 1.0053 | 1.0049 | 1.0049 | 1.0050 | 1.0035 |
O3—O3vii—O3xv (°) | 172.747 (14) | 172.70 (8) | 172.67 (14) | 172.576 (14) | 172.10 (18) | 166.21 (5) |
Symmetry codes:
(i) -x + 1/2, y + 1/2, -z + 1/2;
(ii) x - 1/2, -y + 1/2,z - 1/2;
(iii) -x + 1/2, -y + 1/2, -z;
(iv) x - 1/2, y + 1/2, z;
(v) x, -y + 1, z + 1/2;
(vi) x, y + 1, z;
(vii) x, -y, z + 1/2;
(viii) -x, y, -z + 1/2;
(ix) -x + 1/2, -y + 1/2, -z + 1;
(x) x - 1/2, -y + 1/2, z + 1/2;
(xi) -x, -y + 1, -z;
(xii) -x, y + 1, -z + 1/2;
(xiii) x, -y, z - 1/2;
(xiv) -x, 2 - y, 1 - x;
(xv) x, y, z + 1. Notes and references: (a) bond-length distortion BLD = (100/n)Σi = 1n[{(X—O)i - (<X—O>)}/(<X—O>)], where n = number of bonds, (X—O)i = central cation to oxygen length and <X—O> = average cation–oxygen bond length; (b) octahedral angle variance OAV = Σi = 1n(Θi - 90)2/11 (Robinson et al., 1971); (c) octahedral quadratic elongation OQE = Σi = 16(li/lo)2/6, where lo = centre-to-vertex distance for a regular octahedron the volume of which is equal to that of an undistorted octahedron with bond length li (Robinson et al., 1971); (d) tetrahedral angle variance TAV = Σi = 1n(Θi-109.47)2/5 (Robinson et al., 1971); (e) tetrahedral quadratic elongation TQE = Σi = 14(li/lt)2/4, where lt = centre-to-vertex distance for a regular tetrahedron the volume of which is equal to that of an undistorted tetrahedron with bond length li (Robinson et al., 1971); (f) Chen et al. (2013); (g) Genkina et al. (1985). |