Buy article online - an online subscription or single-article purchase is required to access this article.
The structures of tripotassium digallium tris(phosphate), K3Ga2(PO4)3, and trisodium gallium bis(phosphate), Na3Ga(PO4)2, have different irregular one-dimensional alkali ion-containing channels along the a axis of the orthorhombic and triclinic unit cells, respectively. The anionic subsystems consist of vortex-linked PO4 tetrahedra and GaO4 tetrahedra or GaO5 trigonal bipyramids in the first and second structure, respectively.
Supporting information
The GaPO4 compound with the α-quartz structure was obtained in powder form by
dissolving 4 N Ga metal in nitric acid followed by precipitation with
phosphoric acid, as described by Beaurain et al. (2006). K2MoO4 and
Na2PO3F used as starting materials were commercial products (Fluka). The
crystal growth experiments reported were carried out in air in a single
temperature zone in an SiC resistance heater furnace and a Eurotherm
temperature controller. For compound (I), 85 wt% of K2MoO4 was mixed with
15 wt% of α-GaPO4 and homogenized in an agate mortar. For compound (II), 60
wt% of Na2PO3F was mixed with 40 wt% of GaPO4. The mixtures were placed
in Pt crucibles covered with a lid, heated from room temperature to 1223 K at
a ramp rate of 150 K h-1 and held at this temperature for 5 h for
homogenization. The melted charges were then slowly cooled down at a rate of 2 K h-1 to 873 K. After 5 h at 873 K, the charges were cooled to room
temperature at 200 K h-1.
Structure (I) was solved in space group P1 in 216 iterations using
default values for the charge flipping parameters, followed by five
low-density elimination cycles. The systematic reflection extinctions pointed
to P21nb or Pmnb as possible space-group symmetries.
The non-centrosymmetric space group P21nb prevaled over the
centrosymmetric space group Pmnb since an analysis of the symmetry
operations in the resulting electron-density map (Palatinus & Chapuis, 2007),
i.e. before attribution of the atom types, showed that the mx
mirror plane and the inversion centre were clearly absent with agreement
factors of 0.37 and 0.45, respectively (0.10, 0.03, and 0.07 for the 21
screw axis, the n-glide and the b-glide, respectively). The
coordinates were subsequently transformed to those compatable with the
standard setting of P21nb, viz. Pna21. The refined
Flack (1983) parameter of (I) showed that the crystal was single-domain. The
structure of (II) was solved in a similar way and the presence of the
inversion centre was established on the basis of an analysis of the
electron-density map before attribution of the atom types.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996) and DRAWxtl (Finger et al., 2007); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
(I) tripotassium digallium triphosphate
top
Crystal data top
K3Ga2(PO4)3 | F(000) = 1040 |
Mr = 541.65 | Dx = 2.907 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 13242 reflections |
a = 8.67110 (15) Å | θ = 2.6–32.4° |
b = 17.0109 (3) Å | µ = 5.81 mm−1 |
c = 8.38857 (16) Å | T = 293 K |
V = 1237.34 (4) Å3 | Prism, colourless |
Z = 4 | 0.25 × 0.16 × 0.12 mm |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 3885 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3024 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 8.4205 pixels mm-1 | θmax = 32.5°, θmin = 2.6° |
ω scans | h = −12→12 |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2007)] empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | k = −25→24 |
Tmin = 0.507, Tmax = 1.000 | l = −11→12 |
24311 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Method = Modified Sheldrick
w = 1/[σ2(F2) + (0.04P)2], where P = [max(Fo2,0) + 2Fc2]/3 |
R[F2 > 2σ(F2)] = 0.034 | (Δ/σ)max = 0.001 |
wR(F2) = 0.088 | Δρmax = 1.32 e Å−3 |
S = 0.98 | Δρmin = −1.74 e Å−3 |
3885 reflections | Absolute structure: Flack (1983), 1691 Friedel-pairs |
182 parameters | Absolute structure parameter: 0.014 (15) |
1 restraint | |
Crystal data top
K3Ga2(PO4)3 | V = 1237.34 (4) Å3 |
Mr = 541.65 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 8.67110 (15) Å | µ = 5.81 mm−1 |
b = 17.0109 (3) Å | T = 293 K |
c = 8.38857 (16) Å | 0.25 × 0.16 × 0.12 mm |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 3885 independent reflections |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2007)] empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | 3024 reflections with I > 2σ(I) |
Tmin = 0.507, Tmax = 1.000 | Rint = 0.032 |
24311 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.088 | Δρmax = 1.32 e Å−3 |
S = 0.98 | Δρmin = −1.74 e Å−3 |
3885 reflections | Absolute structure: Flack (1983), 1691 Friedel-pairs |
182 parameters | Absolute structure parameter: 0.014 (15) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.15194 (16) | 0.71520 (9) | 1.28804 (18) | 0.0072 | |
P2 | 0.29802 (17) | 0.81310 (9) | 0.79667 (18) | 0.0087 | |
P3 | 0.26191 (18) | 0.50328 (10) | 0.86661 (19) | 0.0107 | |
K4 | 0.45271 (15) | 0.64660 (8) | 0.59513 (16) | 0.0126 | |
K5 | 0.00977 (15) | 0.90013 (8) | 1.12307 (16) | 0.0142 | |
K6 | 0.18095 (18) | 0.51039 (8) | 0.39470 (18) | 0.0212 | |
Ga7 | 0.13278 (6) | 0.66831 (3) | 0.94007 (10) | 0.0080 | |
Ga8 | 0.34700 (6) | 0.84139 (3) | 1.42835 (10) | 0.0079 | |
O9 | 0.2085 (5) | 0.8010 (2) | 1.2861 (5) | 0.0103 | |
O10 | 0.0312 (4) | 0.7091 (2) | 1.4225 (5) | 0.0126 | |
O11 | 0.2809 (5) | 0.6573 (3) | 1.3087 (5) | 0.0148 | |
O12 | 0.0625 (4) | 0.7052 (3) | 1.1300 (5) | 0.0114 | |
O13 | 0.1859 (6) | 0.8666 (3) | 0.8761 (6) | 0.0226 | |
O14 | 0.2647 (5) | 0.8088 (3) | 0.6167 (5) | 0.0218 | |
O15 | 0.2904 (5) | 0.7266 (2) | 0.8591 (5) | 0.0164 | |
O16 | 0.4661 (5) | 0.8404 (3) | 0.8104 (5) | 0.0228 | |
O17 | 0.2189 (5) | 0.5732 (3) | 0.9791 (5) | 0.0143 | |
O18 | 0.4055 (5) | 0.4651 (2) | 0.9277 (6) | 0.0161 | |
O19 | 0.1208 (5) | 0.4443 (2) | 0.8917 (5) | 0.0169 | |
O20 | 0.2674 (5) | 0.5301 (3) | 0.6966 (5) | 0.0156 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0075 (6) | 0.0074 (6) | 0.0068 (6) | −0.0014 (6) | 0.0001 (6) | −0.0001 (5) |
P2 | 0.0107 (7) | 0.0093 (7) | 0.0061 (6) | 0.0000 (6) | 0.0011 (6) | 0.0004 (6) |
P3 | 0.0142 (7) | 0.0060 (7) | 0.0120 (6) | −0.0003 (6) | −0.0010 (6) | 0.0003 (6) |
K4 | 0.0117 (6) | 0.0108 (6) | 0.0154 (6) | 0.0003 (5) | 0.0008 (5) | 0.0001 (5) |
K5 | 0.0119 (6) | 0.0192 (7) | 0.0115 (5) | 0.0002 (6) | −0.0004 (5) | 0.0016 (5) |
K6 | 0.0227 (7) | 0.0143 (7) | 0.0266 (8) | 0.0019 (6) | −0.0056 (5) | −0.0007 (6) |
Ga7 | 0.0083 (3) | 0.0081 (3) | 0.0076 (3) | 0.0012 (2) | −0.0007 (3) | −0.0005 (3) |
Ga8 | 0.0071 (2) | 0.0092 (3) | 0.0073 (3) | 0.0001 (2) | 0.0003 (3) | 0.0004 (3) |
O9 | 0.0125 (19) | 0.0055 (19) | 0.0129 (18) | −0.0025 (17) | −0.0041 (18) | 0.0024 (17) |
O10 | 0.0131 (18) | 0.0157 (19) | 0.0090 (18) | −0.0051 (16) | 0.0009 (19) | −0.0029 (19) |
O11 | 0.018 (2) | 0.012 (2) | 0.015 (2) | 0.0042 (18) | −0.0009 (18) | 0.0003 (19) |
O12 | 0.0090 (18) | 0.016 (2) | 0.0094 (18) | 0.0018 (17) | 0.0001 (16) | −0.0056 (16) |
O13 | 0.026 (3) | 0.015 (2) | 0.027 (2) | 0.003 (2) | 0.016 (2) | 0.003 (2) |
O14 | 0.016 (2) | 0.039 (3) | 0.0099 (18) | −0.005 (2) | 0.0018 (19) | 0.004 (2) |
O15 | 0.019 (2) | 0.010 (2) | 0.020 (2) | −0.005 (2) | 0.0024 (19) | −0.0004 (17) |
O16 | 0.020 (2) | 0.035 (3) | 0.014 (2) | −0.006 (2) | −0.0088 (19) | 0.009 (2) |
O17 | 0.023 (2) | 0.007 (2) | 0.0126 (19) | 0.0040 (19) | −0.0056 (18) | −0.0038 (15) |
O18 | 0.0168 (19) | 0.0145 (19) | 0.017 (2) | 0.0040 (16) | −0.005 (2) | −0.004 (2) |
O19 | 0.017 (2) | 0.0068 (19) | 0.027 (3) | −0.0003 (17) | 0.0070 (18) | 0.0053 (17) |
O20 | 0.017 (2) | 0.018 (2) | 0.013 (2) | −0.0022 (19) | 0.0020 (18) | 0.0006 (18) |
Geometric parameters (Å, º) top
P1—O9 | 1.540 (4) | K4—O11vii | 2.833 (4) |
P1—O10 | 1.542 (4) | K4—O13iv | 3.114 (5) |
P1—O11 | 1.500 (5) | K4—O14 | 3.210 (5) |
P1—O12 | 1.546 (4) | K4—O14iv | 2.815 (5) |
P2—O13 | 1.489 (5) | K4—O15 | 2.956 (5) |
P2—O14 | 1.539 (5) | K4—O18viii | 2.663 (4) |
P2—O15 | 1.563 (5) | K4—O20 | 2.690 (5) |
P2—O16 | 1.534 (5) | K5—P3v | 3.342 (2) |
P3—Ga8i | 2.9570 (18) | K5—O9 | 2.771 (4) |
P3—O17 | 1.564 (4) | K5—O11ii | 2.706 (4) |
P3—O18 | 1.495 (4) | K5—O12 | 3.348 (4) |
P3—O19 | 1.596 (4) | K5—O13 | 2.636 (5) |
P3—O20 | 1.498 (4) | K5—O17ii | 2.833 (4) |
Ga7—O16ii | 1.815 (4) | K5—O18v | 2.879 (5) |
Ga7—O12 | 1.817 (4) | K5—O18ii | 2.960 (4) |
Ga7—O15 | 1.820 (4) | K5—O20v | 3.000 (5) |
Ga7—O17 | 1.812 (4) | K6—O11vii | 2.742 (5) |
Ga8—O14iii | 1.820 (4) | K6—O13i | 2.709 (5) |
Ga8—O10iv | 1.815 (4) | K6—O16i | 3.239 (5) |
Ga8—O19v | 1.798 (4) | K6—O19ix | 2.728 (5) |
Ga8—O9 | 1.827 (4) | K6—O20 | 2.663 (4) |
K4—O10vi | 2.930 (4) | | |
| | | |
O9—P1—O10 | 106.7 (2) | O14iv—K4—O15 | 106.58 (13) |
O9—P1—O11 | 112.7 (3) | O10vi—K4—O18viii | 103.27 (13) |
O10—P1—O11 | 112.2 (2) | O11vii—K4—O18viii | 80.88 (14) |
O9—P1—O12 | 104.8 (3) | O13iv—K4—O18viii | 92.75 (14) |
O10—P1—O12 | 106.2 (2) | O14—K4—O18viii | 151.31 (13) |
O11—P1—O12 | 113.6 (2) | O14iv—K4—O18viii | 77.44 (14) |
O13—P2—O14 | 110.2 (3) | O10vi—K4—O20 | 155.86 (13) |
O13—P2—O15 | 113.4 (3) | O11vii—K4—O20 | 90.11 (14) |
O14—P2—O15 | 106.0 (3) | O13iv—K4—O20 | 95.45 (13) |
O13—P2—O16 | 113.7 (3) | O14—K4—O20 | 108.19 (13) |
O14—P2—O16 | 105.5 (2) | O14iv—K4—O20 | 138.78 (15) |
O15—P2—O16 | 107.4 (3) | O15—K4—O18viii | 160.63 (13) |
Ga8i—P3—O17 | 121.78 (18) | O15—K4—O20 | 79.50 (13) |
Ga8i—P3—O18 | 78.53 (17) | O18viii—K4—O20 | 85.24 (13) |
O17—P3—O18 | 108.8 (3) | P3v—K5—O9 | 69.47 (10) |
Ga8i—P3—O19 | 31.40 (16) | P3v—K5—O11ii | 105.81 (10) |
O17—P3—O19 | 102.5 (2) | O9—K5—O11ii | 87.26 (13) |
O18—P3—O19 | 108.6 (2) | P3v—K5—O12 | 115.37 (8) |
Ga8i—P3—O20 | 117.41 (19) | O9—K5—O12 | 45.91 (11) |
O17—P3—O20 | 110.5 (3) | O11ii—K5—O12 | 74.47 (12) |
O18—P3—O20 | 115.6 (3) | P3v—K5—O13 | 104.52 (12) |
O19—P3—O20 | 110.0 (2) | O9—K5—O13 | 84.05 (15) |
O16ii—Ga7—O12 | 106.64 (18) | O11ii—K5—O13 | 143.06 (15) |
O16ii—Ga7—O15 | 114.7 (2) | O12—K5—O13 | 73.76 (13) |
O12—Ga7—O15 | 113.01 (19) | P3v—K5—O17ii | 134.73 (10) |
O16ii—Ga7—O17 | 111.4 (2) | O9—K5—O17ii | 149.46 (13) |
O12—Ga7—O17 | 106.73 (19) | O11ii—K5—O17ii | 69.52 (13) |
O15—Ga7—O17 | 104.2 (2) | O12—K5—O17ii | 106.71 (12) |
O14iii—Ga8—O10iv | 103.0 (2) | O13—K5—O17ii | 102.44 (15) |
O14iii—Ga8—O19v | 120.4 (2) | P3v—K5—O18v | 26.49 (9) |
O10iv—Ga8—O19v | 108.65 (19) | O9—K5—O18v | 68.70 (12) |
O14iii—Ga8—P3v | 108.08 (17) | O11ii—K5—O18v | 79.34 (12) |
O10iv—Ga8—P3v | 135.85 (13) | O12—K5—O18v | 109.26 (11) |
O19v—Ga8—P3v | 27.55 (14) | O13—K5—O18v | 129.25 (15) |
O14iii—Ga8—O9 | 101.2 (2) | P3v—K5—O18ii | 96.47 (10) |
O10iv—Ga8—O9 | 112.54 (19) | O9—K5—O18ii | 159.12 (12) |
O19v—Ga8—O9 | 110.84 (19) | O11ii—K5—O18ii | 112.00 (13) |
P3v—Ga8—O9 | 91.46 (13) | O12—K5—O18ii | 144.94 (12) |
Ga8—O9—P1 | 124.0 (3) | O13—K5—O18ii | 84.78 (15) |
Ga8ii—O10—P1 | 130.5 (3) | P3v—K5—O20v | 26.62 (8) |
Ga7—O12—P1 | 128.5 (2) | O9—K5—O20v | 86.92 (12) |
Ga8vii—O14—P2 | 139.8 (3) | O11ii—K5—O20v | 128.34 (13) |
Ga7—O15—P2 | 132.1 (3) | O12—K5—O20v | 129.67 (12) |
Ga7iv—O16—P2 | 141.0 (3) | O13—K5—O20v | 87.01 (14) |
Ga7—O17—P3 | 131.9 (3) | O17ii—K5—O18v | 122.96 (13) |
Ga8i—O19—P3 | 121.0 (3) | O17ii—K5—O18ii | 50.81 (11) |
O10vi—K4—O11vii | 69.45 (13) | O18v—K5—O18ii | 105.79 (7) |
O10vi—K4—O13iv | 106.48 (12) | O17ii—K5—O20v | 122.89 (13) |
O11vii—K4—O13iv | 171.18 (13) | O18v—K5—O20v | 50.98 (11) |
O10vi—K4—O14 | 54.96 (11) | O18ii—K5—O20v | 74.91 (12) |
O11vii—K4—O14 | 74.05 (12) | O11vii—K6—O13i | 132.31 (16) |
O13iv—K4—O14 | 110.45 (12) | O11vii—K6—O16i | 151.76 (13) |
O10vi—K4—O14iv | 65.33 (13) | O13i—K6—O16i | 49.39 (13) |
O11vii—K4—O14iv | 122.85 (14) | O11vii—K6—O19ix | 92.46 (13) |
O13iv—K4—O14iv | 49.22 (12) | O13i—K6—O19ix | 131.57 (15) |
O14—K4—O14iv | 104.64 (8) | O16i—K6—O19ix | 82.70 (12) |
O10vi—K4—O15 | 95.46 (12) | O11vii—K6—O20 | 92.66 (14) |
O11vii—K4—O15 | 110.80 (13) | O13i—K6—O20 | 92.78 (15) |
O13iv—K4—O15 | 77.03 (12) | O16i—K6—O20 | 115.53 (13) |
O14—K4—O15 | 47.16 (12) | O19ix—K6—O20 | 104.08 (14) |
Symmetry codes: (i) −x+1/2, y−1/2, z−1/2; (ii) x−1/2, −y+3/2, z; (iii) x, y, z+1; (iv) x+1/2, −y+3/2, z; (v) −x+1/2, y+1/2, z+1/2; (vi) x+1/2, −y+3/2, z−1; (vii) x, y, z−1; (viii) −x+1, −y+1, z−1/2; (ix) −x, −y+1, z−1/2. |
(II) trisodium gallium biphosphate
top
Crystal data top
Na3Ga(PO4)2 | Z = 4 |
Mr = 328.64 | F(000) = 632 |
Triclinic, P1 | Dx = 3.194 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8595 (3) Å | Cell parameters from 7076 reflections |
b = 8.8773 (3) Å | θ = 2.8–32.4° |
c = 9.1972 (3) Å | µ = 4.70 mm−1 |
α = 88.970 (3)° | T = 293 K |
β = 70.982 (3)° | Square plate, grey |
γ = 87.949 (3)° | 0.16 × 0.16 × 0.05 mm |
V = 683.41 (4) Å3 | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 4355 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2972 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.4205 pixels mm-1 | θmax = 32.5°, θmin = 2.8° |
ω scans | h = −13→12 |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | k = −12→13 |
Tmin = 0.713, Tmax = 1.000 | l = −13→13 |
13240 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.043 | Method = Modified Sheldrick, w = 1/[σ2(F2) + (0.09P)2 + 0.01P],
where P = [max(Fo2,0) + 2Fc2]/3 |
wR(F2) = 0.138 | (Δ/σ)max = 0.000367 |
S = 1.00 | Δρmax = 3.29 e Å−3 |
4355 reflections | Δρmin = −1.79 e Å−3 |
253 parameters | |
Crystal data top
Na3Ga(PO4)2 | γ = 87.949 (3)° |
Mr = 328.64 | V = 683.41 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.8595 (3) Å | Mo Kα radiation |
b = 8.8773 (3) Å | µ = 4.70 mm−1 |
c = 9.1972 (3) Å | T = 293 K |
α = 88.970 (3)° | 0.16 × 0.16 × 0.05 mm |
β = 70.982 (3)° | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 4355 independent reflections |
Absorption correction: multi-scan [CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | 2972 reflections with I > 2σ(I) |
Tmin = 0.713, Tmax = 1.000 | Rint = 0.021 |
13240 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 253 parameters |
wR(F2) = 0.138 | 0 restraints |
S = 1.00 | Δρmax = 3.29 e Å−3 |
4355 reflections | Δρmin = −1.79 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.03084 (12) | 0.09021 (12) | 0.28901 (12) | 0.0098 | |
P2 | 0.27862 (13) | 0.58821 (11) | 0.01685 (12) | 0.0086 | |
P3 | 0.53414 (13) | 0.92663 (11) | 0.26700 (12) | 0.0083 | |
P4 | 0.71514 (12) | 0.58554 (11) | 0.45404 (12) | 0.0074 | |
Na5 | 0.6480 (2) | 0.2403 (2) | 0.3250 (3) | 0.0227 | |
Na6 | 0.3468 (3) | 0.2494 (2) | 0.1318 (3) | 0.0281 | |
Na7 | 0.9500 (2) | 0.4186 (2) | 0.1820 (2) | 0.0179 | |
Na8 | 0.9210 (3) | 0.8266 (3) | 0.1086 (3) | 0.0326 | |
Na9 | 0.1012 (2) | 0.6971 (2) | 0.4142 (2) | 0.0215 | |
Na10 | 0.3055 (2) | 0.9074 (2) | 0.0695 (2) | 0.0197 | |
Ga11 | 0.48246 (6) | 0.58319 (5) | 0.24474 (6) | 0.0151 | |
Ga12 | 0.74886 (6) | 0.92008 (5) | 0.48941 (6) | 0.0109 | |
O13 | −0.0390 (4) | −0.0657 (3) | 0.3563 (4) | 0.0149 | |
O14 | −0.0964 (4) | 0.2128 (3) | 0.3468 (4) | 0.0138 | |
O15 | 0.0960 (4) | 0.0772 (4) | 0.1165 (4) | 0.0240 | |
O16 | 0.1756 (4) | 0.1188 (5) | 0.3420 (4) | 0.0274 | |
O17 | 0.2096 (4) | 0.4335 (4) | 0.0419 (4) | 0.0194 | |
O18 | 0.3155 (4) | 0.6488 (4) | 0.1577 (4) | 0.0212 | |
O19 | 0.1723 (4) | 0.7055 (4) | −0.0273 (4) | 0.0191 | |
O20 | 0.4448 (4) | 0.5810 (3) | −0.1156 (4) | 0.0115 | |
O21 | 0.3843 (4) | 0.9157 (3) | 0.4119 (4) | 0.0175 | |
O22 | 0.5097 (4) | 1.0435 (4) | 0.1573 (4) | 0.0271 | |
O23 | 0.5637 (5) | 0.7718 (4) | 0.1911 (4) | 0.0259 | |
O24 | 0.6828 (4) | 0.9619 (4) | 0.3077 (4) | 0.0238 | |
O25 | 0.6360 (4) | 0.7371 (3) | 0.5265 (4) | 0.0195 | |
O26 | 0.6325 (5) | 0.5215 (5) | 0.3472 (5) | 0.0305 | |
O27 | 0.6911 (5) | 0.4724 (4) | 0.5855 (4) | 0.0316 | |
O28 | 0.8876 (5) | 0.6046 (5) | 0.3677 (5) | 0.0369 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0062 (5) | 0.0149 (5) | 0.0074 (5) | 0.0020 (4) | −0.0012 (4) | 0.0013 (4) |
P2 | 0.0076 (4) | 0.0089 (4) | 0.0103 (5) | 0.0019 (3) | −0.0042 (4) | −0.0038 (4) |
P3 | 0.0101 (5) | 0.0063 (4) | 0.0081 (5) | 0.0020 (3) | −0.0025 (4) | 0.0001 (3) |
P4 | 0.0089 (5) | 0.0059 (4) | 0.0083 (5) | −0.0014 (3) | −0.0038 (4) | −0.0016 (3) |
Na5 | 0.0144 (9) | 0.0139 (9) | 0.0397 (13) | −0.0002 (7) | −0.0091 (9) | 0.0039 (8) |
Na6 | 0.0145 (9) | 0.0167 (10) | 0.0484 (15) | −0.0023 (7) | −0.0046 (10) | 0.0147 (9) |
Na7 | 0.0147 (9) | 0.0197 (9) | 0.0165 (9) | −0.0030 (7) | −0.0008 (8) | −0.0022 (7) |
Na8 | 0.0309 (12) | 0.0505 (14) | 0.0149 (10) | 0.0232 (11) | −0.0074 (9) | −0.0060 (10) |
Na9 | 0.0158 (9) | 0.0289 (10) | 0.0220 (10) | 0.0075 (8) | −0.0097 (8) | −0.0104 (8) |
Na10 | 0.0169 (9) | 0.0140 (8) | 0.0251 (11) | 0.0007 (7) | −0.0026 (8) | −0.0017 (7) |
Ga11 | 0.0190 (3) | 0.0133 (2) | 0.0132 (3) | 0.00296 (18) | −0.0059 (2) | −0.00136 (18) |
Ga12 | 0.0094 (2) | 0.0098 (2) | 0.0130 (2) | 0.00012 (15) | −0.00310 (18) | −0.00068 (16) |
O13 | 0.0127 (15) | 0.0101 (13) | 0.0185 (16) | −0.0008 (11) | −0.0003 (13) | −0.0014 (12) |
O14 | 0.0111 (14) | 0.0153 (14) | 0.0145 (15) | 0.0014 (11) | −0.0036 (12) | −0.0060 (12) |
O15 | 0.0243 (19) | 0.036 (2) | 0.0077 (15) | 0.0160 (15) | −0.0013 (14) | 0.0003 (14) |
O16 | 0.0129 (16) | 0.049 (2) | 0.026 (2) | −0.0162 (15) | −0.0140 (15) | 0.0245 (17) |
O17 | 0.0150 (16) | 0.0119 (15) | 0.0273 (19) | −0.0037 (12) | −0.0007 (14) | −0.0027 (13) |
O18 | 0.0172 (16) | 0.0330 (19) | 0.0153 (16) | 0.0136 (14) | −0.0089 (14) | −0.0122 (14) |
O19 | 0.0203 (17) | 0.0182 (16) | 0.0239 (18) | 0.0109 (13) | −0.0149 (15) | −0.0089 (13) |
O20 | 0.0091 (13) | 0.0092 (13) | 0.0143 (15) | −0.0009 (10) | −0.0009 (12) | −0.0060 (11) |
O21 | 0.0190 (16) | 0.0106 (14) | 0.0161 (16) | 0.0044 (12) | 0.0031 (13) | 0.0025 (12) |
O22 | 0.0202 (18) | 0.0259 (18) | 0.026 (2) | 0.0097 (14) | 0.0037 (15) | 0.0187 (15) |
O23 | 0.035 (2) | 0.0139 (15) | 0.0188 (18) | −0.0107 (14) | 0.0071 (16) | −0.0102 (13) |
O24 | 0.0243 (18) | 0.039 (2) | 0.0144 (17) | −0.0195 (16) | −0.0130 (15) | 0.0020 (14) |
O25 | 0.0193 (16) | 0.0078 (13) | 0.0230 (18) | −0.0029 (12) | 0.0051 (14) | −0.0060 (12) |
O26 | 0.040 (2) | 0.033 (2) | 0.029 (2) | 0.0124 (18) | −0.0265 (19) | −0.0161 (17) |
O27 | 0.037 (2) | 0.0233 (18) | 0.0217 (19) | 0.0158 (16) | 0.0061 (17) | 0.0116 (15) |
O28 | 0.0129 (17) | 0.041 (2) | 0.046 (3) | −0.0075 (16) | 0.0070 (17) | −0.027 (2) |
Geometric parameters (Å, º) top
P1—Na10i | 3.044 (2) | Na6—O20iv | 2.390 (4) |
P1—Na7ii | 3.192 (2) | Na6—Na10iv | 3.305 (3) |
P1—Na9iii | 3.214 (2) | Na6—O15 | 2.783 (5) |
P1—Na6 | 3.081 (2) | Na6—O16 | 2.348 (4) |
P1—O13 | 1.569 (3) | Na6—O17 | 2.301 (4) |
P1—O14 | 1.510 (3) | Na7—O14vi | 2.314 (4) |
P1—O15 | 1.506 (3) | Na7—O19iv | 2.358 (4) |
P1—O16 | 1.543 (4) | Na7—O17vi | 2.247 (4) |
P2—Na7iv | 3.143 (2) | Na7—Na8viii | 3.350 (3) |
P2—Na7ii | 3.225 (2) | Na7—O28 | 2.317 (4) |
P2—Na10 | 2.914 (2) | Na8—O15iv | 2.273 (4) |
P2—O17 | 1.507 (3) | Na8—O19vi | 2.395 (4) |
P2—O18 | 1.545 (4) | Na8—O13ix | 2.619 (4) |
P2—O19 | 1.517 (3) | Na8—O15ix | 2.772 (5) |
P2—O20 | 1.575 (3) | Na8—O24 | 2.575 (5) |
P3—Na5v | 3.108 (2) | Na9—O27vii | 2.336 (4) |
P3—Na10 | 3.141 (2) | Na9—O14iii | 2.340 (4) |
P3—O21 | 1.549 (3) | Na9—O28ii | 2.256 (4) |
P3—O22 | 1.494 (3) | Na9—O13v | 2.543 (4) |
P3—O23 | 1.528 (3) | Na9—Na10 | 3.619 (3) |
P3—O24 | 1.525 (4) | Na9—O18 | 2.532 (4) |
P4—Na7 | 3.051 (2) | Na10—O15v | 2.282 (4) |
P4—O25 | 1.551 (3) | Na10—O22x | 2.239 (4) |
P4—O26 | 1.531 (4) | Na10—O18 | 2.429 (4) |
P4—O27 | 1.523 (4) | Na10—O19 | 2.508 (4) |
P4—O28 | 1.489 (4) | Na10—O22 | 2.555 (5) |
Na5—O14vi | 2.341 (4) | Ga11—O27vii | 1.873 (4) |
Na5—O25vii | 2.444 (4) | Ga11—O20iv | 1.857 (3) |
Na5—O24i | 2.481 (4) | Ga11—O18 | 1.966 (3) |
Na5—O21vii | 2.703 (4) | Ga11—O23 | 1.841 (3) |
Na5—O19iv | 2.726 (4) | Ga11—O26 | 1.923 (4) |
Na5—O20iv | 2.781 (4) | Ga12—O16vii | 1.901 (4) |
Na5—Ga12i | 3.422 (2) | Ga12—O21xi | 1.889 (3) |
Na5—Na6 | 3.655 (3) | Ga12—O13ix | 1.886 (3) |
Na5—Na7 | 3.055 (3) | Ga12—O24 | 1.968 (4) |
Na5—O26 | 2.503 (4) | Ga12—O25 | 1.905 (3) |
Na6—O22i | 2.344 (4) | | |
| | | |
Na10i—P1—Na7ii | 118.11 (6) | P4—Na7—P1vi | 109.68 (7) |
Na10i—P1—Na9iii | 149.20 (7) | P2iv—Na7—P1vi | 112.54 (6) |
Na7ii—P1—Na9iii | 71.05 (6) | P4—Na7—P2vi | 114.98 (6) |
Na10i—P1—Na6 | 62.02 (6) | P2iv—Na7—P2vi | 113.91 (6) |
Na7ii—P1—Na6 | 71.42 (6) | P1vi—Na7—P2vi | 109.16 (6) |
Na9iii—P1—Na6 | 97.91 (7) | P4—Na7—O28 | 28.21 (10) |
Na10i—P1—O13 | 85.97 (12) | P2iv—Na7—O28 | 114.99 (14) |
Na7ii—P1—O13 | 145.31 (14) | P1vi—Na7—O28 | 116.21 (15) |
Na9iii—P1—O13 | 101.64 (13) | P2vi—Na7—O28 | 87.54 (11) |
Na6—P1—O13 | 142.69 (13) | O15iv—Na8—O19vi | 90.13 (14) |
Na10i—P1—O14 | 159.83 (15) | O15iv—Na8—Na7viii | 67.23 (11) |
Na7ii—P1—O14 | 42.44 (13) | O19vi—Na8—Na7viii | 44.73 (9) |
Na9iii—P1—O14 | 42.67 (13) | O15iv—Na8—O13ix | 136.23 (17) |
Na6—P1—O14 | 106.66 (14) | O19vi—Na8—O13ix | 104.60 (14) |
O13—P1—O14 | 109.29 (18) | Na7viii—Na8—O13ix | 146.89 (11) |
Na10i—P1—O15 | 46.36 (14) | O15iv—Na8—O15ix | 86.20 (16) |
Na7ii—P1—O15 | 78.24 (15) | O19vi—Na8—O15ix | 86.06 (14) |
Na9iii—P1—O15 | 148.35 (16) | Na7viii—Na8—O15ix | 120.62 (11) |
Na6—P1—O15 | 64.35 (17) | O13ix—Na8—O15ix | 54.89 (11) |
O13—P1—O15 | 108.0 (2) | O15iv—Na8—O24 | 101.84 (14) |
Na10i—P1—O16 | 75.29 (17) | O19vi—Na8—O24 | 165.69 (15) |
Na7ii—P1—O16 | 102.12 (16) | Na7viii—Na8—O24 | 147.99 (13) |
Na9iii—P1—O16 | 73.98 (17) | O13ix—Na8—O24 | 61.26 (11) |
Na6—P1—O16 | 48.02 (14) | O15ix—Na8—O24 | 86.94 (13) |
O13—P1—O16 | 108.4 (2) | O27vii—Na9—O14iii | 89.60 (15) |
O14—P1—O15 | 114.46 (19) | O27vii—Na9—O28ii | 117.67 (19) |
O14—P1—O16 | 110.5 (2) | O14iii—Na9—O28ii | 124.09 (16) |
O15—P1—O16 | 106.0 (2) | O27vii—Na9—O13v | 159.33 (16) |
Na7iv—P2—Na7ii | 66.09 (6) | O14iii—Na9—O13v | 92.69 (13) |
Na7iv—P2—Na10 | 104.55 (6) | O28ii—Na9—O13v | 77.55 (15) |
Na7ii—P2—Na10 | 120.78 (6) | O27vii—Na9—P1iii | 115.54 (13) |
Na7iv—P2—O17 | 74.59 (16) | O14iii—Na9—P1iii | 25.93 (8) |
Na7ii—P2—O17 | 38.37 (13) | O28ii—Na9—P1iii | 107.44 (12) |
Na10—P2—O17 | 158.24 (15) | O13v—Na9—P1iii | 68.57 (9) |
Na7iv—P2—O18 | 149.19 (13) | O27vii—Na9—Na10 | 98.67 (12) |
Na7ii—P2—O18 | 101.05 (15) | O14iii—Na9—Na10 | 119.22 (11) |
Na10—P2—O18 | 56.42 (15) | O28ii—Na9—Na10 | 104.51 (15) |
O17—P2—O18 | 113.6 (2) | O13v—Na9—Na10 | 62.46 (9) |
Na7iv—P2—O19 | 46.05 (13) | P1iii—Na9—Na10 | 112.22 (7) |
Na7ii—P2—O19 | 84.62 (15) | O27vii—Na9—O18 | 63.36 (13) |
Na10—P2—O19 | 59.37 (14) | O14iii—Na9—O18 | 135.32 (14) |
O17—P2—O19 | 113.2 (2) | O28ii—Na9—O18 | 100.38 (15) |
O18—P2—O19 | 107.34 (19) | O13v—Na9—O18 | 101.66 (13) |
Na7iv—P2—O20 | 99.52 (13) | P1iii—Na9—O18 | 147.14 (12) |
Na7ii—P2—O20 | 145.69 (12) | Na10—Na9—O18 | 42.04 (10) |
Na10—P2—O20 | 92.45 (12) | O15v—Na10—O22x | 110.45 (15) |
O17—P2—O20 | 109.21 (17) | O15v—Na10—Na6iv | 155.57 (13) |
O18—P2—O20 | 104.89 (18) | O22x—Na10—Na6iv | 45.13 (10) |
O19—P2—O20 | 108.17 (19) | O15v—Na10—P2 | 123.19 (13) |
Na5v—P3—Na10 | 119.04 (6) | O22x—Na10—P2 | 96.86 (12) |
Na5v—P3—O21 | 99.10 (14) | Na6iv—Na10—P2 | 68.25 (6) |
Na10—P3—O21 | 87.60 (15) | O15v—Na10—P1v | 28.53 (9) |
Na5v—P3—O22 | 68.03 (18) | O22x—Na10—P1v | 134.11 (12) |
Na10—P3—O22 | 53.58 (18) | Na6iv—Na10—P1v | 167.01 (9) |
O21—P3—O22 | 111.24 (19) | P2—Na10—P1v | 121.64 (7) |
Na5v—P3—O23 | 151.94 (15) | O15v—Na10—P3 | 118.15 (12) |
Na10—P3—O23 | 72.75 (18) | O22x—Na10—P3 | 96.16 (13) |
O21—P3—O23 | 107.10 (19) | Na6iv—Na10—P3 | 72.58 (6) |
O22—P3—O23 | 110.1 (2) | P2—Na10—P3 | 106.55 (7) |
Na5v—P3—O24 | 52.05 (16) | P1v—Na10—P3 | 95.58 (6) |
Na10—P3—O24 | 158.88 (15) | O15v—Na10—Na9 | 91.10 (11) |
O21—P3—O24 | 111.9 (2) | O22x—Na10—Na9 | 157.93 (12) |
O22—P3—O24 | 109.2 (2) | Na6iv—Na10—Na9 | 113.17 (7) |
O23—P3—O24 | 107.2 (2) | P2—Na10—Na9 | 66.07 (5) |
Na7—P4—O25 | 148.57 (14) | P1v—Na10—Na9 | 67.85 (5) |
Na7—P4—O26 | 67.91 (16) | O15v—Na10—O18 | 130.38 (15) |
O25—P4—O26 | 112.1 (2) | O22x—Na10—O18 | 114.04 (14) |
Na7—P4—O27 | 102.91 (15) | Na6iv—Na10—O18 | 71.67 (10) |
O25—P4—O27 | 106.9 (2) | P2—Na10—O18 | 32.00 (9) |
O26—P4—O27 | 106.1 (3) | P1v—Na10—O18 | 111.77 (11) |
Na7—P4—O28 | 47.36 (15) | O15v—Na10—O19 | 95.08 (15) |
O25—P4—O28 | 110.5 (2) | O22x—Na10—O19 | 96.07 (16) |
O26—P4—O28 | 109.6 (2) | Na6iv—Na10—O19 | 88.15 (10) |
O27—P4—O28 | 111.7 (3) | P2—Na10—O19 | 31.36 (8) |
O14vi—Na5—O25vii | 143.49 (16) | P1v—Na10—O19 | 104.46 (10) |
O14vi—Na5—O24i | 80.49 (13) | O15v—Na10—O22 | 103.60 (15) |
O25vii—Na5—O24i | 100.04 (13) | O22x—Na10—O22 | 79.26 (17) |
O14vi—Na5—O21vii | 73.34 (13) | Na6iv—Na10—O22 | 75.62 (10) |
O25vii—Na5—O21vii | 74.81 (13) | P2—Na10—O22 | 130.54 (11) |
O24i—Na5—O21vii | 62.36 (11) | P1v—Na10—O22 | 91.42 (10) |
O14vi—Na5—O19iv | 80.43 (12) | P3—Na10—Na9 | 76.80 (6) |
O25vii—Na5—O19iv | 135.16 (14) | P3—Na10—O18 | 77.83 (10) |
O24i—Na5—O19iv | 95.39 (13) | Na9—Na10—O18 | 44.28 (9) |
O21vii—Na5—O19iv | 147.74 (12) | P3—Na10—O19 | 137.40 (11) |
O14vi—Na5—P3i | 109.22 (10) | Na9—Na10—O19 | 76.70 (10) |
O25vii—Na5—P3i | 79.28 (9) | O18—Na10—O19 | 59.93 (12) |
O24i—Na5—P3i | 29.00 (9) | P3—Na10—O22 | 28.07 (8) |
O21vii—Na5—P3i | 75.69 (9) | Na9—Na10—O22 | 100.82 (11) |
O19iv—Na5—P3i | 96.12 (10) | O18—Na10—O22 | 105.13 (14) |
O14vi—Na5—O20iv | 127.46 (13) | O19—Na10—O22 | 161.23 (14) |
O25vii—Na5—O20iv | 82.77 (12) | O27vii—Ga11—O20iv | 109.57 (16) |
O24i—Na5—O20iv | 123.88 (13) | O27vii—Ga11—O18 | 83.71 (17) |
O21vii—Na5—O20iv | 157.56 (12) | O20iv—Ga11—O18 | 95.47 (14) |
O19iv—Na5—O20iv | 54.09 (10) | O27vii—Ga11—O23 | 128.44 (16) |
O14vi—Na5—Ga12i | 60.55 (9) | O20iv—Ga11—O23 | 121.66 (14) |
O25vii—Na5—Ga12i | 99.64 (10) | O18—Ga11—O23 | 85.99 (18) |
O24i—Na5—Ga12i | 34.52 (8) | O27vii—Ga11—O26 | 91.83 (19) |
O21vii—Na5—Ga12i | 33.39 (7) | O20iv—Ga11—O26 | 88.00 (15) |
O19iv—Na5—Ga12i | 116.02 (9) | O18—Ga11—O26 | 175.07 (16) |
O14vi—Na5—Na6 | 156.82 (13) | O23—Ga11—O26 | 95.18 (19) |
O25vii—Na5—Na6 | 59.41 (11) | O16vii—Ga12—O21xi | 93.19 (17) |
O24i—Na5—Na6 | 92.92 (10) | O16vii—Ga12—O13ix | 90.20 (15) |
O21vii—Na5—Na6 | 123.17 (10) | O21xi—Ga12—O13ix | 125.21 (14) |
O19iv—Na5—Na6 | 78.08 (10) | O16vii—Ga12—Na5v | 134.24 (14) |
O14vi—Na5—Na7 | 48.62 (10) | O21xi—Ga12—Na5v | 51.94 (11) |
O25vii—Na5—Na7 | 143.90 (11) | O13ix—Ga12—Na5v | 89.25 (10) |
O24i—Na5—Na7 | 115.95 (12) | O16vii—Ga12—O24 | 176.89 (15) |
O21vii—Na5—Na7 | 118.64 (11) | O21xi—Ga12—O24 | 88.44 (16) |
O19iv—Na5—Na7 | 47.73 (9) | O13ix—Ga12—O24 | 86.70 (15) |
O14vi—Na5—O26 | 95.17 (14) | Na5v—Ga12—O24 | 45.59 (12) |
O25vii—Na5—O26 | 83.11 (14) | O16vii—Ga12—O25 | 91.31 (17) |
O24i—Na5—O26 | 175.63 (15) | O21xi—Ga12—O25 | 111.30 (14) |
O21vii—Na5—O26 | 116.00 (14) | O13ix—Ga12—O25 | 123.27 (13) |
O19iv—Na5—O26 | 84.36 (14) | Na5v—Ga12—O25 | 126.05 (12) |
P3i—Na5—O20iv | 101.19 (9) | O24—Ga12—O25 | 90.56 (16) |
P3i—Na5—Ga12i | 58.74 (4) | Ga12xii—O13—Na9i | 103.96 (14) |
O20iv—Na5—Ga12i | 158.40 (10) | Ga12xii—O13—Na8xii | 98.15 (14) |
P3i—Na5—Na6 | 64.92 (5) | Na9i—O13—Na8xii | 94.83 (12) |
O20iv—Na5—Na6 | 40.83 (7) | Ga12xii—O13—P1 | 121.22 (18) |
Ga12i—Na5—Na6 | 122.76 (6) | Na9i—O13—P1 | 130.02 (18) |
P3i—Na5—Na7 | 134.98 (8) | Na8xii—O13—P1 | 98.49 (17) |
O20iv—Na5—Na7 | 79.60 (9) | Na7ii—O14—Na9iii | 106.22 (14) |
Ga12i—Na5—Na7 | 108.27 (7) | Na7ii—O14—Na5ii | 82.01 (13) |
Na6—Na5—Na7 | 118.19 (8) | Na9iii—O14—Na5ii | 109.48 (14) |
P3i—Na5—O26 | 155.38 (12) | Na7ii—O14—P1 | 111.44 (18) |
O20iv—Na5—O26 | 59.33 (11) | Na9iii—O14—P1 | 111.39 (18) |
Ga12i—Na5—O26 | 142.20 (12) | Na5ii—O14—P1 | 130.46 (19) |
Na6—Na5—O26 | 91.30 (11) | Na10i—O15—Na8iv | 110.17 (15) |
Na7—Na5—O26 | 60.80 (12) | Na10i—O15—P1 | 105.11 (19) |
O22i—Na6—O20iv | 90.85 (15) | Na8iv—O15—P1 | 144.4 (2) |
O22i—Na6—Na10iv | 42.61 (10) | Na10i—O15—Na8xii | 84.20 (13) |
O20iv—Na6—Na10iv | 70.53 (9) | Na8iv—O15—Na8xii | 93.80 (16) |
O22i—Na6—P1 | 94.72 (11) | P1—O15—Na8xii | 93.97 (19) |
O20iv—Na6—P1 | 155.62 (13) | Na10i—O15—Na6 | 76.37 (13) |
Na10iv—Na6—P1 | 127.49 (8) | Na8iv—O15—Na6 | 97.47 (16) |
O22i—Na6—Na5 | 52.48 (12) | P1—O15—Na6 | 86.46 (18) |
O20iv—Na6—Na5 | 49.54 (10) | Na8xii—O15—Na6 | 159.95 (15) |
Na10iv—Na6—Na5 | 65.37 (7) | Na6—O16—Ga12vii | 116.42 (17) |
P1—Na6—Na5 | 118.21 (8) | Na6—O16—P1 | 102.73 (19) |
O22i—Na6—O15 | 95.43 (14) | Ga12vii—O16—P1 | 140.8 (2) |
O20iv—Na6—O15 | 171.63 (14) | Na6—O17—Na7ii | 107.27 (16) |
Na10iv—Na6—O15 | 110.77 (10) | Na6—O17—P2 | 116.9 (2) |
P1—Na6—O15 | 29.19 (7) | Na7ii—O17—P2 | 117.04 (19) |
Na5—Na6—O15 | 138.79 (10) | Ga11—O18—Na10 | 119.71 (18) |
O22i—Na6—O16 | 77.96 (15) | Ga11—O18—Na9 | 95.57 (14) |
O20iv—Na6—O16 | 131.24 (17) | Na10—O18—Na9 | 93.68 (13) |
Na10iv—Na6—O16 | 119.68 (13) | Ga11—O18—P2 | 129.5 (2) |
P1—Na6—O16 | 29.25 (9) | Na10—O18—P2 | 91.58 (18) |
Na5—Na6—O16 | 89.06 (12) | Na9—O18—P2 | 122.8 (2) |
O22i—Na6—O17 | 165.35 (18) | Na7iv—O19—Na8ii | 89.65 (14) |
O20iv—Na6—O17 | 90.86 (13) | Na7iv—O19—Na10 | 160.13 (18) |
Na10iv—Na6—O17 | 125.15 (13) | Na8ii—O19—Na10 | 88.05 (13) |
P1—Na6—O17 | 89.68 (11) | Na7iv—O19—P2 | 106.37 (17) |
Na5—Na6—O17 | 136.04 (12) | Na8ii—O19—P2 | 133.9 (2) |
O15—Na6—O16 | 55.90 (12) | Na10—O19—P2 | 89.27 (16) |
O15—Na6—O17 | 81.68 (13) | Na7iv—O19—Na5iv | 73.45 (12) |
O16—Na6—O17 | 111.39 (15) | Na8ii—O19—Na5iv | 125.95 (15) |
O14vi—Na7—Na5 | 49.37 (9) | Na10—O19—Na5iv | 92.06 (13) |
O14vi—Na7—O19iv | 89.34 (13) | P2—O19—Na5iv | 100.18 (17) |
Na5—Na7—O19iv | 58.82 (11) | Na6iv—O20—Ga11iv | 112.02 (15) |
O14vi—Na7—O17vi | 111.87 (14) | Na6iv—O20—P2 | 122.83 (17) |
Na5—Na7—O17vi | 151.82 (12) | Ga11iv—O20—P2 | 123.59 (18) |
O19iv—Na7—O17vi | 106.34 (15) | Na6iv—O20—Na5iv | 89.63 (12) |
O14vi—Na7—Na8viii | 87.29 (10) | Ga11iv—O20—Na5iv | 96.05 (13) |
Na5—Na7—Na8viii | 90.77 (8) | P2—O20—Na5iv | 96.42 (15) |
O19iv—Na7—Na8viii | 45.62 (10) | Ga12xi—O21—P3 | 125.44 (19) |
O17vi—Na7—Na8viii | 65.11 (11) | Ga12xi—O21—Na5vii | 94.68 (14) |
O14vi—Na7—P4 | 84.71 (10) | P3—O21—Na5vii | 128.36 (18) |
Na5—Na7—P4 | 68.73 (6) | Na6v—O22—Na10x | 92.26 (14) |
O19iv—Na7—P4 | 113.96 (11) | Na6v—O22—Na10 | 80.09 (14) |
O17vi—Na7—P4 | 136.58 (12) | Na10x—O22—Na10 | 100.74 (17) |
Na8viii—Na7—P4 | 158.23 (8) | Na6v—O22—P3 | 144.0 (2) |
O14vi—Na7—P2iv | 109.20 (10) | Na10x—O22—P3 | 123.0 (2) |
Na5—Na7—P2iv | 65.34 (6) | Na10—O22—P3 | 98.4 (2) |
O19iv—Na7—P2iv | 27.59 (8) | Ga11—O23—P3 | 135.4 (2) |
O17vi—Na7—P2iv | 113.80 (12) | Ga12—O24—Na5v | 99.89 (15) |
Na8viii—Na7—P2iv | 67.58 (6) | Ga12—O24—Na8 | 97.44 (17) |
O14vi—Na7—P1vi | 26.12 (8) | Na5v—O24—Na8 | 123.22 (16) |
Na5—Na7—P1vi | 68.42 (6) | Ga12—O24—P3 | 133.5 (2) |
O19iv—Na7—P1vi | 86.21 (10) | Na5v—O24—P3 | 99.0 (2) |
O17vi—Na7—P1vi | 87.89 (11) | Na8—O24—P3 | 106.85 (19) |
Na8viii—Na7—P1vi | 66.85 (6) | Na5vii—O25—Ga12 | 115.87 (15) |
O14vi—Na7—P2vi | 129.34 (11) | Na5vii—O25—P4 | 121.76 (18) |
Na5—Na7—P2vi | 176.26 (8) | Ga12—O25—P4 | 122.1 (2) |
O19iv—Na7—P2vi | 118.68 (12) | Ga11—O26—Na5 | 103.84 (17) |
O17vi—Na7—P2vi | 24.59 (8) | Ga11—O26—P4 | 139.8 (2) |
Na8viii—Na7—P2vi | 85.61 (7) | Na5—O26—P4 | 115.2 (2) |
O14vi—Na7—O28 | 97.52 (16) | Na9vii—O27—Ga11vii | 105.10 (16) |
Na5—Na7—O28 | 96.09 (12) | Na9vii—O27—P4 | 119.7 (2) |
O19iv—Na7—O28 | 138.89 (16) | Ga11vii—O27—P4 | 135.0 (2) |
O17vi—Na7—O28 | 108.37 (15) | Na7—O28—Na9vi | 114.29 (17) |
Na8viii—Na7—O28 | 173.12 (13) | Na7—O28—P4 | 104.4 (2) |
P4—Na7—P2iv | 96.09 (6) | Na9vi—O28—P4 | 137.1 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y, z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x, y+1, z; (vi) x+1, y, z; (vii) −x+1, −y+1, −z+1; (viii) −x+2, −y+1, −z; (ix) x+1, y+1, z; (x) −x+1, −y+2, −z; (xi) −x+1, −y+2, −z+1; (xii) x−1, y−1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | K3Ga2(PO4)3 | Na3Ga(PO4)2 |
Mr | 541.65 | 328.64 |
Crystal system, space group | Orthorhombic, Pna21 | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.67110 (15), 17.0109 (3), 8.38857 (16) | 8.8595 (3), 8.8773 (3), 9.1972 (3) |
α, β, γ (°) | 90, 90, 90 | 88.970 (3), 70.982 (3), 87.949 (3) |
V (Å3) | 1237.34 (4) | 683.41 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 5.81 | 4.70 |
Crystal size (mm) | 0.25 × 0.16 × 0.12 | 0.16 × 0.16 × 0.05 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur diffractometer | Oxford Diffraction Xcalibur diffractometer |
Absorption correction | Multi-scan [CrysAlis RED (Oxford Diffraction, 2007)] empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] | Multi-scan [CrysAlis RED (Oxford Diffraction, 2007); empirical (using intensity measurements) absorption
correction
using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm] |
Tmin, Tmax | 0.507, 1.000 | 0.713, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24311, 3885, 3024 | 13240, 4355, 2972 |
Rint | 0.032 | 0.021 |
(sin θ/λ)max (Å−1) | 0.755 | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.088, 0.98 | 0.043, 0.138, 1.00 |
No. of reflections | 3885 | 4355 |
No. of parameters | 182 | 253 |
No. of restraints | 1 | 0 |
Δρmax, Δρmin (e Å−3) | 1.32, −1.74 | 3.29, −1.79 |
Absolute structure | Flack (1983), 1691 Friedel-pairs | ? |
Absolute structure parameter | 0.014 (15) | ? |
Selected bond lengths (Å) for (I) topP1—O9 | 1.540 (4) | K4—O11vi | 2.833 (4) |
P1—O10 | 1.542 (4) | K4—O13iii | 3.114 (5) |
P1—O11 | 1.500 (5) | K4—O14 | 3.210 (5) |
P1—O12 | 1.546 (4) | K4—O14iii | 2.815 (5) |
P2—O13 | 1.489 (5) | K4—O15 | 2.956 (5) |
P2—O14 | 1.539 (5) | K4—O18vii | 2.663 (4) |
P2—O15 | 1.563 (5) | K4—O20 | 2.690 (5) |
P2—O16 | 1.534 (5) | K5—O9 | 2.771 (4) |
P3—O17 | 1.564 (4) | K5—O11i | 2.706 (4) |
P3—O18 | 1.495 (4) | K5—O12 | 3.348 (4) |
P3—O19 | 1.596 (4) | K5—O13 | 2.636 (5) |
P3—O20 | 1.498 (4) | K5—O17i | 2.833 (4) |
Ga7—O16i | 1.815 (4) | K5—O18iv | 2.879 (5) |
Ga7—O12 | 1.817 (4) | K5—O18i | 2.960 (4) |
Ga7—O15 | 1.820 (4) | K5—O20iv | 3.000 (5) |
Ga7—O17 | 1.812 (4) | K6—O11vi | 2.742 (5) |
Ga8—O14ii | 1.820 (4) | K6—O13viii | 2.709 (5) |
Ga8—O10iii | 1.815 (4) | K6—O16viii | 3.239 (5) |
Ga8—O19iv | 1.798 (4) | K6—O19ix | 2.728 (5) |
Ga8—O9 | 1.827 (4) | K6—O20 | 2.663 (4) |
K4—O10v | 2.930 (4) | | |
Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) x, y, z+1; (iii) x+1/2, −y+3/2, z; (iv) −x+1/2, y+1/2, z+1/2; (v) x+1/2, −y+3/2, z−1; (vi) x, y, z−1; (vii) −x+1, −y+1, z−1/2; (viii) −x+1/2, y−1/2, z−1/2; (ix) −x, −y+1, z−1/2. |
Selected bond lengths (Å) for (II) topP1—O13 | 1.569 (3) | Na7—O19iv | 2.358 (4) |
P1—O14 | 1.510 (3) | Na7—O17i | 2.247 (4) |
P1—O15 | 1.506 (3) | Na7—O28 | 2.317 (4) |
P1—O16 | 1.543 (4) | Na8—O15iv | 2.273 (4) |
P2—O17 | 1.507 (3) | Na8—O19i | 2.395 (4) |
P2—O18 | 1.545 (4) | Na8—O13v | 2.619 (4) |
P2—O19 | 1.517 (3) | Na8—O15v | 2.772 (5) |
P2—O20 | 1.575 (3) | Na8—O24 | 2.575 (5) |
P3—O21 | 1.549 (3) | Na9—O27ii | 2.336 (4) |
P3—O22 | 1.494 (3) | Na9—O14vi | 2.340 (4) |
P3—O23 | 1.528 (3) | Na9—O28vii | 2.256 (4) |
P3—O24 | 1.525 (4) | Na9—O13viii | 2.543 (4) |
P4—O25 | 1.551 (3) | Na9—O18 | 2.532 (4) |
P4—O26 | 1.531 (4) | Na10—O15viii | 2.282 (4) |
P4—O27 | 1.523 (4) | Na10—O22ix | 2.239 (4) |
P4—O28 | 1.489 (4) | Na10—O18 | 2.429 (4) |
Na5—O14i | 2.341 (4) | Na10—O19 | 2.508 (4) |
Na5—O25ii | 2.444 (4) | Na10—O22 | 2.555 (5) |
Na5—O24iii | 2.481 (4) | Ga11—O27ii | 1.873 (4) |
Na5—O21ii | 2.703 (4) | Ga11—O20iv | 1.857 (3) |
Na5—O19iv | 2.726 (4) | Ga11—O18 | 1.966 (3) |
Na5—O20iv | 2.781 (4) | Ga11—O23 | 1.841 (3) |
Na5—O26 | 2.503 (4) | Ga11—O26 | 1.923 (4) |
Na6—O22iii | 2.344 (4) | Ga12—O16ii | 1.901 (4) |
Na6—O20iv | 2.390 (4) | Ga12—O21x | 1.889 (3) |
Na6—O15 | 2.783 (5) | Ga12—O13v | 1.886 (3) |
Na6—O16 | 2.348 (4) | Ga12—O24 | 1.968 (4) |
Na6—O17 | 2.301 (4) | Ga12—O25 | 1.905 (3) |
Na7—O14i | 2.314 (4) | | |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+1, −z; (v) x+1, y+1, z; (vi) −x, −y+1, −z+1; (vii) x−1, y, z; (viii) x, y+1, z; (ix) −x+1, −y+2, −z; (x) −x+1, −y+2, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Several sodium and potassium phosphates containing gallium are known, such as K2Ga2P8O24 (Palkina et al., 1979) and Na3GaP8O23 (Palkina et al., 1993). A short overview of condensed phosphates of alkaline and trivalent metals was given by Grunze et al. (1990). Here, we report the structures of K3Ga2(PO4)3, (I), and Na3Ga(PO4)2, (II). The structure of (I) appears to be isotypic with that of K3Al2(PO4)3 (Nandini Devi & Vidyasagar, 2000). It is noted that these structures are related to the NASICON super ionic conductors, such as Na3Sc2(PO4)3 (Susman et al., 1983) or Na3Fe2(PO4)3 (d'Yvoire et al., 1983).
Fig. 1 shows the constituent polyhedra for the structure of (I). Both trivalent Ga and pentavalent P are in tetrahedral coordination by O, with Ga—O distances ranging between 1.799 (4) and 1.820 (4) Å and P—O distances between 1.489 (4) and 1.597 (4) Å. The coordination environment of the three independent K atoms is variable and irregular. Atom K3 is approximately at the base of a tetrahedron formed by atoms O11, O13, O19 and O20, whereas atom K4 is sixfold and K5 sevenfold coordinated by O. The Brown criterion that a ligand should contribute at least 4% to the total bond-valence sum in order to be considered being bonded [Brown, 2002; calculations using VaList (Wills & Brown, 1999)] gives a maximum bonded distance of about 3.2 Å for K—O. Not including the K4—O13 distance [3.114 Å and a bond valence contribution (BVC) of 0.070] and the K4—O14 distance (3.21 Å, BVC 0.054) gives a bond-valence sum (BVS) for atom K4 of 0.991. For atom K5, the bond-valence calculations are less conclusive: in order to arrive at a BVS close to 1.00, the K5—O20 contribution [3.000 (5) Å, BVC 0.096, thus beyond the Brown criterion of 4%] should not be included. Somewhat arbitrarily, however, in Fig. 1 K—O bonds are drawn up to 3.0 Å, thus including the K4—O20 contact.
The constituent polyhedra for the structure of (II) are given in Fig. 2. The P environment is very similar to that in the structure of (I), with P—O distances in the range 1.488 (4)–1.576 (3) Å. The coordination of Ga, however, is not tetrahedral but trigonal bipyrimadal, with Ga—O distances in the range 1.840 (3)–1.968 (4) Å. The Na environment is like the K environment in (I), variable and irregular. There are six independent Na atoms, one fourfold coordinated, four fivefold coordinated and one sevenfold coordinated.
The crystallographic symmetry of the structures of compounds (I) and (II) is very different, Pna21 and P1, respectively, but their topology is quite similar. They consist of three-dimensional [Ga2P3O12]3- and [GaP2O8]2- anionic frameworks for (I) and (II), respectively, with one-dimensional channels occupied by the countercations K+ and Na+. The anionic subsystem of (I) consists of an interconnected network of corner-sharing tetrahedra, where both types of tetrahedra, viz. GaO4 and PO4, are only connected to each other. Fig. 3 gives a view down the c axis, showing the irregularly shaped K+ one-dimensional channels of different size. The anionic famework of (II) consists of GaO4 trigonal bipyramids which share all five corners with PO4 tetrahedra. Fig. 4 gives a view down the a axis, showing different irregularly shaped one-dimensional Na+ channels. The largest tunnels are delimited by 12 vertex-linked GaO4 trigonal bipyramids and PO4 tetrahedra.