Single crystals of the vanadate garnet Ca2NaCd2V3O12 (dicalcium sodium dicadmium trivanadate) were synthesized using the floating-zone method and the crystal structure was investigated using single-crystal X-ray diffraction. We considered the effectiveness of substitution of the Y-site cation with reference to previous structural studies of vanadate garnets. The structures of vanadate garnets are subject to geometric constraints similar to those of silicate garnets. These constraints force the tetrahedral–dodecahedral shared edge length in vanadate garnets to become shorter than the unshared dodecahedral edge length, as in ugrandite (uvarovite, grossular and andradite) garnets. However, the vanadate garnet Ca2NaCd2V3O12 exhibits the normal structural feature, similar to pyralspite (pyrope, almandine and spessartine) garnets, namely that the dodecahedral–dodecahedral shared edge length is shorter than the unshared dodecahedral edge length. With increasing ionic radius of the Y-site cation, the atomic coordinates x, y and z of oxygen adopt values which satisfy Pauling's third rule.
Supporting information
CCDC reference: 1827502
Data collection: Software for data collection?; cell refinement: Software for cell refinement?; data reduction: Software for data reduction?; program(s) used to solve structure: OLEX2 (Dolomanov et al., 2009) and SHELXT2014 (Sheldrick,
2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: Software for molecular graphics?.
Dicalcium sodium dicadmium trivanadate
top
Crystal data top
Ca2NaCd2V3O12 | Mo Kα radiation, λ = 0.71073 Å |
Mr = 672.77 | Cell parameters from 6959 reflections |
Cubic, Ia3d | θ = 2.2–55.3° |
a = 12.7576 (1) Å | µ = 7.72 mm−1 |
V = 2076.38 (5) Å3 | T = 293 K |
Z = 8 | Sphere, orange |
F(000) = 2496 | 0.12 × 0.12 × 0.12 × 0.06 (radius) mm |
Dx = 4.304 Mg m−3 | |
Data collection top
Rigaku SuperNova Single source diffractometer with an HyPix3000 area detector | 675 reflections with I > 2σ(I) |
ω scans | Rint = 0.016 |
Absorption correction: for a sphere | θmax = 45.0°, θmin = 3.9° |
Tmin = 0.506, Tmax = 0.533 | h = −22→19 |
8486 measured reflections | k = −25→18 |
719 independent reflections | l = −24→25 |
Refinement top
Refinement on F2 | 2 restraints |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.024P)2 + 1.850P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.016 | (Δ/σ)max < 0.001 |
wR(F2) = 0.055 | Δρmax = 0.61 e Å−3 |
S = 1.17 | Δρmin = −1.60 e Å−3 |
719 reflections | Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
22 parameters | Extinction coefficient: 0.00177 (9) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cd01 | 0.500000 | 0.500000 | 0.500000 | 0.01059 (6) | |
V002 | 0.625000 | 0.500000 | 0.250000 | 0.00741 (6) | |
Ca1 | 0.375000 | 0.500000 | 0.250000 | 0.01115 (15) | 0.660 (14) |
O004 | 0.54015 (4) | 0.44169 (4) | 0.33734 (4) | 0.01230 (10) | |
Na1 | 0.375000 | 0.500000 | 0.250000 | 0.01115 (15) | 0.34 (2) |
Cd1 | 0.375000 | 0.500000 | 0.250000 | 0.01115 (15) | 0.021 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd01 | 0.01059 (6) | 0.01059 (6) | 0.01059 (6) | −0.00065 (1) | −0.00065 (1) | −0.00065 (1) |
V002 | 0.00688 (9) | 0.00767 (7) | 0.00767 (7) | 0.000 | 0.000 | 0.000 |
Ca1 | 0.00856 (18) | 0.01245 (16) | 0.01245 (16) | 0.000 | 0.000 | 0.00144 (7) |
O004 | 0.01415 (19) | 0.01295 (19) | 0.00979 (17) | −0.00146 (14) | 0.00159 (14) | 0.00008 (14) |
Na1 | 0.00856 (18) | 0.01245 (16) | 0.01245 (16) | 0.000 | 0.000 | 0.00144 (7) |
Cd1 | 0.00856 (18) | 0.01245 (16) | 0.01245 (16) | 0.000 | 0.000 | 0.00144 (7) |
Geometric parameters (Å, º) top
Cd01—O004 | 2.2632 (5) | V002—O004vii | 1.7224 (5) |
Cd01—O004i | 2.2632 (5) | V002—O004viii | 1.7224 (5) |
Cd01—O004ii | 2.2632 (5) | V002—O004 | 1.7224 (5) |
Cd01—O004iii | 2.2632 (5) | V002—Ca1 | 3.1894 (1) |
Cd01—O004iv | 2.2632 (5) | V002—Ca1ix | 3.1894 (1) |
Cd01—O004v | 2.2632 (5) | Ca1—O004x | 2.4968 (6) |
Cd01—Ca1 | 3.5659 (1) | Ca1—O004xi | 2.4968 (6) |
Cd01—Ca1ii | 3.5659 (1) | Ca1—O004vii | 2.4968 (6) |
Cd01—Ca1i | 3.5659 (1) | Ca1—O004 | 2.4968 (6) |
Cd01—Ca1iii | 3.5659 (1) | Ca1—O004xii | 2.5443 (5) |
Cd01—Ca1iv | 3.5659 (1) | Ca1—O004xiii | 2.5443 (5) |
Cd01—Ca1v | 3.5659 (1) | Ca1—O004xiv | 2.5443 (5) |
V002—O004vi | 1.7224 (5) | Ca1—O004iv | 2.5443 (5) |
| | | |
O004—Cd01—O004i | 91.12 (2) | O004vii—V002—Ca1ix | 128.938 (19) |
O004—Cd01—O004ii | 88.88 (2) | O004viii—V002—Ca1ix | 51.062 (19) |
O004i—Cd01—O004ii | 180.0 | O004—V002—Ca1ix | 128.937 (19) |
O004—Cd01—O004iii | 91.12 (2) | Ca1—V002—Ca1ix | 180.0 |
O004i—Cd01—O004iii | 88.88 (2) | O004x—Ca1—O004xi | 64.90 (2) |
O004ii—Cd01—O004iii | 91.12 (2) | O004x—Ca1—O004vii | 167.96 (2) |
O004—Cd01—O004iv | 88.88 (2) | O004xi—Ca1—O004vii | 116.50 (2) |
O004i—Cd01—O004iv | 91.12 (2) | O004x—Ca1—O004 | 116.50 (2) |
O004ii—Cd01—O004iv | 88.88 (2) | O004xi—Ca1—O004 | 167.96 (2) |
O004iii—Cd01—O004iv | 180.0 | O004vii—Ca1—O004 | 64.90 (2) |
O004—Cd01—O004v | 180.0 | O004x—Ca1—O004xii | 121.891 (11) |
O004i—Cd01—O004v | 88.884 (19) | O004xi—Ca1—O004xii | 77.90 (2) |
O004ii—Cd01—O004v | 91.12 (2) | O004vii—Ca1—O004xii | 69.15 (2) |
O004iii—Cd01—O004v | 88.884 (19) | O004—Ca1—O004xii | 92.131 (14) |
O004iv—Cd01—O004v | 91.116 (19) | O004x—Ca1—O004xiii | 92.130 (14) |
O004—Cd01—Ca1 | 44.037 (14) | O004xi—Ca1—O004xiii | 69.15 (2) |
O004i—Cd01—Ca1 | 86.822 (14) | O004vii—Ca1—O004xiii | 77.90 (2) |
O004ii—Cd01—Ca1 | 93.178 (14) | O004—Ca1—O004xiii | 121.891 (11) |
O004iii—Cd01—Ca1 | 134.753 (13) | O004xii—Ca1—O004xiii | 115.00 (2) |
O004iv—Cd01—Ca1 | 45.247 (13) | O004x—Ca1—O004xiv | 77.90 (2) |
O004v—Cd01—Ca1 | 135.964 (14) | O004xi—Ca1—O004xiv | 121.891 (11) |
O004—Cd01—Ca1ii | 45.246 (13) | O004vii—Ca1—O004xiv | 92.130 (14) |
O004i—Cd01—Ca1ii | 135.964 (14) | O004—Ca1—O004xiv | 69.15 (2) |
O004ii—Cd01—Ca1ii | 44.036 (14) | O004xii—Ca1—O004xiv | 158.23 (2) |
O004iii—Cd01—Ca1ii | 86.822 (14) | O004xiii—Ca1—O004xiv | 69.43 (3) |
O004iv—Cd01—Ca1ii | 93.178 (14) | O004x—Ca1—O004iv | 69.15 (2) |
O004v—Cd01—Ca1ii | 134.753 (13) | O004xi—Ca1—O004iv | 92.130 (14) |
Ca1—Cd01—Ca1ii | 66.4 | O004vii—Ca1—O004iv | 121.891 (11) |
O004—Cd01—Ca1i | 134.754 (13) | O004—Ca1—O004iv | 77.90 (2) |
O004i—Cd01—Ca1i | 44.036 (14) | O004xii—Ca1—O004iv | 69.43 (3) |
O004ii—Cd01—Ca1i | 135.964 (14) | O004xiii—Ca1—O004iv | 158.23 (2) |
O004iii—Cd01—Ca1i | 93.178 (14) | O004xiv—Ca1—O004iv | 115.00 (2) |
O004iv—Cd01—Ca1i | 86.822 (14) | O004x—Ca1—V002xv | 32.451 (12) |
O004v—Cd01—Ca1i | 45.247 (13) | O004xi—Ca1—V002xv | 32.451 (12) |
Ca1—Cd01—Ca1i | 113.6 | O004vii—Ca1—V002xv | 147.549 (12) |
Ca1ii—Cd01—Ca1i | 180.0 | O004—Ca1—V002xv | 147.548 (12) |
O004—Cd01—Ca1iii | 86.823 (14) | O004xii—Ca1—V002xv | 100.886 (12) |
O004i—Cd01—Ca1iii | 45.247 (13) | O004xiii—Ca1—V002xv | 79.114 (12) |
O004ii—Cd01—Ca1iii | 134.753 (13) | O004xiv—Ca1—V002xv | 100.886 (12) |
O004iii—Cd01—Ca1iii | 44.036 (14) | O004iv—Ca1—V002xv | 79.114 (12) |
O004iv—Cd01—Ca1iii | 135.964 (14) | O004x—Ca1—V002 | 147.549 (12) |
O004v—Cd01—Ca1iii | 93.178 (14) | O004xi—Ca1—V002 | 147.549 (12) |
Ca1—Cd01—Ca1iii | 113.6 | O004vii—Ca1—V002 | 32.451 (12) |
Ca1ii—Cd01—Ca1iii | 113.6 | O004—Ca1—V002 | 32.452 (12) |
Ca1i—Cd01—Ca1iii | 66.4 | O004xii—Ca1—V002 | 79.114 (12) |
O004—Cd01—Ca1iv | 93.177 (14) | O004xiii—Ca1—V002 | 100.886 (12) |
O004i—Cd01—Ca1iv | 134.753 (13) | O004xiv—Ca1—V002 | 79.114 (12) |
O004ii—Cd01—Ca1iv | 45.247 (13) | O004iv—Ca1—V002 | 100.886 (12) |
O004iii—Cd01—Ca1iv | 135.964 (14) | V002xv—Ca1—V002 | 180.0 |
O004iv—Cd01—Ca1iv | 44.036 (14) | O004x—Ca1—Cd01xvi | 39.056 (12) |
O004v—Cd01—Ca1iv | 86.822 (14) | O004xi—Ca1—Cd01xvi | 91.247 (12) |
Ca1—Cd01—Ca1iv | 66.4 | O004vii—Ca1—Cd01xvi | 130.081 (12) |
Ca1ii—Cd01—Ca1iv | 66.4 | O004—Ca1—Cd01xvi | 96.366 (12) |
Ca1i—Cd01—Ca1iv | 113.6 | O004xii—Ca1—Cd01xvi | 160.758 (12) |
Ca1iii—Cd01—Ca1iv | 180.0 | O004xiii—Ca1—Cd01xvi | 74.662 (12) |
O004—Cd01—Ca1v | 135.963 (14) | O004xiv—Ca1—Cd01xvi | 39.175 (11) |
O004i—Cd01—Ca1v | 93.178 (14) | O004iv—Ca1—Cd01xvi | 95.486 (13) |
O004ii—Cd01—Ca1v | 86.822 (14) | V002xv—Ca1—Cd01xvi | 63.4 |
O004iii—Cd01—Ca1v | 45.247 (13) | V002—Ca1—Cd01xvi | 116.6 |
O004iv—Cd01—Ca1v | 134.753 (13) | O004x—Ca1—Cd01 | 96.367 (12) |
O004v—Cd01—Ca1v | 44.036 (14) | O004xi—Ca1—Cd01 | 130.081 (12) |
Ca1—Cd01—Ca1v | 180.0 | O004vii—Ca1—Cd01 | 91.247 (12) |
Ca1ii—Cd01—Ca1v | 113.6 | O004—Ca1—Cd01 | 39.056 (12) |
Ca1i—Cd01—Ca1v | 66.4 | O004xii—Ca1—Cd01 | 74.662 (12) |
Ca1iii—Cd01—Ca1v | 66.4 | O004xiii—Ca1—Cd01 | 160.758 (12) |
Ca1iv—Cd01—Ca1v | 113.6 | O004xiv—Ca1—Cd01 | 95.486 (13) |
O004vi—V002—O004vii | 113.27 (2) | O004iv—Ca1—Cd01 | 39.175 (11) |
O004vi—V002—O004viii | 102.12 (4) | V002xv—Ca1—Cd01 | 116.6 |
O004vii—V002—O004viii | 113.27 (2) | V002—Ca1—Cd01 | 63.4 |
O004vi—V002—O004 | 113.26 (2) | Cd01xvi—Ca1—Cd01 | 101.5 |
O004vii—V002—O004 | 102.13 (4) | V002—O004—Cd01 | 126.40 (3) |
O004viii—V002—O004 | 113.26 (2) | V002—O004—Ca1 | 96.48 (2) |
O004vi—V002—Ca1 | 128.938 (19) | Cd01—O004—Ca1 | 96.91 (2) |
O004vii—V002—Ca1 | 51.062 (19) | V002—O004—Ca1ii | 131.59 (3) |
O004viii—V002—Ca1 | 128.938 (19) | Cd01—O004—Ca1ii | 95.580 (18) |
O004—V002—Ca1 | 51.063 (19) | Ca1—O004—Ca1ii | 101.582 (19) |
O004vi—V002—Ca1ix | 51.062 (19) | | |
Symmetry codes: (i) −y+1, −z+1, −x+1; (ii) y, z, x; (iii) −z+1, −x+1, −y+1; (iv) z, x, y; (v) −x+1, −y+1, −z+1; (vi) −x+5/4, z+1/4, −y+3/4; (vii) x, −y+1, −z+1/2; (viii) −x+5/4, −z+3/4, y−1/4; (ix) x+1/2, y, −z+1/2; (x) −x+3/4, −z+3/4, −y+3/4; (xi) −x+3/4, z+1/4, y−1/4; (xii) −z+3/4, y+1/4, x−1/4; (xiii) z, −x+1, −y+1/2; (xiv) −z+3/4, −y+3/4, −x+3/4; (xv) x−1/2, y, −z+1/2; (xvi) −y+3/4, −x+3/4, −z+3/4. |
Refined positional parameters topSites | Atoms | Occupancies | x | y | z |
X | Ca | 0.660 (14) | 0.125 | 0 | 0.25 |
| Na | 0.34 (2) | | | |
| Cd | 0.021 (3) | | | |
Y | Cd | 1.000 | 0 | 0 | 0 |
Z | V | 1.000 | 0.375 | 0 | 0.25 |
O | O | 1.000 | -0.04013 (4) | 0.05833 (4) | 0.16267 (4) |
Selected interatomic distances (Å) topCation–oxygen distances | | | |
(Ca,Na)—O1 | 2.4967 (7) | (Ca,Na)—O4 | 2.5442 (7) |
Cd—O1 | 2.2632 (7) | V—O1 | 1.7225 (7) |
| | | |
Cation–cation distances | | | |
(Ca,Na)—(Ca,Na) | 3.90620 (3) | (Ca,Na)—Cd | 3.56586 (3) |
(Ca,Na)—V | 3.18940 (3) | Cd—Cd | 5.52420 (3) |
Cd—V | 3.56586 (3) | V—V | 3.90620 (3) |
| | | |
Oxygen–oxygen distances | | | |
O4—O6 | 2.8609 (10) | O4—O7 | 2.8980 (10) |
O1—O7 | 3.6304 (10) | O7—O8 | 4.2914 (10) |
O1—O4 | 3.1692 (10) | O1—O5 | 3.2318 (10) |
O1—O2 | 2.6796 (11) | O1—O3 | 2.8772 (10) |