Buy article online - an online subscription or single-article purchase is required to access this article.
The crystal structure of the new mineral aravaite Ba
2Ca
18(SiO
4)
6(PO
4)
3(CO
3)F
3O [
,
a = 7.12550 (11),
c = 66.2902 (13) Å,
V = 2914.81 (8) Å
3,
Z = 3] was solved from single-crystal diffraction data, collected using synchrotron radiation at the X06DA beamline of the Swiss Light Source. The unit cell of this modular mineral contains six layers of {Ba(PO
4)
1.5(CO
3)
0.5}
3.5− (T-layer), three triple antiperovskite layers (tAP) {(F
2OCa
12)(SiO
4)
4}
4+, and three single antiperovskite layers (sAP) {(FCa
6)(SiO
4)
2}
3+. The structure refinement confirms a model with a layer sequence of T–sAP–T–tAP as an average structure of this mineral. However, one-dimensional diffuse scattering observed parallel to
c* implies imperfections in the stacking sequence of the average structure. Qualitative modelling of disorder confirms that the alternating sequence of T–sAP and T–tAP blocks is disturbed. The blocks occurring in this new mineral are known from other so-called hexagonal intercalated antiperovskite structures: T–sAP (stracherite and zadovite group), T–tAP (ariegilatite and nabimusaite group).
Supporting information
CCDC reference: 1864463
Data collection: Wojdyla, J. A.; Kaminski, J. W.; Panepucci, E.; Ebner, S.; Wang, X.;
Gabadinho, J. & Wang, M.
DA+ data acquisition and analysis software at the Swiss Light Source
macromolecular crystallography beamlines
Journal of Synchroton Radiation, 2018, 25
doi:10.1107/S1600577517014503; cell refinement: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); data reduction: XDS Version 2016-11-01
Kabsch, W.
Integration, scaling, space-group assignment and post refinement
Acta Crystallographica, 2010, D66, 133-144; program(s) used to solve structure: SIR2004, Burla et al. 2005; program(s) used to refine structure: Jana2006 Version: 6/5/2017; molecular graphics: Vesta 3.
Crystal data top
C0.919Ba2Ca17.621F3.462Na0.379O39.7P2.96Si6 | F(000) = 2854 |
Mr = 1961.8 | Dx = 3.353 Mg m−3 |
Trigonal, R3m | Cell parameters from 2944 reflections |
Hall symbol: -R 3;-2 | θ = 2.8–32.0° |
a = 7.12550 (11) Å | µ = 4.70 mm−1 |
c = 66.2902 (13) Å | T = 293 K |
V = 2914.81 (8) Å3 | Prism, black |
Z = 3 | 0.06 × 0.03 × 0.03 mm |
Data collection top
PRIGo diffractometer | 1291 independent reflections |
Radiation source: SLS super-bending magnet 2.9T, X06DA | 1145 reflections with I > 3σ(I) |
Bartels Monochromator with dual channel cut crystals (DCCM)
in (±∓) geometry monochromator | Rint = 0.049 |
Detector resolution: 5.81 pixels mm-1 | θmax = 32.0°, θmin = 0.9° |
φ scans | h = −8→9 |
Absorption correction: empirical (using intensity measurements) XDS Version 2016-11-01
Kabsch, W.
Integration, scaling, space-group assignment and post refinement
Acta Crystallographica, 2010, D66, 133-144 | k = −10→6 |
| l = −84→96 |
5677 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
R[F2 > 2σ(F2)] = 0.082 | 0 constraints |
wR(F2) = 0.184 | Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0004I2) |
S = 3.60 | (Δ/σ)max = 0.049 |
1291 reflections | Δρmax = 12.08 e Å−3 |
85 parameters | Δρmin = −2.45 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ba1 | 0 | 0 | 0.270337 (10) | 0.0140 (3) | |
Ca1 | 0.49749 (8) | 0.99499 (16) | 0.23253 (2) | 0.0066 (4) | |
Ca2 | 0.98845 (19) | 0.49422 (9) | 0.30918 (2) | 0.0086 (4) | |
Ca3 | 0.48954 (9) | 0.97909 (18) | 0.146883 (19) | 0.0058 (4) | 0.937 (12) |
Na3 | 0.48954 (9) | 0.97909 (18) | 0.146883 (19) | 0.0058 (4) | 0.063 (12) |
T1 | 0.666667 | 0.333333 | 0.19130 (4) | 0.0022 (5) | |
T2 | 0.333333 | 0.666667 | 0.34596 (4) | 0.0015 (5)* | |
T3 | 0 | 0 | 0.21838 (4) | 0.0022 (5) | |
T4 | 0.666667 | 0.333333 | 0.26572 (5) | 0.0063 (8) | 0.940 (12) |
T5p | 0.333333 | 0.666667 | 0.27450 (7) | 0.0071 (13)* | 0.54 (2) |
T5c | 0.333333 | 0.666667 | 0.27450 (7) | 0.0071 (13)* | 0.46 (2) |
O1 | 0.2223 (4) | 0.7777 (4) | 0.28273 (8) | 0.017 (2) | 0.865 (14) |
O2 | 0.333333 | 0.666667 | 0.25243 (12) | 0.012 (2) | |
O3 | 0.4578 (4) | 0.9155 (7) | 0.35310 (8) | 0.0193 (16) | |
O4 | 0.666667 | 0.333333 | 0.28903 (12) | 0.0103 (19) | |
O5 | 0.5421 (3) | 0.0842 (7) | 0.18354 (7) | 0.0101 (8)* | |
O6 | 0.333333 | 0.666667 | 0.32173 (13) | 0.018 (2) | |
O7 | 0.666667 | 0.333333 | 0.21597 (11) | 0.0088 (19) | |
O8 | 0.7482 (6) | 0.8741 (3) | 0.22475 (7) | 0.0111 (14) | |
O9 | 0.7834 (3) | 0.2166 (3) | 0.25706 (6) | 0.0114 (14) | |
O10 | 0 | 0 | 0.19203 (11) | 0.0031* | |
O11 | 0.333333 | 0.666667 | 0.166667 | 0.002 (2)* | 0.53 (16) |
F1 | 0.333333 | 0.666667 | 0.166667 | 0.002 (2)* | 0.47 (16) |
F2 | 0.666667 | 0.333333 | 0.333333 | 0.013 (2) | |
F3 | 0.333333 | 0.666667 | 0.12406 (10) | 0.0082 (18) | 0.993 (19) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ba1 | 0.0142 (3) | 0.0142 (3) | 0.0135 (4) | 0.00711 (16) | 0 | 0 |
Ca1 | 0.0017 (5) | 0.0015 (6) | 0.0164 (7) | 0.0008 (3) | −0.0007 (2) | −0.0014 (4) |
Ca2 | 0.0033 (6) | 0.0028 (5) | 0.0201 (8) | 0.0016 (3) | −0.0010 (4) | −0.0005 (2) |
Ca3 | 0.0023 (5) | 0.0034 (6) | 0.0119 (7) | 0.0017 (3) | 0.0006 (2) | 0.0012 (4) |
Na3 | 0.0023 (5) | 0.0034 (6) | 0.0119 (7) | 0.0017 (3) | 0.0006 (2) | 0.0012 (4) |
T1 | 0.0003 (5) | 0.0003 (5) | 0.0058 (9) | 0.0002 (3) | 0 | 0 |
T3 | 0.0003 (5) | 0.0003 (5) | 0.0058 (9) | 0.0002 (3) | 0 | 0 |
T4 | 0.0069 (10) | 0.0069 (10) | 0.0051 (14) | 0.0035 (5) | 0 | 0 |
O1 | 0.022 (2) | 0.022 (2) | 0.010 (3) | 0.013 (2) | −0.0006 (10) | 0.0006 (10) |
O2 | 0.014 (2) | 0.014 (2) | 0.008 (4) | 0.0072 (12) | 0 | 0 |
O3 | 0.0065 (15) | 0.0035 (19) | 0.047 (3) | 0.0017 (10) | −0.0052 (10) | −0.010 (2) |
O4 | 0.013 (2) | 0.013 (2) | 0.005 (4) | 0.0066 (11) | 0 | 0 |
O6 | 0.021 (3) | 0.021 (3) | 0.012 (4) | 0.0104 (14) | 0 | 0 |
O7 | 0.009 (2) | 0.009 (2) | 0.008 (4) | 0.0046 (11) | 0 | 0 |
O8 | 0.0023 (18) | 0.0063 (14) | 0.023 (3) | 0.0011 (9) | 0.0020 (16) | 0.0010 (8) |
O9 | 0.0129 (15) | 0.0129 (15) | 0.012 (2) | 0.0092 (18) | −0.0013 (8) | 0.0013 (8) |
F2 | 0.016 (3) | 0.016 (3) | 0.007 (4) | 0.0079 (14) | 0 | 0 |
F3 | 0.008 (2) | 0.008 (2) | 0.009 (3) | 0.0038 (10) | 0 | 0 |
Bond lengths (Å) top
Ba1—T2i | 3.339 (3) | T1—O5xii | 1.621 (5) |
Ba1—T3 | 3.444 (3) | T1—O7 | 1.636 (8) |
Ba1—O1ii | 2.864 (4) | T1—O10xxii | 3.314 (8) |
Ba1—O1iii | 2.864 (4) | T2—O3 | 1.607 (5) |
Ba1—O1iv | 2.864 (4) | T2—O3iii | 1.607 (5) |
Ba1—O3i | 3.251 (5) | T2—O3ix | 1.607 (5) |
Ba1—O3v | 3.251 (5) | T2—O6 | 1.606 (9) |
Ba1—O3vi | 3.251 (6) | T3—O8vii | 1.610 (4) |
Ba1—O8vii | 3.398 (5) | T3—O8viii | 1.610 (5) |
Ba1—O8viii | 3.398 (5) | T3—O8ix | 1.610 (4) |
Ba1—O8ix | 3.398 (5) | T3—O10 | 1.747 (7) |
Ba1—O9x | 2.815 (3) | T4—O4 | 1.545 (8) |
Ba1—O9xi | 2.815 (3) | T4—O7 | 3.298 (8) |
Ba1—O9xii | 2.815 (3) | T4—O9 | 1.551 (3) |
Ca1—T1xiii | 3.439 (3) | T4—O9viii | 1.551 (3) |
Ca1—T4xiii | 3.033 (2) | T4—O9xii | 1.551 (3) |
Ca1—T5p | 3.442 (4) | T5p—T5c | 0 |
Ca1—T5c | 3.442 (4) | T5p—O1 | 1.475 (4) |
Ca1—O2 | 2.418 (4) | T5p—O1iii | 1.475 (4) |
Ca1—O5xiii | 3.294 (5) | T5p—O1ix | 1.475 (4) |
Ca1—O7xiii | 2.359 (4) | T5p—O2 | 1.463 (9) |
Ca1—O8 | 2.395 (5) | T5p—O6 | 3.130 (10) |
Ca1—O8iii | 2.395 (3) | T5c—O1 | 1.475 (4) |
Ca1—O9xiii | 2.464 (3) | T5c—O1iii | 1.475 (4) |
Ca1—O9xiv | 2.464 (4) | T5c—O1ix | 1.475 (4) |
Ca1—F3xv | 2.546 (4) | T5c—O2 | 1.463 (9) |
Ca2—Ca2viii | 3.4393 (17) | T5c—O6 | 3.130 (10) |
Ca2—Ca2xii | 3.4393 (12) | O1—O1iii | 2.373 (6) |
Ca2—T2xvi | 3.236 (2) | O1—O1ix | 2.373 (6) |
Ca2—T4 | 3.499 (3) | O1—O2 | 2.431 (8) |
Ca2—T5pxvi | 3.133 (3) | O1—O3xxiv | 3.139 (6) |
Ca2—T5cxvi | 3.133 (3) | O1—O3xxv | 3.139 (7) |
Ca2—O1xvi | 2.563 (4) | O1—O6 | 2.926 (9) |
Ca2—O1xvii | 2.563 (5) | O1—O9xxvi | 3.199 (5) |
Ca2—O3xvii | 2.971 (6) | O1—O9xiv | 3.199 (5) |
Ca2—O3xviii | 2.357 (7) | O2—O8 | 3.150 (6) |
Ca2—O3xix | 2.357 (6) | O2—O8iii | 3.150 (7) |
Ca2—O4 | 2.393 (4) | O2—O8ix | 3.150 (6) |
Ca2—O6xvi | 2.285 (3) | O2—F3xv | 2.861 (10) |
Ca2—F2 | 2.5507 (12) | O3—O3iii | 2.660 (5) |
Ca3—Ca3iii | 3.3392 (12) | O3—O3ix | 2.660 (7) |
Ca3—Ca3ix | 3.3392 (16) | O3—O4xxvii | 3.048 (6) |
Ca3—Ca3xv | 3.2552 (18) | O3—O6 | 2.585 (9) |
Ca3—Ca3xx | 3.2552 (15) | O3—F2xiii | 2.892 (5) |
Ca3—Na3 | 0 | O4—O9 | 2.563 (7) |
Ca3—Na3iii | 3.3392 (12) | O4—O9viii | 2.563 (7) |
Ca3—Na3ix | 3.3392 (16) | O4—O9xii | 2.563 (7) |
Ca3—Na3xv | 3.2552 (18) | O4—F2 | 2.937 (8) |
Ca3—Na3xx | 3.2552 (15) | O5—O5viii | 2.663 (5) |
Ca3—T3xxi | 3.043 (2) | O5—O5xii | 2.663 (6) |
Ca3—O5xiii | 2.515 (5) | O5—O5xxviii | 3.412 (7) |
Ca3—O5xxii | 2.329 (5) | O5—O5xx | 3.412 (5) |
Ca3—O5xxiii | 2.329 (3) | O5—O7 | 2.643 (7) |
Ca3—O8xv | 2.616 (5) | O5—O10xxii | 3.194 (7) |
Ca3—O10xxi | 2.2170 (16) | O5—O11ii | 2.809 (4) |
Ca3—O11 | 2.3317 (12) | O5—F1ii | 2.809 (4) |
Ca3—F1 | 2.3317 (12) | O5—F3xxix | 3.090 (6) |
Ca3—F3 | 2.451 (4) | O7—O9 | 3.081 (8) |
Na3—Na3iii | 3.3392 (12) | O7—O9viii | 3.081 (8) |
Na3—Na3ix | 3.3392 (16) | O7—O9xii | 3.081 (8) |
Na3—Na3xv | 3.2552 (18) | O8—O8xvii | 2.691 (6) |
Na3—Na3xx | 3.2552 (15) | O8—O8xiv | 2.691 (4) |
Na3—T3xxi | 3.043 (2) | O8—O9xiii | 3.162 (5) |
Na3—O5xiii | 2.515 (5) | O8—O9viii | 3.162 (6) |
Na3—O5xxii | 2.329 (5) | O8—O10xxx | 2.668 (7) |
Na3—O5xxiii | 2.329 (3) | O8—F3xv | 2.758 (5) |
Na3—O8xv | 2.616 (5) | O9—O9viii | 2.495 (5) |
Na3—O10xxi | 2.2170 (16) | O9—O9xii | 2.495 (5) |
Na3—O11 | 2.3317 (12) | O11—F1 | 0 |
Na3—F1 | 2.3317 (12) | O11—F3 | 2.825 (6) |
Na3—F3 | 2.451 (4) | O11—F3xv | 2.825 (6) |
T1—O5 | 1.621 (4) | F1—F3 | 2.825 (6) |
T1—O5viii | 1.621 (4) | F1—F3xv | 2.825 (6) |
Symmetry codes: (i) y−2/3, x−1/3, −z+2/3; (ii) x, y−1, z; (iii) −y+1, x−y+1, z; (iv) −x+y−1, −x, z; (v) x−y+1/3, −y+2/3, −z+2/3; (vi) −x+1/3, −x+y−1/3, −z+2/3; (vii) x−1, y−1, z; (viii) −y+1, x−y, z; (ix) −x+y, −x+1, z; (x) x−1, y, z; (xi) −y, x−y−1, z; (xii) −x+y+1, −x+1, z; (xiii) x, y+1, z; (xiv) −x+y+1, −x+2, z; (xv) y−1/3, x+1/3, −z+1/3; (xvi) x+1, y, z; (xvii) −y+2, x−y+1, z; (xviii) x−y+4/3, −y+5/3, −z+2/3; (xix) −x+4/3, −x+y−1/3, −z+2/3; (xx) −x+2/3, −x+y+1/3, −z+1/3; (xxi) y+2/3, x+4/3, −z+1/3; (xxii) y+2/3, x+1/3, −z+1/3; (xxiii) −x+2/3, −x+y+4/3, −z+1/3; (xxiv) y−2/3, x+2/3, −z+2/3; (xxv) x−y+1/3, −y+5/3, −z+2/3; (xxvi) −y, x−y, z; (xxvii) y+1/3, x+2/3, −z+2/3; (xxviii) y+2/3, x−2/3, −z+1/3; (xxix) y−1/3, x−2/3, −z+1/3; (xxx) x+1, y+1, z. |
Subscribe to Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials
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.