research papers
The electron-density distribution of AlPO4-15 has been determined using high-resolution single-crystal X-ray diffraction, and the topological properties of the charge density have been calculated using the `atoms in molecules' (AIM) theory. Analysis of the topological properties at the bond critical points has been used to characterize the interactions within the framework, and between the framework and the extra-framework species (ammonium ions and water molecules), and to define atomic properties, such as volume and net charges, uniquely. A comparison between procrystal and multipolar representations of the density was performed in order to explore to what extent the former representation is likely to reflect the interactions in the solid. Correlation with geometrical properties (P-O and Al-O bond lengths, and Al-O-P angle) is found for topological charges obtained from the multipolar model, but not for the results from the procrystal representation.
Supporting information
Computing details top
Data collection: Nonius Kappa; cell refinement: HKL-2000 (Otwinowski et al.,2000); data reduction: DREAD (Blessing,1989); program(s) used to solve structure: NRCVAX (Gabe et al., 1989); program(s) used to refine structure: MoPro (Guillot et al., 2001).
(BDG2_2) top
Crystal data top
H3Al2O10P2·H4N·H2O | Z = 4 |
Mr = 314.98 | F(000) = 640 |
Monoclinic, P21/n | Dx = 2.450 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.7107 Å |
a = 9.556 (1) Å | µ = 0.76 mm−1 |
b = 9.563 (1) Å | T = 115 K |
c = 9.615 (1) Å | 12-faced polyhedron, colourless |
β = 103.58 (1)° | 0.22 × 0.17 × 0.14 mm |
V = 854.1 (2) Å3 |
Data collection top
Nonius KappaCCD diffractometer | 8561 independent reflections |
Radiation source: fine-focus sealed tube | 8561 reflections with I > 0 u(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 49°, θmin = 3° |
Absorption correction: integration Absorb, (DeTitta, 1985) | h = −19→19 |
Tmin = 0.89, Tmax = 0.93 | k = −20→20 |
145662 measured reflections | l = −20→19 |
Refinement top
Refinement on F | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.010 | Weighting scheme based on measured s.u.'s |
wR(F2) = 0.007 | (Δ/σ)max = 0.09 |
S = 1.65 | Δρmax = 0.20 e Å−3 |
4725 reflections | Δρmin = −0.20 e Å−3 |
510 parameters | Extinction correction: Becker-Coppens, Becker & Coppens 1974 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 870 |
Secondary atom site location: difference Fourier map |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | ||
P1 | 0.301122 (5) | 0.532947 (5) | 0.151339 (5) | 0.00286 (1) | |
P2 | 0.794553 (5) | 0.808911 (5) | 0.136246 (5) | 0.00280 (1) | |
Al1 | 0.613765 (7) | 0.537615 (6) | 0.127745 (6) | 0.00313 (2) | |
Al2 | 0.393032 (7) | 0.229762 (6) | 0.184785 (6) | 0.00327 (2) | |
O1 | 0.456755 (15) | 0.586563 (15) | 0.203054 (15) | 0.00426 (3) | |
O2 | 0.192884 (15) | 0.629269 (14) | 0.193560 (15) | 0.00485 (3) | |
O3 | 0.262779 (16) | 0.520503 (15) | −0.013996 (14) | 0.00426 (3) | |
O4 | 0.289272 (15) | 0.386617 (14) | 0.215291 (14) | 0.00429 (3) | |
O5 | 0.954219 (15) | 0.769346 (15) | 0.165480 (15) | 0.00485 (3) | |
O6 | 0.779190 (15) | 0.950289 (14) | 0.209248 (14) | 0.00437 (3) | |
O7 | 0.708209 (16) | 0.699363 (14) | 0.196520 (15) | 0.00483 (3) | |
O8 | 0.739606 (16) | 0.824787 (15) | −0.024687 (14) | 0.00476 (3) | |
O9 | 0.496655 (16) | 0.364433 (15) | 0.054527 (14) | 0.00439 (3) | |
O10 | 0.500178 (16) | 0.067277 (16) | 0.146993 (16) | 0.00683 (4) | |
O11 | 0.318871 (17) | 0.856812 (16) | 0.038092 (16) | 0.00893 (4) | |
N | 0.987422 (19) | 0.308528 (19) | 0.102664 (19) | 0.00779 (4) | |
H1 | 0.5608 (4) | 0.2984 (6) | 0.0206 (4) | 0.0084 (8)* | |
H2 | 0.4449 (5) | −0.0098 (5) | 0.0992 (4) | 0.0132 (10)* | |
H3 | 0.5961 (4) | 0.0363 (4) | 0.1889 (4) | 0.0131 (10)* | |
H4 | 0.2668 (4) | 0.8587 (5) | 0.1118 (4) | 0.0154 (10)* | |
H5 | 0.2650 (4) | 0.9090 (4) | −0.0409 (4) | 0.0145 (10)* | |
H6 | 0.9988 (4) | 0.2780 (5) | 0.0066 (4) | 0.0132 (10)* | |
H7 | 0.8975 (4) | 0.3652 (4) | 0.0898 (4) | 0.0144 (10)* | |
H8 | 0.9910 (4) | 0.2261 (5) | 0.1671 (4) | 0.0134 (10)* | |
H9 | 1.0756 (4) | 0.3634 (4) | 0.1466 (4) | 0.0134 (10)* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.00269 (2) | 0.00301 (2) | 0.00288 (2) | −0.00020 (2) | 0.00065 (2) | 0.00016 (2) |
P2 | 0.00267 (2) | 0.00285 (2) | 0.00263 (2) | −0.00014 (2) | 0.00011 (2) | 0.00001 (2) |
Al1 | 0.00293 (3) | 0.00345 (3) | 0.00288 (3) | −0.00011 (2) | 0.00044 (2) | −0.00014 (2) |
Al2 | 0.00298 (3) | 0.00359 (3) | 0.00296 (3) | −0.00019 (2) | 0.00015 (2) | −0.00008 (2) |
O1 | 0.00301 (6) | 0.00517 (6) | 0.00459 (6) | −0.00106 (5) | 0.00085 (5) | −0.00055 (5) |
O2 | 0.00466 (6) | 0.00528 (6) | 0.00497 (6) | −0.00086 (5) | 0.00184 (5) | 0.00185 (5) |
O3 | 0.00417 (6) | 0.00584 (6) | 0.00276 (5) | −0.00048 (4) | 0.00078 (5) | 0.00070 (5) |
O4 | 0.00487 (6) | 0.00320 (5) | 0.00516 (6) | 0.00068 (5) | 0.00190 (5) | 0.00029 (5) |
O5 | 0.00297 (6) | 0.00675 (6) | 0.00437 (6) | −0.00015 (5) | −0.00006 (5) | 0.00136 (5) |
O6 | 0.00481 (6) | 0.00359 (6) | 0.00418 (6) | −0.00141 (4) | −0.00003 (5) | 0.00027 (4) |
O7 | 0.00580 (6) | 0.00403 (6) | 0.00469 (6) | −0.00013 (5) | 0.00129 (5) | −0.00189 (5) |
O8 | 0.00518 (6) | 0.00585 (6) | 0.00250 (5) | 0.00006 (5) | −0.00058 (5) | −0.00055 (5) |
O9 | 0.00413 (6) | 0.00453 (6) | 0.00448 (6) | −0.00044 (5) | 0.00098 (5) | 0.00059 (5) |
O10 | 0.00491 (7) | 0.00631 (6) | 0.00889 (6) | −0.00198 (5) | 0.00084 (5) | 0.00096 (5) |
O11 | 0.01051 (7) | 0.00863 (7) | 0.00823 (7) | 0.00091 (5) | 0.00336 (6) | −0.00036 (5) |
N | 0.00693 (8) | 0.00947 (7) | 0.00683 (7) | 0.00152 (6) | 0.00134 (6) | 0.00044 (6) |
Geometric parameters (Å, º) top
P1—O1 | 1.5410 (2) | Al2—O4 | 1.8590 (2) |
P1—O2 | 1.5101 (2) | Al2—O5 | 1.8330 (2) |
P1—O3 | 1.5498 (2) | Al2—O8 | 1.8254 (2) |
P1—O4 | 1.5433 (2) | Al2—O9 | 2.1886 (3) |
P2—O5 | 1.5326 (2) | Al2—O10 | 1.9415 (3) |
P2—O6 | 1.5461 (2) | O9—H1 | 0.987 (5) |
P2—O7 | 1.5293 (2) | O10—H2 | 0.959 (5) |
P2—O8 | 1.5204 (2) | O10—H3 | 0.958 (4) |
Al1—O1 | 1.8721 (3) | O11—H4 | 0.957 (4) |
Al1—O3 | 1.8716 (3) | O11—H5 | 0.953 (4) |
Al1—O6 | 1.8567 (2) | N—H6 | 0.999 (4) |
Al1—O7 | 1.8342 (2) | N—H7 | 0.999 (4) |
Al1—O9 | 2.0300 (3) | N—H8 | 0.998 (4) |
Al1—O9 | 2.0479 (3) | N—H9 | 0.998 (4) |
Al2—O2 | 1.8485 (2) | ||
O1—P1—O2 | 112.36 (1) | O9—Al2—O8 | 90.20 (1) |
O1—P1—O3 | 109.53 (1) | O10—Al2—O2 | 91.97 (1) |
O1—P1—O4 | 109.19 (1) | O2—Al2—O8 | 93.52 (1) |
O2—P1—O3 | 108.10 (1) | O5—Al2—O2 | 90.03 (1) |
O2—P1—O4 | 109.09 (1) | O5—Al2—O4 | 93.74 (1) |
O3—P1—O4 | 108.50 (1) | O5—Al2—O10 | 87.40 (1) |
O5—P2—O6 | 109.22 (1) | O8—Al2—O5 | 171.34 (1) |
O5—P2—O7 | 111.34 (1) | O5—Al2—O9 | 86.79 (1) |
O5—P2—O8 | 107.60 (1) | O10—Al2—O8 | 84.59 (1) |
O6—P2—O7 | 108.05 (1) | P1—O1—Al1 | 126.33 (1) |
O6—P2—O8 | 109.14 (1) | P1—O3—Al1 | 126.34 (1) |
O7—P2—O8 | 111.47 (1) | P2—O5—Al2 | 140.35 (1) |
O1—Al1—O7 | 91.20 (1) | P2—O7—Al1 | 134.80 (1) |
O1—Al1—O9 | 84.92 (1) | P1—O2—Al2 | 157.12 (1) |
O1—Al1—O3 | 166.58 (1) | P1—O4—Al2 | 125.24 (1) |
O1—Al1—O9 | 85.29 (1) | P2—O6—Al1 | 133.18 (1) |
O7—Al1—O9 | 176.02 (1) | P2—O8—Al2 | 146.64 (1) |
O7—Al1—O3 | 97.86 (1) | Al1—O9—Al1 | 93.15 (1) |
O7—Al1—O9 | 91.94 (1) | Al1—O9—Al2 | 124.63 (1) |
O9—Al1—O3 | 85.81 (1) | Al2—O9—Al1 | 123.19 (1) |
O9—Al1—O9 | 86.85 (1) | Al1—O9—H1 | 107.6 (3) |
O3—Al1—O9 | 84.52 (1) | Al2—O9—H1 | 102.2 (3) |
O7—Al1—O6 | 87.02 (1) | H1—O9—Al1 | 104.2 (2) |
O6—Al1—O3 | 93.54 (1) | Al2—O10—H2 | 116.7 (3) |
O6—Al1—O1 | 96.82 (1) | Al2—O10—H3 | 131.6 (2) |
O6—Al1—O9 | 94.32 (1) | H2—O10—H3 | 109.2 (4) |
O6—Al1—O9 | 177.66 (1) | H4—O11—H5 | 107.6 (3) |
O4—Al2—O9 | 86.86 (1) | H6—N—H7 | 108.7 (3) |
O4—Al2—O10 | 178.32 (1) | H6—N—H8 | 110.4 (4) |
O4—Al2—O2 | 89.26 (1) | H6—N—H9 | 106.3 (3) |
O4—Al2—O8 | 94.20 (1) | H7—N—H8 | 114.1 (3) |
O9—Al2—O10 | 91.98 (1) | H7—N—H9 | 112.5 (3) |
O9—Al2—O2 | 174.81 (1) | H8—N—H9 | 104.5 (3) |