Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040512/bt2443sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040512/bt2443Isup2.hkl |
CCDC reference: 660152
All reagents were used as purchased without further purification. The synthesis was carried out in a rational way from a mixture of [(CH3)2CHO]3Al, C3N2H10, H3PO3 and H2O in a molar ratio of 1:1:2:250. The mixture was loaded in a Teflon-lined autoclave (23 ml capacity) and was heated at 443k for 4 d under autogenous pressure. The solid product was collected by filtration, washed with water and dried at room temperature. Colorless crystals of the title compound were isolated.
All H atoms were located in a difference Fourier map. Those bonded to C and N were refined using a riding model with C—H ranging from 0.96 to 0.97Å and N—H = 0.89Å and U(H)= 1.2 Ueq(C,N). The other H atoms were isotropically refined. The distance O5—H1 was restrained to 0.82 (2) Å.
At present, it is well known that a remarkable range of compositions and structures of organically templated inorganic framework solids have been synthesized and studied, because of their potential applications in many fields (Cheetham et al., 1999; Harrison, 2002). There are also lots of studies about the synthesis and characterization of metal phosphates containing V, Zn, Co, etc. (Yamase et al., 1997) and most of the known metal–phosphite compounds have been prepared by various solvent-volatilizing methods. However, only a few organically templated aluminophosphites have been reported. In our present work, we have hydrothermally synthesized and characterized the title compound (Fig. 1).
As seen in Figs. 2 and 3, its structure consists of aluminophosphite lines constructed from AlO6 distorted octahedrons and HPO3 pyramids. Each AlO6 octahedron shares two opposite hydroxy groups with two adjacent AlO6 octahedra to construct an infinte Al—O—Al chain running along the [100] direction. Each P atom shares two oxygen atoms with adjacent Al atoms.
The propane-1,2-diammonium cations and water molecules link Al—O—Al chains via numerous N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 4).
For related literature, see: Cheetham et al. (1999); Harrison (2002); Yamase et al. (1997).
Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).
(C3H12N2)[Al(OH)(HPO3)2]·H2O | F(000) = 624 |
Mr = 298.11 | Dx = 1.701 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.059 (2) Å | Cell parameters from 10198 reflections |
b = 6.9782 (14) Å | θ = 3.0–27.5° |
c = 15.319 (3) Å | µ = 0.48 mm−1 |
β = 100.01 (3)° | T = 170 K |
V = 1164.2 (4) Å3 | Chunk, colorless |
Z = 4 | 0.58 × 0.27 × 0.18 mm |
Rigaku R-AXIS SPIDER diffractometer | 2513 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.5°, θmin = 3.2° |
ω oscillation scans | h = −14→14 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→8 |
Tmin = 0.856, Tmax = 0.917 | l = −19→19 |
10911 measured reflections | 2 standard reflections every 150 reflections |
2654 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0531P)2 + 0.5902P] where P = (Fo2 + 2Fc2)/3 |
2654 reflections | (Δ/σ)max = 0.001 |
169 parameters | Δρmax = 0.26 e Å−3 |
1 restraint | Δρmin = −0.51 e Å−3 |
(C3H12N2)[Al(OH)(HPO3)2]·H2O | V = 1164.2 (4) Å3 |
Mr = 298.11 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.059 (2) Å | µ = 0.48 mm−1 |
b = 6.9782 (14) Å | T = 170 K |
c = 15.319 (3) Å | 0.58 × 0.27 × 0.18 mm |
β = 100.01 (3)° |
Rigaku R-AXIS SPIDER diffractometer | 2513 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Rint = 0.021 |
Tmin = 0.856, Tmax = 0.917 | 2 standard reflections every 150 reflections |
10911 measured reflections | intensity decay: none |
2654 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 1 restraint |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.26 e Å−3 |
2654 reflections | Δρmin = −0.51 e Å−3 |
169 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.95407 (3) | 0.19849 (4) | 0.19018 (2) | 0.00995 (10) | |
P2 | 0.78292 (3) | 0.20388 (4) | 0.42460 (2) | 0.00997 (10) | |
Al1 | 0.75189 (3) | 0.45005 (4) | 0.24929 (2) | 0.00802 (10) | |
O1 | 1.09179 (9) | 0.19119 (13) | 0.19924 (8) | 0.0202 (2) | |
O2 | 0.90558 (8) | 0.01902 (12) | 0.22963 (6) | 0.01556 (19) | |
O3 | 0.90834 (8) | 0.38056 (12) | 0.22784 (6) | 0.0160 (2) | |
O4 | 0.80156 (8) | 0.38466 (12) | 0.37257 (6) | 0.01461 (19) | |
O5 | 0.68994 (8) | 0.20026 (11) | 0.22253 (6) | 0.00947 (18) | |
O6 | 0.86642 (9) | 0.20370 (13) | 0.51352 (6) | 0.0186 (2) | |
O7 | 0.79587 (9) | 0.01972 (12) | 0.37372 (6) | 0.0165 (2) | |
C1 | 1.11228 (12) | 0.30966 (18) | 0.42461 (9) | 0.0162 (3) | |
H1D | 1.0536 | 0.4074 | 0.4003 | 0.019* | |
H1E | 1.0867 | 0.1898 | 0.3950 | 0.019* | |
C2 | 1.23836 (11) | 0.36369 (19) | 0.40522 (9) | 0.0159 (3) | |
C3 | 1.32693 (15) | 0.1959 (2) | 0.41037 (11) | 0.0267 (3) | |
H3A | 1.4043 | 0.2397 | 0.3977 | 0.040* | |
H3B | 1.2937 | 0.1002 | 0.3679 | 0.040* | |
H3C | 1.3387 | 0.1417 | 0.4689 | 0.040* | |
N1 | 1.11006 (11) | 0.28876 (14) | 0.52071 (7) | 0.0143 (2) | |
H1A | 1.0348 | 0.2565 | 0.5284 | 0.022* | |
H1B | 1.1313 | 0.3994 | 0.5481 | 0.022* | |
H1C | 1.1628 | 0.1979 | 0.5433 | 0.022* | |
N2 | 1.21957 (10) | 0.44677 (16) | 0.31407 (7) | 0.0163 (2) | |
H2A | 1.2918 | 0.4807 | 0.3007 | 0.024* | |
H2B | 1.1713 | 0.5494 | 0.3118 | 0.024* | |
H2C | 1.1844 | 0.3598 | 0.2753 | 0.024* | |
OW1 | 0.90717 (12) | 0.20990 (16) | 0.68934 (8) | 0.0274 (3) | |
HW1B | 0.951 (2) | 0.136 (4) | 0.7146 (17) | 0.049 (7)* | |
HW1A | 0.887 (2) | 0.181 (3) | 0.6364 (19) | 0.049 (7)* | |
H1 | 0.6189 (14) | 0.201 (3) | 0.2196 (14) | 0.026 (5)* | |
H2 | 1.2722 (16) | 0.463 (3) | 0.4441 (12) | 0.026 (4)* | |
H3 | 0.6632 (16) | 0.207 (2) | 0.4384 (11) | 0.015 (4)* | |
H4 | 0.9074 (16) | 0.193 (2) | 0.1039 (12) | 0.019 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.00979 (17) | 0.00724 (17) | 0.01291 (17) | 0.00029 (10) | 0.00221 (12) | 0.00012 (10) |
P2 | 0.01221 (17) | 0.00701 (17) | 0.01020 (17) | −0.00064 (10) | 0.00061 (12) | 0.00013 (10) |
Al1 | 0.00911 (18) | 0.00394 (17) | 0.01038 (18) | 0.00018 (12) | −0.00004 (13) | −0.00020 (12) |
O1 | 0.0118 (4) | 0.0137 (5) | 0.0367 (6) | 0.0001 (3) | 0.0089 (4) | −0.0039 (4) |
O2 | 0.0106 (4) | 0.0076 (4) | 0.0287 (5) | 0.0002 (3) | 0.0038 (3) | 0.0037 (3) |
O3 | 0.0126 (4) | 0.0070 (4) | 0.0292 (5) | −0.0002 (3) | 0.0063 (4) | −0.0025 (3) |
O4 | 0.0233 (5) | 0.0067 (4) | 0.0120 (4) | −0.0028 (3) | −0.0021 (3) | 0.0005 (3) |
O5 | 0.0082 (4) | 0.0048 (4) | 0.0146 (4) | −0.0001 (3) | −0.0003 (3) | −0.0002 (3) |
O6 | 0.0250 (5) | 0.0188 (5) | 0.0101 (4) | −0.0025 (4) | −0.0021 (4) | 0.0008 (3) |
O7 | 0.0287 (5) | 0.0066 (4) | 0.0121 (4) | 0.0021 (4) | −0.0028 (3) | −0.0005 (3) |
C1 | 0.0159 (6) | 0.0196 (6) | 0.0128 (6) | −0.0022 (5) | 0.0015 (5) | 0.0002 (4) |
C2 | 0.0150 (6) | 0.0152 (6) | 0.0170 (6) | −0.0014 (5) | 0.0017 (4) | −0.0012 (5) |
C3 | 0.0242 (7) | 0.0284 (8) | 0.0271 (8) | 0.0112 (6) | 0.0036 (6) | 0.0038 (6) |
N1 | 0.0180 (5) | 0.0113 (5) | 0.0132 (5) | −0.0001 (4) | 0.0013 (4) | 0.0010 (4) |
N2 | 0.0149 (5) | 0.0133 (5) | 0.0215 (5) | −0.0009 (4) | 0.0058 (4) | 0.0024 (4) |
OW1 | 0.0371 (6) | 0.0265 (6) | 0.0164 (5) | 0.0170 (5) | −0.0019 (5) | 0.0001 (4) |
P1—O1 | 1.5060 (10) | C1—N1 | 1.4837 (17) |
P1—O3 | 1.5179 (9) | C1—C2 | 1.5226 (18) |
P1—O2 | 1.5276 (9) | C1—H1D | 0.9700 |
P1—H4 | 1.333 (18) | C1—H1E | 0.9700 |
P2—O6 | 1.5070 (11) | C2—N2 | 1.4928 (16) |
P2—O7 | 1.5225 (9) | C2—C3 | 1.5199 (19) |
P2—O4 | 1.5252 (9) | C2—H2 | 0.946 (19) |
P2—H3 | 1.376 (17) | C3—H3A | 0.9600 |
Al1—O3 | 1.8799 (10) | C3—H3B | 0.9600 |
Al1—O5i | 1.8847 (9) | C3—H3C | 0.9600 |
Al1—O2i | 1.8879 (10) | N1—H1A | 0.8900 |
Al1—O5 | 1.8916 (9) | N1—H1B | 0.8900 |
Al1—O4 | 1.9277 (10) | N1—H1C | 0.8900 |
Al1—O7i | 1.9288 (10) | N2—H2A | 0.8900 |
O2—Al1ii | 1.8879 (10) | N2—H2B | 0.8900 |
O5—Al1ii | 1.8847 (9) | N2—H2C | 0.8900 |
O5—H1 | 0.779 (15) | OW1—HW1B | 0.77 (3) |
O7—Al1ii | 1.9288 (10) | OW1—HW1A | 0.83 (3) |
O1—P1—O3 | 113.06 (5) | P2—O7—Al1ii | 132.74 (6) |
O1—P1—O2 | 110.78 (5) | N1—C1—C2 | 113.05 (11) |
O3—P1—O2 | 111.89 (6) | N1—C1—H1D | 109.0 |
O1—P1—H4 | 107.5 (8) | C2—C1—H1D | 109.0 |
O3—P1—H4 | 107.8 (7) | N1—C1—H1E | 109.0 |
O2—P1—H4 | 105.3 (7) | C2—C1—H1E | 109.0 |
O6—P2—O7 | 111.38 (5) | H1D—C1—H1E | 107.8 |
O6—P2—O4 | 110.84 (5) | N2—C2—C3 | 109.36 (11) |
O7—P2—O4 | 113.42 (6) | N2—C2—C1 | 107.18 (10) |
O6—P2—H3 | 108.4 (7) | C3—C2—C1 | 113.75 (12) |
O7—P2—H3 | 105.7 (7) | N2—C2—H2 | 106.4 (11) |
O4—P2—H3 | 106.7 (7) | C3—C2—H2 | 110.4 (11) |
O3—Al1—O5i | 89.49 (4) | C1—C2—H2 | 109.5 (11) |
O3—Al1—O2i | 179.72 (4) | C2—C3—H3A | 109.5 |
O5i—Al1—O2i | 90.74 (4) | C2—C3—H3B | 109.5 |
O3—Al1—O5 | 91.95 (4) | H3A—C3—H3B | 109.5 |
O5i—Al1—O5 | 178.48 (2) | C2—C3—H3C | 109.5 |
O2i—Al1—O5 | 87.82 (4) | H3A—C3—H3C | 109.5 |
O3—Al1—O4 | 89.77 (5) | H3B—C3—H3C | 109.5 |
O5i—Al1—O4 | 88.11 (4) | C1—N1—H1A | 109.5 |
O2i—Al1—O4 | 90.40 (5) | C1—N1—H1B | 109.5 |
O5—Al1—O4 | 91.43 (4) | H1A—N1—H1B | 109.5 |
O3—Al1—O7i | 89.91 (5) | C1—N1—H1C | 109.5 |
O5i—Al1—O7i | 90.85 (4) | H1A—N1—H1C | 109.5 |
O2i—Al1—O7i | 89.93 (5) | H1B—N1—H1C | 109.5 |
O5—Al1—O7i | 89.61 (4) | C2—N2—H2A | 109.5 |
O4—Al1—O7i | 178.92 (4) | C2—N2—H2B | 109.5 |
P1—O2—Al1ii | 132.40 (6) | H2A—N2—H2B | 109.5 |
P1—O3—Al1 | 131.29 (6) | C2—N2—H2C | 109.5 |
P2—O4—Al1 | 131.79 (5) | H2A—N2—H2C | 109.5 |
Al1ii—O5—Al1 | 135.05 (5) | H2B—N2—H2C | 109.5 |
Al1ii—O5—H1 | 108.5 (13) | HW1B—OW1—HW1A | 111 (2) |
Al1—O5—H1 | 109.5 (13) | ||
O1—P1—O2—Al1ii | 172.54 (7) | O2i—Al1—O4—P2 | 82.63 (8) |
O3—P1—O2—Al1ii | 45.39 (10) | O5—Al1—O4—P2 | −5.19 (8) |
O1—P1—O3—Al1 | −170.02 (7) | O7i—Al1—O4—P2 | −170 (2) |
O2—P1—O3—Al1 | −44.11 (10) | O3—Al1—O5—Al1ii | 43.65 (7) |
O5i—Al1—O3—P1 | −172.71 (8) | O5i—Al1—O5—Al1ii | −118.6 (10) |
O2i—Al1—O3—P1 | −28 (11) | O2i—Al1—O5—Al1ii | −136.52 (7) |
O5—Al1—O3—P1 | 7.75 (8) | O4—Al1—O5—Al1ii | −46.17 (7) |
O4—Al1—O3—P1 | 99.18 (8) | O7i—Al1—O5—Al1ii | 133.54 (7) |
O7i—Al1—O3—P1 | −81.86 (8) | O6—P2—O7—Al1ii | −163.64 (7) |
O6—P2—O4—Al1 | 165.35 (7) | O4—P2—O7—Al1ii | −37.76 (10) |
O7—P2—O4—Al1 | 39.19 (10) | N1—C1—C2—N2 | −160.17 (10) |
O3—Al1—O4—P2 | −97.14 (8) | N1—C1—C2—C3 | 78.82 (14) |
O5i—Al1—O4—P2 | 173.36 (8) |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O6 | 0.89 | 1.87 | 2.7425 (16) | 165 |
N1—H1B···O4iii | 0.89 | 2.00 | 2.8751 (14) | 169 |
N1—H1C···O7iv | 0.89 | 1.98 | 2.7833 (14) | 149 |
N2—H2A···O1v | 0.89 | 1.95 | 2.7295 (15) | 145 |
N2—H2A···OW1vi | 0.89 | 2.66 | 3.2446 (18) | 124 |
N2—H2B···OW1iii | 0.89 | 1.89 | 2.7716 (16) | 171 |
N2—H2C···O1 | 0.89 | 1.84 | 2.7218 (16) | 172 |
OW1—HW1B···O2iv | 0.77 (3) | 1.98 (3) | 2.7363 (16) | 167 (3) |
OW1—HW1A···O6 | 0.83 (3) | 1.86 (3) | 2.6528 (16) | 159 (2) |
O5—H1···OW1vii | 0.78 (2) | 2.39 (2) | 3.1429 (17) | 163 (2) |
Symmetry codes: (iii) −x+2, −y+1, −z+1; (iv) −x+2, −y, −z+1; (v) −x+5/2, y+1/2, −z+1/2; (vi) x+1/2, −y+1/2, z−1/2; (vii) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C3H12N2)[Al(OH)(HPO3)2]·H2O |
Mr | 298.11 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 170 |
a, b, c (Å) | 11.059 (2), 6.9782 (14), 15.319 (3) |
β (°) | 100.01 (3) |
V (Å3) | 1164.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.58 × 0.27 × 0.18 |
Data collection | |
Diffractometer | Rigaku R-AXIS SPIDER |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.856, 0.917 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10911, 2654, 2513 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.080, 1.01 |
No. of reflections | 2654 |
No. of parameters | 169 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.51 |
Computer programs: RAPID-AUTO (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O6 | 0.89 | 1.87 | 2.7425 (16) | 165.2 |
N1—H1B···O4i | 0.89 | 2.00 | 2.8751 (14) | 168.8 |
N1—H1C···O7ii | 0.89 | 1.98 | 2.7833 (14) | 149.1 |
N2—H2A···O1iii | 0.89 | 1.95 | 2.7295 (15) | 144.8 |
N2—H2A···OW1iv | 0.89 | 2.66 | 3.2446 (18) | 124.4 |
N2—H2B···OW1i | 0.89 | 1.89 | 2.7716 (16) | 170.7 |
N2—H2C···O1 | 0.89 | 1.84 | 2.7218 (16) | 172.2 |
OW1—HW1B···O2ii | 0.77 (3) | 1.98 (3) | 2.7363 (16) | 167 (3) |
OW1—HW1A···O6 | 0.83 (3) | 1.86 (3) | 2.6528 (16) | 159 (2) |
O5—H1···OW1v | 0.779 (15) | 2.390 (16) | 3.1429 (17) | 163.0 (18) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+5/2, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, z−1/2; (v) x−1/2, −y+1/2, z−1/2. |
At present, it is well known that a remarkable range of compositions and structures of organically templated inorganic framework solids have been synthesized and studied, because of their potential applications in many fields (Cheetham et al., 1999; Harrison, 2002). There are also lots of studies about the synthesis and characterization of metal phosphates containing V, Zn, Co, etc. (Yamase et al., 1997) and most of the known metal–phosphite compounds have been prepared by various solvent-volatilizing methods. However, only a few organically templated aluminophosphites have been reported. In our present work, we have hydrothermally synthesized and characterized the title compound (Fig. 1).
As seen in Figs. 2 and 3, its structure consists of aluminophosphite lines constructed from AlO6 distorted octahedrons and HPO3 pyramids. Each AlO6 octahedron shares two opposite hydroxy groups with two adjacent AlO6 octahedra to construct an infinte Al—O—Al chain running along the [100] direction. Each P atom shares two oxygen atoms with adjacent Al atoms.
The propane-1,2-diammonium cations and water molecules link Al—O—Al chains via numerous N—H···O and O—H···O hydrogen bonds (Table 1 and Fig. 4).