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The title compound, (C4H7N2)2[AlP2O7(OH)], is a one-dimensional extended-chain aluminophosphate prepared by a solvothermal synthesis from an alcohol system. The infinite [AlP2O7(OH)]2- chains composed of AlO4, PO2(=O)2 and PO2(=O)(OH) tetrahedra are linked via hydrogen bonds to the 2-methylimidazolium cations.
Supporting information
CCDC reference: 245859
Aluminium triisopropoxide (1.0 g) was first dispersed in triethylene glycol (8 ml) with stirring, and then 2-methylimidazole (2.02 g) was added so as to make a slurry. H3PO4 (2.04 ml, 85 wt%) was added dropwise to the above reaction mixture. The obtained gel mixture was sealed in a Teflon-lined stainless steel autoclave and heated at 453 K for 4 d. The resulting crystals of (I) were washed with distilled water and dried at 323 K. In order to compensate the negative charge of the infinite [AlP2O7(OH)]2− chains, the template agent is suggested to be protonated. The total weight loss of 48.9% from 353 to 1073 K, observed by the thermogravimetric analysis, corresponds to the calculated weight fraction for 2C4H6N2·1.5H2O (49.8%).
The hydroxy H atom in the infinite chain was positioned from a difference Fourier map (O—H = 0.91 Å), and the remaining aliphatic H atoms were placed in idealized positions (C—H = 0.93 and 0.96 Å). All H atoms were constrained to ride on their parent atoms. Isotropic displacement parameters for all H atoms were assumed to be equal and refined [Uiso(H) = 0.072 (4) Å2].
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Science Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: reference?; program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1997); software used to prepare material for publication: reference?.
Bis(2-methylimidazolium) hydroxodiphosphatoaluminium
top
Crystal data top
2C4H7N2+·AlHO8P22− | Z = 2 |
Mr = 384.16 | F(000) = 396 |
Triclinic, P1 | Dx = 1.688 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 8.4789 (17) Å | Cell parameters from 25 reflections |
b = 9.5233 (11) Å | θ = 14.3–19.3° |
c = 10.3607 (17) Å | µ = 0.39 mm−1 |
α = 108.811 (9)° | T = 298 K |
β = 92.172 (13)° | Elongated prism, colorless |
γ = 105.561 (13)° | 0.20 × 0.07 × 0.04 mm |
V = 755.8 (2) Å3 | |
Data collection top
Rigaku AFC-7R diffractometer | 3125 reflections with I > 2σ(I) |
Radiation source: ratating anode X-ray tube | Rint = 0.043 |
Graphite monochromator | θmax = 30.0°, θmin = 2.1° |
ω–2θ scan | h = −11→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→13 |
Tmin = 0.929, Tmax = 0.980 | l = −14→14 |
4693 measured reflections | 3 standard reflections every 50 reflections |
4417 independent reflections | intensity decay: none |
Refinement top
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.3936P] where P = (Fo2 + 2Fc2)/3 |
4417 reflections | (Δ/σ)max < 0.001 |
209 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Crystal data top
2C4H7N2+·AlHO8P22− | γ = 105.561 (13)° |
Mr = 384.16 | V = 755.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4789 (17) Å | Mo Kα radiation |
b = 9.5233 (11) Å | µ = 0.39 mm−1 |
c = 10.3607 (17) Å | T = 298 K |
α = 108.811 (9)° | 0.20 × 0.07 × 0.04 mm |
β = 92.172 (13)° | |
Data collection top
Rigaku AFC-7R diffractometer | 3125 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.043 |
Tmin = 0.929, Tmax = 0.980 | 3 standard reflections every 50 reflections |
4693 measured reflections | intensity decay: none |
4417 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.43 e Å−3 |
4417 reflections | Δρmin = −0.54 e Å−3 |
209 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P1 | 0.51040 (8) | 0.17146 (8) | 0.70177 (7) | 0.01673 (15) | |
P2 | 0.98863 (8) | 0.11160 (8) | 0.33701 (7) | 0.01893 (15) | |
Al3 | 0.75838 (9) | 0.00863 (9) | 0.54175 (8) | 0.01684 (17) | |
O1 | 0.5554 (2) | 0.3378 (2) | 0.7974 (2) | 0.0244 (4) | |
O2 | 0.4354 (2) | 0.0531 (2) | 0.7692 (2) | 0.0248 (4) | |
O3 | 0.3850 (2) | 0.1511 (2) | 0.57847 (19) | 0.0240 (4) | |
O4 | 0.6662 (2) | 0.1382 (2) | 0.6424 (2) | 0.0287 (5) | |
O5 | 1.0378 (3) | 0.2655 (3) | 0.3203 (2) | 0.0339 (5) | |
O6 | 1.1396 (2) | 0.0548 (3) | 0.3506 (2) | 0.0289 (5) | |
O7 | 0.8996 (2) | 0.1152 (2) | 0.46464 (19) | 0.0243 (4) | |
O8 | 0.8717 (2) | −0.0182 (3) | 0.2094 (2) | 0.0298 (5) | |
H8 | 0.7654 | −0.0175 | 0.2206 | 0.072 (4)* | |
N11 | 0.7815 (3) | 0.4459 (3) | 0.0255 (3) | 0.0292 (5) | |
H11 | 0.7167 | 0.4227 | −0.0490 | 0.072 (4)* | |
C12 | 0.8361 (4) | 0.3457 (3) | 0.0664 (3) | 0.0258 (6) | |
C16 | 0.7974 (5) | 0.1769 (4) | −0.0071 (4) | 0.0416 (8) | |
H16A | 0.8760 | 0.1576 | −0.0699 | 0.072 (4)* | |
H16B | 0.6882 | 0.1378 | −0.0575 | 0.072 (4)* | |
H16C | 0.8029 | 0.1256 | 0.0582 | 0.072 (4)* | |
N13 | 0.9331 (3) | 0.4249 (3) | 0.1859 (3) | 0.0300 (6) | |
H13 | 0.9829 | 0.3858 | 0.2330 | 0.072 (4)* | |
C14 | 0.9413 (4) | 0.5786 (4) | 0.2224 (3) | 0.0358 (7) | |
H14 | 1.0012 | 0.6585 | 0.3013 | 0.072 (4)* | |
C15 | 0.8461 (4) | 0.5927 (4) | 0.1224 (3) | 0.0344 (7) | |
H15 | 0.8278 | 0.6837 | 0.1194 | 0.072 (4)* | |
N21 | 0.4482 (3) | 0.5280 (3) | 0.6902 (3) | 0.0286 (5) | |
H21 | 0.4768 | 0.4588 | 0.7139 | 0.072 (4)* | |
C22 | 0.5047 (4) | 0.6797 (4) | 0.7568 (3) | 0.0299 (6) | |
C26 | 0.6281 (5) | 0.7574 (4) | 0.8813 (4) | 0.0472 (9) | |
H26A | 0.6366 | 0.6834 | 0.9238 | 0.072 (4)* | |
H26B | 0.5947 | 0.8393 | 0.9447 | 0.072 (4)* | |
H26C | 0.7336 | 0.8003 | 0.8564 | 0.072 (4)* | |
N23 | 0.4311 (4) | 0.7482 (3) | 0.6895 (3) | 0.0361 (6) | |
H23 | 0.4473 | 0.8466 | 0.7123 | 0.072 (4)* | |
C24 | 0.3248 (4) | 0.6358 (4) | 0.5774 (4) | 0.0374 (7) | |
H24 | 0.2578 | 0.6523 | 0.5140 | 0.072 (4)* | |
C25 | 0.3371 (4) | 0.4979 (4) | 0.5777 (3) | 0.0359 (7) | |
H25 | 0.2809 | 0.4008 | 0.5139 | 0.072 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P1 | 0.0144 (3) | 0.0151 (3) | 0.0194 (3) | 0.0054 (2) | −0.0014 (2) | 0.0039 (2) |
P2 | 0.0146 (3) | 0.0245 (3) | 0.0208 (3) | 0.0066 (3) | −0.0008 (2) | 0.0118 (3) |
Al3 | 0.0118 (3) | 0.0205 (4) | 0.0182 (4) | 0.0061 (3) | −0.0012 (3) | 0.0059 (3) |
O1 | 0.0279 (10) | 0.0167 (9) | 0.0242 (9) | 0.0088 (8) | −0.0068 (8) | 0.0008 (7) |
O2 | 0.0200 (9) | 0.0246 (10) | 0.0316 (10) | 0.0046 (8) | −0.0016 (8) | 0.0144 (8) |
O3 | 0.0221 (9) | 0.0220 (10) | 0.0246 (10) | 0.0040 (8) | −0.0077 (8) | 0.0071 (8) |
O4 | 0.0199 (10) | 0.0307 (11) | 0.0341 (11) | 0.0130 (8) | 0.0052 (8) | 0.0048 (9) |
O5 | 0.0348 (12) | 0.0318 (12) | 0.0413 (13) | 0.0065 (9) | 0.0025 (10) | 0.0240 (10) |
O6 | 0.0207 (10) | 0.0467 (13) | 0.0297 (11) | 0.0174 (9) | 0.0020 (8) | 0.0210 (10) |
O7 | 0.0203 (9) | 0.0268 (10) | 0.0226 (9) | 0.0036 (8) | 0.0027 (7) | 0.0073 (8) |
O8 | 0.0204 (10) | 0.0395 (12) | 0.0233 (10) | 0.0067 (9) | −0.0017 (8) | 0.0048 (9) |
N11 | 0.0316 (13) | 0.0304 (13) | 0.0254 (12) | 0.0081 (11) | −0.0033 (10) | 0.0111 (11) |
C12 | 0.0273 (14) | 0.0258 (14) | 0.0236 (13) | 0.0049 (11) | −0.0017 (11) | 0.0106 (11) |
C16 | 0.052 (2) | 0.0303 (17) | 0.0380 (18) | 0.0095 (15) | −0.0114 (16) | 0.0105 (14) |
N13 | 0.0302 (13) | 0.0308 (13) | 0.0279 (13) | 0.0047 (11) | −0.0051 (10) | 0.0133 (11) |
C14 | 0.0398 (18) | 0.0255 (15) | 0.0328 (16) | 0.0023 (13) | −0.0071 (14) | 0.0052 (13) |
C15 | 0.0374 (17) | 0.0278 (16) | 0.0366 (17) | 0.0098 (13) | −0.0017 (14) | 0.0100 (13) |
N21 | 0.0337 (14) | 0.0221 (12) | 0.0346 (13) | 0.0125 (10) | 0.0035 (11) | 0.0126 (11) |
C22 | 0.0334 (16) | 0.0267 (15) | 0.0350 (16) | 0.0126 (12) | 0.0112 (13) | 0.0140 (13) |
C26 | 0.047 (2) | 0.040 (2) | 0.047 (2) | 0.0086 (17) | −0.0014 (17) | 0.0092 (17) |
N23 | 0.0442 (16) | 0.0282 (14) | 0.0475 (17) | 0.0188 (12) | 0.0143 (13) | 0.0209 (13) |
C24 | 0.0354 (17) | 0.045 (2) | 0.0432 (19) | 0.0210 (15) | 0.0068 (15) | 0.0229 (16) |
C25 | 0.0349 (17) | 0.0355 (18) | 0.0371 (17) | 0.0121 (14) | 0.0028 (14) | 0.0114 (14) |
Geometric parameters (Å, º) top
P1—O1 | 1.507 (2) | C16—H16C | 0.9600 |
P1—O2 | 1.523 (2) | N13—C14 | 1.370 (4) |
P1—O4 | 1.544 (2) | N13—H13 | 0.8600 |
P1—O3 | 1.558 (2) | C14—C15 | 1.352 (4) |
P2—O5 | 1.481 (2) | C14—H14 | 0.9300 |
P2—O6 | 1.535 (2) | C15—H15 | 0.9300 |
P2—O7 | 1.543 (2) | N21—C22 | 1.324 (4) |
P2—O8 | 1.565 (2) | N21—C25 | 1.373 (4) |
Al3—O4 | 1.723 (2) | N21—H21 | 0.8600 |
Al3—O6i | 1.732 (2) | C22—N23 | 1.334 (4) |
Al3—O3ii | 1.736 (2) | C22—C26 | 1.475 (5) |
Al3—O7 | 1.745 (2) | C26—H26A | 0.9600 |
O3—Al3ii | 1.736 (2) | C26—H26B | 0.9600 |
O6—Al3i | 1.732 (2) | C26—H26C | 0.9600 |
N11—C12 | 1.337 (4) | N23—C24 | 1.381 (5) |
N11—C15 | 1.380 (4) | N23—H23 | 0.8600 |
N11—H11 | 0.8600 | C24—C25 | 1.346 (5) |
C12—N13 | 1.329 (4) | C24—H24 | 0.9300 |
C12—C16 | 1.476 (4) | C25—H25 | 0.9300 |
C16—H16A | 0.9600 | O8—H8 | 0.91 |
C16—H16B | 0.9600 | | |
| | | |
O1—P1—O2 | 114.02 (12) | H16A—C16—H16C | 109.5 |
O1—P1—O4 | 109.09 (12) | H16B—C16—H16C | 109.5 |
O2—P1—O4 | 109.08 (12) | C12—N13—C14 | 109.2 (3) |
O1—P1—O3 | 108.21 (11) | C12—N13—H13 | 125.4 |
O2—P1—O3 | 109.09 (11) | C14—N13—H13 | 125.4 |
O4—P1—O3 | 107.13 (12) | C15—C14—N13 | 107.3 (3) |
O5—P2—O6 | 111.02 (13) | C15—C14—H14 | 126.4 |
O5—P2—O7 | 111.86 (13) | N13—C14—H14 | 126.4 |
O6—P2—O7 | 108.49 (11) | C14—C15—N11 | 106.7 (3) |
O5—P2—O8 | 112.79 (13) | C14—C15—H15 | 126.6 |
O6—P2—O8 | 104.75 (12) | N11—C15—H15 | 126.6 |
O7—P2—O8 | 107.58 (11) | C22—N21—C25 | 109.8 (3) |
O4—Al3—O6i | 107.81 (11) | C22—N21—H21 | 125.1 |
O4—Al3—O3ii | 112.07 (10) | C25—N21—H21 | 125.1 |
O6i—Al3—O3ii | 108.80 (10) | N21—C22—N23 | 107.4 (3) |
O4—Al3—O7 | 105.33 (11) | N21—C22—C26 | 125.9 (3) |
O6i—Al3—O7 | 110.43 (10) | N23—C22—C26 | 126.7 (3) |
O3ii—Al3—O7 | 112.29 (10) | C22—C26—H26A | 109.5 |
P1—O3—Al3ii | 133.68 (13) | C22—C26—H26B | 109.5 |
P1—O4—Al3 | 149.27 (15) | H26A—C26—H26B | 109.5 |
P2—O6—Al3i | 141.69 (14) | C22—C26—H26C | 109.5 |
P2—O7—Al3 | 146.24 (14) | H26A—C26—H26C | 109.5 |
P2—O8—H8 | 108.08 | H26B—C26—H26C | 109.5 |
C12—N11—C15 | 108.9 (2) | C22—N23—C24 | 109.2 (3) |
C12—N11—H11 | 125.6 | C22—N23—H23 | 125.4 |
C15—N11—H11 | 125.6 | C24—N23—H23 | 125.4 |
N13—C12—N11 | 107.9 (3) | C25—C24—N23 | 106.7 (3) |
N13—C12—C16 | 125.4 (3) | C25—C24—H24 | 126.7 |
N11—C12—C16 | 126.7 (3) | N23—C24—H24 | 126.7 |
C12—C16—H16A | 109.5 | C24—C25—N21 | 106.9 (3) |
C12—C16—H16B | 109.5 | C24—C25—H25 | 126.5 |
H16A—C16—H16B | 109.5 | N21—C25—H25 | 126.5 |
C12—C16—H16C | 109.5 | | |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···O2ii | 0.91 | 1.66 | 2.563 (3) | 169 |
N11—H11···O1iii | 0.86 | 1.86 | 2.711 (3) | 169 |
N13—H13···O5 | 0.86 | 1.81 | 2.650 (3) | 166 |
N21—H21···O1 | 0.86 | 1.88 | 2.728 (3) | 169 |
N23—H23···O2iv | 0.86 | 1.89 | 2.740 (3) | 168 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | 2C4H7N2+·AlHO8P22− |
Mr | 384.16 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.4789 (17), 9.5233 (11), 10.3607 (17) |
α, β, γ (°) | 108.811 (9), 92.172 (13), 105.561 (13) |
V (Å3) | 755.8 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.20 × 0.07 × 0.04 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.929, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4693, 4417, 3125 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.130, 1.03 |
No. of reflections | 4417 |
No. of parameters | 209 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.54 |
Selected bond lengths (Å) topP1—O1 | 1.507 (2) | N11—C12 | 1.337 (4) |
P1—O2 | 1.523 (2) | N11—C15 | 1.380 (4) |
P1—O4 | 1.544 (2) | C12—N13 | 1.329 (4) |
P1—O3 | 1.558 (2) | C12—C16 | 1.476 (4) |
P2—O5 | 1.481 (2) | N13—C14 | 1.370 (4) |
P2—O6 | 1.535 (2) | C14—C15 | 1.352 (4) |
P2—O7 | 1.543 (2) | N21—C22 | 1.324 (4) |
P2—O8 | 1.565 (2) | N21—C25 | 1.373 (4) |
Al3—O4 | 1.723 (2) | C22—N23 | 1.334 (4) |
Al3—O6i | 1.732 (2) | C22—C26 | 1.475 (5) |
Al3—O3ii | 1.736 (2) | N23—C24 | 1.381 (5) |
Al3—O7 | 1.745 (2) | C24—C25 | 1.346 (5) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8···O2ii | 0.91 | 1.66 | 2.563 (3) | 169 |
N11—H11···O1iii | 0.86 | 1.86 | 2.711 (3) | 169 |
N13—H13···O5 | 0.86 | 1.81 | 2.650 (3) | 166 |
N21—H21···O1 | 0.86 | 1.88 | 2.728 (3) | 169 |
N23—H23···O2iv | 0.86 | 1.89 | 2.740 (3) | 168 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) x, y+1, z. |
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Recent studies of the synthesis of crystalline aluminophosphates have revealed the extensive diversity of their topology (e.g. Yu et al., 2001). Such crystalline aluminophosphates are classified into one-, two- and three- dimensional structural groups according to the way in which coordination polyhedra around Al and P are linked. An infinite one-dimensional polyhedral chain composed of corner-shared four-membered rings is one of the common structural units found in a variety of one-dimensional aluminophosphates. [NH3(CH2)2NH3][H3O][AlP2O8] (Wang et al., 1990), [CH3(CH2)5NH3][AlP2O6(OH)2] (Jones et al., 1990), [NH3(CH2)2NH3][NH4][AlP2O8] (Gao et al., 1996) and [NH3(CH2)2NH3]0.5[NH3(CH2)3NH3]0.5[AlP2O8] (Sugiyama et al., 1999) are included in this category. The title compound, [CH3C3H4N2]2[AlP2O7(OH)], (I), is another example of this structural group, as well as the first example with a cyclic amine template.
The structure of (I) is composed of Al3O4, P1O2(=O)2 and P2O2(=O)(OH) tetrahedra, forming infinite one-dimensional [AlP2O7(OH)]2− chains (Fig. 1 and Table 1). These chains run parallel to the a axis, and are joined together along the b and c axes by the 2-methylimidazolium cations. The Al3O4 tetrahedra share four O atoms with the P1O2(=O)2 and P2O2(=O)(OH) tetrahedra, with Al3—O distances ranging from 1.723 (2) to 1.745 (2) Å. The P1O2(=O)2 and P2O2(=O)(OH) tetrahedra each share two O atoms with the Al3O4 tetrahedra, and the short P—O distance to the terminal O atoms [P1—O1=1.507 (2) Å, P1—O2=1.523 (2) Å and P2—O5=1.481 (2) Å] suggest their double-bonding character. The longest P—O distance [P2—O8=1.565 (2) Å] indicates the nature of the terminal hydroxy group. Hydrogen bonds (Table 2) are found between atoms N11, N13, N21 and N23 of the protonated 2-methylimidozole and the three terminal atoms O1, O2 and O5. The O8/H8 hydroxy group also forms hydrogen bonds with terminal atom O2. The present study offers a limited discussion of the bond distances for C—C and C—N pairs; nevertheless the obtained configuration is enough to discuss the geometry of the protonated 2-methylimidazole group, including the hydrogen bonding in the title compound.