Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102008934/br1373sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008934/br1373Isup2.hkl |
CCDC reference: 192942
The title compound was prepared hydrothermally from a mixture of gallium oxide, phenylphosphonic acid, hydrofluoric acid, 1,3-diaminopropane and deionized water in the molar ratio 1:5.3:7:2.5:290. This mixture was sealed in a teflon-lined Parr autoclave and then heated for 48 h at 453 K under autogeneous pressure. The pH was 4 during the synthesis. After cooling to room temperature, the solid was separated from the liquid phase by filtration, washed with water then dried in air. A single-crystal was optically selected for the diffraction study and glued to a glass fiber. The presence of fluorine on the gallium bridging sites was confirmed by the chemical analysis [% '[%' %]F experimental = 7.4 (3); %F theorical = 7.7]. This observation is in agreeement with bond-valence calculations (O'Keeffe et al., 1992).
Data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1994); program(s) used to solve structure: SHELXTL); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: DIAMOND (Brandenburg, 1996); software used to prepare material for publication: SHELXTL.
GaFPO3(C6H5) | F(000) = 960 |
Mr = 244.79 | Dx = 2.053 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4648 reflections |
a = 29.7810 (4) Å | θ = 1.4–29.9° |
b = 5.4220 (1) Å | µ = 3.65 mm−1 |
c = 9.8768 (2) Å | T = 293 K |
β = 96.618 (1)° | Needle, colourless |
V = 1584.21 (5) Å3 | 0.80 × 0.08 × 0.01 mm |
Z = 8 |
Siemens SMART diffractometer | 2111 independent reflections |
Radiation source: fine-focus sealed tube | 1797 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 29.9°, θmin = 1.4° |
Absorption correction: empirical (using intensity measurements) Blessing (1995) | h = −40→37 |
Tmin = 0.606, Tmax = 0.807 | k = −6→7 |
5433 measured reflections | l = −13→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0476P)2 + 6.8305P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2111 reflections | Δρmax = 1.12 e Å−3 |
96 parameters | Δρmin = −0.99 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0007 (2) |
GaFPO3(C6H5) | V = 1584.21 (5) Å3 |
Mr = 244.79 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.7810 (4) Å | µ = 3.65 mm−1 |
b = 5.4220 (1) Å | T = 293 K |
c = 9.8768 (2) Å | 0.80 × 0.08 × 0.01 mm |
β = 96.618 (1)° |
Siemens SMART diffractometer | 2111 independent reflections |
Absorption correction: empirical (using intensity measurements) Blessing (1995) | 1797 reflections with I > 2σ(I) |
Tmin = 0.606, Tmax = 0.807 | Rint = 0.034 |
5433 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.10 | Δρmax = 1.12 e Å−3 |
2111 reflections | Δρmin = −0.99 e Å−3 |
96 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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | Occ. (<1) | |
Ga1 | 0.5000 | 0.16390 (9) | 0.7500 | 0.0147 (2) | |
Ga2 | 0.5000 | 0.5000 | 1.0000 | 0.0137 (2) | |
P | 0.44071 (3) | 0.69303 (15) | 0.73275 (8) | 0.0130 (2) | |
F | 0.47404 (8) | 0.2134 (4) | 0.9123 (2) | 0.0285 (5) | |
O1 | 0.45382 (9) | 0.6894 (4) | 0.8862 (2) | 0.0177 (5) | |
O2 | 0.54616 (9) | −0.0613 (5) | 0.8272 (2) | 0.0181 (5) | |
O3 | 0.46236 (8) | 0.4778 (4) | 0.6588 (2) | 0.0146 (5) | |
C1 | 0.38100 (13) | 0.6551 (7) | 0.6980 (4) | 0.0223 (7) | |
C4 | 0.2886 (2) | 0.5895 (15) | 0.6458 (7) | 0.064 (2) | |
H4 | 0.2578 | 0.5626 | 0.6283 | 0.076* | |
C2 | 0.3525 (4) | 0.856 (2) | 0.6822 (11) | 0.045 (2)* | 0.50 |
H2 | 0.3644 | 1.014 | 0.6891 | 0.054* | 0.50 |
C3 | 0.3063 (5) | 0.822 (2) | 0.6562 (14) | 0.062 (3)* | 0.50 |
H3 | 0.2872 | 0.959 | 0.6457 | 0.074* | 0.50 |
C5 | 0.3157 (4) | 0.393 (2) | 0.6608 (12) | 0.050 (3)* | 0.50 |
H5 | 0.3032 | 0.236 | 0.6539 | 0.059* | 0.50 |
C6 | 0.3618 (2) | 0.4205 (10) | 0.6864 (6) | 0.037 (2)* | 0.50 |
H6 | 0.3803 | 0.2818 | 0.6960 | 0.044* | 0.50 |
C21 | 0.3576 (2) | 0.6661 (10) | 0.8047 (6) | 0.051 (3)* | 0.50 |
H21 | 0.3717 | 0.6950 | 0.8923 | 0.062* | 0.50 |
C31 | 0.3055 (2) | 0.6283 (10) | 0.7755 (6) | 0.067 (4)* | 0.50 |
H31 | 0.2870 | 0.6326 | 0.8452 | 0.080* | 0.50 |
C51 | 0.3145 (2) | 0.5693 (10) | 0.5437 (6) | 0.071 (4)* | 0.50 |
H51 | 0.3017 | 0.5297 | 0.4561 | 0.085* | 0.50 |
C61 | 0.3605 (2) | 0.6083 (10) | 0.5707 (6) | 0.049 (3)* | 0.50 |
H61 | 0.3781 | 0.6023 | 0.4989 | 0.059* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ga1 | 0.0244 (3) | 0.0120 (3) | 0.0082 (2) | 0.000 | 0.0040 (2) | 0.000 |
Ga2 | 0.0218 (3) | 0.0109 (3) | 0.0086 (3) | 0.0004 (2) | 0.0018 (2) | −0.0010 (2) |
P | 0.0177 (4) | 0.0119 (4) | 0.0095 (4) | 0.0006 (3) | 0.0023 (3) | −0.0002 (3) |
F | 0.0389 (14) | 0.0251 (12) | 0.0221 (12) | −0.0022 (10) | 0.0067 (10) | −0.0017 (9) |
O1 | 0.0241 (12) | 0.0175 (12) | 0.0115 (11) | 0.0044 (10) | 0.0025 (9) | 0.0009 (9) |
O2 | 0.0274 (13) | 0.0135 (11) | 0.0129 (11) | 0.0014 (10) | −0.0005 (10) | −0.0005 (9) |
O3 | 0.0208 (12) | 0.0129 (11) | 0.0105 (11) | 0.0000 (9) | 0.0036 (9) | −0.0014 (8) |
C1 | 0.020 (2) | 0.025 (2) | 0.022 (2) | −0.0001 (15) | 0.0018 (14) | 0.0006 (14) |
C4 | 0.024 (2) | 0.102 (5) | 0.063 (4) | −0.005 (3) | −0.002 (2) | 0.004 (4) |
Ga1—F | 1.877 (2) | C1—C2 | 1.377 (11) |
Ga1—Fi | 1.878 (2) | C1—C6 | 1.394 (7) |
Ga1—O2i | 1.929 (3) | C4—C31 | 1.338 (8) |
Ga1—O2 | 1.929 (2) | C4—C5 | 1.334 (13) |
Ga1—O3 | 2.175 (2) | C4—C51 | 1.344 (8) |
Ga1—O3i | 2.175 (2) | C4—C3 | 1.368 (15) |
Ga2—F | 1.900 (2) | C4—H4 | 0.93 |
Ga2—Fii | 1.900 (2) | C2—C3 | 1.38 (2) |
Ga2—O1ii | 1.963 (2) | C2—H2 | 0.93 |
Ga2—O1 | 1.963 (2) | C3—H3 | 0.93 |
Ga2—O3iii | 2.034 (2) | C5—C6 | 1.377 (13) |
Ga2—O3i | 2.034 (2) | C5—H5 | 0.93 |
P—O1 | 1.521 (2) | C6—H6 | 0.93 |
P—O2iv | 1.527 (3) | C21—C31 | 1.559 (10) |
P—O3 | 1.556 (2) | C21—H21 | 0.93 |
P—C1 | 1.784 (4) | C31—H31 | 0.93 |
O2—Pv | 1.527 (3) | C51—C61 | 1.381 (10) |
O3—Ga2i | 2.034 (2) | C51—H51 | 0.93 |
C1—C21 | 1.329 (7) | C61—H61 | 0.93 |
C1—C61 | 1.357 (7) | ||
F—Ga1—Fi | 163.55 (15) | C21—C1—C2 | 71.5 (5) |
F—Ga1—O2i | 94.78 (10) | C61—C1—C2 | 80.6 (5) |
Fi—Ga1—O2i | 95.61 (10) | C21—C1—C6 | 81.9 (4) |
F—Ga1—O2 | 95.60 (10) | C61—C1—C6 | 67.5 (3) |
Fi—Ga1—O2 | 94.78 (10) | C2—C1—C6 | 118.0 (6) |
O2i—Ga1—O2 | 101.47 (15) | C21—C1—P | 116.4 (3) |
F—Ga1—O3 | 89.91 (10) | C61—C1—P | 122.1 (3) |
Fi—Ga1—O3 | 77.16 (9) | C2—C1—P | 121.2 (5) |
O2i—Ga1—O3 | 91.24 (9) | C6—C1—P | 120.8 (3) |
O2—Ga1—O3 | 165.64 (10) | C31—C4—C5 | 82.1 (7) |
F—Ga1—O3i | 77.16 (10) | C31—C4—C51 | 123.0 (6) |
Fi—Ga1—O3i | 89.91 (10) | C5—C4—C51 | 68.0 (6) |
O2i—Ga1—O3i | 165.64 (10) | C31—C4—C3 | 71.6 (7) |
O2—Ga1—O3i | 91.24 (9) | C5—C4—C3 | 120.5 (9) |
O3—Ga1—O3i | 77.04 (12) | C51—C4—C3 | 83.2 (7) |
F—Ga2—Fii | 179.998 (1) | C31—C4—H4 | 117.4 |
F—Ga2—O1ii | 93.13 (10) | C5—C4—H4 | 118.0 |
Fii—Ga2—O1ii | 86.87 (10) | C51—C4—H4 | 119.3 |
F—Ga2—O1 | 86.87 (10) | C3—C4—H4 | 121.6 |
Fii—Ga2—O1 | 93.13 (10) | C1—C2—C3 | 120.4 (10) |
O1ii—Ga2—O1 | 179.999 (1) | C1—C2—H2 | 119.8 |
F—Ga2—O3iii | 99.71 (10) | C3—C2—H2 | 119.8 |
Fii—Ga2—O3iii | 80.29 (10) | C4—C3—C2 | 120.0 (11) |
O1ii—Ga2—O3iii | 90.09 (10) | C4—C3—H3 | 120.0 |
O1—Ga2—O3iii | 89.91 (10) | C2—C3—H3 | 120.0 |
F—Ga2—O3i | 80.30 (10) | C4—C5—C6 | 120.8 (9) |
Fii—Ga2—O3i | 99.70 (10) | C4—C5—H5 | 119.6 |
O1ii—Ga2—O3i | 89.91 (10) | C6—C5—H5 | 119.6 |
O1—Ga2—O3i | 90.10 (10) | C5—C6—C1 | 120.3 (6) |
O3iii—Ga2—O3i | 179.997 (2) | C5—C6—H6 | 119.8 |
O1—P—O2iv | 110.49 (14) | C1—C6—H6 | 119.8 |
O1—P—O3 | 112.68 (14) | C1—C21—C31 | 116.7 (3) |
O2iv—P—O3 | 109.49 (14) | C1—C21—H21 | 121.7 |
O1—P—C1 | 109.0 (2) | C31—C21—H21 | 121.7 |
O2iv—P—C1 | 108.7 (2) | C4—C31—C21 | 117.1 (3) |
O3—P—C1 | 106.3 (2) | C4—C31—H31 | 121.5 |
Ga1—F—Ga2 | 108.68 (12) | C21—C31—H31 | 121.5 |
P—O1—Ga2 | 131.27 (15) | C4—C51—C61 | 119.1 (3) |
Pv—O2—Ga1 | 126.97 (15) | C4—C51—H51 | 120.5 |
P—O3—Ga2i | 127.80 (14) | C61—C51—H51 | 120.5 |
P—O3—Ga1 | 127.89 (14) | C1—C61—C51 | 122.5 (3) |
Ga2i—O3—Ga1 | 93.57 (9) | C1—C61—H61 | 118.8 |
C21—C1—C61 | 121.5 (5) | C51—C61—H61 | 118.8 |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) x, −y+1, z+1/2; (iv) −x+1, y+1, −z+3/2; (v) −x+1, y−1, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | GaFPO3(C6H5) |
Mr | 244.79 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 29.7810 (4), 5.4220 (1), 9.8768 (2) |
β (°) | 96.618 (1) |
V (Å3) | 1584.21 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 3.65 |
Crystal size (mm) | 0.80 × 0.08 × 0.01 |
Data collection | |
Diffractometer | Siemens SMART diffractometer |
Absorption correction | Empirical (using intensity measurements) Blessing (1995) |
Tmin, Tmax | 0.606, 0.807 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5433, 2111, 1797 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.701 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.104, 1.10 |
No. of reflections | 2111 |
No. of parameters | 96 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −0.99 |
Computer programs: SMART (Siemens, 1994), SMART, SHELXTL (Sheldrick, 1994), SHELXTL), SHELXL93 (Sheldrick, 1993), DIAMOND (Brandenburg, 1996), SHELXTL.
Ga1—F | 1.877 (2) | P—C1 | 1.784 (4) |
Ga1—O2i | 1.929 (3) | C1—C2 | 1.377 (11) |
Ga1—O3 | 2.175 (2) | C1—C6 | 1.394 (7) |
Ga2—F | 1.900 (2) | C4—C5 | 1.334 (13) |
Ga2—O1ii | 1.963 (2) | C4—C3 | 1.368 (15) |
Ga2—O3iii | 2.034 (2) | C2—C3 | 1.38 (2) |
P—O1 | 1.521 (2) | C5—C6 | 1.377 (13) |
P—O2iv | 1.527 (3) | C21—C31 | 1.559 (10) |
P—O3 | 1.556 (2) | C51—C61 | 1.381 (10) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) x, −y+1, z+1/2; (iv) −x+1, y+1, −z+3/2. |
Metal organophosphonates are a class of materials with diverse structural varieties displaying properties in the fields of catalysis, ion exchange and non-linear optics. Their versatility comes from the possibility of incorporating different organic groups into an inorganic matrix composed of di-, tri- or tetravalent metal phosphonate (Clearfield, 1996). More recently, these phosphonates have been used for the synthesis of molecular solids whose structures resemble the secondary building units (SBUs) encountered in the microporous phosphate family (Mason et al., 1996). Despite the successful syntheses of a large number of open-framework phosphates (Cheetham et al., 1999), the formation mechanisms occurring during the hydrothermal treatment are still poorly understood. For example, several works have been devoted to the synthesis of microporous fluorinated gallium phosphates exhibiting extra-large pore systems (Estermann et al., 1991; Sassoye et al., 2000). The isolated clusters prepared by using the phosphonates route might play the role of molecular precursors in the formation of three-dimensional networks. For the gallium phosphonate system, the four-ring unit Ga2P2O4 (4R) and the double four-ring unit Ga4P4O12 (D4R) have been isolated in non-aqueous solvents (Mason et al., 1997, 1998). The D4R entity is analogous to the basic building block observed in cloverite (Estermann et al., 1991) or ULM-5 (Loiseau & Ferey, 1994). In this context, we studied the reactivity of organophosphonate with gallium in the presence of HF and water. Two fluorinated gallium hydroxomethyphosphonates were previously identified utilizing methylphosphonic acid (Paulet et al., 1999). The structure of GaF0.72(OH)0.28(H2O)PO3CH3 is similar to that of the aluminium methylphosphonate Al(OH)(H2O)PO3CH3 (Sawers et al. 1996). It is based on the connection by corner-sharing of the gallium GaO3(OH,F)(H2O) octahedra with the tetrahedral CH3PO3 entity. The second solid, Ga3(OH)3F3PO3CH3 (MIL-23), built up from the hexagonal arrangement of gallium Ga(OH,F)4O2 octahedra sharing corners with CH3PO3, was also reported. The resulting structures were lamellar. In the absence of F- anions, the preparation and structural characterization of layered gallium methylphosphonates and gallium phenylphosphonates have been recently described (Bujoli-Doeuff et al. 2000; Morizzi et al., 2000). Both compounds have a two-dimensional network formed by infinite straight chains of edge-sharing gallium GaO2(OH)4 octahedra linked to each other by PO3CH3 groups. Similar inorganic networks are observed in gallium ethylenediphosphonic (Bujoli-Doeuff et al., 2001) or in gallium phosphate intercalated with ethylenediamine (Jones et al., 1991). This paper deals with the synthesis and structural characterization of a fluorinated gallium phenylphosphonate, which exhibits a lamellar structure (Figs. 1 and 3). The Ga atoms are octahedrally coordinated to four O atoms and two F atoms in trans positions. Both Ga atoms are on special positions; Ga2 lies on an inversion center (4a), whereas Ga1 is located on a twofold axis (4 e). The gallium octahedral entities are connected to each other by a shared edge composed of one F and one O atom. The connection of the octahedra generates infinite zigzag chains running along [001] with a cis–trans sequence. The gallium chains are linked to each other via the phenylphosphonate groups (Fig. 2). Two O atoms of the PO3 species connect to two adjacent gallium octahedra belonging to the same chain, whereas the third O atom links Ga atoms from a different chain. This Ga—O—P connection mode ensures the cohesion of the inorganic sheet. One of the O atoms (O3) is threefold coordinated and is characterized by longer cation–anion distances. All the other anions are twofold coordinated, with classical P—O and Ga—(O,F) bond distances (Table 1). The inorganic arrangement of the layer is identical to that of the gallium fluorophosphate MIL-35 (Sassoye et al., 2001) obtained with 1,12-diaminododecane. The phenyl substituents are oriented perpendicular to the sheet and are statistically located on two on two positions related by a 90° rotation around the P—C axis.