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Crystals of gallium fluoro­phenyl­phospho­nate were synthesized hydro­thermally at 453 K under autogenous pressure. The solid crystallizes in the monoclinic system and its structure is built up by the connection of zigzag chains of edge-sharing GaO4F2 octahedra to phenyl­phosphonate groups. This results in the formation of a layered structure, in which the phenyl groups point upward and downward from the inorganic sheet. The Ga atoms occupy the special positions 4a (inversion center) and 4e (twofold axis).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102008934/br1373sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008934/br1373Isup2.hkl
Contains datablock I

CCDC reference: 192942

Comment top

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.

Experimental top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Projection of the structure of GaFPO3(C6H5) along [010], showing the connection of the GaFPO3C sheets to the phenyl groups. The phenyl species are statistically oriented in the (101) or (110) planes.
[Figure 2] Fig. 2. Polyhedral representation of a GaFPO3C layer along [100], showing the infinite zigzag chain of gallium octahedra linked with phosphonate groups (grey octahedra: GaO4F2; white tetrahedra: PO3C; black circles: carbon; dark-grey circles: fluorine). The O atoms and the phenyl groups have been omitted for clarity.
[Figure 3] Fig. 3. Displacement ellipsoid plot (50% probability) of the structure of GaFPO3(C6H5) along [010]. The phenyl species are statistically oriented in the (101) or (110) planes.
Gallium fluorophenylphosphonate top
Crystal data top
GaFPO3(C6H5)F(000) = 960
Mr = 244.79Dx = 2.053 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4648 reflections
a = 29.7810 (4) Åθ = 1.4–29.9°
b = 5.4220 (1) ŵ = 3.65 mm1
c = 9.8768 (2) ÅT = 293 K
β = 96.618 (1)°Needle, colourless
V = 1584.21 (5) Å30.80 × 0.08 × 0.01 mm
Z = 8
Data collection top
Siemens SMART
diffractometer
2111 independent reflections
Radiation source: fine-focus sealed tube1797 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 29.9°, θmin = 1.4°
Absorption correction: empirical (using intensity measurements)
Blessing (1995)
h = 4037
Tmin = 0.606, Tmax = 0.807k = 67
5433 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-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 reflectionsΔρmax = 1.12 e Å3
96 parametersΔρmin = 0.99 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0007 (2)
Crystal data top
GaFPO3(C6H5)V = 1584.21 (5) Å3
Mr = 244.79Z = 8
Monoclinic, C2/cMo Kα radiation
a = 29.7810 (4) ŵ = 3.65 mm1
b = 5.4220 (1) ÅT = 293 K
c = 9.8768 (2) Å0.80 × 0.08 × 0.01 mm
β = 96.618 (1)°
Data collection top
Siemens SMART
diffractometer
2111 independent reflections
Absorption correction: empirical (using intensity measurements)
Blessing (1995)
1797 reflections with I > 2σ(I)
Tmin = 0.606, Tmax = 0.807Rint = 0.034
5433 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.10Δρmax = 1.12 e Å3
2111 reflectionsΔρmin = 0.99 e Å3
96 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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ga10.50000.16390 (9)0.75000.0147 (2)
Ga20.50000.50001.00000.0137 (2)
P0.44071 (3)0.69303 (15)0.73275 (8)0.0130 (2)
F0.47404 (8)0.2134 (4)0.9123 (2)0.0285 (5)
O10.45382 (9)0.6894 (4)0.8862 (2)0.0177 (5)
O20.54616 (9)0.0613 (5)0.8272 (2)0.0181 (5)
O30.46236 (8)0.4778 (4)0.6588 (2)0.0146 (5)
C10.38100 (13)0.6551 (7)0.6980 (4)0.0223 (7)
C40.2886 (2)0.5895 (15)0.6458 (7)0.064 (2)
H40.25780.56260.62830.076*
C20.3525 (4)0.856 (2)0.6822 (11)0.045 (2)*0.50
H20.36441.0140.68910.054*0.50
C30.3063 (5)0.822 (2)0.6562 (14)0.062 (3)*0.50
H30.28720.9590.64570.074*0.50
C50.3157 (4)0.393 (2)0.6608 (12)0.050 (3)*0.50
H50.30320.2360.65390.059*0.50
C60.3618 (2)0.4205 (10)0.6864 (6)0.037 (2)*0.50
H60.38030.28180.69600.044*0.50
C210.3576 (2)0.6661 (10)0.8047 (6)0.051 (3)*0.50
H210.37170.69500.89230.062*0.50
C310.3055 (2)0.6283 (10)0.7755 (6)0.067 (4)*0.50
H310.28700.63260.84520.080*0.50
C510.3145 (2)0.5693 (10)0.5437 (6)0.071 (4)*0.50
H510.30170.52970.45610.085*0.50
C610.3605 (2)0.6083 (10)0.5707 (6)0.049 (3)*0.50
H610.37810.60230.49890.059*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ga10.0244 (3)0.0120 (3)0.0082 (2)0.0000.0040 (2)0.000
Ga20.0218 (3)0.0109 (3)0.0086 (3)0.0004 (2)0.0018 (2)0.0010 (2)
P0.0177 (4)0.0119 (4)0.0095 (4)0.0006 (3)0.0023 (3)0.0002 (3)
F0.0389 (14)0.0251 (12)0.0221 (12)0.0022 (10)0.0067 (10)0.0017 (9)
O10.0241 (12)0.0175 (12)0.0115 (11)0.0044 (10)0.0025 (9)0.0009 (9)
O20.0274 (13)0.0135 (11)0.0129 (11)0.0014 (10)0.0005 (10)0.0005 (9)
O30.0208 (12)0.0129 (11)0.0105 (11)0.0000 (9)0.0036 (9)0.0014 (8)
C10.020 (2)0.025 (2)0.022 (2)0.0001 (15)0.0018 (14)0.0006 (14)
C40.024 (2)0.102 (5)0.063 (4)0.005 (3)0.002 (2)0.004 (4)
Geometric parameters (Å, º) top
Ga1—F1.877 (2)C1—C21.377 (11)
Ga1—Fi1.878 (2)C1—C61.394 (7)
Ga1—O2i1.929 (3)C4—C311.338 (8)
Ga1—O21.929 (2)C4—C51.334 (13)
Ga1—O32.175 (2)C4—C511.344 (8)
Ga1—O3i2.175 (2)C4—C31.368 (15)
Ga2—F1.900 (2)C4—H40.93
Ga2—Fii1.900 (2)C2—C31.38 (2)
Ga2—O1ii1.963 (2)C2—H20.93
Ga2—O11.963 (2)C3—H30.93
Ga2—O3iii2.034 (2)C5—C61.377 (13)
Ga2—O3i2.034 (2)C5—H50.93
P—O11.521 (2)C6—H60.93
P—O2iv1.527 (3)C21—C311.559 (10)
P—O31.556 (2)C21—H210.93
P—C11.784 (4)C31—H310.93
O2—Pv1.527 (3)C51—C611.381 (10)
O3—Ga2i2.034 (2)C51—H510.93
C1—C211.329 (7)C61—H610.93
C1—C611.357 (7)
F—Ga1—Fi163.55 (15)C21—C1—C271.5 (5)
F—Ga1—O2i94.78 (10)C61—C1—C280.6 (5)
Fi—Ga1—O2i95.61 (10)C21—C1—C681.9 (4)
F—Ga1—O295.60 (10)C61—C1—C667.5 (3)
Fi—Ga1—O294.78 (10)C2—C1—C6118.0 (6)
O2i—Ga1—O2101.47 (15)C21—C1—P116.4 (3)
F—Ga1—O389.91 (10)C61—C1—P122.1 (3)
Fi—Ga1—O377.16 (9)C2—C1—P121.2 (5)
O2i—Ga1—O391.24 (9)C6—C1—P120.8 (3)
O2—Ga1—O3165.64 (10)C31—C4—C582.1 (7)
F—Ga1—O3i77.16 (10)C31—C4—C51123.0 (6)
Fi—Ga1—O3i89.91 (10)C5—C4—C5168.0 (6)
O2i—Ga1—O3i165.64 (10)C31—C4—C371.6 (7)
O2—Ga1—O3i91.24 (9)C5—C4—C3120.5 (9)
O3—Ga1—O3i77.04 (12)C51—C4—C383.2 (7)
F—Ga2—Fii179.998 (1)C31—C4—H4117.4
F—Ga2—O1ii93.13 (10)C5—C4—H4118.0
Fii—Ga2—O1ii86.87 (10)C51—C4—H4119.3
F—Ga2—O186.87 (10)C3—C4—H4121.6
Fii—Ga2—O193.13 (10)C1—C2—C3120.4 (10)
O1ii—Ga2—O1179.999 (1)C1—C2—H2119.8
F—Ga2—O3iii99.71 (10)C3—C2—H2119.8
Fii—Ga2—O3iii80.29 (10)C4—C3—C2120.0 (11)
O1ii—Ga2—O3iii90.09 (10)C4—C3—H3120.0
O1—Ga2—O3iii89.91 (10)C2—C3—H3120.0
F—Ga2—O3i80.30 (10)C4—C5—C6120.8 (9)
Fii—Ga2—O3i99.70 (10)C4—C5—H5119.6
O1ii—Ga2—O3i89.91 (10)C6—C5—H5119.6
O1—Ga2—O3i90.10 (10)C5—C6—C1120.3 (6)
O3iii—Ga2—O3i179.997 (2)C5—C6—H6119.8
O1—P—O2iv110.49 (14)C1—C6—H6119.8
O1—P—O3112.68 (14)C1—C21—C31116.7 (3)
O2iv—P—O3109.49 (14)C1—C21—H21121.7
O1—P—C1109.0 (2)C31—C21—H21121.7
O2iv—P—C1108.7 (2)C4—C31—C21117.1 (3)
O3—P—C1106.3 (2)C4—C31—H31121.5
Ga1—F—Ga2108.68 (12)C21—C31—H31121.5
P—O1—Ga2131.27 (15)C4—C51—C61119.1 (3)
Pv—O2—Ga1126.97 (15)C4—C51—H51120.5
P—O3—Ga2i127.80 (14)C61—C51—H51120.5
P—O3—Ga1127.89 (14)C1—C61—C51122.5 (3)
Ga2i—O3—Ga193.57 (9)C1—C61—H61118.8
C21—C1—C61121.5 (5)C51—C61—H61118.8
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, y1, z+3/2.

Experimental details

Crystal data
Chemical formulaGaFPO3(C6H5)
Mr244.79
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)29.7810 (4), 5.4220 (1), 9.8768 (2)
β (°) 96.618 (1)
V3)1584.21 (5)
Z8
Radiation typeMo Kα
µ (mm1)3.65
Crystal size (mm)0.80 × 0.08 × 0.01
Data collection
DiffractometerSiemens SMART
diffractometer
Absorption correctionEmpirical (using intensity measurements)
Blessing (1995)
Tmin, Tmax0.606, 0.807
No. of measured, independent and
observed [I > 2σ(I)] reflections
5433, 2111, 1797
Rint0.034
(sin θ/λ)max1)0.701
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.104, 1.10
No. of reflections2111
No. of parameters96
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.12, 0.99

Computer programs: SMART (Siemens, 1994), SMART, SHELXTL (Sheldrick, 1994), SHELXTL), SHELXL93 (Sheldrick, 1993), DIAMOND (Brandenburg, 1996), SHELXTL.

Selected bond lengths (Å) top
Ga1—F1.877 (2)P—C11.784 (4)
Ga1—O2i1.929 (3)C1—C21.377 (11)
Ga1—O32.175 (2)C1—C61.394 (7)
Ga2—F1.900 (2)C4—C51.334 (13)
Ga2—O1ii1.963 (2)C4—C31.368 (15)
Ga2—O3iii2.034 (2)C2—C31.38 (2)
P—O11.521 (2)C5—C61.377 (13)
P—O2iv1.527 (3)C21—C311.559 (10)
P—O31.556 (2)C51—C611.381 (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.
 

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