Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001344/na6132sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001344/na6132Isup2.hkl |
CCDC reference: 182572
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.028
- wR factor = 0.074
- Data-to-parameter ratio = 12.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Single crystals of [NH3(CH2)3NH3][Ga(P2O7)(H2PO4)] were prepared under solvothermal conditions. Ga2O3 (0.876 g) was dispersed in ethylene glycol (5.6 ml) by stirring followed by addition of 1,3-diaminopropane (1.1 ml) and a small amount of Si(OEt)4 which acts as a mineralizer. Aqueous H3PO4 (3 ml, 85 wt%) was then added and the gel stirred until homogeneous, sealed in a Teflon-lined steel autoclave and heated at 433 K for 7 d. The solid product was collected by filtration, washed copiously with water and dried in air at 353 K. A clear colourless crystal was isolated from the bulk sample for analysis. Powder X-ray diffraction and CHN analysis (calculated for C3H14GaN2O11P3: C 8.65, H 3.39, N 6.72%; experimental: C 8.61, H 3.56, N 6.76%) showed that the sample was monophasic. This was confirmed by Energy Dispersive Analytical X-rays (EDAX) performed using a Phillips CM20 Transmission Electron Microscope which showed that all crystallites contained Ga and P but no Si and had a Ga:P ratio of 0.33 (2). Thermogravimetric analysis using a Stanton Redcroft STA 1000 Thermal Analyser over the range 553–883 K at a heating rate of 10 K min-1 under flowing N2, showed a smooth weight loss of 18.2%, over the range 553–883 K to give a black X-ray amorphous product. Loss of 1,3-diaminopropane would correspond to a weight loss of 17.8%.
The C, N and H template atoms and the framework H atoms were located in difference Fourier maps. The fractional coordinates and isotropic displacement parameters of the framework H atoms were refined. However, the template H atoms were placed geometrically during the final refinement procedure and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C/N).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: ATOMS (Shape Software, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).
(C3H12N2)[Ga(P2O7)(H2PO4)] | F(000) = 840 |
Mr = 416.79 | Dx = 2.235 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -C 2yc | Cell parameters from 23 reflections |
a = 8.5390 (7) Å | θ = 10–27° |
b = 15.9795 (15) Å | µ = 7.36 mm−1 |
c = 9.2826 (6) Å | T = 293 K |
β = 102.007 (5)° | Needle, colourless |
V = 1238.89 (17) Å3 | 0.3 × 0.05 × 0.03 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.036 |
Graphite monochromator | θmax = 74.2°, θmin = 5.5° |
Serial Detector scans | h = −10→10 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −19→19 |
Tmin = 0.675, Tmax = 0.809 | l = −11→0 |
2586 measured reflections | 3 standard reflections every 60 min |
1267 independent reflections | intensity decay: 2.8% |
1082 reflections with I > 2σ(I) |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0406P)2 + 1.2495P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.074 | (Δ/σ)max = 0.002 |
S = 1.11 | Δρmax = 0.76 e Å−3 |
1267 reflections | Δρmin = −0.86 e Å−3 |
99 parameters |
(C3H12N2)[Ga(P2O7)(H2PO4)] | V = 1238.89 (17) Å3 |
Mr = 416.79 | Z = 4 |
Monoclinic, C2/c | Cu Kα radiation |
a = 8.5390 (7) Å | µ = 7.36 mm−1 |
b = 15.9795 (15) Å | T = 293 K |
c = 9.2826 (6) Å | 0.3 × 0.05 × 0.03 mm |
β = 102.007 (5)° |
Enraf-Nonius CAD-4 diffractometer | 1082 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.036 |
Tmin = 0.675, Tmax = 0.809 | 3 standard reflections every 60 min |
2586 measured reflections | intensity decay: 2.8% |
1267 independent reflections |
R[F2 > 2σ(F2)] = 0.028 | 1 restraint |
wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.76 e Å−3 |
1267 reflections | Δρmin = −0.86 e Å−3 |
99 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 | Occ. (<1) | |
Ga1 | 0.0000 | 0.0000 | 0.0000 | 0.00394 (14) | |
P1 | 0.0000 | 0.14771 (5) | −0.2500 | 0.00442 (18) | |
P2 | −0.16711 (6) | 0.10312 (3) | 0.22366 (6) | 0.00409 (16) | |
O1 | −0.0496 (2) | 0.09882 (10) | −0.12939 (19) | 0.0108 (4) | |
O2 | 0.1388 (2) | 0.20867 (10) | −0.1748 (2) | 0.0107 (4) | |
H1 | 0.163 (5) | 0.2560 (19) | −0.231 (4) | 0.057 (14)* | |
O3 | −0.16159 (19) | 0.03811 (10) | 0.10564 (18) | 0.0075 (3) | |
O4 | 0.17472 (19) | 0.06243 (10) | 0.12872 (17) | 0.0078 (3) | |
O5 | −0.2987 (2) | 0.16654 (10) | 0.18000 (19) | 0.0116 (4) | |
O6 | 0.0000 | 0.15381 (13) | 0.2500 | 0.0072 (5) | |
N1 | 0.0852 (3) | 0.36775 (15) | 0.0096 (2) | 0.0154 (5) | |
H2 | 0.1367 | 0.3211 | 0.0438 | 0.019* | |
H3 | 0.1475 | 0.3987 | −0.0352 | 0.019* | |
H4 | −0.0044 | 0.3547 | −0.0544 | 0.019* | |
C1 | 0.0448 (4) | 0.41581 (17) | 0.1339 (3) | 0.0192 (6) | |
H5 | −0.0438 | 0.4532 | 0.0959 | 0.023* | |
H6 | 0.1360 | 0.4499 | 0.1784 | 0.023* | |
C2 | 0.0000 | 0.3607 (2) | 0.2500 | 0.0166 (7) | |
H7 | −0.0896 | 0.3252 | 0.2068 | 0.020* | 0.50 |
H8 | 0.0896 | 0.3252 | 0.2932 | 0.020* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ga1 | 0.0049 (2) | 0.0041 (2) | 0.0037 (2) | −0.00099 (13) | 0.00279 (15) | −0.00090 (14) |
P1 | 0.0062 (4) | 0.0026 (3) | 0.0046 (4) | 0.000 | 0.0015 (3) | 0.000 |
P2 | 0.0043 (3) | 0.0040 (3) | 0.0043 (3) | 0.00169 (19) | 0.0015 (2) | 0.0002 (2) |
O1 | 0.0160 (9) | 0.0075 (8) | 0.0108 (8) | 0.0004 (6) | 0.0070 (7) | 0.0043 (7) |
O2 | 0.0107 (8) | 0.0076 (8) | 0.0126 (8) | −0.0044 (6) | −0.0003 (7) | −0.0004 (7) |
O3 | 0.0081 (8) | 0.0074 (8) | 0.0083 (8) | −0.0019 (6) | 0.0048 (6) | −0.0032 (6) |
O4 | 0.0079 (8) | 0.0109 (8) | 0.0057 (8) | −0.0032 (6) | 0.0037 (6) | −0.0032 (7) |
O5 | 0.0101 (8) | 0.0098 (8) | 0.0133 (9) | 0.0074 (6) | −0.0009 (7) | −0.0007 (7) |
O6 | 0.0071 (11) | 0.0022 (10) | 0.0120 (12) | 0.000 | 0.0015 (9) | 0.000 |
N1 | 0.0122 (10) | 0.0241 (11) | 0.0109 (11) | 0.0013 (9) | 0.0048 (9) | 0.0028 (9) |
C1 | 0.0274 (14) | 0.0155 (12) | 0.0175 (14) | −0.0050 (10) | 0.0109 (12) | −0.0018 (11) |
C2 | 0.0238 (19) | 0.0135 (16) | 0.0164 (18) | 0.000 | 0.0130 (16) | 0.000 |
Ga1—O3i | 1.949 (2) | O4—P2iii | 1.530 (2) |
Ga1—O3 | 1.949 (2) | O6—P2iii | 1.615 (1) |
Ga1—O1i | 1.976 (2) | O2—H1 | 0.97 (2) |
Ga1—O1 | 1.976 (2) | N1—C1 | 1.485 (3) |
Ga1—O4 | 1.977 (2) | N1—H2 | 0.890 |
Ga1—O4i | 1.977 (2) | N1—H3 | 0.890 |
P1—O1ii | 1.497 (2) | N1—H4 | 0.890 |
P1—O1 | 1.497 (2) | C1—C2 | 1.502 (3) |
P1—O2 | 1.580 (2) | C1—H5 | 0.970 |
P1—O2ii | 1.580 (2) | C1—H6 | 0.970 |
P2—O5 | 1.505 (2) | C2—C1iii | 1.502 (3) |
P2—O3 | 1.518 (2) | C2—H7 | 0.970 |
P2—O4iii | 1.530 (2) | C2—H8 | 0.970 |
P2—O6 | 1.615 (1) | ||
O1i—Ga1—O1 | 180 | O3—P2—O6 | 107.07 (8) |
O3i—Ga1—O3 | 180 | O4iii—P2—O6 | 106.16 (7) |
O4—Ga1—O4i | 180 | P1—O1—Ga1 | 144.43 (11) |
O3i—Ga1—O1i | 88.36 (7) | P1—O2—H1 | 118 (3) |
O3—Ga1—O1i | 91.64 (7) | P2—O3—Ga1 | 135.12 (10) |
O3i—Ga1—O1 | 91.64 (7) | P2iii—O4—Ga1 | 126.05 (10) |
O3—Ga1—O1 | 88.36 (7) | P2—O6—P2iii | 119.78 (14) |
O3i—Ga1—O4 | 86.42 (7) | C1—N1—H2 | 109.5 |
O3—Ga1—O4 | 93.58 (7) | C1—N1—H3 | 109.5 |
O1i—Ga1—O4 | 89.79 (7) | H2—N1—H3 | 109.5 |
O1—Ga1—O4 | 90.21 (7) | C1—N1—H4 | 109.5 |
O3i—Ga1—O4i | 93.58 (7) | H2—N1—H4 | 109.5 |
O3—Ga1—O4i | 86.42 (7) | H3—N1—H4 | 109.5 |
O1i—Ga1—O4i | 90.21 (7) | N1—C1—C2 | 112.9 (2) |
O1—Ga1—O4i | 89.79 (7) | N1—C1—H5 | 109.0 |
O1ii—P1—O1 | 117.08 (14) | C2—C1—H5 | 109.0 |
O1ii—P1—O2 | 110.44 (9) | N1—C1—H6 | 109.0 |
O1—P1—O2 | 107.11 (9) | C2—C1—H6 | 109.0 |
O1ii—P1—O2ii | 107.11 (9) | H5—C1—H6 | 107.8 |
O1—P1—O2ii | 110.44 (9) | C1iii—C2—C1 | 108.2 (3) |
O2—P1—O2ii | 103.88 (13) | C1iii—C2—H7 | 110.1 |
O5—P2—O3 | 113.59 (10) | C1—C2—H7 | 110.1 |
O5—P2—O4iii | 111.03 (10) | C1iii—C2—H8 | 110.1 |
O3—P2—O4iii | 111.65 (9) | C1—C2—H8 | 110.1 |
O5—P2—O6 | 106.84 (10) | H7—C2—H8 | 108.4 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, y, −z−1/2; (iii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O5iv | 0.97 (2) | 1.56 (2) | 2.526 (2) | 179 (4) |
N1—H2···O2v | 0.89 | 2.10 | 2.810 (3) | 136 |
N1—H3···O4v | 0.89 | 2.00 | 2.862 (3) | 163 |
N1—H4···O5vi | 0.89 | 1.87 | 2.755 (3) | 175 |
Symmetry codes: (iv) x+1/2, −y+1/2, z−1/2; (v) −x+1/2, −y+1/2, −z; (vi) −x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | (C3H12N2)[Ga(P2O7)(H2PO4)] |
Mr | 416.79 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.5390 (7), 15.9795 (15), 9.2826 (6) |
β (°) | 102.007 (5) |
V (Å3) | 1238.89 (17) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 7.36 |
Crystal size (mm) | 0.3 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.675, 0.809 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2586, 1267, 1082 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.074, 1.11 |
No. of reflections | 1267 |
No. of parameters | 99 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.86 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), XCAD4 (Harms, 1995), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997b), ATOMS (Shape Software, 1998), WinGX (Farrugia, 1999).
Ga1—O3 | 1.949 (2) | P2—O3 | 1.518 (2) |
Ga1—O1 | 1.976 (2) | P2—O4i | 1.530 (2) |
Ga1—O4 | 1.977 (2) | P2—O6 | 1.615 (1) |
P1—O1 | 1.497 (2) | N1—C1 | 1.485 (3) |
P1—O2 | 1.580 (2) | C1—C2 | 1.502 (3) |
P2—O5 | 1.505 (2) | ||
O1ii—Ga1—O1 | 180 | O5—P2—O3 | 113.59 (10) |
O3ii—Ga1—O3 | 180 | O5—P2—O4i | 111.03 (10) |
O4—Ga1—O4ii | 180 | O3—P2—O4i | 111.65 (9) |
O3—Ga1—O1ii | 91.64 (7) | O5—P2—O6 | 106.84 (10) |
O3—Ga1—O1 | 88.36 (7) | O3—P2—O6 | 107.07 (8) |
O3—Ga1—O4 | 93.58 (7) | O4i—P2—O6 | 106.16 (7) |
O1—Ga1—O4 | 90.21 (7) | P1—O1—Ga1 | 144.43 (11) |
O3—Ga1—O4ii | 86.42 (7) | P2—O3—Ga1 | 135.12 (10) |
O1—Ga1—O4ii | 89.79 (7) | P2i—O4—Ga1 | 126.05 (10) |
O1iii—P1—O1 | 117.08 (14) | P2—O6—P2i | 119.78 (14) |
O1iii—P1—O2 | 110.44 (9) | N1—C1—C2 | 112.9 (2) |
O1—P1—O2 | 107.11 (9) | C1i—C2—C1 | 108.2 (3) |
O2—P1—O2iii | 103.88 (13) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y, −z; (iii) −x, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O5iv | 0.97 (2) | 1.56 (2) | 2.526 (2) | 179 (4) |
N1—H2···O2v | 0.89 | 2.10 | 2.810 (3) | 136 |
N1—H3···O4v | 0.89 | 2.00 | 2.862 (3) | 163 |
N1—H4···O5vi | 0.89 | 1.87 | 2.755 (3) | 175 |
Symmetry codes: (iv) x+1/2, −y+1/2, z−1/2; (v) −x+1/2, −y+1/2, −z; (vi) −x−1/2, −y+1/2, −z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Reported here is the second example of an organically templated gallophosphate in which PO4 and P2O7 groups coexist as independent units. The title compound, [NH3(CH2)3NH3] [Ga(P2O7)(H2PO4)], consists of one-dimensional polymeric gallium-phosphate-diphosphate anions of formula [Ga(P2O7)(H2PO4)]x2- running parallel to the c axis which are charge balanced by 1,3-diaminopropane dications lying in the interchain spaces (Fig. 1). The chains are isostructural with those found in [NH3(CH2)2NH3][Ga(P2O7)(H2PO4)] (Chippindale, 2000). However, the packing of the chains and amine dications is different in the two materials; the title compound crystallizes in C2/c, whereas [NH3(CH2)2NH3][Ga(P2O7)(H2PO4)] crystallizes in Cc.
One crystallographically distinct Ga atom and two distinct P atoms are present in octahedral GaO6 and tetrahedral-based PO4 and P2O7 units with site symmetries 1, 2 and 1, respectively (Fig. 2.). The GaO6 octahedra share all their vertices with phosphorus-based bridging units. The P1-based phosphate group bridges adjacent Ga atoms via O1. The remaining P1—O2 bonds are substantially longer, consistent with the observation in difference Fourier maps of protons associated with these atoms. This is confirmed by bond-valence calculations (Brown & Altermatt, 1985). The P2-based diphosphate group has an eclipsed conformation and bridges the Ga atoms through O3—P2—O4 linkages. The P2—O6 bond is significantly longer than the other P2—O bonds but is of comparable length to P—O bonds of P—O—P diphosphate linkages in other metal diphosphates (Chippindale, 2000; Mandel, 1975). The remaining P2—O5 bond corresponds to a P—O bond with some degree of multiple-bond character.
The structure is held together by both interchain and chain-amine hydrogen bonding. The P1—O2H groups of the P1O2(OH)2 units and the terminal P2—O5 groups of the diphosphate units in neighbouring chains are sufficiently close for hydrogen bonding to occur between them to generate a three-dimensional assembly. Additional hydrogen bonding occurs between the NH3 group of the diaminocation and the framework atoms O2, O4 and O5 (Table 2).