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Hydro­thermally prepared ethyl­enedi­ammonium beryl­lo­phosphate, (C2H10N2)0.5[BePO4], is an analogue of aluminosilicate zeolite gismondine. A three-dimensional network of vertex-sharing BeO4 and PO4 tetrahedra [dav(Be—O) = 1.618 (3) Å, dav(P—O) = 1.5246 (14) Å and θav(Be—O—P) = 139.8°] encapsulates the disordered ethyl­enedi­ammonium cations in an eight-ring channel system.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101006928/gd1154sup1.cif
Contains datablocks I, bep-gis

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101006928/gd1154Isup2.hkl
Contains datablock I

CCDC reference: 170162

Comment top

Both beryllium and phosphorus adopt tetrahedral coordination [dav(Be—O) = 1.618 (3) Å; dav(P—O) = 1.5246 (14) Å] with typical geometrical parameters (Harrison, 2001a). Be1 makes four links to nearby P1 atoms via bicoordinate O atom bridges [θav = 139.8°] and vice versa, thus a fully connected, three-dimensional, tetrahedral framework arises. Perfect 1:1 alternation of the Be and P species occurs.

The anionic [BePO4]- framework encloses fairly regular eight-ring (i.e. eight tetrahedral centres made up of four BeO4 and four PO4 units) channels propagating along [100] and [001], with atom-to-atom dimensions of 5.42 Å × 5.42 Å and 5.62 Å × 5.62 Å, respectively. Conversely, there are no channels apparent in the [010] direction. A topological analysis with the program KRIBER (Grosse Kunstleve & Bialek, 1995) indicated that the title compound has the same tetrahedral connectivity as the zeolite gismondine family, as exemplified by the type material Ca(AlSiO4)2·4H2O (Vezzalini et al., 1993).

A CALC SOLV analysis with PLATON (Spek, 1990) indicated that the amount of void space encapsulated by the framework in [H3N(CH2)2NH3]0.5[BePO4] is 295.7 Å3, or 35.5% of the unit cell volume. However, when the extra framework species are included, there is no 'solvent accessible' volume, indicating that the channels are essentially filled by the organic cations.

To achieve charge balance, we assume that the extra-framework organic species is doubly protonated, as the ethylene diammonium cation. Geometrical placement of H atoms resulted in a situation where all six N—H bonds are involved in N—H···O interactions, with one of the hydrogen bonds being bifurcated (Table 2). This situation is similar to that seen in other organically templated beryllophosphate frameworks (Harrison, 2001a), although the present results should not be regarded as definitive in this aspect due to the substantial template disorder.

[H3N(CH2)2NH3]0.5[BePO4] complements several other non-aluminosilicate gismondine analogues that have been characterized recently, including the cobaltophosphate CoPO-GIS, or [H3N(CH2)2NH3]0.5[CoPO4] (Yuan et al., 2000), and the zincophosphate ZnPO-GIS, or [H3N(CH2)3NH3]0.5[ZnPO4] (Neeraj & Natarajan, 2000; Harrison, 2001b), as well as novel GIS-frameworks containing three distinct tetrahedral atom types [Al/Co/P (Feng et al., 1997), Zn/Ga/P (Chippindale et al., 1998), and Zn/B/P (Kneip et al., 1999)]. Interestingly, in CoPO-GIS, which crystallizes in the same space group as [H3N(CH2)2NH3]0.5[BePO4], the same template cation occupies a different location in the channels and is completely ordered. A CALC SOLV analysis showed that some 302.4 Å3 of free space, essentially the same value as that for the title compound, is available to the template in CoPO-GIS. Conversely, for ZnPO-GIS, well ordered 1,3 diammonium propane cations template the [ZnPO4]- framework, suggesting that a bulkier template molecule is appropriate for the zincophosphate phase. This is supported by the fact that in each unit cell of [H3N(CH2)3NH3]0.5[ZnPO4], a pore volume of 395.7 Å3 (some 100 Å3 more than the equivalent value for [H3N(CH2)2NH3]0.5[BePO4]) is available to the extra-framework species. However, this simple approach takes no account of the shape (or preferred conformation) of the template, nor its hydrogen bonding capability.

Related literature top

For related literature, see: Chippindale et al. (1998); Feng et al. (1997); Grosse & Bialek (1995); Harrison (2001a, 2001b); Kneip et al. (1999); Neeraj & Natarajan (2000); Spek (1990); Vezzalini et al. (1993); Yuan et al. (2000).

Experimental top

Ethylenediamine (en) (0.3 g), BeO (0.125 g) and P2O5 (1.065 g) were dissolved in water (10 ml). This mixture (en:Be:P ratio 1:1:3) was heated to 423 K for 3 d in a 23 ml capacity sealed teflon-lined hydrothermal bomb. After cooling the bomb to ambient temperature over 2 or 3 h, a small yield of perfectly faceted prismatic rods of the title compound was recovered by vacuum filtration and washing with water. Unidentified white powder products arise from 1:1:2 or 1:1:4 en:Be:P starting ratios under the same hydrothermal conditions. Caution! Beryllium compounds are highly toxic. Take all appropriate safely precautions, especially to avoid dust contamination.

Refinement top

A handful of very weak reflections, possibly corresponding to a 2a × 2 b × 2c supercell were observed, but no convincing models could be established in the larger cell. The site occupancies of the disordered N and C atoms were varied and refined to 0.5 within experimental error and were fixed at this value for the final cycles of least squares. H atoms were treated as riding with C—H 0.93–0.94 Å and N—H 0.94–0.95 Å

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Fragment of [H3N(CH2)2NH3]0.5BePO4 with 50% displacement ellipsoids. Symmetry codes as in Table 1.
[Figure 2] Fig. 2. View down [001] for [H3N(CH2)2NH3]0.5BePO4 showing the topological connectivity between the Be (small shaded circles) and P (large open circles) tetrahedral nodes resulting in an infinite framework of four and eight rings.
(I) top
Crystal data top
(C2H10N2)0.5·(BePO4)Dx = 2.153 Mg m3
Mr = 135.04Melting point: not measured K
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
a = 9.6165 (7) ÅCell parameters from 1618 reflections
b = 9.0032 (7) Åθ = 3.0–30.0°
c = 9.6231 (7) ŵ = 0.56 mm1
β = 90.951 (2)°T = 298 K
V = 833.05 (11) Å3Rod, colourless
Z = 80.40 × 0.06 × 0.05 mm
F(000) = 552
Data collection top
Bruker SMART1000 CCD
diffractometer
1227 independent reflections
Radiation source: fine-focus sealed tube1001 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 30.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1310
Tmin = 0.912, Tmax = 0.974k = 1112
3583 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0587P)2]
where P = (Fo2 + 2Fc2)/3
1227 reflections(Δ/σ)max < 0.001
81 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
(C2H10N2)0.5·(BePO4)V = 833.05 (11) Å3
Mr = 135.04Z = 8
Monoclinic, I2/aMo Kα radiation
a = 9.6165 (7) ŵ = 0.56 mm1
b = 9.0032 (7) ÅT = 298 K
c = 9.6231 (7) Å0.40 × 0.06 × 0.05 mm
β = 90.951 (2)°
Data collection top
Bruker SMART1000 CCD
diffractometer
1227 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1001 reflections with I > 2σ(I)
Tmin = 0.912, Tmax = 0.974Rint = 0.031
3583 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.58 e Å3
1227 reflectionsΔρmin = 0.37 e Å3
81 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
xyzUiso*/UeqOcc. (<1)
Be10.0888 (2)0.1478 (3)0.1311 (2)0.0111 (4)
P10.38754 (5)0.10285 (5)0.16681 (4)0.00864 (14)
O10.23221 (15)0.06926 (16)0.17490 (15)0.0203 (3)
O20.42344 (15)0.18611 (16)0.03443 (13)0.0183 (3)
O30.43633 (17)0.19378 (16)0.29234 (14)0.0223 (3)
O40.46021 (15)0.04672 (16)0.18027 (16)0.0220 (3)
N10.4273 (4)0.5102 (4)0.0092 (4)0.0236 (8)0.50
H10.43730.40690.02770.028*0.50
H20.47080.56580.08100.028*0.50
H30.46810.53300.07730.028*0.50
N20.2559 (4)0.7428 (4)0.1801 (3)0.0221 (7)0.50
H40.24210.84610.19160.027*0.50
H50.34220.71360.21520.027*0.50
H60.18250.68940.22380.027*0.50
C10.2762 (4)0.5474 (4)0.0020 (5)0.0209 (9)*0.50
H110.23460.52680.08830.025*0.50
H120.23190.49410.07000.025*0.50
C20.2549 (5)0.7089 (4)0.0285 (4)0.0206 (9)*0.50
H210.32650.76150.01690.025*0.50
H220.16690.73730.00820.025*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Be10.0096 (10)0.0127 (10)0.0109 (9)0.0003 (8)0.0008 (8)0.0007 (8)
P10.0089 (2)0.0081 (2)0.0089 (2)0.00121 (17)0.00107 (14)0.00124 (15)
O10.0089 (6)0.0303 (8)0.0217 (7)0.0024 (6)0.0003 (5)0.0112 (6)
O20.0203 (7)0.0248 (8)0.0097 (6)0.0086 (6)0.0009 (5)0.0018 (5)
O30.0398 (9)0.0144 (7)0.0125 (6)0.0020 (6)0.0067 (6)0.0045 (5)
O40.0178 (7)0.0148 (7)0.0334 (8)0.0095 (6)0.0017 (6)0.0020 (6)
N10.031 (2)0.0174 (17)0.0226 (16)0.0047 (15)0.0102 (15)0.0069 (14)
N20.0229 (18)0.0184 (17)0.0252 (18)0.0038 (14)0.0044 (15)0.0043 (13)
Geometric parameters (Å, º) top
Be1—O11.600 (3)C1—C21.496 (5)
Be1—O4i1.613 (3)C1—C2iii1.506 (5)
Be1—O3ii1.625 (3)C2—C2iii0.557 (7)
Be1—O2iii1.632 (3)N1—H10.9511
P1—O41.5216 (15)N1—H20.9452
P1—O21.5226 (14)N1—H30.9482
P1—O31.5267 (13)N2—H40.9457
P1—O11.5273 (15)N2—H50.9384
N1—N1iv1.423 (8)N2—H60.9465
N1—C11.492 (5)C1—H110.9454
N2—N2v1.355 (7)C1—H120.9396
N2—C21.491 (5)C2—H210.9376
C1—C1iii0.505 (8)C2—H220.9570
O1—Be1—O4i109.56 (16)H1—N1—H2109.8
O1—Be1—O3ii113.72 (16)C1—N1—H3109.1
O4i—Be1—O3ii103.98 (15)H1—N1—H3109.5
O1—Be1—O2iii113.48 (16)H2—N1—H3110.1
O4i—Be1—O2iii111.25 (16)C2—N2—H4108.2
O3ii—Be1—O2iii104.38 (15)C2—N2—H5108.4
O4—P1—O2113.37 (9)H4—N2—H5110.9
O4—P1—O3105.81 (8)C2—N2—H6108.3
O2—P1—O3109.09 (8)H4—N2—H6110.1
O4—P1—O1105.58 (8)H5—N2—H6110.8
O2—P1—O1112.06 (8)N1—C1—H11109.9
O3—P1—O1110.72 (9)C2—C1—H11107.7
P1—O1—Be1137.59 (13)N1—C1—H12110.4
P1—O2—Be1iii134.33 (13)C2—C1—H12107.0
P1—O3—Be1ii141.57 (13)H11—C1—H12110.8
P1—O4—Be1vi145.86 (14)N2—C2—H21109.6
N1—C1—C2111.0 (3)C1—C2—H21107.6
N2—C2—C1112.8 (3)N2—C2—H22109.1
C1—N1—H1108.9C1—C2—H22107.8
C1—N1—H2109.5H21—C2—H22109.9
N1—C1—C2—N285.3 (5)
Symmetry codes: (i) x1/2, y, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y, z; (iv) x+1, y+1, z; (v) x+1/2, y+3/2, z1/2; (vi) x+1/2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.951.992.928 (4)167
N1—H2···O3vii0.951.892.831 (4)173
N1—H3···O4viii0.952.343.203 (4)152
N2—H4···O1ix0.952.032.942 (4)161
N2—H5···O4viii0.942.142.978 (4)148
N2—H6···O3x0.952.383.112 (4)134
N2—H6···O1viii0.952.573.143 (4)119
Symmetry codes: (vii) x+1, y+1/2, z+1/2; (viii) x, y+1/2, z1/2; (ix) x+1/2, y+1, z; (x) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula(C2H10N2)0.5·(BePO4)
Mr135.04
Crystal system, space groupMonoclinic, I2/a
Temperature (K)298
a, b, c (Å)9.6165 (7), 9.0032 (7), 9.6231 (7)
β (°) 90.951 (2)
V3)833.05 (11)
Z8
Radiation typeMo Kα
µ (mm1)0.56
Crystal size (mm)0.40 × 0.06 × 0.05
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.912, 0.974
No. of measured, independent and
observed [I > 2σ(I)] reflections
3583, 1227, 1001
Rint0.031
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.093, 1.02
No. of reflections1227
No. of parameters81
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.58, 0.37

Computer programs: SMART (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Be1—O11.600 (3)P1—O31.5267 (13)
Be1—O4i1.613 (3)P1—O11.5273 (15)
Be1—O3ii1.625 (3)N1—C11.492 (5)
Be1—O2iii1.632 (3)N2—C21.491 (5)
P1—O41.5216 (15)C1—C21.496 (5)
P1—O21.5226 (14)
O1—Be1—O4i109.56 (16)O2—P1—O3109.09 (8)
O1—Be1—O3ii113.72 (16)O4—P1—O1105.58 (8)
O4i—Be1—O3ii103.98 (15)O2—P1—O1112.06 (8)
O1—Be1—O2iii113.48 (16)O3—P1—O1110.72 (9)
O4i—Be1—O2iii111.25 (16)P1—O1—Be1137.59 (13)
O3ii—Be1—O2iii104.38 (15)P1—O2—Be1iii134.33 (13)
O4—P1—O2113.37 (9)P1—O3—Be1ii141.57 (13)
O4—P1—O3105.81 (8)P1—O4—Be1iv145.86 (14)
Symmetry codes: (i) x1/2, y, z; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y, z; (iv) x+1/2, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.951.992.928 (4)167.0
N1—H2···O3v0.951.892.831 (4)173.0
N1—H3···O4vi0.952.343.203 (4)151.7
N2—H4···O1vii0.952.032.942 (4)161.3
N2—H5···O4vi0.942.142.978 (4)147.5
N2—H6···O3viii0.952.383.112 (4)134.3
N2—H6···O1vi0.952.573.143 (4)119.1
Symmetry codes: (v) x+1, y+1/2, z+1/2; (vi) x, y+1/2, z1/2; (vii) x+1/2, y+1, z; (viii) x1/2, y+1/2, z1/2.
 

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