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Cocrystallization of the inorganic [BeF4]2- unit with the organic moiety [NH3CH2CH(NH3)CH3]2+ results in the three-dimensional network of the title compound, (C3H12N2)[BeF4] or C3H12N22+·BeF42-, created by hydrogen bonds between the protonated ammonium groups and the highly electronegative F atoms of the anion. The structure is described in terms of layers related to each other by crystallographic centres of symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102015718/bm1505sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102015718/bm1505Isup2.hkl
Contains datablock I

CCDC reference: 197318

Comment top

Three-dimensional tetrahedral Be frameworks are very rare (Le Fur et al., 1991). Using various organic templating units, Be salts have been synthesized to provide precursors for the production of fluoro-frameworks (Le Fur et al., 1991; Vilminot et al., 1973). Aqueous/HF solutions, under either hydrothermal or ambient conditions, have proved to be satisfactory for the synthesis of such salts and the title compound, (I), is an example. \sch

The coordination of Be in (I) is in the form of a slightly distorted tetrahedron (Fig. 1 and Table 1). The Be—F bond lengths [1.5352 (17)–1.5752 (17) Å] and the F—Be—F angles [106.86 (11)–111.12 (11)°] show little variation and are in good agreement with other similar geometries (Srivastava et al., 1999; Tedenac et al., 1971; Collins et al., 1983; Hahn & Chung, 1972). In the doubly protonated 1,2-diaminopropane group, average C—N [1.492 (1) Å] and C—C [1.521 (2) Å] distances (Table 1) are in good agreement with normal values (Orpen et al., 1992).

Each BeF4 tetrahedron in (I) is linked to six doubly protonated 1,2-diaminopropane units through N—H···F hydrogen bonds, characterized by H···F distances of 1.78 (2)–1.91 (2) Å (Table 2, Figs. 1–3). Four of these interactions, namely those involving atoms H1, H3, H8 and H9, connect the ions to form sheets perpendicular to (001) (Fig. 2), in which R43(10) and R44(18) connectivity is evident (Motherwell et al., 1999). These sheets, related to each other by crystallographic centres of symmetry and stacked in the direction of c, are connected by two further hydrogen bonds (Fig. 3) involving atoms H2 and H7 to create, as the smallest and simplest examples, centrosymmetric R44(12) and non-centrosymmetric R65(19) connectivities.

Experimental top

BeF2 (0.100 g, 0.0022 mol) was dissolved in an acidic aqueous mixture of distilled water (2 ml) and 30% hydrofluoric acid (0.085 ml, 0.002 mol). 1,2-Diaminopropane (0.17 ml, 0.002 mol) was added to give an overall molar ratio of 1:1:1. The resulting solution was placed in a plastic sample vial and left to concentrate slowly by evaporation, yielding colourless crystals of (I) which were recovered by filtration and air dried.

Refinement top

All H atoms, with one exception, were located in difference maps and refined isotropically. The exception, atom H6 attached to tertiary C2, which could not be refined satisfactorily in this manner, was fixed in a position with C—H = 1.00 Å and refined with a riding model with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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: WinGX (Farrugia, 1999) and PLATON (Spek, 1990, 1998).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the role of the [BeF4]2- anion in hydrogen-bond formation (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. H atoms connected to C atoms of symmetry-related cations have been omitted for clarity, while the remaining H atoms are shown as open circles. The labelling scheme encompasses all non-H atoms of the asymmetric unit and selected other atoms [symmetry codes: (i) 3/2 - x, y - 1/2, 1/2 - z; (ii) 1/2 + x, 1/2 - y, z - 1/2; (iii) 1/2 - x, y - 1/2, 1/2 - z; (iv) 1/2 + x, 1/2 - y, 1/2 + z; (v) 1 + x, y, z].
[Figure 2] Fig. 2. A portion of a hydrogen-bonded layer in (I) viewed parallel to (001), c/2 thick and centred on z = 1/4.
[Figure 3] Fig. 3. The cell of (I) viewed along a.
(I) top
Crystal data top
[C3H12N2][BeF4]F(000) = 336
Mr = 161.16Dx = 1.55 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 5.5355 (11) ÅCell parameters from 1114 reflections
b = 13.560 (3) Åθ = 2.9–27.5°
c = 9.6048 (19) ŵ = 0.17 mm1
β = 106.73 (3)°T = 120 K
V = 690.4 (3) Å3Block, colourless
Z = 40.14 × 0.08 × 0.04 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
1294 reflections with I > 2σ(I)
Detector resolution: 9.091 pixels mm-1Rint = 0.045
ϕ and ω scans to fill the Ewald sphereθmax = 27.5°, θmin = 3.7°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 67
Tmin = 0.745, Tmax = 0.993k = 1417
3623 measured reflectionsl = 129
1530 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030 w = 1/[σ2(Fo2) + (0.033P)2 + 0.118P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max = 0.001
S = 1.04Δρmax = 0.25 e Å3
1530 reflectionsΔρmin = 0.25 e Å3
135 parameters
Crystal data top
[C3H12N2][BeF4]V = 690.4 (3) Å3
Mr = 161.16Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.5355 (11) ŵ = 0.17 mm1
b = 13.560 (3) ÅT = 120 K
c = 9.6048 (19) Å0.14 × 0.08 × 0.04 mm
β = 106.73 (3)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1530 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1294 reflections with I > 2σ(I)
Tmin = 0.745, Tmax = 0.993Rint = 0.045
3623 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.25 e Å3
1530 reflectionsΔρmin = 0.25 e Å3
135 parameters
Special details top

Refinement. Anisotropic displacement parameters were refined for all non-H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Be10.8249 (3)0.11896 (11)0.20714 (16)0.0101 (4)
F10.83401 (13)0.03151 (5)0.31004 (7)0.0157 (2)
F20.78697 (13)0.21905 (5)0.28142 (7)0.0123 (2)
F31.06996 (13)0.12440 (5)0.15815 (8)0.0148 (2)
F40.59600 (12)0.10718 (5)0.07028 (7)0.0123 (2)
N10.1427 (2)0.45684 (7)0.31922 (11)0.0098 (3)
N20.3330 (2)0.27513 (7)0.07421 (12)0.0097 (3)
C10.2447 (2)0.36643 (9)0.26951 (12)0.0105 (3)
C20.2130 (2)0.36790 (8)0.10672 (12)0.0093 (3)
C30.0605 (2)0.36782 (9)0.01410 (13)0.0122 (3)
H10.240 (3)0.5093 (11)0.3166 (15)0.012 (3)*
H20.132 (3)0.4460 (11)0.4077 (17)0.016 (4)*
H30.015 (3)0.4711 (12)0.2652 (18)0.022 (4)*
H40.159 (3)0.3119 (11)0.2922 (15)0.009 (3)*
H50.423 (3)0.3626 (10)0.3195 (14)0.011 (3)*
H60.302200.426500.081700.0110*
H70.326 (3)0.2754 (11)0.0187 (18)0.016 (4)*
H80.250 (3)0.2227 (12)0.0944 (16)0.017 (4)*
H90.497 (3)0.2673 (12)0.1365 (18)0.022 (4)*
H100.143 (3)0.3091 (12)0.0356 (17)0.022 (4)*
H110.068 (3)0.3681 (11)0.0865 (17)0.017 (4)*
H120.151 (3)0.4261 (12)0.0359 (16)0.018 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Be10.0127 (7)0.0105 (7)0.0084 (7)0.0000 (6)0.0051 (6)0.0004 (5)
F10.0155 (4)0.0157 (4)0.0152 (4)0.0010 (3)0.0035 (3)0.0070 (3)
F20.0152 (3)0.0131 (4)0.0096 (3)0.0001 (3)0.0050 (3)0.0022 (3)
F30.0144 (4)0.0135 (4)0.0202 (4)0.0015 (3)0.0109 (3)0.0024 (3)
F40.0149 (4)0.0134 (4)0.0083 (3)0.0007 (3)0.0027 (3)0.0014 (3)
N10.0129 (5)0.0099 (5)0.0076 (5)0.0003 (4)0.0044 (4)0.0008 (4)
N20.0125 (5)0.0098 (5)0.0081 (5)0.0009 (4)0.0049 (4)0.0002 (4)
C10.0129 (6)0.0104 (6)0.0085 (6)0.0006 (5)0.0035 (5)0.0011 (4)
C20.0119 (6)0.0081 (5)0.0083 (5)0.0014 (4)0.0035 (5)0.0000 (4)
C30.0130 (6)0.0147 (6)0.0088 (6)0.0023 (5)0.0028 (5)0.0002 (5)
Geometric parameters (Å, º) top
Be1—F11.5352 (17)N2—H70.882 (17)
Be1—F21.5752 (17)N2—H80.897 (16)
Be1—F31.5603 (19)C1—C21.5225 (16)
Be1—F41.5492 (17)C2—C31.5192 (17)
N1—C11.4849 (16)C1—H40.937 (16)
N2—C21.4969 (15)C1—H50.967 (16)
N1—H20.881 (16)C2—H61.00
N1—H30.899 (17)C3—H100.969 (17)
N1—H10.897 (16)C3—H110.955 (16)
N2—H90.938 (17)C3—H120.990 (17)
H2—N1—H3105.6 (16)N1—C1—H4108.2 (10)
C1—N1—H2108.0 (10)H4—C1—H5110.8 (13)
C1—N1—H3112.8 (10)C2—C1—H5108.1 (8)
C1—N1—H1111.0 (10)N2—C2—H6109.75
H1—N1—H3107.7 (14)C3—C2—H6109.72
H1—N1—H2111.5 (14)C1—C2—H6109.76
C2—N2—H8109.6 (11)C2—C3—H12110.8 (9)
C2—N2—H7108.3 (10)H10—C3—H11109.4 (13)
H7—N2—H8110.2 (14)H11—C3—H12109.5 (13)
H7—N2—H9113.5 (15)C2—C3—H10109.1 (10)
C2—N2—H9111.6 (10)H10—C3—H12108.2 (14)
H8—N2—H9103.5 (14)C2—C3—H11109.8 (10)
N1—C1—C2112.17 (10)F1—Be1—F2110.97 (10)
C1—C2—C3113.71 (10)F1—Be1—F3111.12 (11)
N2—C2—C3107.73 (10)F1—Be1—F4109.50 (11)
N2—C2—C1106.04 (10)F2—Be1—F3109.67 (11)
N1—C1—H5108.2 (8)F2—Be1—F4106.86 (11)
C2—C1—H4109.4 (9)F3—Be1—F4108.59 (10)
N1—C1—C2—N2177.69 (9)N1—C1—C2—C364.12 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F3i0.90 (2)1.86 (2)2.7461 (13)169.8 (13)
N1—H2···F4ii0.88 (2)1.78 (2)2.6446 (13)165.4 (15)
N1—H3···F1iii0.90 (2)1.89 (2)2.7646 (15)163.5 (15)
N2—H7···F2iv0.88 (2)1.87 (2)2.7507 (14)175.5 (14)
N2—H8···F3v0.90 (2)1.87 (2)2.7611 (13)171.8 (13)
N2—H9···F20.94 (2)1.91 (2)2.8240 (16)163.3 (14)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x1/2, y+1/2, z1/2; (v) x1, y, z.

Experimental details

Crystal data
Chemical formula[C3H12N2][BeF4]
Mr161.16
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)5.5355 (11), 13.560 (3), 9.6048 (19)
β (°) 106.73 (3)
V3)690.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.17
Crystal size (mm)0.14 × 0.08 × 0.04
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.745, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
3623, 1530, 1294
Rint0.045
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.077, 1.04
No. of reflections1530
No. of parameters135
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.25

Computer programs: COLLECT (Nonius, 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 1990, 1998).

Selected geometric parameters (Å, º) top
Be1—F11.5352 (17)Be1—F41.5492 (17)
Be1—F21.5752 (17)N1—C11.4849 (16)
Be1—F31.5603 (19)N2—C21.4969 (15)
N1—C1—C2112.17 (10)F1—Be1—F4109.50 (11)
N2—C2—C3107.73 (10)F2—Be1—F3109.67 (11)
N2—C2—C1106.04 (10)F2—Be1—F4106.86 (11)
F1—Be1—F2110.97 (10)F3—Be1—F4108.59 (10)
F1—Be1—F3111.12 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F3i0.90 (2)1.86 (2)2.7461 (13)169.8 (13)
N1—H2···F4ii0.88 (2)1.78 (2)2.6446 (13)165.4 (15)
N1—H3···F1iii0.90 (2)1.89 (2)2.7646 (15)163.5 (15)
N2—H7···F2iv0.88 (2)1.87 (2)2.7507 (14)175.5 (14)
N2—H8···F3v0.90 (2)1.87 (2)2.7611 (13)171.8 (13)
N2—H9···F20.94 (2)1.91 (2)2.8240 (16)163.3 (14)
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x1/2, y+1/2, z1/2; (v) x1, y, z.
 

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