organic papers
Acta Cryst.(2004). E60, o2241±o2243 doi: 10.1107/S1600536804027540 Dakhlaouiet al. C6H21N43+HPO42ÿH2PO4ÿ
o2241
Acta Crystallographica Section EStructure Reports
Online
ISSN 1600-5368
A new amine phosphate templated by
tris(2-aminoethyl)amine
Amel Dakhlaoui,aLeila Samia
Smiria* and Ahmed Drissb
aUnite de Recherche 99/UR12-30, DeÂpartement
de Chimie, Faculte des Sciences de Bizerte, 7021 Jarzouna, Tunisia, andbDeÂpartement de
Chimie, Faculte des Sciences, 1060 Campus Universitaire, Tunis, Tunisia
Correspondence e-mail: leila.smiri@fsb.rnu.tn
Key indicators Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.035
wRfactor = 0.103
Data-to-parameter ratio = 17.7
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, tris(2-ammonioethyl)amine dihydrogen-phosphate monohydrogendihydrogen-phosphate, C6H21N43+HPO42ÿ
-H2PO4ÿ, was prepared hydrothermally at 413 K over a period
of 15 d. The structure exhibits extended polyanions, [(HPO4
)-(H2PO4)]n3nÿ, constructed as OÐH O hydrogen-bonded
ribbons. The triprotonated amine cations connect adjacent ribbons via NÐH O hydrogen bonds, giving rise to molecular sheets parallel to (010).
Comment
The synthesis of hybrid phosphates is of continuing interest because of their potential application in various ®elds (catal-ysis, fuel cells, protonic conductors, non-linear optics, etc.). Thus, numerous hydrogen phosphates with organic cations have been characterized, but to our knowledge, only three compounds with HPO42ÿand H2PO4ÿentities together have
been reported: 3C10H16NO+H2PO4ÿHPO42ÿH2O
(Mukho-padhyay et al., 1989), C12H32N33+H2PO4ÿHPO42ÿ6H2O
(Neeraj & Natarajan, 2001) and 6C3H7N6+4H2PO4ÿ
-HPO42ÿH2O (Janczak & Perpetuo, 2002). This paper
describes the synthesis and crystal structure determination of a new organic hydrogen and dihydrogen monophosphate C6H21N43+HPO42ÿH2PO4ÿ, (I). Two crystallographically
independent phosphate groups and a single triprotonated amine cation are present in the asymmetric unit of (I) (Fig. 1). The HP2O42ÿanions are assembled in dimers through
strong [O7 O5ii= 2.584 (2) AÊ; symmetry code: (ii) 1ÿx, 1-y,
1-z] hydrogen bonds. Each dimer aggregates with four H2P1O4ÿ groups via hydrogen bonding [O3 O8 =
2.526 (2) AÊ and O4 O6i= 2.558 (2) AÊ; symmetry code: (i)
1 +x, y, z], forming extended inorganic ribbons, [(HPO4
)-(H2PO4)]n3nÿ, parallel to theaaxis (Fig. 2). These ribbons can
be considered as polyanions, since the O O distances in the hydrogen-bond scheme maintaining their cohesion is of the same order of magnitude as in the (PO4) tetrahedron.
The triprotonated amine cations link adjacent polyanions
via relatively weak hydrogen bonding (Table 2), forming molecular layers parallel to the (010) plane (Fig. 3). The
geometrical features of the two distinct phosphorus groups are quite regular (Table 1). For P2,dav= 1.538 AÊ for PÐO, with
the longest distance [P2ÐO7 = 1.5826 (16) AÊ] corresponding to the protonated atom O7 and withav= 109.44for OÐPÐ
O. For P1,dav= 1.541 AÊ for PÐO, with the longest distances
[P1ÐO3 = 1.5729 (15) AÊ and P1ÐO4 = 1.5671 (16) AÊ] corresponding to the PÐO(H) bonds and withav= 109.38
for OÐPÐO. The NÐC and CÐC distances and the CÐNÐ C and CÐCÐN angles observed in the triprotonated amine
cations lie within the ranges 1.474 (2)±1.516 (3) AÊ and 109.57 (15)±113.20 (16), respectively.
Experimental
The title compound was prepared from a starting mixture of Co(acetate)2H2O±H3PO4 (85%)±tris(2-aminoethyl)amine±ethanol in a 1:3.5:2.5:80 molar ratio under mild hydrothermal conditions (413 K, 15 d, autogenous pressure) in a Te¯on-lined autoclave. The resulting product was washed with ethanol and dried in air. A suitable colorless single crystal of (I) was selected under a polarizing micro-scope.
Crystal data
C6H21N43+HO4P2ÿH2O4Pÿ Mr= 342.23
Triclinic,P1
a= 7.905 (2) AÊ
b= 9.441 (2) AÊ
c= 10.974 (3) AÊ
= 76.37 (2) = 101.29 (3) = 105.96 (3) V= 757.7 (3) AÊ3
Z= 2
Dx= 1.500 Mg mÿ3 MoKradiation Cell parameters from 25
re¯ections
= 5.3±7.5 = 0.33 mmÿ1 T= 293 (2) K
Parallelepiped, colorless 0.260.190.10 mm Data collection
Enraf±Nonius CAD-4 diffractometer Non-pro®led!/2scans Absorption correction: none 3534 measured re¯ections 3290 independent re¯ections 2774 re¯ections withI> 2(I)
Rint= 0.012
max= 27.0 h= 0!10
k=ÿ12!11
l=ÿ14!13 2 standard re¯ections
frequency: 120 min intensity decay: 3%
Refinement Re®nement onF2 R[F2> 2(F2)] = 0.035 wR(F2) = 0.103 S= 1.05 3290 re¯ections 186 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0528P)2 + 0.417P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.33 e AÊÿ3 min=ÿ0.38 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.014 (3)
Table 1
Selected geometric parameters (AÊ,).
P1ÐO2 1.5116 (15) P1ÐO1 1.5118 (14) P1ÐO4 1.5671 (16) P1ÐO3 1.5729 (15) P2ÐO8 1.5117 (15) P2ÐO6 1.5231 (15) P2ÐO5 1.5354 (15) P2ÐO7 1.5826 (16)
NÐC5 1.475 (3)
NÐC3 1.478 (2)
NÐC1 1.480 (2)
N1ÐC2 1.484 (3)
N2ÐC4 1.477 (3)
N3ÐC6 1.482 (2)
C1ÐC2 1.516 (3)
C3ÐC4 1.518 (3)
C5ÐC6 1.516 (3)
O2ÐP1ÐO1 113.86 (9) O2ÐP1ÐO4 109.98 (10) O1ÐP1ÐO4 111.09 (9) O2ÐP1ÐO3 105.03 (8) O1ÐP1ÐO3 111.70 (9) O4ÐP1ÐO3 104.63 (9) O8ÐP2ÐO6 111.98 (9) O8ÐP2ÐO5 110.52 (10) O6ÐP2ÐO5 110.84 (9) O8ÐP2ÐO7 109.20 (10) O6ÐP2ÐO7 105.76 (9)
O5ÐP2ÐO7 108.37 (8) C5ÐNÐC3 111.24 (15) C5ÐNÐC1 109.90 (15) C3ÐNÐC1 109.57 (15) NÐC1ÐC2 112.86 (16) N1ÐC2ÐC1 112.14 (16) NÐC3ÐC4 112.37 (16) N2ÐC4ÐC3 112.38 (16) NÐC5ÐC6 113.20 (16) N3ÐC6ÐC5 112.56 (16)
organic papers
o2242
Dakhlaouiet al. C6H21N43+HPO42ÿH2PO4ÿ Acta Cryst.(2004). E60, o2241±o2243 Figure 2Extended [(HPO4)(H2PO4)]n3nÿ ribbons in (I). Dashed lines indicate
hydrogen bonds. Figure 1
ORTEPview (Farrugia, 1997) of the asymmetric unit of (I). Displace-ment ellipsoids are shown at the 50% probability level.
Figure 3
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O3ÐH3 O8 0.82 1.77 2.526 (2) 152 N1ÐH1C O1 0.89 2.16 2.968 (2) 151 N2ÐH2C O1 0.89 2.01 2.859 (2) 160 N3ÐH3A O5 0.89 2.08 2.905 (2) 153 N3ÐH3A O8 0.89 2.54 3.161 (3) 127 N3ÐH3C O1 0.89 2.00 2.846 (2) 158 O4ÐH4 O6i 0.82 1.77 2.558 (2) 161
O7ÐH7 O5ii 0.82 1.79 2.584 (2) 162
N1ÐH1A O8iii 0.89 1.97 2.760 (2) 147
N1ÐH1B O2iv 0.89 1.93 2.715 (2) 146
N2ÐH2A O5i 0.89 2.00 2.804 (2) 149
N3ÐH3B O2iii 0.89 1.97 2.733 (2) 142
N3ÐH3B O3iii 0.89 2.60 3.417 (2) 154
Symmetry codes: (i) 1x;y;z; (ii) 1ÿx;1ÿy;1ÿz; (iii) 1ÿx;1ÿy;ÿz; (iv) 2ÿx;1ÿy;ÿz.
All H atoms were allowed to ride on their parent atoms, with OÐ H distances of 0.82 AÊ, NÐH distances of 0.89 AÊ and CÐH distances
of 0.97 AÊ, with Uiso(H) = 1.2Ueq(O,N). A common isotropic dis-placement parameter for C-bound H atoms re®ned to 0.0416 (19) AÊ2. Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell re®nement:CAD-4EXPRESS; data reduction:XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGXpublication routines (Farrugia, 1999).
References
Duisenberg, A. J. M. (1992).J. Appl. Cryst.25, 92±96. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.
Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Germany. Janczak, J. & Perpetuo, G. J. (2002).Acta Cryst.C58, o455±o459.
Mukhopadhyay, B. P., Dattagupta, J. K. & Simonetta, M. (1989).Z. Kristallogr.
187, 221±229.
Neeraj, S. & Natarajan, S. (2001).Cryst. Growth Des.1, 491±499.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, o2241–o2243
supporting information
Acta Cryst. (2004). E60, o2241–o2243 [https://doi.org/10.1107/S1600536804027540]
A new amine phosphate templated by tris(2-aminoethyl)amine
Amel Dakhlaoui, Leila Samia Smiri and Ahmed Driss
(I)
Crystal data
C6H21N43+·HO4P2−·H2O4P−
Mr = 342.23 Triclinic, P1 Hall symbol: -P 1
a = 7.905 (2) Å
b = 9.441 (2) Å
c = 10.974 (3) Å
α = 76.37 (2)°
β = 101.29 (3)°
γ = 105.96 (3)°
V = 757.7 (3) Å3
Z = 2
F(000) = 364
Dx = 1.500 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections
θ = 5.3–7.5°
µ = 0.33 mm−1
T = 293 K
Parallelepiped, colourless 0.26 × 0.19 × 0.10 mm
Data collection
Enraf–Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
non–profiled ω/2θ scans 3534 measured reflections 3290 independent reflections 2774 reflections with I > 2σ(I)
Rint = 0.012
θmax = 27.0°, θmin = 2.3°
h = 0→10
k = −12→11
l = −14→13
2 standard reflections every 120 min intensity decay: 3%
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.035
wR(F2) = 0.103
S = 1.05 3290 reflections 186 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0528P)2 + 0.417P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.33 e Å−3 Δρmin = −0.38 e Å−3
supporting information
sup-2 Acta Cryst. (2004). E60, o2241–o2243
Special details
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)
x y z Uiso*/Ueq
supporting information
sup-3 Acta Cryst. (2004). E60, o2241–o2243
C4 0.9250 (3) 0.1755 (2) 0.4314 (2) 0.0324 (4) H4A 0.9696 0.1360 0.5181 0.0416 (19)* H4B 1.0017 0.1649 0.3768 0.0416 (19)* C5 0.4730 (3) 0.0736 (2) 0.2397 (2) 0.0304 (4) H5A 0.4393 −0.0315 0.2794 0.0416 (19)* H5B 0.4347 0.0811 0.1494 0.0416 (19)* C6 0.3775 (3) 0.1616 (2) 0.2904 (2) 0.0311 (4) H6A 0.2509 0.1160 0.2794 0.0416 (19)* H6B 0.4176 0.1561 0.3804 0.0416 (19)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
P1 0.0207 (2) 0.0239 (2) 0.0223 (2) 0.00700 (18) 0.00197 (17) −0.00190 (18) O1 0.0308 (7) 0.0262 (7) 0.0319 (7) 0.0074 (6) 0.0035 (6) 0.0006 (6) O2 0.0264 (7) 0.0505 (9) 0.0273 (7) 0.0129 (6) 0.0072 (6) −0.0033 (6) O3 0.0293 (7) 0.0466 (9) 0.0295 (7) 0.0201 (7) 0.0086 (6) 0.0037 (6) O4 0.0471 (9) 0.0271 (7) 0.0469 (10) 0.0106 (7) −0.0181 (7) −0.0083 (7) P2 0.0204 (2) 0.0260 (2) 0.0187 (2) 0.00759 (18) 0.00050 (17) −0.00442 (17) O5 0.0262 (7) 0.0270 (7) 0.0390 (8) 0.0046 (6) −0.0037 (6) −0.0021 (6) O6 0.0360 (8) 0.0517 (9) 0.0252 (7) 0.0255 (7) 0.0004 (6) −0.0102 (6) O7 0.0437 (9) 0.0270 (7) 0.0477 (10) 0.0107 (7) −0.0216 (7) −0.0103 (7) O8 0.0323 (8) 0.0684 (11) 0.0248 (7) 0.0186 (8) 0.0090 (6) −0.0030 (7) N 0.0260 (8) 0.0209 (7) 0.0243 (8) 0.0059 (6) 0.0044 (6) −0.0037 (6) N1 0.0239 (8) 0.0355 (9) 0.0248 (8) 0.0069 (7) 0.0053 (6) −0.0061 (7) N2 0.0233 (8) 0.0303 (8) 0.0245 (8) 0.0045 (6) 0.0042 (6) −0.0049 (6) N3 0.0258 (8) 0.0300 (8) 0.0284 (8) 0.0106 (7) 0.0027 (6) −0.0069 (7) C1 0.0384 (11) 0.0284 (10) 0.0345 (11) 0.0142 (8) 0.0069 (9) −0.0079 (8) C2 0.0344 (11) 0.0345 (11) 0.0309 (10) 0.0065 (9) 0.0056 (8) −0.0133 (8) C3 0.0359 (11) 0.0255 (9) 0.0256 (9) 0.0067 (8) 0.0029 (8) −0.0001 (7) C4 0.0319 (10) 0.0354 (11) 0.0330 (11) 0.0148 (8) −0.0006 (8) −0.0089 (8) C5 0.0279 (10) 0.0238 (9) 0.0389 (11) 0.0034 (8) 0.0039 (8) −0.0087 (8) C6 0.0283 (10) 0.0326 (10) 0.0322 (10) 0.0061 (8) 0.0115 (8) −0.0017 (8)
Geometric parameters (Å, º)
supporting information
sup-4 Acta Cryst. (2004). E60, o2241–o2243
N—C3 1.478 (2) C3—H3E 0.9700 N—C1 1.480 (2) C4—H4A 0.9700 N1—C2 1.484 (3) C4—H4B 0.9700 N1—H1A 0.8900 C5—C6 1.516 (3) N1—H1B 0.8900 C5—H5A 0.9700 N1—H1C 0.8900 C5—H5B 0.9700 N2—C4 1.477 (3) C6—H6A 0.9700 N2—H2A 0.8900 C6—H6B 0.9700 N2—H2B 0.8900
O2—P1—O1 113.86 (9) N—C1—C2 112.86 (16) O2—P1—O4 109.98 (10) N—C1—H1D 109.0 O1—P1—O4 111.09 (9) C2—C1—H1D 109.0 O2—P1—O3 105.03 (8) N—C1—H1E 109.0 O1—P1—O3 111.70 (9) C2—C1—H1E 109.0 O4—P1—O3 104.63 (9) H1D—C1—H1E 107.8 P1—O3—H3 109.5 N1—C2—C1 112.14 (16) P1—O4—H4 109.5 N1—C2—H2D 109.2 O8—P2—O6 111.98 (9) C1—C2—H2D 109.2 O8—P2—O5 110.52 (10) N1—C2—H2E 109.2 O6—P2—O5 110.84 (9) C1—C2—H2E 109.2 O8—P2—O7 109.20 (10) H2D—C2—H2E 107.9 O6—P2—O7 105.76 (9) N—C3—C4 112.37 (16) O5—P2—O7 108.37 (8) N—C3—H3D 109.1 P2—O7—H7 109.5 C4—C3—H3D 109.1 C5—N—C3 111.24 (15) N—C3—H3E 109.1 C5—N—C1 109.90 (15) C4—C3—H3E 109.1 C3—N—C1 109.57 (15) H3D—C3—H3E 107.9 C2—N1—H1A 109.5 N2—C4—C3 112.38 (16) C2—N1—H1B 109.5 N2—C4—H4A 109.1 H1A—N1—H1B 109.5 C3—C4—H4A 109.1 C2—N1—H1C 109.5 N2—C4—H4B 109.1 H1A—N1—H1C 109.5 C3—C4—H4B 109.1 H1B—N1—H1C 109.5 H4A—C4—H4B 107.9 C4—N2—H2A 109.5 N—C5—C6 113.20 (16) C4—N2—H2B 109.5 N—C5—H5A 108.9 H2A—N2—H2B 109.5 C6—C5—H5A 108.9 C4—N2—H2C 109.5 N—C5—H5B 108.9 H2A—N2—H2C 109.5 C6—C5—H5B 108.9 H2B—N2—H2C 109.5 H5A—C5—H5B 107.8 C6—N3—H3A 109.5 N3—C6—C5 112.56 (16) C6—N3—H3B 109.5 N3—C6—H6A 109.1 H3A—N3—H3B 109.5 C5—C6—H6A 109.1 C6—N3—H3C 109.5 N3—C6—H6B 109.1 H3A—N3—H3C 109.5 C5—C6—H6B 109.1 H3B—N3—H3C 109.5 H6A—C6—H6B 107.8
supporting information
sup-5 Acta Cryst. (2004). E60, o2241–o2243
C3—N—C1—C2 −163.34 (16) C3—N—C5—C6 72.2 (2) N—C1—C2—N1 57.8 (2) C1—N—C5—C6 −166.28 (16) C5—N—C3—C4 −162.07 (16) N—C5—C6—N3 63.9 (2) C1—N—C3—C4 76.2 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O3—H3···O8 0.82 1.77 2.526 (2) 152 N1—H1C···O1 0.89 2.16 2.968 (2) 151 N2—H2C···O1 0.89 2.01 2.859 (2) 160 N3—H3A···O5 0.89 2.08 2.905 (2) 153 N3—H3A···O8 0.89 2.54 3.161 (3) 127 N3—H3C···O1 0.89 2.00 2.846 (2) 158 O4—H4···O6i 0.82 1.77 2.558 (2) 161 O7—H7···O5ii 0.82 1.79 2.584 (2) 162 N1—H1A···O8iii 0.89 1.97 2.760 (2) 147 N1—H1B···O2iv 0.89 1.93 2.715 (2) 146 N2—H2A···O5i 0.89 2.00 2.804 (2) 149 N3—H3B···O2iii 0.89 1.97 2.733 (2) 142 N3—H3B···O3iii 0.89 2.60 3.417 (2) 154
