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Bis(3-azoniapentane-1,5-diaminium) cyclohexaphosphate dihydrate: a monoclinic polymorph
aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and bPetrochemical Research Chair, College of Science, King Saud, University, Riyadh, Saudi Arabia.
*Correspondence e-mail: khedhirilamia@yahoo.fr
In the title hydrated molecular salt, 2C4H16N33+·P6O186−·2H2O, the complete cyclohexaphosphate anion is generated by crystallographic inversion symmetry. The six P atoms of the P6O186− anion form a chair conformation and the organic cation has a corrugated linear geometry. In the crystal, the cations and the anions are connected by N—H⋯O hydrogen bonds into slabs propagating in the ac plane. The water molecules link the slabs by accepting N—H⋯O links and forming O—H⋯O links. The triclinic polymorph was reported by Gharbi et al. [(1995). J. Solid State Chem. 114, 42–51].
Related literature
For the triclinic polymorph of the title compound, see: Gharbi et al. (1995). For related structures, see: Averbuch-Pouchot & Durif (1991
); Bridi & Jouini (1989
); Kamoun et al. (1990
); Khedhiri et al. (2007
); Schülke & Kayser (1985
); Khedhiri et al. (2003
).
Experimental
Crystal data
|
Data collection
|
Refinement
|
|
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995
); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEP-3 (Farrugia, 1997
) and DIAMOND (Brandenburg & Putz, 2005
); software used to prepare material for publication: WinGX (Farrugia, 1999
).
Supporting information
https://doi.org/10.1107/S1600536812025172/hb6809sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025172/hb6809Isup2.hkl
Single crystals of the title compound were prepared in two steps. In the first one, 50 ml of an aqueous solution of cyclohexaphosphoric acid was prepared by protonation of 4 g of Li6P6O18.6H2O, obtained by the Schülke process (Schülke et al., 1985), with an ion-exchange resin (Amberlite IR 120). In the second one, the frech acidic solution (20 ml, 2.6 mmol) was immediately neutralized with a solution of aza-3 pentanediyl-1,5 diamine (2.8 mmol in 10 ml of ehanol) under continuous stirring. Good quality of prismatic-shaped crystals were obtained after a slow evaporation during few days at ambient temperature
All H atoms attached to C and N atoms were fixed geometrically and treated as riding, with C—H = 0.97 Å and N—H = 0.89 Å and with Uiso(H) = 1.2Ueq(C or N).The water H atoms were refined using restraints [O— H = 0.85 (1) A °, H···H = 1.44 (2) A ° and Uiso(H) = 1.5Ueq(O)].
The title compound (I), was prepared as part of our ongoing structural studies of inorganic-organic cyclohexaphosphates systems. Its chemical composition includes three entities, P6O18 ring, water molecules and organic cations [C4N3H16]3+ and is polymorphic with a previously described triclinic phase (Gharbi et al., 1995). The geometrical configuration of these entities is depicted in Figure 1, whereas Figure 2 shows the complete atomic arrangement.
The packing of (I) consists of hybrid layers where the organic and inorganic species are alternated. Theses layers, extended perpendicularly to the b axis, are also connected between them in the two other directions via H-bonds assuring the cohesion of the network. The P6O18 rings are located around the inversion centers (0, 0, 0) and (1/2, 1/2, 1/2) and are built up by only three independent PO4 tetrahedra. The P—P—P angles of 98.85 (1), 109.09 (1) and 138.42 (1)° show that the rings are significantly distorted from the ideal threefold symmetry. It should be noted that these large deviations are commonly observed in cyclohexaphosphates with a ring of low
(Khedhiri et al., 2003, Khedhiri et al., 2007), as in the title compound. Nevertheless, this distortion is comparatively less important than that observed in Cs6P6O18.6H2O, which shows the greatest distortion for the same angles, ranging between 93.2 and 145.5° (Averbuch-Pouchot and Durif, 1991). The great flexibility of the hexamembered P6O18 rings can probably explain the pronounced distortion observed for the big rings compared with their smaller ring analogues. Examination of the main geometrical features of the three independent PO4 tetrahedra (P—O and P–P distances as well as P–O–P or O–P–O angles) shows clearly that, in spite of the P–P–P angles deformation, they are in accordance with values generally observed in condensed phosphate anions.In the organic entity, N–C and C–C distances and N–C–C and C–N–C angles, spreading within the respective ranges 1.477 (1) - 1.512 (2) Å and 109 (1) -111.5 (9)°, are similar to those observed in others compounds (Kamoun et al., 1990; Bridi et al., 1989). All nitrogen atoms of the used amine are protonated and so it is formulated by [C4N3H16]3+. Among the eight hydrogen atoms of this group, only one, H1B, establishes a hydrogen bond with a water molecule, the remaining ones are connected to the external oxygen atoms of three phosphoric rings to form an anionic entity of formula [C4N3H16(P6O18)3]15-. The two hydrogen atoms of the water molecule act as a link between successive anions. A three dimensional network of N–H···O and O–H···O hydrogen bonds interconnects the structural arrangement.
This study shows that (I) is a polymorph of the triclinic structure published elsewhere (Gharbi et al., 1995). Both phases have the same chemical formula and some structural analogeous but they present several differences in their crystal data, H-bonding scheme, internal symmetry of the cyclohexaphosphoric anions and particularly the aza-3 pentanediyl-1,5 diaminium which has different conformations where the torsion angles N2–C3–C4–N3, C2–N2–C3–C4, N1–C1–C2–N2 and C3–N2–C2–C1 exhibit the following values -175.34 (9)°, -178.34 (9)°, 171.15 (9)° and 177.79 (9)° in the title compound and 177.67°, 175.32°, 66.45° and -69.92° in the bibliography one.
For the triclinic polymorph of the title compound, see: Gharbi et al. (1995). For related structures, see: Averbuch-Pouchot & Durif (1991); Bridi & Jouini (1989); Kamoun et al. (1990); Khedhiri et al. (2007); Schülke & Kayser (1985); Khedhiri et al. (2003).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell
CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).2C4H16N33+·P6O186−·2H2O | F(000) = 752 |
Mr = 722.25 | Dx = 1.863 Mg m−3 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.56087 Å |
a = 10.033 (4) Å | Cell parameters from 25 reflections |
b = 16.597 (2) Å | θ = 9–11° |
c = 8.007 (3) Å | µ = 0.27 mm−1 |
β = 105.07 (2)° | T = 293 K |
V = 1287.6 (7) Å3 | Prism, colorless |
Z = 2 | 0.32 × 0.27 × 0.21 mm |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.014 |
Radiation source: fine-focus sealed tube | θmax = 28.0°, θmin = 2.3° |
Graphite monochromator | h = −16→3 |
non–profiled ω scans | k = −27→2 |
9091 measured reflections | l = −13→13 |
6303 independent reflections | 2 standard reflections every 120 min |
5211 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0609P)2 + 0.1509P] where P = (Fo2 + 2Fc2)/3 |
6303 reflections | (Δ/σ)max = 0.003 |
189 parameters | Δρmax = 0.47 e Å−3 |
3 restraints | Δρmin = −0.97 e Å−3 |
2C4H16N33+·P6O186−·2H2O | V = 1287.6 (7) Å3 |
Mr = 722.25 | Z = 2 |
Monoclinic, P21/c | Ag Kα radiation, λ = 0.56087 Å |
a = 10.033 (4) Å | µ = 0.27 mm−1 |
b = 16.597 (2) Å | T = 293 K |
c = 8.007 (3) Å | 0.32 × 0.27 × 0.21 mm |
β = 105.07 (2)° |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.014 |
9091 measured reflections | 2 standard reflections every 120 min |
6303 independent reflections | intensity decay: 2% |
5211 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.034 | 3 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.47 e Å−3 |
6303 reflections | Δρmin = −0.97 e Å−3 |
189 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 | ||
P1 | 0.20977 (2) | 0.430603 (15) | 0.26986 (3) | 0.01668 (6) | |
P2 | 0.22574 (3) | 0.561419 (16) | 0.52233 (3) | 0.01743 (6) | |
P3 | 0.50730 (2) | 0.627794 (15) | 0.61516 (3) | 0.01533 (5) | |
O1 | 0.14711 (9) | 0.48310 (6) | 0.11911 (10) | 0.02688 (16) | |
O2 | 0.15970 (10) | 0.34709 (5) | 0.26697 (13) | 0.03036 (18) | |
O3 | 0.37237 (8) | 0.43405 (4) | 0.29127 (10) | 0.01950 (13) | |
O4 | 0.19351 (8) | 0.47242 (5) | 0.44433 (9) | 0.01962 (13) | |
O5 | 0.16446 (10) | 0.62392 (5) | 0.39346 (12) | 0.02936 (17) | |
O6 | 0.18261 (11) | 0.55876 (6) | 0.68613 (12) | 0.03256 (19) | |
O7 | 0.38893 (8) | 0.56033 (5) | 0.56188 (13) | 0.02876 (18) | |
O8 | 0.47732 (10) | 0.68151 (5) | 0.74802 (10) | 0.02667 (16) | |
O9 | 0.53563 (11) | 0.66399 (6) | 0.46030 (11) | 0.0340 (2) | |
O1W | 0.00786 (13) | 0.72797 (7) | 0.5688 (2) | 0.0500 (3) | |
H1W1 | 0.061 (2) | 0.6947 (11) | 0.540 (3) | 0.060* | |
H2W1 | −0.0488 (19) | 0.7066 (13) | 0.618 (3) | 0.060* | |
N1 | 0.13894 (10) | 0.63794 (6) | −0.02369 (13) | 0.02486 (17) | |
H1A | 0.1317 | 0.6212 | −0.1313 | 0.037* | |
H1B | 0.0692 | 0.6709 | −0.0228 | 0.037* | |
H1C | 0.1363 | 0.5957 | 0.0438 | 0.037* | |
N2 | 0.52234 (9) | 0.66493 (5) | 0.10700 (11) | 0.01944 (14) | |
H2A | 0.5252 | 0.6967 | 0.0169 | 0.023* | |
H2B | 0.5298 | 0.6966 | 0.2003 | 0.023* | |
N3 | 0.88883 (10) | 0.59139 (7) | 0.20294 (12) | 0.02576 (18) | |
H3A | 0.8737 | 0.5500 | 0.2663 | 0.039* | |
H3B | 0.9692 | 0.6143 | 0.2545 | 0.039* | |
H3C | 0.8911 | 0.5739 | 0.0986 | 0.039* | |
C1 | 0.27111 (11) | 0.68116 (7) | 0.04148 (16) | 0.02540 (19) | |
H1D | 0.2726 | 0.7076 | 0.1499 | 0.030* | |
H1E | 0.2810 | 0.7220 | −0.0411 | 0.030* | |
C2 | 0.38863 (11) | 0.62149 (6) | 0.06828 (14) | 0.02173 (17) | |
H2C | 0.3865 | 0.5857 | 0.1634 | 0.026* | |
H2D | 0.3784 | 0.5891 | −0.0351 | 0.026* | |
C3 | 0.63924 (10) | 0.60786 (6) | 0.14047 (14) | 0.02126 (17) | |
H3D | 0.6324 | 0.5748 | 0.0387 | 0.026* | |
H3E | 0.6344 | 0.5725 | 0.2352 | 0.026* | |
C4 | 0.77604 (12) | 0.65144 (8) | 0.18517 (19) | 0.0315 (2) | |
H4A | 0.7791 | 0.6898 | 0.0948 | 0.038* | |
H4B | 0.7874 | 0.6807 | 0.2928 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.01475 (10) | 0.01827 (10) | 0.01602 (10) | −0.00204 (7) | 0.00221 (8) | −0.00203 (7) |
P2 | 0.01514 (10) | 0.01911 (11) | 0.01686 (10) | 0.00136 (8) | 0.00204 (8) | −0.00171 (7) |
P3 | 0.01797 (10) | 0.01535 (10) | 0.01216 (9) | 0.00046 (7) | 0.00302 (7) | 0.00027 (7) |
O1 | 0.0259 (4) | 0.0339 (4) | 0.0167 (3) | 0.0062 (3) | −0.0019 (3) | 0.0011 (3) |
O2 | 0.0304 (4) | 0.0226 (4) | 0.0406 (5) | −0.0104 (3) | 0.0137 (4) | −0.0089 (3) |
O3 | 0.0149 (3) | 0.0209 (3) | 0.0223 (3) | 0.0003 (2) | 0.0043 (2) | 0.0044 (2) |
O4 | 0.0214 (3) | 0.0203 (3) | 0.0178 (3) | −0.0036 (2) | 0.0063 (2) | −0.0028 (2) |
O5 | 0.0276 (4) | 0.0240 (4) | 0.0311 (4) | 0.0032 (3) | −0.0020 (3) | 0.0059 (3) |
O6 | 0.0412 (5) | 0.0361 (5) | 0.0248 (4) | −0.0009 (4) | 0.0165 (4) | −0.0082 (3) |
O7 | 0.0154 (3) | 0.0231 (3) | 0.0438 (5) | −0.0011 (3) | 0.0005 (3) | −0.0097 (3) |
O8 | 0.0383 (4) | 0.0210 (3) | 0.0211 (3) | 0.0043 (3) | 0.0083 (3) | −0.0055 (3) |
O9 | 0.0430 (5) | 0.0408 (5) | 0.0204 (3) | 0.0056 (4) | 0.0121 (3) | 0.0133 (3) |
O1W | 0.0487 (7) | 0.0299 (5) | 0.0854 (9) | 0.0048 (4) | 0.0424 (7) | 0.0120 (6) |
N1 | 0.0197 (4) | 0.0278 (4) | 0.0272 (4) | 0.0013 (3) | 0.0063 (3) | −0.0007 (3) |
N2 | 0.0197 (3) | 0.0188 (3) | 0.0203 (3) | 0.0004 (3) | 0.0059 (3) | 0.0006 (3) |
N3 | 0.0182 (4) | 0.0354 (5) | 0.0225 (4) | −0.0010 (3) | 0.0031 (3) | −0.0015 (3) |
C1 | 0.0205 (4) | 0.0232 (4) | 0.0324 (5) | 0.0012 (3) | 0.0067 (4) | −0.0026 (4) |
C2 | 0.0188 (4) | 0.0215 (4) | 0.0241 (4) | 0.0003 (3) | 0.0042 (3) | 0.0004 (3) |
C3 | 0.0183 (4) | 0.0207 (4) | 0.0242 (4) | 0.0011 (3) | 0.0044 (3) | 0.0010 (3) |
C4 | 0.0209 (4) | 0.0270 (5) | 0.0436 (7) | −0.0024 (4) | 0.0031 (4) | −0.0081 (5) |
P1—O2 | 1.4725 (9) | N2—C3 | 1.4769 (14) |
P1—O1 | 1.4889 (9) | N2—C2 | 1.4831 (14) |
P1—O3 | 1.5964 (10) | N2—H2A | 0.9000 |
P1—O4 | 1.6058 (9) | N2—H2B | 0.9000 |
P2—O5 | 1.4796 (9) | N3—C4 | 1.4867 (16) |
P2—O6 | 1.4847 (10) | N3—H3A | 0.8900 |
P2—O7 | 1.5849 (11) | N3—H3B | 0.8900 |
P2—O4 | 1.6037 (8) | N3—H3C | 0.8900 |
P3—O9 | 1.4706 (9) | C1—C2 | 1.5119 (15) |
P3—O8 | 1.4776 (9) | C1—H1D | 0.9700 |
P3—O7 | 1.6072 (9) | C1—H1E | 0.9700 |
P3—O3i | 1.6132 (8) | C2—H2C | 0.9700 |
O3—P3i | 1.6132 (8) | C2—H2D | 0.9700 |
O1W—H1W1 | 0.840 (9) | C3—C4 | 1.5099 (16) |
O1W—H2W1 | 0.849 (9) | C3—H3D | 0.9700 |
N1—C1 | 1.4783 (15) | C3—H3E | 0.9700 |
N1—H1A | 0.8900 | C4—H4A | 0.9700 |
N1—H1B | 0.8900 | C4—H4B | 0.9700 |
N1—H1C | 0.8900 | ||
O2—P1—O1 | 117.88 (6) | C2—N2—H2B | 109.4 |
O2—P1—O3 | 111.74 (5) | H2A—N2—H2B | 108.0 |
O1—P1—O3 | 105.69 (5) | C4—N3—H3A | 109.5 |
O2—P1—O4 | 108.01 (5) | C4—N3—H3B | 109.5 |
O1—P1—O4 | 109.60 (5) | H3A—N3—H3B | 109.5 |
O3—P1—O4 | 102.90 (4) | C4—N3—H3C | 109.5 |
O5—P2—O6 | 118.24 (6) | H3A—N3—H3C | 109.5 |
O5—P2—O7 | 111.58 (6) | H3B—N3—H3C | 109.5 |
O6—P2—O7 | 110.27 (6) | N1—C1—C2 | 109.10 (9) |
O5—P2—O4 | 111.65 (5) | N1—C1—H1D | 109.9 |
O6—P2—O4 | 103.95 (5) | C2—C1—H1D | 109.9 |
O7—P2—O4 | 99.24 (4) | N1—C1—H1E | 109.9 |
O9—P3—O8 | 118.73 (6) | C2—C1—H1E | 109.9 |
O9—P3—O7 | 110.62 (6) | H1D—C1—H1E | 108.3 |
O8—P3—O7 | 109.68 (6) | N2—C2—C1 | 109.94 (9) |
O9—P3—O3i | 111.48 (5) | N2—C2—H2C | 109.7 |
O8—P3—O3i | 108.51 (5) | C1—C2—H2C | 109.7 |
O7—P3—O3i | 95.29 (5) | N2—C2—H2D | 109.7 |
P1—O3—P3i | 130.36 (5) | C1—C2—H2D | 109.7 |
P2—O4—P1 | 132.93 (5) | H2C—C2—H2D | 108.2 |
P2—O7—P3 | 134.33 (6) | N2—C3—C4 | 111.46 (9) |
H1W1—O1W—H2W1 | 113.7 (19) | N2—C3—H3D | 109.3 |
C1—N1—H1A | 109.5 | C4—C3—H3D | 109.3 |
C1—N1—H1B | 109.5 | N2—C3—H3E | 109.3 |
H1A—N1—H1B | 109.5 | C4—C3—H3E | 109.3 |
C1—N1—H1C | 109.5 | H3D—C3—H3E | 108.0 |
H1A—N1—H1C | 109.5 | N3—C4—C3 | 108.90 (10) |
H1B—N1—H1C | 109.5 | N3—C4—H4A | 109.9 |
C3—N2—C2 | 111.02 (9) | C3—C4—H4A | 109.9 |
C3—N2—H2A | 109.4 | N3—C4—H4B | 109.9 |
C2—N2—H2A | 109.4 | C3—C4—H4B | 109.9 |
C3—N2—H2B | 109.4 | H4A—C4—H4B | 108.3 |
O2—P1—O3—P3i | −28.76 (9) | O6—P2—O7—P3 | −82.21 (10) |
O1—P1—O3—P3i | −158.18 (6) | O4—P2—O7—P3 | 169.10 (9) |
O4—P1—O3—P3i | 86.88 (7) | O9—P3—O7—P2 | −89.73 (10) |
O5—P2—O4—P1 | 50.02 (9) | O8—P3—O7—P2 | 43.13 (11) |
O6—P2—O4—P1 | 178.57 (7) | O3i—P3—O7—P2 | 154.95 (9) |
O7—P2—O4—P1 | −67.73 (8) | C3—N2—C2—C1 | 177.79 (9) |
O2—P1—O4—P2 | −178.70 (7) | N1—C1—C2—N2 | 171.15 (9) |
O1—P1—O4—P2 | −49.08 (8) | C2—N2—C3—C4 | −178.34 (9) |
O3—P1—O4—P2 | 63.01 (8) | N2—C3—C4—N3 | −175.34 (9) |
O5—P2—O7—P3 | 51.30 (11) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O5 | 0.84 (1) | 2.12 (1) | 2.9274 (17) | 163 (2) |
O1W—H2W1···O2ii | 0.85 (1) | 1.85 (1) | 2.6938 (16) | 175 (2) |
N1—H1B···O1Wiii | 0.89 | 1.99 | 2.7817 (15) | 147 |
N1—H1C···O1 | 0.89 | 1.96 | 2.8054 (14) | 159 |
N1—H1A···O6iv | 0.89 | 1.96 | 2.8013 (15) | 156 |
N2—H2A···O8iv | 0.90 | 2.10 | 2.8049 (16) | 135 |
N2—H2A···O9iii | 0.90 | 2.36 | 3.0891 (15) | 138 |
N2—H2B···O9 | 0.90 | 2.14 | 2.7973 (16) | 130 |
N2—H2B···O8iii | 0.90 | 2.15 | 2.8706 (13) | 137 |
N3—H3B···O5v | 0.89 | 1.99 | 2.8414 (17) | 159 |
N3—H3C···O1vi | 0.89 | 1.93 | 2.7973 (16) | 164 |
N3—H3A···O6i | 0.89 | 1.96 | 2.8008 (16) | 157 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x, −y+3/2, z−1/2; (iv) x, y, z−1; (v) x+1, y, z; (vi) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | 2C4H16N33+·P6O186−·2H2O |
Mr | 722.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.033 (4), 16.597 (2), 8.007 (3) |
β (°) | 105.07 (2) |
V (Å3) | 1287.6 (7) |
Z | 2 |
Radiation type | Ag Kα, λ = 0.56087 Å |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.32 × 0.27 × 0.21 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9091, 6303, 5211 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.836 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.099, 1.07 |
No. of reflections | 6303 |
No. of parameters | 189 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.97 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O5 | 0.840 (9) | 2.115 (11) | 2.9274 (17) | 163 (2) |
O1W—H2W1···O2i | 0.849 (9) | 1.847 (10) | 2.6938 (16) | 175 (2) |
N1—H1B···O1Wii | 0.89 | 1.99 | 2.7817 (15) | 147 |
N1—H1C···O1 | 0.89 | 1.96 | 2.8054 (14) | 159 |
N1—H1A···O6iii | 0.89 | 1.96 | 2.8013 (15) | 156 |
N2—H2A···O8iii | 0.90 | 2.10 | 2.8049 (16) | 135 |
N2—H2A···O9ii | 0.90 | 2.36 | 3.0891 (15) | 138 |
N2—H2B···O9 | 0.90 | 2.14 | 2.7973 (16) | 130 |
N2—H2B···O8ii | 0.90 | 2.15 | 2.8706 (13) | 137 |
N3—H3B···O5iv | 0.89 | 1.99 | 2.8414 (17) | 159 |
N3—H3C···O1v | 0.89 | 1.93 | 2.7973 (16) | 164 |
N3—H3A···O6vi | 0.89 | 1.96 | 2.8008 (16) | 157 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, y, z−1; (iv) x+1, y, z; (v) −x+1, −y+1, −z; (vi) −x+1, −y+1, −z+1. |
Acknowledgements
The authors extend their appreciation to the Deanship of Scientific Research at King Saud University.
References
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The title compound (I), was prepared as part of our ongoing structural studies of inorganic-organic cyclohexaphosphates systems. Its chemical composition includes three entities, P6O18 ring, water molecules and organic cations [C4N3H16]3+ and is polymorphic with a previously described triclinic phase (Gharbi et al., 1995). The geometrical configuration of these entities is depicted in Figure 1, whereas Figure 2 shows the complete atomic arrangement.
The packing of (I) consists of hybrid layers where the organic and inorganic species are alternated. Theses layers, extended perpendicularly to the b axis, are also connected between them in the two other directions via H-bonds assuring the cohesion of the network. The P6O18 rings are located around the inversion centers (0, 0, 0) and (1/2, 1/2, 1/2) and are built up by only three independent PO4 tetrahedra. The P—P—P angles of 98.85 (1), 109.09 (1) and 138.42 (1)° show that the rings are significantly distorted from the ideal threefold symmetry. It should be noted that these large deviations are commonly observed in cyclohexaphosphates with a ring of low local symmetry (Khedhiri et al., 2003, Khedhiri et al., 2007), as in the title compound. Nevertheless, this distortion is comparatively less important than that observed in Cs6P6O18.6H2O, which shows the greatest distortion for the same angles, ranging between 93.2 and 145.5° (Averbuch-Pouchot and Durif, 1991). The great flexibility of the hexamembered P6O18 rings can probably explain the pronounced distortion observed for the big rings compared with their smaller ring analogues. Examination of the main geometrical features of the three independent PO4 tetrahedra (P—O and P–P distances as well as P–O–P or O–P–O angles) shows clearly that, in spite of the P–P–P angles deformation, they are in accordance with values generally observed in condensed phosphate anions.
In the organic entity, N–C and C–C distances and N–C–C and C–N–C angles, spreading within the respective ranges 1.477 (1) - 1.512 (2) Å and 109 (1) -111.5 (9)°, are similar to those observed in others compounds (Kamoun et al., 1990; Bridi et al., 1989). All nitrogen atoms of the used amine are protonated and so it is formulated by [C4N3H16]3+. Among the eight hydrogen atoms of this group, only one, H1B, establishes a hydrogen bond with a water molecule, the remaining ones are connected to the external oxygen atoms of three phosphoric rings to form an anionic entity of formula [C4N3H16(P6O18)3]15-. The two hydrogen atoms of the water molecule act as a link between successive anions. A three dimensional network of N–H···O and O–H···O hydrogen bonds interconnects the structural arrangement.
This study shows that (I) is a polymorph of the triclinic structure published elsewhere (Gharbi et al., 1995). Both phases have the same chemical formula and some structural analogeous but they present several differences in their crystal data, H-bonding scheme, internal symmetry of the cyclohexaphosphoric anions and particularly the aza-3 pentanediyl-1,5 diaminium which has different conformations where the torsion angles N2–C3–C4–N3, C2–N2–C3–C4, N1–C1–C2–N2 and C3–N2–C2–C1 exhibit the following values -175.34 (9)°, -178.34 (9)°, 171.15 (9)° and 177.79 (9)° in the title compound and 177.67°, 175.32°, 66.45° and -69.92° in the bibliography one.