Bis(3-azoniapentane-1,5-diaminium) cyclo-hexa-phosphate dihydrate: a monoclinic polymorph.

In the title hydrated mol-ecular salt, 2C(4)H(16)N(3) (3+)·P(6)O(18) (6-)·2H(2)O, the complete cyclo-hexa-phosphate anion is generated by crystallographic inversion symmetry. The six P atoms of the P(6)O(18) (6-) 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 mol-ecules 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

2C4H16N3 3+·P6O18 6−·2H2O

M = 722.25

Monoclinic,

a = 10.033 (4) Å

b = 16.597 (2) Å

c = 8.007 (3) Å

β = 105.07 (2)°

V = 1287.6 (7) Å3

Z = 2

Ag Kα radiation

λ = 0.56087 Å

μ = 0.27 mm−1

T = 293 K

0.32 × 0.27 × 0.21 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

9091 measured reflections

6303 independent reflections

5211 reflections with I > 2σ(I)

R int = 0.014

2 standard reflections every 120 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.099

S = 1.07

6303 reflections

189 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.97 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994) ▶; cell refinement: 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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025172/hb6809sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025172/hb6809Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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⋯O2i	0.85 (1)	1.85 (1)	2.6938 (16)	175 (2)
N1—H1B⋯O1W ii	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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .