Bis[1-(2,3-di-methyl-phen-yl)piperazine-1,4-diium] bis-(oxonium) cyclo-hexa-phosphate dihydrate.

In the title compound, 2C12H20N2 (2+)·2H3O(+)·P6O18 (6-)·2H2O, a protonated water mol-ecule bridges the centrosymmetrical anionic P6O18 ring via O-H⋯O hydrogen bonds. The centrosymmetric hydrogen-bonded rings formed by four oxonium cations and four phosphate anions can be described by an R 4 (8)(36) graph-set motif. The ring motifs are connected by hydrogen bonds into inorganic layers perpendicular to [100]. The 1-(2,3-di-methyl-phen-yl)piperazine-1,4-diium cations are located between the layers, compensating their negative charge and establishing N-H⋯O hydrogen bonds with the O atoms of the anionic framework.

Related literature

For background to the chemistry of cyclo­hexa­phosphate, see: Durif (1995 ▶); Amri et al. (2008 ▶); Marouani et al. (2010 ▶). For applications of piperazine derivatives, see: Kaur et al. (2010 ▶); Eswaran et al. (2010 ▶); Chou et al. (2010 ▶); Chen et al. (2004 ▶); Shingalapur et al. (2009 ▶). For related structures with cyclo­hexa­phosphate rings, see: Abid et al. (2011 ▶); Ameur et al. (2013 ▶); Amri et al. (2009 ▶). For related structures with 1-phenyl­piperazine-1,4-diium salts, see: Marouani et al. (2010 ▶); Ben Gharbia et al. (2005 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For the synthesis of the precursor, see: Schülke & Kayser (1985 ▶).

Experimental

Crystal data

2C12H20N2 2+·2H3O+·P6O18 6−·2H2O

M = 932.50

Monoclinic,

a = 8.630 (6) Å

b = 14.495 (4) Å

c = 17.072 (3) Å

β = 114.93 (4)°

V = 1936.6 (15) Å3

Z = 2

Ag Kα radiation

λ = 0.56085 Å

μ = 0.20 mm−1

T = 293 K

0.60 × 0.40 × 0.10 mm

Data collection

Nonius MACH-3 diffractometer

Absorption correction: refined from ΔF (Walker & Stuart, 1983 ▶) T min = 0.892, T max = 0.981

12060 measured reflections

9442 independent reflections

5475 reflections with I > 2σ(I)

R int = 0.031

2 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.152

S = 0.99

9442 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.87 e Å−3

Δρmin = −0.67 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813016759/jj2168sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016759/jj2168Isup2.hkl

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

2C12H20N22+·2H3O+·P6O186−·2H2O	F(000) = 976
Mr = 932.50	Dx = 1.599 Mg m−3
Monoclinic, P21/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.630 (6) Å	θ = 9.3–10.5°
b = 14.495 (4) Å	µ = 0.20 mm−1
c = 17.072 (3) Å	T = 293 K
β = 114.93 (4)°	Prism, colourless
V = 1936.6 (15) Å3	0.60 × 0.40 × 0.10 mm
Z = 2

Nonius MACH-3 diffractometer	5475 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 28.0°, θmin = 2.1°
non–profiled ω scans	h = −14→14
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −24→2
Tmin = 0.892, Tmax = 0.981	l = −28→16
12060 measured reflections	2 standard reflections every 120 min
9442 independent reflections	intensity decay: none

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0763P)2] where P = (Fo2 + 2Fc2)/3
9442 reflections	(Δ/σ)max < 0.001
253 parameters	Δρmax = 0.87 e Å−3
0 restraints	Δρmin = −0.67 e Å−3
0 constraints

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	0.31249 (5)	0.34945 (3)	−0.07303 (3)	0.02004 (9)
P2	0.37416 (6)	0.39535 (3)	0.10432 (3)	0.02228 (10)
P3	0.69777 (6)	0.49655 (3)	0.18679 (3)	0.02396 (10)
O1	0.42651 (16)	0.30040 (10)	−0.10364 (9)	0.0287 (3)
O2	0.14736 (17)	0.30794 (10)	−0.08650 (11)	0.0345 (3)
O3	0.2778 (2)	0.45146 (10)	−0.11034 (11)	0.0385 (4)
O4	0.42266 (17)	0.36921 (13)	0.02683 (9)	0.0403 (4)
O5	0.19648 (16)	0.42960 (10)	0.07175 (10)	0.0321 (3)
O6	0.4264 (2)	0.31760 (10)	0.16614 (10)	0.0351 (3)
O7	0.49427 (17)	0.48166 (9)	0.14480 (10)	0.0325 (3)
O8	0.7354 (2)	0.55904 (12)	0.26036 (10)	0.0448 (4)
O9	0.7852 (2)	0.40717 (10)	0.19877 (12)	0.0419 (4)
OW1	1.0380 (3)	0.2895 (2)	0.25912 (15)	0.0936 (10)
H1W1	0.9712	0.3308	0.2474	0.140*
H2W1	1.0790	0.2734	0.3123	0.140*
OW2	0.79099 (19)	0.72073 (11)	0.31371 (10)	0.0372 (3)
H1W2	0.7581	0.6706	0.2912	0.056*
H2W2	0.8182	0.7360	0.2764	0.056*
H3W2	0.7184	0.7547	0.3209	0.056*
C1	0.8112 (2)	0.37054 (13)	0.00581 (13)	0.0295 (4)
H1A	0.6935	0.3897	−0.0121	0.035*
H1B	0.8824	0.4074	0.0554	0.035*
C2	0.8290 (3)	0.26990 (14)	0.03063 (13)	0.0302 (4)
H2C	0.9484	0.2523	0.0532	0.036*
H2D	0.7907	0.2605	0.0759	0.036*
C3	0.7820 (3)	0.22745 (13)	−0.11665 (13)	0.0282 (4)
H3A	0.7134	0.1904	−0.1667	0.034*
H3B	0.9005	0.2093	−0.0976	0.034*
C4	0.7625 (3)	0.32817 (13)	−0.14143 (14)	0.0299 (4)
H4A	0.8012	0.3384	−0.1865	0.036*
H4B	0.6429	0.3454	−0.1640	0.036*
C5	0.7366 (2)	0.10980 (12)	−0.02396 (12)	0.0258 (3)
C6	0.6060 (2)	0.05226 (13)	−0.07716 (12)	0.0265 (3)
C7	0.6213 (3)	−0.04254 (14)	−0.05737 (14)	0.0335 (4)
C8	0.7617 (3)	−0.07472 (15)	0.01414 (17)	0.0421 (5)
H8	0.7708	−0.1374	0.0270	0.051*
C9	0.8877 (3)	−0.01554 (16)	0.06639 (17)	0.0433 (5)
H9	0.9801	−0.0383	0.1144	0.052*
C10	0.8771 (3)	0.07749 (16)	0.04755 (15)	0.0364 (5)
H10	0.9623	0.1178	0.0821	0.044*
C11	0.4528 (3)	0.08562 (15)	−0.15409 (13)	0.0354 (4)
H13	0.4447	0.1515	−0.1513	0.053*
H11	0.3517	0.0578	−0.1544	0.053*
H14	0.4639	0.0690	−0.2059	0.053*
C12	0.4877 (4)	−0.10878 (16)	−0.11266 (19)	0.0477 (6)
H122	0.3770	−0.0866	−0.1210	0.072*
H121	0.5077	−0.1680	−0.0850	0.072*
H123	0.4924	−0.1144	−0.1676	0.072*
N1	0.72640 (18)	0.20991 (10)	−0.04534 (10)	0.0227 (3)
H1	0.6150	0.2273	−0.0649	0.027*
N2	0.8629 (2)	0.38610 (11)	−0.06582 (12)	0.0298 (3)
H2A	0.8476	0.4459	−0.0813	0.036*
H2B	0.9746	0.3729	−0.0475	0.036*

	U11	U22	U33	U12	U13	U23
P1	0.01473 (16)	0.02149 (19)	0.0252 (2)	−0.00054 (15)	0.00971 (15)	−0.00045 (17)
P2	0.02042 (19)	0.02102 (19)	0.0271 (2)	−0.00034 (15)	0.01164 (17)	−0.00057 (17)
P3	0.02164 (19)	0.02002 (19)	0.0283 (2)	0.00048 (16)	0.00867 (17)	0.00217 (17)
O1	0.0217 (6)	0.0296 (7)	0.0363 (7)	0.0055 (5)	0.0137 (5)	−0.0021 (6)
O2	0.0221 (6)	0.0335 (7)	0.0522 (9)	−0.0093 (5)	0.0197 (6)	−0.0100 (7)
O3	0.0558 (10)	0.0228 (6)	0.0560 (10)	0.0102 (6)	0.0420 (8)	0.0084 (7)
O4	0.0196 (6)	0.0758 (12)	0.0257 (7)	0.0018 (7)	0.0099 (5)	−0.0072 (8)
O5	0.0205 (6)	0.0297 (7)	0.0475 (8)	0.0007 (5)	0.0157 (6)	−0.0001 (6)
O6	0.0388 (8)	0.0270 (7)	0.0420 (8)	0.0021 (6)	0.0195 (7)	0.0086 (6)
O7	0.0224 (6)	0.0209 (6)	0.0518 (9)	−0.0013 (5)	0.0132 (6)	−0.0039 (6)
O8	0.0574 (10)	0.0368 (9)	0.0331 (8)	−0.0078 (8)	0.0122 (7)	−0.0075 (7)
O9	0.0328 (8)	0.0290 (7)	0.0603 (10)	0.0119 (6)	0.0160 (7)	0.0105 (7)
OW1	0.0987 (18)	0.134 (2)	0.0705 (14)	0.0923 (17)	0.0579 (14)	0.0573 (15)
OW2	0.0349 (7)	0.0385 (8)	0.0389 (8)	−0.0028 (6)	0.0162 (7)	−0.0106 (7)
C1	0.0236 (8)	0.0264 (8)	0.0393 (10)	−0.0026 (7)	0.0139 (8)	−0.0055 (8)
C2	0.0283 (9)	0.0289 (9)	0.0304 (9)	−0.0021 (7)	0.0093 (7)	−0.0018 (8)
C3	0.0316 (9)	0.0249 (8)	0.0363 (10)	0.0015 (7)	0.0223 (8)	0.0021 (7)
C4	0.0297 (9)	0.0280 (9)	0.0369 (10)	0.0011 (7)	0.0188 (8)	0.0048 (8)
C5	0.0272 (8)	0.0216 (8)	0.0324 (9)	0.0038 (6)	0.0164 (7)	0.0035 (7)
C6	0.0323 (9)	0.0245 (8)	0.0299 (9)	0.0023 (7)	0.0200 (7)	0.0014 (7)
C7	0.0459 (11)	0.0222 (8)	0.0442 (11)	0.0000 (8)	0.0305 (10)	−0.0008 (8)
C8	0.0526 (14)	0.0252 (9)	0.0598 (15)	0.0097 (9)	0.0346 (12)	0.0128 (10)
C9	0.0426 (12)	0.0339 (11)	0.0497 (13)	0.0126 (9)	0.0158 (10)	0.0146 (10)
C10	0.0310 (10)	0.0325 (10)	0.0413 (11)	0.0075 (8)	0.0110 (9)	0.0076 (9)
C11	0.0364 (10)	0.0329 (10)	0.0335 (10)	−0.0052 (8)	0.0115 (8)	−0.0028 (8)
C12	0.0568 (15)	0.0290 (10)	0.0662 (17)	−0.0098 (10)	0.0346 (13)	−0.0116 (11)
N1	0.0199 (6)	0.0212 (6)	0.0289 (7)	0.0015 (5)	0.0120 (6)	0.0014 (6)
N2	0.0210 (6)	0.0226 (7)	0.0483 (10)	0.0014 (6)	0.0170 (7)	0.0031 (7)

P1—O2	1.4729 (16)	C3—H3A	0.9700
P1—O1	1.4766 (15)	C3—H3B	0.9700
P1—O3	1.5878 (15)	C4—N2	1.476 (3)
P1—O4	1.5894 (16)	C4—H4A	0.9700
P2—O6	1.4785 (15)	C4—H4B	0.9700
P2—O5	1.4792 (17)	C5—C6	1.388 (3)
P2—O7	1.5855 (15)	C5—C10	1.390 (3)
P2—O4	1.5924 (15)	C5—N1	1.490 (2)
P3—O8	1.4696 (17)	C6—C7	1.408 (3)
P3—O9	1.4696 (15)	C6—C11	1.497 (3)
P3—O3i	1.5964 (15)	C7—C8	1.389 (3)
P3—O7	1.6073 (19)	C7—C12	1.491 (3)
O3—P3i	1.5964 (15)	C8—C9	1.377 (4)
OW1—H1W1	0.7950	C8—H8	0.9300
OW1—H2W1	0.8565	C9—C10	1.380 (3)
OW2—H1W2	0.8154	C9—H9	0.9300
OW2—H2W2	0.7977	C10—H10	0.9300
OW2—H3W2	0.8458	C11—H13	0.9600
C1—N2	1.485 (3)	C11—H11	0.9600
C1—C2	1.509 (3)	C11—H14	0.9600
C1—H1A	0.9700	C12—H122	0.9600
C1—H1B	0.9700	C12—H121	0.9600
C2—N1	1.501 (2)	C12—H123	0.9600
C2—H2C	0.9700	N1—H1	0.9100
C2—H2D	0.9700	N2—H2A	0.9000
C3—N1	1.506 (2)	N2—H2B	0.9000
C3—C4	1.509 (3)
O2—P1—O1	119.56 (9)	N2—C4—H4B	109.6
O2—P1—O3	108.13 (9)	C3—C4—H4B	109.6
O1—P1—O3	110.35 (8)	H4A—C4—H4B	108.1
O2—P1—O4	110.06 (9)	C6—C5—C10	122.63 (18)
O1—P1—O4	106.25 (9)	C6—C5—N1	118.49 (16)
O3—P1—O4	100.89 (10)	C10—C5—N1	118.88 (17)
O6—P2—O5	118.69 (9)	C5—C6—C7	117.46 (18)
O6—P2—O7	110.10 (9)	C5—C6—C11	123.56 (17)
O5—P2—O7	106.42 (9)	C7—C6—C11	118.97 (18)
O6—P2—O4	107.69 (10)	C8—C7—C6	119.8 (2)
O5—P2—O4	111.19 (9)	C8—C7—C12	119.7 (2)
O7—P2—O4	101.38 (9)	C6—C7—C12	120.5 (2)
O8—P3—O9	120.58 (11)	C9—C8—C7	121.2 (2)
O8—P3—O3i	110.49 (10)	C9—C8—H8	119.4
O9—P3—O3i	107.03 (9)	C7—C8—H8	119.4
O8—P3—O7	105.68 (10)	C8—C9—C10	120.0 (2)
O9—P3—O7	110.14 (9)	C8—C9—H9	120.0
O3i—P3—O7	101.25 (9)	C10—C9—H9	120.0
P1—O3—P3i	134.42 (10)	C9—C10—C5	118.8 (2)
P1—O4—P2	133.32 (10)	C9—C10—H10	120.6
P2—O7—P3	133.71 (9)	C5—C10—H10	120.6
H1W1—OW1—H2W1	113.9	C6—C11—H13	109.5
H1W2—OW2—H2W2	91.8	C6—C11—H11	109.5
H1W2—OW2—H3W2	117.1	H13—C11—H11	109.5
H2W2—OW2—H3W2	116.2	C6—C11—H14	109.5
N2—C1—C2	110.34 (16)	H13—C11—H14	109.5
N2—C1—H1A	109.6	H11—C11—H14	109.5
C2—C1—H1A	109.6	C7—C12—H122	109.5
N2—C1—H1B	109.6	C7—C12—H121	109.5
C2—C1—H1B	109.6	H122—C12—H121	109.5
H1A—C1—H1B	108.1	C7—C12—H123	109.5
N1—C2—C1	111.36 (16)	H122—C12—H123	109.5
N1—C2—H2C	109.4	H121—C12—H123	109.5
C1—C2—H2C	109.4	C5—N1—C2	113.59 (15)
N1—C2—H2D	109.4	C5—N1—C3	110.88 (14)
C1—C2—H2D	109.4	C2—N1—C3	109.11 (14)
H2C—C2—H2D	108.0	C5—N1—H1	107.7
N1—C3—C4	110.72 (15)	C2—N1—H1	107.7
N1—C3—H3A	109.5	C3—N1—H1	107.7
C4—C3—H3A	109.5	C4—N2—C1	111.35 (15)
N1—C3—H3B	109.5	C4—N2—H2A	109.4
C4—C3—H3B	109.5	C1—N2—H2A	109.4
H3A—C3—H3B	108.1	C4—N2—H2B	109.4
N2—C4—C3	110.49 (16)	C1—N2—H2B	109.4
N2—C4—H4A	109.6	H2A—N2—H2B	108.0
C3—C4—H4A	109.6
O2—P1—O3—P3i	−116.25 (16)	C5—C6—C7—C8	1.2 (3)
O1—P1—O3—P3i	16.22 (19)	C11—C6—C7—C8	−179.47 (19)
O4—P1—O3—P3i	128.25 (16)	C5—C6—C7—C12	−178.77 (18)
O2—P1—O4—P2	−31.2 (2)	C11—C6—C7—C12	0.6 (3)
O1—P1—O4—P2	−162.03 (16)	C6—C7—C8—C9	−0.2 (3)
O3—P1—O4—P2	82.82 (18)	C12—C7—C8—C9	179.7 (2)
O6—P2—O4—P1	114.23 (17)	C7—C8—C9—C10	−0.8 (4)
O5—P2—O4—P1	−17.4 (2)	C8—C9—C10—C5	0.8 (4)
O7—P2—O4—P1	−130.16 (17)	C6—C5—C10—C9	0.2 (3)
O6—P2—O7—P3	53.82 (17)	N1—C5—C10—C9	−178.9 (2)
O5—P2—O7—P3	−176.32 (13)	C6—C5—N1—C2	157.24 (16)
O4—P2—O7—P3	−59.98 (16)	C10—C5—N1—C2	−23.6 (2)
O8—P3—O7—P2	−140.97 (14)	C6—C5—N1—C3	−79.5 (2)
O9—P3—O7—P2	−9.23 (18)	C10—C5—N1—C3	99.7 (2)
O3i—P3—O7—P2	103.78 (15)	C1—C2—N1—C5	−178.79 (15)
N2—C1—C2—N1	−56.9 (2)	C1—C2—N1—C3	57.0 (2)
N1—C3—C4—N2	58.0 (2)	C4—C3—N1—C5	176.94 (15)
C10—C5—C6—C7	−1.2 (3)	C4—C3—N1—C2	−57.2 (2)
N1—C5—C6—C7	177.91 (16)	C3—C4—N2—C1	−57.5 (2)
C10—C5—C6—C11	179.48 (19)	C2—C1—N2—C4	56.8 (2)
N1—C5—C6—C11	−1.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1W1···O9	0.79	1.84	2.614 (3)	166
OW1—H2W1···O2ii	0.86	1.97	2.781 (3)	159
OW2—H1W2···O8	0.82	1.69	2.487 (2)	167
OW2—H2W2···OW1iii	0.80	1.77	2.503 (3)	152
OW2—H3W2···O6iv	0.85	1.64	2.481 (2)	178
N1—H1···O1	0.91	1.82	2.690 (2)	160
N2—H2A···O5i	0.90	1.87	2.714 (2)	156
N2—H2B···O2v	0.90	2.10	2.858 (3)	142
N2—H2B···O5v	0.90	2.28	2.916 (3)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—H1W1⋯O9	0.79	1.84	2.614 (3)	166
OW1—H2W1⋯O2i	0.86	1.97	2.781 (3)	159
OW2—H1W2⋯O8	0.82	1.69	2.487 (2)	167
OW2—H2W2⋯OW1ii	0.80	1.77	2.503 (3)	152
OW2—H3W2⋯O6iii	0.85	1.64	2.481 (2)	178
N1—H1⋯O1	0.91	1.82	2.690 (2)	160
N2—H2A⋯O5iv	0.90	1.87	2.714 (2)	156
N2—H2B⋯O2v	0.90	2.10	2.858 (3)	142
N2—H2B⋯O5v	0.90	2.28	2.916 (3)	127

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .