Poly[bis­(piperazine-1,4-diium) [(μ4-cyclo-hexa­phosphato)dilithium] tetra­hydrate]

Ameur, I.; Abid, S.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536813011756

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m305-m306

doi:10.1107/S1600536813011756

Open

access

Poly[bis(piperazine-1,4-diium) [(μ₄-cyclo-hexaphosphato)dilithium] tetrahydrate]

Iness Ameur,^a Sonia Abid,^a ^* Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a

^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: sonia.abid@fsb.rnu.tn

(Received 9 April 2013; accepted 29 April 2013; online 11 May 2013)

In the title compound, {(C₄H₁₂N₂)₂[Li₂(P₆O₁₈)]·4H₂O}_n, the phosphate ring anion, located around an inversion center, adopts a chair conformation. Adjacent P₆O₁₈ rings are linked via corner-sharing by LiO₄ tetrahedra, generating anionic porous {[Li₂(P₆O₁₈)]⁴⁻}_n layers parallel to (101). The piperazine-1,4-diium cations occupy the pores and develop hydrogen bonds with the inorganic framework. An extensive network of N—H⋯O and O—H⋯O hydrogen-bonding interactions link the components into a three-dimensional network and additional stabilization is provided by weak C—H⋯O hydrogen bonds.

Related literature

For applications of compounds with open-framework structures, see: Assani et al. (2012 ); Mahesh et al. (2002 ); Natarajan (2000 ). For related structures with cyclohexaphosphate rings, see: Abid et al. (2011 ), Amri et al. (2009 ); Marouani et al. (2010 ); For related structures with piperazine rings, see: Essid et al. (2010 ), Xu et al. (2007 ). For the synthesis of the precursor, see: Schülke & Kayser (1985 ).

Experimental

Crystal data

(C₄H₁₂N₂)₂[Li₂(P₆O₁₈)]·4H₂O
M_r = 736.08
Monoclinic, P 2₁ /c
a = 10.245 (3) Å
b = 12.966 (4) Å
c = 10.910 (4) Å
β = 111.00 (3)°
V = 1352.8 (7) Å³
Z = 2
Ag Kα radiation
λ = 0.56085 Å
μ = 0.26 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
7884 measured reflections
6469 independent reflections
3904 reflections with I > 2σ(I)
R_int = 0.038
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.128
S = 1.00
6469 reflections
202 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2A⋯O8	0.90	1.99	2.792 (3)	147
N1—H2B⋯O7ⁱ	0.90	1.88	2.763 (3)	166
N2—H3A⋯O11	0.90	1.83	2.707 (4)	165
N2—H3B⋯O4ⁱⁱ	0.90	1.91	2.802 (2)	168
O10—H110⋯O1ⁱⁱⁱ	0.84 (4)	1.99 (4)	2.792 (4)	159 (5)
O11—H111⋯O5ⁱⁱⁱ	0.84 (3)	2.49 (4)	3.001 (3)	120 (3)
O11—H111⋯O8ⁱⁱⁱ	0.84 (3)	2.07 (3)	2.826 (3)	150 (4)
O10—H210⋯O5ⁱ	0.82 (4)	1.95 (4)	2.764 (3)	170 (4)
O11—H211⋯O10ⁱⁱⁱ	0.86 (4)	1.87 (4)	2.720 (4)	170 (4)
C1—H1A⋯O6^iv	0.97	2.51	3.273 (4)	135
C4—H1D⋯O10	0.97	2.56	3.227 (4)	126
C2—H2C⋯O2^v	0.97	2.29	3.078 (3)	137
C3—H4B⋯O5ⁱⁱⁱ	0.97	2.46	3.324 (4)	148
Symmetry codes: (i) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) -x+2, -y+2, -z; (iv) -x+1, -y+2, -z; (v) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: SHELXS86 (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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813011756/pk2476sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813011756/pk2476Isup2.hkl

checkCIF report

Comment top

The area of framework materials continues to be of interest not only because of the wide variety of structures but also due to their potential applications in the areas of catalysis, sorption and separation processes (Mahesh et al., 2002) Natarajan, 2000). Much attention has been devoted to the synthesis of open-framework phosphates which exhibit a rich structural diversity and have been widely studied as catalysts, ion-exchangers and as positive electrode in the lithium and sodium batteries (Assani et al., 2012). Within this family of compounds, the resulting anionic frameworks, generally constructed from PO₄ tetrahedra that are vertex linked with MO_n polyhedra (with n = 4, 5 and 6), generate pores and channels offering suitable environment to accommodate different other cations. The piperazine (C₄N₂H₁₀), which is a common heterocyclic nitrogen compound, has been indicated as excellent template for preparing microporous materials (Xu et al., 2007). The crystal structure reported here gives another illustration of this type of material. The corresponding compound, (C₄H₁₂N₂)₂Li₂P₆O₁₈.4H₂O (I), is an organic-inorganic hybrid built of two main cyclic components, C₄H₁₂N₂ and P₆O₁₈ (Fig. 1). The phosphoric rings are interconnected by the Li⁺ cations via LiO₄ tetrahedra sharing corners to form a two-dimensional inorganic framework extending along the (101) plane as shown in Fig. 2. The diprotonated (C₄H₁₂N₂)²⁺ cations are trapped within the 10-membered ring pore of the layer, whereas the water molecules are located in the interlayer region and are grafted onto the framework oxygen atoms through hydrogen bonds (Fig. 3). The asymmetric unit of this atomic arrangement is built of one half of the P₆O₁₈ ring lying on an inversion center (1/2, 1/2, 1/2), one Li⁺ cation, two water molecules and one piperazine-1,4-diium cation. The organic and inorganic rings adopt a chair conformation with different geometrical characteristics due to their different size and flexibility. However, the P₆O₁₈ ring has (P–O and O–O) distances and (O–P–O, P–O–P and P–P–P angles) comparable to those observed in other cyclohexaphosphates having the same internal inversion symmetry (Abid et al., 2011; Amri et al., 2009; Marouani et al., 2010). The LiO₄ tetrahedra is slightly distorted with Li–O distances ranging from 1.877 (4) to 1.969 (4) Å. The smallest distance between two tetrahedral centers is 5.548 (2) Å. The organic ring has for carbon atoms (C1, C2, C3 and C4) almost coplanar (r.m.s. deviation from the mean plane = 0.014 Å) and N1 and N2 displaced from the plane by 0.672 (2) and -0.663 (2) Å, respectively. These characteristics do not differ from those particular values observed in other compounds of the piperazinium despite the different constraints of their solid states (Essid et al., 2010).

Related literature top

For applications of compounds with open-framework structures, see: Assani et al. (2012); Mahesh et al. (2002); Natarajan (2000). For related structures with cyclohexaphosphate rings, see: Abid et al. (2011), Amri et al. (2009); Marouani et al. (2010); For related structures with piperazine rings, see: Essid et al. (2010), Xu et al. (2007). For the synthesis of the precursor, see: Schülke & Kayser (1985).

Experimental top

Crystals of the title compound were prepared by adding dropwise and stirring an ethanolic solution (5 mL) of piperazine (10 mmol) then an aquous solution (10 mL) of KOH (10 mmol) to an aqueous solution (10 mL) of cyclohexaphosphoric acid (5 mmol). Colourless prismatic crystals were obtained after a slow evaporation over a few days at ambient temperature. The cyclohexaphosphoric acid H₆P₆O₁₈,was produced from Li₆P₆O₁₈.6H₂O, prepared according to the procedure of Schülke and Kayser (Schülke & Kayser, 1985), through an ion-exchange resin in H-state (Amberlite IR 120).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (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).

Figures top

	Fig. 1. An ellipsoid plot of (I) with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
	Fig. 2. Projection in the [101] direction, showing the pores and their occupancy by the organic groups.
	Fig. 3. Projection of the framework of (I) along the c direction.

Poly[bis(piperazine-1,4-diium) [(µ₄-cyclo-hexaphosphato)dilithium] tetrahydrate] top

Crystal data top

(C₄H₁₂N₂)₂[Li₂(P₆O₁₈)]·4H₂O	F(000) = 760
M_r = 736.08	D_x = 1.807 Mg m⁻³
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.245 (3) Å	θ = 9.1–10.9°
b = 12.966 (4) Å	µ = 0.26 mm⁻¹
c = 10.910 (4) Å	T = 293 K
β = 111.00 (3)°	Parallelepiped, colourless
V = 1352.8 (7) Å³	0.50 × 0.40 × 0.30 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.038
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.0°
Graphite monochromator	h = −17→15
non–profiled ω–scans	k = −3→21
7884 measured reflections	l = 0→18
6469 independent reflections	2 standard reflections every 120 min
3904 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.059P)²] where P = (F_o² + 2F_c²)/3
6469 reflections	(Δ/σ)_max = 0.001
202 parameters	Δρ_max = 0.57 e Å⁻³
6 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

(C₄H₁₂N₂)₂[Li₂(P₆O₁₈)]·4H₂O	V = 1352.8 (7) Å³
M_r = 736.08	Z = 2
Monoclinic, P2₁/c	Ag Kα radiation, λ = 0.56085 Å
a = 10.245 (3) Å	µ = 0.26 mm⁻¹
b = 12.966 (4) Å	T = 293 K
c = 10.910 (4) Å	0.50 × 0.40 × 0.30 mm
β = 111.00 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.038
7884 measured reflections	2 standard reflections every 120 min
6469 independent reflections	intensity decay: 1%
3904 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.050	6 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.57 e Å⁻³
6469 reflections	Δρ_min = −0.47 e Å⁻³
202 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
P1	0.67085 (5)	0.82511 (4)	0.10243 (4)	0.01597 (10)
P2	0.73450 (5)	0.99726 (4)	0.28486 (5)	0.01656 (10)
P3	0.60626 (5)	1.16305 (4)	0.09894 (5)	0.01660 (10)
O3	0.75517 (14)	0.92532 (11)	0.17300 (12)	0.0195 (3)
O6	0.61176 (15)	1.07330 (12)	0.20122 (14)	0.0232 (3)
O5	0.86457 (16)	1.05454 (13)	0.34765 (15)	0.0287 (3)
O2	0.6560 (2)	0.75209 (12)	0.19975 (15)	0.0325 (4)
O4	0.67240 (16)	0.93559 (11)	0.36583 (13)	0.0227 (3)
O1	0.73374 (16)	0.78864 (13)	0.00746 (14)	0.0267 (3)
O8	0.73427 (15)	1.16386 (13)	0.06704 (14)	0.0251 (3)
O7	0.56459 (15)	1.26004 (11)	0.14913 (14)	0.0232 (3)
O9	0.52184 (15)	0.87728 (12)	0.02453 (14)	0.0265 (3)
N1	0.7657 (2)	1.11939 (14)	−0.17128 (17)	0.0267 (4)
H2A	0.7908	1.1407	−0.0875	0.032*
H2B	0.7086	1.1673	−0.2230	0.032*
C1	0.6902 (3)	1.01996 (18)	−0.1870 (2)	0.0304 (5)
H1A	0.6079	1.0284	−0.1637	0.036*
H1B	0.7501	0.9687	−0.1291	0.036*
C4	0.8925 (2)	1.1093 (2)	−0.2064 (2)	0.0354 (5)
H1C	0.9576	1.0617	−0.1464	0.042*
H1D	0.9381	1.1758	−0.1984	0.042*
C3	0.8530 (3)	1.0702 (2)	−0.3449 (2)	0.0335 (5)
H4A	0.7966	1.1217	−0.4054	0.040*
H4B	0.9370	1.0592	−0.3647	0.040*
N2	0.7735 (2)	0.97230 (15)	−0.36309 (18)	0.0290 (4)
H3A	0.8288	0.9229	−0.3127	0.035*
H3B	0.7476	0.9522	−0.4474	0.035*
Li1	0.6251 (4)	0.7890 (3)	0.3536 (3)	0.0246 (7)
C2	0.6474 (3)	0.98435 (18)	−0.3276 (2)	0.0307 (5)
H2C	0.5984	0.9190	−0.3383	0.037*
H2D	0.5846	1.0344	−0.3853	0.037*
O10	1.0185 (2)	1.28956 (19)	0.0074 (2)	0.0502 (6)
O11	0.9729 (2)	0.8504 (2)	−0.1959 (3)	0.0704 (9)
H110	1.094 (3)	1.281 (4)	−0.006 (4)	0.106*
H210	0.967 (4)	1.330 (3)	−0.047 (4)	0.106*
H111	1.058 (2)	0.863 (4)	−0.179 (4)	0.106*
H211	0.969 (5)	0.802 (3)	−0.144 (4)	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0187 (2)	0.0152 (2)	0.01382 (18)	0.00116 (17)	0.00556 (15)	−0.00189 (16)
P2	0.0190 (2)	0.0153 (2)	0.01505 (19)	−0.00225 (17)	0.00565 (15)	−0.00241 (16)
P3	0.0162 (2)	0.0158 (2)	0.01738 (19)	0.00004 (17)	0.00551 (15)	−0.00147 (16)
O3	0.0212 (6)	0.0209 (6)	0.0181 (6)	−0.0030 (5)	0.0091 (5)	−0.0058 (5)
O6	0.0217 (7)	0.0207 (7)	0.0302 (7)	0.0029 (5)	0.0128 (6)	0.0062 (6)
O5	0.0250 (7)	0.0285 (8)	0.0271 (7)	−0.0091 (6)	0.0027 (6)	−0.0082 (6)
O2	0.0594 (12)	0.0183 (7)	0.0234 (7)	−0.0060 (7)	0.0191 (7)	−0.0004 (6)
O4	0.0337 (8)	0.0192 (6)	0.0185 (6)	−0.0016 (6)	0.0137 (6)	0.0005 (5)
O1	0.0254 (7)	0.0347 (8)	0.0224 (6)	0.0018 (6)	0.0114 (6)	−0.0110 (6)
O8	0.0205 (6)	0.0345 (8)	0.0224 (6)	−0.0001 (6)	0.0103 (5)	0.0014 (6)
O7	0.0242 (7)	0.0161 (6)	0.0275 (7)	0.0000 (5)	0.0071 (6)	−0.0063 (5)
O9	0.0196 (7)	0.0258 (7)	0.0267 (7)	0.0058 (6)	−0.0007 (5)	−0.0122 (6)
N1	0.0352 (10)	0.0237 (9)	0.0192 (7)	0.0056 (7)	0.0076 (7)	−0.0028 (6)
C1	0.0372 (12)	0.0262 (10)	0.0362 (11)	0.0027 (9)	0.0235 (10)	0.0068 (9)
C4	0.0259 (11)	0.0373 (13)	0.0395 (12)	−0.0065 (10)	0.0075 (9)	−0.0058 (10)
C3	0.0349 (12)	0.0400 (13)	0.0333 (11)	0.0017 (10)	0.0215 (10)	0.0040 (10)
N2	0.0398 (11)	0.0255 (9)	0.0213 (8)	0.0097 (8)	0.0104 (7)	−0.0012 (7)
Li1	0.0339 (19)	0.0211 (17)	0.0196 (15)	−0.0037 (15)	0.0106 (14)	0.0038 (13)
C2	0.0304 (11)	0.0208 (10)	0.0384 (12)	−0.0015 (8)	0.0091 (9)	−0.0031 (9)
O10	0.0547 (13)	0.0556 (13)	0.0526 (12)	0.0314 (11)	0.0343 (11)	0.0273 (10)
O11	0.0229 (9)	0.0848 (19)	0.1003 (19)	0.0123 (11)	0.0183 (11)	0.0638 (16)

Geometric parameters (Å, º) top

P1—O2	1.4707 (16)	N1—H2B	0.9000
P1—O1	1.4801 (15)	C1—C2	1.509 (3)
P1—O3	1.5970 (15)	C1—H1A	0.9700
P1—O9	1.6063 (16)	C1—H1B	0.9700
P1—Li1	2.978 (4)	C4—C3	1.505 (3)
P1—Li1ⁱ	2.978 (4)	C4—H1C	0.9700
P2—O5	1.4636 (16)	C4—H1D	0.9700
P2—O4	1.4925 (15)	C3—N2	1.483 (3)
P2—O6	1.6011 (16)	C3—H4A	0.9700
P2—O3	1.6091 (14)	C3—H4B	0.9700
P2—Li1	3.117 (4)	N2—C2	1.483 (3)
P3—O8	1.4725 (15)	N2—H3A	0.9000
P3—O7	1.4937 (15)	N2—H3B	0.9000
P3—O9ⁱⁱ	1.5945 (16)	Li1—O1^iv	1.931 (4)
P3—O6	1.5991 (15)	Li1—O7^v	1.969 (4)
P3—Li1ⁱⁱⁱ	3.071 (4)	Li1—P1^iv	2.978 (4)
O2—Li1	1.877 (4)	Li1—P3^v	3.071 (4)
O4—Li1	1.954 (4)	C2—H2C	0.9700
O1—Li1ⁱ	1.931 (4)	C2—H2D	0.9700
O7—Li1ⁱⁱⁱ	1.969 (4)	O10—H110	0.846 (18)
O9—P3ⁱⁱ	1.5945 (16)	O10—H210	0.822 (18)
N1—C1	1.482 (3)	O11—H111	0.840 (18)
N1—C4	1.485 (3)	O11—H211	0.851 (18)
N1—H2A	0.9000

O2—P1—O1	118.91 (10)	N1—C4—H1C	109.6
O2—P1—O3	110.72 (9)	C3—C4—H1C	109.6
O1—P1—O3	107.54 (9)	N1—C4—H1D	109.6
O2—P1—O9	109.16 (11)	C3—C4—H1D	109.6
O1—P1—O9	109.50 (9)	H1C—C4—H1D	108.2
O3—P1—O9	99.19 (8)	N2—C3—C4	111.03 (19)
O1—P1—Li1	147.71 (11)	N2—C3—H4A	109.4
O3—P1—Li1	85.45 (9)	C4—C3—H4A	109.4
O9—P1—Li1	96.89 (10)	N2—C3—H4B	109.4
O2—P1—Li1ⁱ	108.38 (10)	C4—C3—H4B	109.4
O1—P1—Li1ⁱ	33.78 (10)	H4A—C3—H4B	108.0
O3—P1—Li1ⁱ	136.45 (9)	C3—N2—C2	111.29 (17)
O9—P1—Li1ⁱ	85.28 (10)	C3—N2—H3A	109.4
Li1—P1—Li1ⁱ	137.36 (7)	C2—N2—H3A	109.4
O5—P2—O4	120.31 (9)	C3—N2—H3B	109.4
O5—P2—O6	110.58 (10)	C2—N2—H3B	109.4
O4—P2—O6	104.65 (8)	H3A—N2—H3B	108.0
O5—P2—O3	107.69 (9)	O2—Li1—O1^iv	114.5 (2)
O4—P2—O3	109.77 (9)	O2—Li1—O4	101.07 (17)
O6—P2—O3	102.40 (8)	O1^iv—Li1—O4	113.3 (2)
O5—P2—Li1	132.28 (10)	O2—Li1—O7^v	114.8 (2)
O4—P2—Li1	29.20 (9)	O1^iv—Li1—O7^v	99.89 (17)
O6—P2—Li1	113.21 (9)	O4—Li1—O7^v	113.9 (2)
O3—P2—Li1	80.59 (9)	O2—Li1—P1	23.82 (7)
O8—P3—O7	118.45 (10)	O1^iv—Li1—P1	130.56 (19)
O8—P3—O9ⁱⁱ	109.62 (9)	O4—Li1—P1	78.06 (12)
O7—P3—O9ⁱⁱ	109.20 (8)	O7^v—Li1—P1	119.75 (16)
O8—P3—O6	111.01 (9)	O2—Li1—P1^iv	131.81 (19)
O7—P3—O6	107.46 (9)	O1^iv—Li1—P1^iv	25.22 (7)
O9ⁱⁱ—P3—O6	99.40 (9)	O4—Li1—P1^iv	117.81 (16)
O8—P3—Li1ⁱⁱⁱ	147.42 (10)	O7^v—Li1—P1^iv	75.57 (12)
O7—P3—Li1ⁱⁱⁱ	31.94 (9)	P1—Li1—P1^iv	153.12 (15)
O9ⁱⁱ—P3—Li1ⁱⁱⁱ	82.27 (9)	O2—Li1—P3^v	113.75 (17)
O6—P3—Li1ⁱⁱⁱ	96.05 (9)	O1^iv—Li1—P3^v	79.37 (12)
P1—O3—P2	129.92 (9)	O4—Li1—P3^v	133.85 (18)
P3—O6—P2	132.05 (9)	O7^v—Li1—P3^v	23.66 (7)
P1—O2—Li1	125.14 (15)	P1—Li1—P3^v	128.64 (13)
P2—O4—Li1	128.93 (14)	P1^iv—Li1—P3^v	57.37 (7)
P1—O1—Li1ⁱ	121.01 (15)	O2—Li1—P2	79.37 (12)
P3—O7—Li1ⁱⁱⁱ	124.41 (14)	O1^iv—Li1—P2	121.05 (17)
P3ⁱⁱ—O9—P1	130.33 (10)	O4—Li1—P2	21.87 (6)
C1—N1—C4	111.21 (18)	O7^v—Li1—P2	126.83 (17)
C1—N1—H2A	109.4	P1—Li1—P2	56.88 (6)
C4—N1—H2A	109.4	P1^iv—Li1—P2	134.19 (13)
C1—N1—H2B	109.4	P3^v—Li1—P2	150.11 (14)
C4—N1—H2B	109.4	N2—C2—C1	109.55 (19)
H2A—N1—H2B	108.0	N2—C2—H2C	109.8
N1—C1—C2	109.47 (17)	C1—C2—H2C	109.8
N1—C1—H1A	109.8	N2—C2—H2D	109.8
C2—C1—H1A	109.8	C1—C2—H2D	109.8
N1—C1—H1B	109.8	H2C—C2—H2D	108.2
C2—C1—H1B	109.8	H110—O10—H210	111 (3)
H1A—C1—H1B	108.2	H111—O11—H211	107 (3)
N1—C4—C3	110.11 (19)

O2—P1—O3—P2	−48.29 (15)	O3—P1—Li1—O1^iv	−91.0 (2)
O1—P1—O3—P2	−179.72 (12)	O9—P1—Li1—O1^iv	170.3 (2)
O9—P1—O3—P2	66.34 (13)	Li1ⁱ—P1—Li1—O1^iv	79.8 (4)
Li1—P1—O3—P2	−29.92 (13)	O2—P1—Li1—O4	164.8 (3)
Li1ⁱ—P1—O3—P2	159.16 (13)	O1—P1—Li1—O4	135.73 (16)
O5—P2—O3—P1	160.31 (12)	O3—P1—Li1—O4	19.62 (12)
O4—P2—O3—P1	27.66 (14)	O9—P1—Li1—O4	−79.12 (13)
O6—P2—O3—P1	−83.09 (13)	Li1ⁱ—P1—Li1—O4	−169.63 (10)
Li1—P2—O3—P1	28.79 (13)	O2—P1—Li1—O7^v	−84.4 (2)
O8—P3—O6—P2	8.74 (17)	O1—P1—Li1—O7^v	−113.4 (2)
O7—P3—O6—P2	−122.24 (13)	O3—P1—Li1—O7^v	130.49 (19)
O9ⁱⁱ—P3—O6—P2	124.08 (14)	O9—P1—Li1—O7^v	31.8 (2)
Li1ⁱⁱⁱ—P3—O6—P2	−152.78 (14)	Li1ⁱ—P1—Li1—O7^v	−58.8 (3)
O5—P2—O6—P3	46.37 (16)	O2—P1—Li1—P1^iv	35.2 (3)
O4—P2—O6—P3	177.31 (12)	O1—P1—Li1—P1^iv	6.1 (4)
O3—P2—O6—P3	−68.15 (15)	O3—P1—Li1—P1^iv	−110.0 (3)
Li1—P2—O6—P3	−153.10 (13)	O9—P1—Li1—P1^iv	151.3 (3)
O1—P1—O2—Li1	162.77 (19)	Li1ⁱ—P1—Li1—P1^iv	60.8 (5)
O3—P1—O2—Li1	37.5 (2)	O2—P1—Li1—P3^v	−57.7 (2)
O9—P1—O2—Li1	−70.7 (2)	O1—P1—Li1—P3^v	−86.8 (2)
Li1ⁱ—P1—O2—Li1	−162.0 (2)	O3—P1—Li1—P3^v	157.13 (17)
O5—P2—O4—Li1	−123.45 (19)	O9—P1—Li1—P3^v	58.39 (17)
O6—P2—O4—Li1	111.54 (19)	Li1ⁱ—P1—Li1—P3^v	−32.1 (3)
O3—P2—O4—Li1	2.3 (2)	O2—P1—Li1—P2	158.8 (2)
O2—P1—O1—Li1ⁱ	79.75 (19)	O1—P1—Li1—P2	129.75 (16)
O3—P1—O1—Li1ⁱ	−153.48 (16)	O3—P1—Li1—P2	13.64 (6)
O9—P1—O1—Li1ⁱ	−46.64 (19)	O9—P1—Li1—P2	−85.09 (7)
Li1—P1—O1—Li1ⁱ	96.36 (17)	Li1ⁱ—P1—Li1—P2	−175.60 (15)
O8—P3—O7—Li1ⁱⁱⁱ	160.49 (16)	O5—P2—Li1—O2	−110.53 (15)
O9ⁱⁱ—P3—O7—Li1ⁱⁱⁱ	34.12 (19)	O4—P2—Li1—O2	172.7 (3)
O6—P3—O7—Li1ⁱⁱⁱ	−72.80 (18)	O6—P2—Li1—O2	94.41 (14)
O2—P1—O9—P3ⁱⁱ	−83.58 (15)	O3—P2—Li1—O2	−5.13 (12)
O1—P1—O9—P3ⁱⁱ	48.19 (17)	O5—P2—Li1—O1^iv	1.8 (3)
O3—P1—O9—P3ⁱⁱ	160.59 (13)	O4—P2—Li1—O1^iv	−75.0 (2)
Li1—P1—O9—P3ⁱⁱ	−112.92 (15)	O6—P2—Li1—O1^iv	−153.24 (17)
Li1ⁱ—P1—O9—P3ⁱⁱ	24.26 (15)	O3—P2—Li1—O1^iv	107.2 (2)
C4—N1—C1—C2	−59.4 (2)	O5—P2—Li1—O4	76.8 (2)
C1—N1—C4—C3	57.2 (3)	O6—P2—Li1—O4	−78.3 (2)
N1—C4—C3—N2	−55.0 (3)	O3—P2—Li1—O4	−177.8 (2)
C4—C3—N2—C2	56.3 (3)	O5—P2—Li1—O7^v	136.35 (18)
P1—O2—Li1—O1^iv	−137.38 (19)	O4—P2—Li1—O7^v	59.6 (2)
P1—O2—Li1—O4	−15.2 (3)	O6—P2—Li1—O7^v	−18.7 (2)
P1—O2—Li1—O7^v	107.9 (2)	O3—P2—Li1—O7^v	−118.2 (2)
P1—O2—Li1—P1^iv	−159.56 (17)	O5—P2—Li1—P1	−119.08 (11)
P1—O2—Li1—P3^v	133.82 (15)	O4—P2—Li1—P1	164.1 (2)
P1—O2—Li1—P2	−17.96 (18)	O6—P2—Li1—P1	85.86 (9)
P2—O4—Li1—O2	−7.3 (3)	O3—P2—Li1—P1	−13.68 (6)
P2—O4—Li1—O1^iv	115.71 (19)	O5—P2—Li1—P1^iv	29.2 (3)
P2—O4—Li1—O7^v	−130.98 (17)	O4—P2—Li1—P1^iv	−47.53 (18)
P2—O4—Li1—P1	−13.53 (18)	O6—P2—Li1—P1^iv	−125.81 (18)
P2—O4—Li1—P1^iv	143.28 (13)	O3—P2—Li1—P1^iv	134.6 (2)
P2—O4—Li1—P3^v	−146.51 (15)	O5—P2—Li1—P3^v	129.8 (2)
O1—P1—Li1—O2	−29.0 (3)	O4—P2—Li1—P3^v	53.0 (2)
O3—P1—Li1—O2	−145.1 (2)	O6—P2—Li1—P3^v	−25.3 (3)
O9—P1—Li1—O2	116.1 (2)	O3—P2—Li1—P3^v	−124.8 (3)
Li1ⁱ—P1—Li1—O2	25.6 (3)	C3—N2—C2—C1	−58.0 (2)
O2—P1—Li1—O1^iv	54.2 (2)	N1—C1—C2—N2	59.0 (2)
O1—P1—Li1—O1^iv	25.1 (4)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+2, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2; (v) −x+1, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2A···O8	0.90	1.99	2.792 (3)	147
N1—H2B···O7^vi	0.90	1.88	2.763 (3)	166
N2—H3A···O11	0.90	1.83	2.707 (4)	165
N2—H3B···O4^vii	0.90	1.91	2.802 (2)	168
O10—H110···O1^viii	0.84 (4)	1.99 (4)	2.792 (4)	159 (5)
O11—H111···O5^viii	0.84 (3)	2.49 (4)	3.001 (3)	120 (3)
O11—H111···O8^viii	0.84 (3)	2.07 (3)	2.826 (3)	150 (4)
O10—H210···O5^vi	0.82 (4)	1.95 (4)	2.764 (3)	170 (4)
O11—H211···O10^viii	0.86 (4)	1.87 (4)	2.720 (4)	170 (4)
C1—H1A···O6ⁱⁱ	0.97	2.51	3.273 (4)	135
C4—H1D···O10	0.97	2.56	3.227 (4)	126
C2—H2C···O2ⁱ	0.97	2.29	3.078 (3)	137
C3—H4B···O5^viii	0.97	2.46	3.324 (4)	148

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, −y+2, −z; (vi) x, −y+5/2, z−1/2; (vii) x, y, z−1; (viii) −x+2, −y+2, −z.

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)₂[Li₂(P₆O₁₈)]·4H₂O
M_r	736.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.245 (3), 12.966 (4), 10.910 (4)
β (°)	111.00 (3)
V (Å³)	1352.8 (7)
Z	2
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.26
Crystal size (mm)	0.50 × 0.40 × 0.30

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7884, 6469, 3904
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.128, 1.00
No. of reflections	6469
No. of parameters	202
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.47

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2A···O8	0.9000	1.9900	2.792 (3)	147.00
N1—H2B···O7ⁱ	0.9000	1.8800	2.763 (3)	166.00
N2—H3A···O11	0.9000	1.8300	2.707 (4)	165.00
N2—H3B···O4ⁱⁱ	0.9000	1.9100	2.802 (2)	168.00
O10—H110···O1ⁱⁱⁱ	0.84 (4)	1.99 (4)	2.792 (4)	159 (5)
O11—H111···O5ⁱⁱⁱ	0.84 (3)	2.49 (4)	3.001 (3)	120 (3)
O11—H111···O8ⁱⁱⁱ	0.84 (3)	2.07 (3)	2.826 (3)	150 (4)
O10—H210···O5ⁱ	0.82 (4)	1.95 (4)	2.764 (3)	170 (4)
O11—H211···O10ⁱⁱⁱ	0.86 (4)	1.87 (4)	2.720 (4)	170 (4)
C1—H1A···O6^iv	0.9700	2.5100	3.273 (4)	135.00
C4—H1D···O10	0.9700	2.5600	3.227 (4)	126.00
C2—H2C···O2^v	0.9700	2.2900	3.078 (3)	137.00
C3—H4B···O5ⁱⁱⁱ	0.9700	2.4600	3.324 (4)	148.00

Symmetry codes: (i) x, −y+5/2, z−1/2; (ii) x, y, z−1; (iii) −x+2, −y+2, −z; (iv) −x+1, −y+2, −z; (v) x, −y+3/2, z−1/2.

Acknowledgements

This work was supported by the Tunisian Ministry of HEScR and the Deanship of Scientific Research at King Saud University (research group project No. RGP-VPP-089).

References

Abid, S., Al-Deyab, S. S. & Rzaigui, M. (2011). Acta Cryst. E67, m1549–m1550. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Amri, O., Abid, S. & Rzaigui, M. (2009). Acta Cryst. E65, o654. Web of Science CSD CrossRef IUCr Journals Google Scholar
Assani, A., Saadi, M., Zriouil, M. & El Ammari, L. (2012). Acta Cryst. E68, i30. CrossRef IUCr Journals Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Essid, M., Marouani, H., Rzaigui, M. & Al-Deyab, S. S. (2010). Acta Cryst. E66, o2244–o2245. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Mahesh, S., Green, M. A. & Natarajan, S. (2002). J. Solid State Chem. 165, 334–342. Web of Science CSD CrossRef CAS Google Scholar
Marouani, H., Rzaigui, M. & Al-Deyab, S. S. (2010). Acta Cryst. E66, o702. Web of Science CSD CrossRef IUCr Journals Google Scholar
Natarajan, S. (2000). Proc. Indian Acad. Sci. Chem. Sci. 112, 249–272. CrossRef CAS Google Scholar
Schülke, U. & Kayser, R. (1985). Z. Anorg. Allg. Chem. 531, 167–175. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, H., Dong, P., Liu, L., Wang, J.-G., Deng, F. & Dong, J.-X. (2007). J. Porous Mater. 14, 97–101. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.