Bis(adamantan-1-aminium) hydrogen phosphate fumaric acid sesquisolvate

Mrad, M.L.; Zeller, M.; Hernandez, K.J.; Rzaigui, M.; Ben Nasr, C.

doi:10.1107/S1600536812032734

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2531-o2532

https://doi.org/10.1107/S1600536812032734

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Bis(adamantan-1-aminium) hydrogen phosphate fumaric acid sesquisolvate

Mohamed Lahbib Mrad,^a Matthias Zeller,^b Kristen J. Hernandez,^b Mohamed Rzaigui ^a and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, and ^bYoungstown State University, Department of Chemistry, One University Plaza, Youngstown, Ohio 44555-3663, USA
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 6 July 2012; accepted 18 July 2012; online 25 July 2012)

The asymmetric unit of the title compound, 2C₁₀H₁₈N⁺·HPO₄²⁻·1.5C₄H₄O₄, contains two adamantan-1-aminium cations, one hydrogen phosphate anion, and one and a half molecules of fumaric acid, one of which exhibits crystallographic inversion symmetry. Each HPO₄²⁻ anion is hydrogen bonded, via all of its O atoms, to four NH₃⁺ groups of the adamantan-1-aminium cations, forming chains along [100]. These chains are, in turn, interconnected via a set of O—H⋯O hydrogen bonds involving the fumaric acid solvent molecules, forming layers parallel to (001). Weak C—H⋯O interactions lead to a consolidation of the three-dimensional set-up.

Related literature

For common applications of organic phosphate complexes, see: Coombs et al. (1997 ); Gani & Wilkie (1995 ); Masse et al. (1993 ); Oliver et al. (1995 ); Wang et al. (1996 ). For details of graph-set motifs and theory, see: Bernstein et al. (1995 ). For reference structural data, see: Kaabi et al. (2004 ); Chtioui & Jouini (2006 ).

Experimental

Crystal data

2C₁₀H₁₈N⁺·HO₄P²⁻·1.5C₄H₄O₄
M_r = 574.59
Monoclinic, P 2₁ /n
a = 12.7555 (16) Å
b = 11.1850 (14) Å
c = 20.251 (2) Å
β = 105.795 (2)°
V = 2780.1 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.45 × 0.35 × 0.25 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.680, T_max = 0.746
24141 measured reflections
9001 independent reflections
7424 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.113
S = 1.02
9001 reflections
366 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O7ⁱ	0.902 (16)	1.667 (16)	2.5665 (12)	175.0 (15)
O5—H5⋯O2	1.013 (17)	1.486 (17)	2.4918 (12)	171.1 (16)
O8—H8⋯O3ⁱⁱ	1.073 (18)	1.396 (18)	2.4659 (12)	174.6 (17)
O10—H10⋯O4	0.955 (18)	1.595 (18)	2.5407 (12)	170.0 (16)
N1A—H1AA⋯O6ⁱⁱⁱ	0.91	1.93	2.8242 (13)	168
N1A—H1AB⋯O2ⁱⁱⁱ	0.91	2.64	3.1486 (12)	117
N1A—H1AC⋯O2	0.91	1.87	2.7821 (13)	175
N1B—H1BA⋯O3^iv	0.91	1.91	2.8201 (13)	174
N1B—H1BB⋯O4	0.91	1.89	2.8046 (13)	179
N1B—H1BC⋯O9^iv	0.91	1.99	2.9016 (13)	177
C3—H3⋯O5	0.95	2.41	2.7379 (14)	100
C6—H6⋯O10^v	0.95	2.44	2.7730 (15)	100
C7B—H7BA⋯O7^vi	0.99	2.50	3.4742 (16)	167
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z; (iii) -x+1, -y+1, -z+1; (iv) -x, -y+1, -z+1; (v) -x, -y, -z+1; (vi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011 ); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812032734/wm2659sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032734/wm2659Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032734/wm2659Isup3.cml

checkCIF report

Comment top

Organic phosphate complexes have been widely studied due to their numerous practical and potential uses in various fields in biomolecular sciences, catalysis, fuel cell research, liquid crystal-material development and quadratic non-linear optics studies (Coombs et al., 1997; Gani & Wilkie, 1995; Masse et al., 1993; Oliver et al., 1995; Wang et al., 1996). Here, we report the synthesis and the crystal structure of a new hydrogen phosphate with an organic cation, (C₁₀H₁₈N)₂⁺^.HPO₄^-^.1.5(C₄H₄O₄), (I), formed by the reaction of adamantan-1-aminium fumarate with orthophosphoric acid.

Reaction of the starting materials led to a partial proton transfer from the phosphoric acid to the fumarate anions, which are found to be fully protonated in the structure of compound (I). The asymmetric unit of compound (I) contains one hydrogen phosphate anion, two adamantan-1-aminium cations and one and a half molecules of fumaric acid (Fig. 1), one of which is located on a crystallographic inversion center. Arrangement of the ions and molecules in the crystal structure is governed by a series of strong O—H···O and one N—H···O hydrogen bonds, augmented by a few C—H···O interactions (Table 1, Figures 2–4). In the structure, each HPO₄^2- anion is hydrogen-bonded through all of its oxygen atoms to four NH₃⁺ groups of the adamantan-1-aminium cations to build infinite hydrogen bonded chains along [100] with an R₄⁴(12) graph set motif (Bernstein et al., 1995) (Fig. 2). These chains are in turn interconnected via hydrogen bonds involving the fumaric acid molecules, with two distinct types of hydrogen bonding patterns. For the centrosymmetric fumaric acid molecule both carboxyl groups undergo one O—H···O and one N—H···O hydrogen bond. With respect to the O—H···O bonds, the furmaric acid is the H-bond donor and a phosphate O atom is the corresponding acceptor. With respect to the N—H···O bonds, the H donor is an adamantyl ammonium group and the corresponding acceptor the not-protonated fumaric acid oxygen atom. For the second fumaric acid molecule (located on a general position), the situation is different. One of the two carboxyl groups has a hydrogen bonding pattern similar to that of the centrosymmetric molecule. The second carboxyl group, on the other hand, undergoes two O—H···O hydrogen bonds with two oxygen atoms of the same phosphate anion, with an R₂²(8) graph set motif. While the two types of fumaric acid molecules are thus clearly distinct, their roles in the construction of the crystal structure are similar.

The two types of fumaric acid molecules are arranged in skewed stacks where they alternate with one another in an ABBA pattern, with A being the centrosymmetric fumaric acid molecule (Fig. 3). The stacks extend along [100], in-between the chains of adamantan-1-aminium cations and monohydrogenophosphate anions. Pairs of B molecules in the ABBA pattern show π–π stacking interactions with an interplanar spacing of 3.108 Å, and a centroid-to-centroid distance of 4.144 Å, indicating substantial slippage of the molecules against one another. Neighboring A and B molecules are not parallel; the molecular planes are tilted by ca 10.8° against one another. Their centroid-to-centroid distance is 4.306 Å, and actual close contacts are limited to some O···O interactions. A and B molecules are not π—π-stacked with one another.

Through their O—H···O and N—H···O hydrogen bonds to the hydrogen phosphate anions and adamantan-1-aminium cations, the fumaric acid molecules give rise to two-dimensional infinite layers parallel to (001) (Fig. 3). Fig. 4 shows that the adamantan-1-aminium cation and monohydrogenophosphate anion chains extend along [100] at (x, 0, 0) and (x, 1/2, 1/2), while the layers cross the unit cell at c = n/2. The adamantan-1-aminium cations of parallel layers interdigitate with one another and are located in alternate pairs on either side of the layers, leading to an extended three-dimensional structure (Fig. 4), which is further consolidated by a small number of weak C—H···O interactions (Table 1).

The detailed geometry of the HPO₄^2- group shows two kinds of P—O distances. The shorter ones (1.5252 (9), 1.5330 (8) and 1.5148 (8) Å correspond to the non-protonated oxygen atoms, while the largest one (1.5946 (8) Å) is associated with the P—OH bond. This is in agreement with literature data for the monohydrogenophosphate anion in similar arrangements (e.g. Chtioui & Jouini, 2006; Kaabi et al., 2004). The O—H···O interactions show elongated O—H distances typical for very strong hydrogen bonds and range from 0.902 (16) for H1 to 1.073 (18) for H8 (Table 1).

Related literature top

For common applications of organic phosphate complexes, see: Coombs et al. (1997); Gani & Wilkie (1995); Masse et al. (1993); Oliver et al. (1995); Wang et al. (1996). For details of graph-set motifs and theory, see: Bernstein et al. (1995). For reference structural data, see: Kaabi et al. (2004); Chtioui & Jouini (2006).

Experimental top

Crystals of the title compound were prepared at room temperature by slow addition of a solution of orthophosphoric acid (3 mmol in 20 ml of water) to an alcoholic solution of adamantan-1-aminium fumarate (6 mmol in 20 ml of ethanol). The acid was added until the alcoholic solution became turbid. After filtration, the solution was allowed to slowly evaporate at room temperature over several days leading to formation of transparent prismatic crystals with suitable dimensions for single-crystal structural analysis (yield 55%). The crystals are stable for months under normal conditions of temperature and humidity.

Structure description top

For common applications of organic phosphate complexes, see: Coombs et al. (1997); Gani & Wilkie (1995); Masse et al. (1993); Oliver et al. (1995); Wang et al. (1996). For details of graph-set motifs and theory, see: Bernstein et al. (1995). For reference structural data, see: Kaabi et al. (2004); Chtioui & Jouini (2006).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular components of compound (I), showing 50% probability displacement ellipsoids and spheres of arbitrary radius for the H atoms.
	Fig. 2. Projection along [100] showing an inorganic chain in the structure of compound (I) with N—H···O hydrogen bonding interactions as broken lines.
	Fig. 3. Projection along [001] of a layer in the structure of compound (I). Hydrogen bonds are denoted as broken lines.
	Fig. 4. Projection of the structure along [100]. Hydrogen bonds are denoted as dotted lines.

Bis(adamantan-1-aminium) hydrogen phosphate fumaric acid sesquisolvate top

Crystal data top

2C₁₀H₁₈N⁺·HO₄P²⁻·1.5C₄H₄O₄	F(000) = 1232
M_r = 574.59	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6149 reflections
a = 12.7555 (16) Å	θ = 2.5–31.5°
b = 11.1850 (14) Å	µ = 0.16 mm⁻¹
c = 20.251 (2) Å	T = 100 K
β = 105.795 (2)°	Block, colourless
V = 2780.1 (6) Å³	0.45 × 0.35 × 0.25 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	9001 independent reflections
Radiation source: fine-focus sealed tube	7424 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 32.2°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −18→18
T_min = 0.680, T_max = 0.746	k = −16→16
24141 measured reflections	l = −27→28

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0581P)² + 0.684P] where P = (F_o² + 2F_c²)/3
9001 reflections	(Δ/σ)_max = 0.001
366 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

2C₁₀H₁₈N⁺·HO₄P²⁻·1.5C₄H₄O₄	V = 2780.1 (6) Å³
M_r = 574.59	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.7555 (16) Å	µ = 0.16 mm⁻¹
b = 11.1850 (14) Å	T = 100 K
c = 20.251 (2) Å	0.45 × 0.35 × 0.25 mm
β = 105.795 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	9001 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	7424 reflections with I > 2σ(I)
T_min = 0.680, T_max = 0.746	R_int = 0.028
24141 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.51 e Å⁻³
9001 reflections	Δρ_min = −0.39 e Å⁻³
366 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
C1	0.41137 (10)	0.15548 (10)	0.52298 (6)	0.0156 (2)
C2	0.39579 (10)	0.02404 (10)	0.52724 (6)	0.0161 (2)
H2	0.4500	−0.0216	0.5586	0.019*
C3	0.30842 (10)	−0.03144 (10)	0.48851 (6)	0.0171 (2)
H3	0.2547	0.0141	0.4567	0.020*
C4	0.29194 (10)	−0.16227 (10)	0.49331 (6)	0.0166 (2)
O5	0.34561 (7)	0.20545 (7)	0.46935 (4)	0.01976 (18)
H5	0.3451 (13)	0.2959 (15)	0.4725 (8)	0.030*
O6	0.48114 (8)	0.20734 (7)	0.56762 (5)	0.0228 (2)
O7	0.35313 (8)	−0.22223 (8)	0.53892 (5)	0.0284 (2)
O8	0.21020 (8)	−0.20382 (8)	0.44631 (5)	0.0254 (2)
H8	0.2001 (15)	−0.2987 (16)	0.4495 (9)	0.038*
C5	0.01715 (10)	0.16473 (10)	0.47501 (6)	0.0168 (2)
C6	−0.02584 (10)	0.04172 (10)	0.47816 (6)	0.0182 (2)
H6	−0.0940	0.0217	0.4472	0.022*
O9	−0.03696 (8)	0.23937 (8)	0.43612 (5)	0.0260 (2)
O10	0.11474 (7)	0.18302 (8)	0.51613 (5)	0.0228 (2)
H10	0.1367 (14)	0.2640 (16)	0.5132 (9)	0.034*
N1A	0.46741 (8)	0.54933 (8)	0.40323 (5)	0.01350 (18)
H1AA	0.4775	0.6270	0.4168	0.020*
H1AB	0.5325	0.5103	0.4153	0.020*
H1AC	0.4205	0.5138	0.4239	0.020*
C1A	0.42108 (8)	0.54404 (9)	0.32689 (5)	0.01162 (19)
C2A	0.40449 (9)	0.41239 (10)	0.30542 (6)	0.0147 (2)
H2AA	0.3540	0.3740	0.3285	0.018*
H2AB	0.4750	0.3695	0.3192	0.018*
C3A	0.35690 (9)	0.40584 (10)	0.22711 (6)	0.0159 (2)
H3A	0.3457	0.3203	0.2124	0.019*
C4A	0.24735 (9)	0.47186 (11)	0.20731 (6)	0.0183 (2)
H4AA	0.1966	0.4340	0.2303	0.022*
H4AB	0.2148	0.4665	0.1571	0.022*
C5A	0.26430 (9)	0.60354 (10)	0.22878 (6)	0.0166 (2)
H5A	0.1928	0.6463	0.2153	0.020*
C6A	0.31220 (9)	0.61047 (10)	0.30720 (6)	0.0151 (2)
H6AA	0.3233	0.6951	0.3218	0.018*
H6AB	0.2612	0.5736	0.3304	0.018*
C7A	0.34354 (10)	0.66261 (10)	0.19371 (6)	0.0174 (2)
H7AA	0.3543	0.7475	0.2078	0.021*
H7AB	0.3128	0.6597	0.1433	0.021*
C8A	0.45331 (9)	0.59670 (10)	0.21408 (6)	0.0151 (2)
H8A	0.5049	0.6351	0.1911	0.018*
C9A	0.43597 (9)	0.46543 (10)	0.19196 (6)	0.0168 (2)
H9AA	0.5066	0.4228	0.2047	0.020*
H9AB	0.4059	0.4607	0.1415	0.020*
C10A	0.50088 (9)	0.60313 (10)	0.29247 (6)	0.0142 (2)
H10A	0.5719	0.5613	0.3061	0.017*
H10B	0.5127	0.6876	0.3072	0.017*
N1B	0.03808 (8)	0.50606 (8)	0.59162 (5)	0.01363 (18)
H1BA	−0.0303	0.4753	0.5764	0.020*
H1BB	0.0825	0.4704	0.5691	0.020*
H1BC	0.0360	0.5862	0.5836	0.020*
C1B	0.08106 (9)	0.48352 (9)	0.66724 (5)	0.01162 (19)
C2B	0.19608 (9)	0.53554 (10)	0.69246 (6)	0.0147 (2)
H2BA	0.1943	0.6226	0.6834	0.018*
H2BB	0.2444	0.4976	0.6677	0.018*
C3B	0.23979 (9)	0.51206 (10)	0.76999 (6)	0.0158 (2)
H3B	0.3151	0.5455	0.7869	0.019*
C4B	0.16533 (10)	0.57196 (10)	0.80815 (6)	0.0175 (2)
H4BA	0.1640	0.6594	0.8004	0.021*
H4BB	0.1936	0.5572	0.8580	0.021*
C5B	0.04941 (9)	0.52090 (10)	0.78197 (6)	0.0161 (2)
H5B	0.0006	0.5598	0.8068	0.019*
C6B	0.00607 (9)	0.54468 (10)	0.70445 (6)	0.0150 (2)
H6BA	−0.0689	0.5129	0.6873	0.018*
H6BB	0.0040	0.6318	0.6956	0.018*
C7B	0.05222 (10)	0.38520 (10)	0.79445 (6)	0.0174 (2)
H7BA	0.0788	0.3688	0.8443	0.021*
H7BB	−0.0222	0.3520	0.7776	0.021*
C8B	0.12762 (9)	0.32495 (10)	0.75694 (6)	0.0157 (2)
H8B	0.1296	0.2369	0.7657	0.019*
C9B	0.24281 (9)	0.37652 (10)	0.78298 (6)	0.0174 (2)
H9BA	0.2916	0.3377	0.7589	0.021*
H9BB	0.2717	0.3605	0.8327	0.021*
C10B	0.08390 (9)	0.34840 (9)	0.67946 (6)	0.0145 (2)
H10C	0.1317	0.3096	0.6546	0.017*
H10D	0.0097	0.3146	0.6622	0.017*
O1	0.31637 (7)	0.55891 (7)	0.56349 (4)	0.01518 (16)
H1	0.3252 (13)	0.6363 (14)	0.5537 (8)	0.023*
O2	0.33124 (7)	0.42767 (7)	0.46675 (4)	0.01513 (16)
O3	0.17816 (6)	0.57897 (7)	0.44840 (4)	0.01517 (16)
O4	0.17691 (7)	0.39954 (7)	0.52248 (4)	0.01583 (16)
P1	0.24805 (2)	0.48755 (2)	0.497620 (14)	0.01113 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0193 (5)	0.0112 (4)	0.0168 (5)	−0.0023 (4)	0.0059 (4)	−0.0016 (4)
C2	0.0224 (6)	0.0105 (4)	0.0156 (5)	−0.0006 (4)	0.0057 (4)	0.0005 (4)
C3	0.0234 (6)	0.0105 (4)	0.0166 (5)	−0.0019 (4)	0.0043 (4)	0.0007 (4)
C4	0.0219 (6)	0.0107 (4)	0.0162 (5)	−0.0037 (4)	0.0036 (4)	−0.0006 (4)
O5	0.0249 (4)	0.0106 (4)	0.0205 (4)	−0.0016 (3)	0.0006 (3)	0.0001 (3)
O6	0.0289 (5)	0.0134 (4)	0.0219 (4)	−0.0050 (3)	0.0000 (4)	−0.0023 (3)
O7	0.0360 (5)	0.0137 (4)	0.0252 (5)	−0.0072 (4)	−0.0093 (4)	0.0042 (3)
O8	0.0279 (5)	0.0117 (4)	0.0279 (5)	−0.0054 (3)	−0.0072 (4)	0.0030 (3)
C5	0.0189 (5)	0.0123 (5)	0.0199 (5)	−0.0022 (4)	0.0062 (4)	0.0007 (4)
C6	0.0186 (5)	0.0117 (5)	0.0234 (6)	−0.0034 (4)	0.0043 (4)	0.0005 (4)
O9	0.0270 (5)	0.0151 (4)	0.0299 (5)	−0.0032 (3)	−0.0024 (4)	0.0068 (3)
O10	0.0200 (4)	0.0124 (4)	0.0322 (5)	−0.0042 (3)	0.0004 (4)	0.0041 (3)
N1A	0.0132 (4)	0.0131 (4)	0.0137 (4)	−0.0023 (3)	0.0028 (3)	−0.0004 (3)
C1A	0.0108 (4)	0.0111 (4)	0.0127 (5)	−0.0008 (3)	0.0028 (4)	−0.0007 (4)
C2A	0.0165 (5)	0.0110 (4)	0.0162 (5)	−0.0019 (4)	0.0035 (4)	−0.0002 (4)
C3A	0.0168 (5)	0.0138 (5)	0.0163 (5)	−0.0028 (4)	0.0033 (4)	−0.0030 (4)
C4A	0.0136 (5)	0.0229 (6)	0.0173 (5)	−0.0047 (4)	0.0022 (4)	−0.0016 (4)
C5A	0.0112 (5)	0.0199 (5)	0.0176 (5)	0.0023 (4)	0.0020 (4)	0.0007 (4)
C6A	0.0119 (5)	0.0168 (5)	0.0168 (5)	0.0015 (4)	0.0043 (4)	−0.0007 (4)
C7A	0.0171 (5)	0.0179 (5)	0.0158 (5)	0.0013 (4)	0.0020 (4)	0.0030 (4)
C8A	0.0139 (5)	0.0174 (5)	0.0145 (5)	−0.0024 (4)	0.0049 (4)	0.0018 (4)
C9A	0.0147 (5)	0.0199 (5)	0.0162 (5)	0.0004 (4)	0.0049 (4)	−0.0024 (4)
C10A	0.0113 (5)	0.0152 (5)	0.0158 (5)	−0.0026 (4)	0.0034 (4)	0.0005 (4)
N1B	0.0134 (4)	0.0132 (4)	0.0135 (4)	−0.0001 (3)	0.0024 (3)	0.0012 (3)
C1B	0.0108 (4)	0.0116 (4)	0.0122 (5)	−0.0003 (3)	0.0026 (4)	0.0008 (3)
C2B	0.0124 (5)	0.0160 (5)	0.0161 (5)	−0.0022 (4)	0.0047 (4)	0.0011 (4)
C3B	0.0116 (5)	0.0184 (5)	0.0162 (5)	−0.0024 (4)	0.0017 (4)	−0.0001 (4)
C4B	0.0195 (5)	0.0169 (5)	0.0156 (5)	−0.0026 (4)	0.0041 (4)	−0.0020 (4)
C5B	0.0144 (5)	0.0189 (5)	0.0161 (5)	0.0016 (4)	0.0063 (4)	−0.0003 (4)
C6B	0.0124 (5)	0.0156 (5)	0.0173 (5)	0.0025 (4)	0.0044 (4)	0.0007 (4)
C7B	0.0165 (5)	0.0192 (5)	0.0173 (5)	−0.0035 (4)	0.0058 (4)	0.0033 (4)
C8B	0.0181 (5)	0.0119 (4)	0.0160 (5)	0.0001 (4)	0.0030 (4)	0.0022 (4)
C9B	0.0143 (5)	0.0185 (5)	0.0179 (5)	0.0039 (4)	0.0020 (4)	0.0022 (4)
C10B	0.0161 (5)	0.0109 (4)	0.0163 (5)	0.0001 (4)	0.0040 (4)	0.0006 (4)
O1	0.0176 (4)	0.0111 (3)	0.0147 (4)	−0.0020 (3)	0.0007 (3)	0.0000 (3)
O2	0.0170 (4)	0.0109 (3)	0.0198 (4)	−0.0002 (3)	0.0089 (3)	0.0008 (3)
O3	0.0142 (4)	0.0101 (3)	0.0186 (4)	−0.0009 (3)	0.0000 (3)	0.0011 (3)
O4	0.0163 (4)	0.0115 (3)	0.0215 (4)	−0.0036 (3)	0.0083 (3)	−0.0003 (3)
P1	0.01134 (13)	0.00869 (12)	0.01317 (13)	−0.00120 (9)	0.00301 (10)	0.00048 (9)

Geometric parameters (Å, º) top

C1—O6	1.2280 (13)	C8A—C10A	1.5392 (15)
C1—O5	1.3036 (14)	C8A—H8A	1.0000
C1—C2	1.4891 (15)	C9A—H9AA	0.9900
C2—C3	1.3291 (16)	C9A—H9AB	0.9900
C2—H2	0.9500	C10A—H10A	0.9900
C3—C4	1.4853 (15)	C10A—H10B	0.9900
C3—H3	0.9500	N1B—C1B	1.5006 (13)
C4—O7	1.2328 (14)	N1B—H1BA	0.9100
C4—O8	1.2918 (13)	N1B—H1BB	0.9100
O5—H5	1.013 (17)	N1B—H1BC	0.9100
O8—H8	1.073 (18)	C1B—C10B	1.5303 (15)
C5—O9	1.2237 (14)	C1B—C6B	1.5307 (16)
C5—O10	1.3117 (14)	C1B—C2B	1.5310 (15)
C5—C6	1.4889 (16)	C2B—C3B	1.5390 (15)
C6—C6ⁱ	1.330 (2)	C2B—H2BA	0.9900
C6—H6	0.9500	C2B—H2BB	0.9900
O10—H10	0.955 (18)	C3B—C4B	1.5322 (17)
N1A—C1A	1.4984 (13)	C3B—C9B	1.5375 (16)
N1A—H1AA	0.9100	C3B—H3B	1.0000
N1A—H1AB	0.9100	C4B—C5B	1.5384 (16)
N1A—H1AC	0.9100	C4B—H4BA	0.9900
C1A—C6A	1.5291 (15)	C4B—H4BB	0.9900
C1A—C10A	1.5314 (16)	C5B—C7B	1.5376 (16)
C1A—C2A	1.5337 (15)	C5B—C6B	1.5390 (16)
C2A—C3A	1.5379 (15)	C5B—H5B	1.0000
C2A—H2AA	0.9900	C6B—H6BA	0.9900
C2A—H2AB	0.9900	C6B—H6BB	0.9900
C3A—C4A	1.5341 (17)	C7B—C8B	1.5341 (17)
C3A—C9A	1.5359 (17)	C7B—H7BA	0.9900
C3A—H3A	1.0000	C7B—H7BB	0.9900
C4A—C5A	1.5343 (17)	C8B—C9B	1.5322 (16)
C4A—H4AA	0.9900	C8B—C10B	1.5379 (15)
C4A—H4AB	0.9900	C8B—H8B	1.0000
C5A—C7A	1.5342 (17)	C9B—H9BA	0.9900
C5A—C6A	1.5405 (16)	C9B—H9BB	0.9900
C5A—H5A	1.0000	C10B—H10C	0.9900
C6A—H6AA	0.9900	C10B—H10D	0.9900
C6A—H6AB	0.9900	O1—P1	1.5946 (8)
C7A—C8A	1.5361 (16)	O1—H1	0.902 (16)
C7A—H7AA	0.9900	O2—P1	1.5252 (9)
C7A—H7AB	0.9900	O3—P1	1.5330 (8)
C8A—C9A	1.5335 (16)	O4—P1	1.5148 (8)

O6—C1—O5	125.72 (10)	H9AA—C9A—H9AB	108.2
O6—C1—C2	120.33 (10)	C1A—C10A—C8A	108.97 (9)
O5—C1—C2	113.94 (10)	C1A—C10A—H10A	109.9
C3—C2—C1	122.03 (10)	C8A—C10A—H10A	109.9
C3—C2—H2	119.0	C1A—C10A—H10B	109.9
C1—C2—H2	119.0	C8A—C10A—H10B	109.9
C2—C3—C4	122.16 (11)	H10A—C10A—H10B	108.3
C2—C3—H3	118.9	C1B—N1B—H1BA	109.5
C4—C3—H3	118.9	C1B—N1B—H1BB	109.5
O7—C4—O8	125.16 (10)	H1BA—N1B—H1BB	109.5
O7—C4—C3	120.86 (10)	C1B—N1B—H1BC	109.5
O8—C4—C3	113.98 (10)	H1BA—N1B—H1BC	109.5
C1—O5—H5	112.9 (9)	H1BB—N1B—H1BC	109.5
C4—O8—H8	113.4 (9)	N1B—C1B—C10B	108.48 (8)
O9—C5—O10	125.00 (11)	N1B—C1B—C6B	108.88 (8)
O9—C5—C6	120.55 (11)	C10B—C1B—C6B	110.62 (9)
O10—C5—C6	114.45 (10)	N1B—C1B—C2B	109.10 (9)
C6ⁱ—C6—C5	123.72 (14)	C10B—C1B—C2B	110.06 (9)
C6ⁱ—C6—H6	118.1	C6B—C1B—C2B	109.66 (9)
C5—C6—H6	118.1	C1B—C2B—C3B	108.88 (9)
C5—O10—H10	110.6 (10)	C1B—C2B—H2BA	109.9
C1A—N1A—H1AA	109.5	C3B—C2B—H2BA	109.9
C1A—N1A—H1AB	109.5	C1B—C2B—H2BB	109.9
H1AA—N1A—H1AB	109.5	C3B—C2B—H2BB	109.9
C1A—N1A—H1AC	109.5	H2BA—C2B—H2BB	108.3
H1AA—N1A—H1AC	109.5	C4B—C3B—C9B	109.57 (10)
H1AB—N1A—H1AC	109.5	C4B—C3B—C2B	109.74 (9)
N1A—C1A—C6A	108.97 (9)	C9B—C3B—C2B	109.15 (9)
N1A—C1A—C10A	109.17 (8)	C4B—C3B—H3B	109.5
C6A—C1A—C10A	109.91 (9)	C9B—C3B—H3B	109.5
N1A—C1A—C2A	108.40 (8)	C2B—C3B—H3B	109.5
C6A—C1A—C2A	110.31 (9)	C3B—C4B—C5B	109.48 (9)
C10A—C1A—C2A	110.05 (9)	C3B—C4B—H4BA	109.8
C1A—C2A—C3A	108.87 (9)	C5B—C4B—H4BA	109.8
C1A—C2A—H2AA	109.9	C3B—C4B—H4BB	109.8
C3A—C2A—H2AA	109.9	C5B—C4B—H4BB	109.8
C1A—C2A—H2AB	109.9	H4BA—C4B—H4BB	108.2
C3A—C2A—H2AB	109.9	C7B—C5B—C4B	109.43 (9)
H2AA—C2A—H2AB	108.3	C7B—C5B—C6B	108.90 (9)
C4A—C3A—C9A	109.65 (9)	C4B—C5B—C6B	109.39 (10)
C4A—C3A—C2A	108.80 (10)	C7B—C5B—H5B	109.7
C9A—C3A—C2A	109.43 (9)	C4B—C5B—H5B	109.7
C4A—C3A—H3A	109.6	C6B—C5B—H5B	109.7
C9A—C3A—H3A	109.6	C1B—C6B—C5B	109.02 (9)
C2A—C3A—H3A	109.6	C1B—C6B—H6BA	109.9
C3A—C4A—C5A	109.88 (9)	C5B—C6B—H6BA	109.9
C3A—C4A—H4AA	109.7	C1B—C6B—H6BB	109.9
C5A—C4A—H4AA	109.7	C5B—C6B—H6BB	109.9
C3A—C4A—H4AB	109.7	H6BA—C6B—H6BB	108.3
C5A—C4A—H4AB	109.7	C8B—C7B—C5B	110.00 (9)
H4AA—C4A—H4AB	108.2	C8B—C7B—H7BA	109.7
C7A—C5A—C4A	109.99 (10)	C5B—C7B—H7BA	109.7
C7A—C5A—C6A	109.22 (9)	C8B—C7B—H7BB	109.7
C4A—C5A—C6A	109.04 (9)	C5B—C7B—H7BB	109.7
C7A—C5A—H5A	109.5	H7BA—C7B—H7BB	108.2
C4A—C5A—H5A	109.5	C9B—C8B—C7B	109.63 (9)
C6A—C5A—H5A	109.5	C9B—C8B—C10B	109.54 (10)
C1A—C6A—C5A	108.76 (9)	C7B—C8B—C10B	109.15 (9)
C1A—C6A—H6AA	109.9	C9B—C8B—H8B	109.5
C5A—C6A—H6AA	109.9	C7B—C8B—H8B	109.5
C1A—C6A—H6AB	109.9	C10B—C8B—H8B	109.5
C5A—C6A—H6AB	109.9	C8B—C9B—C3B	109.59 (9)
H6AA—C6A—H6AB	108.3	C8B—C9B—H9BA	109.8
C5A—C7A—C8A	109.65 (9)	C3B—C9B—H9BA	109.8
C5A—C7A—H7AA	109.7	C8B—C9B—H9BB	109.8
C8A—C7A—H7AA	109.7	C3B—C9B—H9BB	109.8
C5A—C7A—H7AB	109.7	H9BA—C9B—H9BB	108.2
C8A—C7A—H7AB	109.7	C1B—C10B—C8B	108.63 (9)
H7AA—C7A—H7AB	108.2	C1B—C10B—H10C	110.0
C9A—C8A—C7A	109.43 (9)	C8B—C10B—H10C	110.0
C9A—C8A—C10A	109.33 (9)	C1B—C10B—H10D	110.0
C7A—C8A—C10A	109.22 (9)	C8B—C10B—H10D	110.0
C9A—C8A—H8A	109.6	H10C—C10B—H10D	108.3
C7A—C8A—H8A	109.6	P1—O1—H1	111.7 (10)
C10A—C8A—H8A	109.6	O4—P1—O2	113.41 (5)
C8A—C9A—C3A	109.93 (9)	O4—P1—O3	110.77 (5)
C8A—C9A—H9AA	109.7	O2—P1—O3	111.89 (5)
C3A—C9A—H9AA	109.7	O4—P1—O1	106.72 (5)
C8A—C9A—H9AB	109.7	O2—P1—O1	106.25 (5)
C3A—C9A—H9AB	109.7	O3—P1—O1	107.38 (4)

O6—C1—C2—C3	166.16 (13)	C2A—C1A—C10A—C8A	60.76 (11)
O5—C1—C2—C3	−13.71 (17)	C9A—C8A—C10A—C1A	−59.81 (12)
C1—C2—C3—C4	−179.17 (11)	C7A—C8A—C10A—C1A	59.90 (11)
C2—C3—C4—O7	8.1 (2)	N1B—C1B—C2B—C3B	−179.94 (9)
C2—C3—C4—O8	−171.71 (12)	C10B—C1B—C2B—C3B	−61.02 (12)
O9—C5—C6—C6ⁱ	−176.14 (16)	C6B—C1B—C2B—C3B	60.89 (11)
O10—C5—C6—C6ⁱ	4.2 (2)	C1B—C2B—C3B—C4B	−60.08 (12)
N1A—C1A—C2A—C3A	179.99 (9)	C1B—C2B—C3B—C9B	60.01 (12)
C6A—C1A—C2A—C3A	60.75 (12)	C9B—C3B—C4B—C5B	−60.17 (12)
C10A—C1A—C2A—C3A	−60.69 (11)	C2B—C3B—C4B—C5B	59.67 (12)
C1A—C2A—C3A—C4A	−60.09 (12)	C3B—C4B—C5B—C7B	59.62 (12)
C1A—C2A—C3A—C9A	59.70 (12)	C3B—C4B—C5B—C6B	−59.62 (12)
C9A—C3A—C4A—C5A	−58.77 (12)	N1B—C1B—C6B—C5B	179.56 (9)
C2A—C3A—C4A—C5A	60.88 (12)	C10B—C1B—C6B—C5B	60.44 (11)
C3A—C4A—C5A—C7A	58.94 (12)	C2B—C1B—C6B—C5B	−61.14 (11)
C3A—C4A—C5A—C6A	−60.81 (12)	C7B—C5B—C6B—C1B	−59.38 (12)
N1A—C1A—C6A—C5A	−179.36 (9)	C4B—C5B—C6B—C1B	60.18 (12)
C10A—C1A—C6A—C5A	61.06 (11)	C4B—C5B—C7B—C8B	−59.23 (12)
C2A—C1A—C6A—C5A	−60.47 (12)	C6B—C5B—C7B—C8B	60.30 (12)
C7A—C5A—C6A—C1A	−60.38 (11)	C5B—C7B—C8B—C9B	59.24 (12)
C4A—C5A—C6A—C1A	59.84 (12)	C5B—C7B—C8B—C10B	−60.74 (12)
C4A—C5A—C7A—C8A	−59.30 (12)	C7B—C8B—C9B—C3B	−59.46 (12)
C6A—C5A—C7A—C8A	60.33 (12)	C10B—C8B—C9B—C3B	60.29 (12)
C5A—C7A—C8A—C9A	59.57 (12)	C4B—C3B—C9B—C8B	60.13 (12)
C5A—C7A—C8A—C10A	−60.07 (12)	C2B—C3B—C9B—C8B	−60.06 (12)
C7A—C8A—C9A—C3A	−59.78 (12)	N1B—C1B—C10B—C8B	−179.85 (9)
C10A—C8A—C9A—C3A	59.79 (12)	C6B—C1B—C10B—C8B	−60.49 (11)
C4A—C3A—C9A—C8A	59.42 (12)	C2B—C1B—C10B—C8B	60.85 (12)
C2A—C3A—C9A—C8A	−59.85 (12)	C9B—C8B—C10B—C1B	−60.14 (12)
N1A—C1A—C10A—C8A	179.61 (8)	C7B—C8B—C10B—C1B	59.90 (12)
C6A—C1A—C10A—C8A	−60.93 (11)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7ⁱⁱ	0.902 (16)	1.667 (16)	2.5665 (12)	175.0 (15)
O5—H5···O2	1.013 (17)	1.486 (17)	2.4918 (12)	171.1 (16)
O8—H8···O3ⁱⁱⁱ	1.073 (18)	1.396 (18)	2.4659 (12)	174.6 (17)
O10—H10···O4	0.955 (18)	1.595 (18)	2.5407 (12)	170.0 (16)
N1A—H1AA···O6^iv	0.91	1.93	2.8242 (13)	168
N1A—H1AB···O2^iv	0.91	2.64	3.1486 (12)	117
N1A—H1AC···O2	0.91	1.87	2.7821 (13)	175
N1B—H1BA···O3^v	0.91	1.91	2.8201 (13)	174
N1B—H1BB···O4	0.91	1.89	2.8046 (13)	179
N1B—H1BC···O9^v	0.91	1.99	2.9016 (13)	177
C3—H3···O5	0.95	2.41	2.7379 (14)	100
C6—H6···O10ⁱ	0.95	2.44	2.7730 (15)	100
C7B—H7BA···O7^vi	0.99	2.50	3.4742 (16)	167

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

Experimental details

Crystal data
Chemical formula	2C₁₀H₁₈N⁺·HO₄P²⁻·1.5C₄H₄O₄
M_r	574.59
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.7555 (16), 11.1850 (14), 20.251 (2)
β (°)	105.795 (2)
V (Å³)	2780.1 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.45 × 0.35 × 0.25

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.680, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	24141, 9001, 7424
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.750

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.02
No. of reflections	9001
No. of parameters	366
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.39

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXTL (Sheldrick, 2008), SHELXLE (Hübschle et al., 2011), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7ⁱ	0.902 (16)	1.667 (16)	2.5665 (12)	175.0 (15)
O5—H5···O2	1.013 (17)	1.486 (17)	2.4918 (12)	171.1 (16)
O8—H8···O3ⁱⁱ	1.073 (18)	1.396 (18)	2.4659 (12)	174.6 (17)
O10—H10···O4	0.955 (18)	1.595 (18)	2.5407 (12)	170.0 (16)
N1A—H1AA···O6ⁱⁱⁱ	0.91	1.93	2.8242 (13)	167.5
N1A—H1AB···O2ⁱⁱⁱ	0.91	2.64	3.1486 (12)	116.5
N1A—H1AC···O2	0.91	1.87	2.7821 (13)	174.7
N1B—H1BA···O3^iv	0.91	1.91	2.8201 (13)	173.8
N1B—H1BB···O4	0.91	1.89	2.8046 (13)	178.6
N1B—H1BC···O9^iv	0.91	1.99	2.9016 (13)	177.4
C3—H3···O5	0.95	2.41	2.7379 (14)	100
C6—H6···O10^v	0.95	2.44	2.7730 (15)	100
C7B—H7BA···O7^vi	0.99	2.50	3.4742 (16)	167

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

Acknowledgements

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia. The diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491, and by YSU.

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