Bis(4-meth­oxy­benzyl­ammonium) dihydrogen diphosphate

Elboulali, A.; Akriche, S.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536812051616

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages o213-o214

doi:10.1107/S1600536812051616

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Bis(4-methoxybenzylammonium) dihydrogen diphosphate

Adel Elboulali,^a Samah Akriche,^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: samah.akriche@fsb.rnu.tn

(Received 27 November 2012; accepted 21 December 2012; online 9 January 2013)

In the title compound, 2C₈H₁₂NO⁺·H₂P₂O₇²⁻, the linked PO₄ groups of the diphosphate anion are almost eclipsed and the P—O—P angle is 134.45 (7)°. In the crystal, infinite ribbons of H₂P₂O₇²⁻ anions propagate in [100], being linked by strong O—H⋯O hydrogen bonds. The 4-methoxybenzylammonium cations bond to the diphosphate chains by N—H⋯O and C—H⋯O links, and are themselves linked by C—H⋯π interactions.

Related literature

For background to diphosphates, see: Ballarini et al. (2006 ); For intermolecular interactions, see: Brown (1976 ); Tiekink & Zukerman-Schpector (2012 ). For a related structure, see: Ahmed et al. (2006 ).

Experimental

Crystal data

2C₈H₁₂NO⁺·H₂P₂O₇²⁻
M_r = 452.33
Triclinic, $[P \overline 1]$
a = 9.184 (3) Å
b = 6.737 (4) Å
c = 17.066 (2) Å
α = 97.61 (2)°
β = 91.39 (4)°
γ = 85.72 (3)°
V = 1043.6 (7) Å³
Z = 2
Ag Kα radiation
λ = 0.56087 Å
μ = 0.14 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.17 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
12631 measured reflections
10225 independent reflections
5553 reflections with I > 2σ(I)
R_int = 0.026
2 standard reflections every 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.143
S = 0.98
10225 reflections
268 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6ⁱ	0.82	1.82	2.6347 (18)	176
O5—H5⋯O2ⁱⁱ	0.82	1.75	2.5535 (18)	164
N1—H1A⋯O3ⁱⁱⁱ	0.89	2.09	2.941 (2)	160
N1—H1B⋯O3ⁱⁱ	0.89	1.97	2.857 (2)	172
N1—H1C⋯O2	0.89	2.03	2.915 (2)	173
N2—H2B⋯O6	0.89	2.35	3.156 (2)	151
N2—H2A⋯O6^iv	0.89	1.89	2.734 (2)	157
N2—H2B⋯O4	0.89	2.38	3.150 (2)	145
N2—H2C⋯O7ⁱ	0.89	1.85	2.724 (2)	168
C1—H1D⋯O7ⁱⁱ	0.97	2.49	3.242 (3)	134
C7—H7⋯O2	0.93	2.54	3.195 (2)	127
C16—H16C⋯Cg1^v	0.96	2.93	3.73 (7)	142
C8—H8A⋯Cg2	0.96	2.97	3.72 (7)	137
C1—H1D⋯Cg2^vi	0.97	2.90	3.54 (7)	124
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1; (iii) x, y+1, z; (iv) -x+1, -y+1, -z+1; (v) x-1, y, z; (vi) x+1, y, z.

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 (Farrugia, 2012 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812051616/hb7003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812051616/hb7003Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812051616/hb7003Isup3.cml

checkCIF report

Comment top

Diphosphates are known to play an important role as catalysts (Ballarini et al., 2006). As part of our studies in this area, we report the synthesis and the crystal structure of the title compound, (I) (Fig. 1).

In this structure, [H₂P₂O₇]^2- species are connected by means of strong hydrogen bonds of type O—H···O with O···O distances less than 2.7 Å, limit as recommended by Brown (1976). This infinite sequence forms ribbons extending along a axis.

Except the H atoms, the P₂O₇ group, has an eclipsed conformation evidenced by the torsion angle O3—P1—P2—O7 = -1.5°. As usually observed for diphosphate groups (Ahmed et al., 2006), there are three different types of P—O distances, the longest one corresponds to the bridging oxygen atom with average value d(P—O4) = 1,608 (1) Å, the intermediate ones are the P—OH bonding [d(P1—O1) = 1.566 (1) Å, d(P2—O5) = 1.552 (1) Å], whereas the shortest ones, spreading between 1.474 (1) Å and 1.503 (1) Å are related to the external oxygen atoms. The average values of the P—O distances and O—P—O angles are 1,536 (1) Å and 109,24 (7)° respectively.

The organic cations linked by C–H···π interaction (Tiekink and Zukerman-Schpector, 2012) into chains along a axis, are anchored onto successive inorganic ribbons [H₂P₂O₇]_n^2n- through hydrogen bonds of type N—H···O and C—H···O with donor-acceptor distances varying between 2.724 (2) Å and 3.156 (2) Å.

It should be noticed that another diphosphate with the same organic molecule, [4-(OCH₃)C₆H₄CH₂NH₃]₄P₂O₇.6H₂O, has been reported by Ahmed et al. (2006). Structure of this hydrated diphosphate is different from that of the non-hydrated one described here. This difference may be explained by the role of water of crystallization as directing structure agent.

Related literature top

For background to diphosphates, see: Ballarini et al. (2006); For intermolecular interactions, see: Brown (1976); Tiekink & Zukerman-Schpector (2012). For a related structure, see: Ahmed et al. (2006).

Experimental top

An aqueous solution of diphosphoric acid H₄P₂O₇ was first obtained by passing a solution of Na₄P₂O₇ (3 g, 11.2 mmol), through an ion exchange resin (Amberlite IR 120) in its H-state. To 20 ml of this acidic solution (1.5 mmol) cooled to 5°C, a solution of 4-methoxybenzylamine (3 mmol) in ethanol (3 mL),was added drop by drop with slow stirring. The obtained solution was slowly evapored at room temperature until crystallization of colourless prisms.

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 (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are represented as dashed lines.
	Fig. 2. Perspective view of the packing of (I). The H-atoms not involved in H-bonding are omitted.

Bis(4-methoxybenzylammonium) dihydrogen diphosphate top

Crystal data top

2C₈H₁₂NO⁺·H₂O₇P₂²⁻	Z = 2
M_r = 452.33	F(000) = 476
Triclinic, P1	D_x = 1.439 Mg m⁻³
a = 9.184 (3) Å	Ag Kα radiation, λ = 0.56087 Å
b = 6.737 (4) Å	Cell parameters from 25 reflections
c = 17.066 (2) Å	θ = 9–11°
α = 97.61 (2)°	µ = 0.14 mm⁻¹
β = 91.39 (4)°	T = 296 K
γ = 85.72 (3)°	Prism, colorless
V = 1043.6 (7) Å³	0.30 × 0.25 × 0.17 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.0°
Graphite monochromator	h = −15→15
non–profiled ω scans	k = −11→11
12631 measured reflections	l = −4→28
10225 independent reflections	2 standard reflections every 120 min
5553 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0674P)²] where P = (F_o² + 2F_c²)/3
10225 reflections	(Δ/σ)_max = 0.001
268 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

2C₈H₁₂NO⁺·H₂O₇P₂²⁻	γ = 85.72 (3)°
M_r = 452.33	V = 1043.6 (7) Å³
Triclinic, P1	Z = 2
a = 9.184 (3) Å	Ag Kα radiation, λ = 0.56087 Å
b = 6.737 (4) Å	µ = 0.14 mm⁻¹
c = 17.066 (2) Å	T = 296 K
α = 97.61 (2)°	0.30 × 0.25 × 0.17 mm
β = 91.39 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.026
12631 measured reflections	2 standard reflections every 120 min
10225 independent reflections	intensity decay: none
5553 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 0.98	Δρ_max = 0.38 e Å⁻³
10225 reflections	Δρ_min = −0.51 e Å⁻³
268 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	0.77375 (4)	−0.16843 (5)	0.42717 (2)	0.02283 (9)
P2	0.71445 (4)	0.14070 (5)	0.56549 (2)	0.02389 (9)
O1	0.65658 (11)	−0.21336 (18)	0.36026 (7)	0.0321 (2)
H1	0.5815	−0.2428	0.3796	0.048*
O2	0.90518 (11)	−0.09884 (18)	0.39193 (7)	0.0347 (3)
O3	0.80044 (12)	−0.33687 (15)	0.47500 (7)	0.0309 (2)
O4	0.69102 (12)	0.02214 (16)	0.47816 (7)	0.0327 (3)
O5	0.85320 (11)	0.25556 (17)	0.55945 (8)	0.0361 (3)
H5	0.9218	0.2006	0.5819	0.054*
O6	0.58394 (11)	0.29007 (16)	0.57185 (7)	0.0341 (3)
O7	0.73241 (13)	−0.00463 (17)	0.62306 (7)	0.0359 (3)
O8	0.65303 (18)	0.1234 (3)	0.06727 (9)	0.0624 (4)
O9	0.14301 (19)	0.4144 (3)	0.07212 (10)	0.0663 (5)
N1	0.98380 (14)	0.31496 (19)	0.40133 (8)	0.0301 (3)
H1A	0.9110	0.4056	0.4165	0.045*
H1B	1.0568	0.3266	0.4365	0.045*
H1C	0.9523	0.1923	0.3980	0.045*
N2	0.45655 (14)	0.30089 (19)	0.39890 (8)	0.0323 (3)
H2A	0.4183	0.4264	0.4106	0.048*
H2B	0.5181	0.2707	0.4374	0.048*
H2C	0.3854	0.2171	0.3941	0.048*
C1	1.03636 (18)	0.3492 (3)	0.32239 (10)	0.0365 (4)
H1D	1.1277	0.2697	0.3113	0.044*
H1E	1.0554	0.4895	0.3242	0.044*
C2	0.92910 (18)	0.2956 (3)	0.25659 (10)	0.0327 (3)
C3	0.8548 (2)	0.4405 (3)	0.21786 (12)	0.0419 (4)
H3	0.8676	0.5751	0.2348	0.050*
C4	0.7619 (2)	0.3905 (3)	0.15447 (12)	0.0473 (5)
H4	0.7144	0.4906	0.1286	0.057*
C5	0.7401 (2)	0.1919 (3)	0.12986 (11)	0.0443 (4)
C6	0.8102 (3)	0.0456 (3)	0.16945 (12)	0.0507 (5)
H6	0.7930	−0.0885	0.1543	0.061*
C7	0.9056 (2)	0.0964 (3)	0.23126 (11)	0.0447 (4)
H7	0.9548	−0.0041	0.2562	0.054*
C8	0.5843 (3)	0.2674 (5)	0.02229 (15)	0.0744 (8)
H8A	0.5198	0.3591	0.0555	0.112*
H8B	0.5293	0.2004	−0.0205	0.112*
H8C	0.6572	0.3402	0.0015	0.112*
C9	0.53647 (18)	0.2817 (3)	0.32319 (11)	0.0395 (4)
H9A	0.5868	0.1492	0.3133	0.047*
H9B	0.6091	0.3801	0.3271	0.047*
C10	0.43368 (18)	0.3132 (3)	0.25591 (11)	0.0360 (4)
C11	0.3878 (2)	0.5050 (3)	0.23911 (12)	0.0465 (5)
H11	0.4236	0.6163	0.2695	0.056*
C12	0.2903 (3)	0.5326 (3)	0.17823 (13)	0.0526 (5)
H12	0.2606	0.6620	0.1682	0.063*
C13	0.2364 (2)	0.3700 (3)	0.13206 (12)	0.0455 (4)
C14	0.2793 (2)	0.1798 (3)	0.14782 (12)	0.0491 (5)
H14	0.2433	0.0692	0.1171	0.059*
C15	0.3766 (2)	0.1526 (3)	0.20981 (12)	0.0445 (4)
H15	0.4038	0.0231	0.2205	0.053*
C16	0.0827 (3)	0.2508 (4)	0.02453 (16)	0.0760 (8)
H16A	0.1601	0.1615	0.0004	0.114*
H16B	0.0210	0.3002	−0.0159	0.114*
H16C	0.0263	0.1799	0.0569	0.114*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.01629 (14)	0.02364 (17)	0.0285 (2)	−0.00016 (12)	−0.00173 (13)	0.00439 (14)
P2	0.01804 (15)	0.02244 (16)	0.0311 (2)	−0.00183 (12)	−0.00096 (14)	0.00320 (14)
O1	0.0211 (5)	0.0425 (6)	0.0319 (6)	−0.0046 (4)	−0.0042 (4)	0.0013 (5)
O2	0.0191 (4)	0.0422 (6)	0.0458 (7)	−0.0045 (4)	0.0003 (5)	0.0157 (5)
O3	0.0299 (5)	0.0262 (5)	0.0373 (7)	0.0021 (4)	−0.0002 (5)	0.0096 (5)
O4	0.0319 (5)	0.0297 (5)	0.0337 (6)	0.0072 (4)	−0.0070 (5)	−0.0003 (5)
O5	0.0195 (5)	0.0337 (6)	0.0582 (8)	−0.0066 (4)	−0.0068 (5)	0.0160 (5)
O6	0.0200 (4)	0.0297 (5)	0.0504 (8)	0.0015 (4)	0.0020 (5)	−0.0009 (5)
O7	0.0371 (6)	0.0362 (6)	0.0371 (7)	−0.0085 (5)	−0.0051 (5)	0.0124 (5)
O8	0.0640 (10)	0.0773 (11)	0.0443 (9)	−0.0109 (8)	−0.0196 (8)	0.0029 (8)
O9	0.0745 (11)	0.0750 (11)	0.0490 (10)	−0.0068 (9)	−0.0228 (8)	0.0100 (8)
N1	0.0280 (6)	0.0303 (6)	0.0313 (7)	0.0010 (5)	−0.0034 (5)	0.0038 (5)
N2	0.0325 (6)	0.0291 (6)	0.0364 (8)	−0.0037 (5)	−0.0072 (6)	0.0090 (6)
C1	0.0319 (8)	0.0474 (9)	0.0313 (9)	−0.0057 (7)	0.0016 (7)	0.0071 (7)
C2	0.0343 (8)	0.0377 (8)	0.0265 (8)	−0.0014 (6)	0.0024 (6)	0.0059 (7)
C3	0.0450 (10)	0.0372 (9)	0.0432 (11)	0.0004 (7)	−0.0025 (8)	0.0070 (8)
C4	0.0459 (10)	0.0512 (11)	0.0445 (12)	0.0066 (8)	−0.0079 (9)	0.0121 (9)
C5	0.0417 (9)	0.0587 (12)	0.0319 (10)	−0.0050 (8)	−0.0020 (8)	0.0037 (9)
C6	0.0744 (14)	0.0412 (10)	0.0369 (11)	−0.0123 (9)	−0.0061 (10)	0.0036 (8)
C7	0.0614 (12)	0.0396 (9)	0.0331 (10)	0.0004 (8)	−0.0048 (9)	0.0085 (8)
C8	0.0625 (15)	0.109 (2)	0.0515 (15)	−0.0036 (14)	−0.0244 (12)	0.0165 (15)
C9	0.0296 (7)	0.0436 (9)	0.0453 (11)	0.0017 (7)	0.0023 (7)	0.0077 (8)
C10	0.0348 (8)	0.0395 (8)	0.0341 (9)	−0.0020 (7)	0.0033 (7)	0.0067 (7)
C11	0.0615 (12)	0.0386 (9)	0.0396 (11)	−0.0078 (8)	−0.0079 (9)	0.0058 (8)
C12	0.0701 (14)	0.0441 (10)	0.0449 (12)	−0.0030 (10)	−0.0107 (10)	0.0126 (9)
C13	0.0470 (10)	0.0570 (11)	0.0328 (10)	−0.0039 (9)	−0.0013 (8)	0.0074 (9)
C14	0.0541 (11)	0.0489 (11)	0.0431 (12)	−0.0122 (9)	−0.0006 (9)	−0.0028 (9)
C15	0.0494 (10)	0.0379 (9)	0.0459 (12)	−0.0026 (8)	0.0020 (9)	0.0043 (8)
C16	0.0716 (17)	0.095 (2)	0.0559 (16)	−0.0066 (15)	−0.0233 (13)	−0.0054 (14)

Geometric parameters (Å, º) top

P1—O3	1.4860 (13)	C3—C4	1.383 (3)
P1—O2	1.4942 (12)	C3—H3	0.9300
P1—O1	1.5656 (13)	C4—C5	1.376 (3)
P1—O4	1.6042 (13)	C4—H4	0.9300
P2—O7	1.4744 (13)	C5—C6	1.380 (3)
P2—O6	1.5028 (12)	C6—C7	1.379 (3)
P2—O5	1.5517 (12)	C6—H6	0.9300
P2—O4	1.6126 (12)	C7—H7	0.9300
O1—H1	0.8200	C8—H8A	0.9600
O5—H5	0.8200	C8—H8B	0.9600
O8—C5	1.370 (2)	C8—H8C	0.9600
O8—C8	1.418 (3)	C9—C10	1.495 (3)
O9—C13	1.368 (2)	C9—H9A	0.9700
O9—C16	1.419 (3)	C9—H9B	0.9700
N1—C1	1.494 (2)	C10—C15	1.380 (3)
N1—H1A	0.8900	C10—C11	1.393 (3)
N1—H1B	0.8900	C11—C12	1.377 (3)
N1—H1C	0.8900	C11—H11	0.9300
N2—C9	1.487 (2)	C12—C13	1.378 (3)
N2—H2A	0.8900	C12—H12	0.9300
N2—H2B	0.8900	C13—C14	1.371 (3)
N2—H2C	0.8900	C14—C15	1.390 (3)
C1—C2	1.501 (2)	C14—H14	0.9300
C1—H1D	0.9700	C15—H15	0.9300
C1—H1E	0.9700	C16—H16A	0.9600
C2—C3	1.380 (2)	C16—H16B	0.9600
C2—C7	1.386 (3)	C16—H16C	0.9600

O3—P1—O2	116.25 (7)	O8—C5—C6	115.48 (19)
O3—P1—O1	112.16 (7)	C4—C5—C6	119.39 (18)
O2—P1—O1	108.81 (7)	C7—C6—C5	120.56 (19)
O3—P1—O4	110.72 (7)	C7—C6—H6	119.7
O2—P1—O4	107.92 (8)	C5—C6—H6	119.7
O1—P1—O4	99.63 (6)	C6—C7—C2	120.72 (18)
O7—P2—O6	118.73 (8)	C6—C7—H7	119.6
O7—P2—O5	112.51 (7)	C2—C7—H7	119.6
O6—P2—O5	108.43 (7)	O8—C8—H8A	109.5
O7—P2—O4	109.41 (7)	O8—C8—H8B	109.5
O6—P2—O4	101.55 (7)	H8A—C8—H8B	109.5
O5—P2—O4	104.81 (8)	O8—C8—H8C	109.5
P1—O1—H1	109.5	H8A—C8—H8C	109.5
P1—O4—P2	134.45 (7)	H8B—C8—H8C	109.5
P2—O5—H5	109.5	N2—C9—C10	110.84 (14)
C5—O8—C8	117.59 (19)	N2—C9—H9A	109.5
C13—O9—C16	117.15 (19)	C10—C9—H9A	109.5
C1—N1—H1A	109.5	N2—C9—H9B	109.5
C1—N1—H1B	109.5	C10—C9—H9B	109.5
H1A—N1—H1B	109.5	H9A—C9—H9B	108.1
C1—N1—H1C	109.5	C15—C10—C11	117.43 (18)
H1A—N1—H1C	109.5	C15—C10—C9	120.98 (17)
H1B—N1—H1C	109.5	C11—C10—C9	121.55 (17)
C9—N2—H2A	109.5	C12—C11—C10	121.12 (18)
C9—N2—H2B	109.5	C12—C11—H11	119.4
H2A—N2—H2B	109.5	C10—C11—H11	119.4
C9—N2—H2C	109.5	C11—C12—C13	120.5 (2)
H2A—N2—H2C	109.5	C11—C12—H12	119.8
H2B—N2—H2C	109.5	C13—C12—H12	119.8
N1—C1—C2	112.96 (14)	O9—C13—C14	124.96 (19)
N1—C1—H1D	109.0	O9—C13—C12	115.6 (2)
C2—C1—H1D	109.0	C14—C13—C12	119.42 (19)
N1—C1—H1E	109.0	C13—C14—C15	119.92 (18)
C2—C1—H1E	109.0	C13—C14—H14	120.0
H1D—C1—H1E	107.8	C15—C14—H14	120.0
C3—C2—C7	117.96 (17)	C10—C15—C14	121.60 (19)
C3—C2—C1	121.67 (16)	C10—C15—H15	119.2
C7—C2—C1	120.33 (16)	C14—C15—H15	119.2
C2—C3—C4	121.69 (18)	O9—C16—H16A	109.5
C2—C3—H3	119.2	O9—C16—H16B	109.5
C4—C3—H3	119.2	H16A—C16—H16B	109.5
C5—C4—C3	119.64 (18)	O9—C16—H16C	109.5
C5—C4—H4	120.2	H16A—C16—H16C	109.5
C3—C4—H4	120.2	H16B—C16—H16C	109.5
O8—C5—C4	125.13 (19)

O3—P1—O4—P2	47.66 (13)	C5—C6—C7—C2	2.2 (3)
O2—P1—O4—P2	−80.60 (12)	C3—C2—C7—C6	−0.3 (3)
O1—P1—O4—P2	165.91 (11)	C1—C2—C7—C6	−178.26 (18)
O7—P2—O4—P1	−48.92 (13)	N2—C9—C10—C15	−94.9 (2)
O6—P2—O4—P1	−175.23 (10)	N2—C9—C10—C11	82.7 (2)
O5—P2—O4—P1	71.95 (12)	C15—C10—C11—C12	−0.7 (3)
N1—C1—C2—C3	110.56 (19)	C9—C10—C11—C12	−178.38 (19)
N1—C1—C2—C7	−71.6 (2)	C10—C11—C12—C13	−0.4 (4)
C7—C2—C3—C4	−1.4 (3)	C16—O9—C13—C14	2.2 (3)
C1—C2—C3—C4	176.49 (18)	C16—O9—C13—C12	−178.6 (2)
C2—C3—C4—C5	1.2 (3)	C11—C12—C13—O9	−178.5 (2)
C8—O8—C5—C4	2.6 (3)	C11—C12—C13—C14	0.8 (3)
C8—O8—C5—C6	−177.0 (2)	O9—C13—C14—C15	179.08 (19)
C3—C4—C5—O8	−178.81 (19)	C12—C13—C14—C15	−0.1 (3)
C3—C4—C5—C6	0.7 (3)	C11—C10—C15—C14	1.3 (3)
O8—C5—C6—C7	177.14 (19)	C9—C10—C15—C14	179.06 (18)
C4—C5—C6—C7	−2.4 (3)	C13—C14—C15—C10	−0.9 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6ⁱ	0.82	1.82	2.6347 (18)	176
O5—H5···O2ⁱⁱ	0.82	1.75	2.5535 (18)	164
N1—H1A···O3ⁱⁱⁱ	0.89	2.09	2.941 (2)	160
N1—H1B···O3ⁱⁱ	0.89	1.97	2.857 (2)	172
N1—H1C···O2	0.89	2.03	2.915 (2)	173
N2—H2B···O6	0.89	2.35	3.156 (2)	151
N2—H2A···O6^iv	0.89	1.89	2.734 (2)	157
N2—H2B···O4	0.89	2.38	3.150 (2)	145
N2—H2C···O7ⁱ	0.89	1.85	2.724 (2)	168
C1—H1D···O7ⁱⁱ	0.97	2.49	3.242 (3)	134
C7—H7···O2	0.93	2.54	3.195 (2)	127
C16—H16C···Cg1^v	0.96	2.93	3.73 (7)	142
C8—H8A···Cg2	0.96	2.97	3.72 (7)	137
C1—H1D···Cg2^vi	0.97	2.90	3.54 (7)	124

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

Experimental details

Crystal data
Chemical formula	2C₈H₁₂NO⁺·H₂O₇P₂²⁻
M_r	452.33
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.184 (3), 6.737 (4), 17.066 (2)
α, β, γ (°)	97.61 (2), 91.39 (4), 85.72 (3)
V (Å³)	1043.6 (7)
Z	2
Radiation type	Ag Kα, λ = 0.56087 Å
µ (mm⁻¹)	0.14
Crystal size (mm)	0.30 × 0.25 × 0.17

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	12631, 10225, 5553
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.143, 0.98
No. of reflections	10225
No. of parameters	268
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.51

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6ⁱ	0.82	1.82	2.6347 (18)	176
O5—H5···O2ⁱⁱ	0.82	1.75	2.5535 (18)	164
N1—H1A···O3ⁱⁱⁱ	0.89	2.09	2.941 (2)	160
N1—H1B···O3ⁱⁱ	0.89	1.97	2.857 (2)	172
N1—H1C···O2	0.89	2.03	2.915 (2)	173
N2—H2B···O6	0.89	2.35	3.156 (2)	151
N2—H2A···O6^iv	0.89	1.89	2.734 (2)	157
N2—H2B···O4	0.89	2.38	3.150 (2)	145
N2—H2C···O7ⁱ	0.89	1.85	2.724 (2)	168
C1—H1D···O7ⁱⁱ	0.97	2.49	3.242 (3)	134
C7—H7···O2	0.93	2.54	3.195 (2)	127
C16—H16C···Cg1^v	0.96	2.926	3.73 (7)	142
C8—H8A···Cg2	0.96	2.965	3.72 (7)	137
C1—H1D···Cg2^vi	0.97	2.903	3.54 (7)	124

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

Acknowledgements

This work was supported by the Tunisian Carthage University and the Deanship of Scientific Research at King Saud University through the Research Group Project No. RGP-VPP-089.

References

Ahmed, S., Samah, A. & Mohamed, R. (2006). Acta Cryst. E62, m1796–m1798. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ballarini, N., Cavani, F., Cortelli, C., Ligi, S., Pierelli, F., Trifiro, F., Fumagalli, C., Mazzoni, G. & Monti, T. (2006). Top. Catal. 38, 147–156. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brown, I. D. (1976). Acta Cryst. A32, 24–31. CrossRef IUCr Journals Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. 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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiekink, E. R. T. & Zukerman-Schpector, J. (2012). In Importance of π-Interactions in Crystal Engineering, 1st ed. London: Wiley. Google Scholar

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Volume 69| Part 2| February 2013| Pages o213-o214

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