N,N-Dimethyl­anilinium 2,4,6-trinitro­phenolate

Vembu, N.; Fronczek, F.R.

doi:10.1107/S1600536808041743

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages o111-o112

doi:10.1107/S1600536808041743

Open

access

N,N-Dimethylanilinium 2,4,6-trinitrophenolate

Nagarajan Vembu ^a ^* and Frank R. Fronczek ^b

^aDepartment of Chemistry, Urumu Dhanalakshmi College, Tiruchirappalli 620 019, India, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: vembu57@yahoo.com

(Received 5 December 2008; accepted 9 December 2008; online 13 December 2008)

In the title compound, C₈H₁₂N⁺·C₆H₂N₃O₇⁻, there are N—H⋯O and C—H⋯O interactions which generate R₂¹(5), R₂¹(6) and R₁²(6) ring motifs. The supramolecular aggregation is completed by the presence of edge-to-face and offset face-to-face π–π interactions with centroid–centroid distances of 3.673 and 3.697 Å, respectively.

Related literature

For a detailed account of the design of organic polar crystals, see: Pecaut & Bagieu-Beucher (1993 ). For hydrogen bonding in nitrophenol complexes, see: In et al. (1997 ); Zadrenko et al. (1997 ); Mizutani et al. (1998 ). For the supramolecular architecture of molecular complexes of trinitrophenols, see: Botoshansky et al. (1994 ); Vembu et al. (2003 ). For details of the monoclinic polymorph of the title compound, see: Takayanagi et al. (1996 ). For hydrogen-bonding criteria, see: Desiraju & Steiner (1999 ); Desiraju (1989 ); Jeffrey (1997 ). For graph-set notation, see: Bernstein et al. (1995 ); Etter (1990 ).

Experimental

Crystal data

C₈H₁₂N⁺·C₆H₂N₃O₇⁻
M_r = 350.29
Orthorhombic, P n a 2₁
a = 15.9960 (10) Å
b = 9.1491 (6) Å
c = 10.3899 (9) Å
V = 1520.55 (19) Å³
Z = 4
Cu Kα radiation
μ = 1.08 mm⁻¹
T = 90.0 (5) K
0.26 × 0.24 × 0.08 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.767, T_max = 0.919
16980 measured reflections
2823 independent reflections
2755 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.060
S = 1.03
2823 reflections
283 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1309 Friedel pairs
Flack parameter: 0.07 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯O16	0.892 (17)	1.825 (18)	2.7128 (14)	172.8 (16)
N7—H7⋯O19	0.892 (17)	2.578 (16)	3.0517 (15)	114.0 (12)
C2—H2⋯O16	0.931 (18)	2.341 (17)	3.0464 (16)	132.4 (13)
C2—H2⋯O24	0.931 (18)	2.498 (17)	3.3444 (17)	151.4 (14)
C8—H8A⋯O19	1.001 (18)	2.411 (18)	3.1171 (18)	126.9 (13)
C9—H9C⋯O19	0.997 (18)	2.592 (17)	3.2311 (17)	121.9 (12)
C9—H9B⋯O21ⁱ	0.974 (19)	2.571 (19)	3.5074 (17)	161.3 (14)
C9—H9B⋯O25ⁱⁱ	0.974 (19)	2.476 (18)	3.0794 (18)	119.9 (13)
C4—H4⋯O21ⁱⁱⁱ	0.924 (19)	2.466 (18)	3.1776 (16)	134.0 (14)
C14—H14⋯O19^iv	0.941 (18)	2.564 (18)	3.4988 (16)	172.3 (14)
C9—H9C⋯O22^v	0.997 (18)	2.502 (18)	3.3283 (16)	140.0 (13)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: APEX2 and SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041743/sj2565sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041743/sj2565Isup2.hkl

checkCIF report

Comment top

The design of organic polar crystals for quadratic non-linear optical applications is supported by the observation that the organic molecules containing π-electron systems asymmetrized by electron donor and acceptor groups are highly polarizable entities in which problems of transparency and crystal growth may arise from their molecular crystal packing (Pecaut & Bagieu-Beucher, 1993). It is known that nitrophenols act not only as π-acceptors to form various π-stacking complexes with other aromatic molecules, but also as acidic ligands to form salts through specific electrostatic or H-bonding interactions (In et al., 1997). The bonding of electron-donor acceptor complexes strongly depends on the nature of the partners. The linkage could involve not only electrostatic interactions, but also the formation of molecular complexes (Zadrenko et al., 1997). It has been reported that proton transferred thermochromic complexes were formed between phenols and amines in apolar solvents at low temperature if an appropriate H-bonding network between the phenols and amines was present to stabilize it (Mizutani et al., 1998). Pyridinium picrate has been reported in two crystalline phases and it appears in both phases as an internally linked H-bonded ion pair. These two phases are referred to as molecular crystals rather than salts based on their structural arrangements (Botoshansky et al., 1994). A similar structural arrangement has also been reported for 4-dimethylaminopyridinium picrate (Vembu et al., 2003). The monoclinic polymorph of the title compound (CSD Reference Code: REYDEE) has been reported previously (Takayanagi et al., 1996). We have structurally elucidated the orthorhombic polymorph of the title compound as a forerunner to assessing its optical properties and report its structure here.

The asymmetric unit of (I) contains one N,N-Dimethylanilinium cation, and one 2,4,6-trinitrophenolate anion. (Fig.1). The crystal structure of (I) is stabilized by N—H···O and C—H···O interactions. The range of H···O distances (Table 1) found in (I) agrees with those found for N—H···O (Jeffrey, 1997) and C—H···O hydrogen bonds (Desiraju & Steiner, 1999). The N7—H7···O16 and N7—H7···O19 interactions form a pair of bifurcated donor bonds that link the N,N-dimethylanilinium cation and 2,4,6-trinitrophenolate anion and also form a motif of graph set R²₁(6) (Bernstein et al., 1995; Etter, 1990). Another pair of bifurcated donor bonds consists of the C2—H2···O16 and C2—H2···O24 interactions that also link the cation and the anion and form a R²₁(6) motif. The C8—H8A···O19 and C9—H9C···O19 interactions constitute a pair of bifurcated bonds forming a R¹₂(6) motif that link the cation and the anion. The N7—H7···O19 and C8—H8A···O19 interactions constitute a pair of bifurcated acceptor bonds that form a R¹₂(5) motif. The above two motifs, R¹₂(6) and R¹₂(5), together form a R¹₂(5) motif by the interplay of the trifurcated acceptor bonds formed by N7—H7···O19, C9—H8A···O19 and C9—H9C···O19 interactions. There are five intermolecular C—H···O interactions (Table 1) that contribute to the supramolecular aggregation of the title compound. The intramolecular N—H···O interactions mentioned above also contribute to the formation of cooperative H-bonded network (Fig. 2). There is an offset π···π stacking interaction, Cg1···Cg2 (x, -1+y, z) at 3.697Å with α = 3.19, β = 24.88 and γ = 24.00 and the two perpendicular distances being 3.377 and 3.354Å. There is also an edge to face π···π stacking interaction, Cg1···Cg2 (1.5-x, -0.5+y, 0.5+z) at 3.673Å with α=13.75, β=25.68 and γ=12.78 and the two perpendicular distances being 3.582 and 3.310Å. Cg1 and Cg2 are the centroids of the C1···C6 and C10···.C15 rings.

The interplay of strong N—H···O and weak C—H···O, π···π interactions with different strengths, directional preferences and distance presents a complex mosaic of interactions. The three dimensional arrangement of the 2,4,6-trinitrophenolate and N,N-dimethylanilinium moieties in the unit cell, shows that the title compound is an internally linked hydrogen bonded ion pair and hence can be regarded as a molecular crystal rather than a salt.

Related literature top

For a detailed account of the design of organic polar crystals, see: Pecaut & Bagieu-Beucher (1993). For hydrogen bonding in nitrophenol complexes, see: In et al. (1997); Zadrenko et al. (1997); Mizutani et al. (1998). For the supramolecular architecture of molecular complexes of trinitrophenols, see: Botoshansky et al. (1994); Vembu et al. (2003). For details of the monoclinic polymorph of the title compound, see : Takayanagi et al. (1996)?. For hydrogen-bonding criteria, see: Desiraju & Steiner (1999); Desiraju (1989); Jeffrey (1997). For graph-set notation, see: Bernstein et al. (1995); Etter (1990).

Experimental top

2,4,6-Trinitrophenol (5.2 mmol) dissolved in aqueous ethanol (25 ml) was added dropwise to N,N-dimethylaniline (5.7 mmol) in aqueous ethanol (25 ml). The above solution was constantly stirred at room temperature for 2 hrs. The precipitated product was filtered and recrystallized from aqueous ethanol. Yield 75% (3.9 mmol).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 and SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atoms labelled and displacement ellipsoids depicted at the 50% probability level for all non-H atoms. H-atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The molecular packing viewed down the b-axis. Dashed lines represent the N—H···O and C—H···O interactions within the lattice.

N,N-Dimethylanilinium 2,4,6-trinitrophenolate top

Crystal data top

C₈H₁₂N⁺·C₆H₂N₃O₇⁻	D_x = 1.530 Mg m⁻³
M_r = 350.29	Melting point: 401 K
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 9564 reflections
a = 15.996 (1) Å	θ = 5.5–70.2°
b = 9.1491 (6) Å	µ = 1.08 mm⁻¹
c = 10.3899 (9) Å	T = 90 K
V = 1520.55 (19) Å³	Plate, yellow
Z = 4	0.26 × 0.24 × 0.08 mm
F(000) = 728

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2823 independent reflections
Radiation source: fine-focus sealed tube	2755 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 70.2°, θ_min = 5.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
T_min = 0.767, T_max = 0.919	k = −10→10
16980 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0386P)² + 0.2146P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2823 reflections	Δρ_max = 0.14 e Å⁻³
283 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1309 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (12)

Crystal data top

C₈H₁₂N⁺·C₆H₂N₃O₇⁻	V = 1520.55 (19) Å³
M_r = 350.29	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 15.996 (1) Å	µ = 1.08 mm⁻¹
b = 9.1491 (6) Å	T = 90 K
c = 10.3899 (9) Å	0.26 × 0.24 × 0.08 mm

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2823 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2755 reflections with I > 2σ(I)
T_min = 0.767, T_max = 0.919	R_int = 0.033
16980 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	Δρ_max = 0.14 e Å⁻³
S = 1.03	Δρ_min = −0.16 e Å⁻³
2823 reflections	Absolute structure: Flack (1983), 1309 Friedel pairs
283 parameters	Absolute structure parameter: 0.07 (12)
1 restraint

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	0.37023 (8)	1.31731 (14)	0.30638 (13)	0.0151 (3)
C2	0.28455 (9)	1.29778 (15)	0.30264 (13)	0.0165 (3)
C3	0.23581 (8)	1.40616 (15)	0.24585 (13)	0.0178 (3)
C4	0.27257 (10)	1.53064 (15)	0.19438 (13)	0.0195 (3)
C5	0.35871 (9)	1.54844 (15)	0.20120 (14)	0.0200 (3)
C6	0.40878 (9)	1.44179 (15)	0.25752 (13)	0.0180 (3)
N7	0.42143 (7)	1.20264 (12)	0.37028 (12)	0.0150 (2)
C8	0.49639 (9)	1.15827 (16)	0.29319 (15)	0.0212 (3)
C9	0.44558 (8)	1.25020 (15)	0.50295 (14)	0.0200 (3)
C10	0.28722 (8)	0.85997 (14)	0.41862 (13)	0.0141 (3)
C11	0.34012 (7)	0.75029 (14)	0.47878 (12)	0.0142 (2)
C12	0.31105 (8)	0.62014 (14)	0.52863 (12)	0.0141 (3)
C13	0.22695 (8)	0.58924 (13)	0.52313 (13)	0.0149 (3)
C14	0.17059 (8)	0.68496 (14)	0.46412 (12)	0.0146 (3)
C15	0.20036 (8)	0.81337 (13)	0.41512 (13)	0.0145 (3)
O16	0.31146 (5)	0.97691 (10)	0.36915 (10)	0.0183 (2)
N17	0.42940 (7)	0.77360 (12)	0.48867 (11)	0.0160 (2)
O18	0.47489 (6)	0.66722 (10)	0.50973 (10)	0.0207 (2)
O19	0.45735 (6)	0.89878 (10)	0.47807 (11)	0.0247 (2)
N20	0.19719 (7)	0.45202 (12)	0.57365 (11)	0.0167 (2)
O21	0.24919 (6)	0.36384 (10)	0.61486 (10)	0.0194 (2)
O22	0.12141 (6)	0.42767 (12)	0.57227 (11)	0.0267 (2)
N23	0.13932 (7)	0.90790 (12)	0.35088 (11)	0.0162 (2)
O24	0.14260 (6)	1.04028 (10)	0.36928 (12)	0.0240 (2)
O25	0.08701 (6)	0.84815 (11)	0.28202 (9)	0.0207 (2)
H2	0.2611 (10)	1.2148 (19)	0.3398 (17)	0.017 (4)*
H3	0.1778 (12)	1.3963 (19)	0.2403 (18)	0.023 (4)*
H4	0.2380 (11)	1.600 (2)	0.1572 (16)	0.016 (4)*
H5	0.3856 (11)	1.633 (2)	0.1698 (17)	0.023 (4)*
H6	0.4678 (11)	1.4531 (17)	0.2608 (17)	0.017 (4)*
H7	0.3883 (10)	1.1243 (18)	0.3740 (17)	0.018 (4)*
H8A	0.5236 (11)	1.0734 (18)	0.3373 (18)	0.025 (4)*
H8B	0.5363 (12)	1.2445 (19)	0.2860 (19)	0.028 (5)*
H8C	0.4773 (12)	1.125 (2)	0.208 (2)	0.036 (5)*
H9A	0.4780 (10)	1.3372 (18)	0.4959 (17)	0.017 (4)*
H9B	0.3966 (11)	1.2756 (18)	0.5538 (18)	0.022 (4)*
H9C	0.4760 (11)	1.1692 (19)	0.5467 (17)	0.020 (4)*
H12	0.3479 (11)	0.5528 (18)	0.5656 (17)	0.017 (4)*
H14	0.1134 (11)	0.6615 (17)	0.4590 (17)	0.017 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0177 (6)	0.0136 (6)	0.0140 (6)	0.0022 (5)	−0.0007 (5)	−0.0020 (5)
C2	0.0197 (6)	0.0135 (6)	0.0161 (6)	−0.0011 (5)	0.0012 (5)	−0.0010 (5)
C3	0.0172 (6)	0.0170 (6)	0.0193 (7)	0.0013 (5)	−0.0022 (5)	−0.0039 (5)
C4	0.0281 (7)	0.0146 (6)	0.0158 (6)	0.0041 (6)	−0.0028 (5)	−0.0002 (5)
C5	0.0286 (7)	0.0137 (7)	0.0175 (7)	−0.0029 (5)	0.0024 (6)	−0.0003 (5)
C6	0.0198 (7)	0.0166 (7)	0.0175 (7)	−0.0021 (5)	0.0024 (5)	−0.0017 (5)
N7	0.0142 (5)	0.0132 (5)	0.0174 (5)	−0.0006 (4)	0.0011 (4)	−0.0003 (5)
C8	0.0193 (6)	0.0192 (7)	0.0251 (7)	0.0028 (5)	0.0058 (6)	0.0008 (6)
C9	0.0214 (6)	0.0200 (7)	0.0187 (7)	0.0008 (6)	−0.0046 (6)	−0.0016 (6)
C10	0.0146 (6)	0.0140 (6)	0.0137 (6)	−0.0002 (5)	−0.0013 (5)	−0.0026 (5)
C11	0.0132 (6)	0.0156 (6)	0.0138 (6)	0.0004 (5)	0.0006 (5)	−0.0023 (5)
C12	0.0161 (6)	0.0136 (6)	0.0127 (6)	0.0030 (5)	−0.0003 (5)	−0.0009 (5)
C13	0.0170 (6)	0.0120 (6)	0.0155 (6)	0.0002 (5)	0.0001 (5)	0.0005 (5)
C14	0.0123 (6)	0.0162 (6)	0.0152 (6)	0.0002 (5)	0.0008 (5)	−0.0023 (5)
C15	0.0149 (6)	0.0140 (6)	0.0145 (6)	0.0031 (5)	−0.0007 (5)	0.0000 (5)
O16	0.0177 (4)	0.0152 (5)	0.0219 (5)	−0.0020 (3)	−0.0016 (4)	0.0040 (4)
N17	0.0142 (5)	0.0177 (5)	0.0162 (5)	−0.0005 (4)	−0.0008 (4)	0.0008 (5)
O18	0.0143 (4)	0.0205 (5)	0.0274 (5)	0.0040 (4)	−0.0012 (4)	0.0025 (4)
O19	0.0181 (5)	0.0180 (5)	0.0378 (6)	−0.0050 (4)	−0.0061 (4)	0.0062 (5)
N20	0.0166 (5)	0.0149 (6)	0.0186 (6)	−0.0005 (4)	−0.0009 (5)	0.0007 (4)
O21	0.0201 (4)	0.0144 (5)	0.0235 (5)	0.0035 (4)	−0.0005 (4)	0.0049 (4)
O22	0.0146 (5)	0.0267 (5)	0.0389 (6)	−0.0060 (4)	−0.0035 (4)	0.0098 (5)
N23	0.0135 (5)	0.0193 (6)	0.0156 (5)	0.0017 (4)	0.0009 (4)	0.0034 (5)
O24	0.0221 (5)	0.0140 (5)	0.0360 (6)	0.0036 (4)	−0.0007 (5)	0.0041 (4)
O25	0.0162 (4)	0.0271 (5)	0.0188 (5)	0.0020 (4)	−0.0047 (4)	0.0004 (4)

Geometric parameters (Å, º) top

C1—C2	1.3826 (19)	C9—H9C	0.997 (18)
C1—C6	1.3910 (19)	C10—O16	1.2488 (17)
C1—N7	1.4874 (16)	C10—C15	1.4537 (18)
C2—C3	1.3926 (19)	C10—C11	1.4538 (18)
C2—H2	0.931 (18)	C11—C12	1.3794 (19)
C3—C4	1.389 (2)	C11—N17	1.4475 (16)
C3—H3	0.934 (18)	C12—C13	1.3758 (18)
C4—C5	1.389 (2)	C12—H12	0.935 (18)
C4—H4	0.924 (19)	C13—C14	1.3985 (18)
C5—C6	1.391 (2)	C13—N20	1.4417 (17)
C5—H5	0.942 (19)	C14—C15	1.3661 (18)
C6—H6	0.951 (18)	C14—H14	0.941 (18)
N7—C9	1.4962 (18)	C15—N23	1.4652 (16)
N7—C8	1.4980 (18)	N17—O19	1.2344 (14)
N7—H7	0.892 (17)	N17—O18	1.2348 (14)
C8—H8A	1.001 (18)	N20—O22	1.2326 (15)
C8—H8B	1.017 (18)	N20—O21	1.2353 (15)
C8—H8C	0.99 (2)	N23—O24	1.2273 (15)
C9—H9A	0.953 (17)	N23—O25	1.2291 (15)
C9—H9B	0.974 (19)

C2—C1—C6	122.34 (12)	H9A—C9—H9B	106.3 (14)
C2—C1—N7	117.85 (11)	N7—C9—H9C	109.3 (10)
C6—C1—N7	119.76 (11)	H9A—C9—H9C	113.0 (14)
C1—C2—C3	118.35 (12)	H9B—C9—H9C	108.9 (14)
C1—C2—H2	119.5 (10)	O16—C10—C15	122.53 (12)
C3—C2—H2	122.1 (10)	O16—C10—C11	125.98 (11)
C4—C3—C2	120.66 (13)	C15—C10—C11	111.39 (11)
C4—C3—H3	118.4 (11)	C12—C11—N17	115.67 (11)
C2—C3—H3	120.9 (11)	C12—C11—C10	124.13 (11)
C3—C4—C5	119.77 (13)	N17—C11—C10	120.21 (11)
C3—C4—H4	117.9 (11)	C13—C12—C11	119.44 (12)
C5—C4—H4	122.3 (11)	C13—C12—H12	119.8 (10)
C4—C5—C6	120.67 (13)	C11—C12—H12	120.7 (10)
C4—C5—H5	122.1 (11)	C12—C13—C14	121.33 (12)
C6—C5—H5	117.2 (11)	C12—C13—N20	119.13 (11)
C1—C6—C5	118.20 (13)	C14—C13—N20	119.47 (11)
C1—C6—H6	121.1 (10)	C15—C14—C13	118.50 (11)
C5—C6—H6	120.7 (10)	C15—C14—H14	121.0 (10)
C1—N7—C9	110.38 (10)	C13—C14—H14	120.5 (10)
C1—N7—C8	113.16 (11)	C14—C15—C10	125.18 (12)
C9—N7—C8	111.39 (11)	C14—C15—N23	116.42 (11)
C1—N7—H7	105.0 (10)	C10—C15—N23	118.37 (11)
C9—N7—H7	110.3 (12)	O19—N17—O18	122.24 (10)
C8—N7—H7	106.3 (11)	O19—N17—C11	119.19 (10)
N7—C8—H8A	108.2 (10)	O18—N17—C11	118.55 (10)
N7—C8—H8B	109.3 (11)	O22—N20—O21	123.25 (11)
H8A—C8—H8B	111.3 (14)	O22—N20—C13	118.55 (11)
N7—C8—H8C	108.4 (12)	O21—N20—C13	118.20 (10)
H8A—C8—H8C	108.1 (15)	O24—N23—O25	123.96 (11)
H8B—C8—H8C	111.3 (16)	O24—N23—C15	118.88 (11)
N7—C9—H9A	108.2 (11)	O25—N23—C15	117.15 (11)
N7—C9—H9B	111.2 (11)

C6—C1—C2—C3	1.1 (2)	C12—C13—C14—C15	−2.10 (19)
N7—C1—C2—C3	178.45 (12)	N20—C13—C14—C15	−178.99 (12)
C1—C2—C3—C4	0.0 (2)	C13—C14—C15—C10	0.2 (2)
C2—C3—C4—C5	−0.9 (2)	C13—C14—C15—N23	178.23 (11)
C3—C4—C5—C6	0.9 (2)	O16—C10—C15—C14	177.99 (13)
C2—C1—C6—C5	−1.1 (2)	C11—C10—C15—C14	1.40 (19)
N7—C1—C6—C5	−178.45 (12)	O16—C10—C15—N23	0.00 (19)
C4—C5—C6—C1	0.1 (2)	C11—C10—C15—N23	−176.58 (11)
C2—C1—N7—C9	−100.90 (13)	C12—C11—N17—O19	−161.31 (13)
C6—C1—N7—C9	76.55 (15)	C10—C11—N17—O19	19.03 (18)
C2—C1—N7—C8	133.51 (13)	C12—C11—N17—O18	17.45 (17)
C6—C1—N7—C8	−49.04 (16)	C10—C11—N17—O18	−162.20 (12)
O16—C10—C11—C12	−177.78 (13)	C12—C13—N20—O22	177.52 (12)
C15—C10—C11—C12	−1.34 (18)	C14—C13—N20—O22	−5.53 (19)
O16—C10—C11—N17	1.8 (2)	C12—C13—N20—O21	−3.32 (18)
C15—C10—C11—N17	178.28 (11)	C14—C13—N20—O21	173.63 (12)
N17—C11—C12—C13	−179.98 (11)	C14—C15—N23—O24	138.87 (13)
C10—C11—C12—C13	−0.3 (2)	C10—C15—N23—O24	−42.97 (17)
C11—C12—C13—C14	2.17 (19)	C14—C15—N23—O25	−40.50 (17)
C11—C12—C13—N20	179.06 (12)	C10—C15—N23—O25	137.66 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O16	0.892 (17)	1.825 (18)	2.7128 (14)	172.8 (16)
N7—H7···O19	0.892 (17)	2.578 (16)	3.0517 (15)	114.0 (12)
C2—H2···O16	0.931 (18)	2.341 (17)	3.0464 (16)	132.4 (13)
C2—H2···O24	0.931 (18)	2.498 (17)	3.3444 (17)	151.4 (14)
C8—H8A···O19	1.001 (18)	2.411 (18)	3.1171 (18)	126.9 (13)
C9—H9C···O19	0.997 (18)	2.592 (17)	3.2311 (17)	121.9 (12)
C9—H9B···O21ⁱ	0.974 (19)	2.571 (19)	3.5074 (17)	161.3 (14)
C9—H9B···O25ⁱⁱ	0.974 (19)	2.476 (18)	3.0794 (18)	119.9 (13)
C4—H4···O21ⁱⁱⁱ	0.924 (19)	2.466 (18)	3.1776 (16)	134.0 (14)
C14—H14···O19^iv	0.941 (18)	2.564 (18)	3.4988 (16)	172.3 (14)
C9—H9C···O22^v	0.997 (18)	2.502 (18)	3.3283 (16)	140.0 (13)

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·C₆H₂N₃O₇⁻
M_r	350.29
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	90
a, b, c (Å)	15.996 (1), 9.1491 (6), 10.3899 (9)
V (Å³)	1520.55 (19)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.26 × 0.24 × 0.08

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.767, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	16980, 2823, 2755
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 1.03
No. of reflections	2823
No. of parameters	283
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.16
Absolute structure	Flack (1983), 1309 Friedel pairs
Absolute structure parameter	0.07 (12)

Computer programs: APEX2 (Bruker, 2006), APEX2 and SAINT (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O16	0.892 (17)	1.825 (18)	2.7128 (14)	172.8 (16)
N7—H7···O19	0.892 (17)	2.578 (16)	3.0517 (15)	114.0 (12)
C2—H2···O16	0.931 (18)	2.341 (17)	3.0464 (16)	132.4 (13)
C2—H2···O24	0.931 (18)	2.498 (17)	3.3444 (17)	151.4 (14)
C8—H8A···O19	1.001 (18)	2.411 (18)	3.1171 (18)	126.9 (13)
C9—H9C···O19	0.997 (18)	2.592 (17)	3.2311 (17)	121.9 (12)
C9—H9B···O21ⁱ	0.974 (19)	2.571 (19)	3.5074 (17)	161.3 (14)
C9—H9B···O25ⁱⁱ	0.974 (19)	2.476 (18)	3.0794 (18)	119.9 (13)
C4—H4···O21ⁱⁱⁱ	0.924 (19)	2.466 (18)	3.1776 (16)	134.0 (14)
C14—H14···O19^iv	0.941 (18)	2.564 (18)	3.4988 (16)	172.3 (14)
C9—H9C···O22^v	0.997 (18)	2.502 (18)	3.3283 (16)	140.0 (13)

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

Acknowledgements

NV thanks the University Grants Commission (UGC), Government of India, for a minor research project grant [MRP-2219/06(UGC-SERO)].

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Botoshansky, M., Herbstein, F. H. & Kapon, M. (1994). Acta Cryst. B50, 191–200. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. (1989). Crystal Engineering: The Design of Organic Solids. Amsterdam: Elsevier. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. New York, Oxford University Press. Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
In, Y., Nagata, H., Doi, M., Ishida, T. & Wakahara, A. (1997). Acta Cryst. C53, 367–369. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Jeffrey, G. A. (1997). An Introduction to Hydrogen Bonding. New York, Oxford University Press. Google Scholar
Mizutani, T., Takagi, H., Ueno, Y., Honiguchi, T., Yamamura, K. & Ogoshi, H. (1998). J. Phys. Org. Chem. 11, 737–742. Web of Science CrossRef CAS Google Scholar
Pecaut, J. & Bagieu-Beucher, M. (1993). Acta Cryst. C49, 834–837. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takayanagi, H., Kai, T., Yamaguchi, S.-I., Takeda, K. & Goto, M. (1996). Chem. Pharm. Bull. 44, 2199–2204. CrossRef Google Scholar
Vembu, N., Nallu, M., Garrison, J. & Youngs, W. J. (2003). Acta Cryst. E59, o913–o916. CSD CrossRef IUCr Journals Google Scholar
Zaderenko, P., Gil, M. S., López, P., Ballesteros, P., Fonseca, I. & Albert, A. (1997). Acta Cryst. B53, 961–967. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar