1-(2-Methyl-5-nitro­phenyl)guanidinium picrate

Jasinski, J.P.; Butcher, R.J.; Swamy, M.T.; Yathirajan, H.S.; Ramesha, A.R.

doi:10.1107/S1600536809037647

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages o2788-o2789

https://doi.org/10.1107/S1600536809037647

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1-(2-Methyl-5-nitrophenyl)guanidinium picrate

Jerry P. Jasinski,^a Ray J. Butcher,^b ^* M. T. Swamy,^c H. S. Yathirajan ^c and A. R. Ramesha ^d

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^dRL Fine Chem, Bangalore 560 064, India
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 13 July 2009; accepted 17 September 2009; online 17 October 2009)

In the crystal structure of the title salt, C₈H₁₁N₄O₂⁺·C₆H₂N₃O₇⁻, the pictrate anion participates in extensive hydrogen bonding with the guanidinium ion group of the cation, linking the molecules through N⁺—H⋯O⁻ hydrogen bonds and intermolecular N—H⋯O and C—H⋯O interactions. These hydrogen-bonding configurations involve two three-centre/bifurcated bonds [N—H⋯(O,O)] that are observed between two N atoms from the guanidinium ion group of the cation and the o-NO₂ and phenolate O atoms of the picrate anion. In addition, π–π interactions also contribute to the crystal packing, with a centroid-to-centroid distance of 3.693 (6) Å and a slippage angle of 1.614°. A significant number of conformational differences are observed between the salt in the crystal structure and the models obtained by density functional theory (DFT) calculations of the geometry-optimized structure.

Related literature

For background literature, see: Berlinck (2002 ); Heys et al. (2000 ); Ishikawa & Isobe (2002 ); Kelley et al. (2001 ); Laeckmann et al. (2002 ); Moroni et al. (2001 ); Orner & Hamilton (2001 ); Zyss et al. (1993 ). For related structures, see: Cunningham et al. (1997 ); Demir et al. (2006 ); Gupta & Dutta (1975 ); Moghimi et al. (2005 ); Murtaza et al. (2007 , 2009 ); Pereira Silva et al. (2007 ); Pruszynski et al. (1992 ); Ren et al. (2007 ); Sonar et al. (2007 ); Smith et al. (2007 , 2007a ); Stanford et al. (2007 ); Stępień & Grabowski (1977 ); Wang et al. (2009 ); Wei (2008 ). For density functional theory (DFT), see: Becke (1988 , 1993 ); Frisch et al. (2004 ); Hehre et al. (1986 ); Lee et al. (1988 ); Schmidt & Polik (2007 ). For the Cambridge Structural Database, see: Allen (2002 ); Bruno et al. (2004 ).

Experimental

Crystal data

C₈H₁₁N₄O₂⁺·C₆H₂N₃O₇⁻
M_r = 423.31
Triclinic, $[P \overline 1]$
a = 7.1318 (10) Å
b = 10.6239 (13) Å
c = 11.9564 (13) Å
α = 84.257 (10)°
β = 74.497 (11)°
γ = 77.559 (11)°
V = 851.58 (18) Å³
Z = 2
Cu Kα radiation
μ = 1.23 mm⁻¹
T = 110 K
0.51 × 0.41 × 0.33 mm

Data collection

Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.431, T_max = 1.000
6248 measured reflections
3344 independent reflections
2761 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.07
3344 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O22Bⁱ	0.88	2.20	3.0737 (18)	171
N3A—H3AB⋯O1B	0.88	2.03	2.7866 (18)	143
N3A—H3AB⋯O62B	0.88	2.35	3.0882 (18)	142
N3A—H3AC⋯O1Aⁱⁱ	0.88	2.32	2.9808 (19)	132
N4A—H4AA⋯O1B	0.88	1.98	2.7499 (18)	145
N4A—H4AA⋯O21B	0.88	2.34	3.0683 (19)	141
N4A—H4AB⋯O21Bⁱ	0.88	2.11	2.9572 (18)	163
C3A—H3AA⋯O41Bⁱⁱⁱ	0.95	2.37	3.262 (2)	155
C7A—H7AB⋯O1B^iv	0.98	2.56	3.447 (2)	151
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+1, -y+1, -z+2; (iii) -x+1, -y+2, -z+1; (iv) -x+2, -y+1, -z+1.

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809037647/kp2228sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809037647/kp2228Isup2.hkl

checkCIF report

Comment top

Guanidines, important compounds that have many biological, chemical and medicinal applications (Berlinck, 2002; Heys et al., 2000), have received increasing interest as medicinal agents with antitumour, antihypertensive, antiglaucoma and cardiotonic activities (Laeckmann et al., 2002; Kelley et al., 2001; Moroni et al., 2001). Due to their strong basic character, they can be considered as super-bases that readily undergo protonation to generate resonance-stabilized guanidinium cations (Ishikawa & Isobe, 2002). Guanidine is used in variety of supramolecular recognition processes across the spectrum of organic, biological and medicinal chemistry (Orner & Hamilton, 2001) with special interest motivated by their potential applications in non-linear optics (Zyss et al., 1993).

The crystal structures of a few related guanidine derivatives viz. guanidinium 2-amino-4-nitrobenzoate monohydrate at 130 K (Smith et al., 2007), (2,4,6-trinitrophenyl)guanidine (Smith et al., 2007a), 4-methoxy-phenylguanidinium chloride (Ren et al., 2007), (E)-1-[(2-methoxyphenyl)methyleneamino]guanidinium chloride (Sonar et al., 2007), have been reported. 1-(2-methyl-5-nitrophenyl)guanidine is one of the starting compounds for the synthesis of the anticancer drug, imatinib. In connection with the importance of guanidine derivatives, the present paper reports the crystal structure of the title compound, (I), C₁₄H₁₃N₇O₉.

The title compound, (I), crystallizes as a salt with one independent cation–anion pair [C₈H₁₁O₂N₄⁺.C₆H₂N₃O₇^-] in the asymmetric unit (Fig. 1). Bond lengths and angles can be regarded as normal (Cambridge Structural Database, Version 5.30, February, 2009; Allen, 2002, Mogul, Version 1.1.3; Bruno et al., 2004). In the cation, the angle between the dihedral planes of the guanidinium ion [(CH₅N₃)⁺] and the bonded 2-methyl-5-nitrophenyl group is 83.0 (7)°. All three nitrogen atoms (N2A, N3A & N4A) exhibit sp² hybridization with a sum of angles around each atom of 360.0 (0)° resulting in a planar guanidinium ion group. The dihedral angle between the mean planes of the 5-nitro group and the benzyl ring is 5.0 (3)°. In the picrate anion, the mean plane of two o-NO₂ and single p-NO₂ groups are twisted by 14.6 (4)°, 16.6 (3)° and 5.6 (8)°, respectively, from the mean plane of the benzyl ring. The difference in the twist angles of the mean planes of the two o-NO₂ groups can be attributed to an intermolecular hydrogen bonded interaction between the guanidinium ion of the cation with both of these groups (O21B—N2B—O22B & O61B—N6B—O62B) of the picrate anion, in which the O21B and O62B atoms form intermolecular "side" hydrogen bonds (N4A—H4AA···O21B & N3A—H3AB···O62B) with N4A and N3A from the guanidinium ion (Fig. 2, Table 1). N4A and N3A also both form intermolecular hydrogen bonds with the phenolate oxygen anion O1B (N4A—H4AA···O1B & N3A—H3AB···O1B), each creating a bifrucated (three-centre), N—H···(O,O) hydrogen bond. As a result, O1B and O21B act as the double acceptors. N4A and N3A form additional intermolecular hydrogen bonds with nearby O21B (N4A—H4AB···O21B) and O1A (N3A—H3AC···O1A) atoms, respectively. The dihedral angle between the mean planes of the benzyl ring and guanidinium ion group in the cation and the benzyl ring of the picrate anion are 80.8 (7)° and 7.4 (7)°, respectively. Additional weak N2A—H2AA···O22B and C3A—H3AA···O41B hydrogen bonds and π–π stacking interactions occur (Cg1···Cg1 = 3.693 (6) Å; -x, 1 - y, -z; slippage = 1.614°; Cg1 = C1A–C6A centroid) contributing to the stability of crystal packing.

A density functional theory (DFT) geometry optimization molecular orbital calculation (Schmidt & Polik, 2007) was performed on the C₈H₁₁O₂N₄⁺.C₆H₂N₃O₇^- cation–anion pair of the title molecule, (I), with the GAUSSIAN03 program package (Frisch et al. 2004) employing the B3LYP (Becke three parameter Lee–Yang–Parr) exchange correlation functional, which combines the hybrid exchange functional of Becke (Becke, 1988, 1993) with the gradient-correlation functional of Lee, Yang and Parr (Lee et al. 1988) and the 3-21G basis set (Hehre et al. 1986). Starting geometries were taken from X-ray refinement data. The dihedral angle between the dihedral planes of the guanidinium ion [(CH₅N₃)⁺] and the bonded 2-methyl-5-nitrophenyl group in the cation decreases by 7.1 (2)° to 70.9 (1)° while the mean plane of the 5-nitro group decreases by 5.0 (3)° to become planar with the benzyl ring. In the picrate anion, the twist of the mean planes of two o-NO₂ and single p-NO₂ groups decreases by 12.3 (1)°, 10.4 (9)° and 5.6 (8)° to 4.3 (2)°, 4.1 (5)° and 0.0 (0)°, respectively, from the mean plane of the 6-membered benzyl ring. The dihedral angle between the mean planes of the benzyl ring and guanidinium ion group in the cation and the benzyl ring of the picrate anion change by -17.8 (5)° and +2.1 (9)° to 63.0 (2)° and 9.6 (6)°, respectively. Examination of the partial charges from the DFT geometry optimization indicate that H4AA (0.4.4384) is slightly more positive than H3A (0.402348) producing a slightly delocalized proton charge over the guanidium group and favoring the N4A atom. This coincides with a shorter N4A—H4AA···O1B (= 1.984 Å) hydrogen bond than N3A—H3A···O1B (= 2.033 Å) due to the multiple acceptor function of O1B. In conclusion, the significant number of conformational changes that are observed between the crystalline environment of this cation–anion (1-(2-methyl-5-nitrophenyl)guanidinium picrate) salt and that of a density functional theory calculation of the geometry optimized structure support the effects of strong intermolecular hydrogen bonding interactions and weak π–π ring intermolecular interactions between the guanidinium ion and bonded 2-methyl-5-nitrophenyl group of the cation and the o-NO₂, p-NO₂ and phenolate oxygen groups of the picrate anion as providing the major influence on packing effects in the crystal of the title compound, 1-(2-methyl-5-nitrophenyl)guanidinium picrate, (I).

Related literature top

For background literature, see: Berlinck (2002); Heys et al. (2000); Ishikawa & Isobe (2002); Kelley et al. (2001); Laeckmann et al. (2002); Moroni et al. (2001); Orner & Hamilton (2001); Zyss et al. (1993). For related structures, see: Cunningham et al. (1997); Demir et al. (2006); Gupta & Dutta (1975); Moghimi et al. (2005); Murtaza et al. (2007, 2009); Pereira Silva et al. (2007); Pruszynski et al. (1992); Ren et al. (2007); Sonar et al. (2007); Smith et al. (2007, 2007a); Stanford et al. (2007); Stępień & Grabowski (1977); Wang et al. (2009); Wei (2008). For density functional theory (DFT), see: Becke (1988, 1993); Frisch et al. (2004); Hehre et al. (1986); Lee et al. (1988); Schmidt & Polik (2007). For the Cambridge Structural Database, see: Allen (2002); Bruno et al. (2004).

Experimental top

The title compound was synthesized by adding a solution of picric acid (0.92 g, 2 mmol) in 10 ml of methanol to a solution of 1-(2-methyl-5-nitrophenyl)guanidine (0.45 g, 2 mmol) in 10 ml of methanol (Scheme 2). A yellow colour developed and the solution was allowed to evaporate slowly at room temperature.The yellow colour compound formed was filtered off, washed several times with diethyl ether, and then dried over CaCl₂ (yield: 64.2%). Crystals for X-ray studies were grown by slow evaporation of dimethyl formamide solution. The melting range was found to be 382–385 K. Analysis found (calculated) for C₁₄H₁₃N₇O₉ (%): C: 39.95 (39.72), H: 2.99 (3.1), N: 23.36 (23.16).

Structure description top

For background literature, see: Berlinck (2002); Heys et al. (2000); Ishikawa & Isobe (2002); Kelley et al. (2001); Laeckmann et al. (2002); Moroni et al. (2001); Orner & Hamilton (2001); Zyss et al. (1993). For related structures, see: Cunningham et al. (1997); Demir et al. (2006); Gupta & Dutta (1975); Moghimi et al. (2005); Murtaza et al. (2007, 2009); Pereira Silva et al. (2007); Pruszynski et al. (1992); Ren et al. (2007); Sonar et al. (2007); Smith et al. (2007, 2007a); Stanford et al. (2007); Stępień & Grabowski (1977); Wang et al. (2009); Wei (2008). For density functional theory (DFT), see: Becke (1988, 1993); Frisch et al. (2004); Hehre et al. (1986); Lee et al. (1988); Schmidt & Polik (2007). For the Cambridge Structural Database, see: Allen (2002); Bruno et al. (2004).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), showing the bifrucated (three-centre) N—H···(O,O) donor hydrogen bond configuration and the atom labeling scheme. Hydrogen bonds are shown as dashed lines. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Packing diagram of the title compound, (I), viewed down the b axis. Dashed lines indicate intermolecular bifurcated (three-centre) N—H···(O,O), N—H···O, and C—H···O donor hydrogen bond interactions which produces a 2-D network arranged along the (101) plane.
	Fig. 3. The formation of the title compound.

1-(2-methyl-5-nitrophenyl)guanidinium 2,4,6-trinitrophenolate top

Crystal data top

C₈H₁₁N₄O₂⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 423.31	F(000) = 436
Triclinic, P1	D_x = 1.651 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.1318 (10) Å	Cell parameters from 3632 reflections
b = 10.6239 (13) Å	θ = 4.3–73.8°
c = 11.9564 (13) Å	µ = 1.23 mm⁻¹
α = 84.257 (10)°	T = 110 K
β = 74.497 (11)°	Chunk, pale yellow
γ = 77.559 (11)°	0.51 × 0.41 × 0.33 mm
V = 851.58 (18) Å³

Data collection top

Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector	3344 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.5081 pixels mm^-1	θ_max = 73.9°, θ_min = 4.3°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→13
T_min = 0.431, T_max = 1.000	l = −14→12
6248 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0696P)² + 0.2349P] where P = (F_o² + 2F_c²)/3
3344 reflections	(Δ/σ)_max = 0.001
272 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₈H₁₁N₄O₂⁺·C₆H₂N₃O₇⁻	γ = 77.559 (11)°
M_r = 423.31	V = 851.58 (18) Å³
Triclinic, P1	Z = 2
a = 7.1318 (10) Å	Cu Kα radiation
b = 10.6239 (13) Å	µ = 1.23 mm⁻¹
c = 11.9564 (13) Å	T = 110 K
α = 84.257 (10)°	0.51 × 0.41 × 0.33 mm
β = 74.497 (11)°

Data collection top

Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector	3344 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2761 reflections with I > 2σ(I)
T_min = 0.431, T_max = 1.000	R_int = 0.021
6248 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.07	Δρ_max = 0.27 e Å⁻³
3344 reflections	Δρ_min = −0.29 e Å⁻³
272 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.34d (release 27-02-2009 CrysAlis171 .NET) (compiled Feb 27 2009,15:38:38) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O1A	0.6186 (2)	0.42327 (13)	1.18314 (12)	0.0358 (3)
O2A	0.5417 (2)	0.62511 (13)	1.13392 (12)	0.0383 (3)
N1A	0.6304 (2)	0.51540 (14)	1.11228 (13)	0.0261 (3)
N2A	0.9515 (2)	0.68299 (13)	0.73199 (12)	0.0228 (3)
H2AA	1.0452	0.7222	0.7376	0.027*
N3A	0.7069 (2)	0.67430 (13)	0.64072 (12)	0.0236 (3)
H3AB	0.6416	0.7048	0.5877	0.028*
H3AC	0.6762	0.6076	0.6865	0.028*
N4A	0.8981 (2)	0.82883 (13)	0.58308 (12)	0.0225 (3)
H4AA	0.8336	0.8600	0.5299	0.027*
H4AB	0.9943	0.8644	0.5909	0.027*
C1A	1.0118 (2)	0.44934 (16)	0.77518 (15)	0.0229 (3)
C2A	0.9141 (2)	0.57363 (15)	0.80935 (14)	0.0208 (3)
C3A	0.7870 (2)	0.59582 (16)	0.91843 (14)	0.0221 (3)
H3AA	0.7204	0.6807	0.9400	0.026*
C4A	0.7597 (2)	0.49070 (16)	0.99526 (14)	0.0225 (3)
C5A	0.8533 (2)	0.36602 (16)	0.96653 (15)	0.0246 (4)
H5AA	0.8327	0.2956	1.0208	0.029*
C6A	0.9788 (3)	0.34633 (16)	0.85597 (15)	0.0254 (4)
H6AA	1.0437	0.2610	0.8347	0.030*
C7A	1.1495 (3)	0.42731 (18)	0.65702 (16)	0.0298 (4)
H7AA	1.0824	0.4706	0.5979	0.045*
H7AB	1.1880	0.3345	0.6445	0.045*
H7AC	1.2682	0.4624	0.6513	0.045*
C8A	0.8505 (2)	0.72837 (15)	0.65149 (14)	0.0202 (3)
O1B	0.59719 (17)	0.85654 (11)	0.47353 (10)	0.0254 (3)
O21B	0.84884 (19)	1.00632 (12)	0.36978 (12)	0.0319 (3)
O22B	0.7546 (2)	1.15265 (12)	0.24729 (12)	0.0324 (3)
O41B	0.3034 (2)	1.09649 (12)	0.03718 (11)	0.0318 (3)
O42B	0.1500 (3)	0.93647 (15)	0.08197 (15)	0.0518 (5)
O61B	0.2382 (2)	0.64362 (13)	0.39470 (12)	0.0351 (3)
O62B	0.3584 (2)	0.69013 (14)	0.52904 (12)	0.0353 (3)
N2B	0.7376 (2)	1.05245 (13)	0.30647 (12)	0.0236 (3)
N4B	0.2629 (2)	1.00057 (14)	0.09892 (13)	0.0292 (3)
N6B	0.3236 (2)	0.71124 (14)	0.43296 (12)	0.0243 (3)
C1B	0.5286 (2)	0.88544 (15)	0.38719 (14)	0.0206 (3)
C2B	0.5836 (2)	0.98569 (15)	0.29955 (14)	0.0211 (3)
C3B	0.4980 (2)	1.02404 (16)	0.20829 (14)	0.0224 (3)
H3BA	0.5364	1.0924	0.1555	0.027*
C4B	0.3543 (3)	0.96112 (16)	0.19447 (14)	0.0237 (3)
C5B	0.3011 (2)	0.85874 (16)	0.26861 (14)	0.0230 (3)
H5BA	0.2080	0.8137	0.2554	0.028*
C6B	0.3831 (2)	0.82270 (15)	0.36097 (14)	0.0217 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0411 (8)	0.0400 (8)	0.0270 (7)	−0.0189 (6)	−0.0048 (6)	0.0092 (6)
O2A	0.0393 (8)	0.0368 (8)	0.0319 (7)	−0.0027 (6)	−0.0007 (6)	−0.0020 (6)
N1A	0.0239 (7)	0.0325 (8)	0.0248 (7)	−0.0119 (6)	−0.0070 (6)	0.0014 (6)
N2A	0.0240 (7)	0.0239 (7)	0.0247 (7)	−0.0118 (6)	−0.0099 (6)	0.0048 (6)
N3A	0.0255 (7)	0.0248 (7)	0.0243 (7)	−0.0104 (6)	−0.0114 (6)	0.0063 (5)
N4A	0.0227 (7)	0.0246 (7)	0.0239 (7)	−0.0101 (5)	−0.0096 (6)	0.0042 (5)
C1A	0.0220 (8)	0.0269 (8)	0.0236 (8)	−0.0084 (6)	−0.0096 (6)	−0.0005 (6)
C2A	0.0211 (8)	0.0240 (8)	0.0216 (8)	−0.0101 (6)	−0.0099 (6)	0.0036 (6)
C3A	0.0206 (8)	0.0227 (8)	0.0262 (8)	−0.0064 (6)	−0.0103 (7)	0.0003 (6)
C4A	0.0214 (8)	0.0284 (9)	0.0211 (8)	−0.0105 (6)	−0.0076 (6)	0.0013 (6)
C5A	0.0277 (9)	0.0238 (8)	0.0275 (9)	−0.0126 (7)	−0.0121 (7)	0.0048 (6)
C6A	0.0286 (9)	0.0212 (8)	0.0298 (9)	−0.0073 (7)	−0.0115 (7)	−0.0011 (7)
C7A	0.0312 (9)	0.0307 (9)	0.0271 (9)	−0.0075 (7)	−0.0054 (7)	−0.0024 (7)
C8A	0.0195 (8)	0.0207 (8)	0.0193 (7)	−0.0032 (6)	−0.0031 (6)	−0.0018 (6)
O1B	0.0296 (6)	0.0253 (6)	0.0264 (6)	−0.0099 (5)	−0.0138 (5)	0.0039 (5)
O21B	0.0288 (7)	0.0328 (7)	0.0420 (7)	−0.0141 (5)	−0.0201 (6)	0.0092 (6)
O22B	0.0406 (7)	0.0278 (7)	0.0374 (7)	−0.0190 (6)	−0.0184 (6)	0.0089 (5)
O41B	0.0458 (8)	0.0249 (6)	0.0293 (7)	−0.0084 (5)	−0.0183 (6)	0.0044 (5)
O42B	0.0762 (11)	0.0455 (9)	0.0594 (10)	−0.0350 (8)	−0.0505 (9)	0.0193 (8)
O61B	0.0454 (8)	0.0334 (7)	0.0345 (7)	−0.0234 (6)	−0.0129 (6)	0.0028 (5)
O62B	0.0369 (7)	0.0442 (8)	0.0326 (7)	−0.0218 (6)	−0.0176 (6)	0.0158 (6)
N2B	0.0251 (7)	0.0224 (7)	0.0253 (7)	−0.0087 (6)	−0.0072 (6)	0.0005 (5)
N4B	0.0382 (8)	0.0246 (8)	0.0308 (8)	−0.0088 (6)	−0.0179 (7)	0.0015 (6)
N6B	0.0218 (7)	0.0248 (7)	0.0266 (7)	−0.0076 (6)	−0.0054 (6)	0.0020 (6)
C1B	0.0201 (8)	0.0194 (7)	0.0227 (8)	−0.0032 (6)	−0.0060 (6)	−0.0024 (6)
C2B	0.0209 (8)	0.0203 (8)	0.0237 (8)	−0.0061 (6)	−0.0062 (6)	−0.0024 (6)
C3B	0.0253 (8)	0.0197 (8)	0.0223 (8)	−0.0052 (6)	−0.0056 (6)	−0.0015 (6)
C4B	0.0281 (9)	0.0242 (8)	0.0224 (8)	−0.0060 (7)	−0.0116 (7)	−0.0020 (6)
C5B	0.0227 (8)	0.0227 (8)	0.0259 (8)	−0.0066 (6)	−0.0075 (7)	−0.0034 (6)
C6B	0.0209 (8)	0.0213 (8)	0.0233 (8)	−0.0057 (6)	−0.0055 (6)	0.0001 (6)

Geometric parameters (Å, º) top

O1A—N1A	1.2306 (19)	C7A—H7AA	0.9800
O2A—N1A	1.217 (2)	C7A—H7AB	0.9800
N1A—C4A	1.468 (2)	C7A—H7AC	0.9800
N2A—C8A	1.344 (2)	O1B—C1B	1.241 (2)
N2A—C2A	1.4363 (19)	O21B—N2B	1.2334 (18)
N2A—H2AA	0.8800	O22B—N2B	1.2278 (18)
N3A—C8A	1.317 (2)	O41B—N4B	1.2364 (19)
N3A—H3AB	0.8800	O42B—N4B	1.227 (2)
N3A—H3AC	0.8800	O61B—N6B	1.2250 (19)
N4A—C8A	1.325 (2)	O62B—N6B	1.2280 (19)
N4A—H4AA	0.8800	N2B—C2B	1.4534 (19)
N4A—H4AB	0.8800	N4B—C4B	1.445 (2)
C1A—C2A	1.398 (2)	N6B—C6B	1.463 (2)
C1A—C6A	1.401 (2)	C1B—C2B	1.457 (2)
C1A—C7A	1.497 (2)	C1B—C6B	1.460 (2)
C2A—C3A	1.384 (2)	C2B—C3B	1.374 (2)
C3A—C4A	1.386 (2)	C3B—C4B	1.390 (2)
C3A—H3AA	0.9500	C3B—H3BA	0.9500
C4A—C5A	1.381 (2)	C4B—C5B	1.385 (2)
C5A—C6A	1.391 (2)	C5B—C6B	1.368 (2)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C6A—H6AA	0.9500

O2A—N1A—O1A	123.73 (15)	C1A—C7A—H7AC	109.5
O2A—N1A—C4A	118.54 (14)	H7AA—C7A—H7AC	109.5
O1A—N1A—C4A	117.73 (15)	H7AB—C7A—H7AC	109.5
C8A—N2A—C2A	123.28 (13)	N3A—C8A—N4A	120.59 (14)
C8A—N2A—H2AA	118.4	N3A—C8A—N2A	120.75 (14)
C2A—N2A—H2AA	118.4	N4A—C8A—N2A	118.67 (14)
C8A—N3A—H3AB	120.0	O22B—N2B—O21B	122.00 (13)
C8A—N3A—H3AC	120.0	O22B—N2B—C2B	118.56 (13)
H3AB—N3A—H3AC	120.0	O21B—N2B—C2B	119.43 (13)
C8A—N4A—H4AA	120.0	O42B—N4B—O41B	122.85 (15)
C8A—N4A—H4AB	120.0	O42B—N4B—C4B	118.43 (14)
H4AA—N4A—H4AB	120.0	O41B—N4B—C4B	118.72 (14)
C2A—C1A—C6A	117.73 (16)	O61B—N6B—O62B	122.78 (14)
C2A—C1A—C7A	121.12 (15)	O61B—N6B—C6B	117.97 (14)
C6A—C1A—C7A	121.14 (16)	O62B—N6B—C6B	119.25 (13)
C3A—C2A—C1A	121.89 (14)	O1B—C1B—C2B	124.20 (14)
C3A—C2A—N2A	118.23 (15)	O1B—C1B—C6B	124.04 (15)
C1A—C2A—N2A	119.82 (15)	C2B—C1B—C6B	111.76 (14)
C2A—C3A—C4A	118.15 (15)	C3B—C2B—N2B	116.04 (14)
C2A—C3A—H3AA	120.9	C3B—C2B—C1B	124.33 (14)
C4A—C3A—H3AA	120.9	N2B—C2B—C1B	119.63 (14)
C5A—C4A—C3A	122.45 (16)	C2B—C3B—C4B	118.92 (15)
C5A—C4A—N1A	119.67 (14)	C2B—C3B—H3BA	120.5
C3A—C4A—N1A	117.86 (15)	C4B—C3B—H3BA	120.5
C4A—C5A—C6A	118.22 (15)	C5B—C4B—C3B	121.16 (15)
C4A—C5A—H5AA	120.9	C5B—C4B—N4B	119.33 (14)
C6A—C5A—H5AA	120.9	C3B—C4B—N4B	119.48 (14)
C5A—C6A—C1A	121.56 (16)	C6B—C5B—C4B	119.76 (15)
C5A—C6A—H6AA	119.2	C6B—C5B—H5BA	120.1
C1A—C6A—H6AA	119.2	C4B—C5B—H5BA	120.1
C1A—C7A—H7AA	109.5	C5B—C6B—C1B	123.85 (15)
C1A—C7A—H7AB	109.5	C5B—C6B—N6B	116.32 (14)
H7AA—C7A—H7AB	109.5	C1B—C6B—N6B	119.79 (14)

C6A—C1A—C2A—C3A	−0.7 (2)	O1B—C1B—C2B—C3B	−175.27 (16)
C7A—C1A—C2A—C3A	−179.70 (15)	C6B—C1B—C2B—C3B	4.9 (2)
C6A—C1A—C2A—N2A	176.60 (13)	O1B—C1B—C2B—N2B	4.3 (3)
C7A—C1A—C2A—N2A	−2.4 (2)	C6B—C1B—C2B—N2B	−175.56 (14)
C8A—N2A—C2A—C3A	−94.78 (19)	N2B—C2B—C3B—C4B	177.91 (15)
C8A—N2A—C2A—C1A	87.8 (2)	C1B—C2B—C3B—C4B	−2.5 (3)
C1A—C2A—C3A—C4A	0.8 (2)	C2B—C3B—C4B—C5B	−2.0 (3)
N2A—C2A—C3A—C4A	−176.51 (13)	C2B—C3B—C4B—N4B	179.95 (15)
C2A—C3A—C4A—C5A	−0.3 (2)	O42B—N4B—C4B—C5B	−4.7 (3)
C2A—C3A—C4A—N1A	177.78 (13)	O41B—N4B—C4B—C5B	176.06 (16)
O2A—N1A—C4A—C5A	−176.41 (15)	O42B—N4B—C4B—C3B	173.45 (18)
O1A—N1A—C4A—C5A	3.7 (2)	O41B—N4B—C4B—C3B	−5.8 (3)
O2A—N1A—C4A—C3A	5.4 (2)	C3B—C4B—C5B—C6B	3.5 (3)
O1A—N1A—C4A—C3A	−174.45 (14)	N4B—C4B—C5B—C6B	−178.40 (15)
C3A—C4A—C5A—C6A	−0.3 (2)	C4B—C5B—C6B—C1B	−0.7 (3)
N1A—C4A—C5A—C6A	−178.34 (14)	C4B—C5B—C6B—N6B	−178.21 (15)
C4A—C5A—C6A—C1A	0.4 (2)	O1B—C1B—C6B—C5B	176.90 (16)
C2A—C1A—C6A—C5A	0.1 (2)	C2B—C1B—C6B—C5B	−3.2 (2)
C7A—C1A—C6A—C5A	179.07 (15)	O1B—C1B—C6B—N6B	−5.6 (2)
C2A—N2A—C8A—N3A	1.0 (2)	C2B—C1B—C6B—N6B	174.21 (14)
C2A—N2A—C8A—N4A	−179.04 (15)	O61B—N6B—C6B—C5B	13.8 (2)
O22B—N2B—C2B—C3B	14.1 (2)	O62B—N6B—C6B—C5B	−165.22 (16)
O21B—N2B—C2B—C3B	−164.83 (15)	O61B—N6B—C6B—C1B	−163.84 (16)
O22B—N2B—C2B—C1B	−165.51 (15)	O62B—N6B—C6B—C1B	17.1 (2)
O21B—N2B—C2B—C1B	15.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O22Bⁱ	0.88	2.20	3.0737 (18)	171
N3A—H3AB···O1B	0.88	2.03	2.7866 (18)	143
N3A—H3AB···O62B	0.88	2.35	3.0882 (18)	142
N3A—H3AC···O1Aⁱⁱ	0.88	2.32	2.9808 (19)	132
N4A—H4AA···O1B	0.88	1.98	2.7499 (18)	145
N4A—H4AA···O21B	0.88	2.34	3.0683 (19)	141
N4A—H4AB···O21Bⁱ	0.88	2.11	2.9572 (18)	163
C3A—H3AA···O41Bⁱⁱⁱ	0.95	2.37	3.262 (2)	155
C7A—H7AB···O1B^iv	0.98	2.56	3.447 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₄O₂⁺·C₆H₂N₃O₇⁻
M_r	423.31
Crystal system, space group	Triclinic, P1
Temperature (K)	110
a, b, c (Å)	7.1318 (10), 10.6239 (13), 11.9564 (13)
α, β, γ (°)	84.257 (10), 74.497 (11), 77.559 (11)
V (Å³)	851.58 (18)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.51 × 0.41 × 0.33

Data collection
Diffractometer	Oxford Xcalibur diffractometer with Ruby (Gemini Cu) detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.431, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6248, 3344, 2761
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.07
No. of reflections	3344
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O22Bⁱ	0.88	2.20	3.0737 (18)	171.3
N3A—H3AB···O1B	0.88	2.03	2.7866 (18)	143.0
N3A—H3AB···O62B	0.88	2.35	3.0882 (18)	141.8
N3A—H3AC···O1Aⁱⁱ	0.88	2.32	2.9808 (19)	131.5
N4A—H4AA···O1B	0.88	1.98	2.7499 (18)	144.7
N4A—H4AA···O21B	0.88	2.34	3.0683 (19)	140.7
N4A—H4AB···O21Bⁱ	0.88	2.11	2.9572 (18)	162.7
C3A—H3AA···O41Bⁱⁱⁱ	0.95	2.37	3.262 (2)	155.3
C7A—H7AB···O1B^iv	0.98	2.56	3.447 (2)	151.0

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

Acknowledgements

MTS thanks the University of Mysore for the use of their research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Becke, A. D. (1988). Phys. Rev. A, 38, 3098–100. CrossRef CAS PubMed Web of Science Google Scholar
Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652. CrossRef CAS Web of Science Google Scholar
Berlinck, R. G. S. (2002). Nat. Prod. Rep. 19, 617–649. Web of Science CrossRef PubMed CAS Google Scholar
Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004). J. Chem. Inf. Comput. Sci. 44, 2133–2144. Web of Science CSD CrossRef PubMed CAS Google Scholar
Cunningham, I. D., Wan, N. C., Povey, D. C., Smith, G. W. & Cox, B. G. (1997). Acta Cryst. C53, 984–985. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Demir, S., Dinçer, M. & Sarıpınar, E. (2006). Acta Cryst. E62, o4194–o4195. Web of Science CSD CrossRef IUCr Journals Google Scholar
Frisch, M. J., et al. (2004). GAUSSIAN03. Gaussian Inc., Wallingford, Connecticut, USA. Google Scholar
Gupta, M. P. & Dutta, B. P. (1975). Acta Cryst. B31, 1272–1275. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Hehre, W. J., Random, L., Schleyer, P. von R. & Pople, J. A. (1986). Ab Initio Molecular Orbital Theory. New York: Wiley. Google Scholar
Heys, L., Moore, C. G. & Murphy, P. J. (2000). Chem. Soc. Rev. 29, 57–67. Web of Science CrossRef CAS Google Scholar
Ishikawa, T. & Isobe, T. (2002). Chem. Eur. J. 8, 552–557. CrossRef PubMed CAS Google Scholar
Kelley, M. T., Burckstummer, T., Wenzel-Seifert, K., Dove, S., Buschauer, A. & Seifert, R. (2001). Mol. Pharm. 60, 1210–1225. CAS Google Scholar
Laeckmann, D., Rogister, F., Dejardin, J.-V., Prosperi-Meys, C., Geczy, J., Delarge, J. & Masereel, B. (2002). Bioorg. Med. Chem. 10, 1793–1804. Web of Science CrossRef PubMed CAS Google Scholar
Lee, C., Yang, W. & Parr, R. G. (1988). Phys. Rev. B, 37, 785–789. CrossRef CAS Web of Science Google Scholar
Moghimi, A., Aghabozorg, H., Soleimannejad, J. & Ramezanipour, F. (2005). Acta Cryst. E61, o442–o444. Web of Science CSD CrossRef IUCr Journals Google Scholar
Moroni, M., Koksch, B., Osipov, S. N., Crucianelli, M., Frigerio, M., Bravo, P. & Burger, K. (2001). J. Org. Chem. 66, 130–133. Web of Science CrossRef PubMed CAS Google Scholar
Murtaza, G., Hanif-Ur-Rehman,, Khawar Rauf, M., Ebihara, M. & Badshah, A. (2009). Acta Cryst. E65, o343. Google Scholar
Murtaza, G., Said, M., Rauf, M. K., Ebihara, M. & Badshah, A. (2007). Acta Cryst. E63, o4664. Web of Science CSD CrossRef IUCr Journals Google Scholar
Orner, B. P. & Hamilton, A. D. (2001). J. Inclusion Phenom. Macrocycl. Chem. 41, 141–147. Web of Science CrossRef CAS Google Scholar
Oxford Diffraction (2007). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Pereira Silva, P. S., Ramos Silva, M., Paixão, J. A. & Matos Beja, A. (2007). Acta Cryst. E63, o2524–o2526. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pruszynski, P., Leffek, K. T., Borecka, B. & Cameron, T. S. (1992). Acta Cryst. C48, 1638–1641. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ren, H., Cai, C., Liu, J.-Z. & Wang, J.-W. (2007). Acta Cryst. E63, o306–o307. CSD CrossRef IUCr Journals Google Scholar
Schmidt, J. R. & Polik, W. F. (2007). WebMO Pro. WebMO LLC, Holland, Michigan, USA. http://www.webmo.net. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, G., Wermuth, U. D., Healy, P. C. & White, J. M. (2007). Acta Cryst. E63, o7–o9. CSD CrossRef IUCr Journals Google Scholar
Smith, G., Wermuth, U. D. & White, J. M. (2007a). Acta Cryst. E63, o3759. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sonar, V. N., Neelakantan, S., Siegler, M. & Crooks, P. A. (2007). Acta Cryst. E63, o535–o536. Web of Science CSD CrossRef IUCr Journals Google Scholar
Stanford, D. J., Fernandez, R. A., Zeller, M. & Hunter, A. D. (2007). Acta Cryst. E63, o1934–o1936. Web of Science CSD CrossRef IUCr Journals Google Scholar
Stępień, A. & Grabowski, M. J. (1977). Acta Cryst. B33, 2924–2927. CSD CrossRef IUCr Journals Web of Science Google Scholar
Wang, W.-F., Wei, C.-M. & Zhu, H.-J. (2009). Acta Cryst. E65, o980. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wei, C.-M. (2008). Acta Cryst. E64, o1244. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zyss, J., Pecaut, J., Levy, J. P. & Masse, R. (1993). Acta Cryst. B49, 334–342. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar