1-Methyl-3-(2-oxo-2H-chromen-3-yl)-1H-imidazol-3-ium picrate

Tuyen, N.V.; Anh, L.T.; Festa, A.A.; Voskressensky, L.G.; Khrustalev, V.N.

doi:10.1107/S1600536813011690

organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o839

doi:10.1107/S1600536813011690

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1-Methyl-3-(2-oxo-2H-chromen-3-yl)-1H-imidazol-3-ium picrate

Nguyen Van Tuyen,^a ^* Le Tuan Anh,^b Alexey A. Festa,^c Leonid G. Voskressensky ^c and Victor N. Khrustalev ^d

^aInstitute of Chemistry, Vietnam Academy of Science & Technology, 18 Hoang Quoc Viet, Cau Giay, Hanoi, Vietnam, ^bDepartment of Chemistry, Vietnam National University, 144 Xuan Thuy, Cau Giay, Hanoi, Vietnam, ^cOrganic Chemistry Department, Russian Peoples Friendship University, Miklukho-Maklai St, 6, Moscow 117198, Russian Federation, and ^dX-Ray Structural Centre, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov St 28, B-334, Moscow 119991, Russian Federation
^*Correspondence e-mail: ngvtuyen@hotmail.com

(Received 25 April 2013; accepted 29 April 2013; online 4 May 2013)

The title salt, C₁₃H₁₁N₂O₂⁺·C₆H₂N₃O₇⁻, is the unexpected product of a domino reaction of 3-cyanomethyl-1-methylimidazolium chloride with salicylic aldehyde in the presence of picric acid. In the cation, the 1H-imidazole ring is twisted by 63.2 (1)° from the 2H-chromen plane. In the crystal, cations and anions are alternately stacked along the a axis through π–π stacking interactions between the almost parallel aromatic rings [centroid–centroid distances = 3.458 (2) and 3.678 (2) Å]. The stacks are further linked by C—H⋯O hydrogen bonds into a two-tier layer parallel to (001).

Related literature

For a recent review on coumarin-based drug patents, see: Kontogiorgis et al. (2012 ). For analogous domino reactions, see: Voskressensky et al. (2012a ,b ). For related compounds, see: Yu et al. (2006 ); Morris et al. (2011 ).

Experimental

Crystal data

C₁₃H₁₁N₂O₂⁺·C₆H₂N₃O₇⁻
M_r = 455.34
Monoclinic, P 2₁
a = 6.8142 (12) Å
b = 8.1942 (14) Å
c = 16.832 (3) Å
β = 100.081 (4)°
V = 925.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.30 × 0.21 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.961, T_max = 0.996
10390 measured reflections
4415 independent reflections
3734 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.165
S = 1.00
4415 reflections
299 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O7ⁱ	0.95	2.58	3.349 (4)	138
C9—H9⋯O3	0.95	2.33	3.122 (5)	140
C10—H10⋯O9ⁱⁱ	0.95	2.51	3.303 (5)	141
C11—H11⋯O3ⁱⁱⁱ	0.95	2.42	3.196 (5)	139
C11—H11⋯O5ⁱⁱⁱ	0.95	2.51	3.231 (5)	132
C12—H12A⋯O2^iv	0.98	2.58	3.360 (5)	137
C12—H12B⋯O2^v	0.98	2.48	3.448 (5)	171
C12—H12C⋯O3^iv	0.98	2.39	3.269 (4)	148
C12—H12C⋯O9^iv	0.98	2.42	3.160 (5)	132
C17—H17⋯O5^vi	0.95	2.40	3.345 (5)	172
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+2]$ ; (ii) x+1, y-1, z; (iii) x+1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (v) x, y-1, z; (vi) x, y+1, z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2001 ); data reduction: SAINT; 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: 10.1107/S1600536813011690/is5268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813011690/is5268Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813011690/is5268Isup3.cml

checkCIF report

Comment top

Coumarin derivatives are known to possess a range of different biological activities (Kontogiorgis et al., 2012). The title compound, C₁₃H₁₁N₂O₂⁺.C₆H₂N₃O₇^- (I), is the unexpected product of Knoevenagel condensation of 3-(cyanomethyl)-1-methylimidazolium chloride with salicylic aldehyde followed by the hydrolysis of imino-group and the formation of ammonium salt with picric acid (Fig. 1; Voskressensky et al., 2012a,b).

The cation and anion of I form a tight ionic pair by the C9—H9···O3 hydrogen bond (Table 1) as well as the π–π stacking interactions between the almost parallel aromatic moieties [the dihedral angle between the mean planes of the 2H-chromen (cation) and benzene (anion) fragments is 3.55 (7)°; the shortest C8···C17 distance is 3.280 (5) Å; Fig. 2]. The 1H-imidazole ring is twisted at 63.2 (1)° from the 2H-chromen plane. In the crystal, the tight ionic pairs form stacks along the a axis by the π–π stacking interactions (Fig. 3). The stacks are further bound by the C—H···O hydrogen bonds into two-tier layers parallel to (001) (Fig. 4).

Related literature top

For recent review on coumarin-based drug patents, see: Kontogiorgis et al. (2012). For analogous domino reactions, see: Voskressensky et al. (2012a,b). For related compounds, see: Yu et al. (2006); Morris et al. (2011).

Experimental top

A solid Na₂CO₃ (67.0 mg, 0.63 mmol) was added to a stirred solution of 3-(cyanomethyl)-1-methylimidazolium chloride (500 mg, 3.2 mmol) and salicylic aldehyde (350 mg, 2.9 mmol) in a mixture of methanol (4 ml) and water (1 ml) at reflux. The reaction mixture was heated at reflux for 1 h. Then picric acid (870 mg, 3.8 mmol) was added to the solution. The formed precipitate was filtered-off and washed with acetone (3x) to give 630 mg of yellow crystals of I. The yield is 48%. M.p. = 459 K (decomp.). ¹H NMR (DMSO-d₆, 400 MHz): δ = 4.04 (3H, s, Me), 7.54 (1H, t, J = 7.5 Hz, H6'), 7.63 (1H, d, J = 8.3 Hz, H5'), 7.79–7.85 (1H, m, H7'), 7.87–7.92 (1H, m, H8'), 7.98–8.01 (1H, m, H5), 8.16–8.19 (1H, m, H4), 8.61 (2H, s, picric acid CH), 8.70 (1H, s, H4'), 9.71 (1H, bs, H2); ¹³C NMR (DMSO-d₆, 100 MHz): δ = 36.2, 116.4, 117.6, 121.6, 122.5, 123.7, 124.2, 125.1 (2 C), 125.5, 129.4, 133.5, 137.3, 137.5, 141.8, 152.4 (2 C), 156.1, 160.8. Anal. Calcd for C₁₃H₁₁N₂O₂.C₆H₂N₃O₇: C 50.12, H 2.88, N 15.38; found: C 50.34, H 3.01, N 15.53.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 domino reaction of 3-(cyanomethyl)-1-methylimidazolium chloride with salicylic aldehyde.
	Fig. 2. The molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. Dashed line indicates the (N)C(N⁺)—H···O^- hydrogen bond between cation and anion.
	Fig. 3. A portion of crystal packing of the title compound demonstrating the stacks along the a axis. Dashed lines indicate the intermolecular C—H···O hydrogen bonds.
	Fig. 4. The two-tier layers of the title compound parallel to (001). Dashed lines indicate the intermolecular C—H···O hydrogen bonds.

1-Methyl-3-(2-oxo-2H-chromen-3-yl)-1H-imidazol-3-ium picrate top

Crystal data top

C₁₃H₁₁N₂O₂⁺·C₆H₂N₃O₇⁻	F(000) = 468
M_r = 455.34	D_x = 1.634 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3018 reflections
a = 6.8142 (12) Å	θ = 2.5–30.2°
b = 8.1942 (14) Å	µ = 0.13 mm⁻¹
c = 16.832 (3) Å	T = 100 K
β = 100.081 (4)°	Plate, yellow
V = 925.3 (3) Å³	0.30 × 0.21 × 0.03 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	4415 independent reflections
Radiation source: fine-focus sealed tube	3734 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
T_min = 0.961, T_max = 0.996	k = −10→10
10390 measured reflections	l = −22→22

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0754P)² + 1.86P] where P = (F_o² + 2F_c²)/3
4415 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.46 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₃H₁₁N₂O₂⁺·C₆H₂N₃O₇⁻	V = 925.3 (3) Å³
M_r = 455.34	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.8142 (12) Å	µ = 0.13 mm⁻¹
b = 8.1942 (14) Å	T = 100 K
c = 16.832 (3) Å	0.30 × 0.21 × 0.03 mm
β = 100.081 (4)°

Data collection top

Bruker APEXII CCD diffractometer	4415 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	3734 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.996	R_int = 0.040
10390 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	1 restraint
wR(F²) = 0.165	H-atom parameters constrained
S = 1.00	Δρ_max = 0.46 e Å⁻³
4415 reflections	Δρ_min = −0.36 e Å⁻³
299 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
O1	0.8777 (4)	0.6678 (3)	0.68430 (15)	0.0183 (5)
O2	0.8003 (4)	0.5232 (4)	0.57153 (15)	0.0233 (6)
N1	0.9223 (4)	0.2275 (4)	0.64703 (18)	0.0166 (6)
N2	0.8021 (5)	0.0278 (4)	0.57071 (17)	0.0166 (6)
C2	0.8643 (5)	0.5224 (5)	0.6430 (2)	0.0168 (7)
C3	0.9351 (5)	0.3784 (5)	0.6911 (2)	0.0161 (7)
C4	1.0105 (5)	0.3861 (5)	0.7702 (2)	0.0171 (7)
H4	1.0561	0.2899	0.7992	0.021*
C4A	1.0217 (5)	0.5408 (5)	0.8103 (2)	0.0165 (7)
C5	1.0926 (5)	0.5595 (5)	0.8937 (2)	0.0178 (7)
H5	1.1365	0.4666	0.9257	0.021*
C6	1.0989 (5)	0.7124 (5)	0.9295 (2)	0.0205 (8)
H6	1.1461	0.7240	0.9857	0.025*
C7	1.0352 (6)	0.8501 (5)	0.8821 (2)	0.0223 (8)
H7	1.0420	0.9552	0.9063	0.027*
C8	0.9623 (6)	0.8333 (5)	0.8001 (2)	0.0208 (8)
H8	0.9169	0.9257	0.7681	0.025*
C8A	0.9570 (5)	0.6794 (5)	0.7661 (2)	0.0172 (7)
C9	0.7529 (5)	0.1610 (5)	0.6077 (2)	0.0163 (7)
H9	0.6218	0.2018	0.6064	0.020*
C10	1.0046 (6)	0.0076 (5)	0.5862 (2)	0.0198 (7)
H10	1.0772	−0.0786	0.5671	0.024*
C11	1.0826 (5)	0.1338 (5)	0.6341 (2)	0.0200 (7)
H11	1.2195	0.1536	0.6546	0.024*
C12	0.6615 (6)	−0.0810 (5)	0.5195 (2)	0.0218 (8)
H12A	0.5247	−0.0517	0.5245	0.033*
H12B	0.6878	−0.1942	0.5369	0.033*
H12C	0.6784	−0.0694	0.4632	0.033*
O3	0.4485 (4)	0.3812 (3)	0.67659 (15)	0.0185 (5)
O4	0.7273 (4)	0.1650 (4)	0.85805 (18)	0.0293 (7)
O5	0.4224 (5)	0.1338 (4)	0.79424 (19)	0.0310 (7)
O6	0.6970 (5)	0.6752 (4)	1.02204 (16)	0.0283 (7)
O7	0.5824 (4)	0.8942 (3)	0.95546 (17)	0.0245 (6)
O8	0.4486 (4)	0.8736 (3)	0.66647 (16)	0.0239 (6)
O9	0.2690 (4)	0.6684 (4)	0.61602 (16)	0.0257 (6)
N3	0.5653 (5)	0.2192 (4)	0.82445 (19)	0.0197 (6)
N4	0.6210 (5)	0.7472 (4)	0.95962 (18)	0.0183 (6)
N5	0.3876 (5)	0.7341 (4)	0.67024 (19)	0.0185 (6)
C13	0.4738 (5)	0.4649 (4)	0.7400 (2)	0.0134 (7)
C14	0.5419 (5)	0.3960 (5)	0.8190 (2)	0.0173 (7)
C15	0.5962 (5)	0.4837 (4)	0.8896 (2)	0.0155 (7)
H15	0.6481	0.4310	0.9391	0.019*
C16	0.5717 (5)	0.6527 (5)	0.8853 (2)	0.0159 (7)
C17	0.5037 (5)	0.7321 (5)	0.8138 (2)	0.0161 (7)
H17	0.4908	0.8476	0.8125	0.019*
C18	0.4542 (5)	0.6419 (5)	0.7437 (2)	0.0170 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0207 (13)	0.0180 (13)	0.0157 (12)	0.0025 (11)	0.0020 (9)	−0.0013 (10)
O2	0.0339 (16)	0.0201 (14)	0.0150 (12)	−0.0014 (12)	0.0016 (11)	0.0006 (11)
N1	0.0142 (14)	0.0172 (15)	0.0181 (14)	−0.0001 (12)	0.0019 (11)	−0.0001 (12)
N2	0.0237 (16)	0.0131 (14)	0.0130 (13)	−0.0004 (12)	0.0036 (11)	−0.0013 (11)
C2	0.0155 (17)	0.0147 (16)	0.0212 (17)	0.0007 (14)	0.0062 (13)	0.0011 (14)
C3	0.0155 (16)	0.0133 (16)	0.0195 (17)	0.0007 (13)	0.0035 (13)	−0.0003 (14)
C4	0.0178 (16)	0.0163 (17)	0.0175 (16)	0.0021 (14)	0.0042 (13)	0.0010 (14)
C4A	0.0121 (16)	0.0192 (18)	0.0181 (16)	−0.0026 (14)	0.0024 (13)	−0.0024 (14)
C5	0.0141 (17)	0.0206 (18)	0.0175 (17)	0.0014 (14)	−0.0002 (13)	0.0014 (14)
C6	0.0167 (17)	0.022 (2)	0.0212 (18)	−0.0030 (14)	−0.0002 (13)	−0.0036 (15)
C7	0.0167 (18)	0.022 (2)	0.028 (2)	−0.0007 (15)	0.0040 (15)	−0.0101 (16)
C8	0.0208 (19)	0.0158 (18)	0.0256 (19)	0.0011 (14)	0.0038 (15)	−0.0010 (14)
C8A	0.0176 (17)	0.0215 (18)	0.0117 (15)	−0.0002 (14)	0.0010 (12)	−0.0012 (14)
C9	0.0165 (16)	0.0163 (17)	0.0157 (16)	0.0008 (14)	0.0018 (12)	−0.0001 (13)
C10	0.0222 (18)	0.0217 (19)	0.0169 (16)	0.0009 (15)	0.0072 (13)	0.0022 (14)
C11	0.0163 (17)	0.0250 (19)	0.0192 (18)	0.0025 (15)	0.0047 (13)	0.0031 (14)
C12	0.029 (2)	0.0186 (19)	0.0155 (17)	−0.0051 (15)	−0.0025 (14)	−0.0030 (14)
O3	0.0197 (13)	0.0201 (13)	0.0150 (12)	0.0018 (11)	0.0011 (9)	−0.0049 (11)
O4	0.0266 (15)	0.0243 (15)	0.0361 (16)	0.0091 (12)	0.0032 (12)	0.0054 (13)
O5	0.0455 (18)	0.0140 (14)	0.0279 (15)	−0.0041 (13)	−0.0089 (13)	0.0022 (11)
O6	0.0429 (17)	0.0229 (15)	0.0172 (13)	−0.0014 (13)	0.0000 (12)	−0.0038 (11)
O7	0.0348 (15)	0.0170 (14)	0.0207 (13)	−0.0002 (12)	0.0022 (11)	−0.0069 (11)
O8	0.0346 (16)	0.0162 (13)	0.0212 (13)	−0.0008 (12)	0.0061 (11)	0.0041 (11)
O9	0.0310 (15)	0.0231 (14)	0.0195 (13)	0.0036 (12)	−0.0057 (11)	−0.0036 (11)
N3	0.0268 (17)	0.0144 (15)	0.0179 (15)	0.0034 (13)	0.0041 (12)	0.0003 (12)
N4	0.0204 (15)	0.0182 (16)	0.0172 (15)	−0.0036 (12)	0.0060 (12)	−0.0042 (12)
N5	0.0173 (15)	0.0213 (16)	0.0170 (15)	0.0028 (13)	0.0036 (12)	−0.0008 (12)
C13	0.0079 (16)	0.0186 (18)	0.0135 (15)	−0.0004 (12)	0.0015 (12)	−0.0022 (12)
C14	0.0168 (17)	0.0131 (17)	0.0212 (18)	0.0002 (14)	0.0011 (13)	0.0017 (14)
C15	0.0147 (17)	0.0144 (17)	0.0184 (17)	−0.0013 (13)	0.0051 (13)	−0.0006 (13)
C16	0.0157 (16)	0.0160 (17)	0.0159 (16)	−0.0011 (14)	0.0023 (12)	−0.0057 (14)
C17	0.0129 (16)	0.0159 (17)	0.0205 (17)	−0.0002 (14)	0.0062 (13)	−0.0020 (14)
C18	0.0148 (17)	0.0170 (18)	0.0182 (17)	−0.0003 (14)	0.0002 (13)	0.0003 (14)

Geometric parameters (Å, º) top

O1—C2	1.374 (5)	C10—C11	1.361 (6)
O1—C8A	1.391 (4)	C10—H10	0.9500
O2—C2	1.206 (5)	C11—H11	0.9500
N1—C9	1.342 (5)	C12—H12A	0.9800
N1—C11	1.383 (5)	C12—H12B	0.9800
N1—C3	1.437 (5)	C12—H12C	0.9800
N2—C9	1.328 (5)	O3—C13	1.255 (4)
N2—C10	1.369 (5)	O4—N3	1.232 (4)
N2—C12	1.472 (5)	O5—N3	1.235 (4)
C2—C3	1.464 (5)	O6—N4	1.237 (4)
C3—C4	1.342 (5)	O7—N4	1.232 (4)
C4—C4A	1.433 (5)	O8—N5	1.222 (4)
C4—H4	0.9500	O9—N5	1.232 (4)
C4A—C8A	1.387 (5)	N3—C14	1.458 (5)
C4A—C5	1.410 (5)	N4—C16	1.460 (4)
C5—C6	1.387 (6)	N5—C18	1.452 (5)
C5—H5	0.9500	C13—C14	1.445 (5)
C6—C7	1.405 (6)	C13—C18	1.458 (5)
C6—H6	0.9500	C14—C15	1.383 (5)
C7—C8	1.389 (6)	C15—C16	1.395 (5)
C7—H7	0.9500	C15—H15	0.9500
C8—C8A	1.383 (5)	C16—C17	1.376 (5)
C8—H8	0.9500	C17—C18	1.383 (5)
C9—H9	0.9500	C17—H17	0.9500

C2—O1—C8A	122.7 (3)	C11—C10—H10	126.4
C9—N1—C11	109.4 (3)	N2—C10—H10	126.4
C9—N1—C3	125.0 (3)	C10—C11—N1	106.1 (3)
C11—N1—C3	125.5 (3)	C10—C11—H11	126.9
C9—N2—C10	109.8 (3)	N1—C11—H11	126.9
C9—N2—C12	125.5 (3)	N2—C12—H12A	109.5
C10—N2—C12	124.7 (3)	N2—C12—H12B	109.5
O2—C2—O1	118.7 (3)	H12A—C12—H12B	109.5
O2—C2—C3	125.7 (4)	N2—C12—H12C	109.5
O1—C2—C3	115.6 (3)	H12A—C12—H12C	109.5
C4—C3—N1	122.0 (3)	H12B—C12—H12C	109.5
C4—C3—C2	122.9 (4)	O4—N3—O5	124.3 (3)
N1—C3—C2	115.1 (3)	O4—N3—C14	117.8 (3)
C3—C4—C4A	119.3 (4)	O5—N3—C14	117.9 (3)
C3—C4—H4	120.4	O7—N4—O6	124.6 (3)
C4A—C4—H4	120.4	O7—N4—C16	117.1 (3)
C8A—C4A—C5	117.8 (3)	O6—N4—C16	118.3 (3)
C8A—C4A—C4	119.1 (3)	O8—N5—O9	123.7 (3)
C5—C4A—C4	123.1 (4)	O8—N5—C18	118.2 (3)
C6—C5—C4A	120.6 (4)	O9—N5—C18	118.0 (3)
C6—C5—H5	119.7	O3—C13—C14	122.9 (3)
C4A—C5—H5	119.7	O3—C13—C18	125.4 (3)
C5—C6—C7	119.7 (3)	C14—C13—C18	111.5 (3)
C5—C6—H6	120.1	C15—C14—C13	125.6 (3)
C7—C6—H6	120.1	C15—C14—N3	116.9 (3)
C8—C7—C6	120.3 (4)	C13—C14—N3	117.4 (3)
C8—C7—H7	119.8	C14—C15—C16	117.4 (3)
C6—C7—H7	119.8	C14—C15—H15	121.3
C8A—C8—C7	118.7 (4)	C16—C15—H15	121.3
C8A—C8—H8	120.6	C17—C16—C15	122.3 (3)
C7—C8—H8	120.6	C17—C16—N4	119.4 (3)
C8—C8A—C4A	122.8 (3)	C15—C16—N4	118.3 (3)
C8—C8A—O1	116.8 (3)	C16—C17—C18	119.2 (3)
C4A—C8A—O1	120.5 (3)	C16—C17—H17	120.4
N2—C9—N1	107.4 (3)	C18—C17—H17	120.4
N2—C9—H9	126.3	C17—C18—N5	116.2 (3)
N1—C9—H9	126.3	C17—C18—C13	123.9 (3)
C11—C10—N2	107.3 (3)	N5—C18—C13	119.9 (3)

C8A—O1—C2—O2	−177.4 (3)	C12—N2—C10—C11	178.7 (3)
C8A—O1—C2—C3	1.3 (5)	N2—C10—C11—N1	0.6 (4)
C9—N1—C3—C4	120.5 (4)	C9—N1—C11—C10	−0.5 (4)
C11—N1—C3—C4	−64.0 (5)	C3—N1—C11—C10	−176.6 (3)
C9—N1—C3—C2	−60.9 (5)	O3—C13—C14—C15	171.5 (4)
C11—N1—C3—C2	114.6 (4)	C18—C13—C14—C15	−4.2 (5)
O2—C2—C3—C4	177.9 (4)	O3—C13—C14—N3	−5.2 (5)
O1—C2—C3—C4	−0.7 (5)	C18—C13—C14—N3	179.1 (3)
O2—C2—C3—N1	−0.7 (5)	O4—N3—C14—C15	−50.5 (5)
O1—C2—C3—N1	−179.4 (3)	O5—N3—C14—C15	130.3 (4)
N1—C3—C4—C4A	179.1 (3)	O4—N3—C14—C13	126.5 (4)
C2—C3—C4—C4A	0.6 (5)	O5—N3—C14—C13	−52.7 (5)
C3—C4—C4A—C8A	−1.0 (5)	C13—C14—C15—C16	4.2 (5)
C3—C4—C4A—C5	177.9 (3)	N3—C14—C15—C16	−179.1 (3)
C8A—C4A—C5—C6	−0.7 (5)	C14—C15—C16—C17	−2.4 (5)
C4—C4A—C5—C6	−179.6 (3)	C14—C15—C16—N4	177.7 (3)
C4A—C5—C6—C7	−0.4 (5)	O7—N4—C16—C17	6.1 (5)
C5—C6—C7—C8	1.3 (6)	O6—N4—C16—C17	−174.2 (3)
C6—C7—C8—C8A	−1.1 (6)	O7—N4—C16—C15	−174.1 (3)
C7—C8—C8A—C4A	−0.1 (6)	O6—N4—C16—C15	5.6 (5)
C7—C8—C8A—O1	178.3 (3)	C15—C16—C17—C18	1.2 (5)
C5—C4A—C8A—C8	1.0 (5)	N4—C16—C17—C18	−179.0 (3)
C4—C4A—C8A—C8	179.9 (4)	C16—C17—C18—N5	−178.7 (3)
C5—C4A—C8A—O1	−177.3 (3)	C16—C17—C18—C13	−1.5 (5)
C4—C4A—C8A—O1	1.6 (5)	O8—N5—C18—C17	27.9 (5)
C2—O1—C8A—C8	179.8 (3)	O9—N5—C18—C17	−150.4 (3)
C2—O1—C8A—C4A	−1.8 (5)	O8—N5—C18—C13	−149.4 (3)
C10—N2—C9—N1	0.1 (4)	O9—N5—C18—C13	32.3 (5)
C12—N2—C9—N1	−179.0 (3)	O3—C13—C18—C17	−172.8 (3)
C11—N1—C9—N2	0.3 (4)	C14—C13—C18—C17	2.8 (5)
C3—N1—C9—N2	176.4 (3)	O3—C13—C18—N5	4.3 (5)
C9—N2—C10—C11	−0.4 (4)	C14—C13—C18—N5	179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O7ⁱ	0.95	2.58	3.349 (4)	138
C9—H9···O3	0.95	2.33	3.122 (5)	140
C10—H10···O9ⁱⁱ	0.95	2.51	3.303 (5)	141
C11—H11···O3ⁱⁱⁱ	0.95	2.42	3.196 (5)	139
C11—H11···O5ⁱⁱⁱ	0.95	2.51	3.231 (5)	132
C12—H12A···O2^iv	0.98	2.58	3.360 (5)	137
C12—H12B···O2^v	0.98	2.48	3.448 (5)	171
C12—H12C···O3^iv	0.98	2.39	3.269 (4)	148
C12—H12C···O9^iv	0.98	2.42	3.160 (5)	132
C17—H17···O5^vi	0.95	2.40	3.345 (5)	172

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁N₂O₂⁺·C₆H₂N₃O₇⁻
M_r	455.34
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	6.8142 (12), 8.1942 (14), 16.832 (3)
β (°)	100.081 (4)
V (Å³)	925.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.21 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.961, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	10390, 4415, 3734
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.165, 1.00
No. of reflections	4415
No. of parameters	299
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), 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
C5—H5···O7ⁱ	0.95	2.58	3.349 (4)	138
C9—H9···O3	0.95	2.33	3.122 (5)	140
C10—H10···O9ⁱⁱ	0.95	2.51	3.303 (5)	141
C11—H11···O3ⁱⁱⁱ	0.95	2.42	3.196 (5)	139
C11—H11···O5ⁱⁱⁱ	0.95	2.51	3.231 (5)	132
C12—H12A···O2^iv	0.98	2.58	3.360 (5)	137
C12—H12B···O2^v	0.98	2.48	3.448 (5)	171
C12—H12C···O3^iv	0.98	2.39	3.269 (4)	148
C12—H12C···O9^iv	0.98	2.42	3.160 (5)	132
C17—H17···O5^vi	0.95	2.40	3.345 (5)	172

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

Acknowledgements

The authors are grateful to the Russian Foundation for Basic Research (project No. 12–03-93000-Viet-a) and the Vietnam Academy of Science and Technology (grant VAST·HTQT·NGA. 06/2012–2013) for the financial support of this work.

References

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