3-Benzyl-1-methyl­imidazolium picrate

Pi, M.; Liu, X.-L.; Xu, J.-J.; Jin, C.-M.

doi:10.1107/S1600536809035454

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2386

doi:10.1107/S1600536809035454

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3-Benzyl-1-methylimidazolium picrate

Min Pi,^a Xiu-Ling Liu,^a Ji-Jun Xu ^a and Chuan-Ming Jin ^a ^*

^aHubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Environmental Engineering, Hubei Normal University, Huangshi, Hubei 435002, People's Republic of China
^*Correspondence e-mail: cmjin@email.hbnu.edu.cn

(Received 24 August 2009; accepted 2 September 2009; online 9 September 2009)

In the title salt, C₁₁H₁₃N₂⁺·C₆H₂N₃O₇⁻, the dihedral angles between the benzene ring in the cation and the imidazolium ring and the benzene ring of the picrate anion are 113.7 (2) and 116.3 (2)°, respectively. The imidazolium ring is nearly parallel to the benzene ring of the picrate anion, the dihedral angle between the planes being 2.6 (1)°. The nitro groups in the picrate anions are disordered (occupancy ratio 0.54:0.46). The crystal packing is stabilized by weak C—H⋯O interactions between the cation–anion pairs.

Related literature

For civilian and military applications of energetic materials, see: Sikder & Sikder (2004 ). Heterocyclic organic salts with low melting points are a new class of energetic materials, which have attracted considerable interest because of their `green chemistry' properties, see: Singh et al. (2006 ). Picric acid is a polynitrogen compound with explosive character and imidazolium-based cation picrate salts are good candidates for energetic ionic salts, see: Jin et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₃N₂⁺·C₆H₂N₃O₇⁻
M_r = 401.34
Triclinic, $[P \overline 1]$
a = 9.1322 (6) Å
b = 10.2060 (7) Å
c = 10.8744 (7) Å
α = 63.6190 (10)°
β = 80.1660 (10)°
γ = 86.4820 (10)°
V = 894.52 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.986, T_max = 0.988
5623 measured reflections
3447 independent reflections
2610 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.144
S = 1.04
3447 reflections
320 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17C⋯O7ⁱ	0.96	2.42	3.346 (10)	162
C14—H14⋯O5ⁱⁱ	0.93	2.39	3.283 (11)	161
C17—H17A⋯O2ⁱⁱⁱ	0.96	2.32	3.205 (11)	153
C16—H16⋯O2ⁱⁱⁱ	0.93	2.39	3.159 (9)	140
C16—H16⋯O1ⁱⁱⁱ	0.93	2.19	3.021 (2)	149
C13—H13A⋯O1ⁱⁱⁱ	0.97	2.58	3.382 (3)	140
C17—H17C⋯O7ⁱ	0.96	2.42	3.346 (10)	162
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x+1, y, z; (iii) x, y-1, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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 I, global. DOI: 10.1107/S1600536809035454/jj2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035454/jj2007Isup2.hkl

checkCIF report

Comment top

Energetic materials are used extensively for both civilian and military applications (Sikder & Sikder, 2004). Heterocyclic organic salts with low melting points are a new class of energetic materials that has attracted considerable interest because of their "green chemistry" properties (Singh et al., 2006). Picric acid is a polynitrogen compound with explosive character and imidazolium-based cation picrate salts are good candidates for energetic ionic salts (Jin et al., 2005). Based on our continued interest in these compounds, the title organic salt (scheme 1) was prepared and its structure is reported.

The asymmetric unit of the title compound contains one independent cation (1-methyl-3-benzenylimidazolium)-anion (picrate) pair (Fig. 1). The dihedral angle between the benzene ring in the cation and the imidazolium ring and the benzene ring of the picrate anion is 113.7 (2)° and 116.3 (2) °, respectively. The imidazolium ring is nearly parallel to the benzene ring of the picrate anion with the dihedral angle of separation being 2.6 (1)°. The oxygen atoms in the nitro groups of the picrate anion are disorderd with the o-NO₂ major components (O2, O3, O4, O5) being 0.54 occupied and the p-NO₂major components (O5, O6) at 0.58 occupancy . Crystal packing is stabilized by the weak C—H···O interactions between the cation-anion pairs (Fig. 2, Table 1).

Related literature top

For civilian and military applications of energetic materials, see: Sikder & Sikder (2004). Heterocyclic organic salts with low melting points are a new class of energetic materials, which have attracted considerable interest because of their `green chemistry' properties, see: Singh et al. (2006). Picric acid is a polynitrogen compound with explosive character and imidazolium-based cation picrate salts are good candidates for energetic ionic salts, see: Jin et al. (2005).

Experimental top

The title salt (C₁₁H₁₃N₂)⁺.(C₆H₂N₃O₇)^- was synthesized using a slightly modified literature mothod (Jin et al., 2005). It was crystallized by slow evaporation of an acetonitrile and methanol solution of the salt.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (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 structure of (I) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. Only the predominate nitro oxygen atoms are displayed for the disordered nitro groups [O2,O3,O4,O5 (0.54); O6,O7 (0.58)].
	Fig. 2. The molecular packing diagram of the title compound. Dashed lines indicate weak C—H···O hydrogen bonding interactions between the cation-anion pairs (Table 1). Both of the disordered oxygen atoms in the nitro groups of the picrate anions are displayed.

3-Benzyl-1-methylimidazolium picrate top

Crystal data top

C₁₁H₁₃N₂⁺·C₆H₂N₃O₇⁻	Z = 2
M_r = 401.34	F(000) = 416
Triclinic, P1	D_x = 1.490 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1322 (6) Å	Cell parameters from 1924 reflections
b = 10.2060 (7) Å	θ = 2.2–26.5°
c = 10.8744 (7) Å	µ = 0.12 mm⁻¹
α = 63.619 (1)°	T = 298 K
β = 80.166 (1)°	Block, yellow
γ = 86.482 (1)°	0.20 × 0.10 × 0.10 mm
V = 894.52 (10) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3447 independent reflections
Radiation source: fine-focus sealed tube	2610 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.986, T_max = 0.988	k = −12→12
5623 measured reflections	l = −11→13

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0707P)²] where P = (F_o² + 2F_c²)/3
3447 reflections	(Δ/σ)_max < 0.001
320 parameters	Δρ_max = 0.35 e Å⁻³
15 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₁H₁₃N₂⁺·C₆H₂N₃O₇⁻	γ = 86.482 (1)°
M_r = 401.34	V = 894.52 (10) Å³
Triclinic, P1	Z = 2
a = 9.1322 (6) Å	Mo Kα radiation
b = 10.2060 (7) Å	µ = 0.12 mm⁻¹
c = 10.8744 (7) Å	T = 298 K
α = 63.619 (1)°	0.20 × 0.10 × 0.10 mm
β = 80.166 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3447 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2610 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.988	R_int = 0.046
5623 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	15 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
3447 reflections	Δρ_min = −0.24 e Å⁻³
320 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	Occ. (<1)
C1	0.6669 (2)	0.9523 (2)	0.3757 (2)	0.0412 (5)
C2	0.5960 (2)	0.8381 (2)	0.50638 (19)	0.0391 (5)
C3	0.4985 (2)	0.7359 (2)	0.5166 (2)	0.0417 (5)
H3	0.4582	0.6639	0.6035	0.050*
C4	0.4602 (2)	0.7397 (2)	0.3977 (2)	0.0421 (5)
C5	0.5191 (2)	0.8461 (2)	0.2678 (2)	0.0435 (5)
H5	0.4912	0.8496	0.1881	0.052*
C6	0.6182 (2)	0.9453 (2)	0.25820 (19)	0.0409 (5)
C7	0.9029 (2)	0.4665 (2)	0.16740 (19)	0.0448 (5)
C8	0.7605 (3)	0.4513 (3)	0.1476 (2)	0.0602 (6)
H8	0.7217	0.3584	0.1754	0.072*
C9	0.6758 (3)	0.5720 (4)	0.0873 (3)	0.0767 (8)
H9	0.5803	0.5606	0.0741	0.092*
C10	0.7316 (3)	0.7092 (3)	0.0466 (2)	0.0736 (8)
H10	0.6740	0.7908	0.0058	0.088*
C11	0.8721 (3)	0.7263 (3)	0.0659 (2)	0.0670 (7)
H11	0.9097	0.8194	0.0390	0.080*
C12	0.9572 (3)	0.6063 (2)	0.1247 (2)	0.0525 (6)
H12	1.0532	0.6188	0.1362	0.063*
C13	0.9942 (3)	0.3344 (2)	0.2325 (2)	0.0516 (6)
H13A	0.9526	0.2525	0.2267	0.062*
H13B	1.0944	0.3526	0.1807	0.062*
C14	1.0841 (2)	0.3658 (2)	0.4261 (2)	0.0495 (5)
H14	1.1477	0.4457	0.3713	0.059*
C15	1.0570 (2)	0.2983 (2)	0.5651 (2)	0.0492 (5)
H15	1.0988	0.3221	0.6249	0.059*
C16	0.9239 (2)	0.1884 (2)	0.4886 (2)	0.0428 (5)
H16	0.8581	0.1243	0.4855	0.051*
C17	0.9006 (3)	0.0830 (3)	0.7460 (2)	0.0630 (7)
H17A	0.8231	0.0235	0.7460	0.094*
H17B	0.8617	0.1349	0.7993	0.094*
H17C	0.9802	0.0218	0.7866	0.094*
N1	0.6315 (2)	0.8244 (2)	0.63649 (18)	0.0492 (5)
N2	0.3603 (2)	0.6289 (2)	0.4097 (2)	0.0525 (5)
N3	0.6791 (2)	1.0516 (2)	0.11900 (19)	0.0537 (5)
N4	1.00040 (18)	0.29513 (17)	0.37987 (16)	0.0416 (4)
N5	0.95646 (18)	0.18786 (18)	0.60292 (16)	0.0436 (4)
O1	0.75553 (19)	1.04635 (18)	0.36201 (16)	0.0646 (5)
O2	0.6926 (10)	0.9248 (11)	0.6410 (15)	0.064 (2)	0.54
O3	0.6079 (6)	0.7030 (6)	0.7381 (6)	0.0693 (15)	0.54
O4	0.3127 (14)	0.5302 (14)	0.5267 (10)	0.091 (4)	0.54
O5	0.3362 (16)	0.6282 (15)	0.3029 (9)	0.093 (4)	0.54
O6	0.5945 (15)	1.1147 (16)	0.0366 (15)	0.104 (4)	0.58
O7	0.8115 (7)	1.0704 (12)	0.0890 (11)	0.075 (2)	0.58
O2'	0.5492 (7)	0.7504 (8)	0.7465 (7)	0.0700 (18)	0.46
O3'	0.7363 (11)	0.8962 (12)	0.6320 (17)	0.060 (2)	0.46
O5'	0.3250 (14)	0.6386 (14)	0.3006 (8)	0.061 (3)	0.46
O4'	0.3061 (11)	0.5414 (13)	0.5233 (7)	0.047 (2)	0.46
O6'	0.616 (2)	1.073 (2)	0.027 (2)	0.094 (5)	0.42
O7'	0.7953 (14)	1.1148 (18)	0.0970 (19)	0.114 (6)	0.42

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0384 (10)	0.0434 (11)	0.0450 (11)	−0.0048 (9)	−0.0101 (9)	−0.0205 (9)
C2	0.0363 (10)	0.0451 (11)	0.0391 (11)	0.0023 (9)	−0.0108 (8)	−0.0197 (9)
C3	0.0372 (11)	0.0410 (11)	0.0427 (11)	−0.0032 (9)	−0.0058 (9)	−0.0143 (9)
C4	0.0377 (10)	0.0424 (11)	0.0492 (12)	−0.0051 (9)	−0.0082 (9)	−0.0218 (10)
C5	0.0415 (11)	0.0514 (12)	0.0448 (11)	−0.0017 (9)	−0.0117 (9)	−0.0257 (10)
C6	0.0392 (11)	0.0431 (11)	0.0383 (10)	−0.0037 (9)	−0.0064 (8)	−0.0155 (9)
C7	0.0523 (12)	0.0520 (12)	0.0282 (10)	−0.0094 (10)	0.0025 (9)	−0.0177 (9)
C8	0.0590 (15)	0.0666 (16)	0.0465 (13)	−0.0155 (13)	−0.0010 (11)	−0.0180 (12)
C9	0.0572 (16)	0.106 (2)	0.0563 (16)	0.0023 (16)	−0.0112 (13)	−0.0260 (16)
C10	0.085 (2)	0.0757 (19)	0.0474 (14)	0.0179 (16)	−0.0074 (14)	−0.0192 (13)
C11	0.097 (2)	0.0537 (15)	0.0442 (13)	−0.0012 (14)	−0.0074 (13)	−0.0168 (11)
C12	0.0646 (14)	0.0521 (14)	0.0380 (11)	−0.0117 (11)	−0.0067 (10)	−0.0164 (10)
C13	0.0612 (14)	0.0543 (13)	0.0407 (11)	−0.0084 (11)	0.0008 (10)	−0.0242 (10)
C14	0.0472 (12)	0.0419 (12)	0.0629 (14)	−0.0066 (10)	−0.0119 (10)	−0.0242 (11)
C15	0.0530 (13)	0.0469 (12)	0.0599 (14)	0.0027 (10)	−0.0239 (11)	−0.0293 (11)
C16	0.0446 (11)	0.0424 (11)	0.0447 (11)	−0.0041 (9)	−0.0116 (9)	−0.0199 (9)
C17	0.0752 (16)	0.0644 (15)	0.0433 (13)	−0.0063 (13)	−0.0174 (11)	−0.0147 (11)
N1	0.0475 (11)	0.0565 (12)	0.0424 (10)	−0.0041 (9)	−0.0111 (8)	−0.0188 (9)
N2	0.0482 (11)	0.0498 (12)	0.0635 (13)	−0.0084 (9)	−0.0101 (11)	−0.0272 (11)
N3	0.0581 (13)	0.0584 (12)	0.0426 (11)	−0.0144 (10)	−0.0124 (10)	−0.0170 (9)
N4	0.0448 (9)	0.0405 (9)	0.0417 (9)	−0.0045 (8)	−0.0063 (7)	−0.0196 (8)
N5	0.0471 (10)	0.0443 (10)	0.0427 (10)	0.0013 (8)	−0.0156 (8)	−0.0191 (8)
O1	0.0735 (11)	0.0697 (11)	0.0521 (9)	−0.0361 (9)	−0.0076 (8)	−0.0242 (8)
O2	0.083 (5)	0.064 (4)	0.055 (3)	−0.012 (4)	−0.016 (4)	−0.032 (3)
O3	0.081 (4)	0.077 (4)	0.039 (2)	−0.019 (3)	−0.011 (3)	−0.013 (2)
O4	0.099 (7)	0.054 (5)	0.108 (7)	−0.019 (5)	−0.016 (5)	−0.023 (5)
O5	0.119 (8)	0.103 (7)	0.089 (8)	−0.022 (5)	−0.024 (5)	−0.066 (6)
O6	0.086 (4)	0.118 (8)	0.062 (5)	0.003 (5)	−0.028 (3)	0.005 (4)
O7	0.044 (2)	0.096 (5)	0.056 (3)	−0.021 (2)	0.0098 (19)	−0.011 (3)
O2'	0.068 (4)	0.094 (5)	0.040 (2)	−0.026 (3)	0.000 (3)	−0.022 (3)
O3'	0.064 (5)	0.067 (5)	0.058 (4)	−0.014 (4)	−0.021 (4)	−0.031 (3)
O5'	0.063 (5)	0.059 (5)	0.058 (6)	−0.037 (4)	−0.017 (4)	−0.014 (4)
O4'	0.048 (4)	0.053 (5)	0.039 (4)	−0.031 (4)	0.005 (3)	−0.018 (4)
O6'	0.127 (11)	0.104 (9)	0.047 (4)	−0.047 (7)	−0.034 (6)	−0.017 (5)
O7'	0.126 (9)	0.122 (11)	0.080 (5)	−0.060 (8)	−0.017 (6)	−0.026 (6)

Geometric parameters (Å, º) top

C1—O1	1.235 (2)	C13—H13B	0.9700
C1—C2	1.451 (3)	C14—C15	1.336 (3)
C1—C6	1.454 (3)	C14—N4	1.371 (3)
C2—C3	1.368 (3)	C14—H14	0.9300
C2—N1	1.450 (2)	C15—N5	1.367 (3)
C3—C4	1.379 (3)	C15—H15	0.9300
C3—H3	0.9300	C16—N4	1.319 (2)
C4—C5	1.383 (3)	C16—N5	1.325 (2)
C4—N2	1.443 (3)	C16—H16	0.9300
C5—C6	1.357 (3)	C17—N5	1.464 (3)
C5—H5	0.9300	C17—H17A	0.9600
C6—N3	1.451 (3)	C17—H17B	0.9600
C7—C8	1.383 (3)	C17—H17C	0.9600
C7—C12	1.385 (3)	N1—O2	1.220 (9)
C7—C13	1.493 (3)	N1—O3'	1.222 (10)
C8—C9	1.373 (4)	N1—O2'	1.235 (7)
C8—H8	0.9300	N1—O3	1.240 (6)
C9—C10	1.369 (4)	N2—O4'	1.197 (7)
C9—H9	0.9300	N2—O5	1.222 (9)
C10—C11	1.368 (4)	N2—O5'	1.243 (9)
C10—H10	0.9300	N2—O4	1.245 (9)
C11—C12	1.367 (3)	N3—O6'	1.168 (11)
C11—H11	0.9300	N3—O7	1.201 (7)
C12—H12	0.9300	N3—O7'	1.208 (11)
C13—N4	1.480 (3)	N3—O6	1.215 (10)
C13—H13A	0.9700

O1—C1—C2	126.06 (18)	N4—C14—H14	126.5
O1—C1—C6	122.83 (18)	C14—C15—N5	107.38 (18)
C2—C1—C6	111.10 (16)	C14—C15—H15	126.3
C3—C2—N1	116.05 (17)	N5—C15—H15	126.3
C3—C2—C1	124.07 (18)	N4—C16—N5	108.52 (17)
N1—C2—C1	119.85 (17)	N4—C16—H16	125.7
C2—C3—C4	119.81 (18)	N5—C16—H16	125.7
C2—C3—H3	120.1	N5—C17—H17A	109.5
C4—C3—H3	120.1	N5—C17—H17B	109.5
C3—C4—C5	120.79 (18)	H17A—C17—H17B	109.5
C3—C4—N2	119.28 (18)	N5—C17—H17C	109.5
C5—C4—N2	119.92 (19)	H17A—C17—H17C	109.5
C6—C5—C4	119.12 (19)	H17B—C17—H17C	109.5
C6—C5—H5	120.4	O2—N1—O2'	112.3 (8)
C4—C5—H5	120.4	O3'—N1—O2'	122.1 (8)
C5—C6—N3	116.53 (18)	O2—N1—O3	122.5 (7)
C5—C6—C1	125.09 (18)	O3'—N1—O3	116.7 (8)
N3—C6—C1	118.38 (17)	O2—N1—C2	120.6 (7)
C8—C7—C12	118.2 (2)	O3'—N1—C2	118.2 (8)
C8—C7—C13	120.1 (2)	O2'—N1—C2	119.5 (4)
C12—C7—C13	121.7 (2)	O3—N1—C2	116.6 (3)
C9—C8—C7	120.6 (2)	O4'—N2—O5	123.1 (7)
C9—C8—H8	119.7	O4'—N2—O5'	123.6 (5)
C7—C8—H8	119.7	O5—N2—O4	122.0 (7)
C10—C9—C8	120.2 (3)	O5'—N2—O4	123.2 (7)
C10—C9—H9	119.9	O4'—N2—C4	118.7 (4)
C8—C9—H9	119.9	O5—N2—C4	118.2 (5)
C11—C10—C9	120.1 (3)	O5'—N2—C4	117.4 (4)
C11—C10—H10	120.0	O4—N2—C4	119.5 (6)
C9—C10—H10	120.0	O6'—N3—O7	115.7 (13)
C12—C11—C10	119.9 (2)	O6'—N3—O7'	120.1 (12)
C12—C11—H11	120.0	O7—N3—O6	122.8 (9)
C10—C11—H11	120.0	O7'—N3—O6	115.6 (13)
C11—C12—C7	121.1 (2)	O6'—N3—C6	119.1 (10)
C11—C12—H12	119.5	O7—N3—C6	118.5 (5)
C7—C12—H12	119.5	O7'—N3—C6	120.8 (9)
N4—C13—C7	112.48 (16)	O6—N3—C6	118.6 (8)
N4—C13—H13A	109.1	C16—N4—C14	108.63 (17)
C7—C13—H13A	109.1	C16—N4—C13	125.71 (16)
N4—C13—H13B	109.1	C14—N4—C13	125.65 (17)
C7—C13—H13B	109.1	C16—N5—C15	108.46 (17)
H13A—C13—H13B	107.8	C16—N5—C17	126.17 (18)
C15—C14—N4	107.00 (18)	C15—N5—C17	125.31 (18)
C15—C14—H14	126.5

O1—C1—C2—C3	−179.9 (2)	C3—C2—N1—O2'	−18.1 (4)
C6—C1—C2—C3	1.3 (3)	C1—C2—N1—O2'	164.1 (4)
O1—C1—C2—N1	−2.2 (3)	C3—C2—N1—O3	20.3 (4)
C6—C1—C2—N1	178.93 (17)	C1—C2—N1—O3	−157.5 (3)
N1—C2—C3—C4	−179.13 (17)	C3—C4—N2—O4'	4.4 (8)
C1—C2—C3—C4	−1.4 (3)	C5—C4—N2—O4'	−177.1 (7)
C2—C3—C4—C5	0.0 (3)	C3—C4—N2—O5	−174.9 (10)
C2—C3—C4—N2	178.38 (18)	C5—C4—N2—O5	3.6 (10)
C3—C4—C5—C6	1.5 (3)	C3—C4—N2—O5'	177.9 (9)
N2—C4—C5—C6	−176.96 (18)	C5—C4—N2—O5'	−3.6 (9)
C4—C5—C6—N3	178.34 (19)	C3—C4—N2—O4	−1.4 (8)
C4—C5—C6—C1	−1.5 (3)	C5—C4—N2—O4	177.0 (8)
O1—C1—C6—C5	−178.7 (2)	C5—C6—N3—O6'	19.6 (10)
C2—C1—C6—C5	0.2 (3)	C1—C6—N3—O6'	−160.5 (10)
O1—C1—C6—N3	1.4 (3)	C5—C6—N3—O7	−130.6 (6)
C2—C1—C6—N3	−179.67 (17)	C1—C6—N3—O7	49.3 (7)
C12—C7—C8—C9	−0.1 (3)	C5—C6—N3—O7'	−158.5 (9)
C13—C7—C8—C9	−179.7 (2)	C1—C6—N3—O7'	21.4 (9)
C7—C8—C9—C10	−0.3 (4)	C5—C6—N3—O6	47.4 (7)
C8—C9—C10—C11	0.0 (4)	C1—C6—N3—O6	−132.7 (7)
C9—C10—C11—C12	0.6 (4)	N5—C16—N4—C14	−0.4 (2)
C10—C11—C12—C7	−1.0 (3)	N5—C16—N4—C13	−178.99 (17)
C8—C7—C12—C11	0.7 (3)	C15—C14—N4—C16	0.5 (2)
C13—C7—C12—C11	−179.68 (19)	C15—C14—N4—C13	179.14 (19)
C8—C7—C13—N4	−102.8 (2)	C7—C13—N4—C16	102.4 (2)
C12—C7—C13—N4	77.6 (2)	C7—C13—N4—C14	−76.0 (2)
N4—C14—C15—N5	−0.4 (2)	N4—C16—N5—C15	0.1 (2)
C3—C2—N1—O2	−165.4 (5)	N4—C16—N5—C17	−177.20 (19)
C1—C2—N1—O2	16.8 (5)	C14—C15—N5—C16	0.2 (2)
C3—C2—N1—O3'	167.5 (6)	C14—C15—N5—C17	177.5 (2)
C1—C2—N1—O3'	−10.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17C···O7ⁱ	0.96	2.42	3.346 (10)	162
C14—H14···O5ⁱⁱ	0.93	2.39	3.283 (11)	161
C17—H17A···O2ⁱⁱⁱ	0.96	2.32	3.205 (11)	153
C16—H16···O2ⁱⁱⁱ	0.93	2.39	3.159 (9)	140
C16—H16···O1ⁱⁱⁱ	0.93	2.19	3.021 (2)	149
C13—H13A···O1ⁱⁱⁱ	0.97	2.58	3.382 (3)	140
C17—H17C···O7ⁱ	0.96	2.42	3.346 (10)	162

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₂⁺·C₆H₂N₃O₇⁻
M_r	401.34
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.1322 (6), 10.2060 (7), 10.8744 (7)
α, β, γ (°)	63.619 (1), 80.166 (1), 86.482 (1)
V (Å³)	894.52 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.986, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5623, 3447, 2610
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.144, 1.04
No. of reflections	3447
No. of parameters	320
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.24

Computer programs: SMART (Bruker, 2001), SAINT-Plus (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
C17—H17C···O7ⁱ	0.96	2.42	3.346 (10)	161.5
C14—H14···O5ⁱⁱ	0.93	2.39	3.283 (11)	161.0
C17—H17A···O2ⁱⁱⁱ	0.96	2.32	3.205 (11)	153.4
C16—H16···O2ⁱⁱⁱ	0.93	2.39	3.159 (9)	139.5
C16—H16···O1ⁱⁱⁱ	0.93	2.19	3.021 (2)	148.8
C13—H13A···O1ⁱⁱⁱ	0.97	2.58	3.382 (3)	140.4
C17—H17C···O7ⁱ	0.96	2.42	3.346 (10)	161.5

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

Acknowledgements

We gratefully acknowledge the financial support of the National Science Funds for Distinguished Young Scholars of Hubei Province (grant No. 2006ABB038), the Outstanding Mid-young Scholars' Programs, Hubei Provincial Department of Education (Q20072203) and the project sponsored by SRF for ROCS, SEM (200724).

References

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