Guanidinium quinoline-2-carboxyl­ate

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536809049733

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3220

doi:10.1107/S1600536809049733

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Guanidinium quinoline-2-carboxylate

Graham Smith ^a ^* and Urs D. Wermuth ^a

^aSchool of Physical and Chemical Sciences, Queensland University of Technology, GPO Box 2434, Brisbane, Qld 4001, Australia.
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 16 November 2009; accepted 20 November 2009; online 25 November 2009)

In the structure of the guanidinium salt of quinaldic acid, CH₆N₃⁺·C₁₀H₆NO₂⁻, the asymmetric unit contains two independent cations and anions having similar inter-species hydrogen-bonding environments, which include cyclic R₂²(8), R₂¹(6) and R₁²(5) associations. These and additional weak aromatic ring π–π interactions [minimum ring-centroid separation = 3.662 (2) Å] give a two-dimensional layered structure.

Related literature

For guanidinium salts of aromatic acids, see: Parthasarathi et al. (1982 ); Schürmann et al. (1998 ); Najafpour et al. (2007 ); Pereira Silva et al. (2007 ). For quinaldic acid structures, see: Dobrzyńska & Jerzykiewicz (2004 ); Smith et al. (2004 , 2007 , 2008a ,b ).

Experimental

Crystal data

CH₆N₃⁺·C₁₀H₆NO₂⁻
M_r = 232.25
Monoclinic, P 2₁ /c
a = 7.4318 (3) Å
b = 42.2105 (18) Å
c = 7.3035 (4) Å
β = 94.045 (4)°
V = 2285.40 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 297 K
0.35 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.740, T_max = 0.870
10626 measured reflections
3981 independent reflections
2931 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.162
S = 1.04
3981 reflections
355 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1C—H11C⋯O21B	0.82 (4)	2.12 (4)	2.937 (5)	176 (3)
N1C—H12C⋯O21Aⁱ	0.92 (4)	2.03 (4)	2.852 (5)	149 (3)
N1D—H11D⋯O22A	0.87 (4)	2.04 (4)	2.902 (4)	177 (4)
N1D—H12D⋯O21Bⁱⁱ	0.85 (5)	2.47 (5)	3.312 (5)	173 (4)
N2C—H21C⋯O22A	0.94 (4)	1.87 (4)	2.784 (4)	166 (4)
N2C—H22C⋯O21Aⁱ	0.91 (4)	2.57 (4)	3.163 (5)	124 (4)
N2C—H22C⋯N1Aⁱ	0.91 (4)	2.08 (5)	2.964 (4)	165 (4)
N2D—H21D⋯O21Bⁱⁱⁱ	0.84 (4)	2.11 (4)	2.899 (5)	155 (3)
N2D—H22D⋯O21A	0.89 (4)	2.01 (5)	2.890 (4)	173 (4)
N3C—H31C⋯O22B	0.93 (5)	1.96 (5)	2.891 (4)	173 (4)
N3C—H32C⋯O22A	0.84 (4)	2.57 (5)	3.216 (5)	135 (4)
N3D—H31D⋯O21Bⁱⁱⁱ	0.93 (4)	2.60 (4)	3.268 (5)	130 (3)
N3D—H31D⋯N1Bⁱⁱⁱ	0.93 (4)	2.12 (4)	3.000 (4)	159 (3)
N3D—H32D⋯O22Bⁱⁱ	0.93 (4)	1.95 (4)	2.826 (4)	157 (4)
Symmetry codes: (i) x-1, y, z; (ii) x, y, z-1; (iii) x+1, y, z-1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ) within WinGX (Farrugia, 1999 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049733/wn2367sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049733/wn2367Isup2.hkl

checkCIF report

Comment top

The guanidinium salts of aromatic and heteroaromatic carboxylic acids have proved to be a particularly useful means of generating stable hydrogen-bonded supramolecular framework structures. Three-dimensional structures are most common, largely the result of the interactive efficiency of the symmetrical guanidinium cation in commonly forming cyclic R₂²(8) hydrogen-bonding associations with carboxylate-O acceptors. Among the known structures are the guanidinium salts with the aromatic monocarboxylic acids, 4-chloro-3-nitrobenzoic acid (a monohydrate) (Najafpour et al., 2007), and the anhydrous salts with benzoic acid (Pereira Silva et al., 2007), 4-nitrobenzoic acid (Schürmann et al., 1998), 3,5-dinitrobenzoic acid (Smith et al., 2007) and 4-amino-3,5,6-trichloropicolinic acid (Parthasarathi et al., 1982).

Our 1:1 stoichiometric reaction of quinoline-2-carboxylic acid (quinaldic acid) in 50% 2-propanol-water gave large chemically stable crystals of the title compound, anhydrous guanidinium quinoline-2-carboxylate, CH₆N₃⁺ C₁₀H₆NO₂^- and the structure is reported here. Quinaldic acid in the solid state exists as a zwitterionic hydrogen-bonded dimer (Dobrzyńska & Jerzykiewicz, 2004) and is commonly found in that form as an adduct species in some proton-transfer compounds where it acts as a Lewis base rather than an acid. Examples are the 1/1/1 quinolinium salt adducts with 5-sulfosalicylic acid (Smith et al., 2004), picrylsulfonic acid (Smith et al., 2008a) and 4,5-dichlorophthalic acid (Smith et al., 2008b).

In the structure of the title compound the asymmetric unit contains two guanidinium cations (C and D) and two quinoline-2-carboxylate anions (A and B) (Fig. 1). The H atom donors of the two cations form similar cyclic hydrogen-bonding interactions with carboxylate O and quinoline N acceptors (Table 1) (Fig. 2), both pairs having two guanidinium-N–H, N'–H'···O associations [graph set R₂¹(6)] and one N–H, N'–H'···O,O' association [R₂²(8)]. In addition, each has an R₁²(5) guanidinium N–H···N,O_{quinoline-carboxyl} association. A two-dimensional layered structure is generated (Fig. 3), in which some aromatic ring overlap down the c cell direction gives weak π–π interactions [minimum ring centroid separation,for the six-membered ring N1B–C5B, 3.662 (2) Å]. The quinoline-2-carboxylate cations are conformationally similar with only minor differences in the N1–C2–C21–O22 torsion angles [170.3 (3)° (A), 163.6 (3)° (B)].

Related literature top

For guanidinium salts of aromatic acids, see: Parthasarathi et al. (1982); Schürmann et al. (1998); Najafpour et al. (2007); Smith et al. (2007); Pereira Silva et al. (2007). For quinaldic acid structures, see: Dobrzyńska & Jerzykiewicz (2004); Smith et al. (2004); Smith et al. (2007); Smith et al. (2008a,b).

Experimental top

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of quinoline-2-carboxylic acid and guanidine carbonate in 50 ml of 50% aqueous propan-2-ol. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave colourless prisms [m.p. 543–544 K].

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular configuration and atom naming scheme for the two guanidinium cations (C and D) and the two quinoline-2-carboxylate anions (A and B) in the asymmetric unit. Inter-species hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The hydrogen-bonding extensions of the asymmetric unit, showing hydrogen-bonds as dashed lines. For symmetry codes, see Table 1.
	Fig. 3. The two-dimensional hydrogen-bonded layered structure, viewed down the c axial direction, showing also quinoline ring overlap. Non-interactive hydrogen atoms are omitted. For symmetry codes, see Table 1.

Guanidinium quinoline-2-carboxylate top

Crystal data top

CH₆N₃⁺·C₁₀H₆NO₂⁻	F(000) = 976
M_r = 232.25	D_x = 1.350 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 543–544 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.4318 (3) Å	Cell parameters from 4234 reflections
b = 42.2105 (18) Å	θ = 2.9–28.8°
c = 7.3035 (4) Å	µ = 0.10 mm⁻¹
β = 94.045 (4)°	T = 297 K
V = 2285.40 (18) Å³	Prism, colourless
Z = 8	0.35 × 0.20 × 0.18 mm

Data collection top

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	3981 independent reflections
Radiation source: Enhance (Mo) X-ray source	2931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.740, T_max = 0.870	k = −50→49
10626 measured reflections	l = −8→8

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0614P)² + 2.2259P] where P = (F_o² + 2F_c²)/3
3981 reflections	(Δ/σ)_max = 0.003
355 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

CH₆N₃⁺·C₁₀H₆NO₂⁻	V = 2285.40 (18) Å³
M_r = 232.25	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4318 (3) Å	µ = 0.10 mm⁻¹
b = 42.2105 (18) Å	T = 297 K
c = 7.3035 (4) Å	0.35 × 0.20 × 0.18 mm
β = 94.045 (4)°

Data collection top

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	3981 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2931 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.870	R_int = 0.035
10626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.15 e Å⁻³
3981 reflections	Δρ_min = −0.18 e Å⁻³
355 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
O21A	0.8508 (4)	0.09058 (6)	0.2611 (3)	0.0621 (10)
O22A	0.5996 (3)	0.07308 (6)	0.1162 (4)	0.0645 (10)
N1A	0.9927 (3)	0.03079 (6)	0.2631 (3)	0.0344 (8)
C2A	0.8222 (4)	0.03520 (7)	0.2056 (4)	0.0347 (9)
C3A	0.7048 (4)	0.01015 (8)	0.1538 (4)	0.0432 (11)
C4A	0.7670 (5)	−0.02006 (8)	0.1610 (4)	0.0470 (11)
C5A	1.0237 (5)	−0.05662 (8)	0.2320 (5)	0.0526 (14)
C6A	1.1980 (6)	−0.06067 (9)	0.2937 (5)	0.0607 (14)
C7A	1.3053 (5)	−0.03505 (10)	0.3470 (5)	0.0573 (14)
C8A	1.2375 (4)	−0.00486 (8)	0.3367 (4)	0.0463 (11)
C9A	1.0562 (4)	0.00047 (7)	0.2721 (4)	0.0350 (10)
C10A	0.9469 (4)	−0.02599 (7)	0.2209 (4)	0.0386 (10)
C21A	0.7531 (5)	0.06891 (8)	0.1948 (4)	0.0434 (11)
O21B	0.2113 (4)	0.16103 (6)	0.7760 (4)	0.0595 (9)
O22B	0.4256 (3)	0.17922 (6)	0.6099 (3)	0.0547 (9)
N1B	0.0628 (3)	0.22063 (6)	0.7787 (3)	0.0337 (8)
C2B	0.2260 (4)	0.21671 (7)	0.7234 (4)	0.0331 (9)
C3B	0.3404 (4)	0.24202 (7)	0.6830 (4)	0.0383 (10)
C4B	0.2823 (4)	0.27223 (7)	0.7016 (4)	0.0399 (10)
C5B	0.0359 (5)	0.30838 (8)	0.7780 (4)	0.0467 (11)
C6B	−0.1343 (5)	0.31222 (9)	0.8310 (5)	0.0521 (12)
C7B	−0.2392 (5)	0.28594 (9)	0.8685 (5)	0.0500 (11)
C8B	−0.1739 (4)	0.25609 (8)	0.8528 (4)	0.0417 (11)
C9B	0.0024 (4)	0.25108 (7)	0.7961 (4)	0.0326 (9)
C10B	0.1082 (4)	0.27776 (7)	0.7584 (4)	0.0360 (10)
C21B	0.2913 (4)	0.18309 (8)	0.7021 (4)	0.0389 (10)
N1C	0.1537 (5)	0.11364 (9)	0.4833 (5)	0.0598 (12)
N2C	0.2735 (5)	0.08075 (8)	0.2766 (5)	0.0671 (14)
N3C	0.4496 (5)	0.11943 (9)	0.4200 (5)	0.0622 (12)
C1C	0.2924 (5)	0.10473 (8)	0.3933 (5)	0.0506 (11)
N1D	0.6118 (5)	0.13337 (8)	−0.0734 (5)	0.0553 (11)
N2D	0.9196 (5)	0.13416 (8)	−0.0311 (5)	0.0500 (11)
N3D	0.7754 (5)	0.17077 (7)	−0.2190 (4)	0.0554 (11)
C1D	0.7690 (5)	0.14616 (7)	−0.1083 (4)	0.0415 (11)
H3A	0.58520	0.01430	0.11490	0.0520*
H4A	0.69050	−0.03680	0.12620	0.0560*
H5A	0.95370	−0.07410	0.19660	0.0630*
H6A	1.24640	−0.08100	0.30040	0.0730*
H7A	1.42460	−0.03830	0.39020	0.0680*
H8A	1.31110	0.01220	0.37240	0.0560*
H3B	0.45460	0.23800	0.64390	0.0460*
H4B	0.35710	0.28910	0.67710	0.0480*
H5B	0.10530	0.32610	0.75450	0.0560*
H6B	−0.18120	0.33250	0.84230	0.0630*
H7B	−0.35550	0.28890	0.90470	0.0600*
H8B	−0.24530	0.23880	0.87940	0.0500*
H11C	0.165 (4)	0.1267 (8)	0.567 (5)	0.070 (10)*
H12C	0.046 (6)	0.1036 (9)	0.454 (5)	0.066 (12)*
H21C	0.376 (6)	0.0750 (10)	0.217 (6)	0.079 (13)*
H22C	0.173 (6)	0.0684 (11)	0.272 (6)	0.084 (14)*
H31C	0.448 (6)	0.1394 (11)	0.475 (6)	0.089 (15)*
H32C	0.540 (6)	0.1136 (11)	0.367 (6)	0.081 (15)*
H11D	0.611 (5)	0.1156 (10)	−0.014 (5)	0.068 (13)*
H12D	0.514 (6)	0.1421 (11)	−0.114 (7)	0.091 (17)*
H21D	1.022 (5)	0.1409 (8)	−0.055 (5)	0.064 (10)*
H22D	0.908 (6)	0.1206 (11)	0.060 (6)	0.083 (15)*
H31D	0.882 (5)	0.1819 (9)	−0.227 (5)	0.060 (11)*
H32D	0.670 (6)	0.1793 (10)	−0.273 (6)	0.074 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O21A	0.087 (2)	0.0395 (15)	0.0588 (15)	0.0029 (13)	−0.0028 (14)	0.0009 (11)
O22A	0.0422 (15)	0.0608 (17)	0.092 (2)	0.0122 (12)	0.0149 (14)	0.0230 (14)
N1A	0.0365 (15)	0.0328 (14)	0.0346 (13)	−0.0010 (11)	0.0068 (11)	0.0000 (10)
C2A	0.0352 (17)	0.0373 (17)	0.0327 (15)	−0.0018 (13)	0.0111 (13)	0.0042 (12)
C3A	0.0356 (18)	0.051 (2)	0.0428 (18)	−0.0015 (15)	0.0006 (14)	0.0001 (15)
C4A	0.053 (2)	0.043 (2)	0.0449 (19)	−0.0100 (16)	0.0020 (16)	−0.0061 (15)
C5A	0.076 (3)	0.038 (2)	0.0444 (19)	0.0035 (18)	0.0089 (18)	−0.0019 (15)
C6A	0.085 (3)	0.048 (2)	0.050 (2)	0.021 (2)	0.011 (2)	0.0060 (17)
C7A	0.055 (2)	0.070 (3)	0.047 (2)	0.021 (2)	0.0044 (17)	0.0106 (18)
C8A	0.044 (2)	0.053 (2)	0.0422 (18)	0.0029 (16)	0.0050 (15)	0.0034 (15)
C9A	0.0405 (18)	0.0378 (18)	0.0275 (15)	0.0017 (14)	0.0073 (13)	0.0031 (12)
C10A	0.052 (2)	0.0339 (18)	0.0306 (15)	−0.0008 (14)	0.0090 (14)	−0.0004 (12)
C21A	0.046 (2)	0.044 (2)	0.0421 (18)	0.0062 (16)	0.0173 (15)	0.0097 (15)
O21B	0.0687 (17)	0.0414 (14)	0.0712 (16)	0.0055 (13)	0.0246 (13)	0.0069 (12)
O22B	0.0368 (13)	0.0508 (15)	0.0783 (17)	0.0036 (11)	0.0159 (12)	−0.0133 (12)
N1B	0.0309 (14)	0.0378 (15)	0.0322 (13)	0.0010 (11)	0.0002 (10)	−0.0030 (10)
C2B	0.0286 (16)	0.0401 (17)	0.0304 (15)	0.0018 (13)	−0.0002 (12)	−0.0051 (12)
C3B	0.0292 (16)	0.048 (2)	0.0376 (16)	−0.0003 (14)	0.0027 (13)	−0.0049 (14)
C4B	0.0376 (18)	0.0414 (19)	0.0407 (17)	−0.0082 (14)	0.0023 (14)	−0.0013 (13)
C5B	0.055 (2)	0.0376 (19)	0.0469 (19)	0.0029 (16)	0.0004 (16)	0.0021 (14)
C6B	0.059 (2)	0.044 (2)	0.053 (2)	0.0182 (18)	0.0010 (17)	−0.0025 (16)
C7B	0.043 (2)	0.061 (2)	0.0462 (19)	0.0124 (17)	0.0039 (15)	−0.0062 (16)
C8B	0.0366 (18)	0.048 (2)	0.0406 (18)	0.0015 (15)	0.0027 (14)	−0.0039 (14)
C9B	0.0301 (16)	0.0402 (18)	0.0268 (14)	0.0026 (13)	−0.0032 (12)	−0.0033 (12)
C10B	0.0382 (17)	0.0405 (18)	0.0286 (15)	0.0010 (14)	−0.0028 (12)	−0.0013 (12)
C21B	0.0332 (17)	0.0404 (19)	0.0425 (17)	0.0017 (14)	−0.0007 (14)	−0.0025 (14)
N1C	0.060 (2)	0.054 (2)	0.068 (2)	−0.0068 (18)	0.0225 (18)	−0.0130 (17)
N2C	0.055 (2)	0.052 (2)	0.098 (3)	−0.0159 (17)	0.032 (2)	−0.0300 (18)
N3C	0.055 (2)	0.050 (2)	0.084 (2)	−0.0109 (17)	0.0209 (18)	−0.0184 (17)
C1C	0.056 (2)	0.0367 (19)	0.061 (2)	−0.0033 (17)	0.0166 (18)	0.0032 (16)
N1D	0.050 (2)	0.0452 (19)	0.071 (2)	−0.0032 (16)	0.0071 (16)	0.0158 (16)
N2D	0.047 (2)	0.0478 (19)	0.0550 (19)	−0.0004 (16)	0.0023 (15)	0.0055 (15)
N3D	0.047 (2)	0.0462 (19)	0.072 (2)	−0.0081 (16)	−0.0022 (16)	0.0205 (15)
C1D	0.046 (2)	0.0344 (18)	0.0445 (18)	−0.0033 (15)	0.0051 (15)	−0.0031 (14)

Geometric parameters (Å, º) top

O21A—C21A	1.245 (4)	C4A—C10A	1.400 (5)
O22A—C21A	1.253 (4)	C5A—C6A	1.352 (6)
O21B—C21B	1.248 (4)	C5A—C10A	1.413 (5)
O22B—C21B	1.253 (4)	C6A—C7A	1.383 (6)
N1A—C2A	1.320 (4)	C7A—C8A	1.371 (5)
N1A—C9A	1.364 (4)	C8A—C9A	1.414 (4)
N1B—C2B	1.316 (4)	C9A—C10A	1.416 (4)
N1B—C9B	1.370 (4)	C3A—H3A	0.9300
N1C—C1C	1.316 (5)	C4A—H4A	0.9300
N2C—C1C	1.324 (5)	C5A—H5A	0.9300
N3C—C1C	1.325 (5)	C6A—H6A	0.9300
N1C—H11C	0.82 (4)	C7A—H7A	0.9300
N1C—H12C	0.92 (4)	C8A—H8A	0.9300
N2C—H21C	0.94 (4)	C2B—C21B	1.511 (4)
N2C—H22C	0.91 (4)	C2B—C3B	1.410 (4)
N3C—H32C	0.84 (4)	C3B—C4B	1.356 (4)
N3C—H31C	0.93 (5)	C4B—C10B	1.406 (4)
N1D—C1D	1.328 (5)	C5B—C10B	1.411 (5)
N2D—C1D	1.318 (5)	C5B—C6B	1.358 (5)
N3D—C1D	1.319 (4)	C6B—C7B	1.394 (5)
N1D—H11D	0.87 (4)	C7B—C8B	1.358 (5)
N1D—H12D	0.85 (5)	C8B—C9B	1.418 (4)
N2D—H21D	0.84 (4)	C9B—C10B	1.412 (4)
N2D—H22D	0.89 (4)	C3B—H3B	0.9300
N3D—H31D	0.93 (4)	C4B—H4B	0.9300
N3D—H32D	0.93 (4)	C5B—H5B	0.9300
C2A—C21A	1.513 (5)	C6B—H6B	0.9300
C2A—C3A	1.406 (4)	C7B—H7B	0.9300
C3A—C4A	1.356 (5)	C8B—H8B	0.9300

O21A···N1A	2.735 (4)	C10B···C2B^v	3.455 (4)
O21A···N1Cⁱ	2.852 (5)	C10B···C3B^v	3.541 (4)
O21A···N2Cⁱ	3.163 (5)	C21B···C5B^xi	3.535 (4)
O21A···N2D	2.890 (4)	C1D···H6A^x	3.0900
O21A···C1Cⁱ	3.408 (5)	C2A···H22Cⁱ	2.97 (5)
O21B···N1C	2.937 (5)	C2B···H31Dⁱⁱ	2.99 (4)
O21B···N2Dⁱⁱ	2.899 (5)	C3A···H3A^xiii	2.9900
O21B···N1B	2.748 (4)	C4B···H7Bⁱ	3.0600
O21B···N3Dⁱⁱ	3.268 (5)	C9A···H22Cⁱ	3.00 (5)
O22A···N3C	3.216 (5)	C9B···H31Dⁱⁱ	3.06 (4)
O22A···N1D	2.902 (4)	C21A···H21C	2.83 (4)
O22A···N2C	2.784 (4)	C21A···H32C	2.82 (5)
O22B···N1Dⁱⁱⁱ	3.250 (4)	C21A···H11D	2.66 (4)
O22B···N3C	2.891 (4)	C21A···H22D	2.69 (5)
O22B···N3Dⁱⁱⁱ	2.826 (4)	C21B···H11C	2.72 (3)
O21A···H12Cⁱ	2.03 (4)	C21B···H31C	2.79 (5)
O21A···H11D	2.80 (4)	C21B···H32Dⁱⁱⁱ	2.81 (4)
O21A···H22Cⁱ	2.57 (4)	C21B···H12Dⁱⁱⁱ	2.69 (5)
O21A···H32C	2.67 (5)	H3A···O22A	2.4800
O21A···H22D	2.01 (5)	H3A···C3A^xiii	2.9900
O21B···H21Dⁱⁱ	2.11 (4)	H3A···H3A^xiii	2.3600
O21B···H31Dⁱⁱ	2.60 (4)	H3B···H7B^iv	2.5800
O21B···H11C	2.12 (4)	H3B···O22B	2.5000
O21B···H12Dⁱⁱⁱ	2.47 (5)	H4A···H5A	2.5400
O22A···H3A	2.4800	H4B···H5B	2.5300
O22A···H32C	2.57 (5)	H5A···H4A	2.5400
O22A···H11D	2.04 (4)	H5B···H4B	2.5300
O22A···H21C	1.87 (4)	H5B···N2D^xii	2.9400
O22B···H12Dⁱⁱⁱ	2.60 (5)	H6A···C1D^x	3.0900
O22B···H7B^iv	2.6500	H7B···H3B^xii	2.5800
O22B···H31C	1.96 (5)	H7B···C4B^vi	3.0600
O22B···H32Dⁱⁱⁱ	1.95 (4)	H7B···O22B^xii	2.6500
O22B···H3B	2.5000	H11C···C21B	2.72 (3)
N1A···O21A	2.735 (4)	H11C···O21B	2.12 (4)
N1A···N2Cⁱ	2.964 (4)	H11C···H31C	2.32 (5)
N1B···O21B	2.748 (4)	H11D···H22D	2.25 (6)
N1B···N3Dⁱⁱ	3.000 (4)	H11D···C21A	2.66 (4)
N1B···C4B^v	3.403 (4)	H11D···O21A	2.80 (4)
N1C···O21B	2.937 (5)	H11D···O22A	2.04 (4)
N1C···O21A^vi	2.852 (5)	H12C···H22C	2.25 (6)
N1D···O22A	2.902 (4)	H12C···O21A^vi	2.03 (4)
N1D···O22B^vii	3.250 (4)	H12D···O21B^vii	2.47 (5)
N2C···N1A^vi	2.964 (4)	H12D···C21B^vii	2.69 (5)
N2C···O21A^vi	3.163 (5)	H12D···H32D	2.31 (6)
N2C···O22A	2.784 (4)	H12D···O22B^vii	2.60 (5)
N2D···C5B^iv	3.384 (5)	H21C···C21A	2.83 (4)
N2D···O21B^viii	2.899 (5)	H21C···H32C	2.27 (6)
N2D···O21A	2.890 (4)	H21C···O22A	1.87 (4)
N3C···O22B	2.891 (4)	H21D···O21B^viii	2.11 (4)
N3C···O22A	3.216 (5)	H21D···H31D	2.34 (5)
N3D···O22B^vii	2.826 (4)	H22C···C2A^vi	2.97 (5)
N3D···O21B^viii	3.268 (5)	H22C···C9A^vi	3.00 (5)
N3D···N1B^viii	3.000 (4)	H22C···H12C	2.25 (6)
N1A···H22Cⁱ	2.08 (5)	H22C···N1A^vi	2.08 (5)
N1B···H31Dⁱⁱ	2.12 (4)	H22C···O21A^vi	2.57 (4)
N2D···H5B^iv	2.9400	H22D···O21A	2.01 (5)
C1C···O21A^vi	3.408 (5)	H22D···C21A	2.69 (5)
C2A···C7A^ix	3.466 (5)	H22D···H11D	2.25 (6)
C2A···C5A^x	3.586 (5)	H31C···C21B	2.79 (5)
C2B···C10B^xi	3.455 (4)	H31C···H11C	2.32 (5)
C2B···C4B^v	3.519 (4)	H31C···O22B	1.96 (5)
C3B···C4B^xi	3.563 (4)	H31D···H21D	2.34 (5)
C3B···C10B^xi	3.541 (4)	H31D···O21B^viii	2.60 (4)
C4B···C2B^xi	3.519 (4)	H31D···N1B^viii	2.12 (4)
C4B···C3B^v	3.563 (4)	H31D···C9B^viii	3.06 (4)
C4B···N1B^xi	3.403 (4)	H31D···C2B^viii	2.99 (4)
C5A···C2A^x	3.586 (5)	H32C···C21A	2.82 (5)
C5B···C21B^v	3.535 (4)	H32C···H21C	2.27 (6)
C5B···N2D^xii	3.384 (5)	H32C···O22A	2.57 (5)
C7A···C2A^ix	3.466 (5)	H32C···O21A	2.67 (5)
C8B···C9B^v	3.419 (4)	H32D···O22B^vii	1.95 (4)
C9A···C9A^ix	3.489 (4)	H32D···C21B^vii	2.81 (4)
C9B···C8B^xi	3.419 (4)	H32D···H12D	2.31 (6)

C2A—N1A—C9A	118.0 (3)	C6A—C5A—H5A	120.00
C2B—N1B—C9B	117.5 (3)	C7A—C6A—H6A	120.00
C1C—N1C—H11C	121 (2)	C5A—C6A—H6A	119.00
C1C—N1C—H12C	117 (3)	C8A—C7A—H7A	120.00
H11C—N1C—H12C	122 (3)	C6A—C7A—H7A	120.00
C1C—N2C—H21C	116 (3)	C7A—C8A—H8A	120.00
C1C—N2C—H22C	121 (3)	C9A—C8A—H8A	120.00
H21C—N2C—H22C	122 (4)	N1B—C2B—C21B	117.4 (3)
C1C—N3C—H31C	117 (3)	C3B—C2B—C21B	119.2 (3)
C1C—N3C—H32C	122 (3)	N1B—C2B—C3B	123.5 (3)
H31C—N3C—H32C	120 (4)	C2B—C3B—C4B	119.4 (3)
C1D—N1D—H11D	119 (2)	C3B—C4B—C10B	119.5 (3)
C1D—N1D—H12D	120 (3)	C6B—C5B—C10B	120.5 (3)
H11D—N1D—H12D	121 (4)	C5B—C6B—C7B	120.4 (3)
C1D—N2D—H22D	116 (3)	C6B—C7B—C8B	120.9 (3)
H21D—N2D—H22D	121 (4)	C7B—C8B—C9B	120.4 (3)
C1D—N2D—H21D	122 (2)	C8B—C9B—C10B	118.5 (3)
C1D—N3D—H31D	120 (2)	N1B—C9B—C8B	118.9 (3)
C1D—N3D—H32D	120 (3)	N1B—C9B—C10B	122.7 (3)
H31D—N3D—H32D	119 (4)	C4B—C10B—C9B	117.5 (3)
N1A—C2A—C21A	117.7 (3)	C5B—C10B—C9B	119.3 (3)
N1A—C2A—C3A	122.9 (3)	C4B—C10B—C5B	123.2 (3)
C3A—C2A—C21A	119.4 (3)	O21B—C21B—C2B	119.3 (3)
C2A—C3A—C4A	119.6 (3)	O21B—C21B—O22B	123.8 (3)
C3A—C4A—C10A	119.7 (3)	O22B—C21B—C2B	116.8 (3)
C6A—C5A—C10A	120.6 (3)	C2B—C3B—H3B	120.00
C5A—C6A—C7A	121.0 (4)	C4B—C3B—H3B	120.00
C6A—C7A—C8A	120.6 (3)	C10B—C4B—H4B	120.00
C7A—C8A—C9A	120.3 (3)	C3B—C4B—H4B	120.00
N1A—C9A—C10A	122.5 (3)	C6B—C5B—H5B	120.00
N1A—C9A—C8A	118.9 (3)	C10B—C5B—H5B	120.00
C8A—C9A—C10A	118.6 (3)	C7B—C6B—H6B	120.00
C5A—C10A—C9A	119.0 (3)	C5B—C6B—H6B	120.00
C4A—C10A—C9A	117.3 (3)	C8B—C7B—H7B	120.00
C4A—C10A—C5A	123.7 (3)	C6B—C7B—H7B	120.00
O21A—C21A—C2A	119.0 (3)	C9B—C8B—H8B	120.00
O21A—C21A—O22A	124.2 (3)	C7B—C8B—H8B	120.00
O22A—C21A—C2A	116.8 (3)	N2C—C1C—N3C	120.3 (4)
C2A—C3A—H3A	120.00	N1C—C1C—N2C	119.3 (4)
C4A—C3A—H3A	120.00	N1C—C1C—N3C	120.4 (3)
C3A—C4A—H4A	120.00	N2D—C1D—N3D	119.9 (3)
C10A—C4A—H4A	120.00	N1D—C1D—N2D	119.6 (3)
C10A—C5A—H5A	120.00	N1D—C1D—N3D	120.5 (3)

C9A—N1A—C2A—C3A	0.0 (4)	N1A—C9A—C10A—C5A	179.2 (3)
C9A—N1A—C2A—C21A	−179.6 (2)	C8A—C9A—C10A—C4A	178.7 (3)
C2A—N1A—C9A—C8A	−178.8 (3)	C8A—C9A—C10A—C5A	−1.5 (4)
C2A—N1A—C9A—C10A	0.6 (4)	N1A—C9A—C10A—C4A	−0.6 (4)
C2B—N1B—C9B—C8B	179.1 (3)	N1B—C2B—C3B—C4B	0.2 (5)
C2B—N1B—C9B—C10B	−0.4 (4)	C21B—C2B—C3B—C4B	179.9 (3)
C9B—N1B—C2B—C3B	0.4 (4)	N1B—C2B—C21B—O21B	−16.7 (4)
C9B—N1B—C2B—C21B	−179.3 (2)	N1B—C2B—C21B—O22B	163.6 (3)
C3A—C2A—C21A—O21A	171.5 (3)	C3B—C2B—C21B—O21B	163.6 (3)
N1A—C2A—C21A—O21A	−8.9 (4)	C3B—C2B—C21B—O22B	−16.1 (4)
N1A—C2A—C21A—O22A	170.3 (3)	C2B—C3B—C4B—C10B	−0.9 (4)
N1A—C2A—C3A—C4A	−0.5 (5)	C3B—C4B—C10B—C5B	−178.8 (3)
C21A—C2A—C3A—C4A	179.1 (3)	C3B—C4B—C10B—C9B	0.9 (4)
C3A—C2A—C21A—O22A	−9.4 (4)	C10B—C5B—C6B—C7B	0.6 (5)
C2A—C3A—C4A—C10A	0.4 (4)	C6B—C5B—C10B—C4B	179.1 (3)
C3A—C4A—C10A—C9A	0.1 (4)	C6B—C5B—C10B—C9B	−0.6 (5)
C3A—C4A—C10A—C5A	−179.7 (3)	C5B—C6B—C7B—C8B	−0.1 (5)
C6A—C5A—C10A—C4A	−179.0 (3)	C6B—C7B—C8B—C9B	−0.6 (5)
C6A—C5A—C10A—C9A	1.2 (5)	C7B—C8B—C9B—N1B	−178.9 (3)
C10A—C5A—C6A—C7A	−0.1 (6)	C7B—C8B—C9B—C10B	0.6 (4)
C5A—C6A—C7A—C8A	−0.6 (6)	N1B—C9B—C10B—C4B	−0.2 (4)
C6A—C7A—C8A—C9A	0.3 (5)	N1B—C9B—C10B—C5B	179.5 (3)
C7A—C8A—C9A—N1A	−179.9 (3)	C8B—C9B—C10B—C4B	−179.7 (3)
C7A—C8A—C9A—C10A	0.8 (4)	C8B—C9B—C10B—C5B	0.0 (4)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z+1; (iii) x, y, z+1; (iv) x+1, −y+1/2, z−1/2; (v) x, −y+1/2, z+1/2; (vi) x−1, y, z; (vii) x, y, z−1; (viii) x+1, y, z−1; (ix) −x+2, −y, −z+1; (x) −x+2, −y, −z; (xi) x, −y+1/2, z−1/2; (xii) x−1, −y+1/2, z+1/2; (xiii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1C—H11C···O21B	0.82 (4)	2.12 (4)	2.937 (5)	176 (3)
N1C—H12C···O21A^vi	0.92 (4)	2.03 (4)	2.852 (5)	149 (3)
N1D—H11D···O22A	0.87 (4)	2.04 (4)	2.902 (4)	177 (4)
N1D—H12D···O21B^vii	0.85 (5)	2.47 (5)	3.312 (5)	173 (4)
N2C—H21C···O22A	0.94 (4)	1.87 (4)	2.784 (4)	166 (4)
N2C—H22C···O21A^vi	0.91 (4)	2.57 (4)	3.163 (5)	124 (4)
N2C—H22C···N1A^vi	0.91 (4)	2.08 (5)	2.964 (4)	165 (4)
N2D—H21D···O21B^viii	0.84 (4)	2.11 (4)	2.899 (5)	155 (3)
N2D—H22D···O21A	0.89 (4)	2.01 (5)	2.890 (4)	173 (4)
N3C—H31C···O22B	0.93 (5)	1.96 (5)	2.891 (4)	173 (4)
N3C—H32C···O22A	0.84 (4)	2.57 (5)	3.216 (5)	135 (4)
N3D—H31D···O21B^viii	0.93 (4)	2.60 (4)	3.268 (5)	130 (3)
N3D—H31D···N1B^viii	0.93 (4)	2.12 (4)	3.000 (4)	159 (3)
N3D—H32D···O22B^vii	0.93 (4)	1.95 (4)	2.826 (4)	157 (4)

Symmetry codes: (vi) x−1, y, z; (vii) x, y, z−1; (viii) x+1, y, z−1.

Experimental details

Crystal data
Chemical formula	CH₆N₃⁺·C₁₀H₆NO₂⁻
M_r	232.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	297
a, b, c (Å)	7.4318 (3), 42.2105 (18), 7.3035 (4)
β (°)	94.045 (4)
V (Å³)	2285.40 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.20 × 0.18

Data collection
Diffractometer	Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.740, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	10626, 3981, 2931
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.162, 1.04
No. of reflections	3981
No. of parameters	355
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1C—H11C···O21B	0.82 (4)	2.12 (4)	2.937 (5)	176 (3)
N1C—H12C···O21Aⁱ	0.92 (4)	2.03 (4)	2.852 (5)	149 (3)
N1D—H11D···O22A	0.87 (4)	2.04 (4)	2.902 (4)	177 (4)
N1D—H12D···O21Bⁱⁱ	0.85 (5)	2.47 (5)	3.312 (5)	173 (4)
N2C—H21C···O22A	0.94 (4)	1.87 (4)	2.784 (4)	166 (4)
N2C—H22C···O21Aⁱ	0.91 (4)	2.57 (4)	3.163 (5)	124 (4)
N2C—H22C···N1Aⁱ	0.91 (4)	2.08 (5)	2.964 (4)	165 (4)
N2D—H21D···O21Bⁱⁱⁱ	0.84 (4)	2.11 (4)	2.899 (5)	155 (3)
N2D—H22D···O21A	0.89 (4)	2.01 (5)	2.890 (4)	173 (4)
N3C—H31C···O22B	0.93 (5)	1.96 (5)	2.891 (4)	173 (4)
N3C—H32C···O22A	0.84 (4)	2.57 (5)	3.216 (5)	135 (4)
N3D—H31D···O21Bⁱⁱⁱ	0.93 (4)	2.60 (4)	3.268 (5)	130 (3)
N3D—H31D···N1Bⁱⁱⁱ	0.93 (4)	2.12 (4)	3.000 (4)	159 (3)
N3D—H32D···O22Bⁱⁱ	0.93 (4)	1.95 (4)	2.826 (4)	157 (4)

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

Acknowledgements

The authors acknowledge financial support from the Australian Research Council and the School of Physical and Chemical Sciences, Queensland University of Technology,

References

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