2-(4-Amino­phen­yl)-1-phenyl­diazenium 2,4,6-trinitro­phenolate

Smith, G.; Wermuth, U.D.; White, J.M.

doi:10.1107/S1600536811008968

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o878

doi:10.1107/S1600536811008968

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2-(4-Aminophenyl)-1-phenyldiazenium 2,4,6-trinitrophenolate

Graham Smith,^a ^* Urs D. Wermuth ^a and Jonathan M. White ^b

^aFaculty of Science and Technology, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and ^bBIO-21 Molecular Science and Biotechnology, University of Melbourne, Parkville, Victoria 3052, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 19 February 2011; accepted 9 March 2011; online 12 March 2011)

In the title salt, C₁₂H₁₂N₃⁺·C₆H₂N₃O₇⁻, the diazenyl group of the 4-(phenyldiazenyl)aniline molecule is protonated and forms a hydrogen bond with the phenolate O-atom acceptor of the picrate anion. Structure extension occurs through two symmetrical inter-ion three-centre amine N—H⋯O,O′_nitro hydrogen-bonding associations [graph set R₁²(4)], giving a convoluted two-dimensional network structure.

Related literature

For the diazo-dye precursor aniline yellow [4-(phenyldiazenyl)aniline], see: O'Neil (2001 ). For structural data on diazenyl-protonated salts of aniline yellow, see: Yatsenko et al. (2000 ); Mahmoudkhani & Langer (2001a ); Smith et al. (2009 ). For amine-protonated salts of aniline yellow, see: Mahmoudkhani & Langer (2001b ); Smith et al. (2008 ). For hydrogen-bonding graph-set analysis, see: Etter et al. (1990 ).

Experimental

Crystal data

C₁₂H₁₂N₃⁺·C₆H₂N₃O₇⁻
M_r = 426.35
Monoclinic, P 2₁ /n
a = 5.4506 (2) Å
b = 16.8974 (5) Å
c = 19.9386 (6) Å
β = 94.063 (3)°
V = 1831.75 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 180 K
0.35 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.885, T_max = 0.980
12224 measured reflections
3593 independent reflections
2278 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.075
S = 0.87
3593 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O1A	0.879 (18)	2.045 (18)	2.9039 (18)	165.4 (16)
N4—H41⋯O41Aⁱ	0.89 (2)	2.44 (2)	3.211 (2)	145.0 (16)
N4—H41⋯O42Aⁱ	0.89 (2)	2.29 (2)	3.127 (2)	156.9 (15)
N4—H42⋯O61Aⁱⁱ	0.88 (2)	2.33 (2)	3.170 (2)	159 (2)
N4—H42⋯O62Aⁱⁱ	0.88 (2)	2.36 (2)	3.126 (2)	145 (2)
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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/S1600536811008968/fl2338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008968/fl2338Isup2.hkl

checkCIF report

Comment top

The diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) (O'Neil, 2001) has been found to react with strong acids to form salts through protonation of the diazenyl group rather than the amine group of the molecule, e.g with the hydrochloride (Yatsenko et al., 2000; Mahmoudkhani & Langer, 2001a), and with 5-sulfosalicylic acid (Smith et al., 2009). With benzenesulfonic acid (Smith et al., 2009), the structure of the dichroic salt showed the 1:1 presence of both the diazenyl- and the amine-protonated forms. The phenylhydrazin-1-ium salts are invariably coloured purple-black or red-black as distinct from the amine-protonated salts which are orange-red e.g. the oxalate (Mahmoudkhani & Langer, 2001b) and the nitro-substituted phthalates and isophthalates (Smith et al., 2008). Our 1:1 stoichiometric reaction of aniline yellow with picric acid in 80% ethanol-water gave red-black crystals of the title salt, (I), and the structure is reported here.

In the structure of (I) (Fig. 1) the diazenyl group of the 4-(phenyldiazenyl)aniline molecule is protonated and forms a hydrogen bond with the phenolate O acceptor of the picrate anion (Table 1). A secondary weak C2—H2···O1A interaction [3.344 (2) Å] is also present. Structure extension occurs through two symmetrical inter-ion three-centre amine N—H···O,O'_nitro hydrogen-bonding associations [graph set R²₁(4) (Etter et al., 1990)], giving a convoluted two-dimensional network structure (Fig. 2). There are no π–π interactions involving the phenyl rings of the cations [minimum inter-ring centroid separation, 4.058 (1) Å]. In the crystal packing there are three close non-bonding intermolecular interactions associated with the nitro groups: O21A···N6Aⁱⁱⁱ, 2.8640 (18) Å and O21A···C6Aⁱⁱⁱ, 2.974 (2) Å (symmetry code (iii) x + 1, y, z ) and O22A···N4A^iv, 2.8987 (19) Å (symmetry code (iv) -x + 1, -y + 1, -z ).

The cation in (I) is essentially planar, the C6—C1—N1—N11 and C21—C11—N11—N1 torsion angles being -174.89 (14) and 176.74 (14)° respectively. With the picrate anion, the two ortho-related nitro groups are rotated out of the benzene plane [torsion angles C1A—C2A—N2A—O22A, 145.46 (15)° and C5A—C6A—N6A—O62A, -163.83 (15)°] while the para-related nitro group is essentially coplanar with the ring [C3A—C4A—N4A—O42A, 179.40 (15)°].

Related literature top

For the diazo-dye precursor aniline yellow [4-(phenyldiazenyl)aniline], see: O'Neil (2001). For structural data on diazenyl-protonated salts of aniline yellow, see: Yatsenko et al. (2000); Mahmoudkhani & Langer (2001a); Smith et al. (2009). For amine-protonated salts of aniline yellow, see: Mahmoudkhani & Langer (2001b); Smith et al. (2008). For hydrogen-bonding graph-set analysis, see: Etter et al. (1990).

Experimental top

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol quantities of 4-(phenyldiazenyl)aniline (aniline yellow) and picric acid in 50 ml of 80% ethanol-water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave red-black prisms of (I) (m.p. 443–445 K) from which a specimen was cleaved for the X-ray analysis.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 conformation and atom naming scheme for the diazenyl-protonated cation and the picrate anion in (I). The inter-species hydrogen bond is shown as a dashed line and displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. The hydrogen-bonded sheet structure of (I), with non-associative H atoms omitted and hydrogen bonds shown as dashed lines. For symmetry codes, see Table 1.

2-(4-Aminophenyl)-1-phenyldiazenium 2,4,6-trinitrophenolate top

Crystal data top

C₁₂H₁₂N₃⁺·C₆H₂N₃O₇⁻	F(000) = 880
M_r = 426.35	D_x = 1.546 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 443–445 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.4506 (2) Å	Cell parameters from 3903 reflections
b = 16.8974 (5) Å	θ = 3.2–28.7°
c = 19.9386 (6) Å	µ = 0.12 mm⁻¹
β = 94.063 (3)°	T = 180 K
V = 1831.75 (10) Å³	Prism, red-black
Z = 4	0.35 × 0.18 × 0.15 mm

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	3593 independent reflections
Radiation source: fine-focus sealed tube	2278 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 16.077 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −20→20
T_min = 0.885, T_max = 0.980	l = −22→24
12224 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	w = 1/[σ²(F_o²) + (0.0376P)²] where P = (F_o² + 2F_c²)/3
3593 reflections	(Δ/σ)_max < 0.001
292 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₂N₃⁺·C₆H₂N₃O₇⁻	V = 1831.75 (10) Å³
M_r = 426.35	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.4506 (2) Å	µ = 0.12 mm⁻¹
b = 16.8974 (5) Å	T = 180 K
c = 19.9386 (6) Å	0.35 × 0.18 × 0.15 mm
β = 94.063 (3)°

Data collection top

Oxford Diffraction Gemini-S CCD detector diffractometer	3593 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2278 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.980	R_int = 0.035
12224 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.075	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	Δρ_max = 0.14 e Å⁻³
3593 reflections	Δρ_min = −0.23 e Å⁻³
292 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
N1	0.5298 (2)	0.49802 (8)	0.36091 (6)	0.0251 (4)
N4	−0.2497 (3)	0.32118 (10)	0.25985 (9)	0.0344 (6)
N11	0.6596 (2)	0.54559 (8)	0.32635 (7)	0.0252 (5)
C1	0.3432 (3)	0.45678 (9)	0.33086 (8)	0.0222 (5)
C2	0.2730 (3)	0.45249 (10)	0.26070 (8)	0.0269 (6)
C3	0.0809 (3)	0.40706 (10)	0.23773 (8)	0.0276 (5)
C4	−0.0594 (3)	0.36418 (9)	0.28318 (8)	0.0238 (5)
C5	0.0074 (3)	0.36874 (9)	0.35319 (8)	0.0254 (5)
C6	0.2047 (3)	0.41246 (10)	0.37563 (8)	0.0264 (5)
C11	0.8581 (3)	0.58730 (10)	0.35919 (8)	0.0242 (5)
C21	1.0003 (3)	0.63434 (10)	0.32020 (9)	0.0296 (6)
C31	1.1992 (3)	0.67474 (10)	0.35069 (9)	0.0343 (6)
C41	1.2563 (3)	0.66787 (11)	0.41880 (9)	0.0385 (7)
C51	1.1132 (3)	0.62021 (12)	0.45732 (9)	0.0410 (7)
C61	0.9138 (3)	0.57997 (11)	0.42795 (9)	0.0336 (6)
O1A	0.5381 (2)	0.60880 (7)	0.19268 (6)	0.0355 (4)
O21A	0.9876 (2)	0.55846 (7)	0.15684 (7)	0.0441 (5)
O22A	0.9183 (2)	0.48046 (7)	0.07170 (7)	0.0434 (5)
O41A	0.5231 (2)	0.62072 (8)	−0.12058 (6)	0.0504 (5)
O42A	0.2254 (2)	0.70145 (8)	−0.10480 (6)	0.0402 (4)
O61A	−0.0343 (2)	0.74572 (7)	0.11123 (7)	0.0408 (5)
O62A	0.2079 (2)	0.72543 (7)	0.20024 (6)	0.0392 (5)
N2A	0.8675 (2)	0.53839 (9)	0.10537 (8)	0.0300 (5)
N4A	0.3933 (3)	0.65722 (9)	−0.08305 (7)	0.0330 (5)
N6A	0.1562 (3)	0.71719 (8)	0.13953 (7)	0.0299 (5)
C1A	0.5121 (3)	0.62347 (9)	0.13155 (8)	0.0239 (6)
C2A	0.6597 (3)	0.58734 (9)	0.08148 (8)	0.0238 (5)
C3A	0.6232 (3)	0.59705 (9)	0.01357 (8)	0.0250 (6)
C4A	0.4368 (3)	0.64710 (10)	−0.01148 (8)	0.0251 (5)
C5A	0.2883 (3)	0.68524 (10)	0.03106 (8)	0.0245 (5)
C6A	0.3236 (3)	0.67494 (9)	0.09927 (8)	0.0231 (5)
H2	0.36010	0.48120	0.23050	0.0320*
H3	0.03980	0.40380	0.19170	0.0330*
H5	−0.08410	0.34180	0.38350	0.0300*
H6	0.25080	0.41350	0.42140	0.0320*
H11	0.626 (3)	0.5560 (10)	0.2835 (9)	0.041 (6)*
H21	0.96250	0.63870	0.27410	0.0360*
H31	1.29490	0.70670	0.32500	0.0410*
H41	−0.289 (3)	0.3182 (12)	0.2157 (11)	0.061 (7)*
H42	−0.337 (4)	0.2946 (13)	0.2877 (12)	0.077 (8)*
H43	1.39030	0.69510	0.43900	0.0460*
H51	1.15240	0.61550	0.50330	0.0490*
H61	0.81770	0.54830	0.45380	0.0400*
H3A	0.72160	0.57060	−0.01540	0.0300*
H5A	0.16310	0.71820	0.01350	0.0290*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0268 (7)	0.0258 (8)	0.0234 (8)	0.0003 (7)	0.0058 (6)	0.0002 (6)
N4	0.0355 (9)	0.0423 (10)	0.0250 (10)	−0.0121 (8)	−0.0001 (8)	0.0059 (8)
N11	0.0281 (8)	0.0296 (8)	0.0178 (8)	−0.0013 (7)	0.0017 (6)	0.0019 (7)
C1	0.0235 (8)	0.0239 (9)	0.0195 (9)	0.0015 (7)	0.0027 (7)	−0.0006 (7)
C2	0.0299 (9)	0.0301 (10)	0.0212 (10)	−0.0019 (8)	0.0050 (7)	0.0056 (8)
C3	0.0306 (9)	0.0336 (10)	0.0183 (9)	−0.0029 (8)	0.0005 (7)	0.0039 (8)
C4	0.0228 (8)	0.0245 (9)	0.0243 (9)	0.0020 (8)	0.0031 (7)	0.0016 (7)
C5	0.0304 (9)	0.0261 (9)	0.0206 (9)	−0.0019 (8)	0.0080 (7)	0.0029 (7)
C6	0.0333 (9)	0.0287 (10)	0.0174 (9)	0.0033 (8)	0.0041 (7)	0.0003 (7)
C11	0.0252 (9)	0.0253 (9)	0.0222 (9)	0.0004 (8)	0.0020 (7)	−0.0028 (8)
C21	0.0343 (10)	0.0315 (10)	0.0230 (10)	0.0004 (8)	0.0018 (8)	0.0018 (8)
C31	0.0343 (10)	0.0343 (11)	0.0349 (11)	−0.0081 (9)	0.0059 (9)	0.0008 (9)
C41	0.0359 (10)	0.0438 (12)	0.0352 (12)	−0.0103 (9)	−0.0008 (9)	−0.0113 (9)
C51	0.0437 (11)	0.0564 (13)	0.0228 (10)	−0.0103 (10)	0.0018 (9)	−0.0077 (9)
C61	0.0374 (10)	0.0416 (11)	0.0224 (10)	−0.0081 (9)	0.0073 (8)	−0.0027 (9)
O1A	0.0393 (7)	0.0468 (8)	0.0200 (7)	−0.0047 (6)	−0.0011 (5)	0.0078 (6)
O21A	0.0375 (7)	0.0409 (8)	0.0506 (9)	−0.0030 (6)	−0.0194 (7)	0.0055 (7)
O22A	0.0449 (8)	0.0397 (8)	0.0463 (9)	0.0160 (7)	0.0083 (7)	−0.0007 (7)
O41A	0.0556 (8)	0.0749 (10)	0.0222 (7)	0.0169 (8)	0.0133 (6)	−0.0041 (7)
O42A	0.0471 (8)	0.0470 (8)	0.0252 (7)	0.0101 (7)	−0.0069 (6)	0.0066 (6)
O61A	0.0296 (7)	0.0452 (8)	0.0484 (9)	0.0091 (6)	0.0075 (6)	−0.0098 (7)
O62A	0.0582 (8)	0.0378 (8)	0.0236 (8)	−0.0076 (6)	0.0163 (6)	−0.0070 (6)
N2A	0.0259 (8)	0.0291 (9)	0.0350 (9)	−0.0019 (7)	0.0013 (7)	0.0069 (7)
N4A	0.0368 (8)	0.0425 (10)	0.0200 (8)	0.0007 (8)	0.0040 (7)	0.0005 (7)
N6A	0.0347 (9)	0.0266 (8)	0.0297 (9)	−0.0066 (7)	0.0119 (7)	−0.0060 (7)
C1A	0.0241 (9)	0.0270 (10)	0.0204 (10)	−0.0082 (7)	0.0000 (7)	0.0026 (7)
C2A	0.0201 (8)	0.0233 (9)	0.0276 (10)	−0.0005 (7)	−0.0006 (7)	0.0025 (8)
C3A	0.0244 (9)	0.0279 (10)	0.0231 (10)	0.0000 (8)	0.0049 (7)	−0.0041 (7)
C4A	0.0278 (9)	0.0308 (10)	0.0169 (9)	0.0006 (8)	0.0025 (7)	0.0009 (7)
C5A	0.0236 (8)	0.0256 (9)	0.0242 (9)	0.0035 (8)	0.0004 (7)	0.0016 (7)
C6A	0.0231 (9)	0.0252 (9)	0.0216 (9)	−0.0021 (7)	0.0067 (7)	−0.0040 (7)

Geometric parameters (Å, º) top

O1A—C1A	1.242 (2)	C11—C21	1.387 (2)
O21A—N2A	1.225 (2)	C11—C61	1.389 (2)
O22A—N2A	1.230 (2)	C21—C31	1.385 (2)
O41A—N4A	1.2312 (19)	C31—C41	1.377 (3)
O42A—N4A	1.236 (2)	C41—C51	1.390 (3)
O61A—N6A	1.2434 (19)	C51—C61	1.377 (2)
O62A—N6A	1.2311 (18)	C2—H2	0.9300
N1—C1	1.339 (2)	C3—H3	0.9300
N1—N11	1.3002 (18)	C5—H5	0.9300
N4—C4	1.324 (2)	C6—H6	0.9300
N11—C11	1.413 (2)	C21—H21	0.9300
N4—H41	0.89 (2)	C31—H31	0.9300
N4—H42	0.88 (2)	C41—H43	0.9300
N11—H11	0.879 (18)	C51—H51	0.9300
N2A—C2A	1.455 (2)	C61—H61	0.9300
N4A—C4A	1.440 (2)	C1A—C2A	1.460 (2)
N6A—C6A	1.446 (2)	C1A—C6A	1.460 (2)
C1—C6	1.422 (2)	C2A—C3A	1.365 (2)
C1—C2	1.426 (2)	C3A—C4A	1.388 (2)
C2—C3	1.352 (2)	C4A—C5A	1.374 (2)
C3—C4	1.425 (2)	C5A—C6A	1.371 (2)
C4—C5	1.420 (2)	C3A—H3A	0.9300
C5—C6	1.354 (2)	C5A—H5A	0.9300

N11—N1—C1	120.61 (13)	C3—C2—H2	120.00
N1—N11—C11	119.37 (13)	C2—C3—H3	120.00
C4—N4—H41	120.3 (12)	C4—C3—H3	120.00
C4—N4—H42	120.3 (15)	C6—C5—H5	120.00
H41—N4—H42	119.4 (19)	C4—C5—H5	120.00
C11—N11—H11	116.8 (11)	C1—C6—H6	119.00
N1—N11—H11	123.7 (11)	C5—C6—H6	119.00
O21A—N2A—O22A	123.37 (13)	C11—C21—H21	120.00
O21A—N2A—C2A	118.30 (14)	C31—C21—H21	120.00
O22A—N2A—C2A	118.29 (14)	C41—C31—H31	120.00
O42A—N4A—C4A	119.03 (14)	C21—C31—H31	120.00
O41A—N4A—C4A	118.78 (14)	C51—C41—H43	120.00
O41A—N4A—O42A	122.19 (14)	C31—C41—H43	120.00
O61A—N6A—C6A	118.63 (14)	C41—C51—H51	120.00
O61A—N6A—O62A	121.87 (15)	C61—C51—H51	120.00
O62A—N6A—C6A	119.49 (14)	C51—C61—H61	120.00
N1—C1—C6	114.41 (14)	C11—C61—H61	120.00
N1—C1—C2	127.45 (15)	O1A—C1A—C2A	123.89 (14)
C2—C1—C6	118.13 (14)	O1A—C1A—C6A	125.39 (15)
C1—C2—C3	120.59 (15)	C2A—C1A—C6A	110.63 (14)
C2—C3—C4	120.74 (15)	N2A—C2A—C1A	117.89 (14)
C3—C4—C5	119.09 (14)	N2A—C2A—C3A	116.65 (14)
N4—C4—C5	121.03 (15)	C1A—C2A—C3A	125.44 (15)
N4—C4—C3	119.89 (15)	C2A—C3A—C4A	118.82 (15)
C4—C5—C6	119.79 (15)	N4A—C4A—C3A	119.61 (15)
C1—C6—C5	121.61 (15)	N4A—C4A—C5A	119.56 (15)
N11—C11—C21	117.80 (14)	C3A—C4A—C5A	120.81 (15)
C21—C11—C61	120.86 (16)	C4A—C5A—C6A	120.36 (15)
N11—C11—C61	121.32 (15)	N6A—C6A—C1A	120.09 (14)
C11—C21—C31	119.20 (16)	N6A—C6A—C5A	116.00 (14)
C21—C31—C41	120.45 (16)	C1A—C6A—C5A	123.90 (15)
C31—C41—C51	119.84 (16)	C2A—C3A—H3A	121.00
C41—C51—C61	120.53 (17)	C4A—C3A—H3A	121.00
C11—C61—C51	119.12 (16)	C4A—C5A—H5A	120.00
C1—C2—H2	120.00	C6A—C5A—H5A	120.00

C1—N1—N11—C11	−178.90 (14)	C4—C5—C6—C1	2.4 (2)
N11—N1—C1—C2	5.7 (2)	N11—C11—C21—C31	−178.72 (15)
N11—N1—C1—C6	−174.89 (14)	C61—C11—C21—C31	−0.4 (3)
N1—N11—C11—C21	176.74 (14)	N11—C11—C61—C51	178.27 (16)
N1—N11—C11—C61	−1.6 (2)	C21—C11—C61—C51	0.0 (3)
O21A—N2A—C2A—C1A	−36.9 (2)	C11—C21—C31—C41	0.5 (3)
O21A—N2A—C2A—C3A	141.62 (15)	C21—C31—C41—C51	−0.1 (3)
O22A—N2A—C2A—C1A	145.46 (15)	C31—C41—C51—C61	−0.3 (3)
O22A—N2A—C2A—C3A	−36.1 (2)	C41—C51—C61—C11	0.3 (3)
O41A—N4A—C4A—C5A	−177.77 (16)	O1A—C1A—C2A—N2A	−7.4 (2)
O42A—N4A—C4A—C3A	179.40 (15)	O1A—C1A—C2A—C3A	174.32 (16)
O41A—N4A—C4A—C3A	0.2 (2)	C6A—C1A—C2A—N2A	175.85 (13)
O42A—N4A—C4A—C5A	1.4 (2)	C6A—C1A—C2A—C3A	−2.5 (2)
O61A—N6A—C6A—C1A	−163.87 (14)	O1A—C1A—C6A—N6A	3.5 (2)
O61A—N6A—C6A—C5A	14.6 (2)	O1A—C1A—C6A—C5A	−174.90 (16)
O62A—N6A—C6A—C5A	−163.83 (15)	C2A—C1A—C6A—N6A	−179.79 (14)
O62A—N6A—C6A—C1A	17.7 (2)	C2A—C1A—C6A—C5A	1.8 (2)
C6—C1—C2—C3	−0.4 (2)	N2A—C2A—C3A—C4A	−176.08 (14)
N1—C1—C6—C5	178.82 (15)	C1A—C2A—C3A—C4A	2.3 (2)
N1—C1—C2—C3	179.05 (16)	C2A—C3A—C4A—N4A	−179.13 (15)
C2—C1—C6—C5	−1.7 (2)	C2A—C3A—C4A—C5A	−1.2 (2)
C1—C2—C3—C4	1.7 (3)	N4A—C4A—C5A—C6A	178.58 (15)
C2—C3—C4—N4	178.74 (16)	C3A—C4A—C5A—C6A	0.6 (3)
C2—C3—C4—C5	−1.0 (2)	C4A—C5A—C6A—N6A	−179.50 (15)
C3—C4—C5—C6	−1.1 (2)	C4A—C5A—C6A—C1A	−1.1 (3)
N4—C4—C5—C6	179.24 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O1A	0.879 (18)	2.045 (18)	2.9039 (18)	165.4 (16)
N4—H41···O41Aⁱ	0.89 (2)	2.44 (2)	3.211 (2)	145.0 (16)
N4—H41···O42Aⁱ	0.89 (2)	2.29 (2)	3.127 (2)	156.9 (15)
N4—H42···O61Aⁱⁱ	0.88 (2)	2.33 (2)	3.170 (2)	159 (2)
N4—H42···O62Aⁱⁱ	0.88 (2)	2.36 (2)	3.126 (2)	145 (2)
C2—H2···O1A	0.93	2.50	3.344 (2)	151
C3A—H3A···O22Aⁱⁱⁱ	0.93	2.48	3.384 (2)	163
C5A—H5A···O61A	0.93	2.34	2.663 (2)	100
C21—H21···O62A^iv	0.93	2.53	3.123 (2)	122
C31—H31···O62A^iv	0.93	2.52	3.123 (2)	123

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₃⁺·C₆H₂N₃O₇⁻
M_r	426.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	180
a, b, c (Å)	5.4506 (2), 16.8974 (5), 19.9386 (6)
β (°)	94.063 (3)
V (Å³)	1831.75 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.18 × 0.15

Data collection
Diffractometer	Oxford Diffraction Gemini-S CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.885, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	12224, 3593, 2278
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.075, 0.87
No. of reflections	3593
No. of parameters	292
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.23

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), 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
N11—H11···O1A	0.879 (18)	2.045 (18)	2.9039 (18)	165.4 (16)
N4—H41···O41Aⁱ	0.89 (2)	2.44 (2)	3.211 (2)	145.0 (16)
N4—H41···O42Aⁱ	0.89 (2)	2.29 (2)	3.127 (2)	156.9 (15)
N4—H42···O61Aⁱⁱ	0.88 (2)	2.33 (2)	3.170 (2)	159 (2)
N4—H42···O62Aⁱⁱ	0.88 (2)	2.36 (2)	3.126 (2)	145 (2)

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

Acknowledgements

The authors acknowledge financial support from the Australian Research Council, the Faculty of Science and Technology and the University Library, Queensland University of Technology, and the University of Melbourne.

References

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