2-(4-Amino-phen-yl)-1-phenyl-diazenium 2,4,6-trinitro-phenolate.

In the title salt, C(12)H(12)N(3) (+)·C(6)H(2)N(3)O(7) (-), the diazenyl group of the 4-(phenyl-diazen-yl)aniline mol-ecule 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 R(1) (2)(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 = 426.35

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.075

S = 0.87

3593 reflections

292 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008968/fl2338sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H12N3+·C6H2N3O7−	F(000) = 880
Mr = 426.35	Dx = 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

Oxford Diffraction Gemini-S CCD detector diffractometer	3593 independent reflections
Radiation source: fine-focus sealed tube	2278 reflections with I > 2σ(I)
graphite	Rint = 0.035
Detector resolution: 16.077 pixels mm-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −20→20
Tmin = 0.885, Tmax = 0.980	l = −22→24
12224 measured reflections

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(Fo2) + (0.0376P)2] where P = (Fo2 + 2Fc2)/3
3593 reflections	(Δ/σ)max < 0.001
292 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O62Aiv	0.93	2.53	3.123 (2)	122
C31—H31···O62Aiv	0.93	2.52	3.123 (2)	123

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) ; (ii) .