2-Amino-anilinium picrate.

In the title compound, C(6)H(9)N(2) (+)·C(6)H(2)N(3)O(7) (-), the three nitro groups of the anion are twisted from the central benzene ring at dihedral angles of 5.4 (1), 27.1 (1) and 32.9 (1)°. In the crystal, inter-molecular N-H⋯O, N-H⋯(O,O) and N-H⋯N hydrogen bonds link the cations and anions into layers parallel to the bc plane.

Related literature

For the crystal structures of picric acid complexes, see: Harrison et al. (2007 ▶); Li (2009 ▶); Saminathan et al. (2007 ▶); Sivaramkumar et al. (2010 ▶). For their conformational features and charge-transfer processes, see: Nagata et al. (1995 ▶); Smith et al. (2004 ▶).

Experimental

Crystal data

C6H9N2 +·C6H2N3O7 −

M = 337.26

Monoclinic,

a = 13.2938 (11) Å

b = 6.9959 (6) Å

c = 15.2967 (13) Å

β = 92.629 (1)°

V = 1421.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 298 K

0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.979, T max = 0.987

16897 measured reflections

3514 independent reflections

2394 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.120

S = 0.93

3514 reflections

232 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810047057/cv2788sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047057/cv2788Isup2.hkl

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

C6H9N2+·C6H2N3O7−	F(000) = 696
Mr = 337.26	Dx = 1.576 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3836 reflections
a = 13.2938 (11) Å	θ = 2.7–24.9°
b = 6.9959 (6) Å	µ = 0.13 mm−1
c = 15.2967 (13) Å	T = 298 K
β = 92.629 (1)°	Block, yellow
V = 1421.1 (2) Å3	0.16 × 0.12 × 0.10 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	3514 independent reflections
Radiation source: fine-focus sealed tube	2394 reflections with I > 2σ(I)
graphite	Rint = 0.063
phi and ω scans	θmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −17→17
Tmin = 0.979, Tmax = 0.987	k = −9→9
16897 measured reflections	l = −20→20

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ2(Fo2) + (0.0701P)2] where P = (Fo2 + 2Fc2)/3
3514 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.38865 (11)	0.36646 (19)	0.40921 (9)	0.0336 (3)
C2	0.34942 (10)	0.3253 (2)	0.48958 (9)	0.0325 (3)
C3	0.24721 (11)	0.3359 (2)	0.50234 (12)	0.0467 (4)
H3	0.2225	0.3084	0.5568	0.056*
C4	0.18224 (13)	0.3879 (2)	0.43324 (16)	0.0612 (5)
H4	0.1133	0.3938	0.4407	0.073*
C5	0.22011 (15)	0.4306 (2)	0.35353 (15)	0.0617 (5)
H5	0.1764	0.4655	0.3071	0.074*
C6	0.32123 (14)	0.4227 (2)	0.34162 (11)	0.0484 (4)
H6	0.3455	0.4553	0.2875	0.058*
C7	0.68910 (10)	0.11086 (18)	0.55689 (8)	0.0280 (3)
C8	0.77757 (10)	0.1384 (2)	0.50680 (9)	0.0315 (3)
C9	0.87421 (11)	0.1403 (2)	0.54126 (9)	0.0361 (3)
H9	0.9277	0.1672	0.5061	0.043*
C10	0.89116 (10)	0.1016 (2)	0.62926 (9)	0.0370 (4)
C11	0.81281 (10)	0.0667 (2)	0.68247 (9)	0.0346 (3)
H11	0.8253	0.0365	0.7412	0.042*
C12	0.71596 (10)	0.07703 (19)	0.64812 (8)	0.0291 (3)
N1	0.49196 (10)	0.3622 (2)	0.39598 (9)	0.0406 (3)
H1A	0.5270 (13)	0.274 (2)	0.4304 (11)	0.049*
H1B	0.5052 (13)	0.351 (2)	0.3449 (12)	0.049*
N2	0.41690 (10)	0.2695 (2)	0.56298 (8)	0.0367 (3)
H2A	0.4726 (13)	0.195 (2)	0.5473 (10)	0.044*
H2B	0.3848 (12)	0.218 (2)	0.6043 (11)	0.044*
H2C	0.4430 (12)	0.373 (3)	0.5843 (11)	0.044*
N3	0.76527 (10)	0.1700 (2)	0.41270 (8)	0.0436 (3)
N4	0.99307 (10)	0.0980 (2)	0.66670 (10)	0.0588 (4)
N5	0.63727 (9)	0.04886 (18)	0.70943 (8)	0.0365 (3)
O1	0.60100 (7)	0.11173 (15)	0.52432 (6)	0.0377 (3)
O2	0.69569 (9)	0.0908 (2)	0.37119 (7)	0.0630 (4)
O3	0.82684 (10)	0.2717 (2)	0.37879 (8)	0.0740 (4)
O4	1.06230 (9)	0.1404 (2)	0.61973 (10)	0.0814 (5)
O5	1.00595 (10)	0.0516 (3)	0.74296 (10)	0.1001 (6)
O6	0.65667 (9)	−0.04467 (18)	0.77549 (7)	0.0549 (3)
O7	0.55494 (8)	0.1226 (2)	0.69490 (7)	0.0632 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0363 (8)	0.0312 (8)	0.0327 (7)	−0.0020 (6)	−0.0049 (6)	−0.0030 (6)
C2	0.0295 (7)	0.0315 (7)	0.0361 (8)	−0.0009 (6)	−0.0016 (6)	−0.0024 (6)
C3	0.0334 (8)	0.0406 (9)	0.0666 (11)	0.0004 (7)	0.0061 (8)	−0.0058 (8)
C4	0.0295 (9)	0.0461 (10)	0.1064 (17)	0.0022 (7)	−0.0120 (10)	−0.0108 (11)
C5	0.0573 (12)	0.0437 (10)	0.0804 (14)	0.0053 (8)	−0.0370 (11)	−0.0043 (9)
C6	0.0590 (11)	0.0405 (9)	0.0436 (9)	−0.0007 (8)	−0.0204 (8)	0.0008 (7)
C7	0.0277 (7)	0.0304 (7)	0.0260 (7)	0.0019 (5)	0.0014 (5)	−0.0020 (5)
C8	0.0340 (7)	0.0363 (8)	0.0244 (7)	0.0001 (6)	0.0034 (6)	0.0000 (6)
C9	0.0303 (8)	0.0436 (9)	0.0352 (8)	−0.0035 (6)	0.0088 (6)	−0.0026 (6)
C10	0.0254 (7)	0.0499 (9)	0.0355 (8)	−0.0007 (6)	−0.0014 (6)	−0.0066 (7)
C11	0.0335 (8)	0.0458 (9)	0.0243 (7)	0.0019 (6)	−0.0010 (6)	−0.0029 (6)
C12	0.0262 (7)	0.0372 (8)	0.0242 (7)	−0.0009 (6)	0.0043 (5)	−0.0023 (5)
N1	0.0413 (8)	0.0535 (8)	0.0273 (6)	−0.0016 (6)	0.0048 (6)	0.0025 (6)
N2	0.0340 (7)	0.0485 (8)	0.0280 (6)	0.0019 (6)	0.0048 (5)	−0.0027 (6)
N3	0.0453 (8)	0.0586 (8)	0.0276 (6)	0.0047 (7)	0.0078 (6)	0.0068 (6)
N4	0.0280 (7)	0.0973 (12)	0.0506 (9)	0.0024 (7)	−0.0036 (7)	−0.0095 (8)
N5	0.0316 (7)	0.0518 (8)	0.0263 (6)	−0.0020 (6)	0.0043 (5)	−0.0022 (5)
O1	0.0271 (5)	0.0558 (7)	0.0299 (5)	0.0053 (4)	−0.0026 (4)	−0.0021 (5)
O2	0.0590 (8)	0.1025 (11)	0.0270 (6)	−0.0075 (7)	−0.0025 (6)	−0.0022 (6)
O3	0.0754 (9)	0.1017 (11)	0.0460 (7)	−0.0163 (8)	0.0145 (7)	0.0306 (7)
O4	0.0284 (7)	0.1396 (14)	0.0766 (10)	−0.0101 (7)	0.0079 (6)	−0.0095 (9)
O5	0.0424 (8)	0.199 (2)	0.0570 (9)	0.0039 (10)	−0.0191 (6)	0.0133 (11)
O6	0.0575 (8)	0.0729 (8)	0.0355 (6)	0.0063 (6)	0.0145 (5)	0.0171 (6)
O7	0.0332 (6)	0.1180 (11)	0.0390 (7)	0.0164 (7)	0.0102 (5)	0.0097 (7)

C1—C2	1.387 (2)	C9—H9	0.9300
C1—C6	1.393 (2)	C10—C11	1.373 (2)
C1—N1	1.3977 (19)	C10—N4	1.447 (2)
C2—C3	1.383 (2)	C11—C12	1.3699 (19)
C2—N2	1.4579 (19)	C11—H11	0.9300
C3—C4	1.383 (3)	C12—N5	1.4501 (17)
C3—H3	0.9300	N1—H1A	0.922 (18)
C4—C5	1.373 (3)	N1—H1B	0.813 (18)
C4—H4	0.9300	N2—H2A	0.946 (16)
C5—C6	1.366 (3)	N2—H2B	0.858 (17)
C5—H5	0.9300	N2—H2C	0.858 (18)
C6—H6	0.9300	N3—O3	1.2182 (17)
C7—O1	1.2517 (15)	N3—O2	1.2295 (17)
C7—C12	1.4441 (18)	N4—O5	1.215 (2)
C7—C8	1.4457 (19)	N4—O4	1.2296 (19)
C8—C9	1.366 (2)	N5—O7	1.2211 (16)
C8—N3	1.4580 (18)	N5—O6	1.2214 (15)
C9—C10	1.381 (2)
C2—C1—C6	117.44 (14)	C11—C10—C9	121.21 (13)
C2—C1—N1	122.40 (13)	C11—C10—N4	118.98 (13)
C6—C1—N1	120.08 (15)	C9—C10—N4	119.81 (13)
C3—C2—C1	121.70 (14)	C12—C11—C10	119.25 (13)
C3—C2—N2	118.64 (14)	C12—C11—H11	120.4
C1—C2—N2	119.66 (12)	C10—C11—H11	120.4
C4—C3—C2	119.30 (17)	C11—C12—C7	124.44 (12)
C4—C3—H3	120.4	C11—C12—N5	115.98 (12)
C2—C3—H3	120.4	C7—C12—N5	119.57 (12)
C5—C4—C3	119.63 (17)	C1—N1—H1A	113.9 (10)
C5—C4—H4	120.2	C1—N1—H1B	113.6 (12)
C3—C4—H4	120.2	H1A—N1—H1B	111.0 (16)
C6—C5—C4	120.84 (17)	C2—N2—H2A	114.5 (10)
C6—C5—H5	119.6	C2—N2—H2B	111.7 (11)
C4—C5—H5	119.6	H2A—N2—H2B	112.2 (15)
C5—C6—C1	121.06 (17)	C2—N2—H2C	107.0 (11)
C5—C6—H6	119.5	H2A—N2—H2C	104.6 (15)
C1—C6—H6	119.5	H2B—N2—H2C	106.2 (16)
O1—C7—C12	124.81 (12)	O3—N3—O2	123.18 (13)
O1—C7—C8	123.88 (12)	O3—N3—C8	117.51 (14)
C12—C7—C8	111.28 (12)	O2—N3—C8	119.29 (13)
C9—C8—C7	124.77 (13)	O5—N4—O4	123.30 (15)
C9—C8—N3	116.13 (13)	O5—N4—C10	118.21 (15)
C7—C8—N3	119.10 (12)	O4—N4—C10	118.49 (15)
C8—C9—C10	118.86 (13)	O7—N5—O6	122.04 (12)
C8—C9—H9	120.6	O7—N5—C12	119.47 (12)
C10—C9—H9	120.6	O6—N5—C12	118.46 (12)
C6—C1—C2—C3	1.1 (2)	N4—C10—C11—C12	177.54 (14)
N1—C1—C2—C3	177.94 (14)	C10—C11—C12—C7	4.1 (2)
C6—C1—C2—N2	−178.80 (13)	C10—C11—C12—N5	−176.71 (13)
N1—C1—C2—N2	−2.0 (2)	O1—C7—C12—C11	176.54 (14)
C1—C2—C3—C4	0.3 (2)	C8—C7—C12—C11	−1.78 (19)
N2—C2—C3—C4	−179.72 (14)	O1—C7—C12—N5	−2.6 (2)
C2—C3—C4—C5	−0.9 (2)	C8—C7—C12—N5	179.07 (12)
C3—C4—C5—C6	−0.1 (3)	C9—C8—N3—O3	−30.9 (2)
C4—C5—C6—C1	1.6 (3)	C7—C8—N3—O3	148.08 (14)
C2—C1—C6—C5	−2.1 (2)	C9—C8—N3—O2	147.45 (14)
N1—C1—C6—C5	−178.99 (14)	C7—C8—N3—O2	−33.5 (2)
O1—C7—C8—C9	179.16 (14)	C11—C10—N4—O5	4.8 (3)
C12—C7—C8—C9	−2.51 (19)	C9—C10—N4—O5	−175.38 (17)
O1—C7—C8—N3	0.2 (2)	C11—C10—N4—O4	−175.78 (16)
C12—C7—C8—N3	178.56 (12)	C9—C10—N4—O4	4.0 (2)
C7—C8—C9—C10	4.3 (2)	C11—C12—N5—O7	152.66 (14)
N3—C8—C9—C10	−176.74 (13)	C7—C12—N5—O7	−28.1 (2)
C8—C9—C10—C11	−1.8 (2)	C11—C12—N5—O6	−25.50 (19)
C8—C9—C10—N4	178.44 (14)	C7—C12—N5—O6	153.72 (13)
C9—C10—C11—C12	−2.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.922 (18)	2.048 (19)	2.9607 (18)	170.0 (14)
N2—H2A···O1	0.946 (16)	1.852 (17)	2.7731 (16)	163.9 (14)
N2—H2A···O7	0.946 (16)	2.514 (15)	2.8558 (17)	101.4 (11)
N1—H1B···O7i	0.813 (18)	2.424 (19)	3.2264 (17)	169.6 (16)
N2—H2A···O1ii	0.946 (16)	2.581 (16)	2.9872 (18)	106.2 (11)
N2—H2B···O2ii	0.858 (17)	2.448 (16)	3.122 (2)	135.9 (14)
N2—H2B···O6iii	0.858 (17)	2.556 (16)	2.9956 (17)	112.9 (12)
N2—H2C···N1iv	0.858 (18)	2.063 (18)	2.904 (2)	166.1 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.922 (18)	2.048 (19)	2.9607 (18)	170.0 (14)
N2—H2A⋯O1	0.946 (16)	1.852 (17)	2.7731 (16)	163.9 (14)
N2—H2A⋯O7	0.946 (16)	2.514 (15)	2.8558 (17)	101.4 (11)
N1—H1B⋯O7i	0.813 (18)	2.424 (19)	3.2264 (17)	169.6 (16)
N2—H2A⋯O1ii	0.946 (16)	2.581 (16)	2.9872 (18)	106.2 (11)
N2—H2B⋯O2ii	0.858 (17)	2.448 (16)	3.122 (2)	135.9 (14)
N2—H2B⋯O6iii	0.858 (17)	2.556 (16)	2.9956 (17)	112.9 (12)
N2—H2C⋯N1iv	0.858 (18)	2.063 (18)	2.904 (2)	166.1 (16)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .