Picric acid-2,4,6-trichloro-aniline (1/1).

In the title adduct, C(6)H(4)Cl(3)N·C(6)H(3)N(3)O(7), the two benzene rings are almost coplanar, with a dihedral angle of 1.19 (1)° and an inter-ring centroid-centroid separation of 4.816 (2) Å. The crystal structure is stabilized by inter-molecular N-H⋯O(nitro) hydrogen bonds, giving a chain structure. In addition, there are phenol-nitro O-H⋯O inter-actions.

Related literature

The crystal structures of picrate salts and picric acid complexes have been studied to investigate charge-transfer processes, see: Nagata et al. (1995 ▶); Smith et al. (2004 ▶). For the crystal structures of picric acid complexes, see: Li (2009 ▶); Sivaramkumar et al. (2010 ▶).

Experimental

Crystal data

C6H4Cl3N·C6H3N3O7

M = 425.57

Orthorhombic,

a = 9.2162 (14) Å

b = 10.0174 (14) Å

c = 35.051 (5) Å

V = 3236.0 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.61 mm−1

T = 298 K

0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.908, T max = 0.941

19589 measured reflections

3186 independent reflections

2287 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.120

S = 1.10

3186 reflections

244 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.27 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/S160053681100571X/zs2097sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100571X/zs2097Isup2.hkl

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

C6H4Cl3N·C6H3N3O7	F(000) = 1712
Mr = 425.57	Dx = 1.747 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1781 reflections
a = 9.2162 (14) Å	θ = 2.5–19.2°
b = 10.0174 (14) Å	µ = 0.61 mm−1
c = 35.051 (5) Å	T = 298 K
V = 3236.0 (8) Å3	Block, red
Z = 8	0.16 × 0.12 × 0.10 mm

Bruker SMART CCD area-detector diffractometer	3186 independent reflections
Radiation source: fine-focus sealed tube	2287 reflections with I > 2σ(I)
graphite	Rint = 0.076
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −11→11
Tmin = 0.908, Tmax = 0.941	k = −12→10
19589 measured reflections	l = −41→43

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0381P)2 + 1.3007P] where P = (Fo2 + 2Fc2)/3
3186 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.21 e Å−3
2 restraints	Δρmin = −0.27 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	0.4507 (4)	0.4557 (3)	0.57639 (9)	0.0373 (8)
C2	0.5792 (3)	0.4955 (3)	0.55888 (10)	0.0396 (8)
C3	0.5881 (4)	0.6056 (4)	0.53560 (10)	0.0422 (9)
H3	0.6760	0.6295	0.5245	0.051*
C4	0.4651 (4)	0.6801 (3)	0.52893 (9)	0.0390 (8)
C5	0.3352 (4)	0.6456 (3)	0.54541 (10)	0.0415 (9)
H5	0.2523	0.6960	0.5408	0.050*
C6	0.3293 (3)	0.5361 (3)	0.56874 (9)	0.0375 (8)
C7	0.4085 (3)	0.4501 (3)	0.70238 (9)	0.0325 (7)
C8	0.5325 (3)	0.3724 (3)	0.70914 (9)	0.0343 (8)
C9	0.6640 (3)	0.3992 (3)	0.69253 (9)	0.0360 (8)
H9	0.7437	0.3447	0.6972	0.043*
C10	0.6760 (4)	0.5082 (3)	0.66889 (9)	0.0379 (8)
C11	0.5597 (4)	0.5899 (3)	0.66136 (9)	0.0379 (8)
H11	0.5694	0.6642	0.6456	0.046*
C12	0.4278 (3)	0.5584 (3)	0.67784 (9)	0.0324 (8)
Cl1	0.73498 (10)	0.40282 (11)	0.56753 (3)	0.0607 (3)
Cl2	0.47396 (11)	0.81912 (11)	0.49911 (3)	0.0592 (3)
Cl3	0.16542 (10)	0.49502 (10)	0.59030 (3)	0.0560 (3)
N1	0.5268 (3)	0.2597 (3)	0.73550 (9)	0.0478 (8)
N2	0.8171 (3)	0.5390 (4)	0.65186 (9)	0.0507 (8)
N3	0.3064 (3)	0.6474 (3)	0.66942 (9)	0.0452 (8)
N4	0.4439 (4)	0.3486 (3)	0.60078 (10)	0.0520 (8)
H4A	0.512 (3)	0.290 (3)	0.6009 (11)	0.062*
H4B	0.359 (2)	0.332 (4)	0.6079 (11)	0.062*
O1	0.2826 (3)	0.4170 (2)	0.71812 (7)	0.0494 (7)
H1A	0.218 (5)	0.479 (4)	0.7114 (11)	0.074*
O2	0.4487 (4)	0.2669 (3)	0.76291 (9)	0.0979 (13)
O3	0.6055 (3)	0.1642 (3)	0.72928 (8)	0.0643 (8)
O4	0.9144 (3)	0.4573 (3)	0.65587 (9)	0.0711 (9)
O5	0.8294 (3)	0.6445 (3)	0.63491 (9)	0.0726 (9)
O6	0.3275 (3)	0.7422 (3)	0.64860 (8)	0.0672 (8)
O7	0.1878 (3)	0.6247 (3)	0.68450 (8)	0.0602 (8)

	U11	U22	U33	U12	U13	U23
C1	0.041 (2)	0.035 (2)	0.0352 (19)	−0.0034 (16)	0.0003 (15)	−0.0064 (15)
C2	0.0318 (19)	0.042 (2)	0.045 (2)	0.0053 (16)	−0.0046 (15)	−0.0061 (17)
C3	0.0369 (19)	0.045 (2)	0.045 (2)	−0.0084 (17)	0.0048 (16)	−0.0036 (17)
C4	0.0398 (19)	0.037 (2)	0.040 (2)	−0.0048 (17)	−0.0010 (15)	0.0042 (16)
C5	0.0319 (18)	0.045 (2)	0.047 (2)	0.0040 (16)	−0.0042 (16)	0.0025 (17)
C6	0.0333 (18)	0.040 (2)	0.0395 (19)	−0.0019 (16)	0.0051 (15)	−0.0023 (16)
C7	0.0329 (18)	0.0345 (19)	0.0299 (17)	−0.0024 (15)	0.0016 (14)	−0.0052 (14)
C8	0.0383 (18)	0.0281 (19)	0.0365 (18)	0.0010 (15)	0.0009 (15)	0.0055 (14)
C9	0.0330 (17)	0.037 (2)	0.0377 (18)	0.0034 (15)	−0.0012 (15)	−0.0017 (15)
C10	0.0355 (19)	0.039 (2)	0.0392 (19)	−0.0075 (16)	0.0032 (15)	−0.0038 (16)
C11	0.044 (2)	0.032 (2)	0.0385 (19)	−0.0068 (16)	−0.0021 (15)	0.0007 (15)
C12	0.0355 (18)	0.0322 (19)	0.0296 (17)	−0.0002 (15)	−0.0040 (14)	−0.0033 (14)
Cl1	0.0420 (5)	0.0648 (7)	0.0754 (7)	0.0154 (5)	−0.0015 (5)	−0.0019 (5)
Cl2	0.0527 (6)	0.0609 (7)	0.0641 (6)	−0.0095 (5)	−0.0010 (5)	0.0236 (5)
Cl3	0.0402 (5)	0.0565 (6)	0.0712 (7)	−0.0038 (5)	0.0176 (5)	0.0094 (5)
N1	0.0449 (18)	0.050 (2)	0.0481 (19)	0.0053 (16)	0.0021 (15)	0.0120 (15)
N2	0.0446 (19)	0.052 (2)	0.056 (2)	−0.0106 (17)	0.0097 (16)	−0.0038 (17)
N3	0.0457 (19)	0.041 (2)	0.0492 (19)	0.0058 (15)	−0.0081 (15)	0.0014 (15)
N4	0.049 (2)	0.045 (2)	0.062 (2)	0.0031 (16)	0.0048 (18)	0.0101 (17)
O1	0.0370 (14)	0.0485 (17)	0.0626 (17)	0.0027 (12)	0.0115 (12)	0.0103 (13)
O2	0.105 (3)	0.114 (3)	0.075 (2)	0.052 (2)	0.051 (2)	0.0556 (19)
O3	0.0714 (19)	0.0479 (18)	0.073 (2)	0.0191 (15)	0.0092 (15)	0.0161 (14)
O4	0.0390 (16)	0.079 (2)	0.095 (2)	0.0047 (16)	0.0162 (15)	0.0066 (18)
O5	0.070 (2)	0.0587 (19)	0.089 (2)	−0.0161 (16)	0.0300 (16)	0.0133 (17)
O6	0.0654 (19)	0.0548 (18)	0.081 (2)	0.0084 (15)	−0.0129 (15)	0.0285 (16)
O7	0.0393 (15)	0.0554 (18)	0.086 (2)	0.0101 (13)	0.0032 (14)	0.0066 (15)

C1—N4	1.373 (4)	C9—C10	1.374 (4)
C1—C2	1.392 (5)	C9—H9	0.9300
C1—C6	1.404 (5)	C10—C11	1.375 (5)
C2—C3	1.374 (5)	C10—N2	1.464 (4)
C2—Cl1	1.736 (3)	C11—C12	1.382 (4)
C3—C4	1.377 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—N3	1.461 (4)
C4—C5	1.373 (4)	N1—O2	1.202 (4)
C4—Cl2	1.743 (3)	N1—O3	1.221 (4)
C5—C6	1.370 (4)	N2—O5	1.218 (4)
C5—H5	0.9300	N2—O4	1.222 (4)
C6—Cl3	1.739 (3)	N3—O6	1.213 (4)
C7—O1	1.327 (4)	N3—O7	1.235 (4)
C7—C12	1.396 (4)	N4—H4A	0.854 (18)
C7—C8	1.404 (4)	N4—H4B	0.842 (18)
C8—C9	1.371 (4)	O1—H1A	0.89 (4)
C8—N1	1.460 (4)
N4—C1—C2	122.5 (3)	C8—C9—H9	120.6
N4—C1—C6	122.0 (3)	C10—C9—H9	120.6
C2—C1—C6	115.4 (3)	C9—C10—C11	121.7 (3)
C3—C2—C1	122.8 (3)	C9—C10—N2	119.0 (3)
C3—C2—Cl1	118.9 (3)	C11—C10—N2	119.3 (3)
C1—C2—Cl1	118.3 (3)	C10—C11—C12	118.0 (3)
C2—C3—C4	119.1 (3)	C10—C11—H11	121.0
C2—C3—H3	120.4	C12—C11—H11	121.0
C4—C3—H3	120.4	C11—C12—C7	123.2 (3)
C5—C4—C3	120.7 (3)	C11—C12—N3	116.7 (3)
C5—C4—Cl2	119.6 (3)	C7—C12—N3	120.0 (3)
C3—C4—Cl2	119.8 (3)	O2—N1—O3	123.0 (3)
C6—C5—C4	119.1 (3)	O2—N1—C8	118.8 (3)
C6—C5—H5	120.4	O3—N1—C8	118.1 (3)
C4—C5—H5	120.4	O5—N2—O4	124.7 (3)
C5—C6—C1	122.8 (3)	O5—N2—C10	117.7 (3)
C5—C6—Cl3	118.9 (3)	O4—N2—C10	117.6 (3)
C1—C6—Cl3	118.3 (3)	O6—N3—O7	122.9 (3)
O1—C7—C12	124.2 (3)	O6—N3—C12	118.4 (3)
O1—C7—C8	120.2 (3)	O7—N3—C12	118.6 (3)
C12—C7—C8	115.5 (3)	C1—N4—H4A	120 (3)
C9—C8—C7	122.6 (3)	C1—N4—H4B	112 (3)
C9—C8—N1	116.9 (3)	H4A—N4—H4B	123 (4)
C7—C8—N1	120.4 (3)	C7—O1—H1A	108 (3)
C8—C9—C10	118.9 (3)
N4—C1—C2—C3	−177.4 (3)	C8—C9—C10—C11	−0.4 (5)
C6—C1—C2—C3	−0.1 (5)	C8—C9—C10—N2	178.5 (3)
N4—C1—C2—Cl1	1.6 (5)	C9—C10—C11—C12	−1.0 (5)
C6—C1—C2—Cl1	179.0 (2)	N2—C10—C11—C12	−180.0 (3)
C1—C2—C3—C4	−0.4 (5)	C10—C11—C12—C7	1.7 (5)
Cl1—C2—C3—C4	−179.4 (3)	C10—C11—C12—N3	179.8 (3)
C2—C3—C4—C5	0.4 (5)	O1—C7—C12—C11	−179.0 (3)
C2—C3—C4—Cl2	−179.4 (3)	C8—C7—C12—C11	−0.8 (5)
C3—C4—C5—C6	0.2 (5)	O1—C7—C12—N3	2.9 (5)
Cl2—C4—C5—C6	179.9 (3)	C8—C7—C12—N3	−178.8 (3)
C4—C5—C6—C1	−0.7 (5)	C9—C8—N1—O2	144.8 (4)
C4—C5—C6—Cl3	178.7 (3)	C7—C8—N1—O2	−33.6 (5)
N4—C1—C6—C5	178.0 (3)	C9—C8—N1—O3	−32.8 (5)
C2—C1—C6—C5	0.6 (5)	C7—C8—N1—O3	148.8 (3)
N4—C1—C6—Cl3	−1.4 (5)	C9—C10—N2—O5	−171.2 (3)
C2—C1—C6—Cl3	−178.8 (2)	C11—C10—N2—O5	7.8 (5)
O1—C7—C8—C9	177.6 (3)	C9—C10—N2—O4	8.4 (5)
C12—C7—C8—C9	−0.7 (5)	C11—C10—N2—O4	−172.6 (3)
O1—C7—C8—N1	−4.1 (5)	C11—C12—N3—O6	0.4 (4)
C12—C7—C8—N1	177.6 (3)	C7—C12—N3—O6	178.5 (3)
C7—C8—C9—C10	1.4 (5)	C11—C12—N3—O7	−178.0 (3)
N1—C8—C9—C10	−177.0 (3)	C7—C12—N3—O7	0.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.89 (4)	1.76 (4)	2.546 (4)	145 (4)
N4—H4A···Cl1	0.85 (2)	2.62 (4)	2.975 (3)	106 (3)
N4—H4A···O5i	0.85 (2)	2.39 (2)	3.159 (4)	150 (3)
N4—H4B···Cl3	0.84 (2)	2.49 (3)	2.979 (3)	118 (3)
N4—H4B···O6ii	0.84 (2)	2.40 (2)	3.194 (4)	156 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O7	0.89 (4)	1.76 (4)	2.546 (4)	145 (4)
N4—H4A⋯O5i	0.85 (2)	2.39 (2)	3.159 (4)	150 (3)
N4—H4B⋯O6ii	0.84 (2)	2.40 (2)	3.194 (4)	156 (4)

Symmetry codes: (i) ; (ii) .