3-Chloro-4-fluoro-anilinium picrate.

In the title picrate salt of a dihalogenated aniline derivative, C(6)H(6)ClF(+)·C(6)H(2)N(3)O(7) (-), the intra-cyclic C-C-C angles in the picrate anion cover a broad range [111.95 (12)-125.38 (13)°], while those in the aromatic cation span a much narrower range [118.25 (14)-122.33 (13)°]. In the crystal, classical N-H⋯O hydrogen bonds, as well as C-H⋯O contacts, connect the ions into layers parallel to (001).

Related literature

For related structures, see: Jin et al. (2011 ▶); Wang (2011 ▶); Betz et al. (2011 ▶); Dutkiewicz et al. (2011 ▶); Jasinski et al. (2010a ▶,b ▶, 2011 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H6ClF+·C6H2N3O7 −

M = 374.67

Triclinic,

a = 4.4054 (2) Å

b = 11.9881 (5) Å

c = 13.7010 (5) Å

α = 90.057 (1)°

β = 91.803 (1)°

γ = 97.743 (1)°

V = 716.62 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.33 mm−1

T = 200 K

0.53 × 0.32 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.907, T max = 1.000

12360 measured reflections

3525 independent reflections

2947 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.097

S = 1.06

3525 reflections

238 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000718/bg2490sup1.cif

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000718/bg2490Isup2.cdx

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000718/bg2490Isup3.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000718/bg2490Isup4.cml

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

C6H6ClF+·C6H2N3O7−	Z = 2
Mr = 374.67	F(000) = 380
Triclinic, P1	Dx = 1.736 Mg m−3
Hall symbol: -P 1	Melting point: 438 K
a = 4.4054 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.9881 (5) Å	Cell parameters from 8065 reflections
c = 13.7010 (5) Å	θ = 2.3–28.3°
α = 90.057 (1)°	µ = 0.33 mm−1
β = 91.803 (1)°	T = 200 K
γ = 97.743 (1)°	Needle, yellow
V = 716.62 (5) Å3	0.53 × 0.32 × 0.13 mm

Bruker APEXII CCD diffractometer	3525 independent reflections
Radiation source: fine-focus sealed tube	2947 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
φ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −5→5
Tmin = 0.907, Tmax = 1.000	k = −16→15
12360 measured reflections	l = −18→18

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) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0377P)2 + 0.4436P] where P = (Fo2 + 2Fc2)/3
3525 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

	x	y	z	Uiso*/Ueq
O1	0.6279 (2)	0.56237 (8)	0.18047 (8)	0.0272 (2)
O11	0.1858 (3)	0.60505 (11)	0.04084 (9)	0.0397 (3)
O12	0.4639 (3)	0.69531 (10)	−0.06804 (8)	0.0430 (3)
O21	0.8395 (3)	1.07312 (9)	0.07332 (9)	0.0381 (3)
O22	1.2124 (3)	1.06697 (10)	0.17928 (10)	0.0439 (3)
O31	1.3048 (3)	0.72968 (13)	0.35325 (9)	0.0478 (3)
O32	0.9194 (3)	0.59811 (10)	0.35634 (9)	0.0426 (3)
N1	0.4035 (3)	0.67317 (10)	0.01741 (9)	0.0263 (3)
N2	0.9866 (3)	1.02249 (11)	0.13271 (9)	0.0298 (3)
N3	1.0560 (3)	0.68383 (11)	0.32143 (9)	0.0299 (3)
C11	0.7050 (3)	0.66785 (12)	0.17296 (10)	0.0228 (3)
C12	0.6014 (3)	0.73200 (12)	0.09313 (10)	0.0234 (3)
C13	0.6869 (3)	0.84526 (12)	0.07879 (10)	0.0249 (3)
H13	0.6095	0.8826	0.0242	0.030*
C14	0.8896 (3)	0.90317 (12)	0.14653 (10)	0.0255 (3)
C15	1.0104 (3)	0.84895 (12)	0.22500 (10)	0.0263 (3)
H15	1.1546	0.8894	0.2695	0.032*
C16	0.9185 (3)	0.73573 (12)	0.23741 (10)	0.0246 (3)
Cl1	−0.28986 (12)	0.06232 (4)	0.38057 (4)	0.04913 (14)
F1	0.1550 (3)	0.16950 (9)	0.52432 (7)	0.0473 (3)
N4	0.0749 (3)	0.42503 (11)	0.19073 (9)	0.0252 (2)
H41	−0.080 (5)	0.4671 (18)	0.1987 (15)	0.044 (6)*
H42	0.026 (5)	0.3832 (17)	0.1376 (15)	0.037 (5)*
H43	0.262 (5)	0.4739 (17)	0.1817 (14)	0.040 (5)*
C21	0.0979 (3)	0.35612 (12)	0.27822 (10)	0.0240 (3)
C22	−0.0891 (3)	0.25421 (12)	0.28441 (11)	0.0275 (3)
H22	−0.2287	0.2282	0.2325	0.033*
C23	−0.0676 (4)	0.19100 (12)	0.36846 (12)	0.0311 (3)
C24	0.1372 (4)	0.23142 (14)	0.44313 (11)	0.0331 (3)
C25	0.3238 (4)	0.33270 (14)	0.43629 (11)	0.0340 (3)
H25	0.4635	0.3586	0.4882	0.041*
C26	0.3048 (3)	0.39627 (13)	0.35244 (11)	0.0288 (3)
H26	0.4318	0.4663	0.3460	0.035*

	U11	U22	U33	U12	U13	U23
O1	0.0247 (5)	0.0239 (5)	0.0325 (5)	0.0021 (4)	−0.0024 (4)	0.0049 (4)
O11	0.0309 (6)	0.0452 (7)	0.0386 (6)	−0.0094 (5)	−0.0049 (5)	0.0001 (5)
O12	0.0619 (8)	0.0383 (6)	0.0242 (5)	−0.0074 (6)	−0.0096 (5)	0.0047 (5)
O21	0.0448 (7)	0.0259 (5)	0.0441 (7)	0.0067 (5)	−0.0002 (5)	0.0062 (5)
O22	0.0430 (7)	0.0330 (6)	0.0513 (8)	−0.0089 (5)	−0.0068 (6)	−0.0017 (5)
O31	0.0333 (6)	0.0687 (9)	0.0396 (7)	0.0038 (6)	−0.0145 (5)	0.0077 (6)
O32	0.0586 (8)	0.0348 (6)	0.0334 (6)	0.0051 (6)	−0.0104 (5)	0.0090 (5)
N1	0.0279 (6)	0.0239 (6)	0.0266 (6)	0.0032 (5)	−0.0062 (5)	0.0012 (5)
N2	0.0325 (7)	0.0246 (6)	0.0319 (7)	0.0016 (5)	0.0041 (5)	−0.0013 (5)
N3	0.0312 (6)	0.0362 (7)	0.0238 (6)	0.0115 (5)	−0.0037 (5)	0.0000 (5)
C11	0.0205 (6)	0.0256 (6)	0.0227 (6)	0.0048 (5)	0.0011 (5)	0.0017 (5)
C12	0.0225 (6)	0.0252 (7)	0.0222 (6)	0.0026 (5)	−0.0018 (5)	−0.0011 (5)
C13	0.0260 (7)	0.0247 (7)	0.0244 (6)	0.0049 (5)	−0.0008 (5)	0.0020 (5)
C14	0.0264 (7)	0.0224 (6)	0.0276 (7)	0.0025 (5)	0.0015 (5)	0.0004 (5)
C15	0.0240 (7)	0.0304 (7)	0.0241 (7)	0.0028 (5)	−0.0008 (5)	−0.0031 (5)
C16	0.0228 (6)	0.0296 (7)	0.0217 (6)	0.0059 (5)	−0.0019 (5)	0.0019 (5)
Cl1	0.0631 (3)	0.0281 (2)	0.0538 (3)	−0.00226 (18)	−0.0007 (2)	0.01280 (18)
F1	0.0680 (7)	0.0454 (6)	0.0299 (5)	0.0140 (5)	−0.0025 (5)	0.0148 (4)
N4	0.0270 (6)	0.0236 (6)	0.0249 (6)	0.0038 (5)	−0.0040 (5)	0.0029 (5)
C21	0.0260 (7)	0.0241 (6)	0.0234 (6)	0.0089 (5)	−0.0004 (5)	0.0020 (5)
C22	0.0326 (7)	0.0225 (7)	0.0280 (7)	0.0071 (5)	−0.0031 (5)	0.0002 (5)
C23	0.0386 (8)	0.0222 (7)	0.0335 (8)	0.0077 (6)	0.0024 (6)	0.0044 (6)
C24	0.0442 (9)	0.0338 (8)	0.0239 (7)	0.0149 (7)	0.0017 (6)	0.0074 (6)
C25	0.0385 (8)	0.0394 (9)	0.0244 (7)	0.0078 (7)	−0.0057 (6)	0.0002 (6)
C26	0.0301 (7)	0.0291 (7)	0.0270 (7)	0.0037 (6)	−0.0028 (5)	0.0005 (6)

O1—C11	1.2695 (17)	C15—H15	0.9500
O11—N1	1.2244 (16)	Cl1—C23	1.7234 (16)
O12—N1	1.2300 (17)	F1—C24	1.3439 (17)
O21—N2	1.2345 (17)	N4—C21	1.4651 (17)
O22—N2	1.2240 (18)	N4—H41	0.91 (2)
O31—N3	1.2253 (18)	N4—H42	0.89 (2)
O32—N3	1.2244 (18)	N4—H43	0.96 (2)
N1—C12	1.4524 (17)	C21—C22	1.383 (2)
N2—C14	1.4510 (18)	C21—C26	1.385 (2)
N3—C16	1.4623 (17)	C22—C23	1.387 (2)
C11—C12	1.4355 (19)	C22—H22	0.9500
C11—C16	1.4375 (19)	C23—C24	1.385 (2)
C12—C13	1.3754 (19)	C24—C25	1.377 (2)
C13—C14	1.386 (2)	C25—C26	1.386 (2)
C13—H13	0.9500	C25—H25	0.9500
C14—C15	1.386 (2)	C26—H26	0.9500
C15—C16	1.376 (2)
O11—N1—O12	123.14 (12)	C11—C16—N3	119.69 (12)
O11—N1—C12	119.24 (12)	C21—N4—H41	108.0 (13)
O12—N1—C12	117.62 (12)	C21—N4—H42	112.0 (13)
O22—N2—O21	123.61 (13)	H41—N4—H42	106.5 (18)
O22—N2—C14	118.27 (13)	C21—N4—H43	110.8 (12)
O21—N2—C14	118.10 (13)	H41—N4—H43	109.2 (18)
O32—N3—O31	123.48 (13)	H42—N4—H43	110.1 (17)
O32—N3—C16	119.18 (13)	C22—C21—C26	122.33 (13)
O31—N3—C16	117.33 (13)	C22—C21—N4	119.08 (12)
O1—C11—C12	122.68 (12)	C26—C21—N4	118.59 (13)
O1—C11—C16	125.23 (12)	C21—C22—C23	118.25 (14)
C12—C11—C16	111.95 (12)	C21—C22—H22	120.9
C13—C12—C11	125.38 (13)	C23—C22—H22	120.9
C13—C12—N1	116.10 (12)	C24—C23—C22	119.53 (14)
C11—C12—N1	118.42 (12)	C24—C23—Cl1	119.67 (12)
C12—C13—C14	117.90 (13)	C22—C23—Cl1	120.80 (12)
C12—C13—H13	121.1	F1—C24—C25	119.18 (15)
C14—C13—H13	121.1	F1—C24—C23	118.91 (15)
C13—C14—C15	121.54 (13)	C25—C24—C23	121.91 (14)
C13—C14—N2	119.12 (13)	C24—C25—C26	118.99 (14)
C15—C14—N2	119.29 (13)	C24—C25—H25	120.5
C16—C15—C14	118.98 (13)	C26—C25—H25	120.5
C16—C15—H15	120.5	C21—C26—C25	118.99 (14)
C14—C15—H15	120.5	C21—C26—H26	120.5
C15—C16—C11	124.21 (12)	C25—C26—H26	120.5
C15—C16—N3	116.09 (12)
O1—C11—C12—C13	−177.10 (13)	C12—C11—C16—C15	0.7 (2)
C16—C11—C12—C13	−1.1 (2)	O1—C11—C16—N3	−2.3 (2)
O1—C11—C12—N1	−0.8 (2)	C12—C11—C16—N3	−178.15 (12)
C16—C11—C12—N1	175.13 (12)	O32—N3—C16—C15	155.61 (14)
O11—N1—C12—C13	−137.00 (14)	O31—N3—C16—C15	−24.3 (2)
O12—N1—C12—C13	42.61 (19)	O32—N3—C16—C11	−25.4 (2)
O11—N1—C12—C11	46.39 (19)	O31—N3—C16—C11	154.69 (14)
O12—N1—C12—C11	−134.00 (14)	C26—C21—C22—C23	0.3 (2)
C11—C12—C13—C14	−0.1 (2)	N4—C21—C22—C23	−178.97 (13)
N1—C12—C13—C14	−176.40 (13)	C21—C22—C23—C24	0.3 (2)
C12—C13—C14—C15	1.8 (2)	C21—C22—C23—Cl1	−179.12 (11)
C12—C13—C14—N2	179.32 (13)	C22—C23—C24—F1	179.76 (14)
O22—N2—C14—C13	−164.06 (14)	Cl1—C23—C24—F1	−0.8 (2)
O21—N2—C14—C13	14.7 (2)	C22—C23—C24—C25	−0.6 (2)
O22—N2—C14—C15	13.5 (2)	Cl1—C23—C24—C25	178.80 (13)
O21—N2—C14—C15	−167.71 (14)	F1—C24—C25—C26	180.00 (15)
C13—C14—C15—C16	−2.2 (2)	C23—C24—C25—C26	0.4 (3)
N2—C14—C15—C16	−179.71 (13)	C22—C21—C26—C25	−0.5 (2)
C14—C15—C16—C11	0.9 (2)	N4—C21—C26—C25	178.73 (14)
C14—C15—C16—N3	179.77 (13)	C24—C25—C26—C21	0.2 (2)
O1—C11—C16—C15	176.55 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O1i	0.91 (2)	1.85 (2)	2.7324 (17)	165 (2)
N4—H42···O12ii	0.89 (2)	2.40 (2)	3.0599 (18)	131.2 (16)
N4—H42···O11ii	0.89 (2)	2.60 (2)	3.3425 (17)	141.8 (16)
N4—H43···O1	0.96 (2)	1.81 (2)	2.7579 (16)	172.7 (18)
C13—H13···O21iii	0.95	2.47	3.3152 (19)	148
C26—H26···O32	0.95	2.49	3.378 (2)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H41⋯O1i	0.91 (2)	1.85 (2)	2.7324 (17)	165 (2)
N4—H42⋯O12ii	0.89 (2)	2.40 (2)	3.0599 (18)	131.2 (16)
N4—H42⋯O11ii	0.89 (2)	2.60 (2)	3.3425 (17)	141.8 (16)
N4—H43⋯O1	0.96 (2)	1.81 (2)	2.7579 (16)	172.7 (18)
C13—H13⋯O21iii	0.95	2.47	3.3152 (19)	148
C26—H26⋯O32	0.95	2.49	3.378 (2)	156

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