Bis(4-fluoro-anilinium) sulfate.

In the crystal of the title molecular salt, 2C(6)H(7)FN(+)·SO(4) (2-), the cations and anions are linked by N-H⋯O and C-H⋯O hydrogen bonds into sheets parallel to the ab plane. The crystal studied was found to be a racemic twin with a 0.50 (10):0.50 (10) domain ratio.

Related literature

For related literature on phase transition dielectric materials, see: Fu et al. (2007 ▶, 2008 ▶, 2009 ▶); Fu & Xiong (2008 ▶). For hydrogen bonding studies, see: Zimmerman & Corbin (2000 ▶); Brunsveld et al. (2001 ▶); Desiraju (2002 ▶); Steiner (2002 ▶); Desiraju & Steiner (1999 ▶); Boutobba et al. (2010 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For a related crystal structure, see: Boutobba et al. (2010 ▶)

Experimental

Crystal data

2C6H7FN+·SO4 2−

M = 320.31

Orthorhombic,

a = 6.2907 (5) Å

b = 7.4155 (6) Å

c = 30.168 (3) Å

V = 1407.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 296 K

0.58 × 0.12 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.859, T max = 0.982

31062 measured reflections

4292 independent reflections

3503 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 0.98

4292 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 1794 Friedel pairs

Flack parameter: 0.50 (10)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811033137/wn2446sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033137/wn2446Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811033137/wn2446Isup3.cml

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

2C6H7FN+·SO42−	F(000) = 664
Mr = 320.31	Dx = 1.512 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5694 reflections
a = 6.2907 (5) Å	θ = 2.7–27.5°
b = 7.4155 (6) Å	µ = 0.27 mm−1
c = 30.168 (3) Å	T = 296 K
V = 1407.3 (2) Å3	Needle, colourless
Z = 4	0.58 × 0.12 × 0.07 mm

Bruker SMART APEXII DUO CCD area-detector diffractometer	4292 independent reflections
Radiation source: fine-focus sealed tube	3503 reflections with I > 2σ(I)
graphite	Rint = 0.044
φ and ω scans	θmax = 30.6°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.859, Tmax = 0.982	k = −10→10
31062 measured reflections	l = −43→43

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.103	w = 1/[σ2(Fo2) + (0.0492P)2 + 0.377P] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
4292 reflections	Δρmax = 0.18 e Å−3
191 parameters	Δρmin = −0.39 e Å−3
0 restraints	Absolute structure: Flack (1983), 1794 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.50 (10)

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
S1	−0.00432 (8)	0.47390 (4)	0.013801 (11)	0.02691 (9)
F1	0.5089 (5)	0.3730 (3)	0.25139 (4)	0.1033 (6)
F2	−0.0181 (4)	0.8372 (3)	0.22704 (4)	0.1096 (7)
O1	−0.0040 (3)	0.29560 (14)	0.03416 (4)	0.0452 (3)
O2	−0.2002 (2)	0.5713 (2)	0.02606 (5)	0.0372 (3)
O3	0.1801 (2)	0.5795 (2)	0.02941 (5)	0.0381 (4)
O4	0.0060 (3)	0.45980 (17)	−0.03476 (4)	0.0470 (3)
N1	−0.0142 (3)	0.92624 (16)	0.04544 (4)	0.0309 (3)
H1N1	0.0125	1.0369	0.0384	0.046*
H2N1	−0.1252	0.8982	0.0330	0.046*
H3N1	0.0935	0.8514	0.0315	0.046*
N2	0.4960 (3)	0.37944 (17)	0.06828 (4)	0.0332 (3)
H1N2	0.5163	0.2639	0.0563	0.050*
H2N2	0.3856	0.4288	0.0573	0.050*
H3N2	0.6038	0.4605	0.0553	0.050*
C1	0.3283 (3)	0.4459 (4)	0.13955 (7)	0.0492 (5)
H1A	0.2115	0.4926	0.1245	0.059*
C2	0.3318 (4)	0.4435 (4)	0.18574 (7)	0.0639 (7)
H2A	0.2179	0.4881	0.2020	0.077*
C3	0.5047 (5)	0.3749 (3)	0.20625 (6)	0.0634 (6)
C4	0.6765 (5)	0.3079 (4)	0.18406 (8)	0.0646 (7)
H4A	0.7923	0.2611	0.1994	0.077*
C5	0.6742 (4)	0.3113 (3)	0.13811 (7)	0.0487 (5)
H5A	0.7901	0.2686	0.1221	0.058*
C6	0.4990 (4)	0.37857 (19)	0.11639 (5)	0.0326 (3)
C7	−0.1933 (3)	0.8307 (3)	0.11348 (6)	0.0434 (5)
H7A	−0.3113	0.7982	0.0967	0.052*
C8	−0.1934 (4)	0.8076 (4)	0.15908 (7)	0.0583 (6)
H8A	−0.3101	0.7575	0.1734	0.070*
C9	−0.0178 (5)	0.8602 (4)	0.18240 (6)	0.0636 (7)
C10	0.1576 (4)	0.9328 (4)	0.16300 (8)	0.0671 (7)
H10A	0.2739	0.9677	0.1800	0.081*
C11	0.1593 (4)	0.9536 (3)	0.11737 (7)	0.0496 (5)
H11A	0.2778	1.0015	0.1032	0.059*
C12	−0.0157 (3)	0.9027 (2)	0.09331 (5)	0.0317 (3)

	U11	U22	U33	U12	U13	U23
S1	0.02748 (16)	0.02319 (15)	0.03006 (16)	−0.0005 (2)	0.0004 (2)	0.00064 (11)
F1	0.1150 (14)	0.1674 (18)	0.0274 (6)	−0.006 (2)	−0.0039 (9)	0.0034 (8)
F2	0.1171 (15)	0.1814 (19)	0.0301 (6)	0.013 (2)	0.0030 (10)	0.0157 (9)
O1	0.0549 (8)	0.0257 (5)	0.0550 (7)	0.0033 (10)	0.0022 (10)	0.0096 (5)
O2	0.0269 (6)	0.0333 (9)	0.0515 (8)	0.0032 (6)	0.0029 (6)	−0.0008 (7)
O3	0.0295 (6)	0.0324 (9)	0.0524 (8)	−0.0017 (6)	−0.0039 (6)	−0.0042 (7)
O4	0.0639 (8)	0.0467 (7)	0.0303 (6)	0.0010 (14)	0.0026 (8)	−0.0026 (5)
N1	0.0369 (7)	0.0261 (5)	0.0298 (6)	0.0007 (9)	0.0015 (7)	0.0008 (4)
N2	0.0321 (6)	0.0393 (6)	0.0283 (6)	−0.0015 (10)	0.0003 (9)	0.0001 (4)
C1	0.0423 (10)	0.0681 (15)	0.0373 (10)	0.0054 (11)	0.0034 (8)	−0.0018 (10)
C2	0.0595 (14)	0.095 (2)	0.0372 (11)	0.0064 (16)	0.0121 (10)	−0.0068 (13)
C3	0.0767 (16)	0.0857 (16)	0.0279 (8)	−0.008 (2)	−0.0039 (15)	0.0008 (8)
C4	0.0707 (17)	0.0807 (19)	0.0424 (12)	0.0137 (15)	−0.0198 (11)	0.0016 (12)
C5	0.0482 (12)	0.0584 (14)	0.0394 (10)	0.0137 (11)	−0.0061 (9)	−0.0058 (10)
C6	0.0364 (8)	0.0336 (7)	0.0279 (6)	−0.0029 (12)	−0.0022 (10)	−0.0012 (5)
C7	0.0436 (11)	0.0487 (12)	0.0380 (10)	−0.0036 (10)	0.0068 (8)	−0.0001 (9)
C8	0.0661 (16)	0.0679 (16)	0.0409 (11)	−0.0040 (14)	0.0180 (11)	0.0081 (11)
C9	0.0770 (18)	0.0866 (16)	0.0272 (8)	0.010 (2)	0.0032 (13)	0.0061 (9)
C10	0.0642 (15)	0.097 (2)	0.0400 (11)	−0.0012 (16)	−0.0178 (11)	−0.0017 (14)
C11	0.0458 (11)	0.0629 (14)	0.0399 (10)	−0.0086 (11)	−0.0051 (9)	0.0039 (10)
C12	0.0372 (9)	0.0281 (6)	0.0298 (7)	0.0017 (10)	0.0002 (9)	0.0012 (5)

S1—O1	1.4579 (11)	C2—C3	1.350 (4)
S1—O4	1.4700 (11)	C2—H2A	0.9300
S1—O2	1.4755 (14)	C3—C4	1.365 (4)
S1—O3	1.4767 (14)	C4—C5	1.387 (3)
F1—C3	1.362 (2)	C4—H4A	0.9300
F2—C9	1.357 (2)	C5—C6	1.376 (3)
N1—C12	1.4548 (19)	C5—H5A	0.9300
N1—H1N1	0.8644	C7—C12	1.379 (3)
N1—H2N1	0.8198	C7—C8	1.386 (3)
N1—H3N1	0.9724	C7—H7A	0.9300
N2—C6	1.4513 (17)	C8—C9	1.366 (4)
N2—H1N2	0.9393	C8—H8A	0.9300
N2—H2N2	0.8524	C9—C10	1.360 (4)
N2—H3N2	0.9875	C10—C11	1.385 (3)
C1—C6	1.376 (3)	C10—H10A	0.9300
C1—C2	1.394 (3)	C11—C12	1.371 (3)
C1—H1A	0.9300	C11—H11A	0.9300
O1—S1—O4	110.81 (7)	C3—C4—C5	118.4 (2)
O1—S1—O2	109.84 (10)	C3—C4—H4A	120.8
O4—S1—O2	108.76 (10)	C5—C4—H4A	120.8
O1—S1—O3	110.21 (10)	C6—C5—C4	119.4 (2)
O4—S1—O3	108.71 (10)	C6—C5—H5A	120.3
O2—S1—O3	108.45 (7)	C4—C5—H5A	120.3
C12—N1—H1N1	111.1	C1—C6—C5	121.03 (16)
C12—N1—H2N1	114.8	C1—C6—N2	119.73 (19)
H1N1—N1—H2N1	107.0	C5—C6—N2	119.24 (19)
C12—N1—H3N1	111.5	C12—C7—C8	119.1 (2)
H1N1—N1—H3N1	107.5	C12—C7—H7A	120.5
H2N1—N1—H3N1	104.5	C8—C7—H7A	120.5
C6—N2—H1N2	112.3	C9—C8—C7	118.4 (2)
C6—N2—H2N2	113.7	C9—C8—H8A	120.8
H1N2—N2—H2N2	110.6	C7—C8—H8A	120.8
C6—N2—H3N2	113.0	F2—C9—C10	118.5 (3)
H1N2—N2—H3N2	108.0	F2—C9—C8	118.3 (3)
H2N2—N2—H3N2	98.3	C10—C9—C8	123.19 (19)
C6—C1—C2	119.4 (2)	C9—C10—C11	118.5 (2)
C6—C1—H1A	120.3	C9—C10—H10A	120.7
C2—C1—H1A	120.3	C11—C10—H10A	120.7
C3—C2—C1	118.4 (2)	C12—C11—C10	119.3 (2)
C3—C2—H2A	120.8	C12—C11—H11A	120.4
C1—C2—H2A	120.8	C10—C11—H11A	120.4
C2—C3—F1	118.5 (3)	C11—C12—C7	121.54 (17)
C2—C3—C4	123.4 (2)	C11—C12—N1	119.15 (19)
F1—C3—C4	118.1 (3)	C7—C12—N1	119.31 (18)
C6—C1—C2—C3	0.2 (4)	C12—C7—C8—C9	1.1 (4)
C1—C2—C3—F1	179.8 (2)	C7—C8—C9—F2	−179.9 (2)
C1—C2—C3—C4	0.1 (5)	C7—C8—C9—C10	−0.5 (4)
C2—C3—C4—C5	0.4 (5)	F2—C9—C10—C11	179.0 (3)
F1—C3—C4—C5	−179.3 (2)	C8—C9—C10—C11	−0.4 (5)
C3—C4—C5—C6	−1.1 (4)	C9—C10—C11—C12	0.8 (4)
C2—C1—C6—C5	−0.9 (4)	C10—C11—C12—C7	−0.2 (4)
C2—C1—C6—N2	179.6 (2)	C10—C11—C12—N1	179.4 (2)
C4—C5—C6—C1	1.4 (4)	C8—C7—C12—C11	−0.8 (3)
C4—C5—C6—N2	−179.1 (2)	C8—C7—C12—N1	179.62 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3N1···O3	0.97	2.09	2.887 (3)	138
N2—H2N2···O3	0.85	1.90	2.741 (3)	168
N1—H1N1···O1i	0.86	1.92	2.761 (2)	162
N1—H2N1···O3ii	0.82	2.25	2.967 (2)	146.
N1—H2N1···O4ii	0.82	2.55	3.151 (3)	131.
N1—H3N1···O2iii	0.97	2.24	2.925 (2)	126.
N2—H1N2···O4iv	0.94	1.78	2.7121 (18)	170
N2—H3N2···O2v	0.99	1.72	2.702 (2)	170
C11—H11A···O4iii	0.93	2.53	3.374 (3)	151.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H3N1⋯O3	0.97	2.09	2.887 (3)	138
N2—H2N2⋯O3	0.85	1.90	2.741 (3)	168
N1—H1N1⋯O1i	0.86	1.92	2.761 (2)	162
N1—H2N1⋯O3ii	0.82	2.25	2.967 (2)	146
N1—H2N1⋯O4ii	0.82	2.55	3.151 (3)	131
N1—H3N1⋯O2iii	0.97	2.24	2.925 (2)	126
N2—H1N2⋯O4iv	0.94	1.78	2.7121 (18)	170
N2—H3N2⋯O2v	0.99	1.72	2.702 (2)	170
C11—H11A⋯O4iii	0.93	2.53	3.374 (3)	151

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