2-Trifluoro-methyl-1H-benzimidazol-3-ium tetra-fluoro-borate-2-trifluoro-methyl-1H-benzimidazole-water (1/1/1).

The asymmetric unit of the title compound, C(8)H(6)F(3)N(2) (+)·BF(4) (-)·C(8)H(5)F(3)N(2)·H(2)O, consists of two 2-trifluoro-methyl-benzimidazole mol-ecules, each of which is protonated on a 50% basis, one tetra-fluoro-borate anion and a water mol-ecule. The two 2-trifluoromethylbenzimidazole mol-ecules thus exist as half-neutral half-cation entities. They are linked by N-H⋯N hydrogen bonds involving the half-occupancy hydrogens in each mol-ecule. The F atoms of one of the trifluoro-methyl groups are disordered over two sets of sites [in a 0.518 (14):0.482 (14) ratio], as are the F atoms of the tetra-fluoroborate anion [0.507 (14):0.493 (14) ratio]. The water mol-ecule is linked to one of the 2-trifluoro-methyl-benzimidazole mol-ecules via an N-H⋯O hydrogen bond.

Related literature

The title compound was synthesized as part of our search for ferroelectric complexes. For background to ferroelectric complexes, see: Fu et al. (2011 ▶); Zhang et al. (2010 ▶). For related structures, see: Liu (2011a ▶,b ▶, 2012 ▶).

Experimental

Crystal data

C8H6F3N2 +·BF4 −·C8H5F3N2·H2O

M = 478.11

Triclinic,

a = 8.7897 (18) Å

b = 10.947 (2) Å

c = 11.458 (2) Å

α = 92.48 (3)°

β = 96.59 (3)°

γ = 113.34 (3)°

V = 1000.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.17 mm−1

T = 293 K

0.36 × 0.32 × 0.28 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.566, T max = 0.640

10445 measured reflections

4581 independent reflections

2280 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.195

S = 1.03

4581 reflections

355 parameters

65 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010847/go2047sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010847/go2047Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812010847/go2047Isup3.cml

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

C8H6F3N2+·BF4−·C8H5F3N2·H2O	V = 1000.8 (3) Å3
Mr = 478.11	Z = 2
Triclinic, P1	F(000) = 480
Hall symbol: -P 1	Dx = 1.587 Mg m−3
a = 8.7897 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.947 (2) Å	θ = 0–25°
c = 11.458 (2) Å	µ = 0.17 mm−1
α = 92.48 (3)°	T = 293 K
β = 96.59 (3)°	Block, colourless
γ = 113.34 (3)°	0.36 × 0.32 × 0.28 mm

Rigaku SCXmini diffractometer	4581 independent reflections
Radiation source: fine-focus sealed tube	2280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −11→11
Tmin = 0.566, Tmax = 0.640	k = −14→14
10445 measured reflections	l = −14→14

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)] = 0.066	H-atom parameters constrained
wR(F2) = 0.195	w = 1/[σ2(Fo2) + (0.073P)2 + 0.2894P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4581 reflections	Δρmax = 0.30 e Å−3
355 parameters	Δρmin = −0.21 e Å−3
65 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (4)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
F5	−0.1135 (3)	0.6112 (3)	0.9237 (2)	0.1358 (10)
F6	0.0425 (3)	0.6539 (3)	1.0868 (3)	0.1405 (11)
F7	−0.1136 (3)	0.7537 (3)	1.0522 (3)	0.1382 (10)
N1	0.1904 (3)	0.7918 (2)	0.8667 (2)	0.0594 (6)
H1	0.1676	0.7165	0.8274	0.071*	0.50
N2	0.1829 (3)	0.9413 (3)	0.9962 (2)	0.0671 (7)
H2A	0.1531	0.9753	1.0539	0.081*
C1	−0.0170 (5)	0.7072 (4)	1.0035 (3)	0.0815 (10)
C2	0.1171 (4)	0.8130 (3)	0.9543 (2)	0.0593 (7)
C3	0.3121 (3)	0.9151 (3)	0.8501 (2)	0.0562 (7)
C4	0.4274 (4)	0.9514 (3)	0.7713 (3)	0.0740 (9)
H4	0.4338	0.8885	0.7171	0.089*
C5	0.5317 (5)	1.0842 (4)	0.7770 (3)	0.0882 (11)
H5	0.6102	1.1119	0.7251	0.106*
C6	0.5231 (5)	1.1781 (4)	0.8579 (4)	0.0926 (12)
H6	0.5951	1.2674	0.8580	0.111*
C7	0.4121 (4)	1.1439 (3)	0.9378 (4)	0.0810 (10)
H7	0.4078	1.2068	0.9931	0.097*
C8	0.3070 (4)	1.0102 (3)	0.9311 (2)	0.0587 (7)
N3	0.1071 (3)	0.5575 (2)	0.7327 (2)	0.0622 (6)
H3	0.1364	0.6341	0.7717	0.075*	0.50
N4	0.1163 (3)	0.3728 (2)	0.6582 (2)	0.0627 (6)
H4A	0.1544	0.3135	0.6429	0.075*
C9	0.3685 (3)	0.5281 (2)	0.7895 (2)	0.0757 (9)
C10	0.1977 (3)	0.4870 (3)	0.7266 (2)	0.0569 (7)
F8	0.3784 (12)	0.5766 (11)	0.8977 (4)	0.130 (4)	0.518 (14)
F9	0.4883 (7)	0.6155 (10)	0.7417 (9)	0.163 (5)	0.518 (14)
F10	0.4064 (9)	0.4244 (5)	0.8009 (8)	0.105 (3)	0.518 (14)
F8A	0.4595 (8)	0.4758 (11)	0.7415 (10)	0.161 (5)	0.482 (14)
F9A	0.4470 (9)	0.6579 (3)	0.7890 (10)	0.117 (3)	0.482 (14)
F10A	0.3750 (11)	0.5061 (12)	0.9007 (4)	0.135 (4)	0.482 (14)
C11	−0.0450 (4)	0.4836 (3)	0.6635 (2)	0.0593 (7)
C12	−0.0405 (4)	0.3665 (3)	0.6161 (2)	0.0602 (7)
C13	−0.1752 (4)	0.2705 (3)	0.5431 (3)	0.0771 (9)
H13	−0.1705	0.1930	0.5106	0.093*
C14	−0.3154 (5)	0.2961 (4)	0.5213 (3)	0.0897 (11)
H14	−0.4098	0.2332	0.4743	0.108*
C15	−0.3204 (5)	0.4133 (5)	0.5675 (3)	0.0921 (11)
H15	−0.4180	0.4270	0.5492	0.110*
C16	−0.1879 (5)	0.5100 (4)	0.6388 (3)	0.0786 (9)
H16	−0.1926	0.5884	0.6690	0.094*
F1	0.8155 (16)	0.8437 (14)	0.8026 (9)	0.191 (5)	0.507 (14)
F2	0.9801 (12)	0.8884 (13)	0.6676 (9)	0.164 (5)	0.507 (14)
F3	0.7345 (11)	0.8971 (12)	0.6305 (8)	0.131 (3)	0.507 (14)
F4	0.9301 (13)	1.0476 (8)	0.7603 (10)	0.175 (4)	0.507 (14)
F1A	0.8505 (12)	0.8938 (8)	0.8232 (5)	0.105 (3)	0.493 (14)
F2A	1.0041 (11)	0.9229 (11)	0.6739 (11)	0.123 (3)	0.493 (14)
F3A	0.7326 (12)	0.8392 (17)	0.6363 (9)	0.208 (6)	0.493 (14)
F4A	0.875 (2)	1.0469 (10)	0.7068 (16)	0.233 (6)	0.493 (14)
B1	0.8652 (5)	0.9202 (4)	0.7116 (3)	0.0835 (11)
O1W	0.2248 (3)	0.1817 (2)	0.6036 (2)	0.0972 (8)
H1A	0.2132	0.1781	0.5299	0.146*
H1B	0.1572	0.1131	0.6279	0.146*

	U11	U22	U33	U12	U13	U23
F5	0.121 (2)	0.1109 (18)	0.1217 (19)	−0.0148 (15)	0.0434 (16)	0.0023 (15)
F6	0.122 (2)	0.165 (2)	0.150 (2)	0.0578 (18)	0.0486 (17)	0.103 (2)
F7	0.125 (2)	0.139 (2)	0.180 (3)	0.0620 (17)	0.098 (2)	0.0385 (19)
N1	0.0647 (15)	0.0599 (15)	0.0577 (14)	0.0281 (12)	0.0147 (11)	0.0044 (11)
N2	0.0804 (17)	0.0739 (17)	0.0576 (14)	0.0435 (15)	0.0091 (13)	−0.0042 (13)
C1	0.081 (2)	0.090 (3)	0.085 (2)	0.039 (2)	0.032 (2)	0.021 (2)
C2	0.0667 (18)	0.0633 (19)	0.0581 (17)	0.0347 (15)	0.0152 (14)	0.0105 (14)
C3	0.0581 (17)	0.0588 (17)	0.0529 (16)	0.0254 (14)	0.0055 (13)	0.0079 (13)
C4	0.074 (2)	0.083 (2)	0.0670 (19)	0.0312 (19)	0.0200 (16)	0.0147 (17)
C5	0.076 (2)	0.093 (3)	0.093 (3)	0.026 (2)	0.0198 (19)	0.035 (2)
C6	0.077 (2)	0.067 (2)	0.126 (3)	0.0241 (19)	−0.003 (2)	0.028 (2)
C7	0.078 (2)	0.059 (2)	0.103 (3)	0.0329 (18)	−0.015 (2)	−0.0030 (18)
C8	0.0611 (17)	0.0600 (18)	0.0571 (16)	0.0299 (15)	−0.0016 (14)	0.0015 (14)
N3	0.0662 (15)	0.0575 (14)	0.0627 (14)	0.0228 (13)	0.0174 (12)	0.0043 (11)
N4	0.0675 (16)	0.0614 (15)	0.0619 (14)	0.0271 (12)	0.0180 (12)	0.0018 (12)
C9	0.066 (2)	0.071 (2)	0.084 (2)	0.0213 (18)	0.0118 (18)	−0.0024 (19)
C10	0.0589 (17)	0.0561 (17)	0.0551 (16)	0.0210 (14)	0.0150 (13)	0.0039 (13)
F8	0.117 (5)	0.162 (7)	0.106 (5)	0.075 (6)	−0.042 (4)	−0.067 (4)
F9	0.061 (3)	0.191 (8)	0.237 (10)	0.033 (5)	0.047 (5)	0.130 (8)
F10	0.078 (4)	0.092 (3)	0.151 (6)	0.050 (3)	−0.013 (3)	−0.003 (3)
F8A	0.065 (4)	0.194 (10)	0.207 (10)	0.049 (6)	0.009 (5)	−0.090 (8)
F9A	0.053 (4)	0.098 (4)	0.168 (7)	0.000 (3)	0.001 (3)	0.018 (4)
F10A	0.088 (4)	0.198 (9)	0.100 (5)	0.033 (6)	0.008 (4)	0.068 (5)
C11	0.0651 (18)	0.0645 (18)	0.0503 (15)	0.0260 (15)	0.0143 (14)	0.0116 (13)
C12	0.0653 (19)	0.0672 (19)	0.0472 (15)	0.0237 (15)	0.0153 (14)	0.0080 (13)
C13	0.080 (2)	0.082 (2)	0.0578 (18)	0.0223 (18)	0.0085 (16)	−0.0049 (16)
C14	0.078 (2)	0.114 (3)	0.062 (2)	0.025 (2)	0.0044 (17)	0.002 (2)
C15	0.081 (3)	0.135 (4)	0.070 (2)	0.054 (3)	0.0062 (19)	0.017 (2)
C16	0.085 (2)	0.091 (2)	0.072 (2)	0.048 (2)	0.0146 (19)	0.0147 (18)
F1	0.141 (6)	0.243 (10)	0.136 (7)	0.019 (8)	0.012 (5)	0.086 (8)
F2	0.181 (8)	0.289 (13)	0.104 (6)	0.188 (10)	0.009 (5)	−0.012 (6)
F3	0.102 (5)	0.214 (8)	0.092 (4)	0.093 (5)	−0.016 (4)	−0.020 (4)
F4	0.173 (7)	0.131 (6)	0.174 (8)	0.018 (5)	0.037 (6)	−0.071 (5)
F1A	0.134 (6)	0.129 (5)	0.060 (3)	0.063 (5)	0.018 (3)	−0.015 (3)
F2A	0.091 (4)	0.140 (6)	0.143 (8)	0.039 (4)	0.053 (5)	0.031 (5)
F3A	0.106 (5)	0.339 (14)	0.083 (4)	−0.008 (7)	0.013 (4)	−0.018 (7)
F4A	0.264 (14)	0.170 (7)	0.361 (18)	0.151 (8)	0.140 (12)	0.133 (9)
B1	0.087 (3)	0.095 (3)	0.076 (3)	0.043 (3)	0.015 (2)	0.010 (2)
O1W	0.117 (2)	0.0938 (18)	0.0889 (17)	0.0516 (15)	0.0183 (15)	−0.0090 (13)

F5—C1	1.301 (4)	C9—F8A	1.306 (2)
F6—C1	1.305 (4)	C9—F10A	1.306 (2)
F7—C1	1.311 (4)	C9—F8	1.307 (2)
N1—C2	1.312 (3)	C9—F10	1.311 (2)
N1—C3	1.388 (4)	C9—F9A	1.312 (2)
N1—H1	0.8600	C9—C10	1.471 (3)
N2—C2	1.331 (3)	C11—C12	1.388 (4)
N2—C8	1.378 (4)	C11—C16	1.398 (4)
N2—H2A	0.8600	C12—C13	1.384 (4)
C1—C2	1.475 (5)	C13—C14	1.367 (5)
C3—C8	1.382 (4)	C13—H13	0.9300
C3—C4	1.387 (4)	C14—C15	1.386 (5)
C4—C5	1.371 (5)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.369 (5)
C5—C6	1.385 (5)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.370 (5)	F1—B1	1.368 (7)
C6—H6	0.9300	F2—B1	1.332 (6)
C7—C8	1.379 (4)	F3—B1	1.324 (7)
C7—H7	0.9300	F4—B1	1.346 (7)
N3—C10	1.316 (3)	F1A—B1	1.332 (7)
N3—C11	1.383 (4)	F2A—B1	1.332 (7)
N3—H3	0.8600	F3A—B1	1.332 (7)
N4—C10	1.329 (3)	F4A—B1	1.361 (7)
N4—C12	1.380 (4)	O1W—H1A	0.8362
N4—H4A	0.8600	O1W—H1B	0.8349
C9—F9	1.305 (2)
C2—N1—C3	106.4 (2)	F8A—C9—F9A	106.1 (3)
C2—N1—H1	126.8	F10A—C9—F9A	105.4 (3)
C3—N1—H1	126.8	F9—C9—C10	116.2 (4)
C2—N2—C8	108.2 (2)	F8A—C9—C10	114.7 (4)
C2—N2—H2A	125.9	F10A—C9—C10	114.2 (5)
C8—N2—H2A	125.9	F8—C9—C10	110.4 (4)
F5—C1—F6	107.6 (3)	F10—C9—C10	110.7 (3)
F5—C1—F7	106.9 (3)	F9A—C9—C10	108.2 (4)
F6—C1—F7	105.5 (3)	N3—C10—N4	112.2 (2)
F5—C1—C2	112.5 (3)	N3—C10—C9	124.2 (2)
F6—C1—C2	112.1 (3)	N4—C10—C9	123.6 (2)
F7—C1—C2	111.8 (3)	N3—C11—C12	108.4 (3)
N1—C2—N2	111.6 (3)	N3—C11—C16	130.7 (3)
N1—C2—C1	124.3 (3)	C12—C11—C16	120.9 (3)
N2—C2—C1	124.0 (3)	N4—C12—C13	132.0 (3)
C8—C3—C4	120.4 (3)	N4—C12—C11	105.6 (2)
C8—C3—N1	108.3 (2)	C13—C12—C11	122.3 (3)
C4—C3—N1	131.3 (3)	C14—C13—C12	116.3 (3)
C5—C4—C3	117.0 (3)	C14—C13—H13	121.8
C5—C4—H4	121.5	C12—C13—H13	121.8
C3—C4—H4	121.5	C13—C14—C15	121.6 (3)
C4—C5—C6	121.7 (3)	C13—C14—H14	119.2
C4—C5—H5	119.2	C15—C14—H14	119.2
C6—C5—H5	119.2	C16—C15—C14	122.9 (4)
C7—C6—C5	122.2 (3)	C16—C15—H15	118.6
C7—C6—H6	118.9	C14—C15—H15	118.6
C5—C6—H6	118.9	C15—C16—C11	115.9 (3)
C6—C7—C8	115.8 (3)	C15—C16—H16	122.0
C6—C7—H7	122.1	C11—C16—H16	122.0
C8—C7—H7	122.1	F3—B1—F2	111.2 (6)
N2—C8—C7	131.5 (3)	F2A—B1—F3A	109.3 (8)
N2—C8—C3	105.5 (2)	F2A—B1—F1A	115.8 (7)
C7—C8—C3	123.0 (3)	F3A—B1—F1A	112.5 (7)
C10—N3—C11	106.1 (2)	F3—B1—F4	110.9 (6)
C10—N3—H3	126.9	F2—B1—F4	111.7 (7)
C11—N3—H3	126.9	F1A—B1—F4	82.7 (7)
C10—N4—C12	107.6 (2)	F2A—B1—F4A	105.0 (7)
C10—N4—H4A	126.2	F3A—B1—F4A	107.9 (8)
C12—N4—H4A	126.2	F1A—B1—F4A	105.7 (7)
F8A—C9—F10A	107.6 (4)	F3—B1—F1	109.8 (7)
F9—C9—F8	107.6 (4)	F2—B1—F1	107.6 (7)
F9—C9—F10	106.5 (3)	F4—B1—F1	105.4 (6)
F8—C9—F10	104.6 (3)	H1A—O1W—H1B	112.4
C3—N1—C2—N2	−0.3 (3)	C12—N4—C10—C9	178.8 (2)
C3—N1—C2—C1	−178.0 (3)	F9—C9—C10—N3	−79.8 (7)
C8—N2—C2—N1	0.8 (3)	F8A—C9—C10—N3	−155.5 (8)
C8—N2—C2—C1	178.5 (3)	F10A—C9—C10—N3	79.6 (7)
F5—C1—C2—N1	−33.5 (5)	F8—C9—C10—N3	43.1 (6)
F6—C1—C2—N1	87.9 (4)	F10—C9—C10—N3	158.5 (5)
F7—C1—C2—N1	−153.8 (3)	F9A—C9—C10—N3	−37.4 (6)
F5—C1—C2—N2	149.1 (3)	F9—C9—C10—N4	101.1 (7)
F6—C1—C2—N2	−89.5 (4)	F8A—C9—C10—N4	25.4 (8)
F7—C1—C2—N2	28.8 (5)	F10A—C9—C10—N4	−99.4 (7)
C2—N1—C3—C8	−0.3 (3)	F8—C9—C10—N4	−135.9 (6)
C2—N1—C3—C4	179.1 (3)	F10—C9—C10—N4	−20.6 (6)
C8—C3—C4—C5	−1.1 (4)	F9A—C9—C10—N4	143.6 (6)
N1—C3—C4—C5	179.6 (3)	C10—N3—C11—C12	−0.1 (3)
C3—C4—C5—C6	0.3 (5)	C10—N3—C11—C16	179.6 (3)
C4—C5—C6—C7	0.9 (6)	C10—N4—C12—C13	−179.4 (3)
C5—C6—C7—C8	−1.2 (5)	C10—N4—C12—C11	0.3 (3)
C2—N2—C8—C7	179.7 (3)	N3—C11—C12—N4	−0.1 (3)
C2—N2—C8—C3	−0.9 (3)	C16—C11—C12—N4	−179.8 (3)
C6—C7—C8—N2	179.8 (3)	N3—C11—C12—C13	179.6 (3)
C6—C7—C8—C3	0.4 (4)	C16—C11—C12—C13	−0.2 (4)
C4—C3—C8—N2	−178.8 (3)	N4—C12—C13—C14	178.5 (3)
N1—C3—C8—N2	0.7 (3)	C11—C12—C13—C14	−1.1 (4)
C4—C3—C8—C7	0.7 (4)	C12—C13—C14—C15	1.6 (5)
N1—C3—C8—C7	−179.8 (3)	C13—C14—C15—C16	−1.0 (6)
C11—N3—C10—N4	0.3 (3)	C14—C15—C16—C11	−0.3 (5)
C11—N3—C10—C9	−178.8 (2)	N3—C11—C16—C15	−178.9 (3)
C12—N4—C10—N3	−0.4 (3)	C12—C11—C16—C15	0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1W	0.86	1.84	2.698 (3)	177
N1—H1···N3	0.86	1.86	2.718 (3)	175
N3—H3···N1	0.86	1.86	2.718 (3)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1W	0.86	1.84	2.698 (3)	177
N1—H1⋯N3	0.86	1.86	2.718 (3)	175
N3—H3⋯N1	0.86	1.86	2.718 (3)	175