Benzyl-ammonium tetra-fluoro-borate 18-crown-6 clathrate.

The reaction of benzyl-ammonium tetra-fluoro-borate and 18-crown-6 in a methano-lic solution yields the title compound, C(7)H(10)N(+)·BF(4) (-)·C(12)H(24)O(6)O6, which displays a supra-molecular structure. The -NH(3) (+) substituent of the benzyl-ammonium cation forms a 1:1 supra-molecular rotator-stator structure by N-H⋯O hydrogen-bonding inter-actions.

Related literature

For similar crown ether clathrates, see: Akutagawa et al. (2002 ▶); Kryatova et al. (2004 ▶). For their ferroelectric properties, see: Zhang et al. (2009 ▶); Ye et al. (2009 ▶).

Experimental

Crystal data

C7H10N+·BF4 −·C12H24O6

M = 459.28

Triclinic,

a = 9.281 (6) Å

b = 10.673 (6) Å

c = 11.863 (7) Å

α = 76.418 (16)°

β = 86.244 (17)°

γ = 78.274 (15)°

V = 1118.2 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 293 K

0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.958, T max = 0.976

12286 measured reflections

5057 independent reflections

4153 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.103

S = 1.03

5057 reflections

280 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.24 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021392/im2207sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021392/im2207Isup2.hkl

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

C7H10N+·BF4−·C12H24O6	Z = 2
Mr = 459.28	F(000) = 488
Triclinic, P1	Dx = 1.364 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.281 (6) Å	Cell parameters from 2953 reflections
b = 10.673 (6) Å	θ = 2.9–27.5°
c = 11.863 (7) Å	µ = 0.12 mm−1
α = 76.418 (16)°	T = 293 K
β = 86.244 (17)°	Prism, colorless
γ = 78.274 (15)°	0.40 × 0.30 × 0.20 mm
V = 1118.2 (12) Å3

Rigaku SCXmini diffractometer	5057 independent reflections
Radiation source: fine-focus sealed tube	4153 reflections with I > 2σ(I)
graphite	Rint = 0.031
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 2.7°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.958, Tmax = 0.976	l = −15→15
12286 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0454P)2 + 0.2316P] where P = (Fo2 + 2Fc2)/3
5057 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.24 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
C8	−0.24636 (17)	0.50111 (14)	0.10270 (14)	0.0196 (3)
H8A	−0.3497	0.5175	0.0841	0.024*
H8B	−0.1973	0.5562	0.0418	0.024*
C9	−0.23023 (16)	0.53375 (15)	0.21673 (14)	0.0194 (3)
H9A	−0.2804	0.6232	0.2153	0.023*
H9B	−0.2738	0.4751	0.2785	0.023*
C10	0.27734 (17)	0.10959 (14)	0.00480 (13)	0.0189 (3)
H10A	0.2860	0.0238	0.0573	0.023*
H10B	0.3479	0.1025	−0.0585	0.023*
C11	−0.05246 (17)	0.57472 (15)	0.33132 (13)	0.0203 (3)
H11A	−0.1023	0.5345	0.4007	0.024*
H11B	−0.0922	0.6684	0.3133	0.024*
C12	0.31163 (16)	0.37847 (15)	0.42392 (13)	0.0188 (3)
H12A	0.3308	0.2915	0.4748	0.023*
H12B	0.3345	0.4397	0.4657	0.023*
C13	0.12451 (16)	0.15430 (14)	−0.04151 (12)	0.0176 (3)
H13A	0.1122	0.2444	−0.0861	0.021*
H13B	0.1080	0.0996	−0.0923	0.021*
C14	−0.12985 (16)	0.18795 (15)	0.01623 (13)	0.0186 (3)
H14A	−0.1928	0.1430	0.0735	0.022*
H14B	−0.1384	0.1631	−0.0563	0.022*
C15	−0.18267 (17)	0.33378 (15)	−0.00050 (13)	0.0194 (3)
H15A	−0.1180	0.3802	−0.0547	0.023*
H15B	−0.2811	0.3590	−0.0315	0.023*
C16	0.48137 (16)	0.27382 (15)	0.16325 (13)	0.0180 (3)
H16A	0.5828	0.2546	0.1875	0.022*
H16B	0.4647	0.3574	0.1072	0.022*
C17	0.45350 (16)	0.16760 (15)	0.10879 (13)	0.0189 (3)
H17A	0.5241	0.1570	0.0461	0.023*
H17B	0.4648	0.0849	0.1660	0.023*
C18	0.41154 (16)	0.37904 (14)	0.31845 (13)	0.0184 (3)
H18A	0.3924	0.4650	0.2660	0.022*
H18B	0.5136	0.3596	0.3414	0.022*
C29	0.10945 (17)	0.55084 (14)	0.35178 (13)	0.0195 (3)
H29A	0.1614	0.5798	0.2798	0.023*
H29B	0.1286	0.5993	0.4070	0.023*
O1	0.02026 (11)	0.14543 (10)	0.05354 (8)	0.0168 (2)
O2	0.30731 (11)	0.20280 (9)	0.06498 (9)	0.0164 (2)
O3	−0.07640 (11)	0.51969 (10)	0.23695 (8)	0.0160 (2)
O4	0.15806 (11)	0.41358 (9)	0.39606 (9)	0.0170 (2)
O5	−0.18295 (11)	0.36644 (9)	0.10949 (9)	0.0171 (2)
O6	0.38446 (11)	0.28133 (10)	0.26150 (9)	0.0165 (2)
B1	0.40157 (19)	0.76448 (17)	0.26818 (15)	0.0188 (3)
F1	0.26267 (12)	0.84348 (11)	0.26112 (10)	0.0428 (3)
F2	0.42418 (11)	0.70503 (10)	0.17371 (8)	0.0311 (2)
F3	0.41256 (12)	0.66888 (9)	0.37036 (8)	0.0327 (2)
F4	0.50826 (12)	0.83934 (11)	0.26526 (10)	0.0401 (3)
N2	0.08837 (13)	0.24571 (11)	0.25008 (10)	0.0149 (3)
H2A	0.1771	0.2666	0.2431	0.022*
H2B	0.0208	0.3151	0.2588	0.022*
H2C	0.0698	0.2211	0.1867	0.022*
C1	−0.34030 (17)	0.02500 (15)	0.39415 (13)	0.0193 (3)
H1A	−0.4325	0.0021	0.4017	0.023*
C2	−0.23098 (17)	−0.03380 (14)	0.32762 (13)	0.0186 (3)
H2D	−0.2498	−0.0965	0.2907	0.022*
C3	−0.09306 (16)	0.00054 (14)	0.31579 (12)	0.0171 (3)
H3A	−0.0195	−0.0406	0.2722	0.020*
C4	−0.06450 (16)	0.09625 (14)	0.36893 (12)	0.0158 (3)
C5	−0.17497 (17)	0.15401 (14)	0.43633 (13)	0.0189 (3)
H5A	−0.1568	0.2172	0.4729	0.023*
C6	−0.31203 (17)	0.11841 (15)	0.44960 (13)	0.0202 (3)
H6A	−0.3847	0.1570	0.4955	0.024*
C7	0.08405 (16)	0.13519 (14)	0.35362 (13)	0.0186 (3)
H7A	0.1060	0.1616	0.4225	0.022*
H7B	0.1589	0.0601	0.3446	0.022*

	U11	U22	U33	U12	U13	U23
C8	0.0179 (8)	0.0141 (7)	0.0260 (8)	−0.0017 (6)	−0.0072 (6)	−0.0024 (6)
C9	0.0139 (7)	0.0176 (7)	0.0268 (8)	−0.0023 (6)	−0.0005 (6)	−0.0053 (6)
C10	0.0220 (8)	0.0162 (7)	0.0199 (8)	−0.0036 (6)	0.0026 (6)	−0.0077 (6)
C11	0.0247 (8)	0.0196 (7)	0.0169 (7)	0.0011 (6)	−0.0016 (6)	−0.0092 (6)
C12	0.0185 (8)	0.0198 (7)	0.0192 (7)	−0.0042 (6)	−0.0039 (6)	−0.0047 (6)
C13	0.0231 (8)	0.0161 (7)	0.0149 (7)	−0.0055 (6)	0.0027 (6)	−0.0055 (6)
C14	0.0175 (7)	0.0207 (7)	0.0200 (8)	−0.0065 (6)	−0.0030 (6)	−0.0062 (6)
C15	0.0208 (8)	0.0211 (7)	0.0169 (7)	−0.0050 (6)	−0.0054 (6)	−0.0030 (6)
C16	0.0131 (7)	0.0207 (7)	0.0196 (7)	−0.0041 (6)	0.0031 (6)	−0.0037 (6)
C17	0.0140 (7)	0.0201 (7)	0.0208 (8)	0.0006 (6)	0.0009 (6)	−0.0045 (6)
C18	0.0172 (7)	0.0174 (7)	0.0230 (8)	−0.0060 (6)	−0.0012 (6)	−0.0072 (6)
C29	0.0256 (8)	0.0151 (7)	0.0191 (8)	−0.0035 (6)	−0.0047 (6)	−0.0058 (6)
O1	0.0165 (5)	0.0191 (5)	0.0152 (5)	−0.0044 (4)	0.0002 (4)	−0.0040 (4)
O2	0.0147 (5)	0.0149 (5)	0.0206 (5)	−0.0014 (4)	−0.0010 (4)	−0.0073 (4)
O3	0.0139 (5)	0.0184 (5)	0.0169 (5)	−0.0021 (4)	−0.0010 (4)	−0.0070 (4)
O4	0.0175 (5)	0.0151 (5)	0.0189 (5)	−0.0033 (4)	−0.0019 (4)	−0.0044 (4)
O5	0.0207 (5)	0.0131 (5)	0.0174 (5)	−0.0020 (4)	−0.0043 (4)	−0.0030 (4)
O6	0.0157 (5)	0.0172 (5)	0.0196 (5)	−0.0063 (4)	0.0032 (4)	−0.0080 (4)
B1	0.0194 (9)	0.0190 (8)	0.0189 (8)	−0.0056 (7)	−0.0011 (7)	−0.0040 (7)
F1	0.0308 (6)	0.0468 (7)	0.0417 (7)	0.0136 (5)	−0.0010 (5)	−0.0099 (5)
F2	0.0356 (6)	0.0352 (6)	0.0263 (5)	−0.0055 (4)	−0.0027 (4)	−0.0151 (4)
F3	0.0475 (6)	0.0251 (5)	0.0250 (5)	−0.0125 (5)	−0.0064 (5)	0.0013 (4)
F4	0.0464 (7)	0.0388 (6)	0.0443 (7)	−0.0292 (5)	−0.0010 (5)	−0.0094 (5)
N2	0.0148 (6)	0.0156 (6)	0.0149 (6)	−0.0038 (5)	0.0005 (5)	−0.0040 (5)
C1	0.0156 (7)	0.0234 (8)	0.0170 (7)	−0.0051 (6)	−0.0007 (6)	0.0005 (6)
C2	0.0220 (8)	0.0183 (7)	0.0170 (7)	−0.0072 (6)	−0.0020 (6)	−0.0037 (6)
C3	0.0182 (7)	0.0181 (7)	0.0141 (7)	−0.0026 (6)	0.0020 (6)	−0.0032 (6)
C4	0.0179 (7)	0.0152 (7)	0.0127 (7)	−0.0053 (6)	−0.0033 (6)	0.0026 (5)
C5	0.0249 (8)	0.0156 (7)	0.0160 (7)	−0.0037 (6)	−0.0026 (6)	−0.0026 (6)
C6	0.0194 (8)	0.0206 (8)	0.0176 (7)	0.0001 (6)	0.0021 (6)	−0.0028 (6)
C7	0.0180 (8)	0.0174 (7)	0.0185 (7)	−0.0054 (6)	−0.0042 (6)	0.0024 (6)

C8—O5	1.4236 (19)	C16—H16B	0.9700
C8—C9	1.497 (2)	C17—O2	1.4303 (19)
C8—H8A	0.9700	C17—H17A	0.9700
C8—H8B	0.9700	C17—H17B	0.9700
C9—O3	1.4351 (19)	C18—O6	1.4376 (18)
C9—H9A	0.9700	C18—H18A	0.9700
C9—H9B	0.9700	C18—H18B	0.9700
C10—O2	1.4313 (18)	C29—O4	1.4235 (19)
C10—C13	1.498 (2)	C29—H29A	0.9700
C10—H10A	0.9700	C29—H29B	0.9700
C10—H10B	0.9700	B1—F3	1.383 (2)
C11—O3	1.4290 (18)	B1—F1	1.385 (2)
C11—C29	1.498 (2)	B1—F4	1.387 (2)
C11—H11A	0.9700	B1—F2	1.397 (2)
C11—H11B	0.9700	N2—C7	1.4946 (19)
C12—O4	1.4380 (19)	N2—H2A	0.8900
C12—C18	1.507 (2)	N2—H2B	0.8900
C12—H12A	0.9700	N2—H2C	0.8900
C12—H12B	0.9700	C1—C2	1.384 (2)
C13—O1	1.4355 (18)	C1—C6	1.390 (2)
C13—H13A	0.9700	C1—H1A	0.9300
C13—H13B	0.9700	C2—C3	1.391 (2)
C14—O1	1.4395 (19)	C2—H2D	0.9300
C14—C15	1.503 (2)	C3—C4	1.395 (2)
C14—H14A	0.9700	C3—H3A	0.9300
C14—H14B	0.9700	C4—C5	1.392 (2)
C15—O5	1.4272 (19)	C4—C7	1.507 (2)
C15—H15A	0.9700	C5—C6	1.389 (2)
C15—H15B	0.9700	C5—H5A	0.9300
C16—O6	1.4322 (18)	C6—H6A	0.9300
C16—C17	1.501 (2)	C7—H7A	0.9700
C16—H16A	0.9700	C7—H7B	0.9700
O5—C8—C9	109.25 (12)	O2—C17—H17B	109.9
O5—C8—H8A	109.8	C16—C17—H17B	109.9
C9—C8—H8A	109.8	H17A—C17—H17B	108.3
O5—C8—H8B	109.8	O6—C18—C12	108.68 (12)
C9—C8—H8B	109.8	O6—C18—H18A	110.0
H8A—C8—H8B	108.3	C12—C18—H18A	110.0
O3—C9—C8	108.54 (12)	O6—C18—H18B	110.0
O3—C9—H9A	110.0	C12—C18—H18B	110.0
C8—C9—H9A	110.0	H18A—C18—H18B	108.3
O3—C9—H9B	110.0	O4—C29—C11	107.80 (12)
C8—C9—H9B	110.0	O4—C29—H29A	110.1
H9A—C9—H9B	108.4	C11—C29—H29A	110.1
O2—C10—C13	108.95 (12)	O4—C29—H29B	110.1
O2—C10—H10A	109.9	C11—C29—H29B	110.1
C13—C10—H10A	109.9	H29A—C29—H29B	108.5
O2—C10—H10B	109.9	C13—O1—C14	112.74 (12)
C13—C10—H10B	109.9	C17—O2—C10	111.77 (11)
H10A—C10—H10B	108.3	C11—O3—C9	111.85 (11)
O3—C11—C29	109.20 (12)	C29—O4—C12	113.18 (11)
O3—C11—H11A	109.8	C8—O5—C15	111.32 (11)
C29—C11—H11A	109.8	C16—O6—C18	110.94 (11)
O3—C11—H11B	109.8	F3—B1—F1	109.87 (14)
C29—C11—H11B	109.8	F3—B1—F4	109.19 (13)
H11A—C11—H11B	108.3	F1—B1—F4	110.24 (14)
O4—C12—C18	113.11 (12)	F3—B1—F2	109.64 (14)
O4—C12—H12A	109.0	F1—B1—F2	108.85 (13)
C18—C12—H12A	109.0	F4—B1—F2	109.04 (14)
O4—C12—H12B	109.0	C7—N2—H2A	109.5
C18—C12—H12B	109.0	C7—N2—H2B	109.5
H12A—C12—H12B	107.8	H2A—N2—H2B	109.5
O1—C13—C10	109.27 (13)	C7—N2—H2C	109.5
O1—C13—H13A	109.8	H2A—N2—H2C	109.5
C10—C13—H13A	109.8	H2B—N2—H2C	109.5
O1—C13—H13B	109.8	C2—C1—C6	119.87 (14)
C10—C13—H13B	109.8	C2—C1—H1A	120.1
H13A—C13—H13B	108.3	C6—C1—H1A	120.1
O1—C14—C15	112.86 (12)	C1—C2—C3	120.23 (14)
O1—C14—H14A	109.0	C1—C2—H2D	119.9
C15—C14—H14A	109.0	C3—C2—H2D	119.9
O1—C14—H14B	109.0	C2—C3—C4	120.39 (14)
C15—C14—H14B	109.0	C2—C3—H3A	119.8
H14A—C14—H14B	107.8	C4—C3—H3A	119.8
O5—C15—C14	108.15 (12)	C5—C4—C3	118.85 (14)
O5—C15—H15A	110.1	C5—C4—C7	120.99 (14)
C14—C15—H15A	110.1	C3—C4—C7	120.15 (13)
O5—C15—H15B	110.1	C6—C5—C4	120.80 (14)
C14—C15—H15B	110.1	C6—C5—H5A	119.6
H15A—C15—H15B	108.4	C4—C5—H5A	119.6
O6—C16—C17	109.34 (12)	C5—C6—C1	119.85 (14)
O6—C16—H16A	109.8	C5—C6—H6A	120.1
C17—C16—H16A	109.8	C1—C6—H6A	120.1
O6—C16—H16B	109.8	N2—C7—C4	111.37 (12)
C17—C16—H16B	109.8	N2—C7—H7A	109.4
H16A—C16—H16B	108.3	C4—C7—H7A	109.4
O2—C17—C16	109.06 (12)	N2—C7—H7B	109.4
O2—C17—H17A	109.9	C4—C7—H7B	109.4
C16—C17—H17A	109.9	H7A—C7—H7B	108.0
O5—C8—C9—O3	64.50 (15)	C9—C8—O5—C15	−174.28 (12)
O2—C10—C13—O1	−68.12 (15)	C14—C15—O5—C8	−173.89 (12)
O1—C14—C15—O5	−64.33 (16)	C17—C16—O6—C18	177.97 (12)
O6—C16—C17—O2	64.18 (15)	C12—C18—O6—C16	−177.47 (12)
O4—C12—C18—O6	−62.79 (15)	C6—C1—C2—C3	−0.2 (2)
O3—C11—C29—O4	−68.82 (15)	C1—C2—C3—C4	−1.2 (2)
C10—C13—O1—C14	179.48 (11)	C2—C3—C4—C5	1.7 (2)
C15—C14—O1—C13	−86.11 (15)	C2—C3—C4—C7	−178.64 (13)
C16—C17—O2—C10	176.00 (12)	C3—C4—C5—C6	−0.7 (2)
C13—C10—O2—C17	−178.41 (12)	C7—C4—C5—C6	179.59 (13)
C29—C11—O3—C9	177.14 (12)	C4—C5—C6—C1	−0.7 (2)
C8—C9—O3—C11	167.91 (12)	C2—C1—C6—C5	1.1 (2)
C11—C29—O4—C12	−177.59 (11)	C5—C4—C7—N2	−90.62 (17)
C18—C12—O4—C29	−76.33 (15)	C3—C4—C7—N2	89.72 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6	0.89	1.99	2.866 (2)	167
N2—H2B···O3	0.89	2.15	2.986 (2)	157
N2—H2C···O1	0.89	2.05	2.936 (2)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O6	0.89	1.99	2.866 (2)	167
N2—H2B⋯O3	0.89	2.15	2.986 (2)	157
N2—H2C⋯O1	0.89	2.05	2.936 (2)	173