4-Bromo-anilinium perchlorate 18-crown-6 clathrate.

The reaction of 4-bromo-aniline, 18-crown-6, and perchloric acid in methanol yields the title compound, C(6)H(7)BrN(+)·ClO(4) (-)·C(12)H(24)O(6), in which the protonated -NH(3) (+) group forms three bifurcated N-H⋯O hydrogen bonds to the O atoms of the crown ether.

Related literature

For similar crown ether clathrates, see: Akutagawa et al. (2002 ▶); Ge et al. (2010 ▶); Zhao (2010 ▶). For their ferroelectric properties, see: Zhang, Cheng et al. (2009 ▶); Zhang, Ye et al. (2009 ▶); Ye et al. (2009 ▶). For related structures, see: Ge & Zhao (2010a ▶,b ▶); Zhao & Qu (2010a ▶ b ▶).

Experimental

Crystal data

C6H7BrN+·ClO4 −·C12H24O6

M = 536.79

Orthorhombic,

a = 15.583 (7) Å

b = 11.469 (5) Å

c = 12.633 (6) Å

V = 2257.7 (18) Å3

Z = 4

Mo Kα radiation

μ = 1.99 mm−1

T = 93 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.671, T max = 0.678

23692 measured reflections

2694 independent reflections

2561 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.104

S = 1.01

2694 reflections

146 parameters

H-atom parameters constrained

Δρmax = 0.57 e Å−3

Δρmin = −0.50 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/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810040481/jh2210sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040481/jh2210Isup2.hkl

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

C6H7BrN+·ClO4−·C12H24O6	F(000) = 1112
Mr = 536.79	Dx = 1.579 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 6002 reflections
a = 15.583 (7) Å	θ = 3.1–27.5°
b = 11.469 (5) Å	µ = 1.99 mm−1
c = 12.633 (6) Å	T = 93 K
V = 2257.7 (18) Å3	Prism, colorless
Z = 4	0.20 × 0.20 × 0.20 mm

Rigaku SCXmini diffractometer	2694 independent reflections
Radiation source: fine-focus sealed tube	2561 reflections with I > 2σ(I)
graphite	Rint = 0.046
Detector resolution: 28.5714 pixels mm-1	θmax = 27.4°, θmin = 3.1°
CCD_Profile_fitting scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.671, Tmax = 0.678	l = −16→16
23692 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0645P)2 + 1.990P] where P = (Fo2 + 2Fc2)/3
2694 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.57 e Å−3
0 restraints	Δρmin = −0.49 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	Occ. (<1)
C5	0.28939 (14)	0.14670 (19)	0.53702 (17)	0.0192 (5)
H5A	0.3403	0.1418	0.5796	0.023*
H5B	0.2406	0.1491	0.5834	0.023*
C6	0.28315 (14)	0.0420 (2)	0.46603 (19)	0.0189 (4)
H6A	0.2881	−0.0283	0.5069	0.023*
H6B	0.3289	0.0435	0.4152	0.023*
C7	0.18311 (14)	−0.06318 (18)	0.35971 (17)	0.0172 (4)
H7A	0.2267	−0.0800	0.3083	0.021*
H7B	0.1816	−0.1258	0.4101	0.021*
C8	0.09748 (14)	−0.05164 (18)	0.30595 (17)	0.0171 (4)
H8A	0.0552	−0.0262	0.3561	0.020*
H8B	0.0797	−0.1256	0.2778	0.020*
C9	0.02573 (13)	0.04351 (19)	0.16556 (17)	0.0164 (4)
H9A	0.0147	−0.0262	0.1257	0.020*
H9B	−0.0206	0.0546	0.2145	0.020*
C10	0.03150 (14)	0.14646 (18)	0.09257 (16)	0.0159 (4)
H10A	−0.0190	0.1508	0.0492	0.019*
H10B	0.0806	0.1386	0.0472	0.019*
O1	0.29171 (15)	0.2500	0.47351 (17)	0.0175 (4)
O2	0.20209 (9)	0.04497 (13)	0.41238 (12)	0.0166 (3)
O3	0.10476 (9)	0.03158 (13)	0.22212 (12)	0.0156 (3)
O4	0.03915 (14)	0.2500	0.15568 (16)	0.0148 (4)
O5	0.11943 (10)	0.14672 (14)	0.73375 (13)	0.0243 (4)
O6	0.01814 (13)	0.2500	0.83702 (18)	0.0184 (5)
O7	0.16415 (14)	0.2500	0.88559 (18)	0.0200 (5)
Cl1	0.10535 (4)	0.2500	0.79722 (6)	0.01469 (17)
N1	0.18963 (16)	0.2500	0.2839 (2)	0.0142 (5)
H1A	0.1736	0.1752	0.2975	0.021*	0.50
H1B	0.1462	0.2879	0.2501	0.021*	0.50
H1C	0.2016	0.2870	0.3459	0.021*	0.50
C1	0.4115 (2)	0.2500	0.0932 (2)	0.0179 (6)*
C2	0.37554 (14)	0.35578 (19)	0.12293 (17)	0.0185 (4)*
H2A	0.4006	0.4272	0.1007	0.022*
C3	0.30225 (14)	0.35541 (18)	0.18573 (16)	0.0164 (4)
H3A	0.2769	0.4268	0.2074	0.020*
C4	0.26646 (19)	0.2500	0.2164 (2)	0.0139 (5)
Br1	0.51210 (2)	0.2500	0.00763 (3)	0.02519 (13)

	U11	U22	U33	U12	U13	U23
C5	0.0183 (10)	0.0250 (12)	0.0142 (10)	0.0009 (8)	−0.0030 (8)	0.0049 (9)
C6	0.0143 (10)	0.0211 (11)	0.0212 (10)	0.0029 (8)	−0.0023 (8)	0.0037 (9)
C7	0.0202 (10)	0.0131 (9)	0.0184 (10)	0.0006 (8)	0.0010 (8)	0.0021 (8)
C8	0.0199 (10)	0.0141 (10)	0.0173 (10)	−0.0025 (8)	0.0004 (8)	0.0022 (8)
C9	0.0161 (9)	0.0140 (10)	0.0192 (10)	−0.0025 (8)	−0.0022 (8)	−0.0007 (8)
C10	0.0162 (9)	0.0168 (10)	0.0147 (10)	−0.0008 (8)	−0.0021 (8)	−0.0032 (8)
O1	0.0214 (11)	0.0173 (10)	0.0138 (10)	0.000	−0.0018 (8)	0.000
O2	0.0158 (7)	0.0142 (7)	0.0199 (7)	0.0015 (6)	−0.0036 (6)	0.0005 (6)
O3	0.0158 (7)	0.0138 (7)	0.0172 (7)	−0.0020 (5)	−0.0012 (6)	0.0033 (6)
O4	0.0195 (10)	0.0101 (9)	0.0148 (10)	0.000	−0.0032 (8)	0.000
O5	0.0232 (8)	0.0215 (8)	0.0281 (9)	0.0019 (6)	0.0025 (7)	−0.0111 (7)
O6	0.0130 (10)	0.0196 (11)	0.0227 (12)	0.000	0.0015 (8)	0.000
O7	0.0172 (11)	0.0225 (11)	0.0203 (11)	0.000	−0.0038 (9)	0.000
Cl1	0.0135 (3)	0.0137 (3)	0.0168 (3)	0.000	0.0006 (2)	0.000
N1	0.0141 (12)	0.0124 (11)	0.0162 (12)	0.000	−0.0009 (9)	0.000
C3	0.0182 (10)	0.0148 (10)	0.0161 (10)	0.0001 (8)	−0.0017 (8)	−0.0017 (8)
C4	0.0135 (13)	0.0183 (14)	0.0099 (12)	0.000	−0.0025 (10)	0.000
Br1	0.01691 (19)	0.0359 (2)	0.0227 (2)	0.000	0.00469 (11)	0.000

C5—O1	1.431 (2)	C10—H10B	0.9600
C5—C6	1.502 (3)	O1—C5i	1.431 (2)
C5—H5A	0.9601	O4—C10i	1.435 (2)
C5—H5B	0.9600	O5—Cl1	1.4471 (16)
C6—O2	1.434 (3)	O6—Cl1	1.449 (2)
C6—H6A	0.9601	O7—Cl1	1.444 (2)
C6—H6B	0.9598	Cl1—O5i	1.4471 (16)
C7—O2	1.438 (3)	N1—C4	1.470 (4)
C7—C8	1.503 (3)	N1—H1A	0.9100
C7—H7A	0.9599	N1—H1B	0.9100
C7—H7B	0.9600	N1—H1C	0.9100
C8—O3	1.430 (2)	C1—C2	1.388 (3)
C8—H8A	0.9601	C1—C2i	1.388 (3)
C8—H8B	0.9601	C1—Br1	1.905 (3)
C9—O3	1.430 (3)	C2—C3	1.391 (3)
C9—C10	1.501 (3)	C2—H2A	0.9500
C9—H9A	0.9600	C3—C4	1.387 (3)
C9—H9B	0.9600	C3—H3A	0.9500
C10—O4	1.435 (2)	C4—C3i	1.387 (3)
C10—H10A	0.9600
O1—C5—C6	109.20 (18)	C9—C10—H10A	110.0
O1—C5—H5A	109.9	O4—C10—H10B	110.1
C6—C5—H5A	110.0	C9—C10—H10B	109.9
O1—C5—H5B	109.7	H10A—C10—H10B	108.4
C6—C5—H5B	109.6	C5i—O1—C5	111.7 (2)
H5A—C5—H5B	108.3	C6—O2—C7	112.27 (16)
O2—C6—C5	108.66 (17)	C8—O3—C9	111.43 (15)
O2—C6—H6A	110.2	C10i—O4—C10	111.7 (2)
C5—C6—H6A	110.2	O7—Cl1—O5i	109.40 (9)
O2—C6—H6B	109.8	O7—Cl1—O5	109.40 (9)
C5—C6—H6B	109.7	O5i—Cl1—O5	109.88 (15)
H6A—C6—H6B	108.4	O7—Cl1—O6	109.08 (14)
O2—C7—C8	108.39 (17)	O5i—Cl1—O6	109.53 (9)
O2—C7—H7A	109.9	O5—Cl1—O6	109.53 (9)
C8—C7—H7A	109.9	C4—N1—H1A	109.5
O2—C7—H7B	110.1	C4—N1—H1B	109.5
C8—C7—H7B	110.1	H1A—N1—H1B	109.5
H7A—C7—H7B	108.4	C4—N1—H1C	109.5
O3—C8—C7	108.84 (16)	H1A—N1—H1C	109.5
O3—C8—H8A	109.9	H1B—N1—H1C	109.5
C7—C8—H8A	109.8	C2—C1—C2i	121.9 (3)
O3—C8—H8B	109.8	C2—C1—Br1	119.06 (14)
C7—C8—H8B	110.2	C2i—C1—Br1	119.06 (14)
H8A—C8—H8B	108.4	C1—C2—C3	118.9 (2)
O3—C9—C10	109.31 (17)	C1—C2—H2A	120.6
O3—C9—H9A	109.7	C3—C2—H2A	120.6
C10—C9—H9A	110.1	C4—C3—C2	119.5 (2)
O3—C9—H9B	109.8	C4—C3—H3A	120.3
C10—C9—H9B	109.7	C2—C3—H3A	120.3
H9A—C9—H9B	108.3	C3i—C4—C3	121.4 (3)
O4—C10—C9	108.34 (17)	C3i—C4—N1	119.32 (14)
O4—C10—H10A	110.0	C3—C4—N1	119.32 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.91	2.13	2.864 (2)	137
N1—H1A···O3	0.91	2.18	2.938 (2)	140
N1—H1B···O4	0.91	2.10	2.850 (3)	139
N1—H1B···O3i	0.91	2.20	2.938 (2)	138
N1—H1C···O2i	0.91	2.10	2.864 (2)	141
N1—H1C···O1	0.91	2.18	2.875 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.91	2.13	2.864 (2)	137
N1—H1A⋯O3	0.91	2.18	2.938 (2)	140
N1—H1B⋯O4	0.91	2.10	2.850 (3)	139
N1—H1B⋯O3i	0.91	2.20	2.938 (2)	138
N1—H1C⋯O2i	0.91	2.10	2.864 (2)	141
N1—H1C⋯O1	0.91	2.18	2.875 (3)	133

Symmetry code: (i) .