4-Bromo-3-methyl-anilinium perchlorate 18-crown-6 clathrate.

The reaction of 4-bromo-3-methyl-anilinium perchlorate and 18-crown-6 in methanol solution yielded the title compound, C(7)H(9)BrN(+)·ClO(4) (-)·C(12)H(24)O(6). The protonated 4-bromo-3-methyl-amine unit contains one -NH(3) (+) substituent, resulting in a 1:1 supra-molecular rotator-stator structure, (C(7)H(9)Br-NH(3) (+))(18-crown-6), through three bifurcated N-H⋯(O,O) hydrogen bonds between the ammonium group of the cation and the O atoms of the crown ether mol-ecule.

Related literature

For the structures of similar crown ether clathrates, see: Akutagawa et al. (2002 ▶); Ge & Zhao (2010a ▶,b ▶;); Guo & Zhao (2010 ▶); Zhao (2010 ▶); Zhao & Qu (2010a ▶,b ▶). The title compound was prepared as part of a study of ferroelectric materials. For their properties, see: Fu et al. (2007 ▶); Zhang et al. (2009 ▶); Ye et al. (2009 ▶).

Experimental

Crystal data

C7H9BrN+·ClO4 −·C12H24O6

M = 550.81

Monoclinic,

a = 11.967 (2) Å

b = 13.446 (3) Å

c = 15.677 (3) Å

β = 94.05 (3)°

V = 2516.3 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.79 mm−1

T = 296 K

0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.530, T max = 0.699

25007 measured reflections

5665 independent reflections

4005 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.157

S = 1.09

5665 reflections

289 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.98 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003540/jh2260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003540/jh2260Isup2.hkl

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

C7H9BrN+·ClO4−·C12H24O6	F(000) = 1144
Mr = 550.81	Dx = 1.454 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20001 reflections
a = 11.967 (2) Å	θ = 3.0–27.3°
b = 13.446 (3) Å	µ = 1.79 mm−1
c = 15.677 (3) Å	T = 296 K
β = 94.05 (3)°	Prism, colorless
V = 2516.3 (9) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Rigaku SCXmini diffractometer	5665 independent reflections
Radiation source: fine-focus sealed tube	4005 reflections with I > 2σ(I)
graphite	Rint = 0.066
Detector resolution: 28.5714 pixels mm-1	θmax = 27.3°, θmin = 3.0°
CCD_Profile_fitting scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
Tmin = 0.530, Tmax = 0.699	l = −20→20
25007 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0769P)2 + 0.8528P] where P = (Fo2 + 2Fc2)/3
5665 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.98 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
Br1	0.19928 (4)	1.01458 (3)	−0.00712 (3)	0.06334 (18)
O8	0.0452 (2)	0.60635 (19)	0.30049 (15)	0.0495 (6)
N1	0.2459 (2)	0.72782 (19)	0.29922 (16)	0.0367 (6)
H1A	0.1796	0.7195	0.3206	0.055*
H1B	0.2937	0.7545	0.3389	0.055*
H1E	0.2719	0.6692	0.2833	0.055*
O9	0.0542 (2)	0.78578 (18)	0.39854 (15)	0.0499 (6)
C15	0.3203 (3)	0.8828 (2)	0.1107 (2)	0.0370 (7)
C16	0.2147 (3)	0.9217 (2)	0.08602 (19)	0.0398 (7)
O6	0.4462 (2)	0.59829 (19)	0.29366 (17)	0.0551 (7)
O5	0.4715 (2)	0.78411 (19)	0.37212 (16)	0.0518 (6)
O7	0.2319 (2)	0.53548 (19)	0.21645 (17)	0.0554 (7)
O10	0.2751 (2)	0.84908 (18)	0.45312 (16)	0.0506 (6)
C13	0.2336 (3)	0.7946 (2)	0.22444 (19)	0.0332 (7)
C17	0.1196 (3)	0.8976 (3)	0.1282 (2)	0.0453 (8)
H17A	0.0503	0.9242	0.1098	0.054*
C18	0.1292 (3)	0.8336 (2)	0.1982 (2)	0.0415 (8)
H18A	0.0664	0.8171	0.2270	0.050*
C14	0.3275 (3)	0.8187 (2)	0.1809 (2)	0.0398 (7)
H14A	0.3966	0.7914	0.1990	0.048*
C11	0.5624 (3)	0.7135 (3)	0.3751 (3)	0.0545 (10)
H11A	0.5601	0.6721	0.4256	0.065*
H11B	0.6335	0.7484	0.3781	0.065*
C6	−0.0296 (3)	0.7105 (3)	0.4065 (2)	0.0537 (9)
H6A	−0.0976	0.7405	0.4250	0.064*
H6B	−0.0033	0.6619	0.4490	0.064*
C10	0.4740 (3)	0.8459 (3)	0.4471 (3)	0.0600 (10)
H10A	0.5406	0.8872	0.4499	0.072*
H10B	0.4766	0.8045	0.4979	0.072*
C7	0.0804 (3)	0.8360 (3)	0.4778 (2)	0.0562 (10)
H7A	0.1013	0.7881	0.5224	0.067*
H7B	0.0155	0.8726	0.4944	0.067*
C19	0.4241 (3)	0.9087 (3)	0.0644 (3)	0.0580 (10)
H19A	0.4878	0.8747	0.0911	0.087*
H19B	0.4366	0.9792	0.0673	0.087*
H19C	0.4132	0.8887	0.0056	0.087*
C8	0.1762 (3)	0.9065 (3)	0.4666 (3)	0.0579 (10)
H8A	0.1585	0.9496	0.4180	0.070*
H8B	0.1891	0.9476	0.5172	0.070*
C3	0.1271 (4)	0.4814 (3)	0.2176 (3)	0.0600 (10)
H3A	0.1286	0.4386	0.2675	0.072*
H3B	0.1164	0.4401	0.1670	0.072*
C5	−0.0538 (3)	0.6604 (3)	0.3215 (2)	0.0517 (9)
H5A	−0.1164	0.6149	0.3244	0.062*
H5B	−0.0733	0.7096	0.2778	0.062*
C4	0.0330 (3)	0.5545 (3)	0.2200 (2)	0.0539 (9)
H4A	0.0356	0.6014	0.1731	0.065*
H4B	−0.0383	0.5201	0.2144	0.065*
C9	0.3713 (3)	0.9105 (3)	0.4438 (3)	0.0583 (10)
H9A	0.3780	0.9592	0.4895	0.070*
H9B	0.3633	0.9457	0.3897	0.070*
C12	0.5517 (3)	0.6502 (3)	0.2967 (3)	0.0573 (10)
H12A	0.5554	0.6914	0.2462	0.069*
H12B	0.6128	0.6027	0.2978	0.069*
C1	0.4329 (4)	0.5300 (4)	0.2234 (4)	0.0794 (15)
H1C	0.4969	0.4856	0.2243	0.095*
H1D	0.4290	0.5664	0.1698	0.095*
C2	0.3278 (4)	0.4705 (3)	0.2295 (4)	0.0794 (15)
H2A	0.3239	0.4185	0.1866	0.095*
H2B	0.3280	0.4395	0.2854	0.095*
Cl2	0.75937 (7)	0.70425 (7)	0.09959 (6)	0.0485 (2)
O2	0.7570 (3)	0.6235 (2)	0.15986 (19)	0.0709 (8)
O1	0.6613 (3)	0.7637 (3)	0.1044 (3)	0.0979 (12)
O4	0.7607 (3)	0.6624 (3)	0.01394 (19)	0.0784 (9)
O3	0.8582 (3)	0.7636 (3)	0.1177 (2)	0.0849 (10)

	U11	U22	U33	U12	U13	U23
Br1	0.0687 (3)	0.0700 (3)	0.0526 (3)	0.0157 (2)	0.0132 (2)	0.02676 (19)
O8	0.0416 (13)	0.0607 (16)	0.0458 (13)	−0.0055 (11)	−0.0003 (11)	−0.0053 (11)
N1	0.0388 (14)	0.0358 (14)	0.0359 (14)	−0.0015 (11)	0.0058 (11)	0.0020 (11)
O9	0.0502 (14)	0.0543 (15)	0.0469 (14)	−0.0092 (11)	0.0152 (11)	−0.0020 (11)
C15	0.0384 (17)	0.0343 (16)	0.0393 (17)	0.0015 (13)	0.0110 (14)	−0.0005 (13)
C16	0.052 (2)	0.0352 (17)	0.0332 (16)	0.0051 (14)	0.0053 (14)	0.0025 (13)
O6	0.0451 (14)	0.0589 (16)	0.0627 (16)	0.0068 (12)	0.0125 (12)	−0.0091 (13)
O5	0.0417 (14)	0.0535 (15)	0.0588 (16)	0.0012 (11)	−0.0066 (12)	0.0054 (12)
O7	0.0568 (16)	0.0443 (14)	0.0657 (17)	0.0002 (12)	0.0081 (13)	−0.0090 (12)
O10	0.0548 (15)	0.0390 (13)	0.0585 (16)	−0.0048 (11)	0.0074 (12)	−0.0054 (11)
C13	0.0372 (16)	0.0302 (15)	0.0326 (15)	−0.0003 (12)	0.0049 (13)	0.0004 (12)
C17	0.0337 (17)	0.053 (2)	0.050 (2)	0.0103 (15)	0.0032 (15)	0.0062 (16)
C18	0.0326 (17)	0.0468 (19)	0.0459 (18)	0.0020 (14)	0.0089 (14)	0.0067 (15)
C14	0.0338 (17)	0.0399 (18)	0.0461 (18)	0.0050 (14)	0.0054 (14)	0.0034 (14)
C11	0.0356 (19)	0.056 (2)	0.072 (3)	−0.0006 (16)	0.0029 (18)	0.019 (2)
C6	0.044 (2)	0.064 (2)	0.056 (2)	−0.0041 (17)	0.0191 (17)	0.0041 (18)
C10	0.053 (2)	0.050 (2)	0.073 (3)	−0.0102 (18)	−0.016 (2)	−0.007 (2)
C7	0.065 (3)	0.059 (2)	0.047 (2)	−0.0005 (19)	0.0175 (18)	−0.0075 (17)
C19	0.047 (2)	0.061 (2)	0.068 (3)	0.0070 (18)	0.0247 (19)	0.015 (2)
C8	0.066 (3)	0.051 (2)	0.058 (2)	0.0028 (19)	0.0092 (19)	−0.0115 (18)
C3	0.072 (3)	0.046 (2)	0.062 (3)	−0.0129 (19)	0.003 (2)	−0.0103 (18)
C5	0.0389 (19)	0.057 (2)	0.059 (2)	−0.0073 (17)	0.0030 (17)	0.0075 (18)
C4	0.059 (2)	0.058 (2)	0.045 (2)	−0.0166 (19)	−0.0031 (17)	−0.0041 (17)
C9	0.056 (2)	0.045 (2)	0.073 (3)	−0.0110 (18)	−0.004 (2)	−0.0066 (18)
C12	0.0360 (19)	0.073 (3)	0.064 (2)	0.0088 (18)	0.0142 (17)	0.013 (2)
C1	0.065 (3)	0.084 (3)	0.091 (4)	0.021 (2)	0.015 (3)	−0.035 (3)
C2	0.080 (3)	0.051 (3)	0.107 (4)	0.008 (2)	0.003 (3)	−0.032 (3)
Cl2	0.0381 (4)	0.0543 (5)	0.0526 (5)	0.0011 (4)	−0.0005 (4)	0.0077 (4)
O2	0.075 (2)	0.0661 (19)	0.0713 (19)	−0.0057 (15)	0.0047 (15)	0.0206 (15)
O1	0.074 (2)	0.105 (3)	0.114 (3)	0.043 (2)	0.002 (2)	−0.002 (2)
O4	0.080 (2)	0.101 (3)	0.0551 (18)	−0.0078 (19)	0.0068 (15)	−0.0074 (16)
O3	0.074 (2)	0.097 (2)	0.081 (2)	−0.0366 (19)	−0.0162 (17)	0.0177 (18)

Br1—C16	1.921 (3)	C6—H6B	0.9700
O8—C4	1.440 (4)	C10—C9	1.503 (5)
O8—C5	1.448 (4)	C10—H10A	0.9700
N1—C13	1.476 (4)	C10—H10B	0.9700
N1—H1A	0.8900	C7—C8	1.507 (5)
N1—H1B	0.8900	C7—H7A	0.9700
N1—H1E	0.8900	C7—H7B	0.9700
O9—C7	1.430 (4)	C19—H19A	0.9600
O9—C6	1.437 (4)	C19—H19B	0.9600
C15—C14	1.396 (4)	C19—H19C	0.9600
C15—C16	1.397 (4)	C8—H8A	0.9700
C15—C19	1.523 (4)	C8—H8B	0.9700
C16—C17	1.393 (5)	C3—C4	1.497 (6)
O6—C1	1.435 (5)	C3—H3A	0.9700
O6—C12	1.440 (4)	C3—H3B	0.9700
O5—C10	1.437 (5)	C5—H5A	0.9700
O5—C11	1.442 (4)	C5—H5B	0.9700
O7—C2	1.445 (5)	C4—H4A	0.9700
O7—C3	1.451 (5)	C4—H4B	0.9700
O10—C9	1.432 (4)	C9—H9A	0.9700
O10—C8	1.440 (4)	C9—H9B	0.9700
C13—C18	1.390 (4)	C12—H12A	0.9700
C13—C14	1.394 (4)	C12—H12B	0.9700
C17—C18	1.393 (4)	C1—C2	1.498 (7)
C17—H17A	0.9300	C1—H1C	0.9700
C18—H18A	0.9300	C1—H1D	0.9700
C14—H14A	0.9300	C2—H2A	0.9700
C11—C12	1.493 (6)	C2—H2B	0.9700
C11—H11A	0.9700	Cl2—O1	1.426 (3)
C11—H11B	0.9700	Cl2—O3	1.439 (3)
C6—C5	1.503 (5)	Cl2—O2	1.441 (3)
C6—H6A	0.9700	Cl2—O4	1.457 (3)
C4—O8—C5	114.1 (3)	C15—C19—H19C	109.5
C13—N1—H1A	109.5	H19A—C19—H19C	109.5
C13—N1—H1B	109.5	H19B—C19—H19C	109.5
H1A—N1—H1B	109.5	O10—C8—C7	108.7 (3)
C13—N1—H1E	109.5	O10—C8—H8A	110.0
H1A—N1—H1E	109.5	C7—C8—H8A	110.0
H1B—N1—H1E	109.5	O10—C8—H8B	110.0
C7—O9—C6	111.6 (3)	C7—C8—H8B	110.0
C14—C15—C16	117.0 (3)	H8A—C8—H8B	108.3
C14—C15—C19	120.6 (3)	O7—C3—C4	108.9 (3)
C16—C15—C19	122.3 (3)	O7—C3—H3A	109.9
C17—C16—C15	122.3 (3)	C4—C3—H3A	109.9
C17—C16—Br1	118.3 (2)	O7—C3—H3B	109.9
C15—C16—Br1	119.4 (2)	C4—C3—H3B	109.9
C1—O6—C12	112.7 (3)	H3A—C3—H3B	108.3
C10—O5—C11	112.5 (3)	O8—C5—C6	108.5 (3)
C2—O7—C3	112.0 (3)	O8—C5—H5A	110.0
C9—O10—C8	112.4 (3)	C6—C5—H5A	110.0
C18—C13—C14	120.5 (3)	O8—C5—H5B	110.0
C18—C13—N1	120.1 (3)	C6—C5—H5B	110.0
C14—C13—N1	119.4 (3)	H5A—C5—H5B	108.4
C18—C17—C16	119.5 (3)	O8—C4—C3	108.0 (3)
C18—C17—H17A	120.2	O8—C4—H4A	110.1
C16—C17—H17A	120.2	C3—C4—H4A	110.1
C13—C18—C17	119.2 (3)	O8—C4—H4B	110.1
C13—C18—H18A	120.4	C3—C4—H4B	110.1
C17—C18—H18A	120.4	H4A—C4—H4B	108.4
C13—C14—C15	121.4 (3)	O10—C9—C10	108.9 (3)
C13—C14—H14A	119.3	O10—C9—H9A	109.9
C15—C14—H14A	119.3	C10—C9—H9A	109.9
O5—C11—C12	109.2 (3)	O10—C9—H9B	109.9
O5—C11—H11A	109.8	C10—C9—H9B	109.9
C12—C11—H11A	109.8	H9A—C9—H9B	108.3
O5—C11—H11B	109.8	O6—C12—C11	109.1 (3)
C12—C11—H11B	109.8	O6—C12—H12A	109.9
H11A—C11—H11B	108.3	C11—C12—H12A	109.9
O9—C6—C5	109.3 (3)	O6—C12—H12B	109.9
O9—C6—H6A	109.8	C11—C12—H12B	109.9
C5—C6—H6A	109.8	H12A—C12—H12B	108.3
O9—C6—H6B	109.8	O6—C1—C2	109.9 (4)
C5—C6—H6B	109.8	O6—C1—H1C	109.7
H6A—C6—H6B	108.3	C2—C1—H1C	109.7
O5—C10—C9	109.7 (3)	O6—C1—H1D	109.7
O5—C10—H10A	109.7	C2—C1—H1D	109.7
C9—C10—H10A	109.7	H1C—C1—H1D	108.2
O5—C10—H10B	109.7	O7—C2—C1	109.3 (4)
C9—C10—H10B	109.7	O7—C2—H2A	109.8
H10A—C10—H10B	108.2	C1—C2—H2A	109.8
O9—C7—C8	108.5 (3)	O7—C2—H2B	109.8
O9—C7—H7A	110.0	C1—C2—H2B	109.8
C8—C7—H7A	110.0	H2A—C2—H2B	108.3
O9—C7—H7B	110.0	O1—Cl2—O3	110.3 (2)
C8—C7—H7B	110.0	O1—Cl2—O2	109.5 (2)
H7A—C7—H7B	108.4	O3—Cl2—O2	110.04 (19)
C15—C19—H19A	109.5	O1—Cl2—O4	109.1 (2)
C15—C19—H19B	109.5	O3—Cl2—O4	109.5 (2)
H19A—C19—H19B	109.5	O2—Cl2—O4	108.4 (2)
C14—C15—C16—C17	−0.6 (5)	C6—O9—C7—C8	174.6 (3)
C19—C15—C16—C17	179.8 (3)	C9—O10—C8—C7	−178.6 (3)
C14—C15—C16—Br1	177.5 (2)	O9—C7—C8—O10	−67.0 (4)
C19—C15—C16—Br1	−2.1 (4)	C2—O7—C3—C4	169.7 (4)
C15—C16—C17—C18	0.7 (5)	C4—O8—C5—C6	180.0 (3)
Br1—C16—C17—C18	−177.4 (3)	O9—C6—C5—O8	66.3 (4)
C14—C13—C18—C17	−0.5 (5)	C5—O8—C4—C3	−164.9 (3)
N1—C13—C18—C17	179.1 (3)	O7—C3—C4—O8	−66.0 (4)
C16—C17—C18—C13	−0.2 (5)	C8—O10—C9—C10	169.2 (3)
C18—C13—C14—C15	0.6 (5)	O5—C10—C9—O10	68.3 (4)
N1—C13—C14—C15	−178.9 (3)	C1—O6—C12—C11	−175.7 (4)
C16—C15—C14—C13	−0.1 (5)	O5—C11—C12—O6	−60.0 (4)
C19—C15—C14—C13	179.6 (3)	C12—O6—C1—C2	173.7 (4)
C10—O5—C11—C12	178.1 (3)	C3—O7—C2—C1	177.2 (4)
C7—O9—C6—C5	180.0 (3)	O6—C1—C2—O7	67.1 (5)
C11—O5—C10—C9	−174.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O5	0.89	2.19	2.955 (4)	144
N1—H1E···O6	0.89	2.29	2.970 (4)	133
N1—H1E···O7	0.89	2.12	2.893 (4)	145
N1—H1A···O8	0.89	2.22	2.905 (4)	134
N1—H1A···O9	0.89	2.19	2.966 (4)	145
N1—H1B···O10	0.89	2.22	2.912 (4)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O8	0.89	2.22	2.905 (4)	134
N1—H1A⋯O9	0.89	2.19	2.966 (4)	145
N1—H1B⋯O5	0.89	2.19	2.955 (4)	144
N1—H1B⋯O10	0.89	2.22	2.912 (4)	134
N1—H1E⋯O6	0.89	2.29	2.970 (4)	133
N1—H1E⋯O7	0.89	2.12	2.893 (4)	145