4-Bromo-3-methyl­anilinium perchlorate 18-crown-6 clathrate

Xu, Q.; Zhao, M.M.

doi:10.1107/S1600536811003540

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o579

doi:10.1107/S1600536811003540

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4-Bromo-3-methylanilinium perchlorate 18-crown-6 clathrate

Qian Xu ^a and Min Min Zhao ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical, Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xqchem@yahoo.com.cn

(Received 22 January 2011; accepted 27 January 2011; online 5 February 2011)

The reaction of 4-bromo-3-methylanilinium perchlorate and 18-crown-6 in methanol solution yielded the title compound, C₇H₉BrN⁺·ClO₄⁻·C₁₂H₂₄O₆. The protonated 4-bromo-3-methylamine unit contains one –NH₃⁺ substituent, resulting in a 1:1 supramolecular rotator–stator structure, (C₇H₉Br—NH₃⁺)(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 molecule.

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_r = 550.81
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.060
wR(F²) = 0.157
S = 1.09
5665 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.98 e Å⁻³

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

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.

Supporting information

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

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

checkCIF report

Comment top

There is currently a great deal of interest in crown ethers because of their ability to form non-covalent, H-bonding complexes with ammonium cations both in solid and in solution (Akutagawa et al., 2002; Ge et al., 2010a,b; Guo et al., 2010; Zhao et al., 2010a,b). Not only the size of the crown ether, but also the nature of the ammonium cation (–NH₄⁺, RNH₃⁺, R₂NH₂⁺, etc) can influence on the stoichiometry and stability of these host–guest complexes. The host molecules combine with the guest species by intermolecular interaction, and if the host molecule possess some specific sites, it is easy to realise high selectivity in ion or molecular recognitions. 18-Crown-6 have the highest affinity for ammonium cation RNH₃⁺, while most studies of 18-crown-6 and its derivatives invariably showed a 1:1 stoichiometry with RNH₃⁺ cations.

Dielectric permittivity of the title compound is tested to systematically investigate the ferroelectric phase transitions materials (Ye et al., 2009; Zhang et al., 2009). The title compound has no dielectric anomaly with the value of 5 and 8 under 1M Hz in the temperature from 80 to 433 K (the compound m.p.> 453 K), suggesting that the compound should be no distinct phase transition occurred within the measured temperature range.

The title compound is composed of cationic [C₇H₉NBr(18-Crown-6)]⁺ and one single anionic [ClO₄]^- anions (Fig. 1). Supramolecular rotators was assembled between protonated 4-bromo-3-methylanilinium [C₇H₆Br—NH₃]⁺ and 18-crown-6 by hydrogen-bonding. The ammonium moieties of (–NH₃⁺) cations were interacted with the oxygen atom of crown ethers through six simple N—H···O hydrogen bonding, forming 1:1 supramolecular rotator-stator structures.

The macrocycle adopts a conformation with approximate D_{3 d} symmetry, with all O—C—C—O torsion angles being gauche and alternating in sign, and all C—O—C—C torsion angles being trans. The C—N bonds of [C₇H₆Br—NH₃]⁺ were almost perpendicular to the mean oxygen planes of crown ethers.

Supramolecular cation structure, [C₇H₉NBr(18-Crown-6)]⁺, were introduced as counter cations to [ClO₄]^- anions. Cl has a flattened tetrahedral coordination by four O^2- ions [range of cis-bond angles = 108.4 (2)–110.3 (2) °; dav(Cl—O) = 1.426 (3)–1.457 (3) Å].

The title compound was stabilized by intramolecular N—H···O hydrogen bonds, but no intermolecular hydrogen bond was observed. The intramolecular N—H···O hydrogen bonding length are within the usual range: 2.893 (4) and 2.970 (4) Å.

Related literature top

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 top

C₇H₈NBr. HClO₄ (2 mmol, 0.57 g) and 18-crown-6 (2 mmol, 0.528 g) were dissolved in 40 ml me thanol solution. The precipitate was filtered out. Two days later, single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of methanol solution at 0°C.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The title molecules with the atomic numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.

4-Bromo-3-methylanilinium perchlorate–18-crown-6 (1/1) top

Crystal data top

C₇H₉BrN⁺·ClO₄⁻·C₁₂H₂₄O₆	F(000) = 1144
M_r = 550.81	D_x = 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

Data collection top

Rigaku SCXmini diffractometer	5665 independent reflections
Radiation source: fine-focus sealed tube	4005 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.3°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −15→15
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.530, T_max = 0.699	l = −20→20
25007 measured reflections

Refinement top

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(F_o²) + (0.0769P)² + 0.8528P] where P = (F_o² + 2F_c²)/3
5665 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.98 e Å⁻³

Crystal data top

C₇H₉BrN⁺·ClO₄⁻·C₁₂H₂₄O₆	V = 2516.3 (9) Å³
M_r = 550.81	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.967 (2) Å	µ = 1.79 mm⁻¹
b = 13.446 (3) Å	T = 296 K
c = 15.677 (3) Å	0.40 × 0.30 × 0.20 mm
β = 94.05 (3)°

Data collection top

Rigaku SCXmini diffractometer	5665 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	4005 reflections with I > 2σ(I)
T_min = 0.530, T_max = 0.699	R_int = 0.066
25007 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.09	Δρ_max = 0.41 e Å⁻³
5665 reflections	Δρ_min = −0.98 e Å⁻³
289 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₇H₉BrN⁺·ClO₄⁻·C₁₂H₂₄O₆
M_r	550.81
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.967 (2), 13.446 (3), 15.677 (3)
β (°)	94.05 (3)
V (Å³)	2516.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.530, 0.699
No. of measured, independent and observed [I > 2σ(I)] reflections	25007, 5665, 4005
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.646

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.157, 1.09
No. of reflections	5665
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.98

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.

References

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