Cyclo­benzaprinium salicylate

Fun, H.-K.; Yeap, C.S.; Siddegowda, M.S.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536811020642

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1584

doi:10.1107/S1600536811020642

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Cyclobenzaprinium salicylate

Hoong-Kun Fun,^a ^*‡ Chin Sing Yeap,^a § M. S. Siddegowda,^b H. S. Yathirajan ^b and B. Narayana ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 26 May 2011; accepted 30 May 2011; online 4 June 2011)

In the title molecular salt [systematic name: 3-(5H-dibenzo[a,d]cyclohepten-5-ylidene)-N,N-dimethyl-1-propanaminium 2-hydroxybenzoate], C₂₀H₂₂N⁺·C₇H₅O₃⁻, the benzene rings of the cyclobenzaprinium cation are inclined with a dihedral angle of 61.66 (7)°. An intramolecular O—H⋯O hydrogen bond occurs within the salicylate anion, generating an S(6) ring. In the crystal, the cation and anion are linked by an N—H⋯O interaction.

Related literature

For background to cyclobenzaprine, see: Commissiong et al. (1981 ); Katz & Dube (1988 ); Cimolai (2009 ). For related structures, see: Bindya et al., (2007 ); Hemamalini & Fun (2010 ); Kolev et al. (2009 ); Thanigaimani et al. (2007 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₀H₂₂N⁺·C₇H₅O₃⁻
M_r = 413.50
Triclinic, $[P \overline 1]$
a = 7.4700 (8) Å
b = 10.8408 (12) Å
c = 14.9724 (16) Å
α = 76.073 (2)°
β = 77.357 (1)°
γ = 72.574 (2)°
V = 1108.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.37 × 0.21 × 0.15 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.971, T_max = 0.988
22974 measured reflections
6461 independent reflections
4411 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.134
S = 1.04
6461 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	0.91	1.75	2.6439 (16)	167
O3—H1O3⋯O2	0.99	1.55	2.4890 (19)	157

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811020642/hb5897sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811020642/hb5897Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811020642/hb5897Isup3.cml

checkCIF report

Comment top

Cyclobenzaprine is a muscle relaxant medication used to relieve skeletal muscle spasms and associated pain in acute musculoskeletal conditions. It is the most well studied drug for this application and it also has been used off-label for fibromyalgia treatment. Cyclobenzaprine has been considered structurally related to the first-generation tricyclic antidepressants (Commissiong et al., 1981; Katz & Dube, 1988; Cimolai, 2009). The crystal structures of amitriptylinium picrate (Bindya et al., 2007), benzamidinium salicylate (Kolev et al., 2009), 2-amino-5-chloropyridinium salicylate (Hemamalini & Fun, 2010) and 2-amino-4,6-dimethoxypyrimidinium salicylate (Thanigaimani et al., 2007) have been reported. We now report the crystal structure of the title compound, C₂₀H₂₂N⁺.C₇H₅O₃^-.

The asymmetric unit of the title compound consists of one cyclobenzaprinium cation and one salicylate anion (Fig. 1). The hydrogen atom of the carboxylic acid COOH group is deprotonated to the N1 atom. The two fused benzene rings of the cation make a dihedral angle of 61.66 (7)° whereas the salicylate anion is almost planar with maximum deviation of 0.063 (1) Å for atom O1. The aminium atom adopts a pyramidal conformation. The cation and anion are interconnected by N1—H1N1···O1 interaction (Table 1). An intramolecular O3—H1O3···O2 hydrogen bond (Table 1) stabilize the molecular structure of the anion molecule generating S(6) ring motif (Bernstein et al., 1995).

Related literature top

For background on cyclobenzaprine, see: Commissiong et al. (1981); Katz & Dube (1988); Cimolai (2009). For related structures, see: Bindya et al., (2007); Hemamalini & Fun (2010); Kolev et al. (2009); Thanigaimani et al. (2007). fro graph-set notation, see: Bernstein et al. (1995).

Experimental top

Cyclobenzaprine (10 g, 0.04 mol) and salicylic acid (5.6 g, 0.04 mol) were dissolved in 50 ml of dichloromethane taken in a 100 ml round bottomed flask. Dichloromethane was distilled off under vacuum and 50 ml of ethyl acetate was added and then the flask was cooled to 278–283 K. The product formed was filtered and re-crystallized from dichloromethane to yield colourless blocks of (I) (M.p.: 415–416 K).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, with 30% probability ellipsoids for non-H atoms. Hydrogen bonds (dashed lines) are shown.

3-(5H-Dibenzo[a,d]cyclohepten-5-ylidene)- N,N-dimethyl-1-propanaminium 2-hydroxybenzoate top

Crystal data top

C₂₀H₂₂N⁺·C₇H₅O₃⁻	Z = 2
M_r = 413.50	F(000) = 440
Triclinic, P1	D_x = 1.239 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4700 (8) Å	Cell parameters from 5425 reflections
b = 10.8408 (12) Å	θ = 2.2–29.5°
c = 14.9724 (16) Å	µ = 0.08 mm⁻¹
α = 76.073 (2)°	T = 296 K
β = 77.357 (1)°	Block, colourless
γ = 72.574 (2)°	0.37 × 0.21 × 0.15 mm
V = 1108.6 (2) Å³

Data collection top

Bruker APEXII DUO CCD diffractometer	6461 independent reflections
Radiation source: fine-focus sealed tube	4411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 30.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
T_min = 0.971, T_max = 0.988	k = −15→15
22974 measured reflections	l = −21→21

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0573P)² + 0.147P] where P = (F_o² + 2F_c²)/3
6461 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₂₂N⁺·C₇H₅O₃⁻	γ = 72.574 (2)°
M_r = 413.50	V = 1108.6 (2) Å³
Triclinic, P1	Z = 2
a = 7.4700 (8) Å	Mo Kα radiation
b = 10.8408 (12) Å	µ = 0.08 mm⁻¹
c = 14.9724 (16) Å	T = 296 K
α = 76.073 (2)°	0.37 × 0.21 × 0.15 mm
β = 77.357 (1)°

Data collection top

Bruker APEXII DUO CCD diffractometer	6461 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4411 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.988	R_int = 0.028
22974 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	Δρ_max = 0.21 e Å⁻³
6461 reflections	Δρ_min = −0.18 e Å⁻³
280 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
N1	−0.33126 (15)	0.09099 (10)	0.18470 (7)	0.0423 (2)
H1N1	−0.2275	0.0547	0.2133	0.051*
C1	0.05014 (15)	0.33798 (12)	0.18708 (8)	0.0361 (3)
C2	0.10142 (17)	0.26220 (14)	0.11781 (9)	0.0431 (3)
H2A	0.0675	0.1833	0.1295	0.052*
C3	0.2020 (2)	0.30282 (17)	0.03200 (10)	0.0564 (4)
H3A	0.2353	0.2513	−0.0136	0.068*
C4	0.2527 (2)	0.41904 (18)	0.01409 (11)	0.0640 (4)
H4A	0.3199	0.4464	−0.0437	0.077*
C5	0.2045 (2)	0.49480 (15)	0.08118 (12)	0.0590 (4)
H5A	0.2374	0.5743	0.0677	0.071*
C6	0.10616 (17)	0.45507 (12)	0.17007 (10)	0.0438 (3)
C7	0.0743 (2)	0.53280 (14)	0.24161 (12)	0.0537 (4)
H7A	0.0442	0.6237	0.2222	0.064*
C8	0.0834 (2)	0.48787 (15)	0.33202 (12)	0.0557 (4)
H8A	0.0614	0.5510	0.3684	0.067*
C9	0.12425 (18)	0.35065 (14)	0.38045 (9)	0.0457 (3)
C10	0.2302 (2)	0.31229 (19)	0.45369 (11)	0.0607 (4)
H10A	0.2667	0.3758	0.4723	0.073*
C11	0.2813 (2)	0.1843 (2)	0.49850 (11)	0.0669 (5)
H11A	0.3535	0.1613	0.5462	0.080*
C12	0.2254 (2)	0.08934 (17)	0.47281 (10)	0.0594 (4)
H12A	0.2608	0.0020	0.5028	0.071*
C13	0.11665 (18)	0.12385 (14)	0.40225 (9)	0.0457 (3)
H13A	0.0782	0.0596	0.3857	0.055*
C14	0.06458 (16)	0.25355 (13)	0.35607 (8)	0.0376 (3)
C15	−0.05187 (16)	0.28950 (11)	0.28004 (8)	0.0347 (2)
C16	−0.22561 (17)	0.27224 (12)	0.29535 (9)	0.0392 (3)
H16A	−0.2678	0.2322	0.3553	0.047*
C17	−0.36111 (17)	0.30986 (13)	0.22713 (10)	0.0436 (3)
H17A	−0.2928	0.3319	0.1650	0.052*
H17B	−0.4586	0.3884	0.2404	0.052*
C18	−0.45677 (17)	0.20412 (13)	0.22789 (10)	0.0434 (3)
H18A	−0.5051	0.1707	0.2919	0.052*
H18B	−0.5648	0.2441	0.1951	0.052*
C19	−0.2757 (2)	0.12856 (18)	0.08299 (10)	0.0621 (4)
H19A	−0.1936	0.0531	0.0588	0.093*
H19B	−0.2101	0.1962	0.0704	0.093*
H19C	−0.3874	0.1608	0.0537	0.093*
C20	−0.4273 (3)	−0.01685 (17)	0.20561 (14)	0.0736 (5)
H20A	−0.3458	−0.0895	0.1780	0.110*
H20B	−0.5440	0.0143	0.1805	0.110*
H20C	−0.4540	−0.0450	0.2719	0.110*
O1	−0.05304 (14)	−0.04235 (10)	0.28085 (7)	0.0564 (3)
O2	0.10069 (17)	−0.09085 (12)	0.14508 (7)	0.0724 (4)
O3	0.42092 (17)	−0.24876 (12)	0.13184 (7)	0.0674 (3)
H1O3	0.2980	−0.1850	0.1204	0.101*
C21	0.22965 (19)	−0.23076 (12)	0.37511 (9)	0.0433 (3)
H21A	0.1221	−0.1879	0.4115	0.052*
C22	0.3758 (2)	−0.32023 (15)	0.41757 (11)	0.0570 (4)
H22A	0.3665	−0.3378	0.4821	0.068*
C23	0.5356 (2)	−0.38335 (15)	0.36347 (12)	0.0601 (4)
H23A	0.6346	−0.4429	0.3919	0.072*
C24	0.5504 (2)	−0.35955 (14)	0.26882 (11)	0.0540 (4)
H24A	0.6591	−0.4028	0.2332	0.065*
C25	0.40337 (18)	−0.27075 (13)	0.22540 (9)	0.0429 (3)
C26	0.24146 (16)	−0.20414 (11)	0.27883 (8)	0.0356 (2)
C27	0.08451 (18)	−0.10603 (12)	0.23224 (9)	0.0420 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0371 (5)	0.0432 (6)	0.0491 (6)	−0.0090 (4)	−0.0163 (4)	−0.0070 (5)
C1	0.0256 (5)	0.0387 (6)	0.0429 (6)	−0.0071 (4)	−0.0102 (4)	−0.0030 (5)
C2	0.0332 (6)	0.0510 (7)	0.0451 (7)	−0.0094 (5)	−0.0098 (5)	−0.0078 (6)
C3	0.0451 (8)	0.0727 (10)	0.0442 (7)	−0.0068 (7)	−0.0065 (6)	−0.0088 (7)
C4	0.0516 (9)	0.0745 (11)	0.0502 (9)	−0.0140 (8)	−0.0029 (7)	0.0098 (8)
C5	0.0463 (8)	0.0496 (8)	0.0722 (10)	−0.0172 (7)	−0.0128 (7)	0.0142 (7)
C6	0.0316 (6)	0.0389 (6)	0.0579 (8)	−0.0086 (5)	−0.0121 (5)	0.0002 (5)
C7	0.0446 (7)	0.0371 (7)	0.0827 (11)	−0.0119 (6)	−0.0166 (7)	−0.0098 (7)
C8	0.0485 (8)	0.0519 (8)	0.0783 (11)	−0.0163 (6)	−0.0111 (7)	−0.0290 (7)
C9	0.0358 (6)	0.0596 (8)	0.0490 (7)	−0.0170 (6)	−0.0041 (5)	−0.0208 (6)
C10	0.0550 (9)	0.0886 (12)	0.0540 (9)	−0.0301 (8)	−0.0129 (7)	−0.0239 (8)
C11	0.0573 (9)	0.1065 (14)	0.0440 (8)	−0.0310 (9)	−0.0176 (7)	−0.0063 (8)
C12	0.0522 (8)	0.0754 (10)	0.0450 (8)	−0.0196 (8)	−0.0119 (6)	0.0066 (7)
C13	0.0402 (7)	0.0547 (8)	0.0419 (7)	−0.0172 (6)	−0.0048 (5)	−0.0039 (6)
C14	0.0284 (5)	0.0493 (7)	0.0371 (6)	−0.0126 (5)	−0.0017 (4)	−0.0119 (5)
C15	0.0297 (5)	0.0345 (6)	0.0422 (6)	−0.0094 (4)	−0.0059 (4)	−0.0101 (5)
C16	0.0330 (6)	0.0407 (6)	0.0452 (7)	−0.0120 (5)	−0.0054 (5)	−0.0081 (5)
C17	0.0306 (6)	0.0403 (6)	0.0607 (8)	−0.0071 (5)	−0.0134 (5)	−0.0080 (6)
C18	0.0264 (5)	0.0502 (7)	0.0557 (7)	−0.0107 (5)	−0.0092 (5)	−0.0105 (6)
C19	0.0550 (9)	0.0819 (11)	0.0481 (8)	−0.0085 (8)	−0.0176 (7)	−0.0131 (7)
C20	0.0793 (12)	0.0570 (10)	0.1005 (14)	−0.0321 (9)	−0.0296 (10)	−0.0127 (9)
O1	0.0484 (6)	0.0553 (6)	0.0579 (6)	0.0085 (5)	−0.0183 (5)	−0.0156 (5)
O2	0.0730 (8)	0.0825 (8)	0.0445 (6)	0.0097 (6)	−0.0213 (5)	−0.0066 (5)
O3	0.0636 (7)	0.0813 (8)	0.0473 (6)	−0.0044 (6)	0.0015 (5)	−0.0210 (5)
C21	0.0460 (7)	0.0404 (7)	0.0433 (7)	−0.0075 (5)	−0.0102 (5)	−0.0093 (5)
C22	0.0682 (10)	0.0537 (8)	0.0500 (8)	−0.0087 (7)	−0.0267 (7)	−0.0049 (6)
C23	0.0536 (9)	0.0471 (8)	0.0803 (11)	0.0029 (7)	−0.0348 (8)	−0.0120 (7)
C24	0.0399 (7)	0.0470 (8)	0.0751 (10)	−0.0003 (6)	−0.0117 (7)	−0.0229 (7)
C25	0.0418 (7)	0.0405 (7)	0.0488 (7)	−0.0107 (5)	−0.0066 (5)	−0.0133 (5)
C26	0.0357 (6)	0.0306 (5)	0.0424 (6)	−0.0084 (4)	−0.0108 (5)	−0.0069 (5)
C27	0.0438 (7)	0.0370 (6)	0.0460 (7)	−0.0069 (5)	−0.0159 (5)	−0.0059 (5)

Geometric parameters (Å, º) top

N1—C19	1.4775 (18)	C14—C15	1.4904 (16)
N1—C20	1.4855 (19)	C15—C16	1.3291 (16)
N1—C18	1.4930 (17)	C16—C17	1.4963 (17)
N1—H1N1	0.9057	C16—H16A	0.9300
C1—C2	1.3947 (18)	C17—C18	1.5184 (18)
C1—C6	1.4026 (17)	C17—H17A	0.9700
C1—C15	1.4892 (17)	C17—H17B	0.9700
C2—C3	1.3828 (19)	C18—H18A	0.9700
C2—H2A	0.9300	C18—H18B	0.9700
C3—C4	1.372 (2)	C19—H19A	0.9600
C3—H3A	0.9300	C19—H19B	0.9600
C4—C5	1.369 (2)	C19—H19C	0.9600
C4—H4A	0.9300	C20—H20A	0.9600
C5—C6	1.408 (2)	C20—H20B	0.9600
C5—H5A	0.9300	C20—H20C	0.9600
C6—C7	1.455 (2)	O1—C27	1.2457 (16)
C7—C8	1.333 (2)	O2—C27	1.2586 (16)
C7—H7A	0.9300	O3—C25	1.3468 (16)
C8—C9	1.462 (2)	O3—H1O3	0.9910
C8—H8A	0.9300	C21—C22	1.3819 (18)
C9—C10	1.4017 (19)	C21—C26	1.3888 (17)
C9—C14	1.4061 (18)	C21—H21A	0.9300
C10—C11	1.367 (3)	C22—C23	1.380 (2)
C10—H10A	0.9300	C22—H22A	0.9300
C11—C12	1.378 (2)	C23—C24	1.364 (2)
C11—H11A	0.9300	C23—H23A	0.9300
C12—C13	1.3855 (19)	C24—C25	1.3907 (19)
C12—H12A	0.9300	C24—H24A	0.9300
C13—C14	1.3887 (19)	C25—C26	1.3984 (17)
C13—H13A	0.9300	C26—C27	1.4988 (16)

C19—N1—C20	110.16 (12)	C1—C15—C14	113.33 (9)
C19—N1—C18	112.70 (11)	C15—C16—C17	127.45 (12)
C20—N1—C18	109.75 (12)	C15—C16—H16A	116.3
C19—N1—H1N1	110.9	C17—C16—H16A	116.3
C20—N1—H1N1	103.5	C16—C17—C18	114.56 (11)
C18—N1—H1N1	109.5	C16—C17—H17A	108.6
C2—C1—C6	119.35 (12)	C18—C17—H17A	108.6
C2—C1—C15	119.75 (11)	C16—C17—H17B	108.6
C6—C1—C15	120.77 (11)	C18—C17—H17B	108.6
C3—C2—C1	120.88 (14)	H17A—C17—H17B	107.6
C3—C2—H2A	119.6	N1—C18—C17	114.71 (10)
C1—C2—H2A	119.6	N1—C18—H18A	108.6
C4—C3—C2	120.01 (15)	C17—C18—H18A	108.6
C4—C3—H3A	120.0	N1—C18—H18B	108.6
C2—C3—H3A	120.0	C17—C18—H18B	108.6
C5—C4—C3	120.11 (14)	H18A—C18—H18B	107.6
C5—C4—H4A	119.9	N1—C19—H19A	109.5
C3—C4—H4A	119.9	N1—C19—H19B	109.5
C4—C5—C6	121.47 (15)	H19A—C19—H19B	109.5
C4—C5—H5A	119.3	N1—C19—H19C	109.5
C6—C5—H5A	119.3	H19A—C19—H19C	109.5
C1—C6—C5	118.11 (13)	H19B—C19—H19C	109.5
C1—C6—C7	122.59 (12)	N1—C20—H20A	109.5
C5—C6—C7	119.24 (13)	N1—C20—H20B	109.5
C8—C7—C6	127.09 (13)	H20A—C20—H20B	109.5
C8—C7—H7A	116.5	N1—C20—H20C	109.5
C6—C7—H7A	116.5	H20A—C20—H20C	109.5
C7—C8—C9	127.38 (13)	H20B—C20—H20C	109.5
C7—C8—H8A	116.3	C25—O3—H1O3	102.1
C9—C8—H8A	116.3	C22—C21—C26	120.81 (13)
C10—C9—C14	117.85 (14)	C22—C21—H21A	119.6
C10—C9—C8	119.14 (13)	C26—C21—H21A	119.6
C14—C9—C8	123.00 (12)	C23—C22—C21	119.49 (14)
C11—C10—C9	121.92 (15)	C23—C22—H22A	120.3
C11—C10—H10A	119.0	C21—C22—H22A	120.3
C9—C10—H10A	119.0	C24—C23—C22	120.90 (13)
C10—C11—C12	119.78 (14)	C24—C23—H23A	119.5
C10—C11—H11A	120.1	C22—C23—H23A	119.5
C12—C11—H11A	120.1	C23—C24—C25	120.11 (13)
C11—C12—C13	120.04 (15)	C23—C24—H24A	119.9
C11—C12—H12A	120.0	C25—C24—H24A	119.9
C13—C12—H12A	120.0	O3—C25—C24	119.13 (12)
C12—C13—C14	120.62 (14)	O3—C25—C26	120.96 (12)
C12—C13—H13A	119.7	C24—C25—C26	119.91 (12)
C14—C13—H13A	119.7	C21—C26—C25	118.77 (11)
C13—C14—C9	119.76 (12)	C21—C26—C27	121.09 (11)
C13—C14—C15	120.17 (11)	C25—C26—C27	120.13 (11)
C9—C14—C15	120.06 (11)	O1—C27—O2	123.33 (12)
C16—C15—C1	124.75 (11)	O1—C27—C26	118.89 (11)
C16—C15—C14	121.83 (11)	O2—C27—C26	117.77 (12)

C6—C1—C2—C3	−1.77 (17)	C6—C1—C15—C16	118.97 (14)
C15—C1—C2—C3	−177.74 (11)	C2—C1—C15—C14	111.50 (12)
C1—C2—C3—C4	0.0 (2)	C6—C1—C15—C14	−64.41 (14)
C2—C3—C4—C5	0.2 (2)	C13—C14—C15—C16	61.58 (16)
C3—C4—C5—C6	1.3 (2)	C9—C14—C15—C16	−119.26 (14)
C2—C1—C6—C5	3.19 (17)	C13—C14—C15—C1	−115.15 (12)
C15—C1—C6—C5	179.12 (11)	C9—C14—C15—C1	64.01 (14)
C2—C1—C6—C7	−173.92 (11)	C1—C15—C16—C17	−7.0 (2)
C15—C1—C6—C7	2.01 (17)	C14—C15—C16—C17	176.69 (11)
C4—C5—C6—C1	−3.0 (2)	C15—C16—C17—C18	134.27 (14)
C4—C5—C6—C7	174.19 (13)	C19—N1—C18—C17	−67.76 (14)
C1—C6—C7—C8	36.3 (2)	C20—N1—C18—C17	169.07 (12)
C5—C6—C7—C8	−140.80 (16)	C16—C17—C18—N1	−73.67 (15)
C6—C7—C8—C9	−1.2 (2)	C26—C21—C22—C23	0.3 (2)
C7—C8—C9—C10	144.17 (16)	C21—C22—C23—C24	−0.6 (2)
C7—C8—C9—C14	−34.8 (2)	C22—C23—C24—C25	0.0 (2)
C14—C9—C10—C11	2.4 (2)	C23—C24—C25—O3	−179.97 (14)
C8—C9—C10—C11	−176.58 (15)	C23—C24—C25—C26	1.1 (2)
C9—C10—C11—C12	−1.1 (3)	C22—C21—C26—C25	0.73 (19)
C10—C11—C12—C13	−0.5 (2)	C22—C21—C26—C27	−179.26 (13)
C11—C12—C13—C14	0.7 (2)	O3—C25—C26—C21	179.66 (12)
C12—C13—C14—C9	0.62 (19)	C24—C25—C26—C21	−1.40 (19)
C12—C13—C14—C15	179.78 (12)	O3—C25—C26—C27	−0.35 (19)
C10—C9—C14—C13	−2.13 (18)	C24—C25—C26—C27	178.59 (12)
C8—C9—C14—C13	176.83 (12)	C21—C26—C27—O1	4.18 (19)
C10—C9—C14—C15	178.71 (12)	C25—C26—C27—O1	−175.80 (12)
C8—C9—C14—C15	−2.33 (19)	C21—C26—C27—O2	−176.97 (13)
C2—C1—C15—C16	−65.12 (16)	C25—C26—C27—O2	3.04 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.91	1.75	2.6439 (16)	167
O3—H1O3···O2	0.99	1.55	2.4890 (19)	157

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂N⁺·C₇H₅O₃⁻
M_r	413.50
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.4700 (8), 10.8408 (12), 14.9724 (16)
α, β, γ (°)	76.073 (2), 77.357 (1), 72.574 (2)
V (Å³)	1108.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.21 × 0.15

Data collection
Diffractometer	Bruker APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.971, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	22974, 6461, 4411
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.134, 1.04
No. of reflections	6461
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.91	1.75	2.6439 (16)	167
O3—H1O3···O2	0.99	1.55	2.4890 (19)	157

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5523-2009.

Acknowledgements

H-KF and CSY thank Universiti Sains Malaysia for the Research University Grant 1001/PFIZIK/811160. MSS thanks UOM for research facilities.

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