Orphenadrinium dihydrogen citrate

Kaur, M.; Jasinski, J.P.; Keeley, A.C.; Yathirajan, H.S.; Siddaraju, B.P.

doi:10.1107/S1600536813001207

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o248

doi:10.1107/S1600536813001207

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Orphenadrinium dihydrogen citrate

Manpreet Kaur,^a Jerry P. Jasinski,^b ^* Amanda C. Keeley,^b H. S. Yathirajan ^a and B. P. Siddaraju ^c

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cDepartment of Chemistry, G. Madegowda Institute of Technology, Bharathinagara 571 442, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 11 January 2013; accepted 12 January 2013; online 19 January 2013)

In the title salt, C₁₈H₂₄NO⁺·C₆H₇O₇⁻, the dihedral angle between the benzene rings in the cation is 74.2 (5)°. In the crystal, anion–anion O—H⋯O hydrogen bonds and weak O—H⋯O interactions form infinite chains along [100]. Between these chains, cation–anion N—H—O hydrogen bonds are observed, forming an alternate pattern of cation and anion layers and leading to a two-dimensional network parallel to (100).

Related literature

For a clinical and pharmacological review of the efficacy of orphenadrine, see: Hunskaar & Donnel (1991 ). For related structures, see: Fun et al. (2010 ); Glaser et al. (1992 ); Jasinski et al. (2011 ). For standard bond lengths, see Allen et al. (1987 ).

Experimental

Crystal data

C₁₈H₂₄NO⁺·C₆H₇O₇⁻
M_r = 461.50
Triclinic, $[P \overline 1]$
a = 9.9515 (8) Å
b = 10.7382 (9) Å
c = 12.625 (1) Å
α = 98.863 (7)°
β = 104.391 (7)°
γ = 111.498 (8)°
V = 1170.0 (2) Å³
Z = 2
Cu Kα radiation
μ = 0.82 mm⁻¹
T = 173 K
0.32 × 0.28 × 0.14 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.854, T_max = 1.000
7161 measured reflections
4471 independent reflections
3795 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.161
S = 1.03
4471 reflections
305 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.91	1.83	2.725 (2)	167
O4—H4A⋯O8ⁱⁱ	0.82	2.30	3.067 (2)	156
O7—H7A⋯O5ⁱⁱ	0.82	1.81	2.634 (2)	178
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); 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 global, I. DOI: 10.1107/S1600536813001207/hg5283sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001207/hg5283Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813001207/hg5283Isup3.cml

checkCIF report

Comment top

Orphenadrine (systematic IUPAC name: N,N-dimethyl-2-[(2-methylphenyl) phenyl-methoxy]ethanamine) is an anticholinergic drug of the ethanolamine antihistamine class with prominent CNS and peripheral actions used to treat painful muscle spasm and other symptoms and conditions as well as some aspects of Parkinson's disease. It is closely related to diphenhydramine and therefore related to other drugs used for Parkinson's disease like benztropine and trihexyphenidyl and is also structurally related to nefopam, a centrally acting yet non-opioid analgesic. Clinical and pharmacological review of the efficacy of orphenadrine and its combination with paracetamol has been described (Hunskaar & Donnel, 1991). Orphenadrine citrate is a skeletal muscle relaxant. It acts in the central nervous system to produce its muscle relaxant effects. The orphenadrine salt used for Parkinsonism is the hydrochloride, whereas the muscle relaxant tablet is the citrate. The solid-state structure of orphenadrine hydrochloride and conformational comparisons with diphenhydramine hydrochloride and nefopam hydrochloride is reported (Glaser et al., 1992). The crystal structure of orphenadrinium picrate picric acid (Fun et al., 2010) and orphenadrinium picrate (Jasinski et al., 2011) is recently reported. In view of the importance of orphenadrine, this paper reports the crystal structure of the title salt, (I), C₁₈H₂₄NO⁺. C₆H₇O₇^-.

In the title salt, C₁₈H₂₄NO⁺. C₆H₇O₇^-, one cation-anion pair crystallizes in the asymmetric unit (Fig. 1). The cation contains a positively charged N atom with quaternary character. The anion consists of a dihydrogen citrate counterion. The dihedral angle between the two benzene rings in the cation is 74.2 (5)°. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal anion-anion O—H···O hydrogen bonds and weak O—H···O intermolecular interactions form infinite chains along [100] (Table 1). In between these chains cation-anion N—H—O hydrogen bonds are observed forming an alternate pattern of cation and anion layers forming a two-dimensional network providing additional crystal stability (Fig. 2).

Related literature top

For a clinical and pharmacological review of the efficacy of orphenadrine, see: Hunskaar & Donnel (1991). For related structures, see: Fun et al. (2010); Glaser et al. (1992); Jasinski et al. (2011). For standard bond lengths, see Allen et al. (1987).

Experimental top

The title compound was obtained as a gift sample from R. L. Fine Chem, Bengaluru. The compound was recrystallized from methanol by slow evaporation (m. p.: 410 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); 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. Molecular structure of the title salt showing the atom labeling scheme and 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the c axis. Dashed lines indicate O—H···O anion-anion hydrogen bonds and weak O—H···O intemolecular interactions in concert with cation-anion N—H···O hydrogen bonds forming an infinite two-dimensional network long [100]. The hydrogen atoms not involved in hydrogen bonding have been removed for clarity.

N,N-Dimethyl-2-[(2-methylphenyl)(phenyl)methoxy]ethanaminium 2-carboxylatomethyl-2-hydroxybutanedioic acid top

Crystal data top

C₁₈H₂₄NO⁺·C₆H₇O₇⁻	Z = 2
M_r = 461.50	F(000) = 492
Triclinic, P1	D_x = 1.310 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 9.9515 (8) Å	Cell parameters from 3067 reflections
b = 10.7382 (9) Å	θ = 5.1–72.4°
c = 12.625 (1) Å	µ = 0.82 mm⁻¹
α = 98.863 (7)°	T = 173 K
β = 104.391 (7)°	Chunk, colorless
γ = 111.498 (8)°	0.32 × 0.28 × 0.14 mm
V = 1170.0 (2) Å³

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	4471 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3795 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.0416 pixels mm^-1	θ_max = 72.5°, θ_min = 5.1°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −13→9
T_min = 0.854, T_max = 1.000	l = −11→15
7161 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0849P)² + 0.4888P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4471 reflections	Δρ_max = 0.67 e Å⁻³
305 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (7)

Crystal data top

C₁₈H₂₄NO⁺·C₆H₇O₇⁻	γ = 111.498 (8)°
M_r = 461.50	V = 1170.0 (2) Å³
Triclinic, P1	Z = 2
a = 9.9515 (8) Å	Cu Kα radiation
b = 10.7382 (9) Å	µ = 0.82 mm⁻¹
c = 12.625 (1) Å	T = 173 K
α = 98.863 (7)°	0.32 × 0.28 × 0.14 mm
β = 104.391 (7)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	4471 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	3795 reflections with I > 2σ(I)
T_min = 0.854, T_max = 1.000	R_int = 0.029
7161 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.03	Δρ_max = 0.67 e Å⁻³
4471 reflections	Δρ_min = −0.27 e Å⁻³
305 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O1	0.37357 (15)	0.09276 (13)	0.64965 (11)	0.0291 (3)
N1	0.22933 (17)	−0.11367 (16)	0.42955 (13)	0.0264 (3)
H1	0.2851	−0.1302	0.4902	0.032*
C1	0.3807 (2)	0.16847 (19)	0.75611 (16)	0.0308 (4)
H1A	0.3877	0.2604	0.7502	0.037*
C2	0.5265 (2)	0.1874 (2)	0.84411 (16)	0.0332 (4)
C3	0.5437 (3)	0.0782 (3)	0.8789 (2)	0.0501 (6)
H3	0.4637	−0.0104	0.8503	0.060*
C4	0.6844 (3)	0.1009 (3)	0.9589 (2)	0.0575 (7)
H4	0.6981	0.0274	0.9829	0.069*
C5	0.7998 (3)	0.2326 (3)	1.00022 (19)	0.0528 (6)
H5	0.8914	0.2479	1.0538	0.063*
C6	0.7842 (3)	0.3411 (3)	0.9652 (2)	0.0582 (7)
H6	0.8650	0.4292	0.9931	0.070*
C7	0.6485 (3)	0.3199 (3)	0.8885 (2)	0.0491 (6)
H7	0.6371	0.3946	0.8654	0.059*
C8	0.2379 (2)	0.0950 (2)	0.78589 (16)	0.0328 (4)
C9	0.1917 (3)	0.1694 (3)	0.85948 (19)	0.0458 (6)
C10	0.0579 (3)	0.0950 (4)	0.8824 (2)	0.0572 (7)
H10	0.0255	0.1428	0.9308	0.069*
C11	−0.0264 (3)	−0.0451 (4)	0.8358 (2)	0.0590 (8)
H11	−0.1147	−0.0910	0.8524	0.071*
C12	0.0196 (3)	−0.1178 (3)	0.7648 (2)	0.0498 (6)
H12	−0.0371	−0.2131	0.7330	0.060*
C13	0.1520 (2)	−0.0476 (2)	0.74054 (18)	0.0366 (5)
H13	0.1836	−0.0974	0.6929	0.044*
C14	0.2779 (4)	0.3211 (3)	0.9121 (3)	0.0717 (9)
H14A	0.2768	0.3689	0.8538	0.107*
H14B	0.3817	0.3417	0.9541	0.107*
H14C	0.2310	0.3511	0.9626	0.107*
C15	0.2805 (3)	0.1145 (2)	0.55634 (17)	0.0366 (5)
H15A	0.3163	0.2133	0.5625	0.044*
H15B	0.1755	0.0790	0.5559	0.044*
C16	0.2882 (2)	0.0405 (2)	0.44869 (17)	0.0345 (4)
H16A	0.2293	0.0599	0.3850	0.041*
H16B	0.3938	0.0774	0.4506	0.041*
C17	0.2536 (2)	−0.1766 (2)	0.32629 (17)	0.0358 (5)
H17A	0.3604	−0.1348	0.3348	0.054*
H17B	0.1958	−0.1607	0.2608	0.054*
H17C	0.2203	−0.2748	0.3167	0.054*
C18	0.0653 (2)	−0.1824 (2)	0.41988 (19)	0.0390 (5)
H18A	0.0046	−0.1606	0.3601	0.059*
H18B	0.0529	−0.1497	0.4904	0.059*
H18C	0.0327	−0.2813	0.4029	0.059*
O2	0.96502 (19)	0.50720 (18)	0.23817 (14)	0.0532 (5)
O3	0.95333 (16)	0.41174 (16)	0.38238 (13)	0.0393 (4)
H3A	1.0444	0.4654	0.4097	0.059*
O4	0.71300 (17)	0.54785 (13)	0.37166 (12)	0.0349 (3)
H4A	0.7126	0.5707	0.4366	0.052*
O5	0.74662 (15)	0.41508 (14)	0.53041 (11)	0.0331 (3)
O6	0.63438 (16)	0.20588 (14)	0.40442 (12)	0.0346 (3)
O7	0.3624 (2)	0.49402 (19)	0.31971 (15)	0.0492 (4)
H7A	0.3266	0.5218	0.3652	0.074*
O8	0.37201 (18)	0.34828 (16)	0.42549 (14)	0.0416 (4)
C19	0.3967 (2)	0.3938 (2)	0.34734 (17)	0.0321 (4)
C20	0.4731 (2)	0.3428 (2)	0.27215 (17)	0.0334 (4)
H20A	0.4537	0.3712	0.2027	0.040*
H20B	0.4292	0.2419	0.2518	0.040*
C21	0.6483 (2)	0.40111 (19)	0.33243 (16)	0.0293 (4)
C22	0.6792 (2)	0.33436 (19)	0.43087 (16)	0.0280 (4)
C23	0.7190 (2)	0.3641 (2)	0.24405 (17)	0.0322 (4)
H23A	0.6873	0.2643	0.2233	0.039*
H23B	0.6799	0.3893	0.1762	0.039*
C24	0.8912 (2)	0.4362 (2)	0.28604 (17)	0.0342 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0349 (7)	0.0325 (7)	0.0252 (7)	0.0184 (6)	0.0105 (5)	0.0109 (5)
N1	0.0263 (8)	0.0323 (8)	0.0251 (7)	0.0157 (6)	0.0095 (6)	0.0101 (6)
C1	0.0404 (11)	0.0278 (9)	0.0283 (9)	0.0180 (8)	0.0118 (8)	0.0090 (7)
C2	0.0361 (10)	0.0412 (11)	0.0253 (9)	0.0174 (9)	0.0129 (8)	0.0102 (8)
C3	0.0409 (12)	0.0553 (14)	0.0614 (15)	0.0224 (11)	0.0167 (11)	0.0313 (12)
C4	0.0664 (17)	0.0791 (19)	0.0546 (15)	0.0466 (16)	0.0286 (13)	0.0389 (14)
C5	0.0428 (13)	0.0832 (19)	0.0266 (10)	0.0263 (13)	0.0084 (9)	0.0053 (11)
C6	0.0465 (14)	0.0612 (16)	0.0493 (14)	0.0168 (12)	0.0071 (11)	−0.0025 (12)
C7	0.0484 (13)	0.0443 (12)	0.0469 (13)	0.0179 (11)	0.0130 (11)	0.0005 (10)
C8	0.0368 (10)	0.0464 (11)	0.0268 (9)	0.0272 (9)	0.0116 (8)	0.0150 (8)
C9	0.0537 (14)	0.0657 (15)	0.0340 (11)	0.0427 (12)	0.0143 (10)	0.0136 (10)
C10	0.0616 (16)	0.104 (2)	0.0393 (12)	0.0599 (17)	0.0272 (12)	0.0284 (14)
C11	0.0410 (13)	0.102 (2)	0.0510 (15)	0.0371 (15)	0.0231 (12)	0.0378 (16)
C12	0.0377 (12)	0.0678 (16)	0.0487 (13)	0.0217 (11)	0.0155 (10)	0.0285 (12)
C13	0.0363 (10)	0.0476 (12)	0.0336 (10)	0.0219 (9)	0.0132 (8)	0.0190 (9)
C14	0.096 (2)	0.074 (2)	0.0606 (17)	0.0541 (19)	0.0309 (17)	0.0065 (15)
C15	0.0526 (12)	0.0351 (10)	0.0280 (10)	0.0257 (10)	0.0091 (9)	0.0133 (8)
C16	0.0440 (11)	0.0340 (10)	0.0281 (9)	0.0177 (9)	0.0105 (8)	0.0149 (8)
C17	0.0399 (11)	0.0468 (12)	0.0285 (10)	0.0242 (9)	0.0151 (8)	0.0102 (8)
C18	0.0274 (10)	0.0494 (12)	0.0383 (11)	0.0145 (9)	0.0120 (8)	0.0093 (9)
O2	0.0459 (9)	0.0542 (10)	0.0379 (9)	−0.0012 (8)	0.0148 (7)	0.0088 (7)
O3	0.0296 (7)	0.0457 (8)	0.0417 (8)	0.0149 (6)	0.0121 (6)	0.0121 (7)
O4	0.0454 (8)	0.0265 (7)	0.0360 (7)	0.0169 (6)	0.0155 (6)	0.0095 (6)
O5	0.0300 (7)	0.0403 (8)	0.0317 (7)	0.0180 (6)	0.0104 (6)	0.0092 (6)
O6	0.0375 (8)	0.0299 (7)	0.0388 (8)	0.0170 (6)	0.0096 (6)	0.0137 (6)
O7	0.0714 (11)	0.0648 (11)	0.0521 (10)	0.0544 (10)	0.0361 (9)	0.0359 (9)
O8	0.0487 (9)	0.0396 (8)	0.0515 (9)	0.0239 (7)	0.0257 (7)	0.0246 (7)
C19	0.0279 (9)	0.0339 (10)	0.0366 (10)	0.0155 (8)	0.0083 (8)	0.0134 (8)
C20	0.0347 (10)	0.0382 (10)	0.0322 (10)	0.0212 (9)	0.0088 (8)	0.0121 (8)
C21	0.0321 (10)	0.0267 (9)	0.0329 (10)	0.0151 (8)	0.0114 (8)	0.0108 (7)
C22	0.0249 (9)	0.0325 (9)	0.0323 (10)	0.0159 (8)	0.0108 (7)	0.0122 (8)
C23	0.0347 (10)	0.0313 (9)	0.0324 (10)	0.0156 (8)	0.0120 (8)	0.0083 (8)
C24	0.0368 (10)	0.0307 (9)	0.0313 (10)	0.0116 (8)	0.0133 (8)	0.0016 (8)

Geometric parameters (Å, º) top

O1—C15	1.415 (2)	C14—H14B	0.9600
O1—C1	1.431 (2)	C14—H14C	0.9600
N1—C18	1.488 (2)	C15—C16	1.500 (3)
N1—C17	1.490 (2)	C15—H15A	0.9700
N1—C16	1.496 (2)	C15—H15B	0.9700
N1—H1	0.9100	C16—H16A	0.9700
C1—C2	1.514 (3)	C16—H16B	0.9700
C1—C8	1.522 (3)	C17—H17A	0.9600
C1—H1A	0.9800	C17—H17B	0.9600
C2—C3	1.366 (3)	C17—H17C	0.9600
C2—C7	1.400 (3)	C18—H18A	0.9600
C3—C4	1.418 (4)	C18—H18B	0.9600
C3—H3	0.9300	C18—H18C	0.9600
C4—C5	1.369 (4)	O2—C24	1.200 (3)
C4—H4	0.9300	O3—C24	1.332 (3)
C5—C6	1.354 (4)	O3—H3A	0.8200
C5—H5	0.9300	O4—C21	1.414 (2)
C6—C7	1.367 (4)	O4—H4A	0.8200
C6—H6	0.9300	O5—C22	1.265 (2)
C7—H7	0.9300	O6—C22	1.244 (2)
C8—C13	1.389 (3)	O7—C19	1.313 (2)
C8—C9	1.403 (3)	O7—H7A	0.8200
C9—C10	1.406 (4)	O8—C19	1.206 (2)
C9—C14	1.480 (4)	C19—C20	1.511 (3)
C10—C11	1.368 (4)	C20—C21	1.550 (3)
C10—H10	0.9300	C20—H20A	0.9700
C11—C12	1.368 (4)	C20—H20B	0.9700
C11—H11	0.9300	C21—C23	1.535 (3)
C12—C13	1.394 (3)	C21—C22	1.549 (3)
C12—H12	0.9300	C23—C24	1.505 (3)
C13—H13	0.9300	C23—H23A	0.9700
C14—H14A	0.9600	C23—H23B	0.9700

C15—O1—C1	112.03 (14)	O1—C15—C16	108.73 (16)
C18—N1—C17	109.99 (15)	O1—C15—H15A	109.9
C18—N1—C16	113.44 (15)	C16—C15—H15A	109.9
C17—N1—C16	109.95 (15)	O1—C15—H15B	109.9
C18—N1—H1	107.8	C16—C15—H15B	109.9
C17—N1—H1	107.8	H15A—C15—H15B	108.3
C16—N1—H1	107.8	N1—C16—C15	113.81 (16)
O1—C1—C2	107.13 (15)	N1—C16—H16A	108.8
O1—C1—C8	111.31 (16)	C15—C16—H16A	108.8
C2—C1—C8	112.95 (15)	N1—C16—H16B	108.8
O1—C1—H1A	108.4	C15—C16—H16B	108.8
C2—C1—H1A	108.4	H16A—C16—H16B	107.7
C8—C1—H1A	108.4	N1—C17—H17A	109.5
C3—C2—C7	119.2 (2)	N1—C17—H17B	109.5
C3—C2—C1	121.8 (2)	H17A—C17—H17B	109.5
C7—C2—C1	119.03 (19)	N1—C17—H17C	109.5
C2—C3—C4	119.5 (2)	H17A—C17—H17C	109.5
C2—C3—H3	120.2	H17B—C17—H17C	109.5
C4—C3—H3	120.2	N1—C18—H18A	109.5
C5—C4—C3	119.0 (2)	N1—C18—H18B	109.5
C5—C4—H4	120.5	H18A—C18—H18B	109.5
C3—C4—H4	120.5	N1—C18—H18C	109.5
C6—C5—C4	121.8 (2)	H18A—C18—H18C	109.5
C6—C5—H5	119.1	H18B—C18—H18C	109.5
C4—C5—H5	119.1	C24—O3—H3A	109.5
C5—C6—C7	119.4 (3)	C21—O4—H4A	109.5
C5—C6—H6	120.3	C19—O7—H7A	109.5
C7—C6—H6	120.3	O8—C19—O7	123.69 (19)
C6—C7—C2	121.1 (2)	O8—C19—C20	123.37 (17)
C6—C7—H7	119.5	O7—C19—C20	112.93 (17)
C2—C7—H7	119.5	C19—C20—C21	111.50 (16)
C13—C8—C9	119.1 (2)	C19—C20—H20A	109.3
C13—C8—C1	120.07 (17)	C21—C20—H20A	109.3
C9—C8—C1	120.8 (2)	C19—C20—H20B	109.3
C8—C9—C10	117.7 (2)	C21—C20—H20B	109.3
C8—C9—C14	122.4 (2)	H20A—C20—H20B	108.0
C10—C9—C14	119.9 (2)	O4—C21—C23	107.28 (15)
C11—C10—C9	122.3 (2)	O4—C21—C22	111.65 (15)
C11—C10—H10	118.8	C23—C21—C22	110.56 (15)
C9—C10—H10	118.8	O4—C21—C20	110.38 (14)
C12—C11—C10	119.9 (2)	C23—C21—C20	107.75 (16)
C12—C11—H11	120.1	C22—C21—C20	109.14 (15)
C10—C11—H11	120.1	O6—C22—O5	126.11 (17)
C11—C12—C13	119.4 (3)	O6—C22—C21	116.70 (16)
C11—C12—H12	120.3	O5—C22—C21	117.19 (16)
C13—C12—H12	120.3	C24—C23—C21	113.05 (16)
C8—C13—C12	121.5 (2)	C24—C23—H23A	109.0
C8—C13—H13	119.2	C21—C23—H23A	109.0
C12—C13—H13	119.2	C24—C23—H23B	109.0
C9—C14—H14A	109.5	C21—C23—H23B	109.0
C9—C14—H14B	109.5	H23A—C23—H23B	107.8
H14A—C14—H14B	109.5	O2—C24—O3	123.4 (2)
C9—C14—H14C	109.5	O2—C24—C23	124.1 (2)
H14A—C14—H14C	109.5	O3—C24—C23	112.52 (17)
H14B—C14—H14C	109.5

C15—O1—C1—C2	−156.91 (16)	C10—C11—C12—C13	−0.2 (4)
C15—O1—C1—C8	79.15 (19)	C9—C8—C13—C12	1.2 (3)
O1—C1—C2—C3	−69.6 (2)	C1—C8—C13—C12	−179.11 (19)
C8—C1—C2—C3	53.3 (3)	C11—C12—C13—C8	−0.7 (3)
O1—C1—C2—C7	108.4 (2)	C1—O1—C15—C16	175.89 (16)
C8—C1—C2—C7	−128.6 (2)	C18—N1—C16—C15	61.1 (2)
C7—C2—C3—C4	−0.1 (4)	C17—N1—C16—C15	−175.25 (17)
C1—C2—C3—C4	178.0 (2)	O1—C15—C16—N1	61.9 (2)
C2—C3—C4—C5	0.5 (4)	O8—C19—C20—C21	−76.4 (2)
C3—C4—C5—C6	−1.3 (4)	O7—C19—C20—C21	102.6 (2)
C4—C5—C6—C7	1.6 (4)	C19—C20—C21—O4	−54.0 (2)
C5—C6—C7—C2	−1.1 (4)	C19—C20—C21—C23	−170.86 (15)
C3—C2—C7—C6	0.4 (4)	C19—C20—C21—C22	69.05 (19)
C1—C2—C7—C6	−177.8 (2)	O4—C21—C22—O6	−176.07 (15)
O1—C1—C8—C13	24.5 (2)	C23—C21—C22—O6	−56.7 (2)
C2—C1—C8—C13	−96.0 (2)	C20—C21—C22—O6	61.6 (2)
O1—C1—C8—C9	−155.81 (17)	O4—C21—C22—O5	4.3 (2)
C2—C1—C8—C9	83.6 (2)	C23—C21—C22—O5	123.66 (17)
C13—C8—C9—C10	−0.9 (3)	C20—C21—C22—O5	−117.99 (18)
C1—C8—C9—C10	179.40 (18)	O4—C21—C23—C24	51.0 (2)
C13—C8—C9—C14	179.4 (2)	C22—C21—C23—C24	−71.0 (2)
C1—C8—C9—C14	−0.3 (3)	C20—C21—C23—C24	169.85 (16)
C8—C9—C10—C11	0.1 (3)	C21—C23—C24—O2	−124.6 (2)
C14—C9—C10—C11	179.8 (2)	C21—C23—C24—O3	55.7 (2)
C9—C10—C11—C12	0.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.91	1.83	2.725 (2)	167
O4—H4A···O8ⁱⁱ	0.82	2.30	3.067 (2)	156
O7—H7A···O5ⁱⁱ	0.82	1.81	2.634 (2)	178

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₄NO⁺·C₆H₇O₇⁻
M_r	461.50
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	9.9515 (8), 10.7382 (9), 12.625 (1)
α, β, γ (°)	98.863 (7), 104.391 (7), 111.498 (8)
V (Å³)	1170.0 (2)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.32 × 0.28 × 0.14

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)
T_min, T_max	0.854, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7161, 4471, 3795
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.161, 1.03
No. of reflections	4471
No. of parameters	305
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.27

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), 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—H1···O6ⁱ	0.91	1.83	2.725 (2)	166.5
O4—H4A···O8ⁱⁱ	0.82	2.30	3.067 (2)	155.6
O7—H7A···O5ⁱⁱ	0.82	1.81	2.634 (2)	178.1

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.

Acknowledgements

MK and HSY thank the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

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