organic compounds
of {[2-hydroxy-2-(3-methoxyphenyl)cyclohexyl]methyl}dimethylammonium benzoate
aDepartment of Chemistry, GSSS Institute of Engineering Technology for Women, Mysuru 570 016, India, bDepartment of Chemistry, BET Academy of Higher Education, Bharathi College, Bharthi Nagara, Mandya 571 422, India, cDepartment of Engineering Chemistry, Cauvery Institute of Technology, Mandya 571 402, India, dDepartment of Chemistry, Cambridge institute of Technology, Bengaluru 560 036, India, eDepartment of Materials Science, Mangalagangotri, Mangalore University, Mangaluru 574 199, India, fDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore, 570 006, India, and gPURSE Lab, Mangalagangotri, Mangalore University, Mangaluru 574 199, India
*Correspondence e-mail: madan.mx@gmail.com
The title compound, C16H26NO2+·C7H5O2−, is a benzoate salt of the painkiller Tramadol. The six-membered cyclohexane ring of the cation adopts a slightly distorted chair conformation and carries OH and 3-methoxyphenyl substituents at the 2-position and a protonated methylazaniumylmethyl group at the 3-position. In addition, a weak intramolecular C—H⋯O hydrogen bond is observed in the cation. In the crystal, weak O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the components into chains along [010]. A C—H⋯π contact is also observed.
Keywords: crystal structure; Tramadol; intermolecular hydrogen bonds.
CCDC reference: 1425991
1. Related literature
For pharmaceutical applications of Tramadol and related analgesics, see: Scott & Perry (2000). For related structures, see: Tessler & Goldberg (2004); Arman et al. (2010); Hemamalini & Fun (2010); Siddaraju et al. (2011); Lin & Zhang (2013); Smith (2014); Jasinski et al. (2015); Sun et al. (2012).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: CrystalClear SM Expert (Rigaku, 2011); cell CrystalClear SM Expert; data reduction: CrystalClear SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2.
Supporting information
CCDC reference: 1425991
https://doi.org/10.1107/S2056989015019362/sj5480sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019362/sj5480Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015019362/sj5480Isup3.cml
Tramadol (3 g, 0.01 mol) and benzoic acid (1 g, 0.01 mol) were each dissolved in 10 ml of ethanol. The solutions were mixed and stirred in a beaker at 333 K for 30 minutes. The mixture was kept aside for three days at room temperature. Colourless X-ray quality crystals were formed and one was used for the data collection
Crystal data, data collection and structure
details are summarized in Table 1. The hydrogen atoms were fixed geometrically (C—H = 0.93–0.96 Å, N—H = 0.98 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2Ueq(C/N).2-((dimethylamino)methyl)-1-(3-methoxyphenyl)cyclohexanol hydrochloride (Tramadol) is used in the treatment of disorders of the central nervous system and in treating extreme pain. This molecule is analogous to the phenanthrene alkaloid codeine and is used in the control of pre-operative pain (Scott & Perry, 2000).
There are number of crystal structures reported available related to this salt. These include Venlafaxine [(RS)-1-[2-dimethylamino-1-(4-methoxyphenyl)-ethyl]- cyclohexanol] (Tessler & Goldberg, 2004), benzoic acid-2-{(E)-[(E)-2-(2-pyridylmethylidene) hydrazin-1-ylidene]methyl}pyridine (2/1) (Arman et al., 2010), 2,3-diaminopyridinium benzoate benzoic acid solvate (Hemamalini & Fun, 2010), Tramadol hydrochloride-benzoic acid (1/1) (Siddaraju et al., 2011), 4-(cyclo-propane-carboxamido) benzoic acid (Sun et al., 2012), 3,5-bis[(pyridin-4-yl)meth-oxy]benzoic acid (Lin & Zhang, 2013). The hydrogen-bonded two- and three-dimensional polymeric structures of the ammonium salts of 3,5-di-nitro-benzoic acid, 4-nitro-benzoic acid and 2,4-di-chloro-benzoic acid (Smith, 2014) and 4-[1-(2-hydroxypropyl)-4,5-diphenyl-1H-imidazol-2-yl]benzoic acid (Jasinski et al., 2015) have also been reported. In the view of the importance of Tramadol, we report herein the
of the title compound 2-hydroxy-2-(3-methoxy-phenyl)-cyclohexylmethyl-dimethyl-ammonium benzoate.In the title molecule (Fig. 1), the six membered cyclohexane ring (C9/C11–C15) adopts a slightly distorted chair conformation with ring puckering parameters Q, θ and φ of 0.5605 (16) Å, 5.06 (16)°, and 210.3 (6)°, respectively. An intramolecular C6—H6···O10 hydrogen bond (Fig 1, Table 1) is found in the cation. Bond lengths are within normal ranges.
The
is stabilized with weak intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds and a weak intermolecular C23—H23···Cg1 interaction is also observed Table 1, Fig. 2.For pharmaceutical applications of Tramadol and related analgesics, see: Scott & Perry (2000). For related structures, see: Tessler & Goldberg (2004); Arman et al. (2010); Hemamalini & Fun (2010); Siddaraju et al. (2011); Lin & Zhang (2013); Smith (2014); Jasinski et al. (2015); Sun et al. (2012).
Data collection: CrystalClear SM Expert (Rigaku, 2011); cell
CrystalClear SM Expert (Rigaku, 2011); data reduction: CrystalClear SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).Fig. 1. A view of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level and an intramolecular hydrogen bond is drawn as a dashed line. | |
Fig. 2. A viewed along the a axis of the crystal packing of the title compound. Hydrogen bonds are drawn as a dashed lines. |
C16H26NO2+·C7H5O2− | Z = 2 |
Mr = 385.49 | F(000) = 416 |
Triclinic, P1 | Dx = 1.219 Mg m−3 |
a = 9.013 (4) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 9.767 (4) Å | Cell parameters from 5660 reflections |
c = 12.726 (6) Å | θ = 3.0–29.5° |
α = 75.008 (16)° | µ = 0.08 mm−1 |
β = 89.79 (2)° | T = 293 K |
γ = 76.493 (16)° | Block, colourless |
V = 1050.3 (8) Å3 | 0.55 × 0.51 × 0.3 mm |
Rigaku Saturn724+ diffractometer | 5660 independent reflections |
Radiation source: Sealed tube, Rotating Anode | 3504 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.029 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 29.5°, θmin = 3.0° |
profile data from ω–scans | h = −12→11 |
Absorption correction: multi-scan (NUMABS; Rigaku 1999) | k = −13→13 |
Tmin = 0.955, Tmax = 0.975 | l = −17→14 |
11931 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0598P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
5660 reflections | Δρmax = 0.17 e Å−3 |
257 parameters | Δρmin = −0.21 e Å−3 |
0 restraints |
C16H26NO2+·C7H5O2− | γ = 76.493 (16)° |
Mr = 385.49 | V = 1050.3 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.013 (4) Å | Mo Kα radiation |
b = 9.767 (4) Å | µ = 0.08 mm−1 |
c = 12.726 (6) Å | T = 293 K |
α = 75.008 (16)° | 0.55 × 0.51 × 0.3 mm |
β = 89.79 (2)° |
Rigaku Saturn724+ diffractometer | 5660 independent reflections |
Absorption correction: multi-scan (NUMABS; Rigaku 1999) | 3504 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.975 | Rint = 0.029 |
11931 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
5660 reflections | Δρmin = −0.21 e Å−3 |
257 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.51600 (17) | 0.30154 (17) | 0.58415 (12) | 0.0418 (4) | |
C2 | 0.39216 (17) | 0.38352 (18) | 0.62190 (13) | 0.0502 (4) | |
H2 | 0.2941 | 0.3959 | 0.5925 | 0.060* | |
C3 | 0.41457 (17) | 0.44717 (17) | 0.70353 (14) | 0.0520 (4) | |
H3 | 0.3314 | 0.5032 | 0.7290 | 0.062* | |
C4 | 0.56018 (16) | 0.42788 (16) | 0.74757 (13) | 0.0448 (4) | |
H4 | 0.5738 | 0.4708 | 0.8029 | 0.054* | |
C5 | 0.68653 (15) | 0.34553 (14) | 0.71072 (11) | 0.0332 (3) | |
C6 | 0.66294 (15) | 0.28320 (15) | 0.62715 (11) | 0.0366 (3) | |
H6 | 0.7459 | 0.2291 | 0.6001 | 0.044* | |
C8 | 0.6071 (2) | 0.1648 (2) | 0.45646 (15) | 0.0697 (5) | |
H8A | 0.5688 | 0.1311 | 0.4000 | 0.104* | |
H8B | 0.6659 | 0.0829 | 0.5111 | 0.104* | |
H8C | 0.6707 | 0.2297 | 0.4258 | 0.104* | |
C9 | 0.84766 (14) | 0.31719 (13) | 0.76345 (10) | 0.0310 (3) | |
C11 | 0.85527 (17) | 0.21038 (15) | 0.87622 (11) | 0.0406 (3) | |
H11A | 0.7688 | 0.2473 | 0.9152 | 0.049* | |
H11B | 0.8451 | 0.1174 | 0.8670 | 0.049* | |
C12 | 1.00060 (18) | 0.18474 (16) | 0.94543 (12) | 0.0465 (4) | |
H12A | 1.0865 | 0.1338 | 0.9130 | 0.056* | |
H12B | 0.9923 | 0.1239 | 1.0176 | 0.056* | |
C13 | 1.0282 (2) | 0.32939 (16) | 0.95426 (12) | 0.0491 (4) | |
H13A | 0.9471 | 0.3760 | 0.9929 | 0.059* | |
H13B | 1.1243 | 0.3118 | 0.9954 | 0.059* | |
C14 | 1.03296 (17) | 0.42967 (16) | 0.84145 (11) | 0.0417 (4) | |
H14A | 1.1171 | 0.3845 | 0.8044 | 0.050* | |
H14B | 1.0512 | 0.5210 | 0.8486 | 0.050* | |
C15 | 0.88435 (15) | 0.46093 (13) | 0.77334 (10) | 0.0317 (3) | |
H15 | 0.8016 | 0.5100 | 0.8107 | 0.038* | |
C16 | 0.88662 (16) | 0.56049 (14) | 0.65994 (10) | 0.0358 (3) | |
H16A | 0.9709 | 0.5144 | 0.6235 | 0.043* | |
H16B | 0.7929 | 0.5688 | 0.6190 | 0.043* | |
C18 | 0.77644 (17) | 0.79335 (16) | 0.70698 (14) | 0.0508 (4) | |
H18A | 0.6805 | 0.8004 | 0.6709 | 0.076* | |
H18B | 0.7905 | 0.8896 | 0.7005 | 0.076* | |
H18C | 0.7767 | 0.7434 | 0.7826 | 0.076* | |
C19 | 0.9145 (2) | 0.79324 (17) | 0.54203 (12) | 0.0572 (5) | |
H19A | 0.9985 | 0.7395 | 0.5112 | 0.086* | |
H19B | 0.9315 | 0.8870 | 0.5410 | 0.086* | |
H19C | 0.8215 | 0.8062 | 0.5001 | 0.086* | |
N17 | 0.90203 (13) | 0.71131 (11) | 0.65610 (9) | 0.0337 (3) | |
H17 | 0.9976 | 0.7013 | 0.6970 | 0.040* | |
O7 | 0.48324 (13) | 0.23977 (15) | 0.50425 (10) | 0.0642 (3) | |
O10 | 0.96103 (10) | 0.26098 (10) | 0.69699 (8) | 0.0372 (2) | |
H10 | 0.9774 | 0.1717 | 0.7133 | 0.056* | |
C20 | 0.38473 (18) | 0.75688 (18) | 0.88067 (13) | 0.0492 (4) | |
H20 | 0.3598 | 0.6668 | 0.8964 | 0.059* | |
C21 | 0.29160 (16) | 0.87614 (15) | 0.80738 (11) | 0.0376 (3) | |
C22 | 0.33245 (18) | 1.00897 (17) | 0.78461 (12) | 0.0471 (4) | |
H22 | 0.2706 | 1.0903 | 0.7362 | 0.056* | |
C23 | 0.4632 (2) | 1.0218 (2) | 0.83276 (14) | 0.0564 (4) | |
H23 | 0.4902 | 1.1110 | 0.8155 | 0.068* | |
C24 | 0.5540 (2) | 0.9031 (2) | 0.90636 (14) | 0.0595 (5) | |
H24 | 0.6417 | 0.9121 | 0.9396 | 0.071* | |
C25 | 0.51482 (19) | 0.7706 (2) | 0.93080 (13) | 0.0597 (5) | |
H25 | 0.5757 | 0.6903 | 0.9809 | 0.072* | |
C26 | 0.15086 (16) | 0.86086 (15) | 0.75316 (12) | 0.0385 (3) | |
O27 | 0.05139 (13) | 0.97122 (11) | 0.70637 (10) | 0.0600 (3) | |
O28 | 0.14406 (12) | 0.73144 (11) | 0.75774 (9) | 0.0529 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0387 (8) | 0.0477 (9) | 0.0414 (8) | −0.0137 (7) | 0.0007 (7) | −0.0132 (7) |
C2 | 0.0321 (8) | 0.0561 (10) | 0.0601 (10) | −0.0087 (7) | −0.0010 (7) | −0.0132 (8) |
C3 | 0.0344 (8) | 0.0496 (9) | 0.0740 (12) | −0.0053 (7) | 0.0125 (8) | −0.0245 (8) |
C4 | 0.0378 (8) | 0.0443 (9) | 0.0602 (10) | −0.0115 (7) | 0.0102 (7) | −0.0262 (7) |
C5 | 0.0323 (7) | 0.0281 (7) | 0.0405 (8) | −0.0102 (5) | 0.0069 (6) | −0.0088 (6) |
C6 | 0.0330 (7) | 0.0382 (7) | 0.0400 (8) | −0.0092 (6) | 0.0056 (6) | −0.0123 (6) |
C8 | 0.0581 (11) | 0.0930 (15) | 0.0678 (12) | −0.0084 (10) | −0.0036 (9) | −0.0474 (11) |
C9 | 0.0315 (7) | 0.0276 (6) | 0.0357 (7) | −0.0079 (5) | 0.0060 (6) | −0.0110 (5) |
C11 | 0.0485 (9) | 0.0320 (7) | 0.0422 (8) | −0.0154 (6) | 0.0049 (7) | −0.0066 (6) |
C12 | 0.0566 (10) | 0.0363 (8) | 0.0421 (8) | −0.0103 (7) | −0.0034 (7) | −0.0031 (6) |
C13 | 0.0608 (10) | 0.0446 (9) | 0.0418 (8) | −0.0145 (8) | −0.0104 (8) | −0.0094 (7) |
C14 | 0.0459 (8) | 0.0378 (8) | 0.0459 (8) | −0.0181 (7) | −0.0024 (7) | −0.0117 (6) |
C15 | 0.0373 (7) | 0.0265 (6) | 0.0340 (7) | −0.0107 (5) | 0.0048 (6) | −0.0103 (5) |
C16 | 0.0453 (8) | 0.0308 (7) | 0.0353 (7) | −0.0145 (6) | 0.0059 (6) | −0.0109 (6) |
C18 | 0.0457 (9) | 0.0358 (8) | 0.0688 (11) | −0.0039 (7) | 0.0084 (8) | −0.0157 (8) |
C19 | 0.0827 (13) | 0.0446 (9) | 0.0448 (9) | −0.0267 (9) | 0.0087 (9) | −0.0026 (7) |
N17 | 0.0359 (6) | 0.0283 (6) | 0.0367 (6) | −0.0095 (5) | 0.0029 (5) | −0.0068 (5) |
O7 | 0.0439 (7) | 0.0989 (10) | 0.0628 (7) | −0.0173 (6) | −0.0012 (6) | −0.0441 (7) |
O10 | 0.0351 (5) | 0.0303 (5) | 0.0485 (6) | −0.0063 (4) | 0.0100 (4) | −0.0159 (4) |
C20 | 0.0484 (9) | 0.0480 (9) | 0.0520 (9) | −0.0139 (7) | 0.0082 (8) | −0.0130 (7) |
C21 | 0.0389 (8) | 0.0382 (8) | 0.0414 (8) | −0.0117 (6) | 0.0102 (7) | −0.0181 (6) |
C22 | 0.0516 (9) | 0.0422 (9) | 0.0537 (9) | −0.0166 (7) | 0.0031 (8) | −0.0189 (7) |
C23 | 0.0552 (10) | 0.0590 (11) | 0.0692 (11) | −0.0273 (9) | 0.0082 (9) | −0.0298 (9) |
C24 | 0.0468 (10) | 0.0835 (14) | 0.0627 (11) | −0.0240 (10) | 0.0060 (9) | −0.0373 (10) |
C25 | 0.0486 (10) | 0.0716 (12) | 0.0551 (10) | −0.0090 (9) | −0.0020 (8) | −0.0146 (9) |
C26 | 0.0404 (8) | 0.0322 (7) | 0.0480 (9) | −0.0109 (6) | 0.0092 (7) | −0.0180 (6) |
O27 | 0.0577 (7) | 0.0345 (6) | 0.0870 (8) | −0.0044 (5) | −0.0161 (7) | −0.0205 (6) |
O28 | 0.0441 (6) | 0.0321 (5) | 0.0852 (8) | −0.0119 (5) | −0.0046 (6) | −0.0178 (5) |
C1—C2 | 1.377 (2) | C14—C15 | 1.5229 (19) |
C1—C6 | 1.389 (2) | C15—H15 | 0.9800 |
C1—O7 | 1.3739 (19) | C15—C16 | 1.5204 (18) |
C2—H2 | 0.9300 | C16—H16A | 0.9700 |
C2—C3 | 1.379 (2) | C16—H16B | 0.9700 |
C3—H3 | 0.9300 | C16—N17 | 1.5000 (17) |
C3—C4 | 1.381 (2) | C18—H18A | 0.9600 |
C4—H4 | 0.9300 | C18—H18B | 0.9600 |
C4—C5 | 1.3881 (18) | C18—H18C | 0.9600 |
C5—C6 | 1.3944 (19) | C18—N17 | 1.4771 (17) |
C5—C9 | 1.5359 (19) | C19—H19A | 0.9600 |
C6—H6 | 0.9300 | C19—H19B | 0.9600 |
C8—H8A | 0.9600 | C19—H19C | 0.9600 |
C8—H8B | 0.9600 | C19—N17 | 1.4833 (18) |
C8—H8C | 0.9600 | N17—H17 | 0.9800 |
C8—O7 | 1.4126 (19) | O10—H10 | 0.8200 |
C9—C11 | 1.5314 (19) | C20—H20 | 0.9300 |
C9—C15 | 1.5507 (18) | C20—C21 | 1.385 (2) |
C9—O10 | 1.4257 (15) | C20—C25 | 1.386 (2) |
C11—H11A | 0.9700 | C21—C22 | 1.389 (2) |
C11—H11B | 0.9700 | C21—C26 | 1.502 (2) |
C11—C12 | 1.515 (2) | C22—H22 | 0.9300 |
C12—H12A | 0.9700 | C22—C23 | 1.376 (2) |
C12—H12B | 0.9700 | C23—H23 | 0.9300 |
C12—C13 | 1.522 (2) | C23—C24 | 1.376 (2) |
C13—H13A | 0.9700 | C24—H24 | 0.9300 |
C13—H13B | 0.9700 | C24—C25 | 1.379 (2) |
C13—C14 | 1.521 (2) | C25—H25 | 0.9300 |
C14—H14A | 0.9700 | C26—O27 | 1.2412 (17) |
C14—H14B | 0.9700 | C26—O28 | 1.2661 (17) |
C2—C1—C6 | 120.59 (14) | C9—C15—H15 | 107.9 |
O7—C1—C2 | 115.75 (14) | C14—C15—C9 | 110.98 (11) |
O7—C1—C6 | 123.65 (14) | C14—C15—H15 | 107.9 |
C1—C2—H2 | 120.2 | C16—C15—C9 | 109.26 (10) |
C1—C2—C3 | 119.53 (14) | C16—C15—C14 | 112.67 (11) |
C3—C2—H2 | 120.2 | C16—C15—H15 | 107.9 |
C2—C3—H3 | 119.9 | C15—C16—H16A | 108.4 |
C2—C3—C4 | 120.17 (15) | C15—C16—H16B | 108.4 |
C4—C3—H3 | 119.9 | H16A—C16—H16B | 107.5 |
C3—C4—H4 | 119.4 | N17—C16—C15 | 115.49 (10) |
C3—C4—C5 | 121.20 (14) | N17—C16—H16A | 108.4 |
C5—C4—H4 | 119.4 | N17—C16—H16B | 108.4 |
C4—C5—C6 | 118.22 (13) | H18A—C18—H18B | 109.5 |
C4—C5—C9 | 121.36 (12) | H18A—C18—H18C | 109.5 |
C6—C5—C9 | 120.36 (12) | H18B—C18—H18C | 109.5 |
C1—C6—C5 | 120.28 (13) | N17—C18—H18A | 109.5 |
C1—C6—H6 | 119.9 | N17—C18—H18B | 109.5 |
C5—C6—H6 | 119.9 | N17—C18—H18C | 109.5 |
H8A—C8—H8B | 109.5 | H19A—C19—H19B | 109.5 |
H8A—C8—H8C | 109.5 | H19A—C19—H19C | 109.5 |
H8B—C8—H8C | 109.5 | H19B—C19—H19C | 109.5 |
O7—C8—H8A | 109.5 | N17—C19—H19A | 109.5 |
O7—C8—H8B | 109.5 | N17—C19—H19B | 109.5 |
O7—C8—H8C | 109.5 | N17—C19—H19C | 109.5 |
C5—C9—C15 | 111.34 (10) | C16—N17—H17 | 107.6 |
C11—C9—C5 | 107.75 (10) | C18—N17—C16 | 112.99 (11) |
C11—C9—C15 | 110.47 (11) | C18—N17—C19 | 110.77 (12) |
O10—C9—C5 | 110.85 (11) | C18—N17—H17 | 107.6 |
O10—C9—C11 | 111.47 (11) | C19—N17—C16 | 110.13 (10) |
O10—C9—C15 | 105.01 (10) | C19—N17—H17 | 107.6 |
C9—C11—H11A | 108.6 | C1—O7—C8 | 117.87 (12) |
C9—C11—H11B | 108.6 | C9—O10—H10 | 109.5 |
H11A—C11—H11B | 107.6 | C21—C20—H20 | 119.7 |
C12—C11—C9 | 114.67 (12) | C21—C20—C25 | 120.58 (16) |
C12—C11—H11A | 108.6 | C25—C20—H20 | 119.7 |
C12—C11—H11B | 108.6 | C20—C21—C22 | 118.47 (14) |
C11—C12—H12A | 109.6 | C20—C21—C26 | 120.42 (13) |
C11—C12—H12B | 109.6 | C22—C21—C26 | 121.10 (13) |
C11—C12—C13 | 110.42 (12) | C21—C22—H22 | 119.5 |
H12A—C12—H12B | 108.1 | C23—C22—C21 | 120.94 (15) |
C13—C12—H12A | 109.6 | C23—C22—H22 | 119.5 |
C13—C12—H12B | 109.6 | C22—C23—H23 | 119.9 |
C12—C13—H13A | 109.6 | C24—C23—C22 | 120.10 (16) |
C12—C13—H13B | 109.6 | C24—C23—H23 | 119.9 |
H13A—C13—H13B | 108.1 | C23—C24—H24 | 120.1 |
C14—C13—C12 | 110.39 (12) | C23—C24—C25 | 119.87 (16) |
C14—C13—H13A | 109.6 | C25—C24—H24 | 120.1 |
C14—C13—H13B | 109.6 | C20—C25—H25 | 120.0 |
C13—C14—H14A | 109.3 | C24—C25—C20 | 120.03 (16) |
C13—C14—H14B | 109.3 | C24—C25—H25 | 120.0 |
C13—C14—C15 | 111.70 (12) | O27—C26—C21 | 120.10 (13) |
H14A—C14—H14B | 107.9 | O27—C26—O28 | 124.15 (14) |
C15—C14—H14A | 109.3 | O28—C26—C21 | 115.75 (13) |
C15—C14—H14B | 109.3 | ||
C1—C2—C3—C4 | −0.4 (2) | C12—C13—C14—C15 | 59.28 (17) |
C2—C1—C6—C5 | 1.2 (2) | C13—C14—C15—C9 | −56.84 (15) |
C2—C1—O7—C8 | 174.83 (15) | C13—C14—C15—C16 | −179.74 (12) |
C2—C3—C4—C5 | 0.4 (2) | C14—C15—C16—N17 | −63.19 (16) |
C3—C4—C5—C6 | 0.4 (2) | C15—C9—C11—C12 | −51.00 (15) |
C3—C4—C5—C9 | −176.79 (13) | C15—C16—N17—C18 | −59.79 (16) |
C4—C5—C6—C1 | −1.23 (19) | C15—C16—N17—C19 | 175.76 (12) |
C4—C5—C9—C11 | 71.47 (15) | O7—C1—C2—C3 | 178.80 (14) |
C4—C5—C9—C15 | −49.81 (16) | O7—C1—C6—C5 | −177.88 (13) |
C4—C5—C9—O10 | −166.32 (11) | O10—C9—C11—C12 | 65.34 (15) |
C5—C9—C11—C12 | −172.82 (11) | O10—C9—C15—C14 | −68.97 (13) |
C5—C9—C15—C14 | 171.00 (10) | O10—C9—C15—C16 | 55.87 (13) |
C5—C9—C15—C16 | −64.15 (13) | C20—C21—C22—C23 | 0.7 (2) |
C6—C1—C2—C3 | −0.3 (2) | C20—C21—C26—O27 | 164.70 (14) |
C6—C1—O7—C8 | −6.0 (2) | C20—C21—C26—O28 | −16.30 (19) |
C6—C5—C9—C11 | −105.71 (14) | C21—C20—C25—C24 | −1.2 (2) |
C6—C5—C9—C15 | 133.01 (13) | C21—C22—C23—C24 | −1.4 (2) |
C6—C5—C9—O10 | 16.51 (16) | C22—C21—C26—O27 | −16.0 (2) |
C9—C5—C6—C1 | 176.03 (12) | C22—C21—C26—O28 | 163.00 (13) |
C9—C11—C12—C13 | 53.62 (16) | C22—C23—C24—C25 | 0.8 (2) |
C9—C15—C16—N17 | 172.96 (11) | C23—C24—C25—C20 | 0.5 (2) |
C11—C9—C15—C14 | 51.32 (14) | C25—C20—C21—C22 | 0.6 (2) |
C11—C9—C15—C16 | 176.17 (11) | C25—C20—C21—C26 | 179.94 (13) |
C11—C12—C13—C14 | −56.17 (17) | C26—C21—C22—C23 | −178.64 (13) |
Cg1 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O10 | 0.93 | 2.42 | 2.775 (2) | 102 |
C14—H14B···O28i | 0.97 | 2.41 | 3.251 (2) | 144 |
N17—H17···O28i | 0.98 | 1.65 | 2.6120 (18) | 165 |
O10—H10···O27ii | 0.82 | 1.94 | 2.7269 (17) | 161 |
C23—H23···Cg1iii | 0.93 | 2.83 | 3.684 (3) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) x, y+1, z. |
Cg1 is the centroid of the C1–C6 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O10 | 0.93 | 2.42 | 2.775 (2) | 102 |
C14—H14B···O28i | 0.97 | 2.41 | 3.251 (2) | 144 |
N17—H17···O28i | 0.98 | 1.65 | 2.6120 (18) | 165 |
O10—H10···O27ii | 0.82 | 1.94 | 2.7269 (17) | 161 |
C23—H23···Cg1iii | 0.93 | 2.83 | 3.684 (3) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) x, y+1, z. |
Acknowledgements
The authors thank DST–PURSE, Mangalore University, Mangaluru, for providing the single-crystal X-ray diffraction facility. PN thanks Bharthi College, Maddur, for research facilities.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
2-((dimethylamino)methyl)-1-(3-methoxyphenyl)cyclohexanol hydrochloride (Tramadol) is used in the treatment of disorders of the central nervous system and in treating extreme pain. This molecule is analogous to the phenanthrene alkaloid codeine and is used in the control of pre-operative pain (Scott & Perry, 2000).
There are number of crystal structures reported available related to this salt. These include Venlafaxine [(RS)-1-[2-dimethylamino-1-(4-methoxyphenyl)-ethyl]- cyclohexanol] (Tessler & Goldberg, 2004), benzoic acid-2-{(E)-[(E)-2-(2-pyridylmethylidene) hydrazin-1-ylidene]methyl}pyridine (2/1) (Arman et al., 2010), 2,3-diaminopyridinium benzoate benzoic acid solvate (Hemamalini & Fun, 2010), Tramadol hydrochloride-benzoic acid (1/1) (Siddaraju et al., 2011), 4-(cyclo-propane-carboxamido) benzoic acid (Sun et al., 2012), 3,5-bis[(pyridin-4-yl)meth-oxy]benzoic acid (Lin & Zhang, 2013). The hydrogen-bonded two- and three-dimensional polymeric structures of the ammonium salts of 3,5-di-nitro-benzoic acid, 4-nitro-benzoic acid and 2,4-di-chloro-benzoic acid (Smith, 2014) and 4-[1-(2-hydroxypropyl)-4,5-diphenyl-1H-imidazol-2-yl]benzoic acid (Jasinski et al., 2015) have also been reported. In the view of the importance of Tramadol, we report herein the crystal structure of the title compound 2-hydroxy-2-(3-methoxy-phenyl)-cyclohexylmethyl-dimethyl-ammonium benzoate.
In the title molecule (Fig. 1), the six membered cyclohexane ring (C9/C11–C15) adopts a slightly distorted chair conformation with ring puckering parameters Q, θ and φ of 0.5605 (16) Å, 5.06 (16)°, and 210.3 (6)°, respectively. An intramolecular C6—H6···O10 hydrogen bond (Fig 1, Table 1) is found in the cation. Bond lengths are within normal ranges.
The crystal structure is stabilized with weak intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds and a weak intermolecular C23—H23···Cg1 interaction is also observed Table 1, Fig. 2.