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Volume 61 
Part 8 
Pages o2502-o2503  
August 2005  

Received 22 June 2005
Accepted 4 July 2005
Online 13 July 2005

Key indicators
Single-crystal X-ray study
T = 150 K
Mean [sigma](C-C) = 0.004 Å
R = 0.051
wR = 0.058
Data-to-parameter ratio = 8.4
Details

2-[(Dimethylamino)(phenyl)methyl]benzoic acid

aUniversity of Oxford, Department of Chemistry, Chemistry Research Laboratory, 12 Mansfield Road, Oxford OX1 3TA, England
Correspondence e-mail: harry.anderson@chemistry.ox.ac.uk

The title compound {systematic name: [(2-carboxylatophenyl)(phenyl)methyl]-N,N-dimethylammonium}, C16H17NO2, crystallizes as a hydrogen-bonded zwitterion.

Comment

The title compound, (I)[link], was prepared as described and shown in the scheme. This compound crystallizes as the zwitterion [(2-carboxylatophenyl)(phenyl)methyl]-N,N-dimethylammonium (Fig. 1[link]). There are infinite chains of hydrogen-bonded molecules, with alternating stereochemistry at C1, running parallel to the crystallographic c axis (Fig. 2[link]). The molecules are connected by hydrogen bonds between N1H and O1 of a neighbouring molecule [N1...O1i = 2.670 (3) Å; symmetry code: (i) [x, -y+1, z-{\script{1\over 2}}]]. There also appears to be intramolecular C1-H11...O1 hydrogen bonding (Desiraju, 2005[Desiraju, G. R. (2005). Chem. Commun. 2995-3001.]), as shown by the C...O distance of 2.848 (3) Å. This interaction is strengthened by the increased CH acidity due to the adjacent positively-charged N atom.

[Scheme 1]
[Figure 1]
Figure 1
The zwitterionic form of compound (I)[link], showing 40% probability displacement ellipsoids and H atoms of fixed radii.
[Figure 2]
Figure 2
View of one of the infinite hydrogen-bonded chains of (I)[link] parallel to the c axis. The H...O interactions are shown as green and white lines (CrystalMaker Software Limited, 2002[CrystalMaker Software Limited (2002). CrystalMaker. Version 5.0. CrystalMaker Software Limited, Begbroke Science Park, Building 5, Sandy Lane, Yarnton, Oxfordshire, OX5 1PF, England.]).

Experimental

Dimethylamine (4.7 ml of a 40 wt% solution in water, 35 mmol) and 1-bromo-2-[chloro(phenyl)methyl]benzene, (II) (Katsura et al., 1997[Katsura, Y., Zhang, X. Y., Homma, K., Rice, K. C., Calderon, S. N., Rothman, R. B., Yamamura, H. I., Davis, P., Flippen-Anderson, J. L., Xu, H., Becketts, K., Foltz, E. J. & Porreca, F. J. (1997). J. Med. Chem. 40, 2936-2947.]) (500 mg, 1.78 mmol), in dimethyl sulfoxide (3.8 ml) were heated at reflux for 24 h. The product was purified by column chromatography and recrystallisation from dichloromethane/light petroleum to give [(2-bromophenyl)(phenyl)methyl]-N,N-dimethylamine, (III), as a white crystalline solid (234 mg, 45%, m.p. 333 K). Butyllithium (0.86 ml of 1.6 M hexane solution, 1.38 mmol) was added dropwise to a solution of (III) (200 mg, 0.69 mmol) in anhydrous tetrahydrofuran (4 ml) at 195 K and stirred for 2 h. The reaction mixture was warmed to room temperature whilst dry carbon dioxide was bubbled through the solution for a further 2 h. Water (5 ml) and acetic acid (0.13 ml, 2.27 mmol) were added until a pH of 7 was achieved. The product was purified by column chromatography (2:25 methanol-dichloromethane) to yield (I)[link] as colourless crystals (136 mg, 77%). Crystals suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation of a solution in propan-2-ol.

Crystal data
  • C16H17NO2

  • Mr = 255.32

  • Monoclinic, C 2/c

  • a = 24.5562 (10) Å

  • b = 9.2464 (4) Å

  • c = 11.9764 (5) Å

  • [beta] = 91.559 (2)°

  • V = 2718.3 (2) Å3

  • Z = 8

  • Dx = 1.248 Mg m-3

  • Mo K[alpha] radiation

  • Cell parameters from 3144 reflections

  • [theta] = 5-27°

  • [mu] = 0.08 mm-1

  • T = 150 K

  • Block, colourless

  • 0.32 × 0.18 × 0.14 mm

Data collection
  • Nonius KappaCCD diffractometer

  • [omega] scans

  • Absorption correction: multi-scanSCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.])Tmin = 0.97, Tmax = 0.99

  • 13569 measured reflections

  • 3079 independent reflections

  • 1487 reflections with I > 3[sigma](I)

  • Rint = 0.075

  • [theta]max = 27.5°

  • h = -31 [rightwards arrow] 31

  • k = -11 [rightwards arrow] 12

  • l = -15 [rightwards arrow] 15

Refinement
  • Refinement on F

  • R[F2 > 2[sigma](F2)] = 0.051

  • wR(F2) = 0.058

  • S = 1.14

  • 1487 reflections

  • 176 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Weighting scheme: see below

  • ([Delta]/[sigma])max = 0.010

  • [Delta][rho]max = 0.25 e Å-3

  • [Delta][rho]min = -0.22 e Å-3

Table 1
Selected geometric parameters (Å, °)[link]

N1-C1 1.515 (3)
N1-C9 1.485 (4)
N1-C10 1.487 (3)
N1-H1 1.04 (3)
C1-C2 1.523 (4)
C1-C11 1.516 (4)
C2-C7 1.404 (4)
C7-C8 1.531 (3)
C8-O1 1.270 (3)
C8-O2 1.232 (3)
C1-N1-C9 110.3 (2)
C1-N1-C10 111.8 (2)
C9-N1-C10 109.0 (2)
C1-N1-H1 112.9 (18)
C9-N1-H1 106.7 (19)
C10-N1-H1 106.0 (18)
N1-C1-C2 110.8 (2)
N1-C1-C11 111.7 (2)
C2-C1-C11 112.6 (2)
C1-C2-C7 123.4 (2)
C2-C7-C8 126.6 (2)
C7-C8-O1 118.7 (2)
C7-C8-O2 117.6 (2)
O1-C8-O2 123.7 (2)

Table 2
Hydrogen-bond geometry (Å, °)[link]

D-H...A D-H H...A D...A D-H...A
N1-H1...O1i 1.04 (3) 1.64 (3) 2.670 (3) 176 (3)
C1-H11...O1 1.00 2.02 2.848 (3) 139
Symmetry codes: (i) [x, -y+1, z-{\script{1\over 2}}].

A Chebychev polynomial (Carruthers & Watkin, 1979[Carruthers, J. R. & Watkin, D. J. (1979). Acta Cryst. A35, 698-699.]; Prince, 1982[Prince, E. (1982). Mathematical Techniques in Crystallography and Material Science. New York: Springer-Verlag.]) was used in the weighting scheme, [weight] = 1.0/[A0T0(x) + A1T1(x) + ... + An-1Tn-1(x)], where Ai are the Chebychev coefficients 0.491, 0.269 and 0.192, and x = F/Fmax; robust weighting (Prince, 1982[Prince, E. (1982). Mathematical Techniques in Crystallography and Material Science. New York: Springer-Verlag.]) W = [weight] [1 - ([delta]F/6[sigma]F)2]2. The N-bound H atom was located in a difference Fourier map and its coordinates and isotropic displacement parameter subsequently refined. Other H atoms were positioned geometrically, with C-H = 1.00 Å and Uiso(H) = 1.2Ueq(C).

Data collection: COLLECT (Nonius, 2000[Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Issue 12; Betteridge et al., 2003[Betteridge, P. W., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CrystalMaker (CrystalMaker Software Limited, 2002); software used to prepare material for publication: CRYSTALS.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. [details]
Betteridge, P. W., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. [details]
Carruthers, J. R. & Watkin, D. J. (1979). Acta Cryst. A35, 698-699. [CrossRef] [details]
CrystalMaker Software Limited (2002). CrystalMaker. Version 5.0. CrystalMaker Software Limited, Begbroke Science Park, Building 5, Sandy Lane, Yarnton, Oxfordshire, OX5 1PF, England.
Desiraju, G. R. (2005). Chem. Commun. 2995-3001.
Katsura, Y., Zhang, X. Y., Homma, K., Rice, K. C., Calderon, S. N., Rothman, R. B., Yamamura, H. I., Davis, P., Flippen-Anderson, J. L., Xu, H., Becketts, K., Foltz, E. J. & Porreca, F. J. (1997). J. Med. Chem. 40, 2936-2947. [CrossRef] [ChemPort] [PubMed]
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.
Prince, E. (1982). Mathematical Techniques in Crystallography and Material Science. New York: Springer-Verlag.


Acta Cryst (2005). E61, o2502-o2503   [ doi:10.1107/S1600536805021215 ]