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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2769.
Published online 2009 October 17. doi:  10.1107/S1600536809036903
PMCID: PMC2971192

Adamantane-1-ammonium benzoate

Abstract

In the title molecular salt, C10H15NH3 +·C7H5O2 , both carboxyl O atoms act as acceptors for strong N—H(...)O inter­molecular hydrogen-bond inter­actions with the ammonium group in the cation, generating infinite chains along the b axis. A weak C—H(...)π inter­action is also present.

Related literature

For related structures, see: Tukada & Mochizuki (2003 [triangle]); Zhao et al. (2003 [triangle]); He & Wen (2006 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]).

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Object name is e-65-o2769-scheme1.jpg

Experimental

Crystal data

  • C10H18N+·C7H5O2
  • M r = 273.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2769-efi1.jpg
  • a = 10.918 (2) Å
  • b = 6.5664 (13) Å
  • c = 21.197 (4) Å
  • β = 100.07 (3)°
  • V = 1496.3 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.774, T max = 1.000
  • 15027 measured reflections
  • 3437 independent reflections
  • 2453 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.147
  • S = 1.04
  • 3437 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CrystalClear (Rigaku 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809036903/jj2008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036903/jj2008Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

Owing to its highly symmetrical and stable structure, adamantane and its derivatives have generated much interest in the past and continue to be actively studied as evidenced by the large number of compounds containing amantadine that have been synthesized (Tukada & Mochizuki, 2003; Zhao et al., 2003; He & Wen, 2006). Here we report the synthesis and crystal structure of the title compound,(I), C10H15NH3+ . C7H5O2-, a salt obtained from the reaction of adamantane-1-ammonium hydrochloride and sodium benzoate (Fig. 1).

The adamantane-1-ammonium cation contains four 6-membered rings in a cage-like structure each in a slightly distorted boat conformation and with a protonated N atom at the 1-position. Puckering parameters (Cremer & Pople, 1975) Q, θ and [var phi] are for rings 1–4 [(1) 0.630 (2) Å, 1.48 (18)°,272 (54)°; (2) 0.6247 (19)Å,178.36 (17)°, 251 (423)°; (3) 0.621 (4)Å,0.67 (18)°, 240 (54)°; (4)0.6207 (19)Å, 0.55 (18)°, 218 (39)°] where (1) = C7–C9/C13–C15, (2) = C7/C8/C10/C11/C16/C15, (3) = C8/C9/C13/C12/C11/C10 and (4) = C11–C16. C—C distances range from 1.518 (2)Å to 1.531 (3)Å and C—C—C angles range from 108.93 (13)° to 109.91 (13)°, while the exocyclic C—N bond length is 1.4924 (19)Å. These values are similar to that observed in adamantane-1-ammonium 2-nitrobenzoate (C—C = 1.5254 (18)Å to 1.532 (2)Å, C—C—C 109.06 (13)° to 109.84 (11)°, C—N = 1.4967 (18)Å (He & Wen, 2006). Both the negativly charged and neutral oxygen atoms in the benzoate anion are involved in strong N—H···O intermolecular hydrogen bond interactions with the ammonium cation group generating infinite one-dimensional chains along the b axis of the unit cell (Fig. 2, Table 1). In addition, weak π-ring C16–H16A···Cg1 interactions exist which contribute to crystal stability (Cg1 is the center of gravity of ring 1).

Experimental

A mixture of adamantane-1- ammonium hydrochloride (10 mmol), sodiumbenzoate (10 mmol) and methanol (50 ml) was stirred in a beaker. There were many solid powders produced and the solution was filtered. Colorless single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of the solvents over a period of 20 h.

Refinement

Positional parameters of all the H atoms were calculated geometrically (aromatic C–H = 0.93 A°, aliphatic C–H = 0.97 A°) & N–H = 0.89Å) and were allowed to ride on the C,N atoms to which they are bonded, with Uiso(H) = 1.2-1.5Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme and displacement ellipsoids drawn at the 30% probability level. All H atoms except those on the N atom have been omitted for clarity.
Fig. 2.
A view of the crystal packing of the title compound. Dashed lines indicate N–H···O hydrogen bonds which form infinite, one-dimensional chains along the b axis of the unit cell. H atoms not involved in hydrogen bonding have ...

Crystal data

C10H18N+·C7H5O2F(000) = 592
Mr = 273.36Dx = 1.214 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 12490 reflections
a = 10.918 (2) Åθ = 3.2–27.7°
b = 6.5664 (13) ŵ = 0.08 mm1
c = 21.197 (4) ÅT = 298 K
β = 100.07 (3)°Prism, colourless
V = 1496.3 (5) Å30.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer3437 independent reflections
Radiation source: fine-focus sealed tube2453 reflections with I > 2σ(I)
graphiteRint = 0.043
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scansh = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.774, Tmax = 1.000l = −27→26
15027 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0654P)2 + 0.3147P] where P = (Fo2 + 2Fc2)/3
3437 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.26 e Å3

Special details

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)

xyzUiso*/Ueq
C10.56217 (14)0.6892 (3)0.15342 (7)0.0405 (4)
C20.47020 (13)0.7614 (2)0.09647 (7)0.0365 (3)
C30.41146 (17)0.6184 (3)0.05392 (8)0.0551 (5)
H3A0.42820.48070.06120.066*
C40.3278 (2)0.6789 (3)0.00041 (9)0.0718 (6)
H4A0.28990.5820−0.02860.086*
C50.30094 (19)0.8799 (4)−0.00983 (9)0.0707 (6)
H5A0.24390.9201−0.04550.085*
C60.35764 (18)1.0225 (3)0.03223 (9)0.0651 (5)
H6A0.33851.15960.02530.078*
C70.44324 (15)0.9646 (3)0.08504 (8)0.0481 (4)
H7A0.48281.06290.11300.058*
C80.93359 (16)0.8861 (2)0.16653 (8)0.0463 (4)
H8A0.95681.00030.19520.056*
H8B0.84830.90570.14520.056*
C90.94432 (13)0.6891 (2)0.20453 (7)0.0347 (3)
C100.90627 (16)0.5096 (2)0.15964 (8)0.0472 (4)
H10A0.91230.38380.18400.057*
H10B0.82070.52600.13830.057*
C110.99218 (19)0.5007 (3)0.11014 (9)0.0591 (5)
H11A0.96810.38590.08110.071*
C120.98200 (19)0.6977 (3)0.07187 (9)0.0633 (5)
H12A0.89720.71580.04960.076*
H12B1.03600.69150.04010.076*
C131.01933 (18)0.8766 (3)0.11689 (9)0.0548 (5)
H13A1.01261.00350.09220.066*
C141.07795 (14)0.6598 (3)0.23908 (8)0.0474 (4)
H14A1.08460.53470.26380.057*
H14B1.10210.77230.26830.057*
C151.16369 (16)0.6503 (3)0.18941 (9)0.0596 (5)
H15A1.24970.63170.21130.071*
C161.15367 (17)0.8477 (3)0.15120 (10)0.0628 (5)
H16A1.20890.84280.12000.075*
H16B1.17830.96160.17970.075*
C171.1262 (2)0.4714 (3)0.14452 (11)0.0689 (6)
H17A1.13300.34550.16880.083*
H17B1.18130.46290.11340.083*
N10.85951 (11)0.69816 (19)0.25257 (6)0.0393 (3)
H1A0.88100.80250.27900.059*
H1B0.86540.58280.27490.059*
H1C0.78150.71460.23240.059*
O10.57302 (14)0.5030 (2)0.16200 (6)0.0744 (5)
O20.62592 (11)0.81896 (19)0.18784 (6)0.0594 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0380 (8)0.0485 (9)0.0338 (8)0.0034 (7)0.0030 (6)−0.0005 (7)
C20.0332 (7)0.0430 (8)0.0325 (7)−0.0025 (6)0.0039 (6)0.0033 (6)
C30.0573 (10)0.0494 (10)0.0514 (10)−0.0022 (8)−0.0102 (8)−0.0026 (8)
C40.0713 (13)0.0782 (15)0.0541 (11)−0.0070 (11)−0.0218 (10)−0.0098 (10)
C50.0622 (12)0.0890 (16)0.0518 (11)0.0029 (11)−0.0148 (9)0.0201 (11)
C60.0635 (12)0.0581 (12)0.0670 (12)0.0025 (9)−0.0073 (10)0.0234 (10)
C70.0473 (9)0.0454 (9)0.0482 (9)−0.0030 (7)−0.0012 (7)0.0045 (7)
C80.0529 (9)0.0362 (9)0.0467 (9)0.0043 (7)−0.0002 (7)0.0037 (7)
C90.0346 (7)0.0325 (7)0.0343 (7)−0.0002 (6)−0.0019 (6)−0.0008 (6)
C100.0521 (9)0.0385 (9)0.0493 (9)−0.0068 (7)0.0046 (8)−0.0090 (7)
C110.0723 (12)0.0516 (11)0.0546 (11)−0.0037 (9)0.0137 (9)−0.0182 (8)
C120.0675 (12)0.0823 (14)0.0398 (9)−0.0007 (10)0.0083 (9)−0.0031 (9)
C130.0648 (11)0.0487 (10)0.0507 (10)−0.0016 (8)0.0092 (9)0.0150 (8)
C140.0391 (8)0.0527 (10)0.0461 (9)0.0016 (7)−0.0045 (7)0.0046 (7)
C150.0375 (8)0.0759 (13)0.0635 (11)0.0061 (8)0.0036 (8)0.0076 (10)
C160.0528 (10)0.0718 (13)0.0651 (12)−0.0150 (9)0.0134 (9)0.0019 (10)
C170.0717 (13)0.0601 (12)0.0810 (14)0.0191 (10)0.0297 (11)0.0009 (10)
N10.0371 (6)0.0397 (7)0.0375 (7)0.0005 (5)−0.0030 (5)−0.0023 (5)
O10.0912 (11)0.0536 (9)0.0663 (9)0.0002 (7)−0.0200 (8)0.0209 (6)
O20.0484 (7)0.0625 (8)0.0575 (7)0.0142 (6)−0.0177 (6)−0.0197 (6)

Geometric parameters (Å, °)

C1—O11.238 (2)C10—H10B0.9700
C1—O21.2512 (19)C11—C121.520 (3)
C1—C21.505 (2)C11—C171.528 (3)
C2—C71.378 (2)C11—H11A0.9800
C2—C31.380 (2)C12—C131.523 (3)
C3—C41.384 (3)C12—H12A0.9700
C3—H3A0.9300C12—H12B0.9700
C4—C51.361 (3)C13—C161.531 (3)
C4—H4A0.9300C13—H13A0.9800
C5—C61.365 (3)C14—C151.528 (2)
C5—H5A0.9300C14—H14A0.9700
C6—C71.380 (2)C14—H14B0.9700
C6—H6A0.9300C15—C171.522 (3)
C7—H7A0.9300C15—C161.522 (3)
C8—C91.518 (2)C15—H15A0.9800
C8—C131.527 (2)C16—H16A0.9700
C8—H8A0.9700C16—H16B0.9700
C8—H8B0.9700C17—H17A0.9700
C9—N11.4925 (19)C17—H17B0.9700
C9—C141.526 (2)N1—H1A0.8900
C9—C101.526 (2)N1—H1B0.8900
C10—C111.526 (2)N1—H1C0.8900
C10—H10A0.9700
O1—C1—O2123.88 (15)C17—C11—H11A109.4
O1—C1—C2117.52 (14)C11—C12—C13109.58 (14)
O2—C1—C2118.55 (15)C11—C12—H12A109.8
C7—C2—C3118.90 (15)C13—C12—H12A109.8
C7—C2—C1122.54 (14)C11—C12—H12B109.8
C3—C2—C1118.55 (14)C13—C12—H12B109.8
C2—C3—C4120.31 (18)H12A—C12—H12B108.2
C2—C3—H3A119.8C12—C13—C8109.53 (15)
C4—C3—H3A119.8C12—C13—C16109.35 (16)
C5—C4—C3120.12 (18)C8—C13—C16109.25 (15)
C5—C4—H4A119.9C12—C13—H13A109.6
C3—C4—H4A119.9C8—C13—H13A109.6
C4—C5—C6120.05 (17)C16—C13—H13A109.6
C4—C5—H5A120.0C9—C14—C15108.92 (13)
C6—C5—H5A120.0C9—C14—H14A109.9
C5—C6—C7120.41 (18)C15—C14—H14A109.9
C5—C6—H6A119.8C9—C14—H14B109.9
C7—C6—H6A119.8C15—C14—H14B109.9
C2—C7—C6120.18 (16)H14A—C14—H14B108.3
C2—C7—H7A119.9C17—C15—C16109.76 (16)
C6—C7—H7A119.9C17—C15—C14109.41 (15)
C9—C8—C13109.32 (13)C16—C15—C14109.63 (15)
C9—C8—H8A109.8C17—C15—H15A109.3
C13—C8—H8A109.8C16—C15—H15A109.3
C9—C8—H8B109.8C14—C15—H15A109.3
C13—C8—H8B109.8C15—C16—C13109.38 (15)
H8A—C8—H8B108.3C15—C16—H16A109.8
N1—C9—C8109.18 (12)C13—C16—H16A109.8
N1—C9—C14109.45 (12)C15—C16—H16B109.8
C8—C9—C14109.91 (13)C13—C16—H16B109.8
N1—C9—C10108.82 (12)H16A—C16—H16B108.2
C8—C9—C10109.89 (12)C15—C17—C11109.36 (15)
C14—C9—C10109.58 (13)C15—C17—H17A109.8
C11—C10—C9108.97 (13)C11—C17—H17A109.8
C11—C10—H10A109.9C15—C17—H17B109.8
C9—C10—H10A109.9C11—C17—H17B109.8
C11—C10—H10B109.9H17A—C17—H17B108.3
C9—C10—H10B109.9C9—N1—H1A109.5
H10A—C10—H10B108.3C9—N1—H1B109.5
C12—C11—C10109.76 (15)H1A—N1—H1B109.5
C12—C11—C17109.64 (17)C9—N1—H1C109.5
C10—C11—C17109.22 (15)H1A—N1—H1C109.5
C12—C11—H11A109.4H1B—N1—H1C109.5
C10—C11—H11A109.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.891.832.7134 (17)176
N1—H1B···O2ii0.891.902.7840 (18)173
N1—H1C···O20.891.922.7915 (18)166
C16—H16A···Cg1iii0.972.743.702 (2)174

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JJ2008).

References

  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Ferguson, G. (1999). PRPKAPPA University of Guelph, Canada.
  • He, Y.-H. & Wen, Y.-H. (2006). Acta Cryst. E62, o1312–o1313.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tukada, H. & Mochizuki, K. (2003). J. Mol. Struct. 655, 473–478.
  • Zhao, G. L., Feng, Y. L., Hu, X. C. & Kong, L. C. (2003). Chin. J. Appl. Chem.20, 806–808.

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