A new polymorph of N-(prop-2-yn­yl)tricyclo­[3.3.1.13,7]decane-1-carbox­amide

Frey, W.; Schetter, S.; Rominger, F.; Hashmi, A.S.K.

doi:10.1107/S1600536808021466

Volume 64
Part 8
Page o1495
August 2008

Received 23 June 2008
Accepted 10 July 2008
Online 16 July 2008

Key indicators
Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R = 0.062
wR = 0.131
Data-to-parameter ratio = 12.4
Details

A new polymorph of N-(prop-2-ynyl)tricyclo[3.3.1.1^3,7]decane-1-carboxamide

Wolfgang Frey,^a Stefanie Schetter,^a Frank Rominger ^b and A. Stephen K. Hashmi ^b ^*

^aInstitut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany, and ^bOrganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, 70569 Stuttgart, Germany
Correspondence e-mail: hashmi@hashmi.de

The alkynyl bond of the title compound, C₁₄H₁₉NO, has a length of 1.170 (5) Å. The amide function shows a trans conformation with respect to the carbonyl group characterized by the torsion angle O-C-N-H of -176 (2)°. There is an intermolecular N-HO hydrogen bond between the amide function and the carbonyl group. In addition, weak intermolecular hydrogen bonds stabilize the crystal structure. A comparison with a polymorphic structure shows conformational differences with regard to the orientation of the carbonyl groups with respect to the adamantyl group [O-C-C-C = 96.2 (3)° in the title compound and 123.7 (2)° in the polymorph] and the orientations of the propargyl groups in relation to the carbonyl groups [O-C-C-C = -87.7 (3) and -58.7 (2)°, respectively].

Related literature

For the monoclinic polymorph, see: Hashmi et al. (2004). For gold catalysis research, see: Hashmi (2003, 2004, 2005, 2007); Hashmi & Hutchings (2006); Hashmi, Frost & Bats (2000); Hashmi, Schwarz et al. (2000); Hashmi et al. (2006). For the synthesis of heterocyclic compounds, see: Milton et al. (2004).

Experimental

Crystal data

C₁₄H₁₉NO
M_r = 217.30
Orthorhombic, I b a 2
a = 9.862 (2) Å
b = 28.095 (5) Å
c = 8.664 (3) Å
V = 2400.4 (10) Å³
Z = 8
Mo K radiation
= 0.07 mm^-1
T = 293 (2) K
0.9 × 0.4 × 0.1 mm

Data collection

Nicolet P3 diffractometer
Absorption correction: none
13418 measured reflections
1853 independent reflections
1442 reflections with I > 2(I)
R_int = 0.084
3 standard reflections every 50 reflections intensity decay: 2%

Refinement

R[F² > 2(F²)] = 0.061
wR(F²) = 0.130
S = 1.09
1853 reflections
150 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
_max = 0.21 e Å^-3
_min = -0.14 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

X1 is the midpoint of the alkynyl bond.

D-HA	D-H	HA	DA	D-HA
N1-H1AO1ⁱ	0.86 (3)	2.16 (4)	2.984 (4)	161 (3)
C1-H1O1ⁱⁱ	0.93	2.41	3.188 (5)	141
C10-H10BO1ⁱ	0.97	2.57	3.515 (4)	164
C3-H3AX1ⁱⁱⁱ	0.97	2.93	3.833	157
C3-H3BX1^iv	0.97	2.93	3.813	151
C6-H6AX1^v	0.97	2.81	3.689	151
Symmetry codes: (i) $[-x, y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x, y, z-{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: P3/PC Software (Siemens, 1991); cell refinement: P3/PC Software; data reduction: XDISK in SHELXTL-Plus (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus; software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2731 ).

References

Hashmi, A. S. K. (2003). Gold Bull. 36, 3-9.
Hashmi, A. S. K. (2004). Gold Bull. 37, 51-65.
Hashmi, A. S. K. (2005). Angew. Chem. Int. Ed. 44, 6690-6693.
Hashmi, A. S. K. (2007). Chem. Rev. 107, 3180-3211.
Hashmi, A. S. K., Frost, T. M. & Bats, J. W. (2000). J. Am. Chem. Soc. 122, 11553-11554.
Hashmi, A. S. K. & Hutchings, G. (2006). Angew. Chem. Int. Ed. 45, 7896-7936.
Hashmi, A. S. K., Rudolph, M., Schymura, S., Visus, J. & Frey, W. (2006). Eur. J. Org. Chem. pp. 4905-4909.
Hashmi, A. S. K., Schwarz, L., Choi, J.-H. & Frost, T. M. (2000). Angew. Chem. Int. Ed. Engl. 39, 2285-2288.
Hashmi, A. S. K., Weyrauch, J. P., Frey, W. & Bats, J. W. (2004). Org. Lett. 6, 4391-4394.
Milton, M. D., Inada, Y., Nishibayashi, Y. & Uemura, S. (2004). Chem. Commun. pp. 2712-2713.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Siemens (1991). P3/PC Data Collection Software. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.

organic compounds

A new polymorph of N-(prop-2-ynyl)tricyclo[3.3.1.13,7]decane-1-carboxamide