A new polymorph of N-(prop-2-yn-yl)tricyclo-[3.3.1.1]decane-1-carbox-amide.

The alkynyl bond of the title compound, C(14)H(19)NO, 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 inter-molecular N-H⋯O hydrogen bond between the amide function and the carbonyl group. In addition, weak inter-molecular 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 = 217.30

Orthorhombic,

a = 9.862 (2) Å

b = 28.095 (5) Å

c = 8.664 (3) Å

V = 2400.4 (10) Å3

Z = 8

Mo Kα radiation

μ = 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 > 2σ(I)

R int = 0.084

3 standard reflections every 50 reflections intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.130

S = 1.09

1853 reflections

150 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.14 e Å−3

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 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808021466/bt2731sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021466/bt2731Isup2.hkl

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

C14H19NO	F000 = 944
Mr = 217.30	Dx = 1.203 Mg m−3
Orthorhombic, Iba2	Mo Kα radiation λ = 0.71073 Å
Hall symbol: I 2 -2c	Cell parameters from 32 reflections
a = 9.862 (2) Å	θ = 9–13º
b = 28.095 (5) Å	µ = 0.08 mm−1
c = 8.664 (3) Å	T = 293 (2) K
V = 2400.4 (10) Å3	Plates, colourless
Z = 8	0.9 × 0.4 × 0.1 mm

Nicolet P3 diffractometer	Rint = 0.084
Radiation source: fine-focus sealed tube	θmax = 30.0º
Monochromator: graphite	θmin = 2.2º
T = 293(2) K	h = −13→13
Wyckoff ccan scans	k = −39→39
Absorption correction: none	l = −12→12
13418 measured reflections	3 standard reflections
1853 independent reflections	every 50 reflections
1442 reflections with I > 2σ(I)	intensity decay: 2%

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)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130	w = 1/[σ2(Fo2) + (0.0432P)2 + 1.5609P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max < 0.001
1853 reflections	Δρmax = 0.21 e Å−3
150 parameters	Δρmin = −0.14 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0008 (7)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

	x	y	z	Uiso*/Ueq
O1	0.1418 (2)	0.17494 (8)	0.6152 (3)	0.0516 (6)
N1	0.0006 (3)	0.18653 (8)	0.8136 (3)	0.0417 (5)
H1A	−0.023 (3)	0.1792 (9)	0.906 (4)	0.030 (8)*
C1	0.1177 (4)	0.29834 (13)	0.8851 (6)	0.0648 (11)
H1	0.1746	0.3204	0.9322	0.078*
C2	0.0462 (3)	0.27061 (10)	0.8258 (5)	0.0471 (7)
C3	−0.0418 (3)	0.23362 (9)	0.7609 (4)	0.0466 (7)
H3A	−0.1348	0.2394	0.7923	0.056*
H3B	−0.0380	0.2349	0.6491	0.056*
C4	0.1019 (3)	0.16321 (9)	0.7436 (3)	0.0362 (6)
C5	0.1706 (2)	0.12334 (9)	0.8342 (3)	0.0321 (5)
C6	0.2719 (3)	0.14739 (9)	0.9446 (4)	0.0408 (7)
H6A	0.3346	0.1669	0.8858	0.049*
H6B	0.2233	0.1680	1.0155	0.049*
C7	0.3511 (3)	0.10992 (10)	1.0360 (4)	0.0454 (7)
H7	0.4157	0.1258	1.1049	0.055*
C8	0.2518 (3)	0.08042 (11)	1.1315 (4)	0.0464 (7)
H8A	0.3010	0.0570	1.1916	0.056*
H8B	0.2028	0.1009	1.2021	0.056*
C9	0.1523 (3)	0.05549 (9)	1.0236 (4)	0.0441 (7)
H9	0.0889	0.0363	1.0847	0.053*
C10	0.0723 (3)	0.09276 (9)	0.9302 (4)	0.0413 (6)
H10A	0.0087	0.0768	0.8622	0.050*
H10B	0.0213	0.1130	0.9999	0.050*
C11	0.2495 (3)	0.09040 (11)	0.7245 (4)	0.0482 (8)
H11A	0.1868	0.0748	0.6546	0.058*
H11B	0.3124	0.1091	0.6633	0.058*
C12	0.3275 (3)	0.05301 (11)	0.8169 (4)	0.0524 (8)
H12	0.3773	0.0323	0.7458	0.063*
C13	0.2292 (3)	0.02307 (10)	0.9121 (5)	0.0527 (8)
H13A	0.2788	−0.0009	0.9696	0.063*
H13B	0.1657	0.0070	0.8443	0.063*
C14	0.4276 (3)	0.07773 (12)	0.9248 (5)	0.0538 (8)
H14A	0.4784	0.0541	0.9824	0.065*
H14B	0.4913	0.0965	0.8649	0.065*

	U11	U22	U33	U12	U13	U23
O1	0.0513 (12)	0.0591 (13)	0.0445 (12)	0.0059 (10)	0.0039 (11)	0.0162 (11)
N1	0.0433 (12)	0.0404 (11)	0.0415 (14)	0.0062 (11)	0.0031 (12)	0.0088 (12)
C1	0.0506 (17)	0.0527 (18)	0.091 (3)	0.0030 (16)	−0.006 (2)	−0.008 (2)
C2	0.0398 (14)	0.0402 (14)	0.061 (2)	0.0096 (12)	0.0003 (16)	0.0059 (15)
C3	0.0440 (15)	0.0423 (14)	0.0533 (19)	0.0089 (12)	−0.0061 (15)	0.0083 (14)
C4	0.0355 (13)	0.0356 (12)	0.0376 (15)	−0.0056 (10)	−0.0048 (12)	0.0012 (12)
C5	0.0320 (12)	0.0327 (12)	0.0316 (14)	−0.0013 (9)	0.0006 (11)	0.0011 (11)
C6	0.0393 (14)	0.0337 (12)	0.0495 (18)	−0.0075 (11)	−0.0055 (14)	0.0026 (13)
C7	0.0413 (15)	0.0443 (14)	0.0507 (18)	−0.0048 (12)	−0.0143 (15)	0.0036 (15)
C8	0.0570 (18)	0.0448 (15)	0.0375 (16)	0.0059 (13)	−0.0032 (15)	0.0103 (14)
C9	0.0437 (15)	0.0325 (12)	0.056 (2)	−0.0045 (11)	0.0028 (14)	0.0126 (14)
C10	0.0340 (12)	0.0351 (12)	0.0550 (18)	−0.0039 (10)	0.0027 (14)	0.0066 (14)
C11	0.0561 (18)	0.0492 (17)	0.0393 (18)	0.0108 (14)	0.0026 (15)	−0.0028 (13)
C12	0.0593 (19)	0.0477 (16)	0.050 (2)	0.0201 (14)	0.0100 (17)	−0.0022 (16)
C13	0.0624 (19)	0.0313 (13)	0.065 (2)	0.0051 (13)	−0.0091 (19)	−0.0010 (15)
C14	0.0365 (14)	0.0611 (18)	0.064 (2)	0.0086 (13)	0.0026 (16)	0.0153 (19)

O1—C4	1.225 (4)	C8—C9	1.525 (4)
N1—C4	1.340 (4)	C8—H8A	0.9700
N1—C3	1.461 (3)	C8—H8B	0.9700
N1—H1A	0.86 (3)	C9—C13	1.529 (5)
C1—C2	1.170 (5)	C9—C10	1.541 (4)
C1—H1	0.9300	C9—H9	0.9800
C2—C3	1.466 (4)	C10—H10A	0.9700
C3—H3A	0.9700	C10—H10B	0.9700
C3—H3B	0.9700	C11—C12	1.529 (4)
C4—C5	1.526 (4)	C11—H11A	0.9700
C5—C11	1.538 (4)	C11—H11B	0.9700
C5—C10	1.539 (4)	C12—C13	1.526 (5)
C5—C6	1.540 (4)	C12—C14	1.527 (5)
C6—C7	1.531 (4)	C12—H12	0.9800
C6—H6A	0.9700	C13—H13A	0.9700
C6—H6B	0.9700	C13—H13B	0.9700
C7—C14	1.521 (5)	C14—H14A	0.9700
C7—C8	1.527 (4)	C14—H14B	0.9700
C7—H7	0.9800
C4—N1—C3	121.0 (3)	H8A—C8—H8B	108.3
C4—N1—H1A	120.7 (19)	C8—C9—C13	110.0 (3)
C3—N1—H1A	115.4 (19)	C8—C9—C10	109.8 (2)
C2—C1—H1	180.0	C13—C9—C10	109.1 (3)
C1—C2—C3	175.9 (4)	C8—C9—H9	109.3
N1—C3—C2	110.7 (2)	C13—C9—H9	109.3
N1—C3—H3A	109.5	C10—C9—H9	109.3
C2—C3—H3A	109.5	C5—C10—C9	109.9 (2)
N1—C3—H3B	109.5	C5—C10—H10A	109.7
C2—C3—H3B	109.5	C9—C10—H10A	109.7
H3A—C3—H3B	108.1	C5—C10—H10B	109.7
O1—C4—N1	121.3 (3)	C9—C10—H10B	109.7
O1—C4—C5	121.5 (3)	H10A—C10—H10B	108.2
N1—C4—C5	117.2 (2)	C12—C11—C5	110.1 (3)
C4—C5—C11	110.4 (2)	C12—C11—H11A	109.6
C4—C5—C10	114.1 (2)	C5—C11—H11A	109.6
C11—C5—C10	108.5 (2)	C12—C11—H11B	109.6
C4—C5—C6	106.6 (2)	C5—C11—H11B	109.6
C11—C5—C6	108.7 (2)	H11A—C11—H11B	108.1
C10—C5—C6	108.5 (2)	C13—C12—C11	110.0 (3)
C7—C6—C5	110.5 (2)	C13—C12—C14	109.3 (3)
C7—C6—H6A	109.5	C11—C12—C14	109.5 (3)
C5—C6—H6A	109.5	C13—C12—H12	109.3
C7—C6—H6B	109.5	C11—C12—H12	109.3
C5—C6—H6B	109.5	C14—C12—H12	109.3
H6A—C6—H6B	108.1	C12—C13—C9	109.1 (2)
C14—C7—C8	109.8 (2)	C12—C13—H13A	109.9
C14—C7—C6	109.5 (3)	C9—C13—H13A	109.9
C8—C7—C6	109.0 (2)	C12—C13—H13B	109.9
C14—C7—H7	109.5	C9—C13—H13B	109.9
C8—C7—H7	109.5	H13A—C13—H13B	108.3
C6—C7—H7	109.5	C7—C14—C12	109.7 (2)
C9—C8—C7	109.3 (3)	C7—C14—H14A	109.7
C9—C8—H8A	109.8	C12—C14—H14A	109.7
C7—C8—H8A	109.8	C7—C14—H14B	109.7
C9—C8—H8B	109.8	C12—C14—H14B	109.7
C7—C8—H8B	109.8	H14A—C14—H14B	108.2
C4—N1—C3—C2	−82.6 (4)	C8—C9—C10—C5	59.7 (3)
C3—N1—C4—O1	−16.5 (4)	C13—C9—C10—C5	−60.9 (3)
C3—N1—C4—C5	160.2 (3)	C4—C5—C11—C12	175.3 (3)
O1—C4—C5—C11	−21.6 (4)	C10—C5—C11—C12	−59.0 (3)
N1—C4—C5—C11	161.8 (3)	C6—C5—C11—C12	58.8 (3)
O1—C4—C5—C10	−144.0 (3)	C5—C11—C12—C13	60.0 (4)
N1—C4—C5—C10	39.4 (3)	C5—C11—C12—C14	−60.2 (3)
O1—C4—C5—C6	96.2 (3)	C11—C12—C13—C9	−60.3 (4)
N1—C4—C5—C6	−80.4 (3)	C14—C12—C13—C9	60.0 (3)
C4—C5—C6—C7	−177.4 (2)	C8—C9—C13—C12	−60.1 (3)
C11—C5—C6—C7	−58.4 (3)	C10—C9—C13—C12	60.4 (3)
C10—C5—C6—C7	59.3 (3)	C8—C7—C14—C12	59.9 (3)
C5—C6—C7—C14	59.4 (3)	C6—C7—C14—C12	−59.8 (3)
C5—C6—C7—C8	−60.8 (3)	C13—C12—C14—C7	−60.2 (3)
C14—C7—C8—C9	−59.3 (3)	C11—C12—C14—C7	60.4 (3)
C6—C7—C8—C9	60.7 (3)	O1—C4—C3—C2	−87.7 (3)
C7—C8—C9—C13	59.5 (3)	C4—N1—C3—C2	−82.6 (4)
C7—C8—C9—C10	−60.5 (3)	O1—C4—N1—H1A	−176 (2)
C4—C5—C10—C9	−176.9 (2)	H1A—N1—C3—C2	78 (2)
C11—C5—C10—C9	59.6 (3)	O1—C4—C5—C6	96.2 (3)
C6—C5—C10—C9	−58.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.86 (3)	2.16 (4)	2.984 (4)	161 (3)
C1—H1···O1ii	0.93	2.41	3.188 (5)	141
C10—H10B···O1i	0.97	2.57	3.515 (4)	164
C3—H3A···X1iii	0.97	2.93	3.833	157
C3—H3B···X1iv	0.97	2.93	3.813	151
C6—H6A···X1v	0.97	2.81	3.689	151

Table 1

Hydrogen-bond geometry (Å, °)

X1 is the midpoint of the alkynyl bond.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86 (3)	2.16 (4)	2.984 (4)	161 (3)
C1—H1⋯O1ii	0.93	2.41	3.188 (5)	141
C10—H10B⋯O1i	0.97	2.57	3.515 (4)	164
C3—H3A⋯X1iii	0.97	2.93	3.833	157
C3—H3B⋯X1iv	0.97	2.93	3.813	151
C6—H6A⋯X1v	0.97	2.81	3.689	151

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .