Crystal structure of rac-3-hy-droxy-2-(p-tol-yl)-2,3,3a,4,7,7a-hexa-hydro-1H-4,7-methano-isoindol-1-one.

In the title compound, C16H17NO2, the cyclo-hexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51 (7)°. The mol-ecular structure is stabilized by a short intra-molecular C-H⋯O contact. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds forming chains propagating along [100]. The chains are linked by C-H⋯π inter-actions, forming slabs parallel to (001).

Related literature

For medical and pharmaceutical applications of chiral tricyclic compounds, see: Abel et al. (1996 ▸); Salvati et al. (2005 ▸). For the synthesis of the starting reagent, 2-(p-tol­yl)-3a,4,7,7a-tetra­hydro-1H-4,7-methano­iso­indole-1,3(2H)-dione, see: Andrade & Evilazio (2004 ▸). For the reduction reaction used to synthesise the title compound, see: Hubert et al. (1975 ▸). For the crystal structure of a similar compound, see: Takebayashi et al. (2010 ▸).

Experimental

Crystal data

C16H17NO2

M = 255.31

Monoclinic,

a = 6.5067 (2) Å

b = 9.7385 (2) Å

c = 21.0780 (5) Å

β = 97.154 (1)°

V = 1325.22 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 296 K

0.45 × 0.25 × 0.15 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▸) T min = 0.963, T max = 0.988

28760 measured reflections

5019 independent reflections

3930 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.180

S = 1.09

5019 reflections

180 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001942/su5074sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001942/su5074Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015001942/su5074Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015001942/su5074fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015001942/su5074fig2.tif

A partial view along the b axis of the crystal packing of the title compound. Dashed lines indicate the O—H⋯O hydrogen bonds (see Table 1 for details).

CCDC reference: 1046290

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H17NO2	F(000) = 544
Mr = 255.31	Dx = 1.280 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5019 reflections
a = 6.5067 (2) Å	θ = 3.6–33.2°
b = 9.7385 (2) Å	µ = 0.08 mm−1
c = 21.0780 (5) Å	T = 296 K
β = 97.154 (1)°	Prism, colourless
V = 1325.22 (6) Å3	0.45 × 0.25 × 0.15 mm
Z = 4

Bruker APEXII diffractometer	5019 independent reflections
Radiation source: fine-focus sealed tube	3930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 33.2°, θmin = 3.6°
Absorption correction: multi-scan (Blessing, 1995)	h = −5→9
Tmin = 0.963, Tmax = 0.988	k = −14→15
28760 measured reflections	l = −32→32

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0762P)2 + 0.4345P] where P = (Fo2 + 2Fc2)/3
5019 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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	0.45122 (14)	1.12217 (12)	0.27036 (6)	0.0443 (3)
H2	0.5256	1.0905	0.3011	0.066*
O2	−0.18121 (15)	0.99108 (14)	0.30186 (6)	0.0498 (3)
C16	−0.0698 (3)	1.0387 (2)	0.09543 (8)	0.0528 (4)
C1	0.4966 (4)	0.7713 (3)	0.53749 (9)	0.0695 (6)
H1A	0.4064	0.7943	0.5686	0.104*
H1B	0.6307	0.8110	0.5498	0.104*
H1C	0.5094	0.6733	0.5350	0.104*
H16A	−0.073 (3)	1.138 (2)	0.0867 (10)	0.057 (6)*
H16B	−0.110 (4)	0.990 (2)	0.0570 (12)	0.066 (6)*
N1	0.16608 (15)	0.98524 (11)	0.29178 (5)	0.0303 (2)
C11	0.30916 (17)	1.02207 (13)	0.24528 (6)	0.0323 (2)
H11	0.3825	0.9402	0.2330	0.039*
C5	0.24201 (17)	0.92979 (12)	0.35282 (6)	0.0303 (2)
C8	−0.03527 (18)	1.01463 (13)	0.27142 (7)	0.0337 (2)
C9	−0.05367 (19)	1.07927 (14)	0.20645 (7)	0.0363 (3)
H9	−0.1068	1.1733	0.2075	0.044*
C10	0.16740 (19)	1.07774 (14)	0.18773 (6)	0.0351 (3)
H10	0.2096	1.1710	0.1777	0.042*
C6	0.4272 (2)	0.85725 (15)	0.36000 (7)	0.0387 (3)
H6	0.4973	0.8419	0.3248	0.046*
C2	0.4079 (2)	0.82658 (16)	0.47322 (7)	0.0440 (3)
C7	0.5078 (2)	0.80753 (17)	0.41974 (7)	0.0455 (3)
H7	0.6327	0.7600	0.4239	0.055*
C12	−0.1801 (2)	0.99380 (17)	0.15201 (8)	0.0470 (3)
H12	−0.3307	1.0066	0.1470	0.056*
C15	0.1436 (3)	0.98780 (17)	0.12617 (7)	0.0448 (3)
H15	0.2563	0.9944	0.0995	0.054*
C4	0.1392 (2)	0.94992 (18)	0.40597 (7)	0.0459 (3)
H4	0.0148	0.9981	0.4021	0.055*
C13	−0.1047 (3)	0.84754 (17)	0.16019 (8)	0.0530 (4)
H13	−0.1791	0.7734	0.1733	0.064*
C3	0.2228 (3)	0.8979 (2)	0.46493 (8)	0.0534 (4)
H3	0.1517	0.9115	0.5001	0.064*
C14	0.0870 (3)	0.84423 (17)	0.14533 (8)	0.0520 (4)
H14	0.1720	0.7672	0.1465	0.062*

	U11	U22	U33	U12	U13	U23
O1	0.0241 (4)	0.0503 (6)	0.0575 (6)	−0.0066 (4)	0.0005 (4)	0.0026 (5)
O2	0.0203 (4)	0.0751 (8)	0.0549 (6)	0.0010 (4)	0.0079 (4)	0.0096 (5)
C16	0.0568 (9)	0.0558 (9)	0.0421 (8)	−0.0040 (8)	−0.0091 (7)	0.0114 (7)
C1	0.0762 (14)	0.0834 (14)	0.0453 (9)	−0.0020 (11)	−0.0064 (9)	0.0202 (9)
N1	0.0193 (4)	0.0366 (5)	0.0347 (5)	0.0025 (3)	0.0030 (3)	0.0021 (4)
C11	0.0218 (4)	0.0375 (6)	0.0380 (6)	0.0015 (4)	0.0058 (4)	0.0020 (5)
C5	0.0244 (5)	0.0332 (5)	0.0328 (5)	0.0007 (4)	0.0022 (4)	−0.0013 (4)
C8	0.0204 (4)	0.0377 (6)	0.0424 (6)	0.0021 (4)	0.0019 (4)	0.0008 (5)
C9	0.0254 (5)	0.0377 (6)	0.0444 (7)	0.0034 (4)	−0.0011 (4)	0.0061 (5)
C10	0.0300 (5)	0.0356 (6)	0.0395 (6)	−0.0011 (4)	0.0037 (4)	0.0071 (5)
C6	0.0287 (5)	0.0496 (7)	0.0379 (6)	0.0092 (5)	0.0050 (5)	0.0037 (5)
C2	0.0466 (7)	0.0473 (8)	0.0361 (6)	−0.0043 (6)	−0.0026 (5)	0.0045 (5)
C7	0.0358 (6)	0.0540 (8)	0.0450 (7)	0.0090 (6)	−0.0013 (5)	0.0087 (6)
C12	0.0351 (6)	0.0562 (9)	0.0464 (8)	−0.0055 (6)	−0.0089 (6)	0.0091 (6)
C15	0.0477 (8)	0.0496 (8)	0.0372 (7)	0.0010 (6)	0.0063 (6)	0.0052 (6)
C4	0.0422 (7)	0.0590 (9)	0.0377 (7)	0.0157 (6)	0.0093 (5)	−0.0018 (6)
C13	0.0641 (10)	0.0452 (8)	0.0459 (8)	−0.0178 (7)	−0.0079 (7)	0.0030 (6)
C3	0.0587 (9)	0.0672 (10)	0.0358 (7)	0.0103 (8)	0.0121 (6)	−0.0004 (7)
C14	0.0711 (11)	0.0396 (7)	0.0436 (8)	0.0024 (7)	−0.0003 (7)	−0.0026 (6)

O1—C11	1.4008 (16)	C9—C12	1.566 (2)
O1—H2	0.8200	C9—H9	0.9800
O2—C8	1.2320 (16)	C10—C15	1.557 (2)
C16—C12	1.531 (2)	C10—H10	0.9800
C16—C15	1.539 (2)	C6—C7	1.3893 (19)
C16—H16A	0.99 (2)	C6—H6	0.9300
C16—H16B	0.95 (2)	C2—C7	1.382 (2)
C1—C2	1.505 (2)	C2—C3	1.383 (2)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C12—C13	1.509 (3)
C1—H1C	0.9600	C12—H12	0.9800
N1—C8	1.3574 (14)	C15—C14	1.513 (2)
N1—C5	1.4256 (16)	C15—H15	0.9800
N1—C11	1.4776 (15)	C4—C3	1.389 (2)
C11—C10	1.5290 (18)	C4—H4	0.9300
C11—H11	0.9800	C13—C14	1.324 (3)
C5—C4	1.3884 (18)	C13—H13	0.9300
C5—C6	1.3885 (17)	C3—H3	0.9300
C8—C9	1.4984 (19)	C14—H14	0.9300
C9—C10	1.5383 (18)
C11—O1—H2	109.5	C11—C10—H10	110.0
C12—C16—C15	93.78 (12)	C9—C10—H10	110.0
C12—C16—H16A	115.2 (12)	C15—C10—H10	110.0
C15—C16—H16A	113.0 (13)	C5—C6—C7	120.04 (13)
C12—C16—H16B	114.7 (15)	C5—C6—H6	120.0
C15—C16—H16B	109.9 (15)	C7—C6—H6	120.0
H16A—C16—H16B	109.4 (19)	C7—C2—C3	117.07 (13)
C2—C1—H1A	109.5	C7—C2—C1	121.32 (16)
C2—C1—H1B	109.5	C3—C2—C1	121.61 (16)
H1A—C1—H1B	109.5	C2—C7—C6	121.98 (13)
C2—C1—H1C	109.5	C2—C7—H7	119.0
H1A—C1—H1C	109.5	C6—C7—H7	119.0
H1B—C1—H1C	109.5	C13—C12—C16	100.44 (15)
C8—N1—C5	125.28 (10)	C13—C12—C9	106.51 (11)
C8—N1—C11	113.71 (10)	C16—C12—C9	99.46 (12)
C5—N1—C11	120.96 (9)	C13—C12—H12	116.0
O1—C11—N1	111.06 (11)	C16—C12—H12	116.0
O1—C11—C10	110.93 (11)	C9—C12—H12	116.0
N1—C11—C10	104.17 (9)	C14—C15—C16	99.98 (14)
O1—C11—H11	110.2	C14—C15—C10	107.43 (12)
N1—C11—H11	110.2	C16—C15—C10	99.24 (13)
C10—C11—H11	110.2	C14—C15—H15	115.9
C4—C5—C6	118.85 (12)	C16—C15—H15	115.9
C4—C5—N1	121.80 (11)	C10—C15—H15	115.9
C6—C5—N1	119.32 (11)	C5—C4—C3	119.75 (14)
O2—C8—N1	124.90 (13)	C5—C4—H4	120.1
O2—C8—C9	125.12 (11)	C3—C4—H4	120.1
N1—C8—C9	109.98 (11)	C14—C13—C12	107.37 (14)
C8—C9—C10	105.05 (10)	C14—C13—H13	126.3
C8—C9—C12	114.92 (11)	C12—C13—H13	126.3
C10—C9—C12	103.28 (12)	C2—C3—C4	122.30 (14)
C8—C9—H9	111.0	C2—C3—H3	118.9
C10—C9—H9	111.0	C4—C3—H3	118.9
C12—C9—H9	111.0	C13—C14—C15	107.95 (15)
C11—C10—C9	106.91 (10)	C13—C14—H14	126.0
C11—C10—C15	116.70 (11)	C15—C14—H14	126.0
C9—C10—C15	102.71 (11)
C8—N1—C11—O1	117.43 (12)	C3—C2—C7—C6	−0.1 (3)
C5—N1—C11—O1	−60.01 (14)	C1—C2—C7—C6	179.60 (17)
C8—N1—C11—C10	−2.04 (14)	C5—C6—C7—C2	0.7 (2)
C5—N1—C11—C10	−179.48 (11)	C15—C16—C12—C13	−50.25 (14)
C8—N1—C5—C4	−26.3 (2)	C15—C16—C12—C9	58.64 (14)
C11—N1—C5—C4	150.86 (14)	C8—C9—C12—C13	−45.60 (17)
C8—N1—C5—C6	155.78 (13)	C10—C9—C12—C13	68.21 (15)
C11—N1—C5—C6	−27.09 (17)	C8—C9—C12—C16	−149.55 (12)
C5—N1—C8—O2	−3.7 (2)	C10—C9—C12—C16	−35.73 (14)
C11—N1—C8—O2	178.96 (13)	C12—C16—C15—C14	49.62 (15)
C5—N1—C8—C9	176.52 (11)	C12—C16—C15—C10	−60.06 (14)
C11—N1—C8—C9	−0.79 (15)	C11—C10—C15—C14	51.45 (17)
O2—C8—C9—C10	−176.50 (14)	C9—C10—C15—C14	−65.11 (15)
N1—C8—C9—C10	3.26 (15)	C11—C10—C15—C16	155.05 (12)
O2—C8—C9—C12	−63.72 (19)	C9—C10—C15—C16	38.49 (13)
N1—C8—C9—C12	116.04 (13)	C6—C5—C4—C3	0.1 (2)
O1—C11—C10—C9	−115.65 (11)	N1—C5—C4—C3	−177.82 (15)
N1—C11—C10—C9	3.91 (13)	C16—C12—C13—C14	33.93 (16)
O1—C11—C10—C15	130.13 (12)	C9—C12—C13—C14	−69.31 (17)
N1—C11—C10—C15	−110.31 (12)	C7—C2—C3—C4	−0.6 (3)
C8—C9—C10—C11	−4.38 (14)	C1—C2—C3—C4	179.80 (19)
C12—C9—C10—C11	−125.16 (11)	C5—C4—C3—C2	0.5 (3)
C8—C9—C10—C15	118.98 (12)	C12—C13—C14—C15	−0.61 (18)
C12—C9—C10—C15	−1.79 (13)	C16—C15—C14—C13	−32.66 (17)
C4—C5—C6—C7	−0.7 (2)	C10—C15—C14—C13	70.41 (17)
N1—C5—C6—C7	177.28 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2	0.93	2.33	2.860 (2)	116
O1—H2···O2i	0.82	2.14	2.7194 (15)	128
C13—H13···Cg1ii	0.93	2.94	3.6903 (18)	139
C16—H16A···Cg4iii	0.99 (2)	2.86 (2)	3.692 (2)	143.4 (15)

Table 1

Hydrogen-bond geometry (, )

Cg1 and Cg4 are the centroids of the N1/C8C11 and C2C7 rings, respectively.

DHA	DH	HA	D A	DHA
C4H4O2	0.93	2.33	2.860(2)	116
O1H2O2i	0.82	2.14	2.7194(15)	128
C13H13Cg1ii	0.93	2.94	3.6903(18)	139
C16H16A Cg4iii	0.99(2)	2.86(2)	3.692(2)	143.4(15)

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