2,10-Dihydr-oxy-13-methyl-13-aza-tetra-cyclo-[9.3.1.0.0]penta-deca-3(8),4,6-triene-9,15-dione.

In the title compound, C(15)H(15)NO(4), the n-methyl-piperidone ring adopts a chair conformation and both five-membered rings adopt a twist conformation. An intra-molecular O-H⋯O hydrogen bond is observed. Inversion-related mol-ecules are linked into R(2) (2)(10) dimers by pairs of O-H⋯O hydrogen bonds. The crystal structure is further stabilized by C-H⋯O hydrogen bonds.

Related literature

For the biological activity of piperidine compounds, see: Watson et al. (2000 ▶). For ring conformation details, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H15NO4

M = 273.28

Triclinic,

a = 7.5616 (7) Å

b = 8.9033 (8) Å

c = 10.8091 (11) Å

α = 72.764 (11)°

β = 80.486 (12)°

γ = 72.369 (11)°

V = 660.09 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.18 × 0.15 × 0.11 mm

Data collection

Nonius MACH-3 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.982, T max = 0.989

2890 measured reflections

2316 independent reflections

2025 reflections with I > 2σ(I)

R int = 0.010

2 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.097

S = 1.11

2316 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.23 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809015785/ci2789sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015785/ci2789Isup2.hkl

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

C15H15NO4	Z = 2
Mr = 273.28	F(000) = 288
Triclinic, P1	Dx = 1.375 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5616 (7) Å	Cell parameters from 25 reflections
b = 8.9033 (8) Å	θ = 2–25°
c = 10.8091 (11) Å	µ = 0.10 mm−1
α = 72.764 (11)°	T = 293 K
β = 80.486 (12)°	Block, colourless
γ = 72.369 (11)°	0.18 × 0.15 × 0.11 mm
V = 660.09 (11) Å3

Nonius MACH-3 diffractometer	2025 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.010
graphite	θmax = 25.0°, θmin = 2.5°
ω–2θ scans	h = −1→8
Absorption correction: ψ scan (North et al., 1968)	k = −10→10
Tmin = 0.982, Tmax = 0.989	l = −12→12
2890 measured reflections	2 standard reflections every 60 min
2316 independent reflections	intensity decay: none

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0454P)2 + 0.1839P] where P = (Fo2 + 2Fc2)/3
2316 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.23 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	0.29809 (15)	0.41843 (13)	0.00498 (10)	0.0446 (3)
O2	−0.04087 (14)	0.29519 (13)	0.08496 (10)	0.0421 (3)
H2	−0.1139	0.3846	0.0581	0.063*
O3	−0.02584 (16)	0.06248 (14)	0.30007 (11)	0.0499 (3)
H3	−0.0724	0.0852	0.2313	0.075*
N1	0.29935 (17)	0.38335 (15)	0.28995 (12)	0.0388 (3)
O4	−0.19177 (16)	0.40313 (16)	0.45054 (11)	0.0538 (3)
C8	0.2679 (2)	0.30815 (17)	0.09849 (13)	0.0353 (3)
C4	0.2670 (2)	0.26334 (19)	0.41090 (14)	0.0403 (3)
H4A	0.2445	0.3121	0.4832	0.048*
H4B	0.3768	0.1712	0.4252	0.048*
C10	0.3067 (2)	0.04870 (17)	0.24458 (14)	0.0372 (3)
C7	0.07412 (19)	0.30768 (16)	0.17048 (13)	0.0322 (3)
C5	0.0984 (2)	0.20371 (18)	0.40485 (13)	0.0375 (3)
H5	0.0730	0.1229	0.4847	0.045*
C6	0.1144 (2)	0.14491 (16)	0.28236 (13)	0.0348 (3)
C9	0.3957 (2)	0.14516 (17)	0.14346 (14)	0.0372 (3)
C1	−0.0622 (2)	0.35556 (19)	0.37706 (14)	0.0383 (3)
C3	0.1375 (2)	0.52059 (18)	0.25385 (15)	0.0406 (3)
H3A	0.1661	0.5959	0.1728	0.049*
H3B	0.0969	0.5788	0.3209	0.049*
C2	−0.0144 (2)	0.44610 (17)	0.23864 (13)	0.0362 (3)
H2A	−0.1220	0.5275	0.1970	0.043*
C14	0.5784 (2)	0.0851 (2)	0.09741 (16)	0.0486 (4)
H14	0.6375	0.1503	0.0301	0.058*
C11	0.3986 (2)	−0.11196 (19)	0.30063 (17)	0.0496 (4)
H11	0.3394	−0.1777	0.3674	0.059*
C12	0.5804 (3)	−0.1720 (2)	0.25488 (18)	0.0565 (5)
H12	0.6442	−0.2794	0.2917	0.068*
C13	0.6699 (2)	−0.0751 (2)	0.15496 (19)	0.0572 (5)
H13	0.7927	−0.1183	0.1263	0.069*
C18	0.4702 (3)	0.4293 (3)	0.2839 (2)	0.0624 (5)
H18A	0.4881	0.5036	0.2010	0.094*
H18B	0.5737	0.3334	0.2949	0.094*
H18C	0.4615	0.4811	0.3517	0.094*

	U11	U22	U33	U12	U13	U23
O1	0.0438 (6)	0.0456 (6)	0.0332 (5)	−0.0098 (5)	0.0005 (4)	0.0021 (5)
O2	0.0419 (6)	0.0433 (6)	0.0416 (6)	−0.0060 (5)	−0.0146 (5)	−0.0116 (5)
O3	0.0522 (7)	0.0488 (6)	0.0518 (7)	−0.0269 (5)	−0.0081 (5)	−0.0022 (5)
N1	0.0360 (7)	0.0438 (7)	0.0393 (7)	−0.0155 (5)	0.0001 (5)	−0.0116 (5)
O4	0.0413 (6)	0.0706 (8)	0.0475 (7)	−0.0118 (6)	0.0104 (5)	−0.0234 (6)
C8	0.0365 (8)	0.0379 (7)	0.0285 (7)	−0.0084 (6)	−0.0037 (6)	−0.0053 (6)
C4	0.0413 (8)	0.0455 (8)	0.0329 (7)	−0.0085 (6)	−0.0075 (6)	−0.0095 (6)
C10	0.0422 (8)	0.0343 (7)	0.0341 (7)	−0.0068 (6)	−0.0073 (6)	−0.0090 (6)
C7	0.0320 (7)	0.0335 (7)	0.0289 (7)	−0.0067 (6)	−0.0057 (5)	−0.0053 (6)
C5	0.0396 (8)	0.0413 (8)	0.0268 (7)	−0.0130 (6)	0.0003 (6)	−0.0013 (6)
C6	0.0369 (8)	0.0322 (7)	0.0338 (7)	−0.0120 (6)	−0.0039 (6)	−0.0030 (6)
C9	0.0378 (8)	0.0387 (8)	0.0326 (7)	−0.0050 (6)	−0.0052 (6)	−0.0101 (6)
C1	0.0350 (8)	0.0468 (8)	0.0360 (8)	−0.0141 (6)	0.0002 (6)	−0.0135 (6)
C3	0.0491 (9)	0.0361 (8)	0.0370 (8)	−0.0128 (7)	−0.0008 (6)	−0.0100 (6)
C2	0.0349 (7)	0.0354 (7)	0.0339 (7)	−0.0028 (6)	−0.0053 (6)	−0.0080 (6)
C14	0.0396 (8)	0.0557 (10)	0.0453 (9)	−0.0037 (7)	−0.0015 (7)	−0.0160 (8)
C11	0.0600 (10)	0.0342 (8)	0.0482 (9)	−0.0044 (7)	−0.0111 (8)	−0.0064 (7)
C12	0.0617 (11)	0.0404 (9)	0.0592 (11)	0.0085 (8)	−0.0191 (9)	−0.0161 (8)
C13	0.0442 (9)	0.0592 (11)	0.0625 (11)	0.0096 (8)	−0.0102 (8)	−0.0286 (9)
C18	0.0456 (10)	0.0723 (12)	0.0787 (13)	−0.0281 (9)	0.0013 (9)	−0.0244 (10)

O1—C8	1.2285 (17)	C5—C1	1.509 (2)
O2—C7	1.4171 (16)	C5—C6	1.537 (2)
O2—H2	0.82	C5—H5	0.98
O3—C6	1.4219 (17)	C9—C14	1.387 (2)
O3—H3	0.82	C1—C2	1.517 (2)
N1—C3	1.453 (2)	C3—C2	1.541 (2)
N1—C18	1.455 (2)	C3—H3A	0.97
N1—C4	1.4613 (19)	C3—H3B	0.97
O4—C1	1.2088 (18)	C2—H2A	0.98
C8—C9	1.471 (2)	C14—C13	1.385 (3)
C8—C7	1.5419 (19)	C14—H14	0.93
C4—C5	1.539 (2)	C11—C12	1.381 (3)
C4—H4A	0.97	C11—H11	0.93
C4—H4B	0.97	C12—C13	1.388 (3)
C10—C11	1.386 (2)	C12—H12	0.93
C10—C9	1.391 (2)	C13—H13	0.93
C10—C6	1.507 (2)	C18—H18A	0.96
C7—C2	1.5443 (19)	C18—H18B	0.96
C7—C6	1.5720 (18)	C18—H18C	0.96
C7—O2—H2	109.5	C14—C9—C8	128.62 (14)
C6—O3—H3	109.5	C10—C9—C8	109.95 (13)
C3—N1—C18	114.32 (13)	O4—C1—C5	128.54 (14)
C3—N1—C4	113.97 (12)	O4—C1—C2	126.94 (14)
C18—N1—C4	112.86 (13)	C5—C1—C2	104.23 (11)
O1—C8—C9	126.53 (13)	N1—C3—C2	105.67 (11)
O1—C8—C7	124.00 (12)	N1—C3—H3A	110.6
C9—C8—C7	108.44 (12)	C2—C3—H3A	110.6
N1—C4—C5	110.50 (11)	N1—C3—H3B	110.6
N1—C4—H4A	109.6	C2—C3—H3B	110.6
C5—C4—H4A	109.6	H3A—C3—H3B	108.7
N1—C4—H4B	109.6	C1—C2—C3	103.05 (11)
C5—C4—H4B	109.6	C1—C2—C7	103.33 (11)
H4A—C4—H4B	108.1	C3—C2—C7	109.41 (11)
C11—C10—C9	120.35 (15)	C1—C2—H2A	113.4
C11—C10—C6	128.39 (14)	C3—C2—H2A	113.4
C9—C10—C6	111.20 (12)	C7—C2—H2A	113.4
O2—C7—C8	108.50 (11)	C13—C14—C9	117.82 (16)
O2—C7—C2	114.39 (11)	C13—C14—H14	121.1
C8—C7—C2	115.40 (12)	C9—C14—H14	121.1
O2—C7—C6	108.69 (11)	C12—C11—C10	118.30 (16)
C8—C7—C6	103.21 (11)	C12—C11—H11	120.8
C2—C7—C6	105.84 (11)	C10—C11—H11	120.8
C1—C5—C6	100.91 (11)	C11—C12—C13	121.32 (15)
C1—C5—C4	105.49 (12)	C11—C12—H12	119.3
C6—C5—C4	112.08 (11)	C13—C12—H12	119.3
C1—C5—H5	112.5	C14—C13—C12	120.77 (16)
C6—C5—H5	112.5	C14—C13—H13	119.6
C4—C5—H5	112.5	C12—C13—H13	119.6
O3—C6—C10	114.30 (12)	N1—C18—H18A	109.5
O3—C6—C5	106.98 (11)	N1—C18—H18B	109.5
C10—C6—C5	114.94 (12)	H18A—C18—H18B	109.5
O3—C6—C7	111.58 (11)	N1—C18—H18C	109.5
C10—C6—C7	104.97 (11)	H18A—C18—H18C	109.5
C5—C6—C7	103.62 (11)	H18B—C18—H18C	109.5
C14—C9—C10	121.43 (14)
C3—N1—C4—C5	54.45 (16)	C6—C10—C9—C14	176.26 (14)
C18—N1—C4—C5	−172.98 (13)	C11—C10—C9—C8	178.38 (14)
O1—C8—C7—O2	66.57 (17)	C6—C10—C9—C8	−4.31 (17)
C9—C8—C7—O2	−102.49 (12)	O1—C8—C9—C14	4.9 (3)
O1—C8—C7—C2	−63.28 (18)	C7—C8—C9—C14	173.60 (15)
C9—C8—C7—C2	127.66 (12)	O1—C8—C9—C10	−174.49 (14)
O1—C8—C7—C6	−178.24 (13)	C7—C8—C9—C10	−5.78 (16)
C9—C8—C7—C6	12.70 (14)	C6—C5—C1—O4	138.05 (16)
N1—C4—C5—C1	−56.97 (15)	C4—C5—C1—O4	−105.16 (17)
N1—C4—C5—C6	51.96 (16)	C6—C5—C1—C2	−47.81 (13)
C11—C10—C6—O3	−48.1 (2)	C4—C5—C1—C2	68.98 (13)
C9—C10—C6—O3	134.84 (13)	C18—N1—C3—C2	168.31 (13)
C11—C10—C6—C5	76.15 (19)	C4—N1—C3—C2	−59.82 (15)
C9—C10—C6—C5	−100.88 (14)	O4—C1—C2—C3	98.33 (17)
C11—C10—C6—C7	−170.70 (15)	C5—C1—C2—C3	−75.95 (13)
C9—C10—C6—C7	12.27 (15)	O4—C1—C2—C7	−147.76 (15)
C1—C5—C6—O3	−80.03 (13)	C5—C1—C2—C7	37.97 (14)
C4—C5—C6—O3	168.14 (11)	N1—C3—C2—C1	69.03 (14)
C1—C5—C6—C10	151.91 (12)	N1—C3—C2—C7	−40.39 (14)
C4—C5—C6—C10	40.09 (16)	O2—C7—C2—C1	106.41 (13)
C1—C5—C6—C7	37.97 (13)	C8—C7—C2—C1	−126.65 (12)
C4—C5—C6—C7	−73.85 (14)	C6—C7—C2—C1	−13.22 (14)
O2—C7—C6—O3	−23.90 (15)	O2—C7—C2—C3	−144.35 (12)
C8—C7—C6—O3	−138.96 (12)	C8—C7—C2—C3	−17.42 (15)
C2—C7—C6—O3	99.41 (13)	C6—C7—C2—C3	96.02 (13)
O2—C7—C6—C10	100.42 (12)	C10—C9—C14—C13	0.3 (2)
C8—C7—C6—C10	−14.64 (14)	C8—C9—C14—C13	−178.97 (15)
C2—C7—C6—C10	−136.28 (11)	C9—C10—C11—C12	1.0 (2)
O2—C7—C6—C5	−138.66 (11)	C6—C10—C11—C12	−175.81 (15)
C8—C7—C6—C5	106.28 (12)	C10—C11—C12—C13	−0.3 (3)
C2—C7—C6—C5	−15.36 (14)	C9—C14—C13—C12	0.4 (3)
C11—C10—C9—C14	−1.1 (2)	C11—C12—C13—C14	−0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	2.11	2.6080 (15)	119
O2—H2···O1i	0.82	1.90	2.7168 (15)	175
C2—H2A···O1i	0.98	2.59	3.3778 (18)	137
C18—H18A···O1ii	0.96	2.57	3.432 (2)	149
C5—H5···O3iii	0.98	2.46	3.4381 (18)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	2.11	2.6080 (15)	119
O2—H2⋯O1i	0.82	1.90	2.7168 (15)	175
C2—H2A⋯O1i	0.98	2.59	3.3778 (18)	137
C18—H18A⋯O1ii	0.96	2.57	3.432 (2)	149
C5—H5⋯O3iii	0.98	2.46	3.4381 (18)	173

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