1-Ethyl-4-hydr­oxy-9-aza­tricyclo­[7.4.1.02,7]tetra­deca-2,4,6-trien-8-one

Zheng, W.; Xie, Q.; Li, F.; Qiu, Z.-B.

doi:10.1107/S160053680903918X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3008

doi:10.1107/S160053680903918X

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1-Ethyl-4-hydroxy-9-azatricyclo[7.4.1.0^2,7]tetradeca-2,4,6-trien-8-one

Wei Zheng,^a Qiong Xie,^a Fang Li ^b and Zhui-Bai Qiu ^a ^*

^aDepartment of Medicinal Chemistry, School of Pharmacy, Fudan University, 826 Zhangheng Road, Shanghai 201203, People's Republic of China, and ^bNPFPC Key Laboratory of Contraceptives and Devices, Shanghai Institute of Planned Parenthood Research, 2140 Xietu Road, Shanghai 200032, People's Republic of China
^*Correspondence e-mail: zbqiu@shmu.edu.cn

(Received 23 September 2009; accepted 26 September 2009; online 7 November 2009)

In the molecule of the title compound, C₁₅H₁₉NO₂, the six-membered dihydropyridinone ring assumes a screw-boat conformation. In the crystal structure, molecules are linked via O—H⋯O hydrogen bonding between hydroxy and carbonyl groups, forming supramolecular chains along the a axis.

Related literature

For the synthesis and bioactivity of novel bis-(−)-nor-meptazinols, see Xie et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₉NO₂
M_r = 245.31
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.298 (1) Å
b = 9.9817 (12) Å
c = 14.7324 (18) Å
V = 1220.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.37 × 0.23 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
6713 measured reflections
1397 independent reflections
1280 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.091
S = 1.06
1397 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.92	2.710 (2)	162
Symmetry code: (i) x-1, y, z.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903918X/xu2615sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903918X/xu2615Isup2.hkl

checkCIF report

Comment top

In previous study, our group has reported the synthesis and characterization of novel bis-(-)-nor-meptazinols that inhibit both acetylcholinesterase and butyrylcholinesterase as well as retarding Aβ aggregation (Xie et al., 2008). The title compound (I), was produced serendipitously whilst preparating of (-)-Nor-meptazinol (II), which is the intermediate of bis-(-)-nor-meptazinols. The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The six-membered dihydropyridinone ring assumes a screw-boat conformation. The crystal structure is stabilized by intermolecular O—H···O hydrogen bonding (Table 1 and Fig. 2).

Related literature top

For the synthesis and bioactivity of novel bis-(-)-nor-meptazinols, see Xie et al. (2008).

Experimental top

A white powder (I) was obtained as a by-product of the reaction between (-)-N-carboethoxy-nor-meptazinol and 50% H₂SO₄ (Fig. 3). Single crystals suitable for crystallographic analysis were obtained by slow evaporation of an methanol solution. [α]_D = -60.8° (c 0.332, MeOH).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Intermolecular hydrogen bond is shown as a dashed line.
	Fig. 3. The formation of the title compound.

1-Ethyl-4-hydroxy-9-azatricyclo[7.4.1.0^2,7]tetradeca-2,4,6-trien-8-one top

Crystal data top

C₁₅H₁₉NO₂	F(000) = 528
M_r = 245.31	D_x = 1.335 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2536 reflections
a = 8.298 (1) Å	θ = 2.5–26.4°
b = 9.9817 (12) Å	µ = 0.09 mm⁻¹
c = 14.7324 (18) Å	T = 293 K
V = 1220.3 (3) Å³	Prismatic, colourless
Z = 4	0.37 × 0.23 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1280 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 26.0°, θ_min = 2.5°
ϕ and ω scans	h = −10→10
6713 measured reflections	k = −12→12
1397 independent reflections	l = −11→18

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0557P)²] where P = (F_o² + 2F_c²)/3
1397 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₅H₁₉NO₂	V = 1220.3 (3) Å³
M_r = 245.31	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.298 (1) Å	µ = 0.09 mm⁻¹
b = 9.9817 (12) Å	T = 293 K
c = 14.7324 (18) Å	0.37 × 0.23 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1280 reflections with I > 2σ(I)
6713 measured reflections	R_int = 0.054
1397 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.06	Δρ_max = 0.16 e Å⁻³
1397 reflections	Δρ_min = −0.20 e Å⁻³
165 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	1.0502 (2)	0.76044 (17)	0.90237 (11)	0.0315 (4)
O1	1.16080 (18)	0.96697 (17)	0.91934 (11)	0.0429 (4)
O2	0.4251 (2)	1.11984 (16)	0.94981 (13)	0.0507 (5)
H2	0.3557	1.0686	0.9307	0.076*
C1	1.0402 (2)	0.8931 (2)	0.91820 (13)	0.0301 (5)
C2	0.8763 (2)	0.9473 (2)	0.93043 (13)	0.0285 (5)
C3	0.8531 (3)	1.0689 (2)	0.97449 (13)	0.0328 (5)
H3	0.9410	1.1126	1.0001	0.039*
C4	0.7027 (3)	1.1258 (2)	0.98083 (14)	0.0357 (5)
H4	0.6883	1.2061	1.0118	0.043*
C5	0.5729 (3)	1.0620 (2)	0.94053 (15)	0.0336 (5)
C6	0.5946 (3)	0.9430 (2)	0.89339 (14)	0.0310 (5)
H6	0.5072	0.9031	0.8646	0.037*
C7	0.7454 (2)	0.8827 (2)	0.88863 (12)	0.0262 (4)
C8	0.7732 (2)	0.7468 (2)	0.84288 (13)	0.0279 (4)
C9	0.9025 (3)	0.67983 (19)	0.90089 (14)	0.0312 (5)
H9A	0.8627	0.6687	0.9623	0.037*
H9B	0.9263	0.5917	0.8766	0.037*
C10	1.1831 (3)	0.7095 (2)	0.84858 (15)	0.0416 (6)
H10A	1.2152	0.6222	0.8711	0.050*
H10B	1.2747	0.7694	0.8537	0.050*
C11	1.1318 (3)	0.6983 (2)	0.74892 (15)	0.0431 (6)
H11A	1.2261	0.7101	0.7108	0.052*
H11B	1.0905	0.6087	0.7382	0.052*
C12	1.0037 (3)	0.7998 (2)	0.72030 (14)	0.0386 (6)
H12A	1.0121	0.8133	0.6553	0.046*
H12B	1.0277	0.8847	0.7494	0.046*
C13	0.8296 (3)	0.7620 (2)	0.74266 (13)	0.0336 (5)
H13A	0.8074	0.6777	0.7124	0.040*
H13B	0.7609	0.8288	0.7146	0.040*
C14	0.6173 (3)	0.6630 (2)	0.84401 (15)	0.0351 (5)
H14A	0.5664	0.6741	0.9028	0.042*
H14B	0.5444	0.6993	0.7988	0.042*
C15	0.6367 (3)	0.5130 (2)	0.82599 (18)	0.0477 (6)
H15A	0.6932	0.5000	0.7698	0.072*
H15B	0.5323	0.4719	0.8223	0.072*
H15C	0.6968	0.4729	0.8746	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0219 (9)	0.0378 (9)	0.0348 (9)	0.0014 (8)	−0.0012 (7)	−0.0003 (8)
O1	0.0258 (8)	0.0495 (9)	0.0534 (9)	−0.0093 (7)	−0.0018 (7)	−0.0064 (8)
O2	0.0298 (9)	0.0380 (9)	0.0842 (13)	0.0030 (8)	0.0012 (9)	−0.0190 (9)
C1	0.0256 (11)	0.0373 (11)	0.0273 (10)	−0.0054 (9)	−0.0036 (9)	−0.0018 (9)
C2	0.0254 (11)	0.0343 (11)	0.0259 (9)	−0.0029 (9)	−0.0007 (8)	0.0007 (8)
C3	0.0286 (11)	0.0367 (11)	0.0330 (10)	−0.0075 (10)	−0.0013 (9)	−0.0048 (9)
C4	0.0375 (13)	0.0308 (11)	0.0387 (11)	−0.0019 (10)	0.0035 (10)	−0.0071 (9)
C5	0.0287 (11)	0.0301 (10)	0.0421 (12)	−0.0003 (10)	0.0040 (9)	−0.0020 (9)
C6	0.0243 (11)	0.0315 (10)	0.0371 (11)	−0.0044 (9)	−0.0026 (9)	−0.0034 (9)
C7	0.0247 (11)	0.0311 (10)	0.0229 (9)	−0.0037 (9)	0.0012 (8)	0.0012 (8)
C8	0.0239 (11)	0.0322 (10)	0.0276 (9)	−0.0013 (9)	−0.0003 (8)	−0.0035 (8)
C9	0.0294 (11)	0.0303 (10)	0.0338 (11)	−0.0018 (9)	−0.0003 (9)	−0.0007 (9)
C10	0.0241 (12)	0.0475 (13)	0.0532 (14)	0.0042 (10)	0.0015 (10)	−0.0066 (11)
C11	0.0361 (14)	0.0462 (12)	0.0470 (13)	0.0007 (11)	0.0124 (11)	−0.0097 (11)
C12	0.0425 (14)	0.0433 (12)	0.0302 (10)	−0.0039 (12)	0.0068 (10)	−0.0011 (9)
C13	0.0328 (12)	0.0406 (11)	0.0274 (10)	−0.0005 (10)	−0.0011 (9)	−0.0042 (9)
C14	0.0271 (12)	0.0391 (11)	0.0390 (11)	−0.0039 (10)	0.0015 (10)	−0.0078 (9)
C15	0.0402 (15)	0.0392 (12)	0.0637 (15)	−0.0090 (11)	0.0056 (12)	−0.0131 (11)

Geometric parameters (Å, º) top

N1—C1	1.347 (3)	C9—H9A	0.9700
N1—C10	1.451 (3)	C9—H9B	0.9700
N1—C9	1.466 (3)	C10—C11	1.533 (3)
O1—C1	1.243 (2)	C10—H10A	0.9700
O2—C5	1.362 (3)	C10—H10B	0.9700
O2—H2	0.8200	C11—C12	1.528 (3)
C1—C2	1.475 (3)	C11—H11A	0.9700
C2—C3	1.390 (3)	C11—H11B	0.9700
C2—C7	1.406 (3)	C12—C13	1.529 (3)
C3—C4	1.375 (3)	C12—H12A	0.9700
C3—H3	0.9300	C12—H12B	0.9700
C4—C5	1.385 (3)	C13—H13A	0.9700
C4—H4	0.9300	C13—H13B	0.9700
C5—C6	1.387 (3)	C14—C15	1.529 (3)
C6—C7	1.391 (3)	C14—H14A	0.9700
C6—H6	0.9300	C14—H14B	0.9700
C7—C8	1.532 (3)	C15—H15A	0.9600
C8—C9	1.526 (3)	C15—H15B	0.9600
C8—C14	1.541 (3)	C15—H15C	0.9600
C8—C13	1.556 (3)

C1—N1—C10	119.04 (19)	N1—C10—C11	109.72 (18)
C1—N1—C9	119.42 (17)	N1—C10—H10A	109.7
C10—N1—C9	115.80 (16)	C11—C10—H10A	109.7
C5—O2—H2	109.5	N1—C10—H10B	109.7
O1—C1—N1	122.43 (19)	C11—C10—H10B	109.7
O1—C1—C2	121.54 (18)	H10A—C10—H10B	108.2
N1—C1—C2	115.98 (18)	C12—C11—C10	114.14 (17)
C3—C2—C7	119.91 (19)	C12—C11—H11A	108.7
C3—C2—C1	120.34 (18)	C10—C11—H11A	108.7
C7—C2—C1	119.38 (17)	C12—C11—H11B	108.7
C4—C3—C2	121.2 (2)	C10—C11—H11B	108.7
C4—C3—H3	119.4	H11A—C11—H11B	107.6
C2—C3—H3	119.4	C11—C12—C13	115.73 (18)
C3—C4—C5	119.17 (18)	C11—C12—H12A	108.3
C3—C4—H4	120.4	C13—C12—H12A	108.3
C5—C4—H4	120.4	C11—C12—H12B	108.3
O2—C5—C4	117.53 (18)	C13—C12—H12B	108.3
O2—C5—C6	122.03 (19)	H12A—C12—H12B	107.4
C4—C5—C6	120.4 (2)	C12—C13—C8	120.83 (17)
C5—C6—C7	120.88 (19)	C12—C13—H13A	107.1
C5—C6—H6	119.6	C8—C13—H13A	107.1
C7—C6—H6	119.6	C12—C13—H13B	107.1
C6—C7—C2	118.32 (17)	C8—C13—H13B	107.1
C6—C7—C8	122.77 (18)	H13A—C13—H13B	106.8
C2—C7—C8	118.88 (18)	C15—C14—C8	116.17 (18)
C9—C8—C7	104.31 (15)	C15—C14—H14A	108.2
C9—C8—C14	110.29 (16)	C8—C14—H14A	108.2
C7—C8—C14	110.45 (16)	C15—C14—H14B	108.2
C9—C8—C13	111.28 (17)	C8—C14—H14B	108.2
C7—C8—C13	112.08 (17)	H14A—C14—H14B	107.4
C14—C8—C13	108.41 (16)	C14—C15—H15A	109.5
N1—C9—C8	110.83 (15)	C14—C15—H15B	109.5
N1—C9—H9A	109.5	H15A—C15—H15B	109.5
C8—C9—H9A	109.5	C14—C15—H15C	109.5
N1—C9—H9B	109.5	H15A—C15—H15C	109.5
C8—C9—H9B	109.5	H15B—C15—H15C	109.5
H9A—C9—H9B	108.1

C10—N1—C1—O1	−27.0 (3)	C2—C7—C8—C9	33.5 (2)
C9—N1—C1—O1	−179.22 (17)	C6—C7—C8—C14	−25.7 (2)
C10—N1—C1—C2	150.53 (17)	C2—C7—C8—C14	152.04 (18)
C9—N1—C1—C2	−1.7 (3)	C6—C7—C8—C13	95.3 (2)
O1—C1—C2—C3	−23.0 (3)	C2—C7—C8—C13	−87.0 (2)
N1—C1—C2—C3	159.45 (18)	C1—N1—C9—C8	47.4 (2)
O1—C1—C2—C7	150.1 (2)	C10—N1—C9—C8	−105.69 (19)
N1—C1—C2—C7	−27.5 (3)	C7—C8—C9—N1	−59.9 (2)
C7—C2—C3—C4	2.2 (3)	C14—C8—C9—N1	−178.47 (15)
C1—C2—C3—C4	175.27 (19)	C13—C8—C9—N1	61.2 (2)
C2—C3—C4—C5	−1.6 (3)	C1—N1—C10—C11	−94.0 (2)
C3—C4—C5—O2	178.7 (2)	C9—N1—C10—C11	59.2 (2)
C3—C4—C5—C6	−0.8 (3)	N1—C10—C11—C12	29.3 (3)
O2—C5—C6—C7	−176.9 (2)	C10—C11—C12—C13	−82.8 (2)
C4—C5—C6—C7	2.6 (3)	C11—C12—C13—C8	63.9 (3)
C5—C6—C7—C2	−1.9 (3)	C9—C8—C13—C12	−39.0 (3)
C5—C6—C7—C8	175.79 (18)	C7—C8—C13—C12	77.3 (2)
C3—C2—C7—C6	−0.5 (3)	C14—C8—C13—C12	−160.48 (18)
C1—C2—C7—C6	−173.55 (19)	C9—C8—C14—C15	−48.4 (3)
C3—C2—C7—C8	−178.25 (17)	C7—C8—C14—C15	−163.21 (19)
C1—C2—C7—C8	8.6 (3)	C13—C8—C14—C15	73.6 (2)
C6—C7—C8—C9	−144.15 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.92	2.710 (2)	162

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₉NO₂
M_r	245.31
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.298 (1), 9.9817 (12), 14.7324 (18)
V (Å³)	1220.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.37 × 0.23 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6713, 1397, 1280
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.091, 1.06
No. of reflections	1397
No. of parameters	165
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.92	2.710 (2)	162.3

Symmetry code: (i) x−1, y, z.

Acknowledgements

This work is funded in part by the National Natural Science Foundation of China (grant 30801435).

References

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