3-Methyl-1,2,3,4,5,6,1',2',3',4'-deca-hydro-spiro-[benz[f]isoquinoline-1,2'-naphthalen]-1'-one.

The title compound, C(23)H(23)NO, is the product of a tandem transformation of the double Mannich base bis-(1-oxo-1,2,3,4-tertrahydro-2-naphtho-ylmeth-yl)amine hydro-chloride in HBr solution upon heating. The tetra-hydro-pyridine ring has a non-symmetrical half-chair conformation, whereas the cyclo-hexa-diene and cyclo-hexene rings adopt non-symmetrical half-boat conformations. The dihedral angle between the planes of the terminal benzene rings is 62.85 (6)°. The N atom has a trigonal-pyramidal geometry [sum of the bond angles = 332.4 (3)°]. In the crystal, mol-ecules form [001] chains via weak non-classical C-H⋯N hydrogen bonds. The chains are stacked along the b axis.

Related literature

For general background to the synthesis, chemical properties and probable applications in medicine (including computer program prognosis) of the title compound, see: Plati & Wenner (1949 ▶); Ellefson et al. (1978 ▶); Soldatenkov et al. (2009 ▶). For related compounds, see: Plati & Wenner (1950 ▶); Soldatenkov et al. (2008 ▶); Soldatova et al. (2010 ▶).

Experimental

Crystal data

C23H23NO

M = 329.42

Monoclinic,

a = 27.645 (6) Å

b = 8.1613 (15) Å

c = 16.741 (3) Å

β = 116.037 (5)°

V = 3393.8 (11) Å3

Z = 8

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.25 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.981, T max = 0.986

21756 measured reflections

4065 independent reflections

3080 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.122

S = 1.00

4065 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812043309/rk2383sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043309/rk2383Isup2.hkl

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

C23H23NO	F(000) = 1408
Mr = 329.42	Dx = 1.289 Mg m−3
Monoclinic, C2/c	Melting point = 432–434 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 27.645 (6) Å	Cell parameters from 4458 reflections
b = 8.1613 (15) Å	θ = 2.5–27.6°
c = 16.741 (3) Å	µ = 0.08 mm−1
β = 116.037 (5)°	T = 100 K
V = 3393.8 (11) Å3	Prism, yellow
Z = 8	0.25 × 0.20 × 0.18 mm

Bruker APEXII CCD diffractometer	4065 independent reflections
Radiation source: fine–focus sealed tube	3080 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
φ– and ω–scans	θmax = 28.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −36→36
Tmin = 0.981, Tmax = 0.986	k = −10→10
21756 measured reflections	l = −22→22

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0573P)2 + 3.1P] where P = (Fo2 + 2Fc2)/3
4065 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C1	0.38819 (6)	0.38415 (17)	0.63564 (9)	0.0186 (3)
C2	0.41181 (6)	0.31889 (18)	0.73225 (9)	0.0209 (3)
H2A	0.4336	0.2196	0.7375	0.025*
H2B	0.4357	0.4029	0.7734	0.025*
N3	0.36865 (5)	0.27950 (15)	0.75652 (8)	0.0218 (3)
C4	0.33687 (6)	0.14322 (18)	0.70326 (10)	0.0221 (3)
H4A	0.3016	0.1428	0.7054	0.027*
H4B	0.3555	0.0396	0.7304	0.027*
C4A	0.32718 (6)	0.14692 (17)	0.60802 (9)	0.0195 (3)
C5	0.28684 (6)	0.02231 (18)	0.54966 (10)	0.0228 (3)
H5A	0.2504	0.0713	0.5236	0.027*
H5B	0.2867	−0.0731	0.5861	0.027*
C6	0.30040 (6)	−0.03436 (18)	0.47565 (10)	0.0233 (3)
H6A	0.3335	−0.1018	0.5009	0.028*
H6B	0.2707	−0.1030	0.4332	0.028*
C6A	0.30877 (6)	0.11093 (18)	0.42766 (10)	0.0210 (3)
C7	0.29174 (6)	0.10844 (19)	0.33643 (10)	0.0247 (3)
H7	0.2731	0.0152	0.3032	0.030*
C8	0.30145 (6)	0.2397 (2)	0.29267 (10)	0.0257 (3)
H8	0.2895	0.2361	0.2301	0.031*
C9	0.32863 (6)	0.37597 (19)	0.34078 (10)	0.0245 (3)
H9	0.3358	0.4659	0.3115	0.029*
C10	0.34541 (6)	0.38049 (18)	0.43231 (10)	0.0220 (3)
H10	0.3639	0.4745	0.4648	0.026*
C10A	0.33571 (6)	0.24990 (18)	0.47763 (9)	0.0190 (3)
C10B	0.35079 (6)	0.25256 (17)	0.57463 (9)	0.0187 (3)
C11	0.38899 (7)	0.2413 (2)	0.85111 (10)	0.0274 (3)
H11A	0.3587	0.2200	0.8651	0.041*
H11B	0.4099	0.3344	0.8865	0.041*
H11C	0.4121	0.1441	0.8652	0.041*
O1'	0.46093 (4)	0.29448 (13)	0.60614 (7)	0.0251 (3)
C1'	0.43732 (6)	0.41176 (18)	0.61768 (9)	0.0191 (3)
C3'	0.35611 (6)	0.54404 (17)	0.62726 (10)	0.0203 (3)
H3A	0.3351	0.5709	0.5635	0.024*
H3B	0.3304	0.5258	0.6529	0.024*
C4'	0.39224 (6)	0.68881 (18)	0.67422 (10)	0.0216 (3)
H4C	0.3699	0.7886	0.6641	0.026*
H4D	0.4104	0.6676	0.7390	0.026*
C4'A	0.43388 (6)	0.71699 (18)	0.64079 (10)	0.0210 (3)
C5'	0.45125 (6)	0.87444 (19)	0.63298 (11)	0.0259 (3)
H5C	0.4363	0.9666	0.6487	0.031*
C6'	0.48995 (7)	0.89823 (19)	0.60268 (11)	0.0286 (4)
H6C	0.5008	1.0063	0.5969	0.034*
C7'	0.51303 (6)	0.7651 (2)	0.58076 (10)	0.0263 (3)
H7A	0.5400	0.7814	0.5609	0.032*
C8'	0.49630 (6)	0.60865 (19)	0.58814 (10)	0.0225 (3)
H8A	0.5122	0.5172	0.5736	0.027*
C8'A	0.45636 (6)	0.58295 (18)	0.61671 (9)	0.0201 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0219 (7)	0.0156 (7)	0.0175 (7)	0.0003 (5)	0.0080 (6)	−0.0009 (5)
C2	0.0237 (7)	0.0184 (7)	0.0182 (7)	0.0011 (6)	0.0071 (6)	−0.0007 (5)
N3	0.0268 (6)	0.0213 (6)	0.0169 (6)	−0.0007 (5)	0.0092 (5)	−0.0014 (5)
C4	0.0277 (8)	0.0184 (7)	0.0220 (7)	0.0002 (6)	0.0126 (6)	0.0007 (6)
C4A	0.0216 (7)	0.0162 (7)	0.0199 (7)	0.0018 (5)	0.0082 (6)	−0.0016 (5)
C5	0.0249 (7)	0.0187 (7)	0.0236 (8)	−0.0014 (6)	0.0095 (6)	−0.0005 (6)
C6	0.0266 (8)	0.0173 (7)	0.0233 (7)	−0.0011 (6)	0.0086 (6)	−0.0024 (6)
C6A	0.0230 (7)	0.0179 (7)	0.0209 (7)	0.0031 (5)	0.0085 (6)	−0.0015 (6)
C7	0.0275 (8)	0.0219 (7)	0.0217 (7)	0.0011 (6)	0.0081 (6)	−0.0051 (6)
C8	0.0309 (8)	0.0277 (8)	0.0181 (7)	0.0039 (6)	0.0105 (6)	−0.0010 (6)
C9	0.0297 (8)	0.0233 (8)	0.0217 (7)	0.0023 (6)	0.0125 (6)	0.0024 (6)
C10	0.0254 (7)	0.0191 (7)	0.0213 (7)	0.0003 (6)	0.0100 (6)	−0.0021 (6)
C10A	0.0198 (7)	0.0180 (7)	0.0185 (7)	0.0023 (5)	0.0077 (6)	−0.0010 (5)
C10B	0.0202 (7)	0.0161 (6)	0.0183 (7)	0.0018 (5)	0.0069 (6)	−0.0011 (5)
C11	0.0352 (9)	0.0263 (8)	0.0197 (8)	0.0007 (7)	0.0113 (7)	0.0015 (6)
O1'	0.0272 (6)	0.0189 (5)	0.0299 (6)	0.0037 (4)	0.0132 (5)	−0.0033 (4)
C1'	0.0213 (7)	0.0184 (7)	0.0153 (7)	0.0013 (5)	0.0060 (5)	−0.0005 (5)
C3'	0.0231 (7)	0.0164 (7)	0.0212 (7)	0.0017 (5)	0.0095 (6)	−0.0004 (5)
C4'	0.0261 (7)	0.0166 (7)	0.0220 (7)	0.0023 (6)	0.0105 (6)	−0.0030 (6)
C4'A	0.0219 (7)	0.0185 (7)	0.0184 (7)	0.0007 (5)	0.0049 (6)	−0.0011 (5)
C5'	0.0279 (8)	0.0178 (7)	0.0288 (8)	0.0009 (6)	0.0094 (7)	−0.0018 (6)
C6'	0.0294 (8)	0.0197 (7)	0.0325 (9)	−0.0036 (6)	0.0097 (7)	0.0028 (6)
C7'	0.0259 (8)	0.0276 (8)	0.0255 (8)	−0.0010 (6)	0.0115 (6)	0.0042 (6)
C8'	0.0246 (7)	0.0215 (7)	0.0193 (7)	0.0035 (6)	0.0077 (6)	0.0017 (6)
C8'A	0.0218 (7)	0.0188 (7)	0.0170 (7)	0.0001 (5)	0.0060 (6)	−0.0001 (5)

C1—C10B	1.5292 (19)	C9—C10	1.393 (2)
C1—C1'	1.531 (2)	C9—H9	0.9500
C1—C2	1.549 (2)	C10—C10A	1.401 (2)
C1—C3'	1.5491 (19)	C10—H10	0.9500
C2—N3	1.4554 (19)	C10A—C10B	1.4889 (19)
C2—H2A	0.9900	C11—H11A	0.9800
C2—H2B	0.9900	C11—H11B	0.9800
N3—C4	1.4548 (19)	C11—H11C	0.9800
N3—C11	1.4626 (19)	O1'—C1'	1.2207 (17)
C4—C4A	1.497 (2)	C1'—C8'A	1.495 (2)
C4—H4A	0.9900	C3'—C4'	1.524 (2)
C4—H4B	0.9900	C3'—H3A	0.9900
C4A—C10B	1.343 (2)	C3'—H3B	0.9900
C4A—C5	1.509 (2)	C4'—C4'A	1.502 (2)
C5—C6	1.516 (2)	C4'—H4C	0.9900
C5—H5A	0.9900	C4'—H4D	0.9900
C5—H5B	0.9900	C4'A—C5'	1.398 (2)
C6—C6A	1.506 (2)	C4'A—C8'A	1.402 (2)
C6—H6A	0.9900	C5'—C6'	1.384 (2)
C6—H6B	0.9900	C5'—H5C	0.9500
C6A—C7	1.387 (2)	C6'—C7'	1.389 (2)
C6A—C10A	1.412 (2)	C6'—H6C	0.9500
C7—C8	1.389 (2)	C7'—C8'	1.382 (2)
C7—H7	0.9500	C7'—H7A	0.9500
C8—C9	1.385 (2)	C8'—C8'A	1.398 (2)
C8—H8	0.9500	C8'—H8A	0.9500
C10B—C1—C1'	111.72 (11)	C9—C10—C10A	121.69 (14)
C10B—C1—C2	107.91 (11)	C9—C10—H10	119.2
C1'—C1—C2	104.59 (11)	C10A—C10—H10	119.2
C10B—C1—C3'	109.80 (11)	C10—C10A—C6A	117.82 (13)
C1'—C1—C3'	112.35 (12)	C10—C10A—C10B	123.45 (13)
C2—C1—C3'	110.26 (11)	C6A—C10A—C10B	118.70 (13)
N3—C2—C1	110.24 (12)	C4A—C10B—C10A	119.36 (13)
N3—C2—H2A	109.6	C4A—C10B—C1	118.86 (13)
C1—C2—H2A	109.6	C10A—C10B—C1	121.48 (12)
N3—C2—H2B	109.6	N3—C11—H11A	109.5
C1—C2—H2B	109.6	N3—C11—H11B	109.5
H2A—C2—H2B	108.1	H11A—C11—H11B	109.5
C4—N3—C2	110.27 (11)	N3—C11—H11C	109.5
C4—N3—C11	110.03 (12)	H11A—C11—H11C	109.5
C2—N3—C11	112.12 (12)	H11B—C11—H11C	109.5
N3—C4—C4A	114.52 (12)	O1'—C1'—C8'A	121.05 (13)
N3—C4—H4A	108.6	O1'—C1'—C1	119.84 (13)
C4A—C4—H4A	108.6	C8'A—C1'—C1	119.10 (12)
N3—C4—H4B	108.6	C4'—C3'—C1	112.75 (12)
C4A—C4—H4B	108.6	C4'—C3'—H3A	109.0
H4A—C4—H4B	107.6	C1—C3'—H3A	109.0
C10B—C4A—C4	124.35 (13)	C4'—C3'—H3B	109.0
C10B—C4A—C5	121.30 (13)	C1—C3'—H3B	109.0
C4—C4A—C5	114.34 (12)	H3A—C3'—H3B	107.8
C4A—C5—C6	110.93 (12)	C4'A—C4'—C3'	111.25 (12)
C4A—C5—H5A	109.5	C4'A—C4'—H4C	109.4
C6—C5—H5A	109.5	C3'—C4'—H4C	109.4
C4A—C5—H5B	109.5	C4'A—C4'—H4D	109.4
C6—C5—H5B	109.5	C3'—C4'—H4D	109.4
H5A—C5—H5B	108.0	H4C—C4'—H4D	108.0
C6A—C6—C5	110.29 (12)	C5'—C4'A—C8'A	118.47 (14)
C6A—C6—H6A	109.6	C5'—C4'A—C4'	121.76 (13)
C5—C6—H6A	109.6	C8'A—C4'A—C4'	119.77 (13)
C6A—C6—H6B	109.6	C6'—C5'—C4'A	121.04 (14)
C5—C6—H6B	109.6	C6'—C5'—H5C	119.5
H6A—C6—H6B	108.1	C4'A—C5'—H5C	119.5
C7—C6A—C10A	120.00 (14)	C5'—C6'—C7'	120.39 (14)
C7—C6A—C6	121.23 (13)	C5'—C6'—H6C	119.8
C10A—C6A—C6	118.75 (13)	C7'—C6'—H6C	119.8
C6A—C7—C8	121.25 (14)	C8'—C7'—C6'	119.26 (14)
C6A—C7—H7	119.4	C8'—C7'—H7A	120.4
C8—C7—H7	119.4	C6'—C7'—H7A	120.4
C9—C8—C7	119.58 (14)	C7'—C8'—C8'A	120.98 (14)
C9—C8—H8	120.2	C7'—C8'—H8A	119.5
C7—C8—H8	120.2	C8'A—C8'—H8A	119.5
C8—C9—C10	119.64 (14)	C8'—C8'A—C4'A	119.83 (14)
C8—C9—H9	120.2	C8'—C8'A—C1'	118.57 (13)
C10—C9—H9	120.2	C4'A—C8'A—C1'	121.56 (13)
C10B—C1—C2—N3	−58.09 (15)	C1'—C1—C10B—C4A	141.08 (13)
C1'—C1—C2—N3	−177.18 (11)	C2—C1—C10B—C4A	26.64 (17)
C3'—C1—C2—N3	61.83 (15)	C3'—C1—C10B—C4A	−93.57 (15)
C1—C2—N3—C4	65.76 (15)	C1'—C1—C10B—C10A	−45.28 (17)
C1—C2—N3—C11	−171.26 (12)	C2—C1—C10B—C10A	−159.72 (12)
C2—N3—C4—C4A	−39.30 (17)	C3'—C1—C10B—C10A	80.07 (16)
C11—N3—C4—C4A	−163.49 (13)	C10B—C1—C1'—O1'	−43.04 (18)
N3—C4—C4A—C10B	8.3 (2)	C2—C1—C1'—O1'	73.43 (16)
N3—C4—C4A—C5	−170.33 (12)	C3'—C1—C1'—O1'	−166.97 (13)
C10B—C4A—C5—C6	32.90 (19)	C10B—C1—C1'—C8'A	138.38 (13)
C4—C4A—C5—C6	−148.37 (13)	C2—C1—C1'—C8'A	−105.15 (14)
C4A—C5—C6—C6A	−50.93 (16)	C3'—C1—C1'—C8'A	14.45 (17)
C5—C6—C6A—C7	−142.78 (14)	C10B—C1—C3'—C4'	−170.57 (12)
C5—C6—C6A—C10A	38.82 (18)	C1'—C1—C3'—C4'	−45.58 (16)
C10A—C6A—C7—C8	1.1 (2)	C2—C1—C3'—C4'	70.66 (15)
C6—C6A—C7—C8	−177.28 (14)	C1—C3'—C4'—C4'A	56.09 (16)
C6A—C7—C8—C9	0.0 (2)	C3'—C4'—C4'A—C5'	144.85 (14)
C7—C8—C9—C10	−0.7 (2)	C3'—C4'—C4'A—C8'A	−35.28 (19)
C8—C9—C10—C10A	0.3 (2)	C8'A—C4'A—C5'—C6'	−0.4 (2)
C9—C10—C10A—C6A	0.8 (2)	C4'—C4'A—C5'—C6'	179.52 (14)
C9—C10—C10A—C10B	−177.23 (14)	C4'A—C5'—C6'—C7'	−1.1 (2)
C7—C6A—C10A—C10	−1.5 (2)	C5'—C6'—C7'—C8'	1.0 (2)
C6—C6A—C10A—C10	176.93 (13)	C6'—C7'—C8'—C8'A	0.4 (2)
C7—C6A—C10A—C10B	176.67 (13)	C7'—C8'—C8'A—C4'A	−1.9 (2)
C6—C6A—C10A—C10B	−4.9 (2)	C7'—C8'—C8'A—C1'	176.02 (13)
C4—C4A—C10B—C10A	−176.81 (13)	C5'—C4'A—C8'A—C8'	1.8 (2)
C5—C4A—C10B—C10A	1.8 (2)	C4'—C4'A—C8'A—C8'	−178.06 (13)
C4—C4A—C10B—C1	−3.0 (2)	C5'—C4'A—C8'A—C1'	−176.02 (13)
C5—C4A—C10B—C1	175.55 (13)	C4'—C4'A—C8'A—C1'	4.1 (2)
C10—C10A—C10B—C4A	161.01 (14)	O1'—C1'—C8'A—C8'	10.3 (2)
C6A—C10A—C10B—C4A	−17.0 (2)	C1—C1'—C8'A—C8'	−171.18 (12)
C10—C10A—C10B—C1	−12.6 (2)	O1'—C1'—C8'A—C4'A	−171.88 (14)
C6A—C10A—C10B—C1	169.35 (13)	C1—C1'—C8'A—C4'A	6.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···N3i	0.95	2.59	3.534 (2)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯N3i	0.95	2.59	3.534 (2)	171

Symmetry code: (i) .