(R)-(+)-2,3-Methyl­enedi­oxy-8-oxoberbine

The title compound [systematic name: (R)-(+)-2,3-methyl­ene­di­oxy-5,6,13,13a-tetra­hydro-8H-dibenzo[a,g]quinolizin-8-one], C₁₈H₁₅NO₃, an optically active protoberberine derivative, was synthesized and its absolute configuration has been additionally confirmed by this crystal structure refinement. The H atom at the asymmetric centre assumes a β configuration and is oriented in the bis­ectional position relative to the tetra­hydro­pyridine ring and axial to the tetra­hydro­pyridinone ring.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.087
• Data-to-parameter ratio = 9.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           70.22
           From the CIF: _reflns_number_total               2475
           Count of symmetry unique reflns         1543
           Completeness (_total/calc)            160.40%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       932
           Fraction of Friedel pairs measured     0.604
           Are heavy atom types Z>Si present         no

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(R)-(+)-5,6,13,13a-tetrahydro-2,3-methylenedioxy-8H- dibenzo[a,g]quinolizin-8-one

Crystal data

C18H15NO3	Dx = 1.409 Mg m^−3
Mr = 293.31	Melting point = 467–469 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 61 reflections
a = 7.3595 (8) Å	θ = 14.6–30.0°
b = 9.2465 (14) Å	µ = 0.79 mm^−1
c = 20.323 (3) Å	T = 293 K
V = 1383.0 (3) Å^3	Pillar, colourless
Z = 4	0.55 × 0.15 × 0.12 mm
F(000) = 616

Data collection

Kuma KM-4 diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 70.2°, θmin = 4.4°
Graphite monochromator	h = −8→8
ω–2θ scans	k = 0→11
2673 measured reflections	l = 0→24
2475 independent reflections	2 standard reflections every 100 reflections
2311 reflections with I > 2σ(I)	intensity decay: 3.8%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0667P)^2 + 0.0526P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.21 e Å^−3
2475 reflections	Δρmin = −0.15 e Å^−3
260 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0064 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.1 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.19078 (16)	−0.04829 (12)	0.10710 (6)	0.0553 (3)
O2	1.01657 (18)	−0.16257 (14)	0.02840 (7)	0.0660 (4)
O3	0.32609 (15)	0.54595 (13)	0.13320 (6)	0.0581 (3)
C1	0.97355 (19)	0.14837 (15)	0.12923 (7)	0.0397 (3)
C2	1.0318 (2)	0.02734 (15)	0.09703 (7)	0.0430 (3)
C3	0.9278 (2)	−0.04115 (15)	0.05012 (7)	0.0468 (3)
C4	0.7597 (2)	0.00771 (16)	0.03359 (8)	0.0483 (3)
C4A	0.6959 (2)	0.13322 (15)	0.06517 (7)	0.0411 (3)
C5	0.5094 (2)	0.18995 (17)	0.04902 (8)	0.0497 (4)
C6	0.4316 (2)	0.26980 (18)	0.10695 (9)	0.0493 (4)
N7	0.55659 (15)	0.38470 (13)	0.12647 (6)	0.0427 (3)
C8	0.4893 (2)	0.51737 (16)	0.14035 (7)	0.0428 (3)
C8A	0.6186 (2)	0.62723 (16)	0.16515 (7)	0.0422 (3)
C9	0.5525 (3)	0.75800 (19)	0.18966 (8)	0.0543 (4)
C10	0.6716 (3)	0.86112 (17)	0.21304 (8)	0.0591 (4)
C11	0.8560 (3)	0.83442 (17)	0.21283 (8)	0.0553 (4)
C12	0.9237 (2)	0.70636 (17)	0.18786 (8)	0.0497 (4)
C12A	0.8055 (2)	0.60209 (14)	0.16303 (7)	0.0406 (3)
C13	0.8710 (2)	0.46470 (15)	0.13227 (8)	0.0426 (3)
C13A	0.74094 (18)	0.34119 (15)	0.14579 (7)	0.0377 (3)
C13B	0.80130 (19)	0.20261 (14)	0.11193 (6)	0.0367 (3)
C14	1.1936 (3)	−0.15461 (19)	0.05612 (10)	0.0598 (4)
H1	1.048 (3)	0.194 (2)	0.1662 (10)	0.064 (6)*
H4	0.686 (3)	−0.043 (2)	0.0007 (10)	0.058 (5)*
H51	0.430 (3)	0.106 (2)	0.0383 (10)	0.060 (5)*
H52	0.519 (3)	0.264 (3)	0.0098 (10)	0.061 (5)*
H61	0.417 (3)	0.203 (2)	0.1446 (9)	0.051 (5)*
H62	0.313 (3)	0.316 (2)	0.0941 (10)	0.062 (5)*
H9	0.418 (3)	0.768 (2)	0.1910 (9)	0.057 (5)*
H10	0.628 (3)	0.950 (2)	0.2270 (9)	0.055 (5)*
H11	0.935 (3)	0.911 (2)	0.2307 (10)	0.060 (5)*
H12	1.057 (3)	0.681 (2)	0.1903 (11)	0.072 (7)*
H131	0.995 (3)	0.438 (3)	0.1479 (10)	0.068 (6)*
H132	0.875 (3)	0.478 (2)	0.0836 (10)	0.055 (5)*
H13A	0.741 (3)	0.321 (2)	0.1943 (9)	0.052 (5)*
H141	1.277 (3)	−0.116 (3)	0.0239 (12)	0.076 (7)*
H142	1.230 (3)	−0.250 (2)	0.0734 (10)	0.069 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0449 (6)	0.0409 (5)	0.0800 (7)	0.0120 (5)	−0.0032 (5)	−0.0088 (5)
O2	0.0641 (8)	0.0462 (6)	0.0878 (9)	0.0123 (6)	−0.0046 (7)	−0.0264 (6)
O3	0.0368 (6)	0.0571 (6)	0.0804 (7)	0.0118 (5)	0.0004 (5)	−0.0013 (6)
C1	0.0367 (7)	0.0342 (6)	0.0482 (7)	0.0009 (5)	−0.0032 (6)	−0.0033 (5)
C2	0.0412 (7)	0.0347 (6)	0.0532 (7)	0.0038 (5)	0.0016 (6)	0.0015 (5)
C3	0.0541 (9)	0.0324 (6)	0.0540 (7)	0.0029 (6)	0.0025 (7)	−0.0070 (6)
C4	0.0533 (9)	0.0392 (7)	0.0524 (7)	−0.0025 (6)	−0.0061 (7)	−0.0093 (6)
C4A	0.0404 (8)	0.0377 (6)	0.0450 (7)	−0.0004 (6)	−0.0029 (5)	−0.0018 (5)
C5	0.0417 (9)	0.0471 (8)	0.0603 (9)	−0.0012 (6)	−0.0115 (7)	−0.0051 (7)
C6	0.0327 (8)	0.0474 (8)	0.0679 (9)	−0.0042 (6)	−0.0015 (7)	−0.0036 (7)
N7	0.0302 (6)	0.0399 (6)	0.0581 (7)	0.0017 (5)	−0.0006 (5)	−0.0042 (5)
C8	0.0363 (7)	0.0434 (7)	0.0487 (7)	0.0084 (6)	0.0049 (6)	0.0019 (6)
C8A	0.0443 (8)	0.0385 (7)	0.0439 (6)	0.0060 (6)	0.0035 (6)	0.0001 (6)
C9	0.0573 (11)	0.0490 (8)	0.0566 (8)	0.0127 (8)	0.0096 (7)	−0.0052 (7)
C10	0.0858 (13)	0.0388 (7)	0.0527 (8)	0.0108 (8)	0.0087 (8)	−0.0080 (7)
C11	0.0780 (12)	0.0379 (7)	0.0499 (7)	−0.0056 (8)	−0.0043 (8)	−0.0038 (6)
C12	0.0551 (10)	0.0387 (7)	0.0553 (8)	−0.0042 (7)	−0.0037 (7)	−0.0010 (6)
C12A	0.0435 (8)	0.0342 (6)	0.0439 (6)	0.0015 (6)	0.0015 (6)	0.0003 (5)
C13	0.0359 (7)	0.0362 (7)	0.0556 (8)	0.0004 (5)	0.0009 (6)	−0.0056 (6)
C13A	0.0295 (7)	0.0359 (7)	0.0478 (7)	0.0021 (5)	0.0001 (5)	−0.0030 (5)
C13B	0.0345 (7)	0.0324 (6)	0.0433 (6)	−0.0004 (5)	0.0010 (5)	−0.0009 (5)
C14	0.0612 (11)	0.0414 (8)	0.0770 (11)	0.0121 (8)	0.0074 (9)	−0.0091 (8)

Geometric parameters (Å, º)

O1—C2	1.3782 (18)	N7—C13A	1.4686 (18)
O1—C14	1.428 (2)	C8—C8A	1.480 (2)
O2—C3	1.3720 (18)	C8A—C9	1.395 (2)
O2—C14	1.421 (2)	C8A—C12A	1.396 (2)
O3—C8	1.2381 (18)	C9—C10	1.380 (3)
C1—C2	1.365 (2)	C9—H9	1.00 (2)
C1—C13B	1.408 (2)	C10—C11	1.379 (3)
C1—H1	1.02 (2)	C10—H10	0.93 (2)
C2—C3	1.377 (2)	C11—C12	1.381 (2)
C3—C4	1.359 (2)	C11—H11	0.98 (2)
C4—C4A	1.407 (2)	C12—C12A	1.393 (2)
C4—H4	0.98 (2)	C12—H12	1.01 (2)
C4A—C13B	1.3844 (19)	C12A—C13	1.4956 (18)
C4A—C5	1.505 (2)	C13—C13A	1.5152 (19)
C5—C6	1.503 (2)	C13—H131	1.00 (2)
C5—H51	1.00 (2)	C13—H132	1.00 (2)
C5—H52	1.06 (2)	C13A—C13B	1.5208 (18)
C6—N7	1.460 (2)	C13A—H13A	1.004 (18)
C6—H61	0.989 (19)	C14—H141	0.96 (2)
C6—H62	1.01 (2)	C14—H142	0.98 (2)
N7—C8	1.3527 (18)
C2—O1—C14	104.70 (12)	C12A—C8A—C8	120.58 (13)
C3—O2—C14	105.46 (12)	C10—C9—C8A	120.01 (17)
C2—C1—C13B	117.07 (13)	C10—C9—H9	123.9 (12)
C2—C1—H1	121.7 (12)	C8A—C9—H9	116.0 (12)
C13B—C1—H1	121.1 (12)	C11—C10—C9	120.03 (15)
C1—C2—C3	122.28 (14)	C11—C10—H10	119.9 (12)
C1—C2—O1	127.68 (14)	C9—C10—H10	120.0 (12)
C3—C2—O1	109.97 (12)	C10—C11—C12	120.64 (16)
C4—C3—O2	128.75 (14)	C10—C11—H11	116.8 (12)
C4—C3—C2	121.63 (13)	C12—C11—H11	122.6 (12)
O2—C3—C2	109.53 (14)	C11—C12—C12A	120.04 (16)
C3—C4—C4A	117.72 (14)	C11—C12—H12	121.9 (13)
C3—C4—H4	120.9 (11)	C12A—C12—H12	117.9 (13)
C4A—C4—H4	121.4 (11)	C12—C12A—C8A	119.28 (14)
C13B—C4A—C4	120.56 (14)	C12—C12A—C13	122.53 (14)
C13B—C4A—C5	119.93 (13)	C8A—C12A—C13	118.17 (13)
C4—C4A—C5	119.49 (13)	C12A—C13—C13A	111.15 (12)
C6—C5—C4A	110.35 (13)	C12A—C13—H131	112.0 (13)
C6—C5—H51	109.3 (12)	C13A—C13—H131	109.3 (13)
C4A—C5—H51	108.1 (12)	C12A—C13—H132	108.4 (11)
C6—C5—H52	107.2 (12)	C13A—C13—H132	107.1 (11)
C4A—C5—H52	109.4 (11)	H131—C13—H132	108.8 (17)
H51—C5—H52	112.4 (16)	N7—C13A—C13	109.19 (12)
N7—C6—C5	109.28 (13)	N7—C13A—C13B	112.31 (11)
N7—C6—H61	108.3 (11)	C13—C13A—C13B	111.62 (11)
C5—C6—H61	109.9 (11)	N7—C13A—H13A	108.4 (11)
N7—C6—H62	107.8 (12)	C13—C13A—H13A	108.6 (11)
C5—C6—H62	109.7 (11)	C13B—C13A—H13A	106.6 (11)
H61—C6—H62	111.8 (16)	C4A—C13B—C1	120.72 (12)
C8—N7—C6	119.06 (12)	C4A—C13B—C13A	122.51 (13)
C8—N7—C13A	122.08 (12)	C1—C13B—C13A	116.76 (12)
C6—N7—C13A	117.08 (11)	O2—C14—O1	108.06 (13)
O3—C8—N7	121.63 (14)	O2—C14—H141	109.3 (14)
O3—C8—C8A	121.13 (13)	O1—C14—H141	104.2 (14)
N7—C8—C8A	117.24 (12)	O2—C14—H142	110.3 (13)
C9—C8A—C12A	119.94 (15)	O1—C14—H142	111.1 (12)
C9—C8A—C8	119.47 (14)	H141—C14—H142	113.6 (19)
C13B—C1—C2—C3	−0.7 (2)	C8A—C9—C10—C11	−0.7 (3)
C13B—C1—C2—O1	−177.31 (14)	C9—C10—C11—C12	1.6 (3)
C14—O1—C2—C1	−173.83 (16)	C10—C11—C12—C12A	−0.5 (2)
C14—O1—C2—C3	9.26 (18)	C11—C12—C12A—C8A	−1.5 (2)
C14—O2—C3—C4	174.49 (17)	C11—C12—C12A—C13	176.83 (14)
C14—O2—C3—C2	−9.04 (19)	C9—C8A—C12A—C12	2.4 (2)
C1—C2—C3—C4	−0.5 (2)	C8—C8A—C12A—C12	−178.81 (13)
O1—C2—C3—C4	176.57 (14)	C9—C8A—C12A—C13	−175.98 (13)
C1—C2—C3—O2	−177.30 (14)	C8—C8A—C12A—C13	2.79 (19)
O1—C2—C3—O2	−0.19 (18)	C12—C12A—C13—C13A	146.59 (13)
O2—C3—C4—C4A	177.34 (15)	C8A—C12A—C13—C13A	−35.07 (18)
C2—C3—C4—C4A	1.3 (2)	C8—N7—C13A—C13	−42.63 (17)
C3—C4—C4A—C13B	−0.7 (2)	C6—N7—C13A—C13	152.73 (13)
C3—C4—C4A—C5	−179.17 (14)	C8—N7—C13A—C13B	−167.00 (12)
C13B—C4A—C5—C6	−26.8 (2)	C6—N7—C13A—C13B	28.36 (17)
C4—C4A—C5—C6	151.69 (14)	C12A—C13—C13A—N7	52.41 (15)
C4A—C5—C6—N7	56.01 (18)	C12A—C13—C13A—C13B	177.19 (11)
C5—C6—N7—C8	135.45 (14)	C4—C4A—C13B—C1	−0.6 (2)
C5—C6—N7—C13A	−59.43 (17)	C5—C4A—C13B—C1	177.90 (13)
C6—N7—C8—O3	−4.3 (2)	C4—C4A—C13B—C13A	177.98 (13)
C13A—N7—C8—O3	−168.65 (14)	C5—C4A—C13B—C13A	−3.6 (2)
C6—N7—C8—C8A	175.13 (13)	C2—C1—C13B—C4A	1.3 (2)
C13A—N7—C8—C8A	10.78 (19)	C2—C1—C13B—C13A	−177.36 (12)
O3—C8—C8A—C9	9.2 (2)	N7—C13A—C13B—C4A	3.95 (18)
N7—C8—C8A—C9	−170.23 (14)	C13—C13A—C13B—C4A	−119.06 (15)
O3—C8—C8A—C12A	−169.58 (14)	N7—C13A—C13B—C1	−177.46 (12)
N7—C8—C8A—C12A	11.0 (2)	C13—C13A—C13B—C1	59.53 (16)
C12A—C8A—C9—C10	−1.3 (2)	C3—O2—C14—O1	14.8 (2)
C8—C8A—C9—C10	179.86 (15)	C2—O1—C14—O2	−14.76 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O3	0.99 (2)	2.460 (19)	2.817 (2)	100.5 (12)
C6—H62···O3	1.01 (2)	2.273 (19)	2.722 (2)	105.6 (14)
C14—H142···O3^i	0.986 (19)	2.353 (19)	3.327 (2)	169.2 (16)

Symmetry code: (i) x+1, y−1, z.