(1R,4bS,8aR)-(1,2,3,4b,5,6,7,8,8a,9a-Deca­hydro-4,9a-di­aza­fluoren-1-yl)­methanol

The crystal structure of the title compound, C₁₂H₂₀N₂O, was determined in order to establish the configuration of C4b (S) and C8a (R) with respect to the known configuration of C1 (R). The compound forms infinite chains of hydrogen-bonded mol­ecules parallel to the c axis.

S1. Comment

The title compound was prepared during a study on the synthesis of enantiopure hydroxyamidines (Ostendorf et al., 2000). The crystal structure determination was undertaken in order to establish the configuration of atoms C4b and C8a (note crystallographic numbering) with respect to the known (R) configuration of C4. C4b turned out to have the S configuration, while C8a has the R configuration.

Due to the presence of the double-bond C3═N4 and the sp² hybridization of N9a, the atoms of the nitrogen-containing rings more or less lie within one plane [maximum deviation from the least-squares plane is 0.118 (3) Å for C1], with the exception of atoms C2 [deviation 0.695 (3) Å] and C8a [deviation 0.515 (3) Å] which protrude on opposite sides. The five-membered ring and the six-membered heteroatomic ring are therefore in a somewhat distorted envelope conformation. The six-membered carbon ring has adopted a slightly deformed chair conformation.

The hydroxyl group donates an intermolecular hydrogen bond to N4 (geometric details in Table 2), thus forming an infinite one-dimensional chain parallel to the c axis [graph set C(7); Bernstein et al., 1995]. The two screw-related anti-parallel chains present in the unit cell are joined by C—H···O interactions involving C4a and O11 (geometric details in Table 2), creating a two-dimensional network perpendicular to the a axis. The C—H···O interactions by themselves organize the molecules in infinite one-dimensional chains [graph set C(7)] parallel to the b axis.

S2. Experimental

Details of the preparation of (I) are given by Ostendorf et al. (2000). Crystals were obtained after recrystallization from benzene.

S3. Refinement

Due to the absence of significant anomalous dispersion, the absolute structure cannot be determined reliably. The configuration of C1 was set equal to R, consistent with the starting materials used (see Ostendorf et al., 2000). The 2197 measured reflections reduced to 1924 unique reflections. After merging of the Friedel pairs, 1461 reflections remained. The hydroxyl H atom was located on a difference Fourier map and its coordinates were refined. The other H atoms were also located on a difference Fourier map, but in order to limit the number of refined parameters, they were included in the refinement on calculated positions riding on their carrier atoms. All H-atom displacement parameters were set equal to the equivalent isotropic displacement parameter of their carrier atom, multiplied by a constant factor of 1.5 (hydroxyl H) or 1.2 (other H atoms).

Computing details

Data collection: locally modified CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 (de Boer & Duisenberg, 1984); data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON.

(1R,4bS,8aR)-(1,2,3,4 b,5,6,7,8,8a,9a-Decahydro-4,9a-diazafluoren-1-yl)methanol

Crystal data

C12H20N2O	F(000) = 456
Mr = 208.30	Dx = 1.262 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 24 reflections
a = 8.4691 (9) Å	θ = 10.1–15.6°
b = 10.3985 (8) Å	µ = 0.08 mm^−1
c = 12.4538 (15) Å	T = 150 K
V = 1096.8 (2) Å^3	Block, colourless
Z = 4	0.3 × 0.2 × 0.1 mm

Data collection

Enraf Nonius CAD4T diffractometer	Rint = 0.035
Radiation source: Rotating Anode	θmax = 27.5°, θmin = 2.6°
Graphite monochromator	h = −11→0
ω scans	k = −10→13
2161 measured reflections	l = 0→16
1461 independent reflections	3 standard reflections every 60 min
1007 reflections with I > 2σ(I)	intensity decay: 6%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2(Fo^2) + (0.0478P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.104	(Δ/σ)max < 0.001
S = 0.99	Δρmax = 0.23 e Å^−3
1461 reflections	Δρmin = −0.24 e Å^−3
139 parameters	Absolute structure: Refinement was carried out on a data set with averaged Friedel pairs, therefore no _refine_ls_abs_structure_Flack is reported.

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O11	0.3058 (2)	0.19551 (19)	0.18233 (17)	0.0249 (6)
N4	0.1897 (3)	−0.0947 (2)	0.47817 (19)	0.0237 (8)
N9A	0.1409 (2)	−0.0094 (2)	0.30581 (19)	0.0216 (7)
C1	0.3008 (3)	−0.0194 (3)	0.2635 (2)	0.0197 (8)
C2	0.3912 (3)	−0.1123 (3)	0.3345 (2)	0.0235 (9)
C3	0.3595 (3)	−0.0865 (3)	0.4528 (2)	0.0250 (10)
C4A	0.0978 (3)	−0.0569 (3)	0.4033 (2)	0.0203 (9)
C4B	−0.0812 (3)	−0.0614 (3)	0.4064 (2)	0.0238 (9)
C5	−0.1563 (3)	−0.0402 (3)	0.5159 (2)	0.0281 (10)
C6	−0.1511 (3)	0.0989 (3)	0.5528 (2)	0.0284 (10)
C7	−0.2219 (3)	0.1869 (3)	0.4678 (3)	0.0304 (10)
C8	−0.1279 (4)	0.1745 (3)	0.3639 (2)	0.0270 (9)
C8A	−0.1266 (3)	0.0378 (3)	0.3208 (2)	0.0227 (9)
C9	0.0042 (3)	0.0202 (3)	0.2380 (2)	0.0250 (9)
C10	0.3804 (3)	0.1115 (3)	0.2555 (2)	0.0243 (9)
H1	0.29470	−0.05700	0.18970	0.0240*
H4B	−0.11500	−0.14800	0.38000	0.0290*
H8A	−0.23140	0.01590	0.28880	0.0270*
H11	0.324 (3)	0.161 (3)	0.106 (2)	0.0370*
H21	0.50570	−0.10390	0.32020	0.0280*
H22	0.35950	−0.20160	0.31700	0.0280*
H31	0.41800	−0.14980	0.49680	0.0300*
H32	0.39890	0.00030	0.47150	0.0300*
H51	−0.26770	−0.06870	0.51320	0.0340*
H52	−0.10100	−0.09430	0.56950	0.0340*
H61	−0.04030	0.12430	0.56670	0.0340*
H62	−0.21090	0.10790	0.62070	0.0340*
H71	−0.21920	0.27710	0.49310	0.0360*
H72	−0.33340	0.16290	0.45470	0.0360*
H81	−0.17410	0.23230	0.30910	0.0320*
H82	−0.01790	0.20260	0.37700	0.0320*
H91	−0.01970	−0.05150	0.18830	0.0300*
H92	0.02140	0.09980	0.19600	0.0300*
H101	0.38120	0.15200	0.32750	0.0290*
H102	0.49160	0.09910	0.23310	0.0290*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0276 (10)	0.0226 (12)	0.0244 (11)	−0.0015 (9)	−0.0019 (10)	0.0031 (10)
N4	0.0200 (12)	0.0265 (14)	0.0245 (13)	0.0007 (11)	−0.0011 (11)	0.0029 (13)
N9A	0.0146 (10)	0.0274 (14)	0.0228 (13)	0.0039 (11)	−0.0014 (10)	0.0019 (11)
C1	0.0166 (13)	0.0220 (15)	0.0204 (15)	0.0021 (12)	−0.0004 (12)	−0.0025 (14)
C2	0.0201 (14)	0.0244 (16)	0.0259 (16)	0.0039 (13)	−0.0009 (13)	0.0000 (14)
C3	0.0205 (14)	0.0274 (19)	0.0272 (17)	0.0014 (14)	−0.0062 (13)	0.0052 (15)
C4A	0.0211 (15)	0.0150 (14)	0.0247 (16)	0.0017 (13)	0.0019 (13)	0.0017 (14)
C4B	0.0216 (15)	0.0219 (16)	0.0278 (17)	−0.0053 (13)	−0.0008 (13)	0.0003 (15)
C5	0.0210 (14)	0.0331 (18)	0.0302 (18)	−0.0042 (14)	0.0021 (13)	0.0074 (16)
C6	0.0252 (15)	0.0349 (19)	0.0251 (16)	−0.0010 (15)	0.0048 (13)	−0.0044 (15)
C7	0.0295 (16)	0.0270 (18)	0.0348 (18)	0.0048 (15)	−0.0027 (15)	−0.0039 (17)
C8	0.0309 (16)	0.0214 (16)	0.0287 (17)	0.0052 (15)	−0.0043 (14)	0.0045 (14)
C8A	0.0143 (13)	0.0285 (17)	0.0253 (15)	−0.0024 (13)	−0.0049 (14)	−0.0017 (15)
C9	0.0218 (13)	0.0295 (17)	0.0238 (15)	0.0020 (14)	−0.0079 (13)	0.0005 (15)
C10	0.0219 (14)	0.0269 (16)	0.0240 (16)	0.0000 (14)	−0.0023 (13)	0.0014 (15)

Geometric parameters (Å, º)

O11—C10	1.412 (3)	C2—H21	0.9898
O11—H11	1.03 (3)	C2—H22	0.9909
N4—C3	1.475 (4)	C3—H31	0.9894
N4—C4A	1.277 (4)	C3—H32	0.9901
N9A—C4A	1.361 (3)	C4B—H4B	1.0005
N9A—C9	1.466 (3)	C5—H51	0.9895
N9A—C1	1.457 (3)	C5—H52	0.9907
C1—C2	1.517 (4)	C6—H61	0.9901
C1—C10	1.522 (4)	C6—H62	0.9901
C2—C3	1.521 (4)	C7—H71	0.9897
C4A—C4B	1.517 (4)	C7—H72	0.9903
C4B—C8A	1.532 (4)	C8—H81	0.9900
C4B—C5	1.521 (4)	C8—H82	0.9899
C5—C6	1.518 (4)	C8A—H8A	0.9992
C6—C7	1.522 (4)	C9—H91	0.9899
C7—C8	1.525 (4)	C9—H92	0.9899
C8—C8A	1.519 (4)	C10—H101	0.9907
C8A—C9	1.524 (4)	C10—H102	0.9906
C1—H1	1.0001
O11···N9A	2.976 (3)	H22···C4A	2.8864
O11···C9	3.214 (3)	H22···H52^xi	2.5718
O11···C2^i	3.259 (3)	H22···C10^v	3.0732
O11···N4^ii	2.750 (3)	H22···H81^vi	2.3247
O11···C3^ii	3.379 (3)	H22···H102^v	2.5049
O11···C4B^iii	3.351 (3)	H31···H11^iv	2.4624
O11···H92	2.6117	H31···H92^iv	2.5861
O11···H4B^iii	2.4211	H32···C10	2.9322
O11···H21^i	2.6268	H32···H101	2.3931
N4···O11^iv	2.750 (3)	H32···H71^xii	2.5598
N9A···O11	2.976 (3)	H51···H72	2.5769
N4···H11^iv	1.74 (3)	H52···N4	2.7120
N4···H52	2.7120	H52···C10^iv	2.9813
N9A···H82	2.7303	H52···H11^iv	2.4882
C2···O11^v	3.259 (3)	H52···H102^iv	2.2388
C3···O11^iv	3.379 (3)	H52···H22^xiii	2.5718
C4B···O11^vi	3.351 (3)	H61···C4A	3.0098
C9···O11	3.214 (3)	H61···H82	2.5060
C1···H81^vi	2.9386	H62···H8A^xiv	2.5057
C2···H81^vi	3.0315	H62···H91^xiv	2.5017
C3···H11^iv	2.58 (3)	H71···H32^vii	2.5598
C3···H101	2.9359	H71···H101^vii	2.5017
C4A···H82	2.8894	H72···H51	2.5769
C4A···H22	2.8864	H81···H92	2.5736
C4A···H61	3.0098	H81···C1^iii	2.9386
C4A···H11^iv	2.83 (3)	H81···C2^iii	3.0315
C6···H101^vii	3.0011	H81···H1^iii	2.4174
C10···H32	2.9322	H81···H22^iii	2.3247
C10···H52^ii	2.9813	H82···N9A	2.7303
C10···H22^i	3.0732	H82···C4A	2.8894
H1···H11	2.5074	H82···H61	2.5060
H1···H81^vi	2.4174	H82···H92	2.5169
H4B···O11^vi	2.4211	H91···H62^ix	2.5017
H8A···H21^viii	2.5811	H92···O11	2.6117
H8A···H102^viii	2.5948	H92···H81	2.5736
H8A···H62^ix	2.5057	H92···H82	2.5169
H11···H1	2.5074	H92···H31^ii	2.5861
H11···N4^ii	1.74 (3)	H101···C3	2.9359
H11···C3^ii	2.58 (3)	H101···H32	2.3931
H11···C4A^ii	2.83 (3)	H101···C6^xii	3.0011
H11···H31^ii	2.4624	H101···H71^xii	2.5017
H11···H52^ii	2.4882	H102···H8A^x	2.5948
H21···H8A^x	2.5811	H102···H21	2.3763
H21···H102	2.3763	H102···H52^ii	2.2388
H21···O11^v	2.6268	H102···H22^i	2.5049
C10—O11—H11	108.3 (16)	H31—C3—H32	107.90
C3—N4—C4A	114.8 (2)	C4A—C4B—H4B	107.78
C1—N9A—C4A	123.1 (2)	C5—C4B—H4B	107.79
C4A—N9A—C9	112.24 (19)	C8A—C4B—H4B	107.79
C1—N9A—C9	122.7 (2)	C4B—C5—H51	108.96
N9A—C1—C2	107.7 (2)	C4B—C5—H52	108.92
N9A—C1—C10	111.8 (2)	C6—C5—H51	108.86
C2—C1—C10	112.6 (2)	C6—C5—H52	108.86
C1—C2—C3	111.3 (2)	H51—C5—H52	107.67
N4—C3—C2	111.7 (2)	C5—C6—H61	109.54
N4—C4A—C4B	125.5 (2)	C5—C6—H62	109.49
N9A—C4A—C4B	107.6 (2)	C7—C6—H61	109.54
N4—C4A—N9A	126.9 (2)	C7—C6—H62	109.61
C4A—C4B—C5	115.9 (2)	H61—C6—H62	108.07
C4A—C4B—C8A	102.3 (2)	C6—C7—H71	109.83
C5—C4B—C8A	114.9 (2)	C6—C7—H72	109.80
C4B—C5—C6	113.4 (2)	C8—C7—H71	109.77
C5—C6—C7	110.5 (2)	C8—C7—H72	109.68
C6—C7—C8	109.5 (2)	H71—C7—H72	108.26
C7—C8—C8A	112.5 (2)	C7—C8—H81	109.11
C4B—C8A—C8	112.7 (2)	C7—C8—H82	109.06
C4B—C8A—C9	102.0 (2)	C8A—C8—H81	109.10
C8—C8A—C9	110.9 (2)	C8A—C8—H82	109.12
N9A—C9—C8A	102.1 (2)	H81—C8—H82	107.84
O11—C10—C1	113.4 (2)	C4B—C8A—H8A	110.30
N9A—C1—H1	108.20	C8—C8A—H8A	110.34
C2—C1—H1	108.23	C9—C8A—H8A	110.38
C10—C1—H1	108.20	N9A—C9—H91	111.32
C1—C2—H21	109.47	N9A—C9—H92	111.33
C1—C2—H22	109.38	C8A—C9—H91	111.39
C3—C2—H21	109.36	C8A—C9—H92	111.34
C3—C2—H22	109.30	H91—C9—H92	109.24
H21—C2—H22	107.97	O11—C10—H101	108.92
N4—C3—H31	109.34	O11—C10—H102	108.92
N4—C3—H32	109.33	C1—C10—H101	108.90
C2—C3—H31	109.31	C1—C10—H102	108.85
C2—C3—H32	109.21	H101—C10—H102	107.68
C4A—N4—C3—C2	−33.8 (3)	N4—C4A—C4B—C5	33.8 (4)
C3—N4—C4A—N9A	−1.0 (4)	N4—C4A—C4B—C8A	159.5 (3)
C3—N4—C4A—C4B	176.8 (3)	N9A—C4A—C4B—C5	−148.1 (3)
C4A—N9A—C1—C2	11.6 (3)	N9A—C4A—C4B—C8A	−22.3 (3)
C1—N9A—C4A—N4	13.3 (5)	C8A—C4B—C5—C6	−44.8 (3)
C1—N9A—C4A—C4B	−164.9 (2)	C5—C4B—C8A—C8	42.4 (3)
C9—N9A—C4A—N4	177.9 (3)	C4A—C4B—C8A—C8	−84.0 (3)
C9—N9A—C4A—C4B	−0.3 (3)	C4A—C4B—C8A—C9	34.9 (3)
C1—N9A—C9—C8A	−172.5 (2)	C4A—C4B—C5—C6	74.3 (3)
C4A—N9A—C9—C8A	22.8 (3)	C5—C4B—C8A—C9	161.3 (2)
C4A—N9A—C1—C10	−112.6 (3)	C4B—C5—C6—C7	53.5 (3)
C9—N9A—C1—C2	−151.5 (2)	C5—C6—C7—C8	−60.2 (3)
C9—N9A—C1—C10	84.4 (3)	C6—C7—C8—C8A	59.1 (3)
C2—C1—C10—O11	174.7 (2)	C7—C8—C8A—C9	−163.4 (2)
N9A—C1—C10—O11	−63.9 (3)	C7—C8—C8A—C4B	−49.8 (3)
N9A—C1—C2—C3	−44.1 (3)	C4B—C8A—C9—N9A	−35.0 (3)
C10—C1—C2—C3	79.6 (3)	C8—C8A—C9—N9A	85.2 (3)
C1—C2—C3—N4	57.6 (3)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1/2, −y, z−1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x+1/2, −y, z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2; (vii) x−1/2, −y+1/2, −z+1; (viii) x−1, y, z; (ix) −x−1/2, −y, z−1/2; (x) x+1, y, z; (xi) x+1/2, −y−1/2, −z+1; (xii) x+1/2, −y+1/2, −z+1; (xiii) x−1/2, −y−1/2, −z+1; (xiv) −x−1/2, −y, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···N4^ii	1.03 (3)	1.74 (3)	2.750 (3)	167 (2)
C4B—H4B···O11^vi	1.0005	2.4211	3.351 (3)	154.33

Symmetry codes: (ii) −x+1/2, −y, z−1/2; (vi) −x, y−1/2, −z+1/2.