4,4'-Dimethyl-2,2'-{[2,3,3a,4,5,6,7,7a-octa-hydro-1H-benzimidazole-1,3-di-yl]bis-(methyl-ene)}diphenol.

The asymmetric unit of the title compound, C23H30N2O2, contains one half-mol-ecule, with a twofold axis splitting the mol-ecule in two identical halves. The structure of the racemic mixture has been reported previously [Rivera et al. (2009 ▶) J. Chem. Crystallogr. 39, 827-830] but the enanti-omer reported here crystallized in the ortho-rhom-bic space group P21212 (Z = 2), whereas the racemate occurs in the triclinic space group P-1 (Z = 2). The observed mol-ecular conformation is stabilized by two intra-molecular O-H⋯N hydrogen bonds, which generate rings with graph-set motif S(6). In the crystal, mol-ecules are linked via non-classical C-H⋯O inter-actions, which stack the mol-ecules along the b axis.

Related literature

For the structure of the original racemate, see: Rivera et al. (2009 ▶). For the use of 1,3-di­aza­heterocyclic-bridged bis­(phenols) in coordination chemistry, see: Kober et al. (2012 ▶); Xu et al. (2007 ▶). For the synthesis of the precursor, (2R,7R)- 1,8,10,12-tetra­aza­tetra­cyclo­[8.3.118,12.02,7]penta­decane, see: Rivera et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set analysis, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H30N2O2

M = 366.49

Orthorhombic,

a = 18.5417 (9) Å

b = 6.0597 (4) Å

c = 8.9415 (5) Å

V = 1004.64 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 173 K

0.31 × 0.27 × 0.12 mm

Data collection

STOE IPDS II two-circle-diffractometer

Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001 ▶) T min = 0.976, T max = 0.991

12723 measured reflections

2168 independent reflections

2058 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.090

S = 1.04

2168 reflections

129 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.13 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL2012.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813015237/sj5327sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015237/sj5327Isup2.hkl

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

C23H30N2O2	Dx = 1.212 Mg m−3
Mr = 366.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212	Cell parameters from 16515 reflections
a = 18.5417 (9) Å	θ = 2.2–27.5°
b = 6.0597 (4) Å	µ = 0.08 mm−1
c = 8.9415 (5) Å	T = 173 K
V = 1004.64 (10) Å3	Plate, colourless
Z = 2	0.31 × 0.27 × 0.12 mm
F(000) = 396

STOE IPDS II two-circle-diffractometer	2058 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.053
ω scans	θmax = 26.9°, θmin = 2.2°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −23→23
Tmin = 0.976, Tmax = 0.991	k = −7→7
12723 measured reflections	l = −11→11
2168 independent reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.034	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.1419P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.090	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.14 e Å−3
2168 reflections	Δρmin = −0.13 e Å−3
129 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.075 (11)

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.

	x	y	z	Uiso*/Ueq
O1	0.41870 (7)	0.5018 (2)	0.60166 (17)	0.0414 (3)
H1	0.4384 (19)	0.376 (6)	0.668 (4)	0.097 (11)*
N1	0.44460 (7)	0.0979 (2)	0.70721 (16)	0.0303 (3)
C1	0.45928 (9)	0.0063 (3)	0.85614 (19)	0.0340 (4)
H1A	0.4393	−0.1468	0.8611	0.041*
C2	0.43253 (11)	0.1352 (4)	0.9905 (2)	0.0477 (5)
H2A	0.3792	0.1414	0.9901	0.057*
H2B	0.4513	0.2880	0.9873	0.057*
C3	0.45917 (12)	0.0182 (5)	1.1318 (2)	0.0596 (7)
H3A	0.4458	0.1074	1.2204	0.071*
H3B	0.4347	−0.1264	1.1405	0.071*
C4	0.5000	0.0000	0.6072 (3)	0.0305 (5)
H4	0.5217	0.1150	0.5427	0.037*
C5	0.36990 (9)	0.0576 (3)	0.6571 (2)	0.0332 (4)
H5A	0.3362	0.1007	0.7378	0.040*
H5B	0.3634	−0.1021	0.6380	0.040*
C11	0.35166 (9)	0.1843 (3)	0.5173 (2)	0.0301 (4)
C12	0.37743 (9)	0.3996 (3)	0.4958 (2)	0.0330 (4)
C13	0.35991 (10)	0.5134 (3)	0.3660 (2)	0.0389 (4)
H13	0.3788	0.6571	0.3496	0.047*
C14	0.31501 (10)	0.4180 (4)	0.2604 (2)	0.0389 (4)
H14	0.3032	0.4983	0.1724	0.047*
C15	0.28681 (10)	0.2075 (3)	0.2801 (2)	0.0359 (4)
C16	0.30625 (9)	0.0935 (3)	0.4097 (2)	0.0320 (4)
H16	0.2878	−0.0511	0.4249	0.038*
C17	0.23790 (11)	0.1007 (4)	0.1658 (2)	0.0452 (5)
H17A	0.2278	0.2060	0.0852	0.068*
H17B	0.1926	0.0571	0.2138	0.068*
H17C	0.2617	−0.0300	0.1241	0.068*

	U11	U22	U33	U12	U13	U23
O1	0.0387 (7)	0.0295 (6)	0.0559 (8)	−0.0030 (6)	−0.0083 (6)	−0.0022 (7)
N1	0.0243 (7)	0.0345 (7)	0.0319 (7)	0.0019 (6)	0.0008 (5)	0.0008 (6)
C1	0.0298 (9)	0.0385 (8)	0.0337 (9)	0.0043 (7)	0.0003 (6)	0.0036 (8)
C2	0.0383 (10)	0.0677 (14)	0.0371 (10)	0.0140 (10)	0.0033 (9)	−0.0034 (10)
C3	0.0501 (13)	0.0951 (19)	0.0335 (10)	0.0207 (13)	0.0048 (9)	0.0018 (12)
C4	0.0262 (10)	0.0315 (11)	0.0339 (11)	0.0007 (9)	0.000	0.000
C5	0.0251 (8)	0.0346 (8)	0.0398 (9)	−0.0014 (7)	−0.0005 (7)	0.0043 (7)
C11	0.0238 (7)	0.0296 (8)	0.0369 (9)	0.0024 (6)	0.0013 (7)	0.0006 (7)
C12	0.0274 (8)	0.0301 (8)	0.0414 (9)	0.0012 (7)	0.0003 (7)	−0.0015 (8)
C13	0.0371 (9)	0.0316 (8)	0.0482 (10)	0.0008 (7)	0.0058 (8)	0.0062 (8)
C14	0.0377 (9)	0.0410 (10)	0.0380 (9)	0.0077 (8)	0.0028 (8)	0.0062 (8)
C15	0.0305 (8)	0.0409 (10)	0.0363 (9)	0.0048 (7)	0.0014 (8)	−0.0021 (8)
C16	0.0270 (8)	0.0303 (8)	0.0388 (9)	0.0001 (7)	0.0020 (7)	−0.0013 (7)
C17	0.0427 (10)	0.0546 (11)	0.0384 (10)	0.0024 (9)	−0.0037 (8)	−0.0041 (10)

O1—C12	1.365 (2)	C5—C11	1.505 (2)
O1—H1	1.03 (4)	C5—H5A	0.9900
N1—C1	1.468 (2)	C5—H5B	0.9900
N1—C5	1.476 (2)	C11—C16	1.392 (3)
N1—C4	1.485 (2)	C11—C12	1.403 (2)
C1—C1i	1.512 (3)	C12—C13	1.389 (3)
C1—C2	1.516 (3)	C13—C14	1.386 (3)
C1—H1A	1.0000	C13—H13	0.9500
C2—C3	1.531 (3)	C14—C15	1.390 (3)
C2—H2A	0.9900	C14—H14	0.9500
C2—H2B	0.9900	C15—C16	1.396 (3)
C3—C3i	1.530 (4)	C15—C17	1.512 (3)
C3—H3A	0.9900	C16—H16	0.9500
C3—H3B	0.9900	C17—H17A	0.9800
C4—N1i	1.485 (2)	C17—H17B	0.9800
C4—H4	0.9900	C17—H17C	0.9800
C12—O1—H1	105 (2)	N1—C5—H5B	109.2
C1—N1—C5	112.75 (14)	C11—C5—H5B	109.2
C1—N1—C4	105.47 (13)	H5A—C5—H5B	107.9
C5—N1—C4	113.58 (14)	C16—C11—C12	118.61 (17)
N1—C1—C1i	101.79 (11)	C16—C11—C5	120.55 (15)
N1—C1—C2	117.60 (15)	C12—C11—C5	120.78 (16)
C1i—C1—C2	110.66 (14)	O1—C12—C13	119.01 (16)
N1—C1—H1A	108.8	O1—C12—C11	121.19 (17)
C1i—C1—H1A	108.8	C13—C12—C11	119.79 (17)
C2—C1—H1A	108.8	C14—C13—C12	120.22 (17)
C1—C2—C3	108.07 (17)	C14—C13—H13	119.9
C1—C2—H2A	110.1	C12—C13—H13	119.9
C3—C2—H2A	110.1	C13—C14—C15	121.48 (18)
C1—C2—H2B	110.1	C13—C14—H14	119.3
C3—C2—H2B	110.1	C15—C14—H14	119.3
H2A—C2—H2B	108.4	C14—C15—C16	117.54 (18)
C3i—C3—C2	112.71 (18)	C14—C15—C17	122.16 (19)
C3i—C3—H3A	109.0	C16—C15—C17	120.28 (18)
C2—C3—H3A	109.0	C11—C16—C15	122.30 (17)
C3i—C3—H3B	109.0	C11—C16—H16	118.8
C2—C3—H3B	109.0	C15—C16—H16	118.8
H3A—C3—H3B	107.8	C15—C17—H17A	109.5
N1i—C4—N1	106.00 (19)	C15—C17—H17B	109.5
N1i—C4—H4	110.5	H17A—C17—H17B	109.5
N1—C4—H4	110.5	C15—C17—H17C	109.5
N1—C5—C11	112.24 (14)	H17A—C17—H17C	109.5
N1—C5—H5A	109.2	H17B—C17—H17C	109.5
C11—C5—H5A	109.2
C5—N1—C1—C1i	160.26 (17)	C16—C11—C12—O1	176.16 (15)
C4—N1—C1—C1i	35.78 (19)	C5—C11—C12—O1	−1.1 (2)
C5—N1—C1—C2	−78.7 (2)	C16—C11—C12—C13	−2.7 (2)
C4—N1—C1—C2	156.83 (15)	C5—C11—C12—C13	180.00 (15)
N1—C1—C2—C3	−175.55 (19)	O1—C12—C13—C14	−176.61 (17)
C1i—C1—C2—C3	−59.2 (2)	C11—C12—C13—C14	2.3 (3)
C1—C2—C3—C3i	53.8 (3)	C12—C13—C14—C15	−0.4 (3)
C1—N1—C4—N1i	−14.09 (8)	C13—C14—C15—C16	−0.9 (3)
C5—N1—C4—N1i	−138.05 (15)	C13—C14—C15—C17	−179.83 (18)
C1—N1—C5—C11	170.22 (14)	C12—C11—C16—C15	1.4 (3)
C4—N1—C5—C11	−69.88 (17)	C5—C11—C16—C15	178.62 (16)
N1—C5—C11—C16	144.70 (16)	C14—C15—C16—C11	0.5 (3)
N1—C5—C11—C12	−38.1 (2)	C17—C15—C16—C11	179.38 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	1.03 (4)	1.73 (4)	2.667 (2)	150 (3)
C4—H4···O1ii	0.99	2.63	3.3749 (13)	133
C5—H5B···O1iii	0.99	2.63	3.522 (2)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	1.03 (4)	1.73 (4)	2.667 (2)	150 (3)
C4—H4⋯O1i	0.99	2.63	3.3749 (13)	133
C5—H5B⋯O1ii	0.99	2.63	3.522 (2)	150

Symmetry codes: (i) ; (ii) .