meso-4,4'-Dimeth-oxy-2,2'-{[(3aR,7aS)-2,3,3a,4,5,6,7,7a-octa-hydro-1H-benz-imidazole-1,3-di-yl]bis-(methyl-ene)}diphenol.

The title compound, C23H30N2O4, a di-Mannich base derived from 4-meth-oxy-phenol and cis-1,2-di-amine-cyclo-hexane, has a perhydro-benzimidazolidine nucleus, in which the cyclo-hexane ring adopts a chair conformation and the heterocyclic ring has a half-chair conformation with a C-N-C-C torsion angles of -48.14 (15) and -14.57 (16)°. The mean plane of the heterocycle makes dihedral angles of 86.29 (6) and 78.92 (6)° with the pendant benzene rings. The mol-ecular structure of the title compound shows the presence of two inter-actions between the N atoms of the imidazolidine ring and the hydroxyl groups through intra-molecular O-H⋯N hydrogen bonds with graph-set motif S(6). The unobserved lone pairs of the N atoms are presumed to be disposed in a syn conformation, being only the second example of an exception to the typical 'rabbit-ears' effect in 1,2-di-amines.

Related literature

For related structures, see: Rivera et al. (2011 ▶, 2013a ▶). For the preparation of the title compound, see: Rivera et al. (2013b ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond graph-set nomenclature, see: Bernstein et al. (1995 ▶). For a discussion of the ‘rabbit-ear’ effect in 1,2-di­amines, see: Hutchins et al. (1968 ▶). For background to this work, see: Van den Enden & Geise (1981 ▶); Geise et al. (1971 ▶). For the extinction correction, see: Becker & Coppens (1974 ▶).

Experimental

Crystal data

C23H30N2O4

M = 398.5

Orthorhombic,

a = 6.4135 (3) Å

b = 11.4099 (6) Å

c = 27.8249 (14) Å

V = 2036.15 (18) Å3

Z = 4

Cu Kα radiation

μ = 0.72 mm−1

T = 120 K

0.21 × 0.13 × 0.13 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.341, T max = 1

5920 measured reflections

3491 independent reflections

3103 reflections with I > 3σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.080

S = 1.13

3491 reflections

269 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.11 e Å−3

Δρmin = −0.09 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis 2007 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: JANA2006.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813015092/sj5324sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015092/sj5324Isup2.hkl

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

C23H30N2O4	F(000) = 856
Mr = 398.5	Dx = 1.300 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3881 reflections
a = 6.4135 (3) Å	θ = 4.2–67.0°
b = 11.4099 (6) Å	µ = 0.72 mm−1
c = 27.8249 (14) Å	T = 120 K
V = 2036.15 (18) Å3	Polygon shape, white
Z = 4	0.21 × 0.13 × 0.13 mm

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3491 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	3103 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.023
Detector resolution: 10.3784 pixels mm-1	θmax = 67.1°, θmin = 3.2°
ω scans	h = −7→4
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→12
Tmin = 0.341, Tmax = 1	l = −30→32
5920 measured reflections

Refinement on F2	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.031	Weighting scheme based on measured s.u.'s w = 1/(σ2(I) + 0.0016I2)
wR(F2) = 0.080	(Δ/σ)max = 0.014
S = 1.13	Δρmax = 0.11 e Å−3
3491 reflections	Δρmin = −0.09 e Å−3
269 parameters	Extinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
1 restraint	Extinction coefficient: 1800 (300)
114 constraints

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

	x	y	z	Uiso*/Ueq
O1	0.9143 (2)	0.54863 (11)	0.19640 (4)	0.0301 (4)
O2	0.5296 (2)	0.11931 (11)	0.22143 (5)	0.0331 (4)
O3	1.1573 (2)	0.56734 (11)	0.02995 (4)	0.0307 (4)
O4	0.75546 (19)	0.25342 (11)	−0.08969 (5)	0.0323 (4)
N1	0.6253 (2)	0.60135 (11)	0.13114 (5)	0.0214 (4)
N2	0.7838 (2)	0.63852 (12)	0.05764 (5)	0.0236 (4)
C1	0.5156 (3)	0.31779 (14)	0.18880 (5)	0.0235 (5)
C2	0.6158 (3)	0.22830 (15)	0.21334 (6)	0.0263 (5)
C3	0.8117 (3)	0.44415 (15)	0.20127 (6)	0.0239 (5)
C4	0.8426 (3)	0.51409 (14)	−0.01265 (5)	0.0227 (4)
C5	0.7086 (3)	0.74987 (14)	0.07934 (6)	0.0240 (5)
C6	1.0495 (3)	0.49232 (15)	0.00056 (6)	0.0249 (5)
C7	0.8898 (3)	0.80893 (16)	0.10624 (6)	0.0291 (5)
C8	0.6101 (3)	0.42686 (14)	0.18311 (5)	0.0225 (5)
C9	0.7333 (3)	0.62223 (15)	0.00643 (6)	0.0241 (5)
C10	1.0459 (3)	0.31475 (16)	−0.04591 (6)	0.0299 (5)
C11	0.4897 (3)	0.52615 (15)	0.16028 (6)	0.0232 (5)
C12	1.1484 (3)	0.39175 (15)	−0.01597 (6)	0.0285 (5)
C13	0.8412 (3)	0.33593 (14)	−0.05968 (6)	0.0253 (5)
C14	0.7399 (3)	0.43469 (14)	−0.04254 (6)	0.0234 (5)
C15	0.3383 (3)	0.09474 (15)	0.19795 (7)	0.0318 (5)
C16	0.6655 (3)	0.84873 (15)	0.17768 (6)	0.0296 (5)
C17	0.6964 (3)	0.54281 (14)	0.08724 (6)	0.0246 (5)
C18	0.4760 (3)	0.79993 (15)	0.15171 (6)	0.0267 (5)
C19	0.8144 (3)	0.24615 (15)	0.23194 (6)	0.0277 (5)
C20	0.8172 (3)	0.90189 (16)	0.14189 (7)	0.0339 (6)
C21	0.5386 (3)	0.26108 (18)	−0.09885 (7)	0.0377 (6)
C22	0.9116 (3)	0.35333 (16)	0.22549 (6)	0.0273 (5)
C23	0.5338 (3)	0.71070 (14)	0.11279 (6)	0.0230 (5)
H1c1	0.379468	0.30444	0.17556	0.0282*
H1c5	0.65943	0.806783	0.0566	0.0288*
H1c7	0.969757	0.750452	0.122842	0.0349*
H2c7	0.983602	0.843718	0.083447	0.0349*
H1c9	0.777998	0.689708	−0.011408	0.0289*
H2c9	0.585279	0.613214	0.002786	0.0289*
H1c10	1.11646	0.245973	−0.057325	0.0359*
H1c11	0.380664	0.494706	0.140473	0.0278*
H2c11	0.424373	0.572215	0.184908	0.0278*
H1c12	1.289471	0.375787	−0.006445	0.0342*
H1c14	0.597307	0.448657	−0.051337	0.028*
H1c15	0.291175	0.017919	0.206897	0.0381*
H2c15	0.235901	0.151753	0.207273	0.0381*
H3c15	0.358284	0.097924	0.163784	0.0381*
H1c16	0.621918	0.907719	0.200132	0.0355*
H2c16	0.733433	0.786893	0.195069	0.0355*
H1c17	0.579091	0.508786	0.070973	0.0295*
H2c17	0.804762	0.487985	0.095061	0.0295*
H1c18	0.398726	0.863134	0.137522	0.0321*
H2c18	0.383947	0.763989	0.174577	0.0321*
H1c19	0.883769	0.184533	0.249162	0.0333*
H1c20	0.935569	0.932931	0.158751	0.0407*
H2c20	0.749972	0.964503	0.124838	0.0407*
H1c21	0.49724	0.198114	−0.119656	0.0453*
H2c21	0.463462	0.255624	−0.069084	0.0453*
H3c21	0.50801	0.334683	−0.114005	0.0453*
H1c22	1.049675	0.365199	0.237874	0.0327*
H1c23	0.400514	0.701537	0.097533	0.0276*
H1o3	1.050 (3)	0.6060 (18)	0.0456 (7)	0.0369*
H1o1	0.834 (3)	0.5936 (17)	0.1758 (7)	0.0361*

	U11	U22	U33	U12	U13	U23
O1	0.0312 (7)	0.0281 (7)	0.0309 (6)	−0.0030 (6)	−0.0068 (5)	0.0021 (5)
O2	0.0438 (7)	0.0216 (6)	0.0340 (6)	0.0000 (6)	−0.0026 (6)	0.0074 (5)
O3	0.0261 (6)	0.0333 (7)	0.0328 (6)	−0.0028 (6)	−0.0018 (5)	−0.0048 (5)
O4	0.0330 (7)	0.0310 (7)	0.0330 (6)	−0.0036 (6)	0.0062 (5)	−0.0123 (5)
N1	0.0260 (7)	0.0180 (6)	0.0202 (6)	0.0011 (6)	0.0004 (5)	−0.0003 (5)
N2	0.0321 (8)	0.0189 (7)	0.0197 (6)	0.0012 (6)	−0.0010 (6)	−0.0011 (5)
C1	0.0268 (9)	0.0236 (9)	0.0202 (7)	0.0013 (7)	0.0010 (7)	0.0005 (6)
C2	0.0346 (10)	0.0240 (9)	0.0204 (7)	0.0042 (8)	0.0044 (7)	0.0022 (6)
C3	0.0284 (9)	0.0239 (8)	0.0194 (7)	0.0018 (7)	−0.0002 (6)	−0.0010 (6)
C4	0.0281 (9)	0.0227 (8)	0.0174 (7)	0.0002 (8)	0.0035 (7)	0.0020 (6)
C5	0.0348 (9)	0.0177 (8)	0.0195 (7)	0.0026 (8)	−0.0015 (7)	0.0017 (6)
C6	0.0268 (8)	0.0263 (9)	0.0217 (7)	−0.0038 (7)	0.0019 (7)	0.0006 (6)
C7	0.0325 (10)	0.0258 (9)	0.0289 (8)	−0.0052 (8)	0.0034 (7)	−0.0014 (7)
C8	0.0269 (9)	0.0240 (8)	0.0165 (7)	0.0029 (7)	0.0011 (6)	−0.0014 (6)
C9	0.0283 (9)	0.0239 (8)	0.0201 (7)	0.0014 (7)	−0.0007 (6)	0.0011 (6)
C10	0.0302 (9)	0.0242 (9)	0.0354 (9)	0.0007 (8)	0.0105 (8)	−0.0022 (7)
C11	0.0240 (8)	0.0235 (8)	0.0220 (7)	0.0001 (7)	−0.0007 (6)	0.0015 (6)
C12	0.0255 (9)	0.0282 (9)	0.0319 (8)	0.0009 (8)	0.0032 (7)	0.0037 (7)
C13	0.0300 (9)	0.0223 (8)	0.0237 (8)	−0.0048 (7)	0.0062 (7)	−0.0014 (6)
C14	0.0242 (8)	0.0253 (8)	0.0206 (7)	−0.0013 (7)	0.0026 (6)	0.0005 (6)
C15	0.0360 (10)	0.0245 (9)	0.0349 (9)	−0.0012 (8)	0.0039 (8)	0.0040 (7)
C16	0.0400 (10)	0.0239 (8)	0.0249 (8)	0.0025 (8)	−0.0039 (8)	−0.0069 (6)
C17	0.0313 (9)	0.0208 (8)	0.0217 (7)	0.0035 (7)	0.0017 (7)	−0.0003 (6)
C18	0.0305 (9)	0.0222 (8)	0.0274 (8)	0.0053 (8)	0.0010 (7)	−0.0010 (7)
C19	0.0334 (10)	0.0275 (9)	0.0222 (7)	0.0091 (8)	0.0003 (7)	0.0035 (7)
C20	0.0425 (11)	0.0244 (9)	0.0348 (9)	−0.0045 (9)	−0.0052 (8)	−0.0047 (7)
C21	0.0345 (10)	0.0397 (11)	0.0389 (10)	−0.0068 (9)	0.0015 (8)	−0.0152 (8)
C22	0.0255 (9)	0.0341 (9)	0.0223 (8)	0.0052 (8)	−0.0024 (7)	0.0008 (7)
C23	0.0248 (9)	0.0202 (8)	0.0239 (7)	0.0020 (7)	−0.0033 (7)	0.0002 (6)

O1—C3	1.368 (2)	C9—H1c9	0.96
O1—H1o1	0.93 (2)	C9—H2c9	0.96
O2—C2	1.380 (2)	C10—C12	1.378 (3)
O2—C15	1.418 (2)	C10—C13	1.389 (3)
O3—C6	1.371 (2)	C10—H1c10	0.96
O3—H1o3	0.93 (2)	C11—H1c11	0.96
O4—C13	1.373 (2)	C11—H2c11	0.96
O4—C21	1.417 (2)	C12—H1c12	0.96
N1—C11	1.466 (2)	C13—C14	1.385 (2)
N1—C17	1.465 (2)	C14—H1c14	0.96
N1—C23	1.470 (2)	C15—H1c15	0.96
N2—C5	1.487 (2)	C15—H2c15	0.96
N2—C9	1.473 (2)	C15—H3c15	0.96
N2—C17	1.478 (2)	C16—C18	1.520 (3)
C1—C2	1.386 (2)	C16—C20	1.519 (3)
C1—C8	1.393 (2)	C16—H1c16	0.96
C1—H1c1	0.96	C16—H2c16	0.96
C2—C19	1.390 (3)	C17—H1c17	0.96
C3—C8	1.402 (2)	C17—H2c17	0.96
C3—C22	1.392 (2)	C18—C23	1.532 (2)
C4—C6	1.399 (3)	C18—H1c18	0.96
C4—C9	1.515 (2)	C18—H2c18	0.96
C4—C14	1.395 (2)	C19—C22	1.384 (3)
C5—C7	1.538 (2)	C19—H1c19	0.96
C5—C23	1.524 (2)	C20—H1c20	0.96
C5—H1c5	0.96	C20—H2c20	0.96
C6—C12	1.390 (2)	C21—H1c21	0.96
C7—C20	1.525 (3)	C21—H2c21	0.96
C7—H1c7	0.96	C21—H3c21	0.96
C7—H2c7	0.96	C22—H1c22	0.96
C8—C11	1.511 (2)	C23—H1c23	0.96
C3—O1—H1o1	106.0 (13)	C6—C12—H1c12	119.71
C2—O2—C15	116.72 (13)	C10—C12—H1c12	119.71
C6—O3—H1o3	101.6 (13)	O4—C13—C10	115.28 (15)
C13—O4—C21	117.40 (14)	O4—C13—C14	125.39 (16)
C11—N1—C17	112.27 (12)	C10—C13—C14	119.32 (16)
C11—N1—C23	116.87 (13)	C4—C14—C13	120.79 (16)
C17—N1—C23	102.81 (12)	C4—C14—H1c14	119.6
C5—N2—C9	115.42 (13)	C13—C14—H1c14	119.6
C5—N2—C17	106.39 (12)	O2—C15—H1c15	109.47
C9—N2—C17	111.24 (13)	O2—C15—H2c15	109.47
C2—C1—C8	120.84 (16)	O2—C15—H3c15	109.47
C2—C1—H1c1	119.58	H1c15—C15—H2c15	109.47
C8—C1—H1c1	119.58	H1c15—C15—H3c15	109.47
O2—C2—C1	123.98 (16)	H2c15—C15—H3c15	109.47
O2—C2—C19	116.01 (15)	C18—C16—C20	110.30 (14)
C1—C2—C19	120.01 (16)	C18—C16—H1c16	109.47
O1—C3—C8	122.03 (15)	C18—C16—H2c16	109.47
O1—C3—C22	118.37 (15)	C20—C16—H1c16	109.47
C8—C3—C22	119.60 (15)	C20—C16—H2c16	109.47
C6—C4—C9	119.44 (14)	H1c16—C16—H2c16	108.63
C6—C4—C14	119.29 (15)	N1—C17—N2	104.22 (12)
C9—C4—C14	121.26 (15)	N1—C17—H1c17	109.47
N2—C5—C7	109.08 (14)	N1—C17—H2c17	109.47
N2—C5—C23	103.65 (13)	N2—C17—H1c17	109.47
N2—C5—H1c5	114.64	N2—C17—H2c17	109.47
C7—C5—C23	112.79 (13)	H1c17—C17—H2c17	114.25
C7—C5—H1c5	105.82	C16—C18—C23	112.72 (15)
C23—C5—H1c5	111.05	C16—C18—H1c18	109.47
O3—C6—C4	121.62 (15)	C16—C18—H2c18	109.47
O3—C6—C12	118.85 (16)	C23—C18—H1c18	109.47
C4—C6—C12	119.52 (16)	C23—C18—H2c18	109.47
C5—C7—C20	113.00 (15)	H1c18—C18—H2c18	106.02
C5—C7—H1c7	109.47	C2—C19—C22	119.58 (16)
C5—C7—H2c7	109.47	C2—C19—H1c19	120.21
C20—C7—H1c7	109.47	C22—C19—H1c19	120.21
C20—C7—H2c7	109.47	C7—C20—C16	110.14 (15)
H1c7—C7—H2c7	105.7	C7—C20—H1c20	109.47
C1—C8—C3	119.06 (15)	C7—C20—H2c20	109.47
C1—C8—C11	119.71 (15)	C16—C20—H1c20	109.47
C3—C8—C11	121.14 (15)	C16—C20—H2c20	109.47
N2—C9—C4	109.87 (13)	H1c20—C20—H2c20	108.8
N2—C9—H1c9	109.47	O4—C21—H1c21	109.47
N2—C9—H2c9	109.47	O4—C21—H2c21	109.47
C4—C9—H1c9	109.47	O4—C21—H3c21	109.47
C4—C9—H2c9	109.47	H1c21—C21—H2c21	109.47
H1c9—C9—H2c9	109.07	H1c21—C21—H3c21	109.47
C12—C10—C13	120.47 (16)	H2c21—C21—H3c21	109.47
C12—C10—H1c10	119.76	C3—C22—C19	120.89 (16)
C13—C10—H1c10	119.76	C3—C22—H1c22	119.56
N1—C11—C8	111.62 (14)	C19—C22—H1c22	119.56
N1—C11—H1c11	109.47	N1—C23—C5	99.62 (13)
N1—C11—H2c11	109.47	N1—C23—C18	114.52 (13)
C8—C11—H1c11	109.47	N1—C23—H1c23	114.61
C8—C11—H2c11	109.47	C5—C23—C18	114.50 (14)
H1c11—C11—H2c11	107.24	C5—C23—H1c23	114.63
C6—C12—C10	120.58 (17)	C18—C23—H1c23	99.77

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1o3···N2	0.93 (2)	1.78 (2)	2.6443 (19)	154.4 (19)
O1—H1o1···N1	0.93 (2)	1.83 (2)	2.6638 (19)	148.8 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1o3⋯N2	0.93 (2)	1.78 (2)	2.6443 (19)	154.4 (19)
O1—H1o1⋯N1	0.93 (2)	1.83 (2)	2.6638 (19)	148.8 (18)