4,4′-Difluoro-2,2′-{[(3aRS,7aRS)-2,3,3a,4,5,6,7,7a-octa­hydro-1H-1,3-benzimidazole-1,3-di­yl]bis­(methyl­ene)]}diphenol

Rivera, A.; Quiroga, D.; Ríos-Motta, J.; Dušek, M.; Fejfarová, K.

doi:10.1107/S1600536811019763

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1542

doi:10.1107/S1600536811019763

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4,4′-Difluoro-2,2′-{[(3aRS,7aRS)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3-benzimidazole-1,3-diyl]bis(methylene)]}diphenol

Augusto Rivera,^a ^* Diego Quiroga,^a Jaime Ríos-Motta,^a Michal Dušek ^b and Karla Fejfarová ^b

^aDepartamento de Química, Universidad Nacional de Colombia, Ciudad Universitaria, Bogotá, Colombia, and ^bInstitute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: ariverau@unal.edu.co

(Received 7 May 2011; accepted 24 May 2011; online 28 May 2011)

In the crystal structure of the title compound, C₂₁H₂₄F₂N₂O₂, the two N atoms of the imidazolidine moiety are linked to the hydroxy groups by intramolecular O—H⋯N hydrogen-bonding interactions. The crystal studied was a racemic mixture of RR and SS enatiomers. The cyclohexane ring adopts a chair conformation and the imidazolidine group to which it is fused has a twisted envelope conformation.

Related literature

For related structures, see: Rivera et al. (2010a ,b , 2011 ). For uses of di-Mannich bases, see: Mitra et al. (2006 ); Elias et al. (1997 ). For related quantum-chemical literature, see: Zierkiewicz & Michalska (2003 ); Zierkiewicz et al. (2004 ).

Experimental

Crystal data

C₂₁H₂₄F₂N₂O₂
M_r = 374.4
Triclinic, $[P \overline 1]$
a = 5.4605 (1) Å
b = 12.4661 (3) Å
c = 14.3363 (4) Å
α = 108.053 (3)°
β = 91.319 (2)°
γ = 97.437 (2)°
V = 917.98 (4) Å³
Z = 2
Cu Kα radiation
μ = 0.84 mm⁻¹
T = 150 K
0.36 × 0.23 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.516, T_max = 1
15846 measured reflections
3248 independent reflections
2819 reflections with I > 3σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.110
S = 1.95
3248 reflections
250 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯N1	0.88 (2)	1.92 (2)	2.7105 (15)	147.6 (19)
O2—H2o⋯N2	0.83 (2)	1.95 (2)	2.6975 (16)	148 (2)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811019763/kj2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019763/kj2178Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811019763/kj2178Isup3.cml

checkCIF report

Comment top

The title compound was obtained by a Mannich type reaction between the aminal (2R,7R,11S,16S)-1,8,10,17-tetraazapentacyclo[8.8.1.1^8,17.0^2,7.0^11,16]icosane and p-fluorophenol. The crystal structure of the title compound was determined as a racemic mixture having (R,R) or (S,S) configurations at the two stereogenic centers and it crystallizes in a centrosymmetric space group. The chiral centers were not affected when the aminal cage reacted, so the title compound is a trans-rac mixture. The molecular structure and atom-numbering scheme for the title compound are shown in Fig. 1. The crystal structure of the title confirms the presence of intramolecular hydrogen bonds between the phenolic hydroxyl groups and nitrogen atoms (Table 1). The C—O bond lengths [C10—O1, 1.3682 (17) Å; C17—O2, 1.3706 (18) Å] and the N···O distances (Table 1) are longer than the values observed in related structures where the p-substituents in the aromatic rings are chloride or bromide (Rivera, et al. 2010b and 2011), showing a decrease in hydrogen-bonding strength. The slight elongation of the C—O bond in the title compound could be explained by the presence of a fluorine substituent, since theoretical results using MP2 and density functional (B3LYP) methods showed that the chlorine and bromine substituents caused a shortening of this bond by a presumable contribution of these halogens in a quinoid-type structure by resonance (mesomeric) effects (Zierkiewicz, et al. 2003), and an electron donation from the pz-orbital on the oxygen atom to π* acceptor orbitals in the ring, which was not observed in p-fluorophenol where an inductive effect and a strong delocalization of electron density from the pz-orbital on the F atom to π* acceptor orbitals in the ring are predominant, leading to a suppression of electron donation from the pz-orbital on the oxygen atom to the aromatic ring (Zierkiewicz, et al. 2004).

The crystal structure showed an angular deformation in the phenol ring which is caused by the presence of the fluorine atom: the C12—C13—C14 and C19—C20—C21 internal ring angles [both 122.7 (1) °] increase by about 3.53° compared to the value of the corresponding angles in the phenol derivative (Rivera, et al. 2010a). The structural changes of the aromatic ring are governed chiefly by the electronegativity of the fluorine substituent (inductive electron withdrawal), which is reflected in an elongation of C-O bond.

Related literature top

For related structures, see: Rivera et al. (2010a,b, 2011). For uses of di-Mannich bases, see: Mitra et al. (2006); Elias et al. (1997). For related quantum-chemical literature, see: Zierkiewicz & Michalska (2003); Zierkiewicz et al. (2004).

Experimental top

Physical Measurements

The melting point was determined with an Electrothermal apparatus, and it has not been corrected. IR spectrum was recorded as KBr pellets at 292 K on a Perkin-Elmer Paragon FT—IR instrument. NMR spectra were performed in CDCl₃ at room temperature on a Bruker AMX 400 Avance spectrometer.

Preparation of 4,4'-Difluoro-{[2,2'-(3aRS,7aRS)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3- benzimidazole-1,3-diyl]bis(methylene)}diphenol

To a solution of(2R,7R,11S,16S)-1,8,10,17-tetraazapentacyclo [8.8.1.1^{8, 17}˙0^2,7.0^11,16]icosane (276 mg, 1.00 mmol) in dioxane (3 ml) and water (4 ml) in a two-necked round-bottomed flask, prepared beforehand following previously described procedures, was added dropwise a dioxane solution (3 ml) containing two equivalents of p-fluorophenol (224 mg, 2.00 mmol). The mixture was refluxed for about 6 h. The solvent was evaporated under reduced pressure until a sticky residue appeared. The product was purified by chromatography on a silica column, and subjected to gradient elution with benzene:ethyl acetate (yield 25%, m.p. = 443–447 K). Single crystals were grown from a CHCl₃ solution by slow evaporation of the solvent at room temperature over a period of about 2 weeks.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SIR2002 (Burla et al., 2003); 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 (Petříček et al., 2006).

Figures top

Fig. 1. Displacement elipsoid plot of the title compound, drawn at 50% probability level.

4-fluoro-2-({3-[(5-fluoro-2-hydroxyphenyl)methyl]-2,3,3a,4,5,6,7,7a-octahydro- 1H-1,3-benzodiazol-1-yl}methyl)phenol top

Crystal data top

C₂₁H₂₄F₂N₂O₂	Z = 2
M_r = 374.4	F(000) = 396
Triclinic, P1	D_x = 1.354 Mg m⁻³
Hall symbol: -P 1	Melting point: 445 K
a = 5.4605 (1) Å	Cu Kα radiation, λ = 1.5418 Å
b = 12.4661 (3) Å	Cell parameters from 8506 reflections
c = 14.3363 (4) Å	θ = 3.3–67°
α = 108.053 (3)°	µ = 0.84 mm⁻¹
β = 91.319 (2)°	T = 150 K
γ = 97.437 (2)°	Prism, colourless
V = 917.98 (4) Å³	0.36 × 0.23 × 0.09 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector	3248 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2819 reflections with I > 3σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.3784 pixels mm^-1	θ_max = 67.1°, θ_min = 3.3°
Rotation method data acquisition using ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −14→14
T_min = 0.516, T_max = 1	l = −17→17
15846 measured reflections

Refinement top

Refinement on F²	90 constraints
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	Weighting scheme based on measured s.u.'s w = 1/[σ²(I) + 0.0016I²]
S = 1.95	(Δ/σ)_max = 0.006
3248 reflections	Δρ_max = 0.25 e Å⁻³
250 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

Crystal data top

C₂₁H₂₄F₂N₂O₂	γ = 97.437 (2)°
M_r = 374.4	V = 917.98 (4) Å³
Triclinic, P1	Z = 2
a = 5.4605 (1) Å	Cu Kα radiation
b = 12.4661 (3) Å	µ = 0.84 mm⁻¹
c = 14.3363 (4) Å	T = 150 K
α = 108.053 (3)°	0.36 × 0.23 × 0.09 mm
β = 91.319 (2)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector	3248 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2819 reflections with I > 3σ(I)
T_min = 0.516, T_max = 1	R_int = 0.024
15846 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.95	Δρ_max = 0.25 e Å⁻³
3248 reflections	Δρ_min = −0.23 e Å⁻³
250 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction (2009), Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.8539 (2)	0.55112 (8)	0.62051 (7)	0.0546 (4)
F2	−0.07887 (18)	0.52089 (7)	0.14954 (7)	0.0466 (4)
O1	0.16405 (19)	0.16846 (9)	0.53377 (8)	0.0378 (4)
O2	0.43069 (19)	0.15534 (9)	0.05535 (8)	0.0355 (4)
N1	0.3641 (2)	0.10643 (9)	0.35698 (7)	0.0241 (4)
N2	0.1999 (2)	0.09975 (9)	0.20184 (7)	0.0239 (4)
C1	0.3018 (2)	0.17945 (11)	0.29872 (9)	0.0268 (4)
C2	0.3651 (2)	−0.00695 (11)	0.28492 (9)	0.0240 (4)
C3	0.1458 (2)	−0.01205 (11)	0.21678 (9)	0.0239 (4)
C4	0.1213 (3)	−0.11590 (11)	0.12581 (10)	0.0311 (5)
C5	0.0996 (3)	−0.22171 (12)	0.15961 (11)	0.0358 (5)
C6	0.3115 (3)	−0.21688 (12)	0.23326 (11)	0.0367 (5)
C7	0.3397 (3)	−0.10836 (12)	0.32279 (10)	0.0312 (5)
C8	0.5907 (2)	0.15502 (11)	0.42136 (9)	0.0270 (4)
C9	0.5514 (2)	0.26236 (12)	0.50104 (9)	0.0267 (4)
C10	0.3397 (3)	0.26295 (12)	0.55485 (10)	0.0298 (5)
C11	0.3077 (3)	0.35923 (13)	0.63185 (10)	0.0375 (5)
C12	0.4816 (3)	0.45585 (13)	0.65482 (11)	0.0404 (5)
C13	0.6831 (3)	0.45507 (13)	0.59942 (11)	0.0374 (5)
C14	0.7225 (3)	0.36067 (12)	0.52322 (10)	0.0316 (5)
C15	−0.0045 (2)	0.13892 (11)	0.15950 (9)	0.0262 (4)
C16	0.0880 (2)	0.24381 (11)	0.13227 (9)	0.0244 (4)
C17	0.3020 (3)	0.24648 (12)	0.08027 (9)	0.0279 (4)
C18	0.3842 (3)	0.34067 (13)	0.05171 (10)	0.0343 (5)
C19	0.2565 (3)	0.43379 (13)	0.07452 (11)	0.0363 (5)
C20	0.0492 (3)	0.43006 (12)	0.12624 (10)	0.0327 (5)
C21	−0.0371 (3)	0.33780 (11)	0.15580 (9)	0.0282 (5)
H1a	0.449729	0.225399	0.290412	0.0321*
H1b	0.177063	0.223466	0.329659	0.0321*
H2	0.522627	−0.013546	0.256934	0.0288*
H3	−0.014925	−0.022658	0.241089	0.0287*
H4a	0.266114	−0.112776	0.089503	0.0374*
H4b	−0.02548	−0.118546	0.086507	0.0374*
H5a	0.095707	−0.288587	0.103492	0.0429*
H5b	−0.055536	−0.230187	0.18856	0.0429*
H6a	0.463729	−0.221271	0.200974	0.0441*
H6b	0.284387	−0.282712	0.254988	0.0441*
H7a	0.194886	−0.108455	0.359483	0.0375*
H7b	0.486083	−0.104889	0.362647	0.0375*
H8a	0.723214	0.172323	0.383113	0.0324*
H8b	0.635885	0.100296	0.450802	0.0324*
H11	0.164157	0.358531	0.669188	0.0449*
H12	0.461937	0.522264	0.708518	0.0484*
H14	0.86615	0.362995	0.486129	0.0379*
H15a	−0.127904	0.156161	0.206435	0.0315*
H15b	−0.078638	0.079531	0.101919	0.0315*
H18	0.530423	0.341557	0.015894	0.0411*
H19	0.311842	0.49916	0.054586	0.0435*
H21	−0.182407	0.338481	0.192316	0.0338*
H1o	0.188 (4)	0.1244 (17)	0.4743 (16)	0.0566*
H2o	0.388 (4)	0.1166 (17)	0.0919 (14)	0.0533*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0699 (7)	0.0323 (5)	0.0487 (5)	−0.0063 (5)	−0.0012 (5)	0.0002 (4)
F2	0.0580 (6)	0.0287 (5)	0.0574 (6)	0.0137 (4)	0.0065 (4)	0.0169 (4)
O1	0.0320 (6)	0.0477 (6)	0.0311 (5)	0.0010 (5)	0.0061 (4)	0.0104 (5)
O2	0.0357 (6)	0.0400 (6)	0.0377 (6)	0.0126 (5)	0.0115 (4)	0.0187 (5)
N1	0.0253 (6)	0.0246 (6)	0.0216 (5)	0.0030 (4)	−0.0016 (4)	0.0067 (4)
N2	0.0263 (6)	0.0227 (5)	0.0227 (5)	0.0023 (4)	−0.0016 (4)	0.0079 (4)
C1	0.0307 (7)	0.0248 (6)	0.0243 (6)	0.0026 (5)	−0.0018 (5)	0.0077 (5)
C2	0.0243 (7)	0.0240 (7)	0.0236 (6)	0.0034 (5)	0.0025 (5)	0.0072 (5)
C3	0.0237 (7)	0.0244 (6)	0.0244 (6)	0.0018 (5)	0.0020 (5)	0.0095 (5)
C4	0.0357 (8)	0.0267 (7)	0.0279 (7)	0.0034 (6)	−0.0030 (6)	0.0051 (5)
C5	0.0387 (8)	0.0245 (7)	0.0404 (8)	0.0016 (6)	−0.0034 (6)	0.0065 (6)
C6	0.0394 (8)	0.0248 (7)	0.0470 (9)	0.0048 (6)	−0.0028 (7)	0.0130 (6)
C7	0.0327 (8)	0.0297 (7)	0.0344 (7)	0.0031 (6)	−0.0031 (6)	0.0155 (6)
C8	0.0249 (7)	0.0313 (7)	0.0230 (6)	0.0037 (6)	−0.0011 (5)	0.0063 (5)
C9	0.0278 (7)	0.0305 (7)	0.0212 (6)	0.0063 (5)	−0.0023 (5)	0.0068 (5)
C10	0.0287 (7)	0.0364 (8)	0.0255 (6)	0.0070 (6)	−0.0009 (5)	0.0106 (6)
C11	0.0373 (8)	0.0492 (9)	0.0266 (7)	0.0171 (7)	0.0046 (6)	0.0085 (6)
C12	0.0507 (10)	0.0369 (8)	0.0306 (7)	0.0187 (7)	−0.0013 (7)	0.0018 (6)
C13	0.0448 (9)	0.0291 (7)	0.0339 (7)	0.0023 (6)	−0.0048 (6)	0.0056 (6)
C14	0.0330 (8)	0.0332 (7)	0.0266 (7)	0.0040 (6)	−0.0007 (6)	0.0072 (6)
C15	0.0246 (7)	0.0282 (7)	0.0273 (6)	0.0030 (5)	−0.0013 (5)	0.0114 (5)
C16	0.0258 (7)	0.0272 (7)	0.0197 (6)	0.0011 (5)	−0.0041 (5)	0.0080 (5)
C17	0.0295 (7)	0.0315 (7)	0.0234 (6)	0.0042 (6)	−0.0005 (5)	0.0099 (5)
C18	0.0308 (8)	0.0423 (8)	0.0331 (7)	0.0003 (6)	0.0026 (6)	0.0189 (6)
C19	0.0409 (9)	0.0331 (8)	0.0377 (8)	−0.0027 (6)	−0.0031 (6)	0.0188 (6)
C20	0.0391 (8)	0.0259 (7)	0.0329 (7)	0.0053 (6)	−0.0039 (6)	0.0094 (6)
C21	0.0299 (7)	0.0294 (7)	0.0252 (6)	0.0040 (6)	−0.0005 (5)	0.0088 (5)

Geometric parameters (Å, º) top

F1—C13	1.3668 (17)	C6—H6b	0.96
F2—C20	1.3654 (18)	C7—H7a	0.96
O1—C10	1.3682 (17)	C7—H7b	0.96
O1—H1o	0.88 (2)	C8—C9	1.5100 (17)
O2—C17	1.3706 (18)	C8—H8a	0.96
O2—H2o	0.83 (2)	C8—H8b	0.96
N1—C1	1.477 (2)	C9—C10	1.4041 (19)
N1—C2	1.4704 (15)	C9—C14	1.3873 (19)
N1—C8	1.4686 (16)	C10—C11	1.3897 (18)
N2—C1	1.4805 (14)	C11—C12	1.380 (2)
N2—C3	1.4686 (18)	C11—H11	0.96
N2—C15	1.4652 (19)	C12—C13	1.371 (2)
C1—H1a	0.96	C12—H12	0.96
C1—H1b	0.96	C13—C14	1.3799 (18)
C2—C3	1.5100 (19)	C14—H14	0.96
C2—C7	1.515 (2)	C15—C16	1.507 (2)
C2—H2	0.96	C15—H15a	0.96
C3—C4	1.5151 (16)	C15—H15b	0.96
C3—H3	0.96	C16—C17	1.4032 (19)
C4—C5	1.532 (2)	C16—C21	1.388 (2)
C4—H4a	0.96	C17—C18	1.385 (2)
C4—H4b	0.96	C18—C19	1.388 (2)
C5—C6	1.531 (2)	C18—H18	0.96
C5—H5a	0.96	C19—C20	1.371 (2)
C5—H5b	0.96	C19—H19	0.96
C6—C7	1.5369 (17)	C20—C21	1.377 (2)
C6—H6a	0.96	C21—H21	0.96

C10—O1—H1o	106.9 (13)	H7a—C7—H7b	111.1929
C17—O2—H2o	106.8 (14)	N1—C8—C9	110.50 (11)
C1—N1—C2	105.24 (9)	N1—C8—H8a	109.471
C1—N1—C8	112.56 (10)	N1—C8—H8b	109.471
C2—N1—C8	116.09 (11)	C9—C8—H8a	109.4713
C1—N2—C3	105.27 (10)	C9—C8—H8b	109.4715
C1—N2—C15	113.08 (10)	H8a—C8—H8b	108.4269
C3—N2—C15	116.39 (10)	C8—C9—C10	119.74 (11)
N1—C1—N2	105.37 (10)	C8—C9—C14	121.22 (12)
N1—C1—H1a	109.4709	C10—C9—C14	119.04 (11)
N1—C1—H1b	109.4714	O1—C10—C9	120.76 (11)
N2—C1—H1a	109.4715	O1—C10—C11	118.91 (13)
N2—C1—H1b	109.4707	C9—C10—C11	120.31 (12)
H1a—C1—H1b	113.2798	C10—C11—C12	120.24 (14)
N1—C2—C3	100.30 (10)	C10—C11—H11	119.8818
N1—C2—C7	117.55 (11)	C12—C11—H11	119.8816
N1—C2—H2	111.2215	C11—C12—C13	118.67 (13)
C3—C2—C7	111.58 (10)	C11—C12—H12	120.6647
C3—C2—H2	117.2277	C13—C12—H12	120.6649
C7—C2—H2	99.8589	F1—C13—C12	119.05 (12)
N2—C3—C2	100.48 (9)	F1—C13—C14	118.23 (14)
N2—C3—C4	116.86 (11)	C12—C13—C14	122.72 (14)
N2—C3—H3	111.6886	C9—C14—C13	118.97 (13)
C2—C3—C4	112.03 (11)	C9—C14—H14	120.5126
C2—C3—H3	116.5452	C13—C14—H14	120.5134
C4—C3—H3	100.0584	N2—C15—C16	110.43 (10)
C3—C4—C5	107.76 (12)	N2—C15—H15a	109.4707
C3—C4—H4a	109.4714	N2—C15—H15b	109.4709
C3—C4—H4b	109.4705	C16—C15—H15a	109.4714
C5—C4—H4a	109.4712	C16—C15—H15b	109.4718
C5—C4—H4b	109.4712	H15a—C15—H15b	108.497
H4a—C4—H4b	111.1273	C15—C16—C17	119.77 (12)
C4—C5—C6	112.74 (11)	C15—C16—C21	121.39 (12)
C4—C5—H5a	109.4709	C17—C16—C21	118.82 (13)
C4—C5—H5b	109.4714	O2—C17—C16	120.69 (13)
C6—C5—H5a	109.4711	O2—C17—C18	118.90 (13)
C6—C5—H5b	109.4715	C16—C17—C18	120.40 (14)
H5a—C5—H5b	105.995	C17—C18—C19	120.43 (14)
C5—C6—C7	112.66 (13)	C17—C18—H18	119.7837
C5—C6—H6a	109.471	C19—C18—H18	119.7831
C5—C6—H6b	109.4713	C18—C19—C20	118.30 (15)
C7—C6—H6a	109.4711	C18—C19—H19	120.8492
C7—C6—H6b	109.4714	C20—C19—H19	120.8486
H6a—C6—H6b	106.0781	F2—C20—C19	119.22 (14)
C2—C7—C6	107.69 (12)	F2—C20—C21	118.08 (13)
C2—C7—H7a	109.4718	C19—C20—C21	122.70 (14)
C2—C7—H7b	109.4711	C16—C21—C20	119.33 (13)
C6—C7—H7a	109.4711	C16—C21—H21	120.3339
C6—C7—H7b	109.4711	C20—C21—H21	120.3327

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.88 (2)	1.92 (2)	2.7105 (15)	147.6 (19)
O1—H1o···C8	0.88 (2)	2.37 (2)	2.8566 (17)	115.3 (15)
O2—H2o···N2	0.83 (2)	1.95 (2)	2.6975 (16)	148 (2)
O2—H2o···C15	0.83 (2)	2.39 (2)	2.8541 (17)	116.0 (18)

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄F₂N₂O₂
M_r	374.4
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	5.4605 (1), 12.4661 (3), 14.3363 (4)
α, β, γ (°)	108.053 (3), 91.319 (2), 97.437 (2)
V (Å³)	917.98 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.36 × 0.23 × 0.09

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.516, 1
No. of measured, independent and observed [I > 3σ(I)] reflections	15846, 3248, 2819
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.110, 1.95
No. of reflections	3248
No. of parameters	250
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.23

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SIR2002 (Burla et al., 2003), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.88 (2)	1.92 (2)	2.7105 (15)	147.6 (19)
O2—H2o···N2	0.83 (2)	1.95 (2)	2.6975 (16)	148 (2)

Acknowledgements

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia for financial support of this work, as well as the Institutional Research Plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae Project of the Academy of Sciences of the Czech Republic. DQ acknowledges the Vicerrectoría Académica de la Universidad Nacional de Colombia for a fellowship.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. CrossRef IUCr Journals Google Scholar
Elias, H., Stock, F. & Röhr, C. (1997). Acta Cryst. C53, 862–864. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
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Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Petříček, V., Dušek, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Praha, Czech Republic. Google Scholar
Rivera, A., Quiroga, D., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2010a). Acta Cryst. E66, o931. Web of Science CrossRef IUCr Journals Google Scholar
Rivera, A., Quiroga, D., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2010b). Acta Cryst. E66, o2643. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rivera, A., Quiroga, D., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2011). Acta Cryst. E67, o753. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Volume 67| Part 6| June 2011| Page o1542

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4,4′-Di­fluoro-2,2′-{[(3aRS,7aRS)-2,3,3a,4,5,6,7,7a-octa­hydro-1H-1,3-benzimidazole-1,3-di­yl]bis­­(methyl­ene)]}diphenol

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4,4′-Difluoro-2,2′-{[(3aRS,7aRS)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3-benzimidazole-1,3-diyl]bis(methylene)]}diphenol