meso-4,4′-Difluoro-2,2′-{[(3aR,7aS)-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.; Kučeraková, M.; Dušek, M.

doi:10.1107/S1600536813000305

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o217

doi:10.1107/S1600536813000305

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meso-4,4′-Difluoro-2,2′-{[(3aR,7aS)-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 Monika Kučeraková ^b and Michal Dušek ^b

^aFacultad de Ciencias, Departamento de Química, Universidad Nacional de Colombia, Sede Bogotá, Cra 30 No. 45-03, Bogotá, Código Postal 111321, Colombia, and ^bInstitute of Physics, Academy of Sciences of the Czech Republic, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: ariverau@unal.edu.co

(Received 24 December 2012; accepted 3 January 2013; online 12 January 2013)

In the crystal structure of the title compound, C₂₁H₂₄F₂N₂O₂, there are two intramolecular O—H⋯N hydrogen bonds involving the N atoms of the imidazolidine ring and the hydroxy groups. The crystal studied was a meso compound obtained by the reaction of the aminal (2S,7R,11S,16R)-1,8,10,17-tetraazapentacyclo[8.8.1.1^8,17.0^2,7.0^11,16]cosane with 4-fluorophenol. The imidazolidine ring has a twisted conformation with a CH—CH—N—CH₂ torsion angle of 44.99 (14)° and, surprisingly, the lone pairs of the N atoms are disposed in a syn isomerism, making the title compound an exception to the typical `rabbit-ear effect' in 1,2-diamines. In the crystal, molecules are linked via C—H⋯F hydrogen bonds, forming chains along the c-axis direction. These chains are linked via another C—H⋯F hydrogen bond, forming a three-dimensional network.

Related literature

For a related structure, see: Rivera et al. (2011 ). For a discussion of the `rabbit-ear effect' in 1,2-diamines, see: Hutchins et al.(1968 ).

Experimental

Crystal data

C₂₁H₂₄F₂N₂O₂
M_r = 374.4
Orthorhombic, P n a 2₁
a = 15.4029 (4) Å
b = 18.7822 (4) Å
c = 6.1639 (2) Å
V = 1783.22 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.86 mm⁻¹
T = 120 K
0.31 × 0.15 × 0.11 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.222, T_max = 1
40310 measured reflections
3177 independent reflections
2984 reflections with I > 3σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.077
S = 1.42
3177 reflections
250 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.85 (2)	1.89 (2)	2.6540 (17)	148 (2)
O2—H2⋯N2	0.85 (2)	1.89 (2)	2.6741 (18)	152 (2)
C13—H1C13⋯F2ⁱ	0.96	2.43	3.2645 (19)	145
C17—H2C17⋯F2ⁱⁱ	0.96	2.54	3.356 (2)	142
Symmetry codes: (i) $[-x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000305/bx2435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000305/bx2435Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813000305/bx2435Isup3.cml

checkCIF report

Comment top

Typically the 1,1-diamines tend to adopt a conformation in which the arrangement of electron pairs is anti periplanar. This behavior is known as `rabbit-ears' effect (Hutchins et al., 1968), however, this effect can be avoided by restriction of the 1,2-diamine in cyclic molecules. Recently, we reported the synthesis and the crystal structure of rac-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 et al., 2011), which has trans stereochemistry in the 1,2-diamine moiety with the lone pairs located in anti disposition avoiding the repulsive interactions. Now we reported the synthesis and crystal structure of the meso diastereoisomer with absolute configuration (R,S) where surprisingly the lone pairs of the N atoms are located in syn disposition.

The molecular structure and atom-numbering scheme for (I) are shown in Fig. 1. In the molecular structure of the title compound, the two N atoms of the heterocyclic ring interact with the H atoms of the hydroxy groups by intramolecular hydrogen bonds O—H···N, with N···O interatomic distance values around 2.66 Å, as well as the values of C—O and O—H bond lengths are 1.363 (3) Å and 0.83 (3) Å, respectively. The cyclohexane ring adopts a chair conformation while the heterocyclic ring arranged diagonally respect to the cyclohexane ring with dihedral angle between planes of 25.46 (96)°. The heterocyclic ring adopts an envelope conformation according to the value of the N2—C5—N1—C16 torsion angle of -7.91°. Bond angles around the N atoms N1 and N2 show a higher sp³ character to the N1 and N2 N atoms with pyramidalization involved in the hydrogen bond type interactions [Σ(CNC) N1 = 331.3°, Σ(CNC) N2 = 330.4°]. Moreover, the benzyl groups are located in an unexpected 1,3-diequatorial syn arrangement in the heterocyclic ring with dihedral angle between the planes containing the aromatic rings of 53.80 (30)°. The nonbonding pairs of amino groups involved in the intermolecular hydrogen bonding interactions do not suffer the `rabbit-ear effect' having a syn arrangement demonstrating that the title compound is an exception of this effect.

The stability of the crystal lattice of the title compound is related with non classical intermolecular interactions C—H···F that hold molecules linked in extended chains along the c axis. There are O—H···C and C—H···F weak interactions (table 1), the latter involve halogen group in molecular contact with an electron-deficient C—H bond of the aromatic ring of a second molecule.

Related literature top

For a related structure, see: Rivera et al. (2011). For a discussion of the `rabbit-ear effect' in 1,2-diamines, see: Hutchins et al.(1968).

Experimental top

To a stirred solution of (2S,7R,11S,16R)-1,8,10,17-tetraazapentacyclo[8.8.1.1.^8,170.^2,70^11,16] icosane (3) (276 mg, 1.00 mmol) in dioxane (3 ml) was added slowly dropwise p-fluorophenol (2.00 mmol) in dioxane (3 ml). After stirring for 15 min at room temperature, water (4 ml) was added and the mixture was heated at 40°C during 30 h. After cooling to room temperature, the solvent was removed in vacuo and the crude product was purified by chromatography on a silica column and subjected to gradient elution with light petroleum ether:ethyl acetate (yield 20%, m.p. = 441–443 K). Single crystals of (I) were grown from a CHCl₃ solution by slow evaporation of the solvent at room temperature over a period of about 2 weeks. FT–IR (KBr) ν_max: 3061, 2848, 1495, 1448, 1387, 1289, 1245, 1194, 1124, 1063, 979, 925, 814, 772, 737, 714, 692, 668 cm^{-1. 1}H NMR (400 MHz, CDCl₃) δ (p.p.m.): 1.36 (m, 2H), 1.55–1.79 (m, 6H), 3.11 (t, 2H, J_H,H = 4.0 Hz), 3.39 (d, 1H,²J_H,H = 6.4 Hz, NCH₂N), 3.63 (d, 2H, ²J_H,H = 14.0 Hz, ArCH₂N), 3.84 (d, 1H, ²J_H,H = 6.4 Hz, NCH₂N), 4.03 (d, 2H, ²J_H,H = 14.0 Hz, ArCH₂N), 6.70 (dd, 2H, ³J_H,F = 8.0 Hz, ⁴J_H,H = 2.8 Hz, Ar—H), 6.76 (dd, 2H, ³J_H,H = 8.0 Hz, ⁴J_H,F = 4.8 Hz, Ar—H), 6.87 (td, 2H, ³J_H,H = 8.0 Hz, ³J_H,F = 8.2 Hz, ⁴J_H,H = 3.1 Hz, Ar—H), 10.34 (s, 2H). ¹³C NMR (100 MHz, CDCl₃) δ (p.p.m.): 21.5, 24.7, 55.0, 61.1, 73.4, 114.7 (d, ²J_H,F = 23.5 Hz), 115.4 (d, ²J_H,F = 22.5 Hz), 117.0 (d, ³J_H,F = 6.3 Hz), 122.0 (d, ³J_H,F = 6.9 Hz), 153.4 (d, ⁴J_H,F = 2.0 Hz), 156.0 (d, ¹J_H,F = 236 Hz).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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 (Petříček et al., 2006).

Figures top

Fig. 1. A perspective view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines.

meso-4,4'-Difluoro-2,2'-{[(3aR,7aS)-2,3,3a,4,5,6,7,7a- octahydro-1H-1,3-benzimidazole-1,3-diyl]bis(methylene)}diphenol top

Crystal data top

C₂₁H₂₄F₂N₂O₂	F(000) = 792
M_r = 374.4	D_x = 1.394 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P -2ac -2n	Cell parameters from 19583 reflections
a = 15.4029 (4) Å	θ = 3.7–67.0°
b = 18.7822 (4) Å	µ = 0.86 mm⁻¹
c = 6.1639 (2) Å	T = 120 K
V = 1783.22 (8) Å³	Polygon shape, white
Z = 4	0.31 × 0.15 × 0.11 mm

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3177 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2984 reflections with I > 3σ(I)
Mirror monochromator	R_int = 0.049
Detector resolution: 10.3784 pixels mm^-1	θ_max = 67.1°, θ_min = 3.7°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −22→22
T_min = 0.222, T_max = 1	l = −7→7
40310 measured reflections

Refinement top

Refinement on F²	91 constraints
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.077	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0016I²)
S = 1.42	(Δ/σ)_max = 0.010
3177 reflections	Δρ_max = 0.15 e Å⁻³
250 parameters	Δρ_min = −0.11 e Å⁻³
0 restraints

Crystal data top

C₂₁H₂₄F₂N₂O₂	V = 1783.22 (8) Å³
M_r = 374.4	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 15.4029 (4) Å	µ = 0.86 mm⁻¹
b = 18.7822 (4) Å	T = 120 K
c = 6.1639 (2) Å	0.31 × 0.15 × 0.11 mm

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3177 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2984 reflections with I > 3σ(I)
T_min = 0.222, T_max = 1	R_int = 0.049
40310 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.42	Δρ_max = 0.15 e Å⁻³
3177 reflections	Δρ_min = −0.11 e Å⁻³
250 parameters

Special details top

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	0.08421 (6)	0.56542 (5)	0.39265 (19)	0.0421 (3)
F2	0.01983 (7)	0.08785 (5)	−0.0670 (2)	0.0464 (3)
O1	0.26711 (8)	0.11965 (6)	0.5638 (2)	0.0355 (4)
O2	0.25923 (8)	0.37737 (7)	0.9132 (2)	0.0369 (4)
N1	0.33271 (8)	0.22874 (7)	0.3446 (2)	0.0231 (3)
N2	0.34150 (7)	0.33314 (6)	0.5557 (2)	0.0238 (4)
C1	0.20351 (10)	0.48809 (8)	0.4427 (3)	0.0283 (5)
C2	0.24882 (10)	0.44012 (8)	0.5731 (3)	0.0257 (4)
C3	0.41911 (9)	0.26109 (8)	0.3064 (2)	0.0230 (4)
C4	0.33424 (10)	0.40923 (8)	0.4988 (3)	0.0270 (4)
C5	0.20680 (10)	0.11405 (8)	0.4035 (3)	0.0274 (4)
C6	0.12823 (10)	0.51814 (8)	0.5218 (3)	0.0314 (5)
C7	0.21420 (10)	0.15102 (8)	0.2071 (3)	0.0254 (4)
C8	0.42966 (9)	0.30360 (8)	0.5158 (3)	0.0237 (4)
C9	0.49248 (9)	0.20825 (8)	0.2612 (3)	0.0267 (4)
C10	0.08186 (11)	0.09680 (8)	0.0901 (3)	0.0324 (5)
C11	0.52047 (10)	0.16567 (8)	0.4592 (3)	0.0299 (5)
C12	0.21650 (10)	0.42368 (8)	0.7793 (3)	0.0289 (5)
C13	0.07318 (10)	0.06018 (9)	0.2813 (3)	0.0343 (5)
C14	0.13982 (11)	0.45439 (9)	0.8526 (3)	0.0333 (5)
C15	0.29291 (10)	0.19587 (8)	0.1527 (3)	0.0259 (4)
C16	0.09529 (11)	0.50248 (9)	0.7232 (3)	0.0340 (5)
C17	0.45886 (10)	0.25765 (9)	0.7059 (3)	0.0275 (5)
C18	0.15019 (10)	0.14217 (8)	0.0499 (3)	0.0284 (4)
C19	0.13591 (10)	0.06908 (8)	0.4391 (3)	0.0331 (5)
C20	0.28071 (9)	0.28869 (8)	0.4282 (3)	0.0270 (4)
C21	0.54005 (11)	0.21507 (9)	0.6489 (3)	0.0321 (5)
H1c1	0.22435	0.499969	0.300447	0.034*
H1c3	0.422455	0.288956	0.176142	0.0276*
H1c4	0.339534	0.414724	0.344506	0.0325*
H2c4	0.381123	0.435124	0.564372	0.0325*
H1c8	0.473781	0.33942	0.502131	0.0284*
H1c9	0.541614	0.233235	0.203	0.032*
H2c9	0.475105	0.176214	0.147852	0.032*
H1c11	0.475029	0.133249	0.499311	0.0359*
H2c11	0.571355	0.138428	0.424659	0.0359*
H1c13	0.024629	0.029077	0.30491	0.0412*
H1c14	0.117621	0.442274	0.993384	0.0399*
H1c15	0.335179	0.167023	0.079409	0.0311*
H2c15	0.276748	0.23231	0.051253	0.0311*
H1c16	0.042627	0.524324	0.773234	0.0408*
H1c17	0.412966	0.225597	0.745425	0.033*
H2c17	0.470585	0.287446	0.828962	0.033*
H1c18	0.153672	0.167458	−0.08517	0.0341*
H1c19	0.13078	0.044152	0.574433	0.0397*
H1c20	0.235882	0.270824	0.521692	0.0324*
H2c20	0.258396	0.315914	0.308761	0.0324*
H1c21	0.585954	0.24712	0.60938	0.0386*
H2c21	0.557641	0.187359	0.772163	0.0386*
H1	0.3046 (14)	0.1501 (12)	0.523 (4)	0.0426*
H2	0.2959 (14)	0.3567 (12)	0.832 (4)	0.0443*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0366 (5)	0.0315 (5)	0.0583 (7)	0.0066 (4)	−0.0117 (5)	0.0030 (5)
F2	0.0397 (5)	0.0393 (5)	0.0602 (7)	−0.0079 (4)	−0.0155 (5)	−0.0076 (5)
O1	0.0400 (6)	0.0352 (6)	0.0312 (6)	−0.0068 (5)	−0.0009 (5)	0.0091 (5)
O2	0.0452 (7)	0.0398 (7)	0.0259 (6)	0.0104 (5)	0.0049 (6)	0.0029 (5)
N1	0.0233 (6)	0.0226 (6)	0.0234 (6)	−0.0014 (5)	0.0034 (5)	−0.0016 (5)
N2	0.0231 (6)	0.0199 (6)	0.0285 (7)	0.0004 (5)	0.0028 (5)	−0.0003 (5)
C1	0.0308 (8)	0.0214 (7)	0.0328 (9)	−0.0035 (6)	−0.0036 (7)	0.0010 (6)
C2	0.0293 (7)	0.0185 (7)	0.0292 (8)	−0.0026 (6)	−0.0007 (7)	−0.0035 (6)
C3	0.0240 (7)	0.0227 (7)	0.0224 (8)	−0.0007 (6)	0.0037 (6)	0.0024 (6)
C4	0.0304 (7)	0.0203 (7)	0.0304 (9)	−0.0002 (6)	0.0035 (6)	0.0009 (6)
C5	0.0292 (7)	0.0220 (7)	0.0311 (8)	0.0018 (6)	0.0045 (7)	0.0006 (6)
C6	0.0294 (8)	0.0208 (7)	0.0441 (10)	−0.0006 (6)	−0.0077 (7)	−0.0044 (7)
C7	0.0266 (7)	0.0200 (7)	0.0295 (8)	0.0028 (6)	0.0035 (6)	−0.0041 (6)
C8	0.0223 (6)	0.0221 (7)	0.0266 (8)	−0.0011 (6)	0.0025 (6)	−0.0003 (6)
C9	0.0246 (7)	0.0288 (8)	0.0267 (8)	0.0015 (6)	0.0063 (6)	−0.0011 (6)
C10	0.0284 (8)	0.0241 (7)	0.0449 (11)	0.0006 (6)	−0.0021 (7)	−0.0076 (7)
C11	0.0287 (7)	0.0280 (7)	0.0331 (9)	0.0055 (6)	0.0031 (6)	−0.0009 (7)
C12	0.0339 (8)	0.0249 (8)	0.0278 (9)	0.0003 (6)	0.0001 (7)	−0.0046 (6)
C13	0.0287 (8)	0.0221 (8)	0.0522 (11)	−0.0038 (6)	0.0107 (8)	−0.0073 (7)
C14	0.0363 (8)	0.0314 (8)	0.0321 (9)	−0.0007 (6)	0.0069 (7)	−0.0081 (7)
C15	0.0290 (7)	0.0248 (7)	0.0239 (8)	−0.0014 (6)	0.0009 (6)	−0.0004 (6)
C16	0.0289 (7)	0.0273 (8)	0.0459 (11)	−0.0001 (7)	0.0012 (7)	−0.0109 (7)
C17	0.0279 (7)	0.0304 (8)	0.0241 (8)	0.0021 (6)	0.0024 (6)	−0.0012 (6)
C18	0.0324 (8)	0.0224 (7)	0.0306 (9)	0.0005 (6)	0.0000 (7)	−0.0033 (7)
C19	0.0354 (8)	0.0234 (7)	0.0405 (10)	−0.0006 (6)	0.0102 (8)	0.0017 (7)
C20	0.0247 (7)	0.0241 (7)	0.0323 (9)	−0.0002 (6)	0.0033 (7)	−0.0036 (7)
C21	0.0299 (7)	0.0364 (9)	0.0302 (9)	0.0076 (7)	0.0000 (7)	0.0005 (7)

Geometric parameters (Å, º) top

F1—C6	1.372 (2)	C8—C17	1.523 (2)
F2—C10	1.370 (2)	C8—H1c8	0.96
O1—C5	1.360 (2)	C9—C11	1.522 (2)
O1—H1	0.85 (2)	C9—H1c9	0.96
O2—C12	1.368 (2)	C9—H2c9	0.96
O2—H2	0.85 (2)	C10—C13	1.371 (3)
N1—C3	1.4818 (18)	C10—C18	1.377 (2)
N1—C15	1.468 (2)	C11—C21	1.523 (2)
N1—C20	1.4747 (19)	C11—H1c11	0.96
N2—C4	1.4758 (19)	C11—H2c11	0.96
N2—C8	1.4874 (18)	C12—C14	1.390 (2)
N2—C20	1.4805 (19)	C13—C19	1.381 (2)
C1—C2	1.395 (2)	C13—H1c13	0.96
C1—C6	1.379 (2)	C14—C16	1.387 (2)
C1—H1c1	0.96	C14—H1c14	0.96
C2—C4	1.509 (2)	C15—H1c15	0.96
C2—C12	1.400 (2)	C15—H2c15	0.96
C3—C8	1.526 (2)	C16—H1c16	0.96
C3—C9	1.530 (2)	C17—C21	1.526 (2)
C3—H1c3	0.96	C17—H1c17	0.96
C4—H1c4	0.96	C17—H2c17	0.96
C4—H2c4	0.96	C18—H1c18	0.96
C5—C7	1.400 (2)	C19—H1c19	0.96
C5—C19	1.398 (2)	C20—H1c20	0.96
C6—C16	1.373 (3)	C20—H2c20	0.96
C7—C15	1.514 (2)	C21—H1c21	0.96
C7—C18	1.392 (2)	C21—H2c21	0.96

C5—O1—H1	107.6 (15)	C13—C10—C18	122.66 (16)
C12—O2—H2	104.7 (16)	C9—C11—C21	110.60 (13)
C3—N1—C15	114.79 (12)	C9—C11—H1c11	109.47
C3—N1—C20	103.30 (11)	C9—C11—H2c11	109.47
C15—N1—C20	112.07 (11)	C21—C11—H1c11	109.47
C4—N2—C8	113.02 (11)	C21—C11—H2c11	109.47
C4—N2—C20	111.82 (11)	H1c11—C11—H2c11	108.32
C8—N2—C20	106.20 (11)	O2—C12—C2	121.15 (14)
C2—C1—C6	118.79 (16)	O2—C12—C14	118.45 (15)
C2—C1—H1c1	120.6	C2—C12—C14	120.40 (15)
C6—C1—H1c1	120.6	C10—C13—C19	118.45 (15)
C1—C2—C4	120.66 (14)	C10—C13—H1c13	120.78
C1—C2—C12	119.20 (14)	C19—C13—H1c13	120.78
C4—C2—C12	120.06 (14)	C12—C14—C16	120.23 (16)
N1—C3—C8	100.13 (11)	C12—C14—H1c14	119.89
N1—C3—C9	115.24 (12)	C16—C14—H1c14	119.89
N1—C3—H1c3	113.88	N1—C15—C7	112.94 (13)
C8—C3—C9	114.52 (12)	N1—C15—H1c15	109.47
C8—C3—H1c3	114.61	N1—C15—H2c15	109.47
C9—C3—H1c3	99.29	C7—C15—H1c15	109.47
N2—C4—C2	111.48 (12)	C7—C15—H2c15	109.47
N2—C4—H1c4	109.47	H1c15—C15—H2c15	105.76
N2—C4—H2c4	109.47	C6—C16—C14	118.49 (15)
C2—C4—H1c4	109.47	C6—C16—H1c16	120.75
C2—C4—H2c4	109.47	C14—C16—H1c16	120.75
H1c4—C4—H2c4	107.38	C8—C17—C21	111.23 (13)
O1—C5—C7	122.28 (13)	C8—C17—H1c17	109.47
O1—C5—C19	117.78 (15)	C8—C17—H2c17	109.47
C7—C5—C19	119.93 (15)	C21—C17—H1c17	109.47
F1—C6—C1	118.40 (16)	C21—C17—H2c17	109.47
F1—C6—C16	118.73 (14)	H1c17—C17—H2c17	107.66
C1—C6—C16	122.88 (16)	C7—C18—C10	119.35 (16)
C5—C7—C15	122.18 (14)	C7—C18—H1c18	120.33
C5—C7—C18	118.99 (14)	C10—C18—H1c18	120.32
C15—C7—C18	118.65 (14)	C5—C19—C13	120.61 (16)
N2—C8—C3	103.77 (11)	C5—C19—H1c19	119.7
N2—C8—C17	110.70 (12)	C13—C19—H1c19	119.7
N2—C8—H1c8	113.54	N1—C20—N2	105.82 (11)
C3—C8—C17	112.67 (12)	N1—C20—H1c20	109.47
C3—C8—H1c8	111.6	N1—C20—H2c20	109.47
C17—C8—H1c8	104.79	N2—C20—H1c20	109.47
C3—C9—C11	113.83 (13)	N2—C20—H2c20	109.47
C3—C9—H1c9	109.47	H1c20—C20—H2c20	112.89
C3—C9—H2c9	109.47	C11—C21—C17	109.50 (13)
C11—C9—H1c9	109.47	C11—C21—H1c21	109.47
C11—C9—H2c9	109.47	C11—C21—H2c21	109.47
H1c9—C9—H2c9	104.73	C17—C21—H1c21	109.47
F2—C10—C13	118.53 (14)	C17—C21—H2c21	109.47
F2—C10—C18	118.81 (16)	H1c21—C21—H2c21	109.45

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.85 (2)	1.89 (2)	2.6540 (17)	148 (2)
O2—H2···N2	0.85 (2)	1.89 (2)	2.6741 (18)	152 (2)
O1—H1···C15	0.85 (2)	2.45 (2)	2.937 (2)	117.4 (18)
O2—H2···C4	0.85 (2)	2.35 (2)	2.867 (2)	119.3 (19)
C13—H1C13···F2ⁱ	0.96	2.43	3.2645 (19)	145
C17—H2C17···F2ⁱⁱ	0.96	2.54	3.356 (2)	142

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

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄F₂N₂O₂
M_r	374.4
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	15.4029 (4), 18.7822 (4), 6.1639 (2)
V (Å³)	1783.22 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.31 × 0.15 × 0.11

Data collection
Diffractometer	Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.222, 1
No. of measured, independent and observed [I > 3σ(I)] reflections	40310, 3177, 2984
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.42
No. of reflections	3177
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)	0.15, −0.11

Computer programs: CrysAlis PRO (Agilent, 2010), SUPERFLIP (Palatinus & Chapuis, 2007), 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—H1···N1	0.85 (2)	1.89 (2)	2.6540 (17)	148 (2)
O2—H2···N2	0.85 (2)	1.89 (2)	2.6741 (18)	152 (2)
C13—H1C13···F2ⁱ	0.96	2.43	3.2645 (19)	144.88
C17—H2C17···F2ⁱⁱ	0.96	2.54	3.356 (2)	142

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

Acknowledgements

The authors acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work, as well as 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

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact, Bonn, Germany. Google Scholar
Hutchins, R. O., Kopp, L. D. & Eliel, E. L. (1968). J. Am. Chem. Soc. 90, 7174–7175. CrossRef CAS Web of Science Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Petříček, V., Dusěk, M. & Palatinus, L. (2006). JANA2006. Institute of Physics, Prague, Czech Republic. Google Scholar
Rivera, A., Quiroga, D., Ríos-Motta, J., Dušek, M. & Fejfarová, K. (2011). Acta Cryst. E67, o1542. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 69| Part 2| February 2013| Page o217

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

meso-4,4′-Di­fluoro-2,2′-{[(3aR,7aS)-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

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