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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
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
In the 21H24F2N2O2, 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 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.
of the title compound, CRelated 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
|
Refinement
|
|
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell 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
10.1107/S1600536811019763/kj2178sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811019763/kj2178Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811019763/kj2178Isup3.cml
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 [8.8.1.18, 17˙02,7.011,16]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
on a silica column, and subjected to 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.All hydrogen atoms were discernible in difference Fourier maps and could be refined to reasonable geometry. According to common practice H atoms attached to C atoms were nevertheless kept in ideal positions during the
The isotropic atomic displacement parameters of hydrogen atoms were evaluated as 1.2*U~eq~ of the parent atom.Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
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). ![]() | Fig. 1. Displacement elipsoid plot of the title compound, drawn at 50% probability level. |
C21H24F2N2O2 | Z = 2 |
Mr = 374.4 | F(000) = 396 |
Triclinic, P1 | Dx = 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 |
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 | Rint = 0.024 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.1°, θmin = 3.3° |
Rotation method data acquisition using ω scans | h = −6→6 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −14→14 |
Tmin = 0.516, Tmax = 1 | l = −17→17 |
15846 measured reflections |
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 | Δρmax = 0.25 e Å−3 |
250 parameters | Δρmin = −0.23 e Å−3 |
0 restraints |
C21H24F2N2O2 | γ = 97.437 (2)° |
Mr = 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)° |
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) |
Tmin = 0.516, Tmax = 1 | Rint = 0.024 |
15846 measured reflections |
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 | Δρmax = 0.25 e Å−3 |
3248 reflections | Δρmin = −0.23 e Å−3 |
250 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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 |
Mr | 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) |
Tmin, Tmax | 0.516, 1 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 15846, 3248, 2819 |
Rint | 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 |
Δρmax, Δρmin (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).
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.
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The title compound was obtained by a Mannich type reaction between the aminal (2R,7R,11S,16S)-1,8,10,17-tetraazapentacyclo[8.8.1.18,17.02,7.011,16]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.