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

In the crystal structure of the title compound, C(21)H(24)F(2)N(2)O(2), there are two intra-molecular O-H⋯N hydrogen bonds involving the N atoms of the imidazolidine ring and the hy-droxy groups. The crystal studied was a meso compound obtained by the reaction of the aminal (2S,7R,11S,16R)-1,8,10,17-tetra-aza-penta-cyclo-[8.8.1.1(8,17).0(2,7).0(11,16)]cosane with 4-fluoro-phenol. The imidazolidine ring has a twisted conformation with a CH-CH-N-CH(2) 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 = 374.4

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.077

S = 1.42

3177 reflections

250 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.15 e Å−3

Δρmin = −0.11 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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000305/bx2435sup1.cif

Click here for additional data file.

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

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813000305/bx2435Isup3.cml

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

C21H24F2N2O2	F(000) = 792
Mr = 374.4	Dx = 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

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	Rint = 0.049
Detector resolution: 10.3784 pixels mm-1	θmax = 67.1°, θmin = 3.7°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −22→22
Tmin = 0.222, Tmax = 1	l = −7→7
40310 measured reflections

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	Δρmax = 0.15 e Å−3
250 parameters	Δρmin = −0.11 e Å−3
0 restraints

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	0.08421 (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*

	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)

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

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

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) ; (ii) .