Crystal structure of rac-3,9-bis-(2,6-di-fluoro-phen-yl)-2,4,8,10-tetra-oxa-spiro[5.5]undeca-ne.

The title compound, C19H16F4O4, was prepared by the condensation reaction of 2,6-di-fluoro-benzaldehyde and penta-erythritol. The whole mol-ecule is generated by twofold rotational symmetry. The two six-membered O-heterocycles adopt chair conformations through a shared spiro-carbon atom that is located on the crystallographic twofold rotation axis. In this conformation, the two aromatic rings are located at the equatorial positions of the O-heterocycles. The conformation of this doubly substituted tetra-oxa-spiro system is chiral. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming layers parallel to (100). These layers are linked by C-H⋯F hydrogen bonds into a three-dimensional structure.

Related literature

For the use of tetra­oxa­spiro­[5.5]undeca­nes, see: Cismaş et al. (2005 ▸); Sondhi et al. (2009 ▸); Sauriat-Dorizon et al. (2003 ▸). For chiral conformations of tetra­oxa­spiro­[5.5]undeca­nes, see: Mihiş et al. (2008 ▸). For opposite enanti­omers of tetra­oxa­spiro­[5.5]undeca­nes, see: Sun et al. (2010 ▸).

Experimental

Crystal data

C19H16F4O4

M = 384.32

Monoclinic,

a = 28.960 (5) Å

b = 5.5627 (11) Å

c = 11.205 (2) Å

β = 95.442 (4)°

V = 1797.0 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 296 K

0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.975, T max = 0.981

4856 measured reflections

1671 independent reflections

1444 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.148

S = 1.01

1671 reflections

124 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015001206/su5070sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001206/su5070Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015001206/su5070Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015001206/su5070fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015001206/su5070fig2.tif

The crystal structure of enanti­omers of the title compound, showing the two opposite enanti­omers.

Click here for additional data file.

b c . DOI: 10.1107/S2056989015001206/su5070fig3.tif

Part of the layered crystal structure of the title compound, showing the weak C—H⋯O inter­actions between the mol­ecules. The same enanti­omers are linked along the b axis, and the different enanti­omers are linked alternatively along the c axis.

Click here for additional data file.

a R via b b c via b . DOI: 10.1107/S2056989015001206/su5070fig4.tif

A view of a part of the crystal structure of the title compound: (a) Left-handed helical chains of mol­ecules with R configuration connected via the weak C—H⋯F inter­actions (represented with the orange dashed lines) along the b axis; (b) the weak C—H⋯F inter­actions of the left-handed helical chains (indicated as the orange dashed line in the orange oval rings), the weak C—H⋯F inter­actions of the right-handed helical chains (represented as the green dashed line in the green oval rings); and the weak C—H⋯O inter­actions (represented as the red dashed lines); (c) Right-handed helical chains of the mol­ecules with S configuration connected via the weak C—H⋯F inter­actions (represented with the green dashed lines) along the b axis.

CCDC reference: 859906

Additional supporting information: crystallographic information; 3D view; checkCIF report

C19H16F4O4	F(000) = 792
Mr = 384.32	Dx = 1.421 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2905 reflections
a = 28.960 (5) Å	θ = 2.8–29.7°
b = 5.5627 (11) Å	µ = 0.13 mm−1
c = 11.205 (2) Å	T = 296 K
β = 95.442 (4)°	Block, colourless
V = 1797.0 (6) Å3	0.20 × 0.18 × 0.15 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	1671 independent reflections
Radiation source: fine-focus sealed tube	1444 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
phi and ω scans	θmax = 25.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −34→34
Tmin = 0.975, Tmax = 0.981	k = −6→6
4856 measured reflections	l = −13→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H-atom parameters constrained
wR(F2) = 0.148	w = 1/[σ2(Fo2) + (0.0997P)2 + 0.5847P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
1671 reflections	Δρmax = 0.26 e Å−3
124 parameters	Δρmin = −0.34 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.057 (5)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C9	0.5000	1.0314 (3)	0.7500	0.0444 (5)
O2	0.56492 (4)	1.05258 (19)	0.62616 (10)	0.0529 (4)
O1	0.56527 (4)	0.75364 (18)	0.77199 (9)	0.0478 (4)
F2	0.57010 (3)	0.5988 (2)	0.51818 (9)	0.0650 (4)
C8	0.53125 (5)	0.8761 (3)	0.83549 (13)	0.0469 (4)
H8A	0.5468	0.9763	0.8978	0.056*
H8B	0.5126	0.7589	0.8734	0.056*
C7	0.59217 (6)	0.9188 (3)	0.71277 (14)	0.0516 (4)
H7	0.6082	1.0281	0.7716	0.062*
C10	0.46902 (7)	1.1913 (3)	0.81939 (15)	0.0569 (5)
H10A	0.4880	1.2783	0.8810	0.068*
H10B	0.4535	1.3082	0.7652	0.068*
C6	0.62720 (6)	0.7791 (3)	0.65080 (16)	0.0587 (5)
C5	0.61516 (6)	0.6237 (3)	0.55644 (18)	0.0614 (5)
C4	0.64657 (9)	0.4916 (5)	0.4995 (3)	0.0962 (8)
H4	0.6369	0.3890	0.4365	0.115*
C1	0.67413 (8)	0.7922 (6)	0.6860 (3)	0.0917 (8)
F1	0.68770 (5)	0.9389 (5)	0.78045 (18)	0.1351 (8)
C2	0.70735 (8)	0.6647 (9)	0.6309 (4)	0.1288 (13)
H2	0.7387	0.6806	0.6563	0.155*
C3	0.69284 (12)	0.5162 (8)	0.5389 (4)	0.1302 (13)
H3	0.7147	0.4287	0.5015	0.156*

	U11	U22	U33	U12	U13	U23
C9	0.0647 (13)	0.0304 (9)	0.0386 (10)	0.000	0.0074 (9)	0.000
O2	0.0676 (8)	0.0444 (6)	0.0482 (7)	−0.0015 (5)	0.0131 (5)	0.0078 (5)
O1	0.0523 (6)	0.0447 (6)	0.0457 (6)	−0.0014 (4)	0.0011 (4)	0.0065 (4)
F2	0.0611 (7)	0.0655 (7)	0.0669 (7)	−0.0013 (4)	−0.0020 (5)	−0.0138 (5)
C8	0.0595 (9)	0.0458 (8)	0.0350 (7)	−0.0063 (6)	0.0023 (6)	0.0012 (6)
C7	0.0543 (9)	0.0527 (9)	0.0464 (8)	−0.0136 (7)	−0.0020 (7)	−0.0004 (6)
C10	0.0834 (12)	0.0336 (8)	0.0560 (10)	0.0014 (7)	0.0177 (8)	−0.0043 (6)
C6	0.0482 (9)	0.0680 (11)	0.0594 (10)	−0.0062 (7)	0.0029 (7)	0.0097 (8)
C5	0.0591 (10)	0.0624 (11)	0.0640 (11)	0.0034 (8)	0.0114 (8)	0.0034 (8)
C4	0.0832 (15)	0.1023 (18)	0.1070 (19)	0.0196 (14)	0.0290 (14)	−0.0103 (16)
C1	0.0510 (11)	0.124 (2)	0.0972 (17)	−0.0138 (12)	−0.0083 (10)	0.0036 (15)
F1	0.0684 (9)	0.195 (2)	0.1355 (14)	−0.0375 (11)	−0.0249 (9)	−0.0258 (13)
C2	0.0455 (12)	0.183 (4)	0.158 (3)	0.0131 (17)	0.0088 (15)	0.019 (3)
C3	0.0830 (19)	0.149 (3)	0.164 (3)	0.038 (2)	0.042 (2)	−0.001 (3)

C9—C8i	1.5226 (19)	C10—O2i	1.4309 (19)
C9—C8	1.5227 (18)	C10—H10A	0.9700
C9—C10	1.5277 (19)	C10—H10B	0.9700
C9—C10i	1.5277 (19)	C6—C1	1.381 (3)
O2—C7	1.405 (2)	C6—C5	1.384 (3)
O2—C10i	1.4309 (19)	C5—C4	1.373 (3)
O1—C7	1.4106 (18)	C4—C3	1.377 (5)
O1—C8	1.4400 (18)	C4—H4	0.9300
F2—C5	1.342 (2)	C1—F1	1.364 (3)
C8—H8A	0.9700	C1—C2	1.386 (5)
C8—H8B	0.9700	C2—C3	1.356 (6)
C7—C6	1.500 (2)	C2—H2	0.9300
C7—H7	0.9800	C3—H3	0.9300
C8i—C9—C8	110.87 (16)	C9—C10—H10A	109.4
C8i—C9—C10	107.93 (9)	O2i—C10—H10B	109.4
C8—C9—C10	110.67 (9)	C9—C10—H10B	109.4
C8i—C9—C10i	110.67 (9)	H10A—C10—H10B	108.0
C8—C9—C10i	107.93 (9)	C1—C6—C5	114.9 (2)
C10—C9—C10i	108.76 (16)	C1—C6—C7	122.08 (19)
C7—O2—C10i	110.78 (12)	C5—C6—C7	123.01 (15)
C7—O1—C8	111.00 (11)	F2—C5—C4	117.6 (2)
O1—C8—C9	110.56 (10)	F2—C5—C6	118.38 (15)
O1—C8—H8A	109.5	C4—C5—C6	124.0 (2)
C9—C8—H8A	109.5	C5—C4—C3	117.7 (3)
O1—C8—H8B	109.5	C5—C4—H4	121.1
C9—C8—H8B	109.5	C3—C4—H4	121.1
H8A—C8—H8B	108.1	F1—C1—C6	117.2 (2)
O2—C7—O1	111.78 (12)	F1—C1—C2	119.4 (2)
O2—C7—C6	108.36 (13)	C6—C1—C2	123.5 (3)
O1—C7—C6	107.94 (13)	C3—C2—C1	118.2 (2)
O2—C7—H7	109.6	C3—C2—H2	120.9
O1—C7—H7	109.6	C1—C2—H2	120.9
C6—C7—H7	109.6	C2—C3—C4	121.8 (3)
O2i—C10—C9	111.29 (12)	C2—C3—H3	119.1
O2i—C10—H10A	109.4	C4—C3—H3	119.1
C7—O1—C8—C9	57.50 (15)	C1—C6—C5—F2	179.13 (19)
C8i—C9—C8—O1	69.20 (9)	C7—C6—C5—F2	0.6 (3)
C10—C9—C8—O1	−171.06 (11)	C1—C6—C5—C4	−0.5 (3)
C10i—C9—C8—O1	−52.16 (15)	C7—C6—C5—C4	−179.1 (2)
C10i—O2—C7—O1	61.60 (16)	F2—C5—C4—C3	−179.8 (3)
C10i—O2—C7—C6	−179.58 (12)	C6—C5—C4—C3	−0.1 (4)
C8—O1—C7—O2	−61.92 (15)	C5—C6—C1—F1	−178.6 (2)
C8—O1—C7—C6	179.00 (11)	C7—C6—C1—F1	0.0 (3)
C8i—C9—C10—O2i	52.40 (16)	C5—C6—C1—C2	1.2 (4)
C8—C9—C10—O2i	−69.09 (16)	C7—C6—C1—C2	179.8 (3)
C10i—C9—C10—O2i	172.51 (17)	F1—C1—C2—C3	178.6 (4)
O2—C7—C6—C1	126.2 (2)	C6—C1—C2—C3	−1.2 (5)
O1—C7—C6—C1	−112.5 (2)	C1—C2—C3—C4	0.5 (6)
O2—C7—C6—C5	−55.3 (2)	C5—C4—C3—C2	0.2 (6)
O1—C7—C6—C5	65.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ii	0.97	2.57	3.334 (2)	136
C10—H10B···O1iii	0.97	2.56	3.410 (2)	146
C2—H2···F1iv	0.93	2.56	3.351 (3)	143

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C8H8AO2i	0.97	2.57	3.334(2)	136
C10H10BO1ii	0.97	2.56	3.410(2)	146
C2H2F1iii	0.93	2.56	3.351(3)	143

Symmetry codes: (i) ; (ii) ; (iii) .