3,5-Di­hydroxy-3,5-bis­(tri­fluoro­methyl)-1,2-dioxolane-1,4-dioxane (1/1) at 173 K

The 1,2-dioxolane of the title adduct, C₅H₄F₆O₄·C₄H₈O₂, is produced slowly by air oxidation of di­aqua­bis(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato)­manganese(II) in the pres­ence of 1,4-dioxane. This dioxolane is formally derived from the addition of H₂O₂ to 1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dione. The hydroxy groups of the dioxolane are hydrogen bonded to dioxane to form an alternating chain structure.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.053
• wR factor = 0.105
• Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

An attempt to synthesize bis(1,4-dioxane)bis(hfac)manganese(II) (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionato) resulted in the isolation of diaquabis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)manganese(II) 1.5(1,4-dioxane) solvate, identified by an X-ray crystal structure analysis. A sample of this solvate kept in a sealed glass vial was observed, after several months, to deposit colourless crystals near the top of the vial, apparently by sublimation. Structure analysis of these crystals revealed the title 1,2-dioxolane, (I), hydrogen bonded to 1,4-dioxane (Fig. 1). The two hydroxy groups are hydrogen bonded to different dioxane molecules to form a chain in which dioxane and dioxolane alternate.

Presumably autoxidation of 1,4-dioxane forms peroxide which then reacts with Mn(hfac)₂(H₂O)₂ to produce 1,2-dioxolane. Fluorinated organic peroxides have been found useful as synthetic reagents (Sawada, 1996).

O1 and O2 are out of the C2–C3–C4 plane by -0.295 (5) and 0.361 (5) Å, respectively. Structure reports of 1,2-dioxolanes in which the dioxolane ring is not fused to other rings are relatively uncommon. Among these are 3,3'-vinylidene-di-(5-phenyl-1,2-dioxolane) and 4-(5'-phenyl-1',2'-dioxolan-3'-yl)-3-vinyl-1,2-dioxolane (Feldman et al., 1986); bis(3,5,5-trimethyl-1,2-dioxolan-3-yl) peroxide (Ramm, 1996); and two steroid derivatives (Hernández et al., 1996; Boto et al., 1998).

S2. Experimental

Mn(hfac)₂(H₂O)₃ was made by a standard procedure (Morris et al., 1968). Mn(hfac)₂(H₂O)₃ (0.5 g) was added to a mixture of n-heptane (50 ml) and 1,4-dioxane (5 ml). This mixture was distilled until nearly 5 ml of the solution had evaporated. The remaining yellow solution was allowed to cool at room temperature in a loosely covered beaker. After about a day, yellow crystals formed. These were identified as Mn(hfac)₂(H₂O)₂ 1.5-(1,4-dioxane) solvate. This compound was isolated by filtration and stored in a sealed glass vial. Colourless crystals of the title formula formed slowly over a period of months.

S3. Refinement

H atoms were refined isotropically in observed positions. C—H distances ranged from 0.94 (2) to 1.06 (3) Å and O–H distances were 0.85 (3) and 0.86 (3) Å.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the title structure. Displacement ellipsoids are drawn at the 50% probability level.

3,5-Dihydroxy-3,5-bis(trifluoromethyl)-1,2-dioxolane 1,4-dioxane

Crystal data

C5H4F6O4·C4H8O2	F(000) = 672
Mr = 330.19	Dx = 1.658 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.1997 (3) Å	Cell parameters from 5471 reflections
b = 18.2477 (6) Å	θ = 2.2–28.3°
c = 8.8871 (3) Å	µ = 0.19 mm^−1
β = 95.798 (1)°	T = 173 K
V = 1322.94 (8) Å^3	Rod, colorless
Z = 4	0.36 × 0.15 × 0.15 mm

Data collection

CCD area-detector diffractometer	1972 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 28.3°, θmin = 2.2°
ω scans	h = −10→10
14324 measured reflections	k = −23→23
3163 independent reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: difference Fourier map
wR(F^2) = 0.105	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.85P] where P = (Fo^2 + 2Fc^2)/3
3163 reflections	(Δ/σ)max < 0.001
238 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. Data set was 97.5% complete to 0.75 angstrom resolution with average redundancy 4.46. Crystal decay was monitored by re-collection of the first 60 frames after regular data collection was complete. No significant change was observed.

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 6.9638 (0.0047) x + 1.0567 (0.0205) y - 3.8773 (0.0087) z = 0.0810 (0.0143)

* -0.1364 (0.0013) C2 * -0.0080 (0.0013) C3 * 0.1519 (0.0013) C4 * 0.2420 (0.0012) O1 * -0.2494 (0.0012) O2

Rms deviation of fitted atoms = 0.1803

6.3830 (0.0067) x - 1.1866 (0.0557) y + 4.8212 (0.0106) z = 0.5330 (0.0358)

Angle to previous plane (with approximate e.s.d.) = 7.02 (0.17)

* 0.0000 (0.0000) C2 * 0.0000 (0.0000) C3 * 0.0000 (0.0000) C4 - 0.2947 (0.0053) O1 0.3607 (0.0052) O2

Rms deviation of fitted atoms = 0.0000

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.2201 (3)	0.60124 (13)	0.3134 (3)	0.0355 (6)
C2	−0.1703 (3)	0.60104 (11)	0.4839 (2)	0.0271 (5)
C3	−0.2440 (3)	0.53778 (12)	0.5659 (3)	0.0279 (5)
C4	−0.3292 (3)	0.57642 (11)	0.6882 (2)	0.0261 (5)
C5	−0.2830 (3)	0.54601 (14)	0.8472 (3)	0.0360 (6)
C6	0.1961 (3)	0.84774 (14)	0.3706 (4)	0.0435 (7)
C7	0.0834 (3)	0.78324 (14)	0.3605 (4)	0.0430 (7)
C8	0.3108 (3)	0.70342 (15)	0.3821 (4)	0.0451 (7)
C9	0.4238 (3)	0.76778 (16)	0.3923 (4)	0.0516 (8)
O1	−0.24388 (19)	0.66614 (8)	0.53627 (17)	0.0314 (4)
O2	−0.26438 (18)	0.64919 (8)	0.69518 (16)	0.0310 (4)
O3	−0.00145 (19)	0.60093 (9)	0.51480 (18)	0.0321 (4)
O4	−0.49705 (18)	0.57478 (9)	0.65256 (18)	0.0308 (4)
O5	0.34649 (19)	0.82868 (9)	0.3109 (2)	0.0428 (4)
O6	0.15997 (19)	0.72218 (8)	0.44301 (19)	0.0383 (4)
F1	−0.15800 (19)	0.65878 (9)	0.24585 (16)	0.0542 (4)
F2	−0.16385 (19)	0.54089 (8)	0.25039 (16)	0.0503 (4)
F3	−0.38182 (17)	0.60265 (8)	0.27995 (16)	0.0463 (4)
F4	−0.12240 (17)	0.54721 (8)	0.88728 (16)	0.0498 (4)
F5	−0.33115 (19)	0.47633 (8)	0.85480 (18)	0.0567 (4)
F6	−0.3550 (2)	0.58357 (10)	0.95058 (16)	0.0593 (5)
H1O3	0.039 (3)	0.6401 (14)	0.484 (3)	0.042 (8)*
H1O4	−0.541 (3)	0.6054 (15)	0.709 (3)	0.059 (9)*
H1C3	−0.157 (3)	0.5085 (12)	0.609 (3)	0.033 (6)*
H2C3	−0.324 (3)	0.5100 (14)	0.500 (3)	0.048 (7)*
H1C6	0.221 (3)	0.8624 (15)	0.479 (3)	0.062 (9)*
H2C6	0.148 (3)	0.8872 (16)	0.308 (3)	0.062 (9)*
H1C7	−0.016 (3)	0.7952 (13)	0.410 (3)	0.045 (7)*
H2C7	0.061 (3)	0.7668 (15)	0.246 (4)	0.067 (9)*
H1C8	0.358 (3)	0.6618 (15)	0.446 (3)	0.058 (8)*
H2C8	0.284 (3)	0.6884 (15)	0.272 (3)	0.063 (9)*
H1C9	0.445 (3)	0.7818 (15)	0.507 (4)	0.064 (9)*
H2C9	0.527 (4)	0.7575 (15)	0.346 (3)	0.064 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0355 (14)	0.0390 (14)	0.0325 (13)	0.0026 (11)	0.0064 (10)	0.0005 (11)
C2	0.0249 (12)	0.0255 (11)	0.0316 (12)	0.0036 (9)	0.0068 (9)	−0.0001 (9)
C3	0.0264 (12)	0.0260 (12)	0.0322 (13)	0.0002 (10)	0.0071 (10)	−0.0018 (10)
C4	0.0237 (11)	0.0253 (11)	0.0297 (12)	−0.0011 (9)	0.0057 (9)	−0.0027 (9)
C5	0.0284 (13)	0.0458 (15)	0.0342 (14)	−0.0001 (11)	0.0049 (10)	0.0023 (11)
C6	0.0391 (15)	0.0344 (14)	0.0582 (19)	0.0042 (12)	0.0102 (13)	0.0096 (14)
C7	0.0292 (14)	0.0384 (14)	0.0623 (19)	0.0040 (11)	0.0083 (13)	0.0182 (13)
C8	0.0369 (15)	0.0377 (15)	0.063 (2)	0.0079 (12)	0.0154 (13)	0.0165 (14)
C9	0.0287 (14)	0.0478 (17)	0.079 (2)	0.0031 (12)	0.0089 (14)	0.0305 (16)
O1	0.0387 (9)	0.0252 (8)	0.0312 (9)	0.0033 (7)	0.0085 (7)	0.0020 (7)
O2	0.0367 (9)	0.0283 (8)	0.0288 (9)	−0.0038 (7)	0.0065 (7)	−0.0058 (7)
O3	0.0253 (9)	0.0316 (9)	0.0398 (10)	−0.0006 (7)	0.0062 (7)	0.0076 (8)
O4	0.0234 (8)	0.0354 (9)	0.0337 (9)	0.0020 (7)	0.0035 (7)	−0.0081 (7)
O5	0.0302 (9)	0.0403 (10)	0.0592 (11)	0.0005 (7)	0.0105 (8)	0.0210 (9)
O6	0.0291 (9)	0.0369 (10)	0.0498 (11)	0.0018 (7)	0.0085 (7)	0.0178 (8)
F1	0.0646 (11)	0.0602 (10)	0.0371 (8)	−0.0139 (8)	0.0015 (7)	0.0154 (7)
F2	0.0609 (10)	0.0562 (10)	0.0346 (8)	0.0134 (8)	0.0089 (7)	−0.0118 (7)
F3	0.0361 (8)	0.0597 (10)	0.0413 (8)	0.0032 (7)	−0.0058 (6)	−0.0041 (7)
F4	0.0338 (8)	0.0650 (10)	0.0483 (9)	0.0012 (7)	−0.0074 (7)	0.0084 (8)
F5	0.0598 (10)	0.0528 (10)	0.0564 (10)	−0.0126 (8)	−0.0004 (8)	0.0244 (8)
F6	0.0601 (10)	0.0910 (13)	0.0274 (8)	0.0181 (9)	0.0077 (7)	−0.0007 (8)

Geometric parameters (Å, º)

C1—F3	1.330 (3)	C6—C7	1.494 (4)
C1—F1	1.336 (3)	C6—H1C6	1.00 (3)
C1—F2	1.338 (3)	C6—H2C6	0.97 (3)
C1—C2	1.530 (3)	C7—O6	1.442 (3)
C2—O3	1.384 (3)	C7—H1C7	0.99 (3)
C2—O1	1.431 (2)	C7—H2C7	1.06 (3)
C2—C3	1.522 (3)	C8—O6	1.440 (3)
C3—C4	1.523 (3)	C8—C9	1.493 (4)
C3—H1C3	0.94 (2)	C8—H1C8	1.00 (3)
C3—H2C3	0.98 (3)	C8—H2C8	1.02 (3)
C4—O4	1.381 (2)	C9—O5	1.438 (3)
C4—O2	1.429 (2)	C9—H1C9	1.04 (3)
C4—C5	1.529 (3)	C9—H2C9	0.99 (3)
C5—F4	1.329 (3)	O1—O2	1.472 (2)
C5—F6	1.331 (3)	O3—H1O3	0.85 (3)
C5—F5	1.335 (3)	O4—H1O4	0.86 (3)
C6—O5	1.433 (3)
F3—C1—F1	107.54 (19)	O5—C6—C7	109.7 (2)
F3—C1—F2	107.50 (19)	O5—C6—H1C6	109.0 (16)
F1—C1—F2	107.21 (19)	C7—C6—H1C6	109.3 (16)
F3—C1—C2	112.45 (18)	O5—C6—H2C6	106.5 (17)
F1—C1—C2	111.79 (19)	C7—C6—H2C6	109.7 (17)
F2—C1—C2	110.10 (19)	H1C6—C6—H2C6	113 (2)
O3—C2—O1	112.52 (17)	O6—C7—C6	110.1 (2)
O3—C2—C3	109.97 (18)	O6—C7—H1C7	106.3 (14)
O1—C2—C3	105.85 (17)	C6—C7—H1C7	109.5 (15)
O3—C2—C1	110.99 (18)	O6—C7—H2C7	107.1 (16)
O1—C2—C1	103.94 (17)	C6—C7—H2C7	109.1 (16)
C3—C2—C1	113.38 (19)	H1C7—C7—H2C7	115 (2)
C2—C3—C4	102.91 (17)	O6—C8—C9	110.0 (2)
C2—C3—H1C3	107.9 (14)	O6—C8—H1C8	105.2 (16)
C4—C3—H1C3	110.6 (14)	C9—C8—H1C8	111.1 (16)
C2—C3—H2C3	112.4 (15)	O6—C8—H2C8	108.4 (16)
C4—C3—H2C3	109.8 (15)	C9—C8—H2C8	110.1 (16)
H1C3—C3—H2C3	113 (2)	H1C8—C8—H2C8	112 (2)
O4—C4—O2	112.80 (17)	O5—C9—C8	109.8 (2)
O4—C4—C3	110.15 (18)	O5—C9—H1C9	108.7 (16)
O2—C4—C3	105.40 (16)	C8—C9—H1C9	107.0 (16)
O4—C4—C5	110.61 (17)	O5—C9—H2C9	106.8 (16)
O2—C4—C5	103.95 (17)	C8—C9—H2C9	112.1 (17)
C3—C4—C5	113.74 (18)	H1C9—C9—H2C9	113 (2)
F4—C5—F6	107.61 (19)	C2—O1—O2	103.30 (13)
F4—C5—F5	106.98 (19)	C4—O2—O1	103.40 (14)
F6—C5—F5	107.5 (2)	C2—O3—H1O3	110.9 (17)
F4—C5—C4	112.81 (19)	C4—O4—H1O4	108.9 (19)
F6—C5—C4	111.42 (19)	C6—O5—C9	110.7 (2)
F5—C5—C4	110.23 (19)	C8—O6—C7	109.80 (19)
F3—C1—C2—O3	−178.89 (17)	O2—C4—C5—F6	63.2 (2)
F1—C1—C2—O3	−57.8 (2)	C3—C4—C5—F6	177.28 (19)
F2—C1—C2—O3	61.3 (2)	O4—C4—C5—F5	61.2 (2)
F3—C1—C2—O1	−57.7 (2)	O2—C4—C5—F5	−177.50 (17)
F1—C1—C2—O1	63.4 (2)	C3—C4—C5—F5	−63.4 (2)
F2—C1—C2—O1	−177.55 (17)	O5—C6—C7—O6	58.5 (3)
F3—C1—C2—C3	56.8 (3)	O6—C8—C9—O5	−58.5 (3)
F1—C1—C2—C3	177.85 (18)	O3—C2—O1—O2	−85.55 (18)
F2—C1—C2—C3	−63.1 (2)	C3—C2—O1—O2	34.6 (2)
O3—C2—C3—C4	109.4 (2)	C1—C2—O1—O2	154.29 (15)
O1—C2—C3—C4	−12.4 (2)	O4—C4—O2—O1	−83.74 (19)
C1—C2—C3—C4	−125.67 (19)	C3—C4—O2—O1	36.48 (19)
C2—C3—C4—O4	106.8 (2)	C5—C4—O2—O1	156.40 (15)
C2—C3—C4—O2	−15.2 (2)	C2—O1—O2—C4	−44.83 (18)
C2—C3—C4—C5	−128.40 (19)	C7—C6—O5—C9	−58.6 (3)
O4—C4—C5—F4	−179.32 (18)	C8—C9—O5—C6	58.6 (3)
O2—C4—C5—F4	−58.0 (2)	C9—C8—O6—C7	58.9 (3)
C3—C4—C5—F4	56.1 (3)	C6—C7—O6—C8	−58.9 (3)
O4—C4—C5—F6	−58.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O6	0.85 (3)	1.85 (3)	2.688 (2)	170 (3)
O4—H1O4···O5^i	0.86 (3)	1.81 (3)	2.663 (2)	173 (3)

Symmetry code: (i) x−1, −y+3/2, z+1/2.