Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802016793/om6104sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802016793/om6104Isup2.hkl |
CCDC reference: 198969
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (C-C) = 0.008 Å
- R factor = 0.056
- wR factor = 0.138
- Data-to-parameter ratio = 10.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
PLAT_031 Alert A Refined Extinction parameter within range .... 0.33 Sigma
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 67.33 From the CIF: _reflns_number_total 1151 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 1218 Completeness (_total/calc) 94.50% Alert C: < 95% complete
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The compound was synthesized as described elsewhere (Winter & Gard, 2000) and crystals suitable for single-crystal X-ray diffraction were obtained by sublimation. Owing to the fact that in the first experiments the crystal either sublimed off the glass fibre it was mounted on, or decomposed by reacting with atmospheric water, for the final experiment the sample was completely encapsulated in a thin layer of epoxy glue. This strategy was sufficient to allow data collection over a period of a few days.
All data was employed in the refinement with the exception of the (−3,10,3) reflection which had strongly negative intensity. During the course of the refinement it became apparent that the displacement ellipsoids of the equatorial fluorine atoms were rather large. Attempts to model these atoms as part of a disordered group were fruitless, and we propose the enlongated ellipsoids should only be attributed to thermal motion. The hydrogen atoms in the molecule were included using a riding model except for the acid hydrogen which was located in a difference Fourier map and refined with a distance restraint of 0.82 (2) Å. The refined isotropic displacement parameter (U) for the acid hydrogen atom is 0.013 (8) Å2.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1999); software used to prepare material for publication: PLEASE PROVIDE.
Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I), showing the atom-numbering scheme (30% probability displacement ellipsoids). |
C3H5F5O2S | F(000) = 400 |
Mr = 200.13 | Dx = 1.952 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 56 reflections |
a = 5.737 (2) Å | θ = 7.9–23.4° |
b = 12.438 (2) Å | µ = 4.90 mm−1 |
c = 9.777 (2) Å | T = 290 K |
β = 102.59 (2)° | Block, colorless |
V = 680.9 (3) Å3 | 0.40 × 0.20 × 0.10 mm |
Z = 4 |
Siemens P4 diffractometer | 615 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.066 |
Graphite monochromator | θmax = 67.3°, θmin = 5.8° |
ω/2θ scans | h = −6→1 |
Absorption correction: multi-scan [SORTAV (Blessing, 1995) in WinGX (Farrugia, 1997)] | k = −3→14 |
Tmin = 0.245, Tmax = 0.640 | l = −11→11 |
1737 measured reflections | 3 standard reflections every 97 reflections |
1151 independent reflections | intensity decay: none |
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)] = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0421P)2 + 0.377P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.047 |
1151 reflections | Δρmax = 0.23 e Å−3 |
106 parameters | Δρmin = −0.17 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0003 (9) |
C3H5F5O2S | V = 680.9 (3) Å3 |
Mr = 200.13 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 5.737 (2) Å | µ = 4.90 mm−1 |
b = 12.438 (2) Å | T = 290 K |
c = 9.777 (2) Å | 0.40 × 0.20 × 0.10 mm |
β = 102.59 (2)° |
Siemens P4 diffractometer | 615 reflections with I > 2σ(I) |
Absorption correction: multi-scan [SORTAV (Blessing, 1995) in WinGX (Farrugia, 1997)] | Rint = 0.066 |
Tmin = 0.245, Tmax = 0.640 | 3 standard reflections every 97 reflections |
1737 measured reflections | intensity decay: none |
1151 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 1 restraint |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.23 e Å−3 |
1151 reflections | Δρmin = −0.17 e Å−3 |
106 parameters |
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 | ||
S1 | 0.0495 (3) | 0.82135 (11) | 0.13457 (14) | 0.0835 (6) | |
F1 | 0.0264 (7) | 0.7296 (3) | 0.0204 (3) | 0.1089 (13) | |
F2 | 0.3122 (6) | 0.7855 (3) | 0.2001 (4) | 0.1178 (13) | |
F3 | 0.0820 (7) | 0.9204 (2) | 0.2374 (4) | 0.1097 (13) | |
F4 | −0.2066 (7) | 0.8639 (3) | 0.0594 (3) | 0.1163 (14) | |
F5 | 0.1564 (9) | 0.8954 (3) | 0.0319 (4) | 0.1310 (15) | |
O1 | −0.4262 (7) | 0.6156 (3) | 0.0770 (4) | 0.0828 (12) | |
O2 | −0.1921 (7) | 0.4708 (3) | 0.1012 (4) | 0.0831 (12) | |
H | −0.294 (4) | 0.451 (2) | 0.035 (2) | 0.013 (8)* | |
C1 | −0.2393 (11) | 0.5697 (4) | 0.1294 (5) | 0.0711 (15) | |
C2 | −0.0486 (11) | 0.6180 (4) | 0.2399 (5) | 0.0780 (16) | |
H2A | 0.1050 | 0.6011 | 0.2190 | 0.091 (9)* | |
H2B | −0.0535 | 0.5845 | 0.3289 | 0.091 (9)* | |
C3 | −0.0654 (11) | 0.7404 (4) | 0.2563 (5) | 0.0753 (16) | |
H3A | 0.0190 | 0.7595 | 0.3502 | 0.091 (9)* | |
H3B | −0.2320 | 0.7591 | 0.2483 | 0.091 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0982 (12) | 0.0654 (8) | 0.0808 (9) | −0.0030 (9) | 0.0066 (8) | −0.0116 (7) |
F1 | 0.160 (3) | 0.087 (2) | 0.0794 (19) | −0.007 (2) | 0.026 (2) | −0.0228 (16) |
F2 | 0.083 (3) | 0.123 (3) | 0.140 (3) | 0.004 (2) | 0.007 (2) | −0.021 (2) |
F3 | 0.131 (3) | 0.0691 (19) | 0.131 (3) | −0.022 (2) | 0.033 (2) | −0.0354 (19) |
F4 | 0.117 (3) | 0.104 (3) | 0.111 (3) | 0.007 (2) | −0.014 (2) | 0.028 (2) |
F5 | 0.181 (4) | 0.094 (2) | 0.129 (3) | −0.033 (3) | 0.058 (3) | −0.001 (2) |
O1 | 0.085 (3) | 0.060 (2) | 0.092 (2) | 0.004 (2) | −0.006 (2) | −0.0111 (19) |
O2 | 0.093 (3) | 0.060 (2) | 0.085 (3) | 0.004 (2) | −0.007 (2) | −0.0128 (19) |
C1 | 0.091 (4) | 0.056 (3) | 0.065 (3) | 0.003 (3) | 0.014 (3) | 0.000 (2) |
C2 | 0.087 (4) | 0.069 (3) | 0.068 (3) | 0.000 (3) | −0.005 (3) | −0.006 (3) |
C3 | 0.088 (4) | 0.065 (3) | 0.067 (3) | −0.002 (3) | 0.002 (3) | −0.010 (2) |
S1—F2 | 1.569 (4) | O2—H | 0.810 (10) |
S1—F3 | 1.575 (3) | C1—C2 | 1.487 (7) |
S1—F5 | 1.581 (4) | C2—C3 | 1.537 (7) |
S1—F4 | 1.584 (4) | C2—H2A | 0.9700 |
S1—F1 | 1.582 (3) | C2—H2B | 0.9700 |
S1—C3 | 1.791 (6) | C3—H3A | 0.9700 |
O1—C1 | 1.224 (6) | C3—H3B | 0.9700 |
O2—C1 | 1.302 (6) | ||
F2—S1—F3 | 89.6 (2) | O1—C1—O2 | 123.8 (5) |
F2—S1—F5 | 87.4 (3) | O1—C1—C2 | 123.7 (5) |
F3—S1—F5 | 86.7 (2) | O2—C1—C2 | 112.4 (5) |
F2—S1—F4 | 175.1 (2) | C1—C2—C3 | 115.0 (5) |
F3—S1—F4 | 90.2 (2) | C1—C2—H2A | 108.5 |
F5—S1—F4 | 87.7 (2) | C3—C2—H2A | 108.5 |
F2—S1—F1 | 90.5 (2) | C1—C2—H2B | 108.5 |
F3—S1—F1 | 174.2 (2) | C3—C2—H2B | 108.5 |
F5—S1—F1 | 87.51 (19) | H2A—C2—H2B | 107.5 |
F4—S1—F1 | 89.3 (2) | C2—C3—S1 | 116.6 (4) |
F2—S1—C3 | 91.6 (2) | C2—C3—H3A | 108.1 |
F3—S1—C3 | 91.4 (2) | S1—C3—H3A | 108.1 |
F5—S1—C3 | 177.8 (2) | C2—C3—H3B | 108.2 |
F4—S1—C3 | 93.3 (2) | S1—C3—H3B | 108.2 |
F1—S1—C3 | 94.4 (2) | H3A—C3—H3B | 107.3 |
C1—O2—H | 108 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H···O1i | 0.81 (1) | 1.92 (1) | 2.706 (5) | 163 (3) |
Symmetry code: (i) −x−1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C3H5F5O2S |
Mr | 200.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 290 |
a, b, c (Å) | 5.737 (2), 12.438 (2), 9.777 (2) |
β (°) | 102.59 (2) |
V (Å3) | 680.9 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.90 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Multi-scan [SORTAV (Blessing, 1995) in WinGX (Farrugia, 1997)] |
Tmin, Tmax | 0.245, 0.640 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1737, 1151, 615 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.138, 1.04 |
No. of reflections | 1151 |
No. of parameters | 106 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.17 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1999), PLEASE PROVIDE.
S1—F2 | 1.569 (4) | S1—F4 | 1.584 (4) |
S1—F3 | 1.575 (3) | S1—F1 | 1.582 (3) |
S1—F5 | 1.581 (4) | S1—C3 | 1.791 (6) |
F2—S1—F3 | 89.6 (2) | F5—S1—F1 | 87.51 (19) |
F2—S1—F5 | 87.4 (3) | F4—S1—F1 | 89.3 (2) |
F3—S1—F5 | 86.7 (2) | F2—S1—C3 | 91.6 (2) |
F2—S1—F4 | 175.1 (2) | F3—S1—C3 | 91.4 (2) |
F3—S1—F4 | 90.2 (2) | F5—S1—C3 | 177.8 (2) |
F5—S1—F4 | 87.7 (2) | F4—S1—C3 | 93.3 (2) |
F2—S1—F1 | 90.5 (2) | F1—S1—C3 | 94.4 (2) |
F3—S1—F1 | 174.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H···O1i | 0.810 (10) | 1.921 (14) | 2.706 (5) | 163 (3) |
Symmetry code: (i) −x−1, −y+1, −z. |
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As part of our ongoing interest in the chemistry and structure of organic SF5 and SFO2 groups and of the applications of compounds containg these groups (Schlueter et al., 2001, and references therein), we have recently devised a method for the preparation of alkyl derivatives of SF5, including the title compound, pentafluorothiopropionic acid, SF5(CH2)2CO2H (I), (Winter & Gard, 2000). At the time the synthesis and spectroscopic characterization of the compound was published, the structure of this acid was not available. Since then we have been able to obtain crystals of sufficient quality for a structural characterization to be possible, and therefore we present it here.
The compound crystallizes as a hydrogen-bonded dimer, as is common for many carboxylic acids. The hydrogen-bonded oxygen–oxygen distance, 2.706 (5) Å, is well within the usual range for strong hydrogen bonds (Jeffrey, 1997). The SF5C group is essentially octahedral, with four nearly identical S—Feq bonds, a longer S—Fax bond and a long S—C one. The equatorial fluorine atoms are slightly displaced away from the carbon atom, as shown by the fact that the Fax—S—Feq bond angles are all somewhat less than 90°. Finally, there are two short intramolecular contacts, F1···H2A, with a separation of 2.479 Å and an F1···H2A—C2 angle of 90.4°, and O1···H3B, with a separation of 2.533 Å and an O1···H3B—C3 angle of 99.7°. Though the X—H distances are very close to the sum of their respective van der Waals radii, the pronounced deviation of the X—H—C angle from linearity would suggest that rather than being viewed as traditional hydrogen bonds, these should be thought of as forced contacts required by the geometry of the molecule in this crystal (Jeffrey, 1997).
Since a number of compounds containing the SF5C– group have been structuraly characterized, either by solid state X-ray diffraction, or by gas phase electron diffraction, it would therefore be useful to discuss the present molelcule in the context of the group. However, the systematical analysis of the structure of this group has not yet been reported, and herefore we include here a brief literature survey of pertinent structural features.
A search of the Cambridge Structural Database reveals that the structures of 20 compounds containing the SF5– group in organic or organometallic compounds other than the structure here reported have been determined (Allen & Kennard, 1993; Refcodes: DIVPAZ, JANYAY, JEBNEZ, JEBNIM, JESJUM, KUYPEZ, KUYYUY, LANWEC, LAYHEY, LECRUG, LECSAN, LECSER, NALWIG, QAFGOT, YAMGIC, YAMGOI, ZEZNIB, ZEZNOH, ZEZNUN, ZOVZAL). Additionally, three molecules are known whose structure was determined by gas phase electron diffraction (Gupta et al., 1986; Weiss et al., 1990; Gard et al., 1998). From the set of X-ray structural determinations we know of, we obtain the following structural parameters: the SF5C– group tends towards a regular octahedron with five identical S—F bonds and a long S—C bond, with the following average bond lengths (population standard deviations given in parentheses): S—Fax 1.574 (14) Å, S—Feq 1.571 (14) Å, S—C 1.823 (28) Å, Fax—S—C 177.1(0.8)°, and Fax—S—Feq 88.1(1.0)°.
The structures determined by gas phase electron diffraction are in agreement with this set of parameters. Namely, from the gas phase determinations, the S—Fax and S—Feq have essentially identical lengths, at 1.560 Å, the Fax—S—Feq angle is 90°, and the Fax—S—C angle does not deviate significantly from 180°.
Therefore, the structure reported here is in excellent agreement with the average parameters listed above. The the S—C bond, with a length of 1.791 (6) Å, and the Fax—S—Feq angles, averaging 88.3 (12)° are also well within the expected values.