Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041256/bt2452sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041256/bt2452Isup2.hkl |
CCDC reference: 660351
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C)= 0.002 Å
- R factor = 0.046
- wR factor = 0.126
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
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The title compound was prepared according to standard procedures (Heine & Wendisch, 1976) by the reaction of bromine and water on 1,2-bis(trimethylsilyloxy)-cyclobut-1,2-ene. Recrystallization of the product was performed from chloroform at room temperature upon free evaporation of the solvent.
All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to Uiso(H) = 0.052 (3) Å2.
The title compound, C4H6O3, was prepared as a chelating molecule bearing the conformational rigid 1,1-cyclopropylene group. It was obtained upon the reaction of bromine and water on 1,2-bis(trimethylsilyloxy)-cyclobut-1,2-ene.
The cyclopropylene ring adopts a perpendicular orientation to the plane containing the atoms of the carboxyl group. All bond lengths between the central C atom and the other C atoms are found to be shorter than the typical value of 1.54 Å. Intermolecular hydrogen bonds are present in the crystal structure resulting in the formation of dimeric units.
The molecular structure (Fig. 1) shows a carboxy- and a hydroxy-group attached to the cyclopropane ring.
The molecular packing (Fig. 2) shows intermolecular hydrogen bonds between the O-bonded H atom of the carboxyl group and the double-bonded O atom of the neighbouring molecule.
The title compound was prepared according to standard procedures (Heine & Wendisch, 1976).
Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms. | |
Fig. 2. The packing of (I), viewed along [010]. |
C4H6O3 | F(000) = 216 |
Mr = 102.09 | Dx = 1.471 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5717 reflections |
a = 9.0310 (3) Å | θ = 3.1–27.5° |
b = 4.7250 (2) Å | µ = 0.13 mm−1 |
c = 12.0343 (4) Å | T = 200 K |
β = 116.119 (2)° | Block, colourless |
V = 461.08 (3) Å3 | 0.20 × 0.13 × 0.09 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 908 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.019 |
MONTEL, graded multilayered X-ray optics monochromator | θmax = 27.5°, θmin = 3.5° |
φ and ω scans | h = −11→11 |
1956 measured reflections | k = −6→6 |
1045 independent reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | Only H-atom displacement parameters refined |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0567P)2 + 0.294P] where P = (Fo2 + 2Fc2)/3 |
1045 reflections | (Δ/σ)max < 0.001 |
65 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C4H6O3 | V = 461.08 (3) Å3 |
Mr = 102.09 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.0310 (3) Å | µ = 0.13 mm−1 |
b = 4.7250 (2) Å | T = 200 K |
c = 12.0343 (4) Å | 0.20 × 0.13 × 0.09 mm |
β = 116.119 (2)° |
Nonius KappaCCD area-detector diffractometer | 908 reflections with I > 2σ(I) |
1956 measured reflections | Rint = 0.019 |
1045 independent reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.127 | Only H-atom displacement parameters refined |
S = 1.07 | Δρmax = 0.39 e Å−3 |
1045 reflections | Δρmin = −0.44 e Å−3 |
65 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 | ||
O2 | 0.03457 (13) | 0.9329 (3) | 0.19543 (11) | 0.0300 (3) | |
H2 | 0.0058 | 0.8649 | 0.2474 | 0.052 (3)* | |
O11 | 0.28515 (15) | 1.0745 (3) | 0.40905 (11) | 0.0372 (4) | |
H11 | 0.3673 | 1.1028 | 0.4773 | 0.052 (3)* | |
O12 | 0.46529 (15) | 0.8034 (3) | 0.37692 (12) | 0.0415 (4) | |
C1 | 0.32519 (19) | 0.9036 (3) | 0.34354 (14) | 0.0270 (4) | |
C2 | 0.19178 (18) | 0.8327 (3) | 0.21967 (14) | 0.0252 (4) | |
C3 | 0.2062 (2) | 0.5619 (4) | 0.15971 (15) | 0.0318 (4) | |
H31 | 0.3021 | 0.4385 | 0.2069 | 0.052 (3)* | |
H32 | 0.1030 | 0.4601 | 0.1071 | 0.052 (3)* | |
C4 | 0.2377 (2) | 0.8372 (4) | 0.11322 (15) | 0.0305 (4) | |
H41 | 0.1540 | 0.9057 | 0.0321 | 0.052 (3)* | |
H42 | 0.3531 | 0.8841 | 0.1319 | 0.052 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0224 (6) | 0.0321 (7) | 0.0356 (6) | 0.0007 (4) | 0.0128 (5) | 0.0009 (5) |
O11 | 0.0331 (7) | 0.0449 (8) | 0.0304 (6) | 0.0060 (5) | 0.0110 (5) | −0.0078 (5) |
O12 | 0.0273 (6) | 0.0526 (9) | 0.0369 (7) | 0.0089 (6) | 0.0069 (5) | −0.0097 (6) |
C1 | 0.0267 (7) | 0.0271 (8) | 0.0293 (8) | 0.0010 (6) | 0.0142 (6) | 0.0004 (6) |
C2 | 0.0233 (7) | 0.0238 (8) | 0.0293 (8) | −0.0002 (6) | 0.0124 (6) | −0.0002 (6) |
C3 | 0.0341 (9) | 0.0260 (8) | 0.0350 (9) | −0.0027 (7) | 0.0149 (7) | −0.0047 (7) |
C4 | 0.0320 (8) | 0.0322 (9) | 0.0292 (8) | −0.0018 (7) | 0.0152 (7) | −0.0009 (7) |
O2—C2 | 1.4001 (18) | C2—C4 | 1.510 (2) |
O2—H2 | 0.8400 | C3—C4 | 1.492 (2) |
O11—C1 | 1.287 (2) | C3—H31 | 0.9900 |
O11—H11 | 0.8400 | C3—H32 | 0.9900 |
O12—C1 | 1.240 (2) | C4—H41 | 0.9900 |
C1—C2 | 1.485 (2) | C4—H42 | 0.9900 |
C2—C3 | 1.502 (2) | ||
C2—O2—H2 | 109.5 | C4—C3—H31 | 117.7 |
C1—O11—H11 | 109.5 | C2—C3—H31 | 117.7 |
O12—C1—O11 | 124.25 (15) | C4—C3—H32 | 117.7 |
O12—C1—C2 | 120.02 (14) | C2—C3—H32 | 117.7 |
O11—C1—C2 | 115.72 (14) | H31—C3—H32 | 114.8 |
O2—C2—C1 | 115.67 (13) | C3—C4—C2 | 60.04 (10) |
O2—C2—C3 | 118.81 (13) | C3—C4—H41 | 117.8 |
C1—C2—C3 | 118.08 (14) | C2—C4—H41 | 117.8 |
O2—C2—C4 | 116.77 (13) | C3—C4—H42 | 117.8 |
C1—C2—C4 | 116.35 (13) | C2—C4—H42 | 117.8 |
C3—C2—C4 | 59.37 (11) | H41—C4—H42 | 114.9 |
C4—C3—C2 | 60.58 (11) | ||
O12—C1—C2—O2 | 173.88 (15) | O11—C1—C2—C4 | 135.37 (15) |
O11—C1—C2—O2 | −7.4 (2) | O2—C2—C3—C4 | 105.77 (16) |
O12—C1—C2—C3 | 24.3 (2) | C1—C2—C3—C4 | −105.60 (16) |
O11—C1—C2—C3 | −156.97 (14) | O2—C2—C4—C3 | −109.19 (16) |
O12—C1—C2—C4 | −43.4 (2) | C1—C2—C4—C3 | 108.49 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2i | 0.84 | 2.23 | 2.9015 (13) | 137 |
O11—H11···O12ii | 0.84 | 1.80 | 2.6336 (17) | 175 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C4H6O3 |
Mr | 102.09 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 200 |
a, b, c (Å) | 9.0310 (3), 4.7250 (2), 12.0343 (4) |
β (°) | 116.119 (2) |
V (Å3) | 461.08 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.20 × 0.13 × 0.09 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1956, 1045, 908 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.127, 1.07 |
No. of reflections | 1045 |
No. of parameters | 65 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.44 |
Computer programs: COLLECT (Nonius, 2004), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2i | 0.84 | 2.23 | 2.9015 (13) | 136.5 |
O11—H11···O12ii | 0.84 | 1.80 | 2.6336 (17) | 174.5 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+2, −z+1. |
The title compound, C4H6O3, was prepared as a chelating molecule bearing the conformational rigid 1,1-cyclopropylene group. It was obtained upon the reaction of bromine and water on 1,2-bis(trimethylsilyloxy)-cyclobut-1,2-ene.
The cyclopropylene ring adopts a perpendicular orientation to the plane containing the atoms of the carboxyl group. All bond lengths between the central C atom and the other C atoms are found to be shorter than the typical value of 1.54 Å. Intermolecular hydrogen bonds are present in the crystal structure resulting in the formation of dimeric units.
The molecular structure (Fig. 1) shows a carboxy- and a hydroxy-group attached to the cyclopropane ring.
The molecular packing (Fig. 2) shows intermolecular hydrogen bonds between the O-bonded H atom of the carboxyl group and the double-bonded O atom of the neighbouring molecule.