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The title compound, C4H6O3, was prepared as a chelating mol­ecule bearing the conformationally rigid 1,1-cyclo­propane group. The cyclo­propane ring is arranged perpendicular to the carboxyl group. Inter­molecular hydrogen bonds between the carboxyl groups link the mol­ecules to form centrosymmetric dimers, which are further connected by O—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041256/bt2452sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041256/bt2452Isup2.hkl
Contains datablock I

CCDC reference: 660351

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.046
  • wR factor = 0.126
  • Data-to-parameter ratio = 16.1

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Comment top

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.

Related literature top

The title compound was prepared according to standard procedures (Heine & Wendisch, 1976).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed along [010].
1-Hydroxycyclopropane-1-carboxylic acid top
Crystal data top
C4H6O3F(000) = 216
Mr = 102.09Dx = 1.471 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5717 reflections
a = 9.0310 (3) Åθ = 3.1–27.5°
b = 4.7250 (2) ŵ = 0.13 mm1
c = 12.0343 (4) ÅT = 200 K
β = 116.119 (2)°Block, colourless
V = 461.08 (3) Å30.20 × 0.13 × 0.09 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer
908 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.019
MONTEL, graded multilayered X-ray optics monochromatorθmax = 27.5°, θmin = 3.5°
φ and ω scansh = 1111
1956 measured reflectionsk = 66
1045 independent reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127Only 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 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.44 e Å3
Crystal data top
C4H6O3V = 461.08 (3) Å3
Mr = 102.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.0310 (3) ŵ = 0.13 mm1
b = 4.7250 (2) ÅT = 200 K
c = 12.0343 (4) Å0.20 × 0.13 × 0.09 mm
β = 116.119 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
908 reflections with I > 2σ(I)
1956 measured reflectionsRint = 0.019
1045 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.127Only H-atom displacement parameters refined
S = 1.07Δρmax = 0.39 e Å3
1045 reflectionsΔρmin = 0.44 e Å3
65 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O20.03457 (13)0.9329 (3)0.19543 (11)0.0300 (3)
H20.00580.86490.24740.052 (3)*
O110.28515 (15)1.0745 (3)0.40905 (11)0.0372 (4)
H110.36731.10280.47730.052 (3)*
O120.46529 (15)0.8034 (3)0.37692 (12)0.0415 (4)
C10.32519 (19)0.9036 (3)0.34354 (14)0.0270 (4)
C20.19178 (18)0.8327 (3)0.21967 (14)0.0252 (4)
C30.2062 (2)0.5619 (4)0.15971 (15)0.0318 (4)
H310.30210.43850.20690.052 (3)*
H320.10300.46010.10710.052 (3)*
C40.2377 (2)0.8372 (4)0.11322 (15)0.0305 (4)
H410.15400.90570.03210.052 (3)*
H420.35310.88410.13190.052 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0224 (6)0.0321 (7)0.0356 (6)0.0007 (4)0.0128 (5)0.0009 (5)
O110.0331 (7)0.0449 (8)0.0304 (6)0.0060 (5)0.0110 (5)0.0078 (5)
O120.0273 (6)0.0526 (9)0.0369 (7)0.0089 (6)0.0069 (5)0.0097 (6)
C10.0267 (7)0.0271 (8)0.0293 (8)0.0010 (6)0.0142 (6)0.0004 (6)
C20.0233 (7)0.0238 (8)0.0293 (8)0.0002 (6)0.0124 (6)0.0002 (6)
C30.0341 (9)0.0260 (8)0.0350 (9)0.0027 (7)0.0149 (7)0.0047 (7)
C40.0320 (8)0.0322 (9)0.0292 (8)0.0018 (7)0.0152 (7)0.0009 (7)
Geometric parameters (Å, º) top
O2—C21.4001 (18)C2—C41.510 (2)
O2—H20.8400C3—C41.492 (2)
O11—C11.287 (2)C3—H310.9900
O11—H110.8400C3—H320.9900
O12—C11.240 (2)C4—H410.9900
C1—C21.485 (2)C4—H420.9900
C2—C31.502 (2)
C2—O2—H2109.5C4—C3—H31117.7
C1—O11—H11109.5C2—C3—H31117.7
O12—C1—O11124.25 (15)C4—C3—H32117.7
O12—C1—C2120.02 (14)C2—C3—H32117.7
O11—C1—C2115.72 (14)H31—C3—H32114.8
O2—C2—C1115.67 (13)C3—C4—C260.04 (10)
O2—C2—C3118.81 (13)C3—C4—H41117.8
C1—C2—C3118.08 (14)C2—C4—H41117.8
O2—C2—C4116.77 (13)C3—C4—H42117.8
C1—C2—C4116.35 (13)C2—C4—H42117.8
C3—C2—C459.37 (11)H41—C4—H42114.9
C4—C3—C260.58 (11)
O12—C1—C2—O2173.88 (15)O11—C1—C2—C4135.37 (15)
O11—C1—C2—O27.4 (2)O2—C2—C3—C4105.77 (16)
O12—C1—C2—C324.3 (2)C1—C2—C3—C4105.60 (16)
O11—C1—C2—C3156.97 (14)O2—C2—C4—C3109.19 (16)
O12—C1—C2—C443.4 (2)C1—C2—C4—C3108.49 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O2i0.842.232.9015 (13)137
O11—H11···O12ii0.841.802.6336 (17)175
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC4H6O3
Mr102.09
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)9.0310 (3), 4.7250 (2), 12.0343 (4)
β (°) 116.119 (2)
V3)461.08 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.20 × 0.13 × 0.09
Data collection
DiffractometerNonius KappaCCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1956, 1045, 908
Rint0.019
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.127, 1.07
No. of reflections1045
No. of parameters65
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)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.

Selected bond lengths (Å) top
C1—C21.485 (2)C2—C41.510 (2)
C2—C31.502 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O2i0.842.232.9015 (13)136.5
O11—H11···O12ii0.841.802.6336 (17)174.5
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x+1, y+2, z+1.
 

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