Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043747/si2033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043747/si2033Isup2.hkl |
CCDC reference: 663746
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.029
- wR factor = 0.079
- Data-to-parameter ratio = 8.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C4
Author Response: correct assignment of element type, atom shows comparatively higher degree of conformational flexibility than neighbouring atoms, splitting not indicated. cf comment item for a comparable example apparent in the literature. |
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 659 From the CIF: _diffrn_reflns_limit_ max hkl 13. 10. 37. From the CIF: _diffrn_reflns_limit_ min hkl -13. -10. -37. TEST1: Expected hkl limits for theta max Calculated maximum hkl 13. 13. 37. Calculated minimum hkl -13. -13. -37. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 659 Count of symmetry unique reflns 663 Completeness (_total/calc) 99.40% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared according to standard procedures (Becker et al., 2001). The pattern of hydrogen bonding differs from that observed for the homologues, 1-hydroxycyclopropane-1-carboxylic acid (Betz & Klüfers, 2007a) and 1-hydroxycyclopentane-1-carboxylic acid (Betz & Klüfers, 2007b). The comparatively high anisotropic displacement parameter observed for one of the C atoms of the cyclobutane moiety is comparable wit the results reported in the literature for a palladium complex including the same cyclic fragment (Muranishi & Okabe, 2004).
For related literature, see: Bernstein et al. (1995).
The title compound was prepared according to standard procedures (Becker et al., 2001) upon acidic hydrolysis of the cyanohydrin of cyclobutanone. Crystals suitable for X-ray analysis were directly obtained from the crystallized reaction product.
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) = 0.062 (3).
Due to the absence of significant anomalous scattering the absolute structure factor, which is -1.2 with an estimated standard deviation of 1.1 for the unmerged data set, is meaningless. Thus, Friedel opposites (327 pairs) have been merged.
The title compound, C5H8O3, was prepared as a potential chelating molecule bearing the conformational rigid cyclobutane group.
The cyclobutane ring adopts a perpendicular orientation to the carboxyl group (Fig. 1). One carbon atom of the cyclobutane ring shows a comparatively high anisotropic displacement parameter – a finding, which is in agreement with the results obtained for a palladium complex including cyclobutane moieties (Muranishi & Okabe, 2004). The observed bond lengths are in agreement with valence considerations. Intermolecular hydrogen bonds determine the crystal structure. Due to the trigonal 3-axes symmetry, trimer ring systems with graph set notation R33(5) and infinite chains C(5) (Bernstein et al., 1995) form the three-dimensional network. The formation of dimeric units upon hydrogen-bond formation – as is apparent in the structures of 1-hydroxycyclopropane-1-carboxylic acid (Betz & Klüfers, 2007a) and the cyclopentane analogue (Betz & Klüfers, 2007b) – is not observed. Instead, infinite bonding sequences of the type (···O=C—O–H···O–H···)n with alternating carboxy and hydroxy functions are formed.
The title compound was prepared according to standard procedures (Becker et al., 2001). The pattern of hydrogen bonding differs from that observed for the homologues, 1-hydroxycyclopropane-1-carboxylic acid (Betz & Klüfers, 2007a) and 1-hydroxycyclopentane-1-carboxylic acid (Betz & Klüfers, 2007b). The comparatively high anisotropic displacement parameter observed for one of the C atoms of the cyclobutane moiety is comparable wit the results reported in the literature for a palladium complex including the same cyclic fragment (Muranishi & Okabe, 2004).
For related literature, see: Bernstein et al. (1995).
Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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 (Sheldrick, 1997).
Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms. |
C5H8O3 | Dx = 1.351 Mg m−3 |
Mr = 116.12 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3c | Cell parameters from 8387 reflections |
Hall symbol: R 3 -2"c | θ = 3.1–27.5° |
a = 10.158 (5) Å | µ = 0.11 mm−1 |
c = 28.747 (5) Å | T = 293 K |
V = 2568.9 (18) Å3 | Block, colourless |
Z = 18 | 0.25 × 0.20 × 0.16 mm |
F(000) = 1116 |
Nonius KappaCCD diffractometer | 629 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.013 |
MONTEL, graded multilayered X-ray optics monochromator | θmax = 27.5°, θmin = 3.7° |
φ/ω–scan | h = −13→13 |
2401 measured reflections | k = −10→10 |
657 independent reflections | l = −37→37 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.8981P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
657 reflections | Δρmax = 0.15 e Å−3 |
82 parameters | Δρmin = −0.11 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: 0.0040 (11) |
C5H8O3 | Z = 18 |
Mr = 116.12 | Mo Kα radiation |
Trigonal, R3c | µ = 0.11 mm−1 |
a = 10.158 (5) Å | T = 293 K |
c = 28.747 (5) Å | 0.25 × 0.20 × 0.16 mm |
V = 2568.9 (18) Å3 |
Nonius KappaCCD diffractometer | 629 reflections with I > 2σ(I) |
2401 measured reflections | Rint = 0.013 |
657 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 1 restraint |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.15 e Å−3 |
657 reflections | Δρmin = −0.11 e Å−3 |
82 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 | 0.18848 (17) | 0.15037 (16) | 0.00859 (5) | 0.0401 (4) | |
H2 | 0.160 (4) | 0.079 (4) | 0.0286 (12) | 0.070 (9)* | |
O11 | 0.2872 (2) | 0.4282 (2) | 0.09671 (6) | 0.0553 (5) | |
H11 | 0.240 (4) | 0.439 (4) | 0.1225 (13) | 0.075 (10)* | |
O12 | 0.06620 (18) | 0.22283 (19) | 0.07944 (6) | 0.0501 (4) | |
C1 | 0.1989 (2) | 0.3086 (2) | 0.07142 (6) | 0.0351 (4) | |
C2 | 0.2812 (2) | 0.2928 (2) | 0.02965 (6) | 0.0324 (4) | |
C3 | 0.3344 (3) | 0.4280 (2) | −0.00422 (7) | 0.0412 (5) | |
H31 | 0.3220 | 0.3988 | −0.0368 | 0.049* | |
H32 | 0.2911 | 0.4922 | 0.0023 | 0.049* | |
C4 | 0.4967 (3) | 0.4924 (3) | 0.01362 (11) | 0.0609 (6) | |
H41 | 0.5287 | 0.5773 | 0.0348 | 0.073* | |
H42 | 0.5711 | 0.5169 | −0.0109 | 0.073* | |
C5 | 0.4496 (3) | 0.3412 (3) | 0.03797 (9) | 0.0459 (5) | |
H51 | 0.4778 | 0.3519 | 0.0706 | 0.055* | |
H52 | 0.4821 | 0.2784 | 0.0218 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0480 (8) | 0.0331 (7) | 0.0344 (7) | 0.0166 (6) | 0.0051 (6) | −0.0051 (6) |
O11 | 0.0485 (9) | 0.0572 (10) | 0.0458 (9) | 0.0155 (8) | 0.0085 (7) | −0.0200 (7) |
O12 | 0.0431 (8) | 0.0510 (9) | 0.0465 (8) | 0.0163 (7) | 0.0117 (6) | −0.0083 (7) |
C1 | 0.0388 (10) | 0.0363 (9) | 0.0316 (9) | 0.0199 (8) | 0.0040 (7) | 0.0000 (7) |
C2 | 0.0372 (9) | 0.0332 (9) | 0.0291 (8) | 0.0193 (7) | 0.0024 (7) | −0.0013 (7) |
C3 | 0.0492 (11) | 0.0400 (10) | 0.0381 (9) | 0.0250 (10) | 0.0093 (8) | 0.0063 (8) |
C4 | 0.0431 (13) | 0.0529 (15) | 0.0701 (15) | 0.0115 (10) | 0.0060 (12) | 0.0073 (12) |
C5 | 0.0402 (11) | 0.0539 (12) | 0.0503 (11) | 0.0284 (10) | −0.0026 (9) | −0.0069 (9) |
O2—C2 | 1.409 (2) | C3—C4 | 1.527 (4) |
O2—H2 | 0.85 (4) | C3—H31 | 0.9700 |
O11—C1 | 1.311 (2) | C3—H32 | 0.9700 |
O11—H11 | 0.92 (4) | C4—C5 | 1.531 (4) |
O12—C1 | 1.207 (2) | C4—H41 | 0.9700 |
C1—C2 | 1.517 (2) | C4—H42 | 0.9700 |
C2—C3 | 1.544 (3) | C5—H51 | 0.9700 |
C2—C5 | 1.544 (3) | C5—H52 | 0.9700 |
C2—O2—H2 | 110 (2) | C2—C3—H32 | 113.7 |
C1—O11—H11 | 114 (2) | H31—C3—H32 | 111.0 |
O12—C1—O11 | 124.26 (18) | C3—C4—C5 | 89.70 (18) |
O12—C1—C2 | 123.42 (17) | C3—C4—H41 | 113.7 |
O11—C1—C2 | 112.28 (17) | C5—C4—H41 | 113.7 |
O2—C2—C1 | 109.16 (15) | C3—C4—H42 | 113.7 |
O2—C2—C3 | 113.53 (15) | C5—C4—H42 | 113.7 |
C1—C2—C3 | 111.77 (15) | H41—C4—H42 | 110.9 |
O2—C2—C5 | 117.34 (17) | C4—C5—C2 | 89.39 (17) |
C1—C2—C5 | 115.15 (16) | C4—C5—H51 | 113.7 |
C3—C2—C5 | 88.59 (15) | C2—C5—H51 | 113.7 |
C4—C3—C2 | 89.54 (17) | C4—C5—H52 | 113.7 |
C4—C3—H31 | 113.7 | C2—C5—H52 | 113.7 |
C2—C3—H31 | 113.7 | H51—C5—H52 | 111.0 |
C4—C3—H32 | 113.7 | ||
O12—C1—C2—O2 | −11.5 (3) | C1—C2—C3—C4 | 104.08 (19) |
O11—C1—C2—O2 | 170.40 (18) | C5—C2—C3—C4 | −12.53 (19) |
O12—C1—C2—C3 | 114.9 (2) | C2—C3—C4—C5 | 12.64 (18) |
O11—C1—C2—C3 | −63.2 (2) | C3—C4—C5—C2 | −12.64 (18) |
O12—C1—C2—C5 | −146.0 (2) | O2—C2—C5—C4 | 128.41 (19) |
O11—C1—C2—C5 | 35.9 (2) | C1—C2—C5—C4 | −101.0 (2) |
O2—C2—C3—C4 | −131.90 (19) | C3—C2—C5—C4 | 12.50 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O12i | 0.85 (4) | 2.07 (4) | 2.895 (2) | 163 (3) |
O2—H2···O2i | 0.85 (4) | 2.51 (3) | 3.037 (3) | 121 (3) |
O11—H11···O2ii | 0.92 (4) | 1.74 (4) | 2.6488 (19) | 170 (4) |
Symmetry codes: (i) −x+y, −x, z; (ii) −y+1/3, −x+2/3, z+1/6. |
Experimental details
Crystal data | |
Chemical formula | C5H8O3 |
Mr | 116.12 |
Crystal system, space group | Trigonal, R3c |
Temperature (K) | 293 |
a, c (Å) | 10.158 (5), 28.747 (5) |
V (Å3) | 2568.9 (18) |
Z | 18 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.25 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2401, 657, 629 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.079, 1.07 |
No. of reflections | 657 |
No. of parameters | 82 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.11 |
Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O12i | 0.85 (4) | 2.07 (4) | 2.895 (2) | 163 (3) |
O2—H2···O2i | 0.85 (4) | 2.51 (3) | 3.037 (3) | 121 (3) |
O11—H11···O2ii | 0.92 (4) | 1.74 (4) | 2.6488 (19) | 170 (4) |
Symmetry codes: (i) −x+y, −x, z; (ii) −y+1/3, −x+2/3, z+1/6. |
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The title compound, C5H8O3, was prepared as a potential chelating molecule bearing the conformational rigid cyclobutane group.
The cyclobutane ring adopts a perpendicular orientation to the carboxyl group (Fig. 1). One carbon atom of the cyclobutane ring shows a comparatively high anisotropic displacement parameter – a finding, which is in agreement with the results obtained for a palladium complex including cyclobutane moieties (Muranishi & Okabe, 2004). The observed bond lengths are in agreement with valence considerations. Intermolecular hydrogen bonds determine the crystal structure. Due to the trigonal 3-axes symmetry, trimer ring systems with graph set notation R33(5) and infinite chains C(5) (Bernstein et al., 1995) form the three-dimensional network. The formation of dimeric units upon hydrogen-bond formation – as is apparent in the structures of 1-hydroxycyclopropane-1-carboxylic acid (Betz & Klüfers, 2007a) and the cyclopentane analogue (Betz & Klüfers, 2007b) – is not observed. Instead, infinite bonding sequences of the type (···O=C—O–H···O–H···)n with alternating carboxy and hydroxy functions are formed.