1-Hydroxy­cyclo­butane-1-carboxylic acid

The title compound, C₅H₈O₃, was prepared as a potentially chelating mol­ecule bearing the conformationally rigid cyclo­butane group. The cyclo­butane ring is arranged perpendicular to the carboxyl group. In the polar crystal structure, each mol­ecule exhibits four hydrogen-bonded contacts to neighbouring mol­ecules. Instead of the formation of typical carboxylic acid dimers, an infinite hydrogen-bonded chain with alternating O-H and O=C-O-H units is observed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(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.

Computing details

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).

Figures

Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 50% probability level) for non-H atoms.

1-Hydroxycyclobutane-1-carboxylic acid

Crystal data

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) Å^3	Block, colourless
Z = 18	0.25 × 0.20 × 0.16 mm
F(000) = 1116

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0483P)^2 + 0.8981P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0040 (11)

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O12^i	0.85 (4)	2.07 (4)	2.895 (2)	163 (3)
O2—H2···O2^i	0.85 (4)	2.51 (3)	3.037 (3)	121 (3)
O11—H11···O2^ii	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.