trans-(±)-2-Carboxy­methyl-3-phenyl­cyclo­propane-1-carboxyl­ic acid

The carboxyl and carboxy­methyl substituents in the title compound, C₁₂H₁₂O₄, lie on opposite sides of the cyclo­propyl ring and each carboxyl group participates in a centrosymmetric hydrogen-bonding scheme, typical for carboxyl­ic acids, leading to the formation of zigzag chains in the crystal.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.114
• Data-to-parameter ratio = 17.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), was prepared by the controlled hydrolysis of the parent methyl diester (Avery et al., 2001). The structure determination confirms the overall stereochemistry, notably the positioning of the substituents around the cyclopropyl ring as shown in Fig. 1. The plane of the C11/O11/O11A carboxylic acid group is almost orthogonal to the cyclopropane plane, as seen in the value of the X—C1—C11—O11 torsion angle of 4.1 (2)°, where X is the midpoint of the C2—C3 bond. By contrast, the dihedral angle formed by the planes of the phenyl and cyclopropyl rings is 68.70 (11)°. The conformation is thus described as cis-bisected in accord with Allen (1980). The distal C2—C3 bond distance of 1.5027 (19) Å is shorter, as expected (Allen, 1980), than the respective vicinal C1—C2 and C1—C3 bond distances of 1.5196 (19) and 1.5195 (17) Å, reflecting the influence of the π-acceptor carboxylic acid group upon the C—C bonds within the cyclopropyl ring.

Molecules associate in the lattice via hydrogen-bonding interactions involving both carboxylic acid residues so that each carboxylic acid group associates with its centrosymmetrically related mate. Thus, O—H11A = 0.92 Å, H11A···O11ⁱ = 1.74 Å and O11A···O11ⁱ = 2.653 (2) Å, and the angle at H11A = 174° [symmetry code: (i) 1 - x, -1 - y, -z]. The comparable parameters for H22A and O22ⁱⁱ are 0.87, 1.78 and 2.646 (2) Å, and 175° [symmetry code: (ii) 2 - x, -y, -z]. Such association leads to the formation of zigzag chains extending in the ab plane.

S2. Experimental

The title compound was prepared according to the literature procedure of Avery et al. (2001). Colourless crystals were obtained by slow evaporation of a dichloromethane/heptane solution of the compound (m.p. 458–460 K).

S3. Refinement

The C-bound H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with an overall isotropic displacement parameter. The H atoms on O atoms were located from a difference map but were not refined.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976).

(I)

Crystal data

C12H12O4	F(000) = 464
Mr = 220.22	Dx = 1.334 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.555 (4) Å	Cell parameters from 24 reflections
b = 8.814 (4) Å	θ = 7.3–10.7°
c = 14.849 (2) Å	µ = 0.10 mm^−1
β = 101.70 (2)°	T = 173 K
V = 1096.5 (6) Å^3	Block, colourless
Z = 4	0.45 × 0.29 × 0.16 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.020
Radiation source: Rotating anode	θmax = 27.5°, θmin = 3.0°
Graphite monochromator	h = −11→6
ω–2θ scans	k = 0→11
4704 measured reflections	l = −19→19
2510 independent reflections	3 standard reflections every 400 reflections
1829 reflections with I > 2σ(I)	intensity decay: 0.3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0728P)^2 + 0.3498P] where P = (Fo^2 + 2Fc^2)/3
2510 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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
O11	0.55130 (14)	−0.42612 (11)	0.10228 (7)	0.0320 (3)
O11A	0.42968 (15)	−0.30476 (12)	−0.02518 (7)	0.0354 (3)
H11A	0.4284	−0.3979	−0.0527	0.0498 (17)*
O22	0.83491 (12)	−0.07007 (12)	0.02195 (7)	0.0301 (3)
O22A	0.98659 (13)	0.10984 (12)	0.10230 (7)	0.0330 (3)
H22A	1.0453	0.1030	0.0607	0.0498 (17)*
C1	0.52950 (16)	−0.15774 (15)	0.10490 (8)	0.0219 (3)
H1	0.4862	−0.0689	0.0658	0.0398 (14)*
C2	0.68966 (16)	−0.13619 (15)	0.16992 (8)	0.0214 (3)
H2	0.7576	−0.2293	0.1811	0.0398 (14)*
C3	0.53970 (15)	−0.14191 (15)	0.20782 (8)	0.0203 (3)
H3	0.5243	−0.2392	0.2396	0.0398 (14)*
C11	0.50386 (17)	−0.30868 (16)	0.06200 (9)	0.0236 (3)
C21	0.77971 (17)	0.00923 (15)	0.16713 (9)	0.0239 (3)
H21A	0.8563	0.0226	0.2262	0.0498 (17)*
H21B	0.7038	0.0953	0.1598	0.0498 (17)*
C22	0.86886 (16)	0.01157 (15)	0.08976 (9)	0.0224 (3)
C31	0.47758 (16)	−0.00532 (15)	0.24848 (9)	0.0215 (3)
C32	0.40565 (19)	0.11704 (18)	0.19765 (10)	0.0314 (3)
H32	0.3934	0.1164	0.1326	0.0398 (14)*
C33	0.3510 (2)	0.24112 (19)	0.24096 (12)	0.0376 (4)
H33	0.3033	0.3248	0.2054	0.0398 (14)*
C34	0.36597 (19)	0.24268 (19)	0.33486 (12)	0.0361 (4)
H34	0.3268	0.3262	0.3641	0.0398 (14)*
C35	0.4381 (2)	0.1225 (2)	0.38613 (11)	0.0418 (4)
H35	0.4497	0.1237	0.4511	0.0398 (14)*
C36	0.4938 (2)	−0.00037 (17)	0.34346 (10)	0.0339 (4)
H36	0.5439	−0.0824	0.3797	0.0398 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0512 (7)	0.0202 (5)	0.0223 (5)	−0.0012 (5)	0.0020 (5)	−0.0009 (4)
O11A	0.0563 (7)	0.0227 (5)	0.0222 (5)	0.0010 (5)	−0.0037 (5)	−0.0037 (4)
O22	0.0308 (6)	0.0372 (6)	0.0245 (5)	−0.0104 (5)	0.0111 (4)	−0.0090 (4)
O22A	0.0346 (6)	0.0320 (6)	0.0376 (6)	−0.0138 (5)	0.0197 (5)	−0.0121 (4)
C1	0.0285 (7)	0.0189 (6)	0.0186 (6)	−0.0025 (5)	0.0055 (5)	−0.0006 (5)
C2	0.0245 (7)	0.0202 (6)	0.0207 (6)	−0.0002 (5)	0.0076 (5)	−0.0023 (5)
C3	0.0231 (7)	0.0197 (6)	0.0186 (6)	−0.0010 (5)	0.0058 (5)	0.0003 (5)
C11	0.0294 (7)	0.0226 (7)	0.0191 (6)	−0.0037 (5)	0.0058 (5)	−0.0012 (5)
C21	0.0263 (7)	0.0232 (7)	0.0237 (6)	−0.0045 (5)	0.0089 (5)	−0.0052 (5)
C22	0.0228 (7)	0.0217 (6)	0.0231 (6)	−0.0006 (5)	0.0056 (5)	−0.0005 (5)
C31	0.0203 (6)	0.0212 (6)	0.0246 (6)	−0.0042 (5)	0.0078 (5)	−0.0029 (5)
C32	0.0316 (8)	0.0339 (8)	0.0278 (7)	0.0086 (6)	0.0039 (6)	−0.0014 (6)
C33	0.0312 (8)	0.0330 (8)	0.0465 (9)	0.0120 (7)	0.0030 (7)	−0.0046 (7)
C34	0.0312 (8)	0.0316 (8)	0.0478 (9)	−0.0001 (6)	0.0139 (7)	−0.0163 (7)
C35	0.0627 (12)	0.0361 (9)	0.0307 (8)	−0.0005 (8)	0.0191 (8)	−0.0101 (7)
C36	0.0538 (10)	0.0252 (7)	0.0250 (7)	0.0009 (7)	0.0135 (7)	−0.0009 (6)

Geometric parameters (Å, º)

O11—C11	1.2230 (18)	C3—C31	1.4921 (18)
O11A—C11	1.3215 (16)	C21—C22	1.5025 (18)
O22—C22	1.2236 (16)	C31—C32	1.387 (2)
O22A—C22	1.3127 (17)	C31—C36	1.3895 (18)
C1—C11	1.4722 (19)	C32—C33	1.396 (2)
C1—C3	1.5195 (17)	C33—C34	1.374 (2)
C1—C2	1.5196 (19)	C35—C34	1.375 (3)
C2—C21	1.5004 (19)	C35—C36	1.388 (2)
C2—C3	1.5027 (19)
C11—C1—C3	119.43 (11)	C2—C21—C22	112.08 (11)
C11—C1—C2	115.08 (12)	O22—C22—O22A	123.51 (12)
C3—C1—C2	59.27 (8)	O22—C22—C21	123.26 (12)
C21—C2—C3	121.41 (11)	O22A—C22—C21	113.23 (11)
C21—C2—C1	119.42 (12)	C32—C31—C36	118.03 (13)
C3—C2—C1	60.36 (9)	C32—C31—C3	124.22 (12)
C31—C3—C2	121.71 (11)	C36—C31—C3	117.75 (12)
C31—C3—C1	121.91 (11)	C31—C32—C33	120.76 (14)
C2—C3—C1	60.37 (9)	C34—C33—C32	120.27 (15)
O11—C11—O11A	123.16 (12)	C34—C35—C36	120.37 (15)
O11—C11—C1	123.22 (12)	C33—C34—C35	119.54 (14)
O11A—C11—C1	113.58 (12)	C35—C36—C31	121.01 (15)