(+)-(1R,2S,3R)-2-[(Benzyl­oxycarbonyl)meth­yl]-3-phenyl­cyclo­propane­carboxylic acid

Avery, T.D.; Greatrex, B.W.; Taylor, D.K.; Tiekink, E.R.T.

doi:10.1107/S1600536807030838

(+)-(1R,2S,3R)-2-[(Benzyloxycarbonyl)methyl]-3-phenylcyclopropanecarboxylic acid

T. D. Avery, B. W. Greatrex, D. K. Taylor and E. R. T. Tiekink

In the title compound, C₁₉H₁₈O₄, the carboxyl group lies on the opposite side of the cyclopropane ring to the other substituents. Molecules associate via (

HOC=O)₂ synthons around centres of symmetry and are linked into double layers by cooperative C—H

O contacts.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030838/hg2238sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030838/hg2238Isup2.hkl Contains datablock I

CCDC reference: 655061

checkCIF report

Key indicators

Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.003 Å
R factor = 0.048
wR factor = 0.149
Data-to-parameter ratio = 17.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C1     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C2     = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C3     = ...          R
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
   4 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound (I) was synthesized in the course of an investigation of selective deprotections of cyclopropanes generated through the reaction of 1,2-dioxines and stabilized phosphorus ylides (Avery et al., 2000, 2001). The molecular structure (Fig. 1) shows the carboxylic acid functional group at the C1 atom to lie to the opposite side of the cyclopropane ring to the substituents at the C2 and C3 atoms. Centrosymmetrically related molecules are connected by the familiar {···HOC=O}₂ synthon and these are connected into a double layer via C—H···O contacts (Table 1). The double layers thus formed stack along the c-direction, being separated by hydrophobic interactions (Fig. 2).

Related literature top

For related literature, see: Avery et al. (2000, 2001).

Experimental top

To a solution of potassium carbonate (335 mg, 1.31 mmol) in water (10 ml) was added a solution of ±(1R,2S,3R)-phenyl 2-(2-(benzyloxy)-2-oxoethyl)-3- phenylcyclopropanecarboxylate (950 mg, 2.46 mmol) in acetone (10 ml). The mixture was allowed to stir overnight after which time the acetone was removed in vacuo and the aqueous solution acidified (conc. HCl). The solution was then extracted with ethyl acetate (3 x 20 ml), dried (MgSO₄), filtered and the volatiles removed in vacuo to give a crude solid consisting of (I) and phenol. Phenol was removed by sublimation and the crude acid recrystallized (dichloromethane/hexanes) to give (I) (701 mg, 92%) as a colourless solid. M.p 409–411 K. Elemental analysis found: C 73.50, H, 5.97%; C₁₉H₁₈O₄ requires: C 73.53, H, 5.85%. IR: 2538, 1732, 1682, 1603, 1449, 1240, 1170, 961 cm^{-1. 1}H NMR (CDCl₃, 300 MHz) δ 2.03 (t, J = 3.9 Hz, 1H), 2.15–2.26 (m, 3H), 2.91–3.00 (m, 1H), 5.03–5.12 (m, 2H), 7.15–7.34 (m, 10H), 12.20 (bs, 1H). ¹³C NMR (CDCl₃, 75 MHz) δ 24.5, 24.6, 31.3, 32.7, 66.4, 127.0, 128.2, 128.2, 128.4, 128.5, 128.8, 134.8, 135.6, 171.5, 179.6.

Structure description top

For related literature, see: Avery et al. (2000, 2001).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. View of the unit-cell contents of (I) highlighting the stacking of double layers along the c-direction. Hydrogen bonds are shown as orange-dashed lines. Colour code: red (oxygen), grey (carbon) and green (hydrogen).

(+)-(1R,2S,3R)-2-[(Benzyloxycarbonyl)methyl]-3-phenylcyclopropanecarboxylic acid top

Crystal data top

C₁₉H₁₈O₄	Z = 2
M_r = 310.33	F(000) = 328
Triclinic, P1	D_x = 1.288 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 5.5550 (5) Å	Cell parameters from 1829 reflections
b = 8.9606 (8) Å	θ = 2.5–29.3°
c = 16.6586 (16) Å	µ = 0.09 mm⁻¹
α = 101.698 (2)°	T = 223 K
β = 98.907 (2)°	Prism, colourless
γ = 92.186 (2)°	0.39 × 0.09 × 0.08 mm
V = 800.11 (13) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2831 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 27.5°, θ_min = 1.3°
ω and φ scans	h = −6→7
5723 measured reflections	k = −11→11
3668 independent reflections	l = −16→21

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0829P)² + 0.0916P] where P = (F_o² + 2F_c²)/3
3668 reflections	(Δ/σ)_max < 0.001
211 parameters	Δρ_max = 0.28 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₉H₁₈O₄	γ = 92.186 (2)°
M_r = 310.33	V = 800.11 (13) Å³
Triclinic, P1	Z = 2
a = 5.5550 (5) Å	Mo Kα radiation
b = 8.9606 (8) Å	µ = 0.09 mm⁻¹
c = 16.6586 (16) Å	T = 223 K
α = 101.698 (2)°	0.39 × 0.09 × 0.08 mm
β = 98.907 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2831 reflections with I > 2σ(I)
5723 measured reflections	R_int = 0.015
3668 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.149	H-atom parameters constrained
S = 1.06	Δρ_max = 0.28 e Å⁻³
3668 reflections	Δρ_min = −0.25 e Å⁻³
211 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

	x	y	z	U_iso*/U_eq
O1	0.6349 (2)	0.36870 (14)	0.37643 (10)	0.0613 (4)
O2	0.3799 (2)	0.16367 (12)	0.36059 (7)	0.0399 (3)
O3	−0.1845 (2)	0.82536 (12)	0.46136 (7)	0.0394 (3)
H3O	−0.1801	0.9142	0.4903	0.059*
O4	0.1916 (2)	0.90033 (12)	0.44703 (8)	0.0452 (3)
C1	0.0252 (3)	0.65051 (15)	0.38033 (9)	0.0302 (3)
H1	−0.1308	0.5863	0.3652	0.036*
C2	0.2544 (3)	0.56716 (15)	0.39526 (9)	0.0303 (3)
H2	0.3883	0.6259	0.4373	0.036*
C3	0.1967 (3)	0.62665 (16)	0.31702 (9)	0.0310 (3)
H3	0.2983	0.7201	0.3174	0.037*
C4	0.0177 (3)	0.80346 (16)	0.43215 (9)	0.0304 (3)
C5	0.2214 (3)	0.40048 (16)	0.39673 (10)	0.0329 (3)
H5A	0.1921	0.3908	0.4520	0.040*
H5B	0.0766	0.3547	0.3565	0.040*
C6	0.4366 (3)	0.31359 (16)	0.37669 (9)	0.0311 (3)
C7	0.5724 (3)	0.06418 (18)	0.34375 (11)	0.0406 (4)
H7A	0.5573	−0.0223	0.3709	0.049*
H7B	0.7306	0.1202	0.3678	0.049*
C8	0.5662 (3)	0.00447 (18)	0.25231 (10)	0.0383 (4)
C9	0.3839 (4)	0.0327 (2)	0.19188 (12)	0.0541 (5)
H9	0.2593	0.0952	0.2071	0.065*
C10	0.3848 (4)	−0.0311 (3)	0.10899 (13)	0.0675 (6)
H10	0.2614	−0.0104	0.0682	0.081*
C11	0.5631 (4)	−0.1240 (3)	0.08567 (13)	0.0633 (6)
H11	0.5609	−0.1678	0.0293	0.076*
C12	0.7448 (4)	−0.1528 (3)	0.14513 (14)	0.0658 (6)
H12	0.8676	−0.2164	0.1295	0.079*
C13	0.7477 (4)	−0.0882 (2)	0.22818 (12)	0.0528 (5)
H13	0.8740	−0.1073	0.2686	0.063*
C14	0.1254 (3)	0.52696 (17)	0.23264 (9)	0.0353 (3)
C15	0.2719 (4)	0.5390 (2)	0.17366 (11)	0.0518 (5)
H15	0.4093	0.6094	0.1877	0.062*
C16	0.2179 (4)	0.4483 (3)	0.09420 (12)	0.0691 (6)
H16	0.3182	0.4582	0.0547	0.083*
C17	0.0195 (4)	0.3443 (3)	0.07291 (12)	0.0686 (6)
H17	−0.0164	0.2829	0.0191	0.082*
C18	−0.1257 (4)	0.3304 (3)	0.13032 (13)	0.0642 (6)
H18	−0.2607	0.2582	0.1160	0.077*
C19	−0.0758 (3)	0.4221 (2)	0.20976 (11)	0.0493 (4)
H19	−0.1794	0.4128	0.2483	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0349 (7)	0.0366 (7)	0.1152 (12)	0.0015 (5)	0.0257 (7)	0.0124 (7)
O2	0.0382 (6)	0.0256 (5)	0.0574 (7)	0.0056 (4)	0.0150 (5)	0.0061 (5)
O3	0.0428 (6)	0.0286 (5)	0.0475 (7)	0.0068 (5)	0.0182 (5)	0.0005 (5)
O4	0.0479 (7)	0.0284 (6)	0.0572 (7)	−0.0027 (5)	0.0216 (5)	−0.0047 (5)
C1	0.0340 (7)	0.0239 (7)	0.0332 (7)	0.0029 (5)	0.0096 (6)	0.0038 (5)
C2	0.0310 (7)	0.0268 (7)	0.0324 (7)	0.0032 (5)	0.0071 (5)	0.0033 (5)
C3	0.0358 (7)	0.0248 (7)	0.0330 (7)	0.0025 (6)	0.0103 (6)	0.0042 (5)
C4	0.0380 (8)	0.0259 (7)	0.0298 (7)	0.0062 (6)	0.0101 (6)	0.0074 (5)
C5	0.0323 (7)	0.0287 (7)	0.0406 (8)	0.0048 (6)	0.0107 (6)	0.0096 (6)
C6	0.0326 (7)	0.0279 (7)	0.0339 (7)	0.0036 (6)	0.0069 (6)	0.0082 (6)
C7	0.0439 (9)	0.0315 (8)	0.0479 (9)	0.0129 (7)	0.0101 (7)	0.0084 (7)
C8	0.0393 (8)	0.0319 (8)	0.0453 (9)	0.0024 (6)	0.0102 (7)	0.0093 (6)
C9	0.0476 (10)	0.0559 (11)	0.0556 (11)	0.0108 (9)	0.0034 (8)	0.0068 (9)
C10	0.0643 (13)	0.0805 (15)	0.0504 (11)	0.0058 (11)	−0.0047 (10)	0.0078 (10)
C11	0.0728 (14)	0.0686 (14)	0.0447 (11)	−0.0010 (11)	0.0141 (10)	0.0006 (9)
C12	0.0713 (14)	0.0698 (14)	0.0608 (12)	0.0204 (11)	0.0308 (11)	0.0066 (10)
C13	0.0532 (11)	0.0608 (12)	0.0489 (10)	0.0212 (9)	0.0154 (8)	0.0132 (9)
C14	0.0412 (8)	0.0342 (8)	0.0311 (7)	0.0082 (6)	0.0088 (6)	0.0052 (6)
C15	0.0569 (11)	0.0581 (11)	0.0412 (9)	0.0003 (9)	0.0191 (8)	0.0048 (8)
C16	0.0796 (15)	0.0891 (16)	0.0400 (10)	0.0082 (13)	0.0283 (10)	0.0025 (10)
C17	0.0748 (14)	0.0848 (16)	0.0350 (10)	0.0105 (12)	0.0057 (9)	−0.0112 (10)
C18	0.0590 (12)	0.0728 (14)	0.0472 (11)	−0.0076 (10)	−0.0005 (9)	−0.0099 (9)
C19	0.0467 (9)	0.0589 (11)	0.0369 (9)	−0.0040 (8)	0.0085 (7)	−0.0018 (8)

Geometric parameters (Å, º) top

O1—C6	1.1910 (18)	C8—C9	1.382 (3)
O2—C6	1.3309 (18)	C9—C10	1.384 (3)
O2—C7	1.4424 (18)	C9—H9	0.9400
O3—C4	1.2978 (18)	C10—C11	1.369 (3)
O3—H3O	0.8401	C10—H10	0.9400
O4—C4	1.2338 (18)	C11—C12	1.371 (3)
C1—C4	1.4701 (19)	C11—H11	0.9400
C1—C2	1.514 (2)	C12—C13	1.385 (3)
C1—C3	1.5168 (19)	C12—H12	0.9400
C1—H1	0.9900	C13—H13	0.9400
C2—C3	1.500 (2)	C14—C19	1.386 (2)
C2—C5	1.5035 (19)	C14—C15	1.387 (2)
C2—H2	0.9900	C15—C16	1.387 (3)
C3—C14	1.491 (2)	C15—H15	0.9400
C3—H3	0.9900	C16—C17	1.369 (3)
C5—C6	1.495 (2)	C16—H16	0.9400
C5—H5A	0.9800	C17—C18	1.364 (3)
C5—H5B	0.9800	C17—H17	0.9400
C7—C8	1.503 (2)	C18—C19	1.390 (2)
C7—H7A	0.9800	C18—H18	0.9400
C7—H7B	0.9800	C19—H19	0.9400
C8—C13	1.386 (2)

C6—O2—C7	117.49 (12)	H7A—C7—H7B	107.8
C4—O3—H3O	110.5	C13—C8—C9	118.80 (17)
C4—C1—C2	117.76 (12)	C13—C8—C7	117.95 (15)
C4—C1—C3	119.46 (12)	C9—C8—C7	123.20 (15)
C2—C1—C3	59.35 (9)	C10—C9—C8	120.03 (18)
C4—C1—H1	116.1	C10—C9—H9	120.0
C2—C1—H1	116.1	C8—C9—H9	120.0
C3—C1—H1	116.1	C11—C10—C9	120.9 (2)
C3—C2—C5	122.65 (12)	C11—C10—H10	119.6
C3—C2—C1	60.43 (9)	C9—C10—H10	119.6
C5—C2—C1	117.10 (12)	C10—C11—C12	119.57 (19)
C3—C2—H2	115.2	C10—C11—H11	120.2
C5—C2—H2	115.2	C12—C11—H11	120.2
C1—C2—H2	115.2	C11—C12—C13	120.13 (19)
C14—C3—C2	123.86 (12)	C11—C12—H12	119.9
C14—C3—C1	122.54 (13)	C13—C12—H12	119.9
C2—C3—C1	60.22 (9)	C8—C13—C12	120.59 (18)
C14—C3—H3	113.4	C8—C13—H13	119.7
C2—C3—H3	113.4	C12—C13—H13	119.7
C1—C3—H3	113.4	C19—C14—C15	118.04 (15)
O4—C4—O3	123.72 (13)	C19—C14—C3	124.23 (14)
O4—C4—C1	122.19 (13)	C15—C14—C3	117.73 (15)
O3—C4—C1	114.08 (13)	C14—C15—C16	120.75 (19)
C6—C5—C2	113.23 (12)	C14—C15—H15	119.6
C6—C5—H5A	108.9	C16—C15—H15	119.6
C2—C5—H5A	108.9	C17—C16—C15	120.40 (19)
C6—C5—H5B	108.9	C17—C16—H16	119.8
C2—C5—H5B	108.9	C15—C16—H16	119.8
H5A—C5—H5B	107.7	C18—C17—C16	119.61 (18)
O1—C6—O2	123.53 (14)	C18—C17—H17	120.2
O1—C6—C5	125.52 (14)	C16—C17—H17	120.2
O2—C6—C5	110.94 (12)	C17—C18—C19	120.6 (2)
O2—C7—C8	112.59 (13)	C17—C18—H18	119.7
O2—C7—H7A	109.1	C19—C18—H18	119.7
C8—C7—H7A	109.1	C14—C19—C18	120.60 (17)
O2—C7—H7B	109.1	C14—C19—H19	119.7
C8—C7—H7B	109.1	C18—C19—H19	119.7

C4—C1—C2—C3	−109.52 (14)	O2—C7—C8—C9	−4.8 (2)
C4—C1—C2—C5	136.49 (13)	C13—C8—C9—C10	0.0 (3)
C3—C1—C2—C5	−113.99 (14)	C7—C8—C9—C10	−177.41 (18)
C5—C2—C3—C14	−6.3 (2)	C8—C9—C10—C11	0.8 (3)
C1—C2—C3—C14	−111.25 (16)	C9—C10—C11—C12	−0.8 (4)
C5—C2—C3—C1	104.97 (15)	C10—C11—C12—C13	0.0 (4)
C4—C1—C3—C14	−139.96 (14)	C9—C8—C13—C12	−0.8 (3)
C2—C1—C3—C14	113.35 (15)	C7—C8—C13—C12	176.76 (18)
C4—C1—C3—C2	106.68 (15)	C11—C12—C13—C8	0.8 (3)
C2—C1—C4—O4	44.4 (2)	C2—C3—C14—C19	58.9 (2)
C3—C1—C4—O4	−24.3 (2)	C1—C3—C14—C19	−14.8 (2)
C2—C1—C4—O3	−134.54 (13)	C2—C3—C14—C15	−120.33 (17)
C3—C1—C4—O3	156.83 (13)	C1—C3—C14—C15	166.00 (15)
C3—C2—C5—C6	85.53 (17)	C19—C14—C15—C16	−0.1 (3)
C1—C2—C5—C6	156.23 (12)	C3—C14—C15—C16	179.20 (18)
C7—O2—C6—O1	1.3 (2)	C14—C15—C16—C17	−0.5 (4)
C7—O2—C6—C5	−177.29 (13)	C15—C16—C17—C18	0.1 (4)
C2—C5—C6—O1	15.3 (2)	C16—C17—C18—C19	0.8 (4)
C2—C5—C6—O2	−166.14 (12)	C15—C14—C19—C18	1.0 (3)
C6—O2—C7—C8	−98.97 (16)	C3—C14—C19—C18	−178.22 (18)
O2—C7—C8—C13	177.73 (15)	C17—C18—C19—C14	−1.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4ⁱ	0.84	1.78	2.6224 (16)	176
C1—H1···O1ⁱⁱ	0.99	2.36	3.249 (2)	149
C5—H5B···O1ⁱⁱ	0.98	2.53	3.219 (2)	127
C7—H7A···O3ⁱⁱⁱ	0.98	2.55	3.368 (2)	141

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈O₄
M_r	310.33
Crystal system, space group	Triclinic, P1
Temperature (K)	223
a, b, c (Å)	5.5550 (5), 8.9606 (8), 16.6586 (16)
α, β, γ (°)	101.698 (2), 98.907 (2), 92.186 (2)
V (Å³)	800.11 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.39 × 0.09 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5723, 3668, 2831
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.149, 1.06
No. of reflections	3668
No. of parameters	211
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.25

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 2006), SHELXL97.