Acta Cryst.(2003). E59, o319±o320 DOI: 10.1107/S1600536803002836 Fischer and Profir C10H10O4
o319
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
(
S
)-Phenylsuccinic acid
Andreas Fischera* and Veronica M. Profirb
aInorganic Chemistry, Royal Institute of
Technology, 100 44 Stockholm, Sweden, and bDepartment of Chemical Engineering and
Technology, Royal Institute of Technology, 100 44 Stockholm, Sweden
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 100 K
Mean(C±C) = 0.003 AÊ Rfactor = 0.032 wRfactor = 0.074 Data-to-parameter ratio = 8.5
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
(S)-Phenylsuccinic acid, C10H10O4, crystallizes from water
with two molecules per asymmetric unit. In the crystal structure, the carboxyl groups of each acid molecule are
connected to those of adjacent moleculesviahydrogen bonds;
each molecule is connected to three other molecules, forming in®nite chains.
Comment
Phenylsuccinic acid (PSA) is an aromatic dicarboxylic acid used as a classical resolving agent for pharmaceuticals (Bayley & Vaidya, 1992; Kozma, 2002). To be able to study and understand the solid-state properties of PSA and its interac-tions with solvents or with other common reagents, it is essential to know the crystal structures of both the pure enantiomer and the racemate. Since the structures of neither
(S)- nor (RS)-PSA were known, we grew crystals of both
compounds in order to determine how the acid molecules are
assembled in each structure. The structure of (S)-PSA is
presented here.
In (S)-PSA, two molecules are present in the asymmetric
unit (see Fig. 1) and the geometry of these is unexceptional.
Received 15 January 2003 Accepted 3 February 2003 Online 14 February 2003
Figure 1
Fig. 2 displays the packing in the unit cell. The acid molecules
are connected viahydrogen bonds (Table 1), each molecule
binding to one adjacent moleculevia both O atoms of one
carboxyl group. The other carboxyl group binds to two
different moleculesviatwo H bonds. Fig. 3 shows the network
which is formed. Molecule 1 of the asymmetric unit is
connected to three molecules of the second andvice versa. The
screw axis then generates a second network which is crystal-lographically equivalent, but not connected to the ®rst.
Experimental
Crystals were grown from aqueous solutions by dissolving the purchased material (Fluka, >99%) in pure, distilled and deionized water at room temperature. The clear solutions were evaporated to dryness under low-pressure conditions at room temperature, yielding single crystals of (S)-PSA.
Crystal data
C10H10O4
Mr= 194.19 Monoclinic,P21
a= 5.4193 (2) AÊ
b= 18.0847 (5) AÊ
c= 9.4713 (3) AÊ = 95.7044 (11)
V= 923.65 (5) AÊ3
Z= 4
Dx= 1.396 Mg mÿ3 MoKradiation Cell parameters from 4591
re¯ections = 4.1±27.5 = 0.11 mmÿ1
T= 100 K Irregular, colourless 0.350.150.07 mm
Data collection
Bruker±Nonius KappaCCD diffractometer
'and!scans
Absorption correction: none 7099 measured re¯ections 2162 independent re¯ections
2009 re¯ections withI> 2(I)
Rint= 0.037
max= 27.4
h=ÿ7!6
k=ÿ22!23
l=ÿ12!12
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.032
wR(F2) = 0.074
S= 1.03 2162 re¯ections 253 parameters
w= 1/[2(F
o2) + (0.0388P)2 + 0.1504P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.19 e AÊÿ3
=ÿ0.18 e AÊÿ3
Table 1
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O1ÐH1O O8i 0.92 1.75 2.659 (2) 170
O3ÐH3O O6ii 0.92 1.71 2.627 (2) 177
O5ÐH5O O4iii 0.89 1.82 2.714 (2) 178
O7ÐH7O O2iv 0.92 1.70 2.615 (2) 178
Symmetry codes: (i) 1ÿx;y ÿ1
2;ÿz; (ii) 2ÿx;y ÿ12;1ÿz; (iii) 1ÿx;12y;1ÿz;
(iv) 1ÿx;1 2y;ÿz.
TheScon®guration is known from a commercial sample. A whole sphere of data was collected and Friedel pairs were merged. All H atoms were located in a difference Fourier map and were re®ned using a riding model, withUisoset equal to 1.2Ueqof the parent atoms.
Data collection:COLLECT(Nonius, 1999); cell re®nement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: maXus
(Mackayet al., 1998).
The work was funded by the Swedish Foundation for Strategic Research (SELCHEM).
References
Bayley, C. R. & Vaidya, N. A. (1992). Resolution of Racemates by Diastereomeric Salt Formation, Chirality in Industry, edited by A. N. Collins, G. N. Sheldrake and J. Crosby. Chichester, UK: John Wiley and Sons.
Brandenburg, K. (2001). DIAMOND. Version 2.1e. Crystal Impact GbR, Bonn, Germany.
Kozma, D. (2002).CRC Handbook of Optical Resolution via Diastereomeric Salt Formation. Boca Raton, USA: CRC Press LLC.
Mackay, S., Gilmore, C. J., Edwards, C., Tremayne, M., Stuart, N. & Shankland, K. (1998).maXus. University of Glasgow, Scotland, UK, Nonius BV, Delft, The Netherlands, and MacScience Co. Ltd, Yokohama, Japan.
Nonius (1999).COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307±326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXS-97 and SHELXL97. University of GoÈttingen, Germany.
Figure 2
The unit cell contents of (S)-PSA, viewed alonga. H atoms have been omitted.
Figure 3
supporting information
sup-1 Acta Cryst. (2003). E59, o319–o320
supporting information
Acta Cryst. (2003). E59, o319–o320 [https://doi.org/10.1107/S1600536803002836]
(
S
)-Phenylsuccinic acid
Andreas Fischer and Veronica M. Profir
(S)-phenylsuccinic acid
Crystal data
C10H10O4
Mr = 194.19 Monoclinic, P21
Hall symbol: P 2yb a = 5.4193 (2) Å b = 18.0847 (5) Å c = 9.4713 (3) Å β = 95.7044 (11)° V = 923.65 (5) Å3
Z = 4
Dx = 1.396 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4591 reflections θ = 4.1–27.5°
µ = 0.11 mm−1
T = 100 K
Irregular, colourless 0.35 × 0.15 × 0.07 mm
Data collection
Bruker Nonius KappaCCD diffractometer
Radiation source: fine-focus sealed tube φ and ω scans
7099 measured reflections 2162 independent reflections
2009 reflections with I > 2σ(I) Rint = 0.037
θmax = 27.4°, θmin = 4.2°
h = −7→6 k = −22→23 l = −12→12
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.032
wR(F2) = 0.074
S = 1.03 2162 reflections 253 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0388P)2 + 0.1504P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.18 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
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
C1 0.4762 (4) 0.23618 (11) −0.0045 (2) 0.0152 (4)
C2 0.5605 (3) 0.29248 (10) 0.1093 (2) 0.0139 (4)
C3 0.8263 (4) 0.28149 (10) 0.1743 (2) 0.0141 (4)
C4 0.8765 (3) 0.20843 (11) 0.2483 (2) 0.0148 (4)
C5 0.5291 (4) 0.36933 (11) 0.0435 (2) 0.0150 (4)
C6 0.6893 (4) 0.39420 (11) −0.0537 (2) 0.0184 (4)
C7 0.6660 (4) 0.46497 (12) −0.1090 (2) 0.0234 (5)
C8 0.4808 (4) 0.51209 (12) −0.0694 (2) 0.0248 (5)
C9 0.3190 (4) 0.48742 (12) 0.0239 (2) 0.0234 (5)
C10 0.3419 (4) 0.41651 (11) 0.0802 (2) 0.0187 (4)
C11 0.5786 (3) 0.54050 (10) 0.5303 (2) 0.0149 (4)
C12 0.6135 (4) 0.48222 (10) 0.4193 (2) 0.0140 (4)
C13 0.8085 (4) 0.50882 (10) 0.3240 (2) 0.0156 (4)
C14 0.7388 (3) 0.58116 (10) 0.2531 (2) 0.0146 (4)
C15 0.6858 (4) 0.40833 (10) 0.4904 (2) 0.0152 (4)
C16 0.5249 (4) 0.34847 (11) 0.4744 (2) 0.0193 (4)
C17 0.5906 (4) 0.28060 (11) 0.5363 (2) 0.0248 (5)
C18 0.8171 (4) 0.27243 (12) 0.6165 (2) 0.0264 (5)
C19 0.9772 (4) 0.33220 (13) 0.6347 (2) 0.0247 (5)
C20 0.9131 (4) 0.40013 (11) 0.5723 (2) 0.0193 (4)
O1 0.6543 (2) 0.20405 (8) −0.06541 (15) 0.0177 (3)
O2 0.2555 (3) 0.22477 (8) −0.03780 (16) 0.0231 (3)
O3 1.1129 (3) 0.20283 (8) 0.29570 (16) 0.0234 (3)
O4 0.7194 (3) 0.16167 (8) 0.26223 (15) 0.0181 (3)
O5 0.3465 (2) 0.54763 (8) 0.55916 (15) 0.0185 (3)
O6 0.7527 (3) 0.57548 (8) 0.58740 (15) 0.0200 (3)
O7 0.9098 (2) 0.60695 (8) 0.17683 (15) 0.0199 (3)
O8 0.5420 (3) 0.61259 (8) 0.26567 (15) 0.0191 (3)
H2 0.4275 0.2816 0.1887 0.017*
H3A 0.8658 0.3212 0.2429 0.017*
H3B 0.9416 0.2833 0.1039 0.017*
H6 0.8184 0.3590 −0.0855 0.022*
H7 0.7772 0.4820 −0.1748 0.028*
H8 0.4723 0.5596 −0.1093 0.030*
H9 0.2022 0.5240 0.0598 0.028*
H10 0.2215 0.4007 0.1469 0.022*
H12 0.4506 0.4740 0.3687 0.017*
H13A 0.9729 0.5152 0.3805 0.019*
H13B 0.8055 0.4710 0.2494 0.019*
H16 0.3826 0.3525 0.4083 0.023*
H17 0.4690 0.2367 0.5339 0.030*
H18 0.8513 0.2237 0.6593 0.032*
H19 1.1469 0.3277 0.7008 0.030*
H20 1.0185 0.4428 0.5953 0.023*
supporting information
sup-3 Acta Cryst. (2003). E59, o319–o320
H3O 1.1544 0.1574 0.3352 0.028*
H5O 0.3270 0.5860 0.6164 0.022*
H7O 0.8549 0.6481 0.1268 0.024*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0150 (9) 0.0135 (8) 0.0173 (9) 0.0012 (7) 0.0020 (7) 0.0008 (7)
C2 0.0150 (9) 0.0128 (9) 0.0140 (9) 0.0000 (7) 0.0024 (7) 0.0002 (7)
C3 0.0154 (9) 0.0105 (8) 0.0162 (9) −0.0021 (7) 0.0008 (7) 0.0009 (7)
C4 0.0150 (9) 0.0156 (9) 0.0141 (9) −0.0004 (8) 0.0020 (7) −0.0012 (7)
C5 0.0157 (9) 0.0144 (9) 0.0143 (9) 0.0011 (7) −0.0022 (7) −0.0010 (8)
C6 0.0224 (10) 0.0166 (10) 0.0164 (9) 0.0031 (8) 0.0025 (8) 0.0002 (8)
C7 0.0324 (12) 0.0192 (10) 0.0186 (10) 0.0007 (9) 0.0020 (9) 0.0055 (9)
C8 0.0334 (12) 0.0165 (9) 0.0230 (11) 0.0027 (9) −0.0055 (9) 0.0018 (8)
C9 0.0242 (10) 0.0178 (10) 0.0267 (11) 0.0068 (8) −0.0049 (9) −0.0049 (9)
C10 0.0164 (9) 0.0190 (9) 0.0202 (10) 0.0015 (8) −0.0009 (7) −0.0035 (9)
C11 0.0164 (9) 0.0132 (9) 0.0151 (9) 0.0010 (7) 0.0013 (7) 0.0021 (7)
C12 0.0138 (9) 0.0126 (9) 0.0156 (9) −0.0006 (7) 0.0015 (7) −0.0012 (7)
C13 0.0162 (9) 0.0141 (9) 0.0165 (9) 0.0023 (7) 0.0016 (7) 0.0000 (7)
C14 0.0161 (10) 0.0136 (9) 0.0138 (9) −0.0006 (7) 0.0001 (7) −0.0001 (7)
C15 0.0184 (9) 0.0134 (9) 0.0146 (9) 0.0020 (7) 0.0060 (7) −0.0015 (7)
C16 0.0214 (10) 0.0177 (10) 0.0194 (10) −0.0018 (8) 0.0058 (8) −0.0014 (8)
C17 0.0365 (12) 0.0155 (10) 0.0244 (11) −0.0041 (9) 0.0125 (9) −0.0007 (9)
C18 0.0363 (13) 0.0181 (10) 0.0273 (11) 0.0089 (9) 0.0162 (10) 0.0070 (9)
C19 0.0234 (11) 0.0283 (11) 0.0239 (11) 0.0084 (9) 0.0092 (9) 0.0086 (9)
C20 0.0189 (9) 0.0183 (10) 0.0214 (10) 0.0018 (8) 0.0050 (8) 0.0026 (8)
O1 0.0140 (6) 0.0191 (7) 0.0203 (7) −0.0013 (5) 0.0038 (5) −0.0070 (6)
O2 0.0140 (7) 0.0240 (8) 0.0311 (8) −0.0001 (6) 0.0009 (6) −0.0115 (7)
O3 0.0165 (7) 0.0174 (7) 0.0347 (8) −0.0001 (6) −0.0045 (6) 0.0113 (6)
O4 0.0192 (7) 0.0144 (6) 0.0207 (7) −0.0034 (6) 0.0020 (6) 0.0032 (6)
O5 0.0151 (7) 0.0192 (7) 0.0217 (7) −0.0001 (6) 0.0042 (5) −0.0051 (6)
O6 0.0163 (7) 0.0185 (7) 0.0248 (7) −0.0022 (5) −0.0003 (6) −0.0061 (6)
O7 0.0170 (7) 0.0193 (7) 0.0240 (7) 0.0020 (6) 0.0046 (6) 0.0070 (6)
O8 0.0184 (7) 0.0180 (7) 0.0215 (7) 0.0052 (6) 0.0044 (5) 0.0041 (6)
Geometric parameters (Å, º)
C1—O2 1.224 (2) C16—C17 1.391 (3)
C1—O1 1.309 (2) C17—C18 1.385 (3)
C1—C2 1.519 (3) C18—C19 1.386 (3)
C2—C3 1.522 (3) C19—C20 1.392 (3)
C2—C5 1.526 (3) C2—H2 1.1097
C3—C4 1.508 (3) C3—H3A 0.9776
C4—O4 1.216 (2) C3—H3B 0.9586
C4—O3 1.318 (2) C6—H6 1.0135
C5—C10 1.396 (3) C7—H7 0.9601
C6—C7 1.384 (3) C9—H9 0.9985
C7—C8 1.396 (3) C10—H10 0.9941
C8—C9 1.380 (3) C12—H12 0.9731
C9—C10 1.390 (3) C13—H13A 0.9993
C11—O6 1.217 (2) C13—H13B 0.9818
C11—O5 1.320 (2) C16—H16 0.9465
C11—C12 1.514 (3) C17—H17 1.0306
C12—C15 1.530 (3) C18—H18 0.9795
C12—C13 1.533 (3) C19—H19 1.0629
C13—C14 1.502 (3) C20—H20 0.9722
C14—O8 1.225 (2) O1—H1O 0.9167
C14—O7 1.316 (2) O3—H3O 0.9207
C15—C16 1.389 (3) O5—H5O 0.8935
C15—C20 1.397 (3) O7—H7O 0.9150
O2—C1—O1 123.78 (18) C5—C2—H2 112.6
O2—C1—C2 120.87 (18) C4—C3—H3A 108.5
O1—C1—C2 115.31 (16) C2—C3—H3A 108.0
C1—C2—C3 113.90 (16) C4—C3—H3B 104.7
C1—C2—C5 107.89 (15) C2—C3—H3B 111.7
C3—C2—C5 110.29 (15) H3A—C3—H3B 108.8
C4—C3—C2 114.97 (15) C7—C6—H6 120.5
O4—C4—O3 125.21 (18) C5—C6—H6 119.0
O4—C4—C3 124.32 (17) C6—C7—H7 120.2
O3—C4—C3 110.47 (16) C8—C7—H7 119.6
C10—C5—C6 118.72 (18) C9—C8—H8 123.1
C10—C5—C2 120.62 (18) C7—C8—H8 117.3
C6—C5—C2 120.65 (17) C8—C9—H9 117.9
C7—C6—C5 120.44 (19) C10—C9—H9 121.1
C6—C7—C8 120.3 (2) C9—C10—H10 118.0
C9—C8—C7 119.6 (2) C5—C10—H10 121.4
C8—C9—C10 120.4 (2) C11—C12—H12 106.1
C9—C10—C5 120.5 (2) C15—C12—H12 105.3
O6—C11—O5 124.74 (18) C13—C12—H12 113.7
O6—C11—C12 121.70 (17) C14—C13—H13A 108.1
O5—C11—C12 113.54 (16) C12—C13—H13A 110.5
C11—C12—C15 110.31 (15) C14—C13—H13B 107.4
C11—C12—C13 109.35 (15) C12—C13—H13B 104.0
C15—C12—C13 111.84 (15) H13A—C13—H13B 114.6
C14—C13—C12 112.29 (15) C15—C16—H16 118.3
O8—C14—O7 123.81 (17) C17—C16—H16 120.2
O8—C14—C13 122.93 (17) C18—C17—H17 117.4
O7—C14—C13 113.26 (16) C16—C17—H17 122.3
C16—C15—C20 119.14 (17) C17—C18—H18 116.3
C16—C15—C12 120.19 (17) C19—C18—H18 124.0
C20—C15—C12 120.67 (17) C18—C19—H19 120.5
C15—C16—C17 120.69 (19) C20—C19—H19 118.8
supporting information
sup-5 Acta Cryst. (2003). E59, o319–o320
C17—C18—C19 119.63 (19) C15—C20—H20 120.4
C18—C19—C20 120.6 (2) C1—O1—H1O 112.5
C19—C20—C15 119.90 (19) C4—O3—H3O 113.4
C1—C2—H2 101.1 C11—O5—H5O 112.0
C3—C2—H2 110.8 C14—O7—H7O 111.2
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1—H1O···O8i 0.92 1.75 2.659 (2) 170
O3—H3O···O6ii 0.92 1.71 2.627 (2) 177
O5—H5O···O4iii 0.89 1.82 2.714 (2) 178
O7—H7O···O2iv 0.92 1.70 2.615 (2) 178