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(RS)-Phenyl­succinic acid, C10H10O4, crystallizes with two molecules of the acid in the asymmetric unit. In the crystal structure, the carboxyl groups of each acid mol­ecule are connected to those of adjacent mol­ecules via hydrogen bonds; each mol­ecule is connected to two other mol­ecules, forming chains. Crystals of (RS)-phenyl­succinic acid are twinned. Data for one twin domain could be obtained and the structure could be solved with satisfactory results.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005658/na6211sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005658/na6211Isup2.hkl
Contains datablock I

CCDC reference: 209958

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.056
  • wR factor = 0.133
  • Data-to-parameter ratio = 13.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.49 From the CIF: _reflns_number_total 3445 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4310 Completeness (_total/calc) 79.93% Alert A: < 85% complete (theta max?)
Yellow Alert Alert Level C:
PLAT_320 Alert C Check Hybridisation of C(13) in Main Residue ?
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Phenylsuccinic acid (PSA) is used as a resolving agent in classical resolutions of pharmaceuticals (Bayley & Vaidya, 1992; Kozma, 2002). In order to be able to study and understand the solid-state properties of PSA and its interactions with solvents or with other reagents commonly used, it is essential to know the cystal structure of both the pure enantiomer and the racemate. Generally, there are three classes of racemates in the solid state (Jacques et al., 1994). Two classes contain both enantiomers mixed in the crystal lattice: the racemic compounds that have an ordered, alternating (R)- and (S)-enantiomer distribution in the structure and the solid solutions which have both enantiomers randomly mixed in the lattice. The third class of racemates, the racemic conglomerate, has an identical crystal lattice to that of the pure enantiomer. This means that although the whole crystal mass is racemic, each crystal itself is enantiomerically pure. Most chiral substances form a racemic compound, while approximately 5–10% form racemic conglomerates. The racemic conglomerate can be separated by direct, seeded crystallization methods. The racemic compound, on the other hand, must be separated by other methods such as diastereomeric salt formation, chromatography or kinetic resolutions. The stability of racemic compounds versus conglomerates has been extensively discussed in the literature. Often, hydrogen bonds within the structures are identified as the key factor influencing the stability of the structures (Böcksei et al., 1996; Brock, 1996; Kinbara et al., 1996; Li et al., 1999). Since the structures of neither (S)- nor (RS)-PSA were known, we grew crystals of both compounds in order to determine to which class of racemates PSA belongs, and how the acid molecules are connected in respective structure. The structure of (S)-PSA was published earlier (Fischer & Profir, 2003). The structure of (RS)-PSA, (I), is presented here.

Fig. 1 shows the unit cell of (RS)-PSA in a view along the crystallographic a axis. The structure contains two molecules (R)-PSA per asymmetric unit, which are shown in Figs. 2 and 3. Since the structure is centrosymmetric, the opposite enantiomer of the respective molecule is generated. Thus, (RS)-PSA belongs to the first class of racemates mentioned above, the racemic compounds with ordered distribution of the molecules. In (RS)-PSA, each (R)-molecule is connected to two adjacent (S)-molecules via hydrogen bonds and vice versa. These hydrogen bonds are built in such a way that both carboxyl groups bind to one other carboxyl group of the other molecule. That way, chains of molecules are formed as shown in Fig. 4. There are two crystallographically different chains in this structure, formed by the two different molecules in the asymmetric unit. The geometry of the molecules is unexceptional, although one quite close H···H contact of 2.03 Å can be observed. This is, however, still slightly larger than the sum of the van der Waals radii (2.0 Å) given by Baur (1972).

Experimental top

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 twinned crystals of (RS)-PSA.

Refinement top

Reflection data for one twin domain was obtained using EVALCCD (Duisenberg, 1998). Orientation matrices for both twin domains were determined. During integration, all overlapping reflections were removed. One fifth of the observable reflections were lost due to overlap. A structural model was obtained using direct methods. All H atoms were located from a difference Fourier map. They were refined with a riding model, with Uiso equal to 1.2Ueq of the non-H atom to which they are attached.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: EVALCCD (Duisenberg, 1998); data reduction: EVALCCD (Duisenberg, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: maXus (Mackay et al., 1998).

Figures top
[Figure 1] Fig. 1. The unit-cell contents of (RS)-PSA, viewed along a. H atoms have been omitted.
[Figure 2] Fig. 2. One of the two crystallographically independent molecules in the structure of (RS)-PSA. Displacement ellipsoids are drawn at the 70% probability level.
[Figure 3] Fig. 3. The second of the two crystallographically independent molecules in the structure of (RS)-PSA. Displacement ellipsoids are drawn at the 70% probability level.
[Figure 4] Fig. 4. The chains formed by the molecules of (RS)-PSA. Only the carboxy H atoms are drawn. Hydrogen bonds are indicated by dashed lines.
(RS)-phenylsuccinic acid top
Crystal data top
C10H10O4V = 944 (2) Å3
Mr = 194.19Z = 4
Triclinic, P1Dx = 1.366 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.428 (12) ÅCell parameters from 154 reflections
b = 10.368 (6) Åθ = 4.2–21.4°
c = 17.625 (9) ŵ = 0.11 mm1
α = 102.82 (5)°T = 100 K
β = 94.10 (14)°Needle, colourless
γ = 100.50 (9)°0.30 × 0.15 × 0.1 mm
Data collection top
Nonius KappaCCD
diffractometer
Rint = 0.075
Radiation source: fine-focus sealed tubeθmax = 27.5°, θmin = 4.6°
ϕ and ω scansh = 66
14054 measured reflectionsk = 1213
3445 independent reflectionsl = 2222
2223 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.133 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.7275P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
3445 reflectionsΔρmax = 0.29 e Å3
253 parametersΔρmin = 0.29 e Å3
0 restraints
Crystal data top
C10H10O4γ = 100.50 (9)°
Mr = 194.19V = 944 (2) Å3
Triclinic, P1Z = 4
a = 5.428 (12) ÅMo Kα radiation
b = 10.368 (6) ŵ = 0.11 mm1
c = 17.625 (9) ÅT = 100 K
α = 102.82 (5)°0.30 × 0.15 × 0.1 mm
β = 94.10 (14)°
Data collection top
Nonius KappaCCD
diffractometer
2223 reflections with I > 2σ(I)
14054 measured reflectionsRint = 0.075
3445 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.03Δρmax = 0.29 e Å3
3445 reflectionsΔρmin = 0.29 e Å3
253 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
xyzUiso*/Ueq
C10.9239 (5)0.5664 (3)0.40993 (15)0.0185 (6)
C20.8656 (4)0.6240 (3)0.34009 (14)0.0191 (6)
C30.6931 (5)0.7255 (3)0.36170 (14)0.0212 (6)
C40.8243 (5)0.8446 (3)0.42450 (15)0.0197 (6)
C50.7569 (4)0.5110 (3)0.26821 (14)0.0195 (6)
C60.8921 (5)0.4912 (3)0.20376 (15)0.0228 (6)
C70.7971 (5)0.3881 (3)0.13808 (15)0.0273 (6)
C80.5674 (5)0.3039 (3)0.13622 (15)0.0266 (6)
C90.4297 (5)0.3227 (3)0.20025 (16)0.0262 (6)
C100.5238 (5)0.4258 (3)0.26592 (15)0.0229 (6)
C110.9419 (5)0.9179 (3)0.08494 (15)0.0218 (6)
C120.8988 (5)0.8579 (3)0.15487 (15)0.0219 (6)
C130.6222 (5)0.7821 (3)0.14725 (15)0.0234 (6)
C140.5678 (5)0.6596 (3)0.08050 (15)0.0229 (6)
C150.9685 (4)0.9705 (3)0.22895 (14)0.0196 (6)
C160.8325 (5)1.0741 (3)0.24376 (16)0.0257 (6)
C170.9015 (5)1.1779 (3)0.31043 (17)0.0297 (7)
C181.1056 (5)1.1794 (3)0.36340 (16)0.0273 (6)
C191.2413 (5)1.0762 (3)0.34896 (15)0.0275 (6)
C201.1724 (5)0.9727 (3)0.28243 (15)0.0238 (6)
O11.1525 (3)0.53905 (19)0.41591 (10)0.0232 (4)
O20.7673 (3)0.54591 (18)0.45501 (10)0.0226 (4)
O30.6901 (3)0.93933 (19)0.44148 (11)0.0281 (5)
O41.0372 (3)0.85106 (18)0.45636 (11)0.0251 (4)
O50.3420 (3)0.5859 (2)0.07813 (11)0.0302 (5)
O60.7207 (3)0.63323 (19)0.03416 (11)0.0272 (5)
O71.1799 (3)0.9357 (2)0.07038 (11)0.0278 (5)
O80.7717 (3)0.9502 (2)0.04812 (11)0.0257 (5)
H21.01520.66020.32150.023*
H3A0.63180.75250.31250.025*
H3B0.55000.68730.37970.025*
H61.03810.54270.20270.027*
H70.90800.38210.09720.033*
H80.50580.22850.08980.032*
H90.27140.25440.20230.031*
H100.43070.43230.31350.027*
H121.02700.79900.16930.026*
H13A0.61040.73640.19500.028*
H13B0.50210.84800.13220.028*
H160.68031.07750.20980.031*
H170.79231.24110.31540.036*
H181.16091.26510.41280.033*
H191.37871.06800.38980.033*
H201.25430.90000.27510.029*
H1O1.19530.50080.46330.028*
H3O0.78341.02300.47720.034*
H5O0.31700.50740.04490.036*
H7O1.20670.98600.02910.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0208 (14)0.0146 (14)0.0167 (13)0.0002 (10)0.0019 (10)0.0010 (10)
C20.0198 (13)0.0221 (14)0.0156 (13)0.0026 (10)0.0017 (10)0.0064 (10)
C30.0244 (14)0.0236 (15)0.0163 (13)0.0055 (11)0.0008 (10)0.0069 (11)
C40.0242 (15)0.0189 (14)0.0178 (13)0.0039 (11)0.0026 (10)0.0087 (11)
C50.0219 (14)0.0193 (14)0.0179 (13)0.0037 (11)0.0011 (10)0.0073 (11)
C60.0233 (14)0.0246 (15)0.0212 (14)0.0026 (11)0.0006 (10)0.0092 (11)
C70.0337 (16)0.0315 (17)0.0185 (14)0.0098 (13)0.0054 (11)0.0064 (12)
C80.0354 (16)0.0258 (16)0.0175 (14)0.0100 (12)0.0034 (11)0.0019 (11)
C90.0267 (15)0.0253 (16)0.0263 (15)0.0046 (11)0.0012 (11)0.0075 (12)
C100.0258 (15)0.0240 (15)0.0201 (14)0.0066 (11)0.0031 (10)0.0067 (11)
C110.0221 (15)0.0234 (15)0.0190 (14)0.0012 (11)0.0020 (10)0.0060 (11)
C120.0235 (14)0.0245 (15)0.0199 (14)0.0056 (11)0.0016 (10)0.0098 (11)
C130.0252 (15)0.0270 (16)0.0195 (14)0.0033 (11)0.0028 (10)0.0103 (12)
C140.0239 (15)0.0292 (16)0.0171 (14)0.0037 (12)0.0020 (11)0.0111 (12)
C150.0222 (14)0.0214 (14)0.0171 (13)0.0030 (11)0.0037 (10)0.0095 (11)
C160.0251 (15)0.0253 (16)0.0288 (16)0.0058 (12)0.0012 (11)0.0108 (12)
C170.0324 (16)0.0264 (16)0.0343 (17)0.0098 (12)0.0072 (12)0.0116 (13)
C180.0355 (16)0.0215 (15)0.0239 (15)0.0024 (12)0.0055 (12)0.0059 (12)
C190.0295 (16)0.0325 (17)0.0202 (14)0.0030 (12)0.0008 (11)0.0093 (12)
C200.0247 (14)0.0282 (16)0.0217 (14)0.0092 (11)0.0036 (11)0.0097 (12)
O10.0220 (10)0.0305 (11)0.0210 (10)0.0096 (8)0.0023 (7)0.0113 (8)
O20.0210 (10)0.0298 (11)0.0190 (10)0.0050 (8)0.0023 (7)0.0100 (8)
O30.0276 (10)0.0211 (11)0.0313 (11)0.0065 (8)0.0050 (8)0.0010 (8)
O40.0251 (10)0.0237 (11)0.0255 (11)0.0055 (8)0.0034 (8)0.0049 (8)
O50.0268 (11)0.0263 (11)0.0318 (12)0.0022 (8)0.0060 (8)0.0007 (9)
O60.0253 (10)0.0307 (11)0.0231 (11)0.0006 (8)0.0062 (8)0.0042 (8)
O70.0206 (10)0.0418 (13)0.0276 (11)0.0065 (8)0.0048 (8)0.0213 (9)
O80.0223 (10)0.0368 (12)0.0230 (10)0.0062 (8)0.0033 (8)0.0172 (9)
Geometric parameters (Å, º) top
C1—O21.226 (4)C16—C171.381 (4)
C1—O11.325 (4)C17—C181.392 (5)
C1—C21.521 (4)C18—C191.394 (4)
C2—C51.520 (4)C19—C201.378 (4)
C2—C31.536 (4)C2—H20.9429
C3—C41.490 (4)C3—H3A1.0205
C4—O41.232 (4)C3—H3B0.9163
C4—O31.321 (3)C6—H60.8753
C5—C61.393 (4)C7—H70.9706
C5—C101.397 (4)C8—H80.9867
C6—C71.383 (4)C9—H91.0171
C7—C81.379 (5)C10—H101.0059
C8—C91.395 (4)C12—H121.0583
C9—C101.382 (4)C13—H13A1.0545
C11—O81.229 (4)C13—H13B1.0862
C11—O71.323 (4)C16—H160.9960
C11—C121.513 (4)C17—H170.9550
C12—C151.518 (4)C18—H181.0769
C12—C131.544 (5)C19—H191.0267
C13—C141.495 (4)C20—H200.9326
C14—O61.229 (4)O1—H1O1.0310
C14—O51.313 (4)O3—H3O0.9784
C15—C201.395 (4)O5—H5O0.8719
C15—C161.400 (4)O7—H7O0.9886
O2—C1—O1124.3 (2)C3—C2—H2113.7
O2—C1—C2121.6 (2)C4—C3—H3A112.1
O1—C1—C2114.1 (2)C2—C3—H3A109.3
C5—C2—C1110.5 (2)C4—C3—H3B107.5
C5—C2—C3113.3 (2)C2—C3—H3B111.5
C1—C2—C3109.5 (2)H3A—C3—H3B105.4
C4—C3—C2111.0 (2)C7—C6—H6117.3
O4—C4—O3124.8 (3)C5—C6—H6122.3
O4—C4—C3121.8 (3)C8—C7—H7126.4
O3—C4—C3113.4 (2)C6—C7—H7113.7
C6—C5—C10119.4 (3)C7—C8—H8118.9
C6—C5—C2119.6 (2)C9—C8—H8120.8
C10—C5—C2121.0 (3)C10—C9—H9118.8
C7—C6—C5120.5 (3)C8—C9—H9120.7
C8—C7—C6119.9 (3)C9—C10—H10118.9
C7—C8—C9120.2 (3)C5—C10—H10120.8
C10—C9—C8120.0 (3)C11—C12—H12117.0
C9—C10—C5120.0 (3)C15—C12—H1296.6
O8—C11—O7124.6 (3)C13—C12—H12111.8
O8—C11—C12122.3 (2)C14—C13—H13A100.4
O7—C11—C12113.0 (2)C12—C13—H13A105.6
C11—C12—C15108.7 (2)C14—C13—H13B105.5
C11—C12—C13110.0 (2)C12—C13—H13B107.7
C15—C12—C13112.1 (2)H13A—C13—H13B125.8
C14—C13—C12111.3 (2)C17—C16—H16115.7
O6—C14—O5125.2 (3)C15—C16—H16124.1
O6—C14—C13122.6 (2)C16—C17—H17112.9
O5—C14—C13112.2 (3)C18—C17—H17126.9
C20—C15—C16119.3 (3)C17—C18—H18117.9
C20—C15—C12120.1 (2)C19—C18—H18122.0
C16—C15—C12120.6 (2)C20—C19—H19117.8
C17—C16—C15120.1 (3)C18—C19—H19121.9
C16—C17—C18120.1 (3)C19—C20—H20119.7
C17—C18—C19119.9 (3)C15—C20—H20119.6
C20—C19—C18119.9 (3)C1—O1—H1O115.0
C19—C20—C15120.6 (3)C4—O3—H3O113.9
C5—C2—H298.4C14—O5—H5O113.3
C1—C2—H2111.0C11—O7—H7O111.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i1.031.632.651 (3)171
O3—H3O···O4ii0.981.652.620 (4)171
O5—H5O···O6iii0.871.752.612 (3)170
O7—H7O···O8iv0.991.642.625 (3)172
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+1; (iii) x+1, y+1, z; (iv) x+2, y+2, z.

Experimental details

Crystal data
Chemical formulaC10H10O4
Mr194.19
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)5.428 (12), 10.368 (6), 17.625 (9)
α, β, γ (°)102.82 (5), 94.10 (14), 100.50 (9)
V3)944 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.30 × 0.15 × 0.1
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
14054, 3445, 2223
Rint0.075
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.133, 1.03
No. of reflections3445
No. of parameters253
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.29

Computer programs: COLLECT (Nonius, 1999), EVALCCD (Duisenberg, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), maXus (Mackay et al., 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i1.031.632.651 (3)171
O3—H3O···O4ii0.981.652.620 (4)171
O5—H5O···O6iii0.871.752.612 (3)170
O7—H7O···O8iv0.991.642.625 (3)172
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+1; (iii) x+1, y+1, z; (iv) x+2, y+2, z.
 

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