Lithium hydrogen (RS) phenylsuccinate

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Andreas Fischer Li+C₁₀H₉O₄ÿ doi:10.1107/S1600536805001017 Acta Cryst.(2005). E61, m320±m322

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Lithium hydrogen (

RS

)-phenylsuccinate

Andreas Fischer

Inorganic Chemistry, Royal Institute of Technology, 100 44 Stockholm, Sweden

Correspondence e-mail: andif@inorg.kth.se

Key indicators Single-crystal X-ray study

T= 200 K

Mean(C±C) = 0.004 AÊ Disorder in main residue

Rfactor = 0.050

wRfactor = 0.130

Data-to-parameter ratio = 10.6

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

From a solution of lithium hydroxide and (RS)-phenylsuccinic acid in water, crystals of the title compound, Li+_C

10H9O4ÿ,

were obtained. The basic structural feature is an approxi-mately square-planar centrosymmetric Li2O2 unit. The Li

atoms in this unit are coordinated by further O atoms, yielding a distorted tetrahedral geometry around Li.

Comment

Carboxylic acids exhibit a fascinating wealth of structures, due to the ability of the acid molecules to form different hydrogen bonds. Possible acceptor atoms are the O atom of another carboxyl group or other acceptors with lone pairs, such as the O atoms of OH groups. Despite this variability, the structural chemistry of many simple carboxylic acids and their salts has not been explored thoroughly. This is particularly true of some technologically important acids, such as mandelic acid and phenylsuccinic acid.

Recently, we determined the structures of both (S)- (Fischer & Pro®r, 2003a) and (RS)-phenylsuccinic acid (Fischer & Pro®r, 2003b). The structural chemistry of the salts of this acid is essentially uninvestigated and we decided to prepare some salts of both the racemate and the pure enantiomer. The structure of the lithium hydrogen salt of (RS)-phenylsuccinic acid, (I), is presented here.

The structure of (I) contains one LiH(RS)-phenylsuccinate unit in the asymmetric unit (Fig. 1). The geometry of the hydrogen (RS)-phenylsuccinate anion is unexceptional. The Li+_{cation is located close to an inversion centre. Coordination}

by one carboxyl O atom thus yields a centrosymmetric LiÐ OÐLiÐO unit (Fig. 2), where each Li+_{cation is coordinated}

by two (symmetry-equivalent) bridging acid molecules. The Li Liiv_{separation is 2.766 (9) AÊ (see Table 1 for symmetry}

code). The coordination sphere is completed by two O atoms from two other carboxyl groups, yielding a distorted tetra-hedral coordination around Li+_{. The bond lengths are in the}

range 1.885 (5)±2.006 (4) AÊ and the OÐLiÐO angles deviate

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signi®cantly from the ideal tetrahedral angle [OÐLiÐO 91.01 (19)±121.2 (2)_{]. An extended sheet structure}

propa-gating in the (100) plane arises from this connectivity, and OÐ H O hydrogen bonds (Table 2) help to stabilize this arrangement.

There are a wealth of structures where Li is four-coordi-nated by oxygen. However, many of these compounds involve ligands such as diethyl ether and tetrahydrofuran. The number of lithium carboxylates, where Li is coordinated only by the O atoms of different carboxy groups, is much smaller. Never-theless, there are a number of different structures that can be compared with that of (I) and a few examples exemplifying different Li geometries are distorted tetrahedral [bis(2

-citrato)aqualithiumantimony dihydrate (Smith et al., 1993); lithium succinate (Klapper & KuÈppers, 1973)], square-pyra-midal [bis(2-dihydrogen dl-malato-O,O0,O00

)-bis(trihydro-gendl-malato-O,O0_{)dilithium (Fleck}_{et al}_{., (2001)], distorted}

trigonal±pyramidal {catena-[diaquabis(3-citrato-O,O0

)di-lithium] (Tobon-Zapataet al., 1998); lithium hydrogen malate (Kirfel et al., 1983)} and distorted octahedral {catena -[2-aqua-2-(+)-tartrato-O,O0,O00,O000-2-tartrato-O,O0,O00

-aquadilithium] (Bott et al., 1994)}. In some structures, crys-tallographically independent Li+_{cations with different}

coor-dination geometries are present. This is the case in dilithium malonate (Soriano-Garcia & Rao, 1983), where one Li atom possesses a distorted tetrahedral coordination, while the other Li atom has a strongly distorted trigonal±bipyramidal environment. Apparently, the coordination geometry around the Li atom in this type of compound depends strongly on the stereochemistry of the acid.

Experimental

A 1MLiOH solution was prepared by dissolving anhydrous lithium hydroxide (Alfa Aesar, 98%) in demineralized water. A quantity of this solution (1 ml) was further diluted with demineralized water

(9 ml). To this solution, (RS)-phenylsuccinic acid (0.001 mol; Aldrich, 99%) was added. The solution was then poured into a small beaker which was placed in a desiccator over potassium hydroxide. After a couple of days, the solution had evaporated, leaving crystals of (I) in almost quantitative yield.

Crystal data

Li+_C10H9Oÿ 4

Mr= 200.12

Monoclinic,P21/c a= 14.350 (4) AÊ

b= 5.3060 (9) AÊ

c= 12.672 (5) AÊ = 109.96 (2)

V= 906.9 (5) AÊ3

Z= 4

Dx= 1.466 Mg mÿ3

MoKradiation Cell parameters from 25

re¯ections = 5.2±16.0 = 0.11 mmÿ1

T= 200 K

Irregular fragment, colourless 0.200.100.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer

'and!scans

6944 measured re¯ections 1533 independent re¯ections 1130 re¯ections withI> 2(I)

Rint= 0.086 max= 24.7

h=ÿ16!16

k=ÿ4!6

l=ÿ14!14

Refinement

Re®nement onF2

R[F2_{> 2}₍_F2_{)] = 0.050}

wR(F2_{) = 0.130}

S= 1.07 1533 re¯ections 145 parameters

H-atom parameters constrained

w= 1/[2₍_F

o2) + (0.0488P)2 + 0.5204P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.26 e AÊÿ3

min=ÿ0.25 e AÊÿ3

metal-organic papers

Acta Cryst.(2005). E61, m320±m322 Andreas Fischer Li+C₁₀H₉O₄ÿ

m321

Figure 1

The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii. Both disorder components are shown.

Figure 2

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Table 1

Selected geometric parameters (AÊ,_). LiÐO1 1.881 (5) LiÐO3i _{1.940 (4)} LiÐO2ii _{1.954 (5)}

LiÐO2iii _{2.006 (4)} Li Liiv _{2.776 (9)}

O1ÐLiÐO3i _{109.9 (2)} O1ÐLiÐO2ii _{114.0 (2)} O3i_ÐLiÐO2ii _{121.2 (2)} O1ÐLiÐO2iii _{109.9 (2)}

O3i_ÐLiÐO2iii _{108.7 (2)} O2ii_ÐLiÐO2iii _{91.01 (19)} Liv_ÐO2ÐLiiii _{88.99 (19)}

Symmetry codes: (i)ÿx2;y1

2;ÿz12; (ii)x;y1;z; (iii)ÿx2;ÿy;ÿz1; (iv)

ÿx2;ÿy1;ÿz1; (v)x;yÿ1;z.

Table 2

Hydrogen-bond geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

O4aÐH4a O2vi _0.98 _1.98 _{2.918 (4)} ₁₆₀ O4bÐH4b O1vii _0.95 _1.86 _{2.686 (4)} ₁₄₅

Symmetry codes: (vi)ÿx2;yÿ1_2;_ÿ_z1

2; (vii)x;ÿyÿ12;zÿ12.

All H atoms were located in a difference Fourier map and were re®ned using a riding model in their as-found relative positions, with CÐH distances in the range 0.88±1.11 AÊ, and with the constraint Uiso(H) = 1.2Ueq(carrier atom) applied in all cases. For atom O4, a

structure model with a split position was applied [site occupancy factors: 0.35 for atom O4Aand 0.65 for atom O4B].

Data collection: COLLECT (Nonius, 1999); cell re®nement: DIRAX/LSQ (Duisenberg, 1992); data reduction: EVALCCD

(Duisenberg et al., 2003); 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 publi-cation:maXus(Mackayet al., 1999).

The Swedish Research Council (VR) is acknowledged for ®nancal support and for funding of the single-crystal diffractometer.

References

Bott, R. C., Sagatys, D. S., Smith, G., Byriel, K. A. & Kennard, C. H. L. (1994).

Polyhedron,13, 3135±3141.

Brandenburg, K. (2001).DIAMOND. Release 2.1e. Crystal Impact GbR, Bonn, Germany.

Duisenberg, A. J. M. (1992).J. Appl. Cryst.25, 92±96.

Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).

J. Appl. Cryst.36, 220±229.

Fischer, A. & Pro®r, V. M. (2003a).Acta Cryst.E59, o319±o320. Fischer, A. & Pro®r, V. M. (2003b).Acta Cryst.E59, o485±o487. Fleck, M., Tillmanns, E. & Bohaty, L. (2001).Z. Kristallogr.216, 633±645. Kirfel, A., Will, G., Recker, K., Wallrafen, F. & Zhangshou, G. (1983).Z.

Kristallogr.165, 117±125.

Klapper, H. & KuÈppers, H. (1973).Acta Cryst.B29, 21±26.

Mackay, S., Gilmore, C. J., Edwards, C., Stewart, N. & Shankland, K. (1999).

maXus. Nonius BV, Delft, The Netherlands, MacScience Co. Ltd., Japan, and University of Glasgow, Scotland.

Nonius (1999).COLLECT. Nonius BV, Delft, The Netherlands.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Smith, G., Sagatys, D. S., Bott, R. C. & Lynch, D. E. (1993).Polyhedron,12, 1491±1497.

Soriano-Garcia, M. & Rao, S. N. (1983).Acta Cryst.C39, 850±852.

Tobon-Zapata, G. E., Piro, O. E., Etcheverry, S. B. & Baran, E. J. (1998).Z. Anorg. Allg. Chem.624, 721±724.

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sup-1 Acta Cryst. (2005). E61, m320–m322

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Acta Cryst. (2005). E61, m320–m322 [https://doi.org/10.1107/S1600536805001017]

Lithium hydrogen (

RS

)-phenylsuccinate

Andreas Fischer

Lithium hydrogen (RS)-phenylsuccinate

Crystal data

Li+_·C 10H9O4−

Mr = 200.12 Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 14.350 (4) Å

b = 5.3060 (9) Å

c = 12.672 (5) Å

β = 109.96 (2)°

V = 906.9 (5) Å3

Z = 4

F(000) = 416

Dx = 1.466 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections

θ = 5.2–16.0°

µ = 0.11 mm−1

T = 200 K

Irregular, colourless 0.20 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Radiation source: fine-focus sealed tube

φ and ω scans

6944 measured reflections 1533 independent reflections

1130 reflections with I > 2σ(I)

Rint = 0.086

θmax = 24.7°, θmin = 4.5°

h = −16→16

k = −4→6

l = −14→14

Refinement

Refinement on F2

Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.050}

wR(F2_{) = 0.130}

S = 1.07 1533 reflections 145 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map H-atom parameters constrained

w = 1/[σ2₍_F

o2) + (0.0488P)2 + 0.5204P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.26 e Å−3

Δρmin = −0.25 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

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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq Occ. (<1)

C1 0.88212 (17) −0.1731 (5) 0.36512 (19) 0.0230 (5) C2 0.78350 (16) −0.2263 (5) 0.2719 (2) 0.0255 (6) C3 0.78476 (17) −0.4664 (5) 0.2077 (2) 0.0293 (6) C4 0.8533 (2) −0.4553 (5) 0.1429 (2) 0.0342 (6) C5 0.70464 (17) −0.2334 (5) 0.3271 (2) 0.0286 (6) C6 0.63121 (18) −0.0515 (6) 0.3024 (2) 0.0372 (7) C7 0.5609 (2) −0.0547 (6) 0.3549 (3) 0.0482 (8) C8 0.5639 (2) −0.2374 (7) 0.4324 (3) 0.0487 (9) C9 0.6366 (2) −0.4205 (6) 0.4580 (2) 0.0454 (8) C10 0.70616 (19) −0.4176 (6) 0.4045 (2) 0.0370 (7) Li 0.9935 (3) 0.3086 (9) 0.4232 (3) 0.0299 (10) O1 0.89720 (12) 0.0530 (3) 0.39444 (14) 0.0297 (5) O2 0.93943 (12) −0.3503 (3) 0.41067 (13) 0.0277 (4) O3 0.90745 (13) −0.2800 (4) 0.14312 (14) 0.0350 (5)

O4A 0.8770 (7) −0.6915 (18) 0.1205 (9) 0.060 (3) 0.35 O4B 0.8348 (3) −0.6400 (10) 0.0683 (3) 0.0424 (11) 0.65 H2 0.7668 −0.0822 0.2170 0.031*

H3A 0.8037 −0.6137 0.2630 0.035* H3B 0.7195 −0.5084 0.1545 0.035* H6 0.6366 0.0792 0.2359 0.045* H7 0.5091 0.0761 0.3378 0.058* H8 0.5179 −0.2335 0.4642 0.058* H9 0.6367 −0.5505 0.5205 0.054* H10 0.7551 −0.5579 0.4219 0.044*

H4A 0.9296 −0.7801 0.1030 0.072* 0.35 H4B 0.8815 −0.6089 0.0319 0.051* 0.65

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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O4B 0.059 (3) 0.035 (3) 0.043 (2) −0.015 (2) 0.0300 (19) −0.0126 (19)

Geometric parameters (Å, º)

C1—O2 1.253 (3) Li—O3i _{1.940 (4)}

C1—O1 1.253 (3) Li—O2ii _{1.954 (5)}

C1—C2 1.528 (3) Li—O2iii _{2.006 (4)}

C2—C3 1.515 (4) Li—Liiv _{2.776 (9)}

C2—C5 1.520 (3) O4A—O4B 0.778 (9) C3—C4 1.482 (3) C2—H2 1.0060 C4—O3 1.211 (3) C3—H3A 1.0226 C4—O4B 1.324 (5) C3—H3B 0.9747 C4—O4A 1.354 (10) C6—H6 1.1141 C5—C10 1.380 (4) C7—H7 0.9857 C5—C6 1.384 (4) C8—H8 0.8826 C6—C7 1.386 (4) C9—H9 1.0500 C7—C8 1.370 (4) C10—H10 0.9949 C8—C9 1.380 (4) O4A—H4A 0.9773 C9—C10 1.385 (4) O4B—H4B 0.949 Li—O1 1.881 (5)

O2—C1—O1 124.2 (2) O2ii_—Li—Liiv _{46.27 (14)}

O2—C1—C2 120.4 (2) O2iii_—Li—Liiv _{44.73 (12)}

O1—C1—C2 115.2 (2) C1—O1—Li 142.1 (2) C3—C2—C5 111.9 (2) C1—O2—Liv _{155.8 (2)}

C3—C2—C1 113.1 (2) C1—O2—Liiii _{113.90 (19)}

C5—C2—C1 106.73 (19) Liv_—O2—Liiii _{88.99 (19)}

C4—C3—C2 113.3 (2) C4—O3—Livi _{138.5 (2)}

O3—C4—O4B 122.8 (3) C3—C2—H2 108.1 O3—C4—O4A 120.3 (5) C5—C2—H2 107.4 O4B—C4—O4A 33.8 (4) C1—C2—H2 109.4 O3—C4—C3 125.2 (2) C4—C3—H3A 109.8 O4B—C4—C3 110.9 (3) C2—C3—H3A 108.9 O4A—C4—C3 109.9 (5) C4—C3—H3B 106.7 C10—C5—C6 118.7 (2) C2—C3—H3B 112.3 C10—C5—C2 120.7 (2) H3A—C3—H3B 105.5 C6—C5—C2 120.5 (2) C5—C6—H6 111.2 C5—C6—C7 120.4 (3) C7—C6—H6 128.3 C8—C7—C6 120.2 (3) C8—C7—H7 119.5 C7—C8—C9 120.2 (3) C6—C7—H7 120.3 C8—C9—C10 119.4 (3) C7—C8—H8 117.7 C5—C10—C9 121.1 (3) C9—C8—H8 122.1 O1—Li—O3i _{109.9 (2)} _C8—C9—H9 _116.5

O1—Li—O2ii _{114.0 (2)} _{C10—C9—H9} _124.1

O3i_—Li—O2ii _{121.2 (2)} _{C5—C10—H10} _121.7

O1—Li—O2iii _{109.9 (2)} _{C9—C10—H10} _117.1

O3i_—Li—O2iii _{108.7 (2)} _{O4B—O4A—H4A} _114.4

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O1—Li—Liiv _{122.2 (3)} _{C4—O4B—H4A} _102.7

O3i_—Li—Liiv _{126.7 (3)}

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O4a—H4a···O2vi _0.98 _1.98 _{2.918 (4)} ₁₆₀

O4b—H4b···O1vii _0.95 _1.86 _{2.686 (4)} ₁₄₅

Lithium hydrogen (RS) phenyl­succinate

metal-organic papers

m320

Lithium hydrogen (

RS

)-phenylsuccinate

metal-organic papers

m321

metal-organic papers

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supporting information

Lithium hydrogen (

RS

)-phenylsuccinate

Andreas Fischer

supporting information

supporting information

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Lithium hydrogen (RS) phenylsuccinate