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Univalent metal ion α-hydroxy and interactions: Part 9. Preparation and crystal structures of lithium hydrogen (+)-tartrate monohydrate, potassium (+)-tartrate hemihydride and thallium(I) (+)-tartrate
Po/yhedron Vol. 13, No. 22, pp. 31353141, 1994 Copyright 0 1994 Elxvier Science Ltd printed in Great Britain. All rights mewed 0277-5387j94 $7.00+0.00
Pergamon
UNIVALENT METAL ION a-HYDROXY ACID INTERACTIONS: PART 9.* PREPARATION AND CRYSTAL STRUCTURES OF LITHIUM HYDROGEN (+)-TARTRATE MONOHYDRATE, POTASSIUM (+)-TARTRATE HEMJHYDRATE AND THALLIUM(I) (+)-TARTRATE RAYMOND
C. BOTT,
DALIUS
S. SAGATYS
and GRAHAM
School of Chemistry, Queensland University of Technology, 400 1, Australia
SMITH?
P.O. Box 2434, Brisbane,
and KARL A. BYRIEL
and COLIN
H. L. KENNARD
Department of Chemistry, The University of Queensland, Brisbane, 4072, Australia (Received 3 December 1993; accepted 29 March 1994) Abstract-The
univalent metal ion compounds of (+)-tartaric acid, lithium hydrogen (+)-tartrate monohydrate (l), potassium (+)-tartrate hemihydrate (2) and thallium (+)-tartrate (3) have been prepared and their structures determined by X-ray diffraction methods. All form network polymer structures similar to the other group one metal tartrates. However, (1) is based on a dimeric repeating unit, with two independent but different five-coordinate square pyramidal lithium centres, [L&O, 1.971-2.322(8) A]. Although both centres involve (+)-tartrate residues in a-hydroxycarboxyl bis-coordinate interactions, one centre has two, the other has one and is also coordinated to both waters (one bridging). The protonated carboxylic acid groups are uncoordinated but hydrogen bonded in both inter- and intra-dimer associations. Potassium (+)-tartrate hemihydrate (2) has two independent and different distorted octahedral potassium centres. About the first, there are five oxygens from (+)-tartrate residues and one from a water which bridges to another symmetry generated potassium. The second potassium has six bonds to (+)-tartrate oxygens, including a j?-hydroxycarboxyl chelate ring, with a K-O range of 2.71 l(2) 2.988(3) A. An unusual feature is a carboxyl oxygen giving a three-centre bonding system to three separate potassium ions. The polymeric structure of thallium(I) (+)-tartrate (3) is based upon two different five-coordinate thallium centres [Tl-O range, 2.59(3)-2.96(2) A]. About one, bonds are to three oxygens from one (+)-tartrate residue (one carboxyl, two hydroxyl), and two from a symmetric bidentate carboxylato-(0,O’) group of a bridging (+)-tartrate. The bonded hydroxyl also bridges to the second Tl [Tl . . . Tl, 3.519(2) A];]. Completing the bonding to this second Tl are oxygens from four different tartrate residues. Crystallographic and analytical data are also provided for silver(I) (+)-tartrate (4).
Due to an interest in our laboratories in the associative role of the univalent metal cations (primarily Group 1) in the stabilization of trivalent Group 15
* Part 8 : ref. 2. 7 Author to whom correspondence should be addressed.
(As, Sb, Bi) (+)-tartrate complex anion species, the structural systematics of both the normal and the acid tartrate salts of these univalent cations have been studied using infrared spectroscopic and Xray diffraction methods. Although this series is generally well described structurally, most of the literature is quite recent, e.g. Na(HC4H40&’
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3136
R. C. BOTT et al.
Na(HC4H.,06) * Hz0 :’ K(HC4H406) :3 Rb(HC4H4 O&“ CS(HC~H~O,J,~ together with the analogous Tl(1) and Ag(1) compounds Tl(HC4H406) and Ag(HC,H,O,) - H20.’ Despite this, the structures of some members of the normal and acid salt series have not been reported in the crystallographic literature. Reported here are the structures of lithium hydrogen (+)-tartrate monohydrate, [Li,(HC, H40& 02H,O], (l), potassium (+)-tartrate hemihydrate, [KZ(C4H406). OSH,O], (2), (useful as the pharmaceutical reagent ‘soluble tartar’6) and thallium(I) (+)-tartrate [T12(C4H406)]n (3). Crystal data are also provided for silver(I) (+)tartrate [AgZ(C4H@6)]n (4).
A, /I = 90.27(5)“, V = 339.6(5) A3, Z = 2, DC = 3.558 g cmp3, Dm = 3.60 g cme3, F(OO0) = 340, p(Mo-K,) = 53.2 cm-‘, T = 298(2) K.
X-ray data collection, structure solution and rejinement
X-ray data were collected on an Enraf-Nonius four-circle diffractometer using graphite crystal monochromated MO-KU radiation (J, = 0.71073 A). Conditions: 20,,, = 50”; data measured for (l), 1387 reflections in the range h, 0 to 9 ; k, 0 to 10; I, 0 to 24, for (2), 771 reflections in the range, h, -18 to 14; k, 0 to 5; 1, 0 to 14: for (3), 742 reflections in the range, h, 0 to 9 ; k, 0 to 7 ; I, EXPERIMENTAL, - 10 to 8. Data were corrected for absorption using empirical methods (MolEN’), maximum, minimum Preparation transmission factors, 1.OO,0.93 (1) ; 1.OO,0.64 (2) ; Compound (1) was prepared by mixing equi1.00, 0.64 (3). Data used in refinement molar amounts of lithium hydroxide with (+)-tar[Fo > 2.0@0)], 992 (l), 711 (2), 608 (3)]. The structures were solved using the Patterson method taric acid in a concentrated aqueous environment. This gave colourless deliquescent needle crystals on with the exception of (l), in which direct methods partial evaporation of the solvent at room tem- were used (SHELXS-86’). Full-matrix least-squares perature. Complexes (2) and (3) were prepared by refinement with anisotropic thermal parameters for all non-hydrogens was used (SHELXL-939), the complete neutralization of an aqueous solution of (+)-tartaric acid by KOH or Tlz(CO3) respec- giving residuals R [ =C 11 Fol - [Fc 11/lFol] of 0.035 (l), 0.019 (2) and 0.042 (3), and wR tively. Complex (4) was prepared by interaction of equimolar amounts of silver nitrate and (+)[= {cw(Fo2-Fcz)~/~w(Fo2)2}“2] of 0.094 (l), 0.049 (2) and 0.055 (3). Values for A in the tartaric acid in a concentrated aqueous solution, colourless diamond-shaped plates forming after weighting scheme w = [a’@~)‘+ (AP)2]-’ [where room temperature evaporation in the absence of P = {max(Fo2, 0) + 2Fc2}/3] were 0.054,0.032, and 0.045 for (l), (2) and (3) respectively. Hydrogens light. [Found for (4), C, 13.0 ; H, 1.1%. C4H4Ag& were located from difference-Fourier syntheses and requires C, 13.2; H, l.l%.] included in the respective refinements with both positional and thermal parameters refined. In the Crystal data case of (3), because of the electronic influence of the Tl, hydrogen atom refinement was unsatA4r = 348.1, orthorhombic, (1) GH14Li&, isfactory so these were included in the refinement space group P212L21, a = 7.6154(7), b = 8.496(2), at fixed positions with isotropic U values fixed at c = 20.777(2) A, V = 1344.1(4) A3, Z = 4, DC = 1.720 g cmp3, Dm = 1.71 g cmp3, F(OO0) = 720, 0.05 A’. The absolute configuration for (2) and (3) was confirmed by parallel refinements of the p(Mo-Ka) = 1.67 cm-‘, T = 298(2) K. (2) C4H5KZ06.5, Mr = 235.3, monoclinic, space two enantiomeric forms using all reflections, and is the same as that obtained by van Bommel and b = 5.046(l), a = 15.483(2) group Bijvoet” for the probable absolute configuration c = 12.591;&, fi = 127.074(5)’ V = 784.9(2) A’ Z = 4, DC = 1.991 g cm-3, Dh = 1.98 g crnm3: for ammonium hydrogen (+)-tar&ate. With the lithium analogue (l), this confirmation was not F(OO0) = 476, p(Mo-K,) = 12.0 cm-‘, T = 295(2) possible so that the absolute configuration was K. (3) C,H406T12, Mr = 556.8, monoclinic, space assumed to be (2R,3R), consistent with that for (2) and (3). group P2,, a = 8.288(5), b = 6.2055(7), c = Bond distances and angles are given in Table 1. 8&O(6) A, /I = 117.54(3)“, V = 384.9(4) A3, Z = 2, DC = 4.805 g cmp3, Dm > 3.60 g cme3, Atomic coordinates and anisotropic thermal parameters and hydrogen atom coordinates are proF(OO0) = 476, p(Mo-KU) = 418.0 cm-‘, T = vided as supplementary material, along with 298(2) K. observed and calculated structure factors. The atom (4) C,H,Ag,06, Mr = 363.8, monoclinic, space numbering scheme for the tartrate residues follows group P2,, a = 7.709(7), b = 4.693(2), c = 9.389(9)
Univalent metal ion cr-hydroxy acid interactions the convention employed in previous publications by the authors” as follows :
04
//
DISCUSSION
[Li2(HC4H406)2.2Hz01, (1) The structure of lithium hydrogen (+)-tartrate dihydrate (1) is a polymer based on a dimeric repeating unit with formula [Li,(HC,H,O,),(H,O),] (Fig. l), which comprises two independent and different Li centres, bridged by hydrogen (+)tartrate residues and a single water [O(lW) ; LiLi, 3.15(l) A]. Both centres have distorted square pyramidal five-coordinate stereochemistry with a Li-0 range of 1.97 l(9)-2.322(8) A. The latter distance is long CJ all other bonds in this structure [2.090(5) A as the next longest bond] and the range 1.967-2.054 A in lithium hydrogen mesotartrate monohydrate. I2 In the present structure, Li(1) has two bidentate-hydroxycarboxyl interactions from tartrate residues (1) and (2), and the bridging water. In contrast, Li(2) has a single bidentate tartrate association (residue 2), a unidentate bridging bond to a carboxyl oxygen [0(121) of residue l] and in addition to the bridging water, a bond to the unidentate second water [0(2W)]. In the approximate sixth (octahedral) site of the coordination sphere about Li( 1) is a longer bond to an hydroxyl oxygen [0(32)] from residue 2 [2.646(8) A]. Neither of the protonated carboxyl oxygens of the hydrogen tartrate residues is involved in coordination. However, both form linear head-to-tail hydrogenbonding associations within the complex polymer chains [O(l 1l)- H(111). . .0(421)“, 2.536(5) A; 0-H.--O, 178(4)“, (a = -1+x, y, z). 0(112)H(112)..-0(422)b, 2.601(5) A; 0-H..*O, 171(5)“, (b = 1 +x, y, z]. Other hydrogen-bonding associations are O(32). . .0(412), 2.682(5) A; 0-H...O, 172(6)“;0(31)...0(412), 2.740(5) A; 0-H.**O, 174(5)“;0(21)-.. 0(121),2.672(5)A; 0-H. * *0, 107(7)“. MGH,W-O.5H,Oln
(2)
The normal potassium (+)-tartrate hemihydrate (2) is a complex polymer (Fig. 2) based on a repeat-
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ing unit containing two independent and different potassium centres. Both of these are distorted octahedral six-coordinate, with a K-O range of 2.71 l(2)-2.988(3) A (Fig. 2). Of the six oxygens about K(l), five are from tartrate residues (four carboxyl and one hydroxyl from four different ligands) and a single water [0( 1W)]. This water lies on a crystallographic two-fold axis and forms a bridge to another K( 1) centre [-x, y, -z) : K. . . K, 4.0382(l) A; K-O-K, 92.6(l)“. The carboxyl oxygen [0( 12)] is unusual in providing three-centre bridging bonds between one K(1) centre and two different K(2) centres [K(l). . . K(2), 4.063(l) A : K(1)-0(12)-K(2), 95.08(8)“; K(2)-0(12)K(l), 111.43(9)’ ; K(2). . . K(2), 4.099(l) A, K(2)0(12)-K(2), 96.1 S(S)O]. The six-coordination about the second potassium comprises oxygens from five different tartrate residues (five carboxyl, one hydroxyl), including a /&hydroxycarboxyl chelate association of the type found in both silver(I) and sodium hydrogen (+)-tartrate hydrate complexes.‘,2 Additional bridging is found between carboxyl oxygens 0(41) (two) and 0(11) (two). Coordination about each of these centres is quite different from that found in the polymeric structure of potassium meso-tartrate dihydrate,13 where the stereochemistry, although six-coordinate is more distorted than in (2). The comparative K-O bond range is 2.72-3.14 A (mean 2.80 A). Furthermore, the water molecule in (2) is less involved in hydrogen-bonding interactions than in the meso-tartrate.
The polymeric structure of thallium(I) (+)-tartrate (3) is based upon two stereochemically different thallium centres [Tl(l) and T1(2)] bridged by a hydroxyl oxygen [O(3) : Tl(l)-O(3)-T1(2), 100.3(8)“;T1(1)~~~T1(2),3.519(2)A].Thisdistance compares with 4.069(l) A within the three-oxygen bridged system in the thallium(I) hydrogen (+)tartrate structure.2 About Tl(l), the coordination is completed by four independent carboxyl oxygens [-0(41)“, 2.63(2) A : a= -l+x,y,l+z;+(41)*, 2.69(3) A: b = 1 -x, ;+y, -z; -0(42)‘, 2.89(2) A: c = l-x, -;+y, -z; -O(ll)$ 2.96(2) A: d = 1 -x, i+y, -z]. A longer contact to the second carboxyl oxygen of the (a) ligand is found [-0(42)“, 3.40(3) A], but cannot be considered a formal bond, such as is found for tartrate (d), which gives a symmetric bidentate interaction to T1(2), [T&0(1 l), 2.89(3) A; -0(12), 2.91(3) A]. About T](2), the coordination is completed by three bonds from one tartrate residue {one carboxyl [O(l l), 2.59(3) A] and two hydroxyl [O(2), O(3), 2.96(2), 2.79(2) A]}. This terdentate interaction is very
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Table 1. Bond distances (A) and angles (“) about the coordination polyhedra for (l), (2) and (3)
Li2GW2A Bond distance Li(l)-O(31)” Li(l)-O(32) Li( l)-0(422) Li( l)-O(421)” Li(l)-O(lW) Li( l)-Li(2) Li(2)-0(121)* Li(2)-0(2W) Li(2)-O(lW) Li(2)-0(22) Li(2)-0(122) Li(2)-0(32)
*2l-W (1)
*0.5H20 (2)
Bond distance 1.971(9) 2.010(9) 2.012(8) 2.067(8) 2.076(9) 3.147(11) 1.990(8) 1.998(8) 2.080(9) 2.090(8) 2.322(8) 2.646(8)
Bond angle 0(31)“-Li(l)-O(32) 0(31)“-Li(l)-O(422) 0(31)“-Li(l)-O(421)” 0(31)“-Li(l)-O(lW) 0(32)-Li(l)-0(422) 0(32)-Li(l)-0(421) 0(32)-Li(l)-O(lW) 0(422)-Li(l)-O(421)” 0(422)-Li(l)-O(lW) 0(421)“-Li(l)-O(lW) 0(121)*-Li(2)-0(2W) 0(121)*-Li(2)-O(lW) 0(121)*-Li(2)-0(22) 0(121)*-Li(2)-0(122) 0(121)*-Li(2)-0(32) 0( 1W)-Li(2)--0(22) O(lW)-Li(2)--0(122) 0( 1W)-Li(2)--0(32) 0(2W)-Li(2)-0( 1W) 0(2W)-Li(2)-0(22) 0(2W)-Li(2)-0(122) 0(2W)-Li(2)-0(32) 0(22)-Li(2)-0(122) 0(22)-Li(2)-0(32) 0(122)-Li(2)-0(32) Li( l)-O( 1W)-Li(2) a = -1+x,y,z b=x+l,l+y,z
K&H.,O,)
158.6(5) 99.0(4) 79.0(3) 103.3(4) 80.8(3) 94.9(4) 97.1(4) 162.9(5) 107.2(4) 89.7(3) 94.1(4) 105.8(4) 153.8(4) 85.7(3) 91.8(3) 90.8(3) 156.5(4) 79.8(3) 98.2(3) 103.7(3) 101.4(3) 174.1(4) 72.1(3) 71.0(2) 79.5(2) 98.2(3)
K(l)-O(lW) K(l)-Q(41) K( 1)-0(42)” K(l)-O(3)* K(l)-0(12)* K(l)-O(ll)’ K(2)-0(41) K(2)--0(2Y K(2)-O(41)d K(2)-0(12)’ K(2)-0( 1l)f K(2)-0(12)* Bond angle 0( 1W)-K( 1)-0(41) 0( 1W)-K( 1)-0(42)’ O(lW)-K(1)-+(3)* O(lW)-K(1)-0(12)* O(lW)-K(I)-O(ll)’ 0(41)-K(1)-0(42)” 0(41)-K(1)-0(3)* 0(41)-K(1)-0(12)* 0(41)-K(1)-O(11)c 0(42)=-K(1)-0(3)* 0(42)“--K(1)--0(12)* 0(42)“-K(l)-O(11)’ O(3)*-K(1)-0(12)* O(3)*-K( l)-0( 11)’ O(lZ)*-K(l)-O(l1)’ 0(41)-K(2)-O(2)d 0(41)-K(2)-O(41)d 0(41)-K(2)-0(12)’ 0(41)-K(2)-0(1 ly 0(41)-K(2)--0(12)* 0(2)d-K(2)-O(41)d 0(2)d-K(2)-O(12)’ 0(2)d-K(2)-O(1 1)’ 0(2)d-K(2)-O(12)b 0(41)d-K(2)-O(12)’ 0(41)d-K(2)-O(1 l)J 0(41)d-K(2)-O(12)b 0(12)e-K(2)-O( 1l)f 0(12)e-K(2)-O(12)b 0(1 l)f-K(2)-O(12)b a = --x,y, -z b = -f+x,&y,z c = ++x,;+y,z d= -x, -l+y,z e= -x,-l+y,-z f= -x,y,l-z
2.792(3) 2.719(3) 2.711(2) 2.832(3) 2.747(3) 2.741(2) 2.851(3) 2.818(3) 2.988(3) 2.749(2) 2.797(2) 2.760(3) 77.51(6) 87.77(7) 72.88(7) 99.19(8) 161.66(7) 120.26(9) 138.01(9) 80.31(8) 110.28(8) 87.87(8) 159.38(10) 110.28(8) 75.86(7) 109.83(9) 65.04(7) 93.54(7) 119.56(6) 154.82(7) 90.69(6) 77.80(7) 66.52(7) 84.82(8) 91.05(9) 168&l(6) 82.81(7) 142.07(7) 110.95(7) 64.27(7) 106.29(8) 96.63(8)
TMGH,Os)
(3)
Bond distance Tl( 1)-0(41)” Tl( 1)-0(41)’ Tl( 1)-0(42)’ TlU)--O(3) Tl(l)-O(l l)d Tl( l)-Tl(2)’ T1(2)-0( 11) T1(2)-O(3) T1(2)-0( 1l)d T1(2)-O(12)d T&2)-0(2) Bond angle 0(41)“-T1(1)-O(41)b 0(41)“--Tl( 1)-0(42)’ 0(41)“-Tl( 1)-O(3) 0(41)“-Tl(l)-O(l l)d 0(41)b-T1(1)-O(42)c 0(41)*-Tl(l)--o(3) 0(41)b-T1(1)-O(ll)d 0(41)‘-Tl(l)-O(3) 0(41)c-Tl(l)-O(1 l)d O(3)-Tl(l)-O(l l)d 0(1 I)-T1(2)-0(3) 0(11)-T1(2)-O(11)d 0( 1l)-T1(2)-0( 12)d 0(1 I)-T1(2)-0(2) O(3)-T1(2)-0(1 l)d 0(3)-T1(2)-O(12)d O(3)-T1(2)-O(2) O(I 1)d-T1(2)-O(12)d 0(1 l)d-T1(2)--o(2) 0(12)d-T1(2)-O(2) a= b= c= d= e=
-1+x,y,1+z 1 -x, f+y, -z I-x, --f+y, -z 1 -x,f+y, -z 1 -x, -f+y, 1 +z
2.63(2) 2.69(3) 2.89(2) 2.93(3) 2.96(2) 3.519(2) 2.59(3) 2.79(2) 2.89(3) 2.91(3) 2.96(2) 92.7(9) 77.5(8) 162.8(7) 96.3(9) 105.6(7) 104.0(7) 99.0(9) 101.8(7) 154.8(8) 77.0(8) 77.7(7) 91.3(10) 81.1(10) 59.4(9) 80.4(7) 117.3(7) 57.8(6) 44.3(7) 133.7(6) 140.2(8)
Univalent metal ion u-hydroxy acid interactions
Fig. 1. Molecular configuration
Fig. 2. Molecular configuration
and atom numbering scheme for compound (1).
and atom numbering scheme for compound (2).
The Tl-0 bond range [2.59(3)-2.96(2) A; mean 2.83(9) A] compares with 2.81-3.19 %( (mean 2.98 gi> for the eight-coordinate thallium(I) hydrogen (+)-tartrate and 2.56-3.05 A for the four-coordinate thallium formate structure.‘4
unusual
for
the
univalent
metal
tartrates.
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Tartrate residues The (+)-tartrate residues in compounds (l), (2) and (3) have the absolute configuration of (+)tartaric acid, confirmed by van Bommel and Bijvoet,” and also found in subsequent structure
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R. C. BOTT er al.
Fig. 3. Molecular configuration and atom numbering scheme for compound (3).
determinations of (+)-tartrates. This 2R, 3R configuration also gives a negative torsion angle for the 2- and 3-hydroxyl groups about the C(2)-C(3) bond vector. The sign and magnitude of this angle then provides a convenient means of identification of the absolute configuration and the conformation of the tartrate residue. The preferred conformation assumed for the parent acid results in a torsion angle of -58”, which is close to the two values found in (1) [ - 60.9(4)’ (residue 1) and - 56.2(4)’ (residue 2)]. However, in the majority of (+)tartrate salts, including potassium (+)-tartrate hemihydrate (2) [ -69.7(3)“] and thallium(I) (+)tartrate (3) [ - 68(3)“], this value is more typically close to -70”. Among the hydrogen (+)-tartrates these values are : NHq+,10 - 69” ; Na (anhydrous),’ - 71’ ; Na (monohydrate),’ - 67” ; K,3 - 68” ; Rb, - 70” ; Cs,’ - 70” ; Tl,* -68” ; Ag (monohydrate), - 69”, and a range of -68 to -72” over eight independent residues in the isomorphous pair [Ag,As,(C,H,o,),(H,O),(X)l (X = NO;, Cl% ‘l). authors thank the Australian Research Council and the Centre for Instrumental and Developmental Chemistry, Queensland University of Technology for financial assistance. The University of
Acknowledgements-The
Queensland is thanked for collection of X-ray data for all compounds. REFERENCES R. C. Bott, G. Smith, D. S. Sagatys, A. N. Reddy and C. H. L. Kennard, Z. Krist. 1994, in press. R. C. Bott, D. S. Sagatys, D. E. Lynch, G. Smith and C. H. L. Kennard, Acta Cryst. 1993, C49,llSO. J. Buschmann and P. Luger, Acta Cryst. 1985, C41, 206; M. Akkurt, T. Hokelek and H. Soylu, Z. Krist. 1987,181, 161. L. K. Templeton and D. H. Templeton, Actu Cryst. 1989, C45,675. L. K. Templeton and D. H. Templeton, Actn Cryst. 1978, A34,368. S. Budavari (Ed.), The Merck Index, 11th edn., p. 1218. Merck, Rahway, New Jersey (1989). C. K. Fair, MolEN. An interactive intelligent system for crystal structure analysis. Enraf-Nonius, Delft (1990). 8. G. M. Sheldrick, SHELXS-86, Structure Solution Package. University of GGttingen (1986). 9. G. M. Sheldrick, SHELXL-93, Program for Crystal Structure Determination. University of Gbttingen (1993). 10. A. J. van Bommel and J. M. Bijvoet, Acta Crust. 1958, 11,61.
Univalent metal ion a-hydroxy acid interactions 11. R. C. Bott, G. Smith, D. S. Sagatys, T. C. W. Mak, D. E. Lynch and C. H. L. Kennard, Aust. J. Chem. 1993,46, 1055. 12. P. F. W. Stouten, P. Venver, B. P. van Eijk and J. Kroon, Actu Cryst. 1988, C44, 1961.
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13. J. Kroon, A. F. Peerdeman and J. M. Bijvoet, Actu Cryst. 1965, 19, 293. 14. Y. Oddon, A. Tranquard and G. F. Mentzen, Znorg. Chim. Actu 1981,48, 129.
Pergamon
UNIVALENT METAL ION a-HYDROXY ACID INTERACTIONS: PART 9.* PREPARATION AND CRYSTAL STRUCTURES OF LITHIUM HYDROGEN (+)-TARTRATE MONOHYDRATE, POTASSIUM (+)-TARTRATE HEMJHYDRATE AND THALLIUM(I) (+)-TARTRATE RAYMOND
C. BOTT,
DALIUS
S. SAGATYS
and GRAHAM
School of Chemistry, Queensland University of Technology, 400 1, Australia
SMITH?
P.O. Box 2434, Brisbane,
and KARL A. BYRIEL
and COLIN
H. L. KENNARD
Department of Chemistry, The University of Queensland, Brisbane, 4072, Australia (Received 3 December 1993; accepted 29 March 1994) Abstract-The
univalent metal ion compounds of (+)-tartaric acid, lithium hydrogen (+)-tartrate monohydrate (l), potassium (+)-tartrate hemihydrate (2) and thallium (+)-tartrate (3) have been prepared and their structures determined by X-ray diffraction methods. All form network polymer structures similar to the other group one metal tartrates. However, (1) is based on a dimeric repeating unit, with two independent but different five-coordinate square pyramidal lithium centres, [L&O, 1.971-2.322(8) A]. Although both centres involve (+)-tartrate residues in a-hydroxycarboxyl bis-coordinate interactions, one centre has two, the other has one and is also coordinated to both waters (one bridging). The protonated carboxylic acid groups are uncoordinated but hydrogen bonded in both inter- and intra-dimer associations. Potassium (+)-tartrate hemihydrate (2) has two independent and different distorted octahedral potassium centres. About the first, there are five oxygens from (+)-tartrate residues and one from a water which bridges to another symmetry generated potassium. The second potassium has six bonds to (+)-tartrate oxygens, including a j?-hydroxycarboxyl chelate ring, with a K-O range of 2.71 l(2) 2.988(3) A. An unusual feature is a carboxyl oxygen giving a three-centre bonding system to three separate potassium ions. The polymeric structure of thallium(I) (+)-tartrate (3) is based upon two different five-coordinate thallium centres [Tl-O range, 2.59(3)-2.96(2) A]. About one, bonds are to three oxygens from one (+)-tartrate residue (one carboxyl, two hydroxyl), and two from a symmetric bidentate carboxylato-(0,O’) group of a bridging (+)-tartrate. The bonded hydroxyl also bridges to the second Tl [Tl . . . Tl, 3.519(2) A];]. Completing the bonding to this second Tl are oxygens from four different tartrate residues. Crystallographic and analytical data are also provided for silver(I) (+)-tartrate (4).
Due to an interest in our laboratories in the associative role of the univalent metal cations (primarily Group 1) in the stabilization of trivalent Group 15
* Part 8 : ref. 2. 7 Author to whom correspondence should be addressed.
(As, Sb, Bi) (+)-tartrate complex anion species, the structural systematics of both the normal and the acid tartrate salts of these univalent cations have been studied using infrared spectroscopic and Xray diffraction methods. Although this series is generally well described structurally, most of the literature is quite recent, e.g. Na(HC4H40&’
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Na(HC4H.,06) * Hz0 :’ K(HC4H406) :3 Rb(HC4H4 O&“ CS(HC~H~O,J,~ together with the analogous Tl(1) and Ag(1) compounds Tl(HC4H406) and Ag(HC,H,O,) - H20.’ Despite this, the structures of some members of the normal and acid salt series have not been reported in the crystallographic literature. Reported here are the structures of lithium hydrogen (+)-tartrate monohydrate, [Li,(HC, H40& 02H,O], (l), potassium (+)-tartrate hemihydrate, [KZ(C4H406). OSH,O], (2), (useful as the pharmaceutical reagent ‘soluble tartar’6) and thallium(I) (+)-tartrate [T12(C4H406)]n (3). Crystal data are also provided for silver(I) (+)tartrate [AgZ(C4H@6)]n (4).
A, /I = 90.27(5)“, V = 339.6(5) A3, Z = 2, DC = 3.558 g cmp3, Dm = 3.60 g cme3, F(OO0) = 340, p(Mo-K,) = 53.2 cm-‘, T = 298(2) K.
X-ray data collection, structure solution and rejinement
X-ray data were collected on an Enraf-Nonius four-circle diffractometer using graphite crystal monochromated MO-KU radiation (J, = 0.71073 A). Conditions: 20,,, = 50”; data measured for (l), 1387 reflections in the range h, 0 to 9 ; k, 0 to 10; I, 0 to 24, for (2), 771 reflections in the range, h, -18 to 14; k, 0 to 5; 1, 0 to 14: for (3), 742 reflections in the range, h, 0 to 9 ; k, 0 to 7 ; I, EXPERIMENTAL, - 10 to 8. Data were corrected for absorption using empirical methods (MolEN’), maximum, minimum Preparation transmission factors, 1.OO,0.93 (1) ; 1.OO,0.64 (2) ; Compound (1) was prepared by mixing equi1.00, 0.64 (3). Data used in refinement molar amounts of lithium hydroxide with (+)-tar[Fo > 2.0@0)], 992 (l), 711 (2), 608 (3)]. The structures were solved using the Patterson method taric acid in a concentrated aqueous environment. This gave colourless deliquescent needle crystals on with the exception of (l), in which direct methods partial evaporation of the solvent at room tem- were used (SHELXS-86’). Full-matrix least-squares perature. Complexes (2) and (3) were prepared by refinement with anisotropic thermal parameters for all non-hydrogens was used (SHELXL-939), the complete neutralization of an aqueous solution of (+)-tartaric acid by KOH or Tlz(CO3) respec- giving residuals R [ =C 11 Fol - [Fc 11/lFol] of 0.035 (l), 0.019 (2) and 0.042 (3), and wR tively. Complex (4) was prepared by interaction of equimolar amounts of silver nitrate and (+)[= {cw(Fo2-Fcz)~/~w(Fo2)2}“2] of 0.094 (l), 0.049 (2) and 0.055 (3). Values for A in the tartaric acid in a concentrated aqueous solution, colourless diamond-shaped plates forming after weighting scheme w = [a’@~)‘+ (AP)2]-’ [where room temperature evaporation in the absence of P = {max(Fo2, 0) + 2Fc2}/3] were 0.054,0.032, and 0.045 for (l), (2) and (3) respectively. Hydrogens light. [Found for (4), C, 13.0 ; H, 1.1%. C4H4Ag& were located from difference-Fourier syntheses and requires C, 13.2; H, l.l%.] included in the respective refinements with both positional and thermal parameters refined. In the Crystal data case of (3), because of the electronic influence of the Tl, hydrogen atom refinement was unsatA4r = 348.1, orthorhombic, (1) GH14Li&, isfactory so these were included in the refinement space group P212L21, a = 7.6154(7), b = 8.496(2), at fixed positions with isotropic U values fixed at c = 20.777(2) A, V = 1344.1(4) A3, Z = 4, DC = 1.720 g cmp3, Dm = 1.71 g cmp3, F(OO0) = 720, 0.05 A’. The absolute configuration for (2) and (3) was confirmed by parallel refinements of the p(Mo-Ka) = 1.67 cm-‘, T = 298(2) K. (2) C4H5KZ06.5, Mr = 235.3, monoclinic, space two enantiomeric forms using all reflections, and is the same as that obtained by van Bommel and b = 5.046(l), a = 15.483(2) group Bijvoet” for the probable absolute configuration c = 12.591;&, fi = 127.074(5)’ V = 784.9(2) A’ Z = 4, DC = 1.991 g cm-3, Dh = 1.98 g crnm3: for ammonium hydrogen (+)-tar&ate. With the lithium analogue (l), this confirmation was not F(OO0) = 476, p(Mo-K,) = 12.0 cm-‘, T = 295(2) possible so that the absolute configuration was K. (3) C,H406T12, Mr = 556.8, monoclinic, space assumed to be (2R,3R), consistent with that for (2) and (3). group P2,, a = 8.288(5), b = 6.2055(7), c = Bond distances and angles are given in Table 1. 8&O(6) A, /I = 117.54(3)“, V = 384.9(4) A3, Z = 2, DC = 4.805 g cmp3, Dm > 3.60 g cme3, Atomic coordinates and anisotropic thermal parameters and hydrogen atom coordinates are proF(OO0) = 476, p(Mo-KU) = 418.0 cm-‘, T = vided as supplementary material, along with 298(2) K. observed and calculated structure factors. The atom (4) C,H,Ag,06, Mr = 363.8, monoclinic, space numbering scheme for the tartrate residues follows group P2,, a = 7.709(7), b = 4.693(2), c = 9.389(9)
Univalent metal ion cr-hydroxy acid interactions the convention employed in previous publications by the authors” as follows :
04
//
DISCUSSION
[Li2(HC4H406)2.2Hz01, (1) The structure of lithium hydrogen (+)-tartrate dihydrate (1) is a polymer based on a dimeric repeating unit with formula [Li,(HC,H,O,),(H,O),] (Fig. l), which comprises two independent and different Li centres, bridged by hydrogen (+)tartrate residues and a single water [O(lW) ; LiLi, 3.15(l) A]. Both centres have distorted square pyramidal five-coordinate stereochemistry with a Li-0 range of 1.97 l(9)-2.322(8) A. The latter distance is long CJ all other bonds in this structure [2.090(5) A as the next longest bond] and the range 1.967-2.054 A in lithium hydrogen mesotartrate monohydrate. I2 In the present structure, Li(1) has two bidentate-hydroxycarboxyl interactions from tartrate residues (1) and (2), and the bridging water. In contrast, Li(2) has a single bidentate tartrate association (residue 2), a unidentate bridging bond to a carboxyl oxygen [0(121) of residue l] and in addition to the bridging water, a bond to the unidentate second water [0(2W)]. In the approximate sixth (octahedral) site of the coordination sphere about Li( 1) is a longer bond to an hydroxyl oxygen [0(32)] from residue 2 [2.646(8) A]. Neither of the protonated carboxyl oxygens of the hydrogen tartrate residues is involved in coordination. However, both form linear head-to-tail hydrogenbonding associations within the complex polymer chains [O(l 1l)- H(111). . .0(421)“, 2.536(5) A; 0-H.--O, 178(4)“, (a = -1+x, y, z). 0(112)H(112)..-0(422)b, 2.601(5) A; 0-H..*O, 171(5)“, (b = 1 +x, y, z]. Other hydrogen-bonding associations are O(32). . .0(412), 2.682(5) A; 0-H...O, 172(6)“;0(31)...0(412), 2.740(5) A; 0-H.**O, 174(5)“;0(21)-.. 0(121),2.672(5)A; 0-H. * *0, 107(7)“. MGH,W-O.5H,Oln
(2)
The normal potassium (+)-tartrate hemihydrate (2) is a complex polymer (Fig. 2) based on a repeat-
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ing unit containing two independent and different potassium centres. Both of these are distorted octahedral six-coordinate, with a K-O range of 2.71 l(2)-2.988(3) A (Fig. 2). Of the six oxygens about K(l), five are from tartrate residues (four carboxyl and one hydroxyl from four different ligands) and a single water [0( 1W)]. This water lies on a crystallographic two-fold axis and forms a bridge to another K( 1) centre [-x, y, -z) : K. . . K, 4.0382(l) A; K-O-K, 92.6(l)“. The carboxyl oxygen [0( 12)] is unusual in providing three-centre bridging bonds between one K(1) centre and two different K(2) centres [K(l). . . K(2), 4.063(l) A : K(1)-0(12)-K(2), 95.08(8)“; K(2)-0(12)K(l), 111.43(9)’ ; K(2). . . K(2), 4.099(l) A, K(2)0(12)-K(2), 96.1 S(S)O]. The six-coordination about the second potassium comprises oxygens from five different tartrate residues (five carboxyl, one hydroxyl), including a /&hydroxycarboxyl chelate association of the type found in both silver(I) and sodium hydrogen (+)-tartrate hydrate complexes.‘,2 Additional bridging is found between carboxyl oxygens 0(41) (two) and 0(11) (two). Coordination about each of these centres is quite different from that found in the polymeric structure of potassium meso-tartrate dihydrate,13 where the stereochemistry, although six-coordinate is more distorted than in (2). The comparative K-O bond range is 2.72-3.14 A (mean 2.80 A). Furthermore, the water molecule in (2) is less involved in hydrogen-bonding interactions than in the meso-tartrate.
The polymeric structure of thallium(I) (+)-tartrate (3) is based upon two stereochemically different thallium centres [Tl(l) and T1(2)] bridged by a hydroxyl oxygen [O(3) : Tl(l)-O(3)-T1(2), 100.3(8)“;T1(1)~~~T1(2),3.519(2)A].Thisdistance compares with 4.069(l) A within the three-oxygen bridged system in the thallium(I) hydrogen (+)tartrate structure.2 About Tl(l), the coordination is completed by four independent carboxyl oxygens [-0(41)“, 2.63(2) A : a= -l+x,y,l+z;+(41)*, 2.69(3) A: b = 1 -x, ;+y, -z; -0(42)‘, 2.89(2) A: c = l-x, -;+y, -z; -O(ll)$ 2.96(2) A: d = 1 -x, i+y, -z]. A longer contact to the second carboxyl oxygen of the (a) ligand is found [-0(42)“, 3.40(3) A], but cannot be considered a formal bond, such as is found for tartrate (d), which gives a symmetric bidentate interaction to T1(2), [T&0(1 l), 2.89(3) A; -0(12), 2.91(3) A]. About T](2), the coordination is completed by three bonds from one tartrate residue {one carboxyl [O(l l), 2.59(3) A] and two hydroxyl [O(2), O(3), 2.96(2), 2.79(2) A]}. This terdentate interaction is very
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Table 1. Bond distances (A) and angles (“) about the coordination polyhedra for (l), (2) and (3)
Li2GW2A Bond distance Li(l)-O(31)” Li(l)-O(32) Li( l)-0(422) Li( l)-O(421)” Li(l)-O(lW) Li( l)-Li(2) Li(2)-0(121)* Li(2)-0(2W) Li(2)-O(lW) Li(2)-0(22) Li(2)-0(122) Li(2)-0(32)
*2l-W (1)
*0.5H20 (2)
Bond distance 1.971(9) 2.010(9) 2.012(8) 2.067(8) 2.076(9) 3.147(11) 1.990(8) 1.998(8) 2.080(9) 2.090(8) 2.322(8) 2.646(8)
Bond angle 0(31)“-Li(l)-O(32) 0(31)“-Li(l)-O(422) 0(31)“-Li(l)-O(421)” 0(31)“-Li(l)-O(lW) 0(32)-Li(l)-0(422) 0(32)-Li(l)-0(421) 0(32)-Li(l)-O(lW) 0(422)-Li(l)-O(421)” 0(422)-Li(l)-O(lW) 0(421)“-Li(l)-O(lW) 0(121)*-Li(2)-0(2W) 0(121)*-Li(2)-O(lW) 0(121)*-Li(2)-0(22) 0(121)*-Li(2)-0(122) 0(121)*-Li(2)-0(32) 0( 1W)-Li(2)--0(22) O(lW)-Li(2)--0(122) 0( 1W)-Li(2)--0(32) 0(2W)-Li(2)-0( 1W) 0(2W)-Li(2)-0(22) 0(2W)-Li(2)-0(122) 0(2W)-Li(2)-0(32) 0(22)-Li(2)-0(122) 0(22)-Li(2)-0(32) 0(122)-Li(2)-0(32) Li( l)-O( 1W)-Li(2) a = -1+x,y,z b=x+l,l+y,z
K&H.,O,)
158.6(5) 99.0(4) 79.0(3) 103.3(4) 80.8(3) 94.9(4) 97.1(4) 162.9(5) 107.2(4) 89.7(3) 94.1(4) 105.8(4) 153.8(4) 85.7(3) 91.8(3) 90.8(3) 156.5(4) 79.8(3) 98.2(3) 103.7(3) 101.4(3) 174.1(4) 72.1(3) 71.0(2) 79.5(2) 98.2(3)
K(l)-O(lW) K(l)-Q(41) K( 1)-0(42)” K(l)-O(3)* K(l)-0(12)* K(l)-O(ll)’ K(2)-0(41) K(2)--0(2Y K(2)-O(41)d K(2)-0(12)’ K(2)-0( 1l)f K(2)-0(12)* Bond angle 0( 1W)-K( 1)-0(41) 0( 1W)-K( 1)-0(42)’ O(lW)-K(1)-+(3)* O(lW)-K(1)-0(12)* O(lW)-K(I)-O(ll)’ 0(41)-K(1)-0(42)” 0(41)-K(1)-0(3)* 0(41)-K(1)-0(12)* 0(41)-K(1)-O(11)c 0(42)=-K(1)-0(3)* 0(42)“--K(1)--0(12)* 0(42)“-K(l)-O(11)’ O(3)*-K(1)-0(12)* O(3)*-K( l)-0( 11)’ O(lZ)*-K(l)-O(l1)’ 0(41)-K(2)-O(2)d 0(41)-K(2)-O(41)d 0(41)-K(2)-0(12)’ 0(41)-K(2)-0(1 ly 0(41)-K(2)--0(12)* 0(2)d-K(2)-O(41)d 0(2)d-K(2)-O(12)’ 0(2)d-K(2)-O(1 1)’ 0(2)d-K(2)-O(12)b 0(41)d-K(2)-O(12)’ 0(41)d-K(2)-O(1 l)J 0(41)d-K(2)-O(12)b 0(12)e-K(2)-O( 1l)f 0(12)e-K(2)-O(12)b 0(1 l)f-K(2)-O(12)b a = --x,y, -z b = -f+x,&y,z c = ++x,;+y,z d= -x, -l+y,z e= -x,-l+y,-z f= -x,y,l-z
2.792(3) 2.719(3) 2.711(2) 2.832(3) 2.747(3) 2.741(2) 2.851(3) 2.818(3) 2.988(3) 2.749(2) 2.797(2) 2.760(3) 77.51(6) 87.77(7) 72.88(7) 99.19(8) 161.66(7) 120.26(9) 138.01(9) 80.31(8) 110.28(8) 87.87(8) 159.38(10) 110.28(8) 75.86(7) 109.83(9) 65.04(7) 93.54(7) 119.56(6) 154.82(7) 90.69(6) 77.80(7) 66.52(7) 84.82(8) 91.05(9) 168&l(6) 82.81(7) 142.07(7) 110.95(7) 64.27(7) 106.29(8) 96.63(8)
TMGH,Os)
(3)
Bond distance Tl( 1)-0(41)” Tl( 1)-0(41)’ Tl( 1)-0(42)’ TlU)--O(3) Tl(l)-O(l l)d Tl( l)-Tl(2)’ T1(2)-0( 11) T1(2)-O(3) T1(2)-0( 1l)d T1(2)-O(12)d T&2)-0(2) Bond angle 0(41)“-T1(1)-O(41)b 0(41)“--Tl( 1)-0(42)’ 0(41)“-Tl( 1)-O(3) 0(41)“-Tl(l)-O(l l)d 0(41)b-T1(1)-O(42)c 0(41)*-Tl(l)--o(3) 0(41)b-T1(1)-O(ll)d 0(41)‘-Tl(l)-O(3) 0(41)c-Tl(l)-O(1 l)d O(3)-Tl(l)-O(l l)d 0(1 I)-T1(2)-0(3) 0(11)-T1(2)-O(11)d 0( 1l)-T1(2)-0( 12)d 0(1 I)-T1(2)-0(2) O(3)-T1(2)-0(1 l)d 0(3)-T1(2)-O(12)d O(3)-T1(2)-O(2) O(I 1)d-T1(2)-O(12)d 0(1 l)d-T1(2)--o(2) 0(12)d-T1(2)-O(2) a= b= c= d= e=
-1+x,y,1+z 1 -x, f+y, -z I-x, --f+y, -z 1 -x,f+y, -z 1 -x, -f+y, 1 +z
2.63(2) 2.69(3) 2.89(2) 2.93(3) 2.96(2) 3.519(2) 2.59(3) 2.79(2) 2.89(3) 2.91(3) 2.96(2) 92.7(9) 77.5(8) 162.8(7) 96.3(9) 105.6(7) 104.0(7) 99.0(9) 101.8(7) 154.8(8) 77.0(8) 77.7(7) 91.3(10) 81.1(10) 59.4(9) 80.4(7) 117.3(7) 57.8(6) 44.3(7) 133.7(6) 140.2(8)
Univalent metal ion u-hydroxy acid interactions
Fig. 1. Molecular configuration
Fig. 2. Molecular configuration
and atom numbering scheme for compound (1).
and atom numbering scheme for compound (2).
The Tl-0 bond range [2.59(3)-2.96(2) A; mean 2.83(9) A] compares with 2.81-3.19 %( (mean 2.98 gi> for the eight-coordinate thallium(I) hydrogen (+)-tartrate and 2.56-3.05 A for the four-coordinate thallium formate structure.‘4
unusual
for
the
univalent
metal
tartrates.
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Tartrate residues The (+)-tartrate residues in compounds (l), (2) and (3) have the absolute configuration of (+)tartaric acid, confirmed by van Bommel and Bijvoet,” and also found in subsequent structure
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Fig. 3. Molecular configuration and atom numbering scheme for compound (3).
determinations of (+)-tartrates. This 2R, 3R configuration also gives a negative torsion angle for the 2- and 3-hydroxyl groups about the C(2)-C(3) bond vector. The sign and magnitude of this angle then provides a convenient means of identification of the absolute configuration and the conformation of the tartrate residue. The preferred conformation assumed for the parent acid results in a torsion angle of -58”, which is close to the two values found in (1) [ - 60.9(4)’ (residue 1) and - 56.2(4)’ (residue 2)]. However, in the majority of (+)tartrate salts, including potassium (+)-tartrate hemihydrate (2) [ -69.7(3)“] and thallium(I) (+)tartrate (3) [ - 68(3)“], this value is more typically close to -70”. Among the hydrogen (+)-tartrates these values are : NHq+,10 - 69” ; Na (anhydrous),’ - 71’ ; Na (monohydrate),’ - 67” ; K,3 - 68” ; Rb, - 70” ; Cs,’ - 70” ; Tl,* -68” ; Ag (monohydrate), - 69”, and a range of -68 to -72” over eight independent residues in the isomorphous pair [Ag,As,(C,H,o,),(H,O),(X)l (X = NO;, Cl% ‘l). authors thank the Australian Research Council and the Centre for Instrumental and Developmental Chemistry, Queensland University of Technology for financial assistance. The University of
Acknowledgements-The
Queensland is thanked for collection of X-ray data for all compounds. REFERENCES R. C. Bott, G. Smith, D. S. Sagatys, A. N. Reddy and C. H. L. Kennard, Z. Krist. 1994, in press. R. C. Bott, D. S. Sagatys, D. E. Lynch, G. Smith and C. H. L. Kennard, Acta Cryst. 1993, C49,llSO. J. Buschmann and P. Luger, Acta Cryst. 1985, C41, 206; M. Akkurt, T. Hokelek and H. Soylu, Z. Krist. 1987,181, 161. L. K. Templeton and D. H. Templeton, Actu Cryst. 1989, C45,675. L. K. Templeton and D. H. Templeton, Actn Cryst. 1978, A34,368. S. Budavari (Ed.), The Merck Index, 11th edn., p. 1218. Merck, Rahway, New Jersey (1989). C. K. Fair, MolEN. An interactive intelligent system for crystal structure analysis. Enraf-Nonius, Delft (1990). 8. G. M. Sheldrick, SHELXS-86, Structure Solution Package. University of GGttingen (1986). 9. G. M. Sheldrick, SHELXL-93, Program for Crystal Structure Determination. University of Gbttingen (1993). 10. A. J. van Bommel and J. M. Bijvoet, Acta Crust. 1958, 11,61.
Univalent metal ion a-hydroxy acid interactions 11. R. C. Bott, G. Smith, D. S. Sagatys, T. C. W. Mak, D. E. Lynch and C. H. L. Kennard, Aust. J. Chem. 1993,46, 1055. 12. P. F. W. Stouten, P. Venver, B. P. van Eijk and J. Kroon, Actu Cryst. 1988, C44, 1961.
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13. J. Kroon, A. F. Peerdeman and J. M. Bijvoet, Actu Cryst. 1965, 19, 293. 14. Y. Oddon, A. Tranquard and G. F. Mentzen, Znorg. Chim. Actu 1981,48, 129.