BEMM, NORRESTAM, NYGREN AND WESTIN References. Acta Cryst. (1995). CSt, (NCCH3)4] (Received 10 March 1994; accepted 28 November 1994)

Transcription

1 BEMM, NORRESTAM, NYGREN AND WESTIN 1263 C(lb) (8) (10) (8) (9) (15) (10) (15) (15) (4) 0.046(4) 0.058(4) 0.041(3) 0.034(3) 0.115(7) (7) (7) (8) (14) (6) (8) (7) (6) (8) (7) (14) (8) (8) (12) (12) 0.036(3) 0.033(3) 0.053(4) 0.095(7) 0.038(3) 0.052(4) 0.100(7) (7) (7) (7) (6) (8) (7) (9) Our study of metal alkoxides is financially supported by the Swedish National Science Research Council. Lists of structure factors, anisotropic displacement parameters, H-atom coordinates and bond distances involving H atoms have been deposited with the IVCr (Reference: AB1151). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CHI 2HU, England. Table 2. Selected geometric parameters (A, 0) [Ni2Sb4(C2HsOh6] [Mn2Sb4(C2HsOh6] Sb(l)--O(I) 2.313(4) Sb(l)--O(I) 2.311(4) Sb(l)--O(2) 1.996(4) Sb(l)--O(2) 1.994(4) Sb(l)--O(3') 1.987(4) Sb(l)--O(3') 1.998(4) Sb(l)--O(6) 1.995(5) Sb(l)--O(6) 2.006(5) Sb(2)--O(4) 2.182(5) Sb(2)--O(4) 2.206(4) Sb(2)--O(5) 2.034(4) Sb(2)--O(5) 2.029(4) Sb(2)--O(7) 2.033(5) Sb(2)--O(7) 2.041(5) Sb(2)--O(8) 1.950(5) Sb(2)--O(8) 1.940(5) Ni(l)--O(I) 2.097(4) Mn(l)--O(I) 2.233(4) Ni(l)--O(2) 2.082(5) Mn(l)--O(2) 2.229(4) Ni(l)--O(3) 2.066(4) Mn(I)--O(3) 2.174(4) Ni(l)--O(4) 2.010(4) Mn(l)--O(4) 2.074(4) Ni(l)--O(5) 2.117(4) Mn(l)--O(5) 2.211(4) O(l)-C(la) 1.446(8) O(l)-C(la) 1.442(7) 0(2)-C(2a) 1.449(8) 0(2)-C(2a) 0(3)-C(3a) 1.474(8) 0(3)-C(3a) 1.436(8) 1.457(8) 0(4)-C(4a) 1.420(8) 0(4)-C(4a) 1.427(8) 0(5)-C(5a) 1.434(8) 0(5)-C(5a) 1.445(8) 0(6)-C(6a) 1.431(10) 0(6)-C(6a) 1.379(10) 0(7)-C(7a) 1.407(10) 0(7)-C(7a) 1.399(9) 0(8)-C(Sa) 1.427(9) 0(8)-C(8a) 1.425(8) O(l}-Sb(l)--O(2) 73.9(2) O(l}-Sb(l)--O(2) 75.1(2) O(l}-Sb(l)--O(3') 73.7(2) 0(I}-Sb(I)--O(3') 74.0(2) O(l}-Sb(l)--O(6) 153.1(2) O(l}-Sb(l)--O(6) 154.8(2) 0(2}-Sb(I)--O(3') 96.3(2) 0(2}-Sb(l)--O(3') 96.2(2) 0(2}-Sb(l)--O(6) 87.7(2) 0(2}-Sb(I)--O(6) 87.2(2) 0(3'}-Sb(I)--O(6) 89.4(2) 0(3'}-Sb(I)--O(6) 90.4(2) 0(4}-Sb(2)--O(5) 72.2(2) 0(4}-Sb(2)--O(5) 72.8(2) 0(4}-Sb(2)--O(7) 154.9(2) 0(4}-sb(2)--O(7) 156.6(2) 0(4}-Sb(2)--O(8) 80.3(2) 0(4}-Sb(2)--O(8) 80.7(2) 0(5}-Sb(2)--O(7) 89.5(2) 0(5}-Sb(2)--O(7) 89.9(2) 0(5}-Sb(2)--O(8) 102.4(2) 0(5}-Sb(2)--O(8) 100.5(2) 0(7}-Sb(2)--O(8) 87.4(2) 0(7}-Sb(2)--O(8) 87.3(2) 0(1}-Ni-O(I ') O(l}-Ni-O(2) 77.9(2) no (2) 0(1}-Mn-O(I ') O(l}-Mn-O(2) 80.4(2) 72.4(2) O(l'}-Ni-O(2) 95.0(2) 0(1'}-Mn-O(2) 96.4(2) O(l}-Ni-O(3) 98.0(2) O(l}-Mn-O(3) 100.6(2) 0(1' }-Ni-O(3) 76.9(2) 0(1'}-Mn-O(3) 72.5(2) O(l}-Ni-O(4) 103.5(2) O(l}-Mn-O(4) 103.9(2) O(l'}-Ni-O(4) 173.9(2) O(l'}-Mn-O(4) 172.2(2) O(l}-Ni-O(5) 173.5(2) O(l}-Mn-O(5) 169.5(2) O(l'}-Ni-O(5) 105.2(2) O(l'}-Mn-O(5) 105.0(2) 0(2}-Ni-O(3) 171.3(2) 0(2}-Mn-O(3) 168.0(2) 0(2}-Ni-O(4) 91.1(2) 0(2}-Mn-O(4) 91.1(2) 0(2}-Ni-O(5) 97.0(2) 0(2}-Mn-O(5) 97.7(2) 0(3}-Ni-O(4) 97.0(2) 0(3}-Mn-O(4) 100.2(2) 0(3}-Ni-O(5) 88.3(2) 0(3}-Mn-O(5) 89.7(2) 0(4}-Ni-O(5) 74.0(2) 0(4}-Mn-O(5) 71.9(2) The structure solution and the structural refinements were performed using SHELXS86 (Sheldrick, 1985) and SHELX76 (Sheldrick, 1976). Non-H atoms were refined with anisotropic displacement parameters, H atoms were refined isotropically with bond constraints of 1.00 A between the C and H atoms. Geometric calculations of bond distances and bond angles were performed with PLATON (Spek, 1990). Molecular graphics were produced using ORTEPII (Johnson, 1976) International Union of Crystallography Printed in Great Britain - all rights reserved References Bemm, U., Lashgari, K., Norrestam, R., Nygren, M. & Westin, G. (1993). J. Solid State Chem. 103, Bemm, U., Norrestam, R., Nygren, M. & Westin, G. (1993). lnorg. Chem. 31, Bradley, D. C., Mehrotra, R. C. & Gaur, D. P. (1978). In Metal Alkoxides. London: Academic Press. Johnson. C. K. (1976). ORTEPII. Report ORNL Oak Ridge National Laboratory, Tennessee, USA. Shannon, R. D. (1976). Acta Cryst. A31, Sheldrick, G. M. (1976). SHELX76. Program for Crystal Structure Determination. Univ. of Cambridge, England. Sheldrick, G. M. (1985). SHELXS86. Program for the Solution of Crystal Structure. Univ. of Cambridge, England. Spek, A. L. (1990). PLATON. Program for the Analysis of Molecular Geometry. Univ. of Utrecht, The Netherlands. Acta Cryst. (1995). CSt, [Mn601{ OlC-3,5-(N01h-C6H3}1O (CsHsNh{ (CH3hCO h] 2(CH3hCO. 2(C1HshO and [Mn601(OlCC6Hsho (NCCH3)4] MALCOLMA. HALCROW,WILLIAM E. STREffi, KIRSTENFOLTING AND GEORGE CHRIsrou* Department of Chemistry and Molecular Structure Center, Indiana University, Bloomington, IN , USA (Received 10 March 1994; accepted 28 November 1994) Abstract The structures of di(acetone)tetrakis(j.t3-3,5-dinitrobenzoato-/\,20: /\,0' )hexakis(j.t- 3,5 -dinitrobenzoato-/\'o: /\'O')-di - j.t4 -oxo-di(pyridine )tetramanganese(ii)dimanganese(iii)-acetone-diethyl ether (1/2/2), (1), and tetrakis( acetonitrile )tetrakis(j.t3 -benzoato-/\,20: /\,0' )hexakis (Jl-benzoato-/\,O: /\'O')-di - Jl4 -oxo-tetramanganese(ii)dimanganese(iii), (2), are reported. Both compounds contain six octahedrally coordinated Mn centres, arranged as two MnlIMnlll(Jl4-0) tetrahedra sharing the MnlII_ MnlII edge. Acta Crystallographica Section C ISSN

2 1264 Comment The title compounds were obtained during our continuing research into manganese carboxylate chemistry (Christou, 1989). Both complexes contain the MI1(;02(02CRho(L)x (x = 4) structural motif previously observed in manganese benzoate and piva1ate chemistry (x = 4; Baikie, Howes, Hursthouse, Quick & Thornton, 1986; Gerbe1eu, Batsanov, Timko, Struchkov, Indrichan & Popovich, 1987; Schake, Vincent, Li, Boyd, Folting, Huffman, Hendrickson & Christou, 1989; Kohler, Roesky, Noltemeyer, Schmidt, Freire-Erdbriigger & Sheldrick, 1993: x = 5; Blackman, Huffman, Lobkovsky & Christou, 1992); since the distances and angles within the [MI1(;02] cores of (1) and (2) are identical to within 30", the structures will be considered together. & Guastini, 1981; di Vaira, Stoppioni & Mani, 1983; Smith, O'Reilly, Kennard, Mak & Yip, 1985; Zhang, Loebach, Wilson & Jacobsen, 1990). No close contacts are observed between the occluded solvent molecules in (I) and the Mn aggregate. Fig. 1. An ORTEP (Johnson, 1965) representation of (I) showing 50% probability ellipsoids. For clarity, only the ipso C atoms of the 3,5-dinitrobenzoate phenyl groups are shown. The Mn aggregates in both structures possess crystallographic C2 symmetry. The Mn.pMn~II oxidation state assignment for the clusters is confirmed by examination of the bond lengths to the Mn centres; Mn(1) exhibits shorter Mn-O distances with a pronounced Jahn-Teller elongation along the (equivalent) 0(5) Mn(1)--O(65) and 0(5)-Mn(1)--O(32) directions in (1) and (2), respectively, and was therefore assigned as the MnIII site. The disposition of the peripheral carboxylate and terminal ligands is in the more commonly observed arrangement for these complexes, with four p,3_k,20:k,o' and six p,2_0,o' carboxylate ligands and one terminal ligand per Mnll centre (Schake, Vincent, Li, Boyd, Folting, Huffman, Hendrickson & Christou, 1989). The Mn-O(carboxylate) and Mn-N distances are unexceptional and identical to within 30" in (1) and (2), despite the differences in carboxylate and terminal ligation between the two compounds; the cis- and trans-o-mn-x (X = 0, N) angles vary from 79 to 103 and from 163 to 176, respectively, the Mnll and MnIII centres showing similar degrees of distortion from ideal octahedral geometry. The acetone ligand in (1) is coordinated in the bent geometry typically observed for first-row metal complexes of this ligand [Mn(2)--O(86) (5), 0(86)--C(87) (10) A, Mn(2)--O(86) C(87) (6) ] (Gambarotta, Pasquali, Floriani, Villa Fig. 2. An ORTEP (Johnson, 1965) representation of (2) showing 50% probability ellipsoids. For clarity, only the ipso C atoms of the benzoate phenyl groups are shown.

3 (3) (3) C(21) C(27) C(23) N(l7) 0(18) C(36) (3) (2) C(4O) (3) (3) (3) (4) N(44) C(43),\ = Mo HALCROW, KCt radiation A STREIB, FOLTING 0(5) C(l2) N(l4) 0(7) C(I!) C(8) Cell h= standard 0(20) 0(22) C(25) C(26) N(29) 0(30) C(38) C(39) Dark 0.24 () parameters J.t k=0-+24 T I Irregular, = equidimensional xorange 0.24 reflections K23 approximately mm-1 xfrom mm 0(35) 0(31) N(32) N(47) C(53) C(54) C(56) C(58) N(59) 0(78) (4) (5) l.1oo (4) Beq 0(79) N(80) C(81) C(82) (3) (2) (2) z (2) y (I) (3) (2) (3) (2) (5) (4) 0(63) 0(46) 0(52) C(57) C(42) monitored insignificant intensity reflections decay: every 300 0(16) 0(48) 0(50) 0(61) N(62) C(69) llpmax Extinction Atomic llpmin for 6.2 secondary, fromx-ray x= International scattering coefficient: correction: Crystallography eisotropic ea-3 A-3 factors 0(67) Tables 0(37) C(lO) C(66) C(72) 0(75) 0(76) C(73) N(74) AND CHRISTOU 1265

4 (37)---Mn(3)---N(80) I M, Z=4 Orthorhombic 3.9(3) l [~02(C7H3N206)IO(C5H5N)2(C3~Oh] Cell B Pbna b JL parameters from 84 AND [M~02(C7H502)IO(C2H3N)4] a Dx Data B-2B / (4) eter c A Needle V (II) collection scans (7) (6) (15) (10) (11) (13) (12) 4h=O--> standard Picker four-circle (2) Mg T 0.34 Orange-brown (3) x 0.20 K A3 m-3 k diffractom- Bmax I = 0 = --> reflections w 0(4)---Mn(3)---N(80) 0(52)---Mn(3)---N(80) 0(37)---Mn(3)---O(52) 0(65)---Mn( Mn(2)---O(7)2.156 Mn(2)---O(22)2.173 Mn(2)---O(50)2.127 Mn(2)---O(5)2.319 Mn(2)---O(4)2.203 independent Absorption [F observed > 3u(F)] correction: (I) reflections reflections insignificant intensity monitored reflections R;n R Mn(l)---O(4)---Mn(l Mn(3)---O(67)2.169 Mn(3)---O(37)2.196(4) Mn(3)---O(65)2.262 Refinement on wr = F (b./u)max b.pmin Extinction b.pmax = = correction: mm-j decay: 0.02 xeverye 0.16 ea-3 A-300 mmnone S 3425 Only 0(52)---Mn(3)---O( 67)---Mn(3)---N z = 4F;/u2(F;) reflections H-atom )---0(67) (80) B's 67) ;) refinedfor Atomic from X-ray International scattering Crystallography factors Tables 7929 measured reflections 491 (1974, Vol. IV) parameters isotropic Biso for (42), C(27) Biso/Beq Mn(2)---O(4)---Mn(3) Mn(3)---O(52)---C(51) 0(14) Mn(2)---O(7)---C(6') Mn(3)---O(67)---C(66; Mn(3)---N(80)---C(85) Mn(2)---O(86)---C(87) Mn(3)---N(80)---C(81 C(l7) C(l8) Mn(2)---O(5)---C(6) 0(5) 0(7) C(8) Mn(2)---O(22)---C(21) Mn(2)---O(50)---C(51) C(l2) C(9) C(lO) C(lI) C(l3) C(l5) 0(16) C(l9) C(20) (5) (2) 3.0(3) (3) (4) Y )---O(4)---Mn(2) 1;)---O(4)---Mn(2) I 1)---O(20)---C(21) 1)---O(35)---C(36) i)---o(4 )---O(5)---Mn(2) 2.0(3) )---O(37)---C(36;) (I) (8) (7) (10) (6) 465)---C( (1) (8) (6) (7) (I) 65)---Mn(3) (4) (4) (4) (5) (6) x66) (21) (15) (18) (19) (20) (16) (17) )) Mo Ko radiation C(21) C(24) A = C(26) displacement Beq C(29) A = (1 /3)L,jL,jBijeiT parameters a; aj.aj (A2)for all others. (2) Table 3. Fractional atomic coordinates and equivalent C(83)

5 C(30) (9) (8) (5) (3) (5) (5) (3) (6) (7) (6) (5) (3) (3) (5) (5) (6) (6) (5) (6) (5) (4) (6) (6) (4) (6) (6) (6) 5.0(4) 2.9(3) 2.2(3) 2.1(2) 2.6(3) 3.1(3) 2.4(3) 2.3(3) 3.7(4) 1.8(3) 1.6(3) (7) (7) (5) (7) (7) (6) (4) (5) (6) (5) (6) (7) (6) (6) (2) (4) (4) (5) (2) (3) (5) (5) (4) (4) (2) (2) (4) (3) (5) (4) (4) (4) (3) (4) (6) (5) (3) (4) (4) 4.0(4) 2.0(3) 1.8(2) 3.4(3) 2.8(3) 2.5(3) 1.7(2) 1.7(3) (7) Table 4. Selected geometric parameters (A, O)for (2) Mn(1}-Mn(1') 2.807(3) Mn(2}-O(4) 2.203(6) Mn(1}-Mn(2) 3.122(3) Mn(2}-O(5) 2.271(6) Mn(1}-Mn(3') 3.142(3) Mn(2}-O(7) 2.115(6) Mn(1}-Mn(2') 3.538(3) Mn(2}-O(16) 2.169(6) Mn(1}-Mn(3) 3.554(3) Mn(2}-O(23) 2.082(7) Mn(2}-Mn(3) 3.789(3) Mn(2}-N(50) 2.252(9) Mn(1}-O(4') 1.883(6) Mn(3}-O(4) 2.187(6) Mn(1}-O(4) 1.895(6) Mn(3}-O(25) 2.122(6) Mn(1}-O(5) 2.246(6) Mn(3}-O(32') 2.294(6) Mn(1}-O(14) 1.970(6) Mn(3}-O(34) 2.120(6) Mn(1}-O(32) 2.232(6) Mn(3}-O(41) 2.148(6) Mn(1}-O(43) 1.955(6) Mn(3}-N(53) 2.283(8) 0(4'}-Mn(1}-O(4) 84.04(26) 0(4}-Mn(3}-N(53) (27) 0(4'}-Mn(1}-O(5) (25) 0(25}-Mn(3}-O(32') (23) 0(4}-Mn(1}-O(5) 86.92(25) 0(25}-Mn(3}-O(34) (24) 0(4'}-Mn(1}-o(14) (27) 0(25}-Mn(3}-O(41) 86.46(25) 0(4}-Mn(1}-O(14) 95.85(26) 0(25}-Mn(3}-N(53) 92.13(27) 0(4'}-Mn(1}-O(32) 85.53(24) 0(32'}-Mn(3}-O(34) 88.79(22) 0(4)-Mn(1}-O(32) 98.78(25) 0(32'}-Mn(3}-O(41) 83.56(23) 0(4'}-Mn(1}-O(43) 94.65(26) 0(32')-Mn(3}-N(53) 95.97(25) 0(4}-Mn(1}-O(43) (26) 0(34}-Mn(3}-O(41) (25) 0(5}-Mn(1}-O(14) 89.94(24) 0(34}-Mn(3}-N(53) 86.81(26) 0(5}-Mn(1}-O(32) (23) 0(41}-Mn(3}-N(53) 83.64(27) 0(5}-Mn(1}-O(43) 82.72(24) Mn(1}-O(4}-Mn(1') 95.96(26) 0(14}-Mn(1}-O(32) 84.38(24) Mn(1'}-O(4}-Mn(2) 119.7(3) 0(14}-Mn(I}-O(43) 87.35(26) Mn(1}-O(4)-Mn(2) 98.96(26) 0(32}-Mn(1}-O(43) 91.83(24) Mn(1'}-O(4}-Mn(3) (27) 0(4}-Mn(2}-O(5) 79.43(22) Mn(1}-O(4}-Mn(3) 120.9(3) 0(4}-Mn(2}-O(7) 96.60(23) Mn(2}-O(4)-Mn(3) (26) 0(4}-Mn(2}-O(16) 91.79(22) Mn(1}-O(5}-Mn(2) 87.45(22) 0(4}-Mn(2}-O(23) 92.37(25) Mn(1}-O(5}-C(6) 118.9(6) 0(4}-Mn(2}-N(50) (28) Mn(2}-O(5}-C(6) 146.8(6) 0(5}-Mn(2}-O(7) 90.15(24) Mn(2}-O(7}-C(6') 132.0(6) O(5}-Mn(2}-O(16) 85.24(23) Mn(1}-O(14}-C(15) 130.7(6) 0(5}-Mn(2}-O(23) (25) Mn(2}-O(16}-C(15) 125.9(6) 0(5}-Mn(2}-N(50) 91.51(27) Mn(2}-O(23}-C(24) 128.1(6) 0(7}-Mn(2}-O(16) (24) Mn(3}-O(25}-C(24) 125.8(6) 0(7}-Mn(2}-O(23) 97.66(26) Mn(1}-O(32}-Mn(3') 87.91(21) 0(7}-Mn(2}-N(50) 85.22(26) Mn(1}-O(32}-C(33) 120.4(5) 0(16)-Mn(2}-O(23) 88.18(25) Mn(3'}-O(32}-C(33) 146.9(6) 0(16}-Mn(2}-N(50) 85.52(26) Mn(3}-O(34}-C(33) 131.5(6) 0(23}-Mn(2}-N(50) 96.4(3) Mn(3}-O(41}-C(42') 126.1(6) 0(4}-Mn(3}-O(25) 93.77(24) Mn(1}-O(43}-C(42) 130.9(6) 0(4}-Mn(3}-O(32') 77.48(21) Mn(2}-N(50}-C(51) 161.8(8) 0(4}-Mn(3}-O(34) 95.75(23) Mn(3}-N(53}-C(54) 168.3(8) 0(4}-Mn(3}-O(41) 92.77(23) Symmetry code: (i) x,!-y, -z. HALCROW, STREIB, FOLTING AND CHRISTOU 1267 Procedures employed by the Molecular Structure Center for data collection and structure solution and refinement have been described elsewhere (Chisholm, Folting, Huffman & Kirkpatrick, 1984). The structures were solved by direct methods and refined using difference Fourier techniques. Anisotropic displacement parameters were refined for all nondisordered non-h atoms [except C(42) in structure (2), which was refined isotropically] while H atoms were included in calculated positions with freely refining Biso. Figures were generated using ORTEP (Johnson, 1965). In addition to the molecule of interest, structure (1) was found to contain a well ordered molecule of acetone lying on a crystallographic twofold axis, and a well ordered molecule of Et20 at a general position. At a different twofold axis, a number of peaks were observed that could not be positively identified: these were refined as C atoms (site occupancy 0.5), and for the purposes of the density calculations this region of the structure was assumed to represent a disordered molecule of acetone. Structure (2) contained no occluded solvent molecules. High displacement parameters on some benzoate aromatic C atoms of structure (2), notably C(27~(31), may be indicative of orientational disorder in these groups, thus accounting for the slightly high R value associated with this structure. This was not modelled, however, because of the relatively low ratio of the number of refined parameters to observed reflections in this refinement. This work was funded by NIH grant GM Lists of structure factors, anisotropic displacement parameters, H atom coordinates and complete geometry have been deposited with the rvcr (Reference: FGlOOO). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CHI 2HU, England. References Baikie, A. R. E., Howes, A. J., Hursthouse, M. B., Quick, A. B. & Thornton, P. (1986). J. Chern. Soc. Chern. Cornrnun. p Blackman, A. G., Huffman, J. C., Lobkovsky, E. B. & Christou, G. (1992). Polyhedron, 11, Chisholm, M. H., Folting, K., Huffman, J. C. & Kirkpatrick, C. C. (1984). Inorg. Chern. 23, Christou, G. (1989). Ace. Chern. Res. 22, Gambarotta, S., Pasquali, M., Floriani, C., Villa, A. C. & Guastini, C. (1981). Inorg. Chern. 20, Gerbeleu, N. V., Batsanov, A. S., Timko, G. A., Struchkov, Yu. T., Indrichan, K. M. & Popovich, G. A. (1987). Dokl. Akad. Nauk SSSR, 294, Johnson, C. K. (1965). ORTEP. Report ORNL Oak Ridge National Laboratory, Tennessee, USA. Kohler, K., Roesky, H. W., Noltemeyer, M., Schmidt, H.-G., Freire Erdbriigger, C. & Sheldrick, G. M. (1993). Chern. Ber. 126, Schake, A. R., Vincent, J. B., Li, Q., Boyd, P. D. W., Folting, K., Huffman, J. c., Hendrickson, D. N. & Christou, G. (1989). Inorg. Chern. 28, Smith, G., O'Reilly, E. J., Kennard, C. H. L., Mak, T. C. W. & Yip, W. H. (1985). Polyhedron, 4, Vaira, M. di, Stoppioni, P. & Mani, F. (1983). J. Organornet. Chern. 247, Zhang, W., Loebach, J. L., Wilson, S. R. & Jacobsen, J. Arn. Chern. Soc. 112, E. N. (1990).

6 1268 [Mn(C7 ~ 03)(C lohgnz)(hzo)z]ci04.hzo Acta Cryst. (1995). CS1, trans-diaqua(bipyridyl)(salicylato) manganese(iii) Perchlorate Monohydrate XIANG-SHI TAN Coordination Chemistry State Key Laboratory, Coordination Chemistry Institute, Nanjing University, Nanjing , People's Republic of China JIAN CHEN AND PEI-JV ZHENG Research Center of Analysis and Measurement, Fudan University, Shanghai , People's Republic of China WEN-XIA TANG Coordination Chemistry State Key Laboratory, Coordination Chemistry Institute, Nanjing University, Nanjing , People's Republic of China (Received 27 April 1994; accepted 10 January 1995) Abstract The mononuclear manganese(iii) complex [Mn(sal) (bpy)(hzo)z]ci04.hzo (sal = salicylate, C7~0:f-; bpy = bipyridyl, CIOHgNz) has been prepared and characterized by X-ray analysis. The manganese(iii) ion displays elongated octahedral coordination with mutually trans water molecules occupying axial sites. The equatorial plane, defined by two sal 0 atoms and two bpy N atoms, nearly coincides with the sal and bpy ligand planes and with the metal ion. The asymmetric unit (Fig. 1) consists of the complex cation [Mn(sal)(bpy)(HzOht, a Cl04- anion and a water molecule. The MoIII ion is hexacoordinate and possesses an NZ04 ligand environment by virtue of the bidentate salicylate and bipyridyl ligands which form the equatorial plane (011, 012, N201 and N208) and the two axial water molecules which complete an octahedron round the metal ion. The phenolate and carboxylate 0 atoms 011 and 012 are cis. The equatorial Mn-011 and Mn-012 bond lengths [1.830 (2) and (4) A, respectively] are similar to those in the complex [Mn(EtOH)4][Mnz(saIMpyh] (py = pyridine) (Vincent, Huffman & Christou, 1986) in which the MnIIl-N bond lengths lie in the range to A. The Mn-N bond lengths in the title complex [2.034 (3) and (4) A] are longer, but agree with the values observed for MnIIl(hgnh (hgn = 8-hydroxyquinolinate) ( A). The axial Mn-O distances [2.225 (4) and (4) A] are distinctly longer than those in the equatorial plane. Such marked axial elongation is typical for high spin d4 systems. With the exceptions of the internal bpy angle N201-Mn-N208 [79.2 (00], which is restricted by the five-membered chelate ring, and 012-Mn-N201 [171.0(2) ], the bond angles at Mn [86.2(1) to 95.6(1), and 174.0(1) ] are reasonably close to those for an ideal octahedron (90 and 180, respectively). The deviation of the Mn atom from the NzOz equatorial plane is A; the Mn atom and all bpy and salicylate atoms are approximately coplanar. The Cl04- anion is linked to a coordinated water molecule by the hydrogen bond 02-Hw ( A, 02-Hw ). Comment The chemistry of manganese is currently receiving much attention owing to its participation in many biological systems (Christou, 1989). Of particular importance has been the realisation that manganese plays an essential and specific role in the water-oxidizing complex of photo system II (Christou, 1989; Wieghardt, 1989). We now report the preparation and structure of the title mononuclear manganese(iii) complex, (I), which contains a salicylate ligand whose phenoxide and carboxylate functions act as convenient models for the side groups of the amino acids tyrosine and aspartic and glutamic acid. 043 CI International Union of Crystallography Printed in Great Britain - all rights reserved (I) ~ 03 Fig. 1. The asymmetric unit showing 50% probability displacement ellipsoids. H atoms are omitted for clarity. 01 Acta Crysta/lographica Section C ISSN