C28H22CdN206, monoclinic, Pl\ln (no. 14), a = 11.505(4) Â, b = 16.787(7) Â, c = 13.457(4) Â,/3 = 106.69(2)°, V = 2489.5 Â, Ζ = 4, Rgt(F) = 0.039, wR^F) = 0.112, Τ =293 Κ. Source of material The salicylatocadmium(II) [Cd(Sal)2] was prepared by reaction of Cd(NC>3)2 · 4H20 with NaSal after neutralizing HSal with a NaOH solution. An amount of 0.387 g of Cd(Sal)2 (1 mmole) and 0.210 g of neocuproine (1 mmole) were dissolved in 20 ml of methanol. The solution was stirred at 50 °C under reflux conditions for 2 hours to give the complex. Single crystals were obtained by slow evaporation of this solution. Discussion In previous work, we have synthesized and structurally characterized the ternary bis(3,5-diisopropylsalicylato)(2,9-dimethyll,10-phenanthroline)zinc complex in an effort to examine their anticonvulsivant properties [1]. Since zinc and cadmium belong to the same group 12 of the Periodic System of elements, following this work, recently we described the crystal structure of bis(3,5-diisopropylsalicylato)(2,9-dimethyl-l,10-phenanthroline)cadmium(II) complex [2] as an extension of an ongoing crystal structure investigation of non-steroidal antiinflammatory drug zinc carboxylate complexes. In the title crystal structure, the Cd atom is surrounded by two bidentate salicylate anionic (sal) ligands via atoms 01 ,02 (L1 ) or O i l , 012 (L2) and one bidentate 2,9-dimethyl-l,10-phenanthroline (neocuproine) ligand coordinated via atoms N21 and N30 (L3). The complex exhibits a highly irregular octahedral environment of the Cd atom, with apical positions occupied by Ol 1 andN21 withOl 1-Cd-N21 angle of 140.6(1)°. The fourdonor atoms Ol, 02,012, N30 form a basal plane with a maximal distance from best mean plane of 0.075(2) Â for 02 and Cd being 0.213(2) Â apart this plane. The degree of deviation from an ideal octahedron is appreciable with angles in the basal plane ranging from 53.9(1)° to 109.3(1)°. The distances Cd—N21 (2.279(3) Â) and Cd—N30 (2.312(3) Â) are in good agreement with those observed in bis(3,5-diisopropylsalicylato)(2,9dimethyl-l,10-phenanthroline)cadmium(II) [2]. Three of the four Cd—O bond lengths range from 2.225(3) Â to 2.350(3) Â which correspond to those found in other Cd complexes [3,4]. The fourth relatively long Cd—-Ol (2.517(4) Â) distance may indicate that the coordination mode of the carboxylato group of the LI salicylato ligand is indeed a hybrid between monodentate and bidentate with the latter contribution being predominant. The chelation of Cd by the salicylato ligands (LI or L2) leads to planar rings pi (01/Cl/02/Cd) and p2 (Ol 1/C11/ 012/Cd) with the maximum deviation is 0.033(3) À for C1 atom and a dihedral angle between planes pi and p2 of 85.7(1)°. L2 bidentate ligand is near to planarity with a maximum deviation of the corresponding mean plane of0.075(3) Â for Ol 1 atom and Cd being 0.232(4) Â apart this plane contrary to LI ligand which is far to the planari ty with maximum deviation of 0.187(3) À for 02 atom and Cd being 0.385(4) Â apart this plane. These values confirm the hybrid character of the chelation for LI. Internal hydrogen bonding interaction are 0 3 H 3 0 1 (2.590(6) Â, 147°) and 013-H13-011 (2.571(5) Â, 146°). The crystal packing of the complex is governed by numerous C-Η—O interactions (the most important being C16-H16-02': 3.312(9) Â, 142°; C24-H24—012": 3.406(5) Â, 150° with symmetry codes i: -Jc+3/2,y-l/2,3/2-z; ii: 2-x,2-y,2-z) and two C-H-Cg (π-ring) interactions (H23 Cgl : 2.61 À; C23-H23-Cgl : 145°; H4—Cg2': 2.95 Â; C4-H4-Cg2: 165°; with Cgl and Cg2 centroid of rings p3 (C2/C7) and p4 (C12/C17) respectively; iii: l-x, -y-z and iv: l+x,y¿). ' Correspondence author (e-mail: pascale.lemoine@parisdescartes.fr) Unauthenticated Download Date | 5/30/19 8:28 PM 144 Cd(C7Hs03)2(Cl4Hl2N2) Table 1. Data collection and handling. Crystal: colorless parallelepiped. size 0.16 χ 0.18 χ 0.25 mm Wavelength: Mo Ka radiation (0.71073 Â) ft9.24 cm" 1 Diffractometer, scan mode: Enraf-Nonius CAD4, ω/θ 2θηαχ. 49.96" NOlUWd, Nf/ i i /W,«: 8709,4365 Criterion for /obs, N(hki)ρ: /obs > 2 a(lobs), 3100 N(param)nfaxA'· 334 Programs: SIR92 [5], SHELXL-97 [6] CAMERON [7], WinGX [8] Table 2. Atomic coordinates and displacement parameters (in A). Atom Site X y ζ í/uo H(3) 4c 0.3344 0.8303 0.7207 0.134 H(4) 4c 0.0380 0.8519 0.6394 0.116 H(5) 4c -0.0580 0.9734 0.6065 0.141 Table 2. Continued. Atom Site χ y ζ UISo H(6) 4c 0.0497 1.0896 0.6219 0.117 H(7) 4c 0.2602 1.0873 0.6756 0.092 H(13) 4e 0.6376 0.8490 0.4864 0.126 H(14) 4c 0.7817 0.7121 0.3958 0.134 H(15) 4c 0.9343 0.6365 0.4952 0.157 H(16) 4c 0.9991 0.6487 0.6719 0.145 H(17) 4c 0.9126 0.7460 0.7544 0.112 H(23) 4c 0.8717 0.9998 1.1560 0.080 H(24) 4c 1.0045 1.0968 1.1424 0.082 H(25) 4c 1.0716 1.1963 1.0294 0.086 H(26) 4c 1.0568 1.2474 0.8732 0.087 H(27) 4e 0.9479 1.2513 0.6795 0.082 H(28) 4c 0.7964 1.2019 0.5420 0.079 H(35A) 4c 0.6178 0.9513 1.0036 0.130 H(35B) 4c 0.7246 0.9006 1.0737 0.130 H(35C) 4c 0.6879 0.8910 0.9528 0.130 H(36A) 4c 0.6642 1.0386 0.5080 0.110 H(36B) 4c 0.6116 1.1248 0.4829 0.110 H(36C) 4c 0.5689 1.0711 0.5610 0.110 Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ Un t/22 ί/33 Un Un t/23 Cd 4c 0.65318(2) 0.97540(2) 0.75493(2) 0.0408(2) 0.0550(2) 0.0589(2) -0.0061(1) 0.0042(1) -0.0062(1) CHD 4c 0.4649(3) 0.9010(2) 0.7595(3) 0.060(2) 0.096(3) 0.089(2) 0.019(2) 0.015(2) 0.015(2) C(l) 4c 0.4100(4) 0.9644(3) 0.7260(3) 0.048(2) 0.076(3) 0.052(2) 0.000(2) 0.008(2) -0.008(2) 0(2) 4c 0.4662(3) 1.0250(2) 0.7162(3) 0.051(2) 0.075(2) 0.120(3) -0.010(2) 0.020(2) -0.017(2) C(2) 4« 0.2749(4) 0.9666(3) 0.6938(3) 0.045(2) 0.079(3) 0.046(2) -0.005(2) 0.011(2) -0.001(2) 0(3) 4c 0.2605(4) 0.8251(3) 0.7007(4) 0.119(3) 0.092(3) 0.131(4) -0.014(3) 0.049(3) 0.004(3) C(3) 4c 0.2080(5) 0.8975(3) 0.6823(4) 0.072(3) 0.088(4) 0.065(3) -0.014(3) 0.023(2) 0.000(3) C(4) 4c 0.0827(5) 0.8988(5) 0.6482(4) 0.065(3) 0.146(6) 0.079(4) -0.037(4) 0.021(3) -0.015(4) C(5) 4c 0.0263(5) 0.9714(6) 0.6276(5) 0.050(3) 0.23(1) 0.067(4) -0.001(5) 0.012(3) 0.000(5) C(6) 4c 0.0906(5) 1.0414(5) 0.6373(4) 0.074(3) 0.143(6) 0.072(3) 0.041(4) 0.015(3) 0.020(4) C(7) 4c 0.2159(4) 1.0403(3) 0.6698(4) 0.061(3) 0.101(4) 0.068(3) 0.023(3) 0.017(2) 0.013(3) C( l l ) 4c 0.7414(3) 0.8515(2) 0.6707(4) 0.046(2) 0.046(2) 0.078(3) -0.011(2) 0.016(2) -0.002(2) OUD 4c 0.6611(3) 0.8977(2) 0.6140(2) 0.069(2) 0.059(2) 0.067(2) 0.013(1) 0.005(2) -0.004(1) 0(12) 4c 0.7757(3) 0.8618(2) 0.7665(2) 0.062(2) 0.068(2) 0.068(2) -0.002(2) 0.003(2) -0.003(2) 0(13) 4c 0.6640(4) 0.8168(2) 0.4525(3) 0.142(4) 0.084(3) 0.087(3) 0.006(3) 0.032(3) -0.008(2) C(12) 4c 0.7933(4) 0.7881(2) 0.6203(4) 0.055(2) 0.044(2) 0.095(3) -0.007(2) 0.032(2) 0.002(2) C(13) 4c 0.7544(5) 0.7765(3) 0.5150(5) 0.086(3) 0.050(3) 0.107(4) -0.008(2) 0.048(3) -0.007(3) C(14) 4c 0.8078(7) 0.7192(4) 0.4673(6) 0.132(6) 0.081(4) 0.151(6) -0.017(4) 0.084(5) -0.030(4) C(15) 4c 0.8978(8) 0.6742(4) 0.5270(9) 0.132(7) 0.070(4) 0.23(1) 0.003(4) 0.114(8) -0.013(6) C(16) 4c 0.9380(6) 0.6818(4) 0.6332(8) 0.082(4) 0.067(4) 0.230(9) 0.014(3) 0.071(6) 0.034(5) C(17) 4e 0.8864(4) 0.7397(3) 0.6828(6) 0.055(3) 0.055(3) 0.176(6) 0.005(2) 0.044(3) 0.020(3) N(21) 4c 0.7755(3) 1.0211(2) 0.9091(2) 0.040(2) 0.058(2) 0.050(2) -0.001(1) 0.006(1) -0.001(2) C(22) 4c 0.7827(4) 0.9917(3) 1.0025(3) 0.053(2) 0.072(3) 0.054(2) 0.000(2) 0.012(2) 0.001(2) C(23) 4c 0.8684(4) 1.0208(3) 1.0912(3) 0.058(3) 0.088(3) 0.049(2) 0.005(2) 0.006(2) 0.000(2) C(24) 4c 0.9461(4) 1.0790(3) 1.0834<3) 0.053(2) 0.091(3) 0.054(3) 0.000(2) 0.001(2) -0.017(2) C(25) 4c 1.0137(4) 1.1757(3) 0.9719(4) 0.053(2) 0.078(3) 0.077(3) -0.021(2) 0.009(2) -0.027(3) C(26) 4c 1.0046(4) 1.2066(3) 0.8795(4) 0.063(3) 0.067(3) 0.088(4) -0.025(2) 0.023(2) -0.020(3) C(27) 4c 0.8985(4) 1.2100(3) 0.6895(4) 0.074(3) 0.056(2) 0.081(3) -0.012(2) 0.032(3) -0.002(2) C(28) 4c 0.8092(4) 1.1803(3) 0.6079(4) 0.078(3) 0.056(3) 0.063(3) 0.002(2) 0.020(2) 0.005(2) C(29) 4c 0.7371(4) 1.1173(3) 0.6237(3) 0.057(2) 0.055(2) 0.052(2) 0.005(2) 0.010(2) -0.001(2) N(30) 4c 0.7535(3) 1.0848(2) 0.7153(2) 0.042(2) 0.049(2) 0.053(2) 0.000(1) 0.006(1) -0.002(2) C(31) 4c 0.8403(3) 1.1146(2) 0.7987(3) 0.042(2) 0.044(2) 0.055(2) 0.000(2) 0.012(2) -0.011(2) C(32) 4c 0.9151(4) 1.1777(2) 0.7889(3) 0.053(2) 0.051(2) 0.073(3) -0.007(2) 0.021(2) -0.011(2) C(33) 4c 0.9390(3) 1.1127(3) 0.9868(3) 0.043(2) 0.064(3) 0.056(2) -0.002(2) 0.006(2) -0.017(2) C(34) 4c 0.8516(3) 1.0815(2) 0.9002(3) 0.038(2) 0.049(2) 0.056(2) 0.001(2) 0.009(2) -0.009(2) C(35) 4c 0.6956(5) 0.9280(4) 1.0087(4) 0.074(3) 0.110(4) 0.072(3) -0.020(3) 0.015(2) 0.019(3) C(36) 4c 0.6364(4) 1.0851(3) 0.5361(3) 0.077(3) 0.075(3) 0.055(3) -0.005(3) 0.000(2) 0.003(2) Unauthenticated Download Date | 5/30/19 8:28 PM C d ( C 7 H 5 0 3 ) 2 ( C i 4 H i 2 N 2 ) 1 4 5

C22H23Br5N4O2, monoclinic, P2/n (no. 13), a = 12.5980(6) Å, b = 6.0596(2) Å, c = 17.9790(8) Å, β= 105.253(2)°, V = 1324.2 Å3, Z = 2, Rgt(F) = 0.0416, wRref(F2) = 0.1100, T = 293 K.

C39H30CdN4O7, monoclinic, P12(1)/n1 (no. 14), a = 10.823(5) angstrom, b = 26.455(9) angstrom, c = 11.703(6) angstrom, beta = 92.37(4)degrees, V = 3348.0 angstrom(3), Z = 4, R-gt(F) = 0.044, wR(ref)(F-2) = 0.129, T = 293 K.

Triazole chelators, synthesized by click chemistry, are convenient ligands for palladium(II) and platinum(II). Conformational changes induced by the complexation of these Pd-II and Pt-II complexes with guanosine are similar to those of cisplatin. In addition, these complexes behave like cisplatin with regard to the relaxation of supercoiled plasmid DNA.

C11H13ClN2O2, triclinic, P (1) over bar (no. 2), a = 7.150(5) angstrom, b = 8.380(2) angstrom, c = 10.586(2) angstrom, alpha = 71.80(2)degrees, beta = 84.05(5)degrees, gamma = 87.47(5)degrees, V = 599.3 angstrom(3), z = 2, R-gt(F) = 0.049, wR(ref)(F-2) = 0.176, T = 293 K.

Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC−) or isoquinolinecarboxylate (IQC−) with 1,10-phenanthroline (phen) in methanol or in dimethylacetamide (DMA) were synthesized and studied by X-ray diffraction and IR spectra. [Mn(C9H6NO2)2(C12H8N2)2]·CH4O (1) crystallizes in the triclinic space group P-1 with cell parameters of a = 10.548(2) Å, b = 14.168(3) Å, c = 14.580(3) Å, α = 62.35(2)°, β = 69.16(2)°, γ = 78.61(2)°, V = 1802.4(6) Å3 and Z = 2; [Mn(C10H6NO2)2(C12H8N2)].C4H9NO (2) crystallizes in the monoclinic space group P21/a with cell parameters of a = 15.304(5) Å, b = 12.871(5) Å, c = 17.421(5) Å, β = 114.39(1), V = 3125(2) Å3 and Z = 4. In 1, Mn is six-coordinate by two bidentate phen ligands and two 2-IC− ligands and exhibits a very distorted octahedral geometry. This complex is solvated by methanol involved in hydrogen bonding. In 2, Mn atom is surrounded by one bidentate phen ligand and two bidentate IQC− ligands. The complex exhibits a distorted octahedral geometry around the MnII atom. The crystal structure is completed by a disordered DMA solvate molecule. The IR spectra of both compounds are slightly different in the range 4000–2400 cm−1 which may be attributed to hydrogen bond lack in 2.

The title compound, [Cd(C7H5O3)2(C10H8N2)2]&#183;CH3OH, contains one monomeric seven-coordinate cadmium complex and one methanol solvate molecule. The CdII atom is coordinated to two 2,2&#8242;-bipyridyl ligands via the N atoms and to two salicylate anions (Hsal&#8722;) via the carboxylate O atoms, which act as monodentate ligand for the one and bidentate ligand for the second. The CdII atom exhibits a {6&#160;+&#160;1} environment, approximately described as a distorted capped octahedron with the apical positions occupied by one of the two N atoms belonging to one bipyridyl ligand and one of the two carboxylate O atoms from the monodentate Hsal&#8722; ligand. Two intramolecular six-membered hydrogen-bonded rings are present, generated from interactions between the carboxylate and hydroxy groups of the salicylate ligands. There is one intermolecular hydrogen-bonding interaction involving the methanol solvent molecule and the carboxylate group from the monodentate Hsal&#8722; ligand. The crystal packing is governed by &#960;&#8211;&#960; stacking interactions [centroid&#8211;centroid distance = 3.783&#8197;(4)&#8197;&#197;] which occur between bipyridyl ligands, by C&#8212;H...O and C&#8212;H...&#960; interactions and by numerous van der Waals contacts.

The title compound, [Cd(C7H5O3)(2)(C10H8N2)(2)]center dot CH3OH, contains one monomeric seven-coordinate cadmium complex and one methanol solvate molecule. The Cd-II atom is coordinated to two 2,2'-bipyridyl ligands via the N atoms and to two salicylate anions (Hsal(-)) via the carboxylate O atoms, which act as monodentate ligand for the one and bidentate ligand for the second. The Cd-II atom exhibits a {6 + 1} environment, approximately described as a distorted capped octahedron with the apical positions occupied by one of the two N atoms belonging to one bipyridyl ligand and one of the two carboxylate O atoms from the monodentate Hsal(-) ligand. Two intramolecular six-membered hydrogen-bonded rings are present, generated from interactions between the carboxylate and hydroxy groups of the salicylate ligands. There is one intermolecular hydrogen-bonding interaction involving the methanol solvent molecule and the carboxylate group from the monodentate Hsal(-) ligand. The crystal packing is governed by pi-pi stacking interactions [centroid-centroid distance = 3.783 (4) angstrom] which occur between bipyridyl ligands, by C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions and by numerous van der Waals contacts.

C30.5H28.5CdN3.5O7.5, triclinic, P1 (no. 2), a = 9.857(2) Å, b = 11.005(2) Å, c = 14.953(2) Å, + = 77.37(2)°, * = 79.27(2)°, & = 69.07(1)°, V = 1467.9 Å, Z = 2, Rgt(F) = 0.044, wRref(F) = 0.135, T = 293 K. Source of material The salicylatocadmium(II) [Cd(Sal)2] was prepared by reaction of Cd(NO3)2.·.4H2O with NaSal obtained by neutralizing HSal with a NaOH solution (Sal = salicylate). An amount of 0.387 g of Cd(Sal)2 (1 mmole) and 0.200 g of 1,10-phenanthroline (phen, 1 mmole) were dissolved in 10 ml of dimethylformamide (DMF). The solution was stirred at 50 °C under reflux for 2 hours. Then solution was layered, and single crystals were obtained after 48 hours by solvent evaporation. Discussion In previous works, we had reported structural characterization of two ternary cadmium(II) complexes with neocuproine(2,9dimethyl-1,10-phenanthroline) and arylcarboxylic acids [1,2] to compare them with analogous zinc(II) complexes [3]. In the title crystal structure, Cd is bonded to one bidentate 1,10phenanthroline (phen) ligand, one dimethylformamide ligand and two salicylate anions (Sal) ligands: one (L1) is monodentate via atom O22 and the other (L2) is bidentate via atoms O31 and O32. The crystal structure is completed by a half molecule of dimethylformamide. The complex exhibits a highly distorded octahedral environment of the Cd(II) atom with apical positions occupied by N10 and O22 with an angle of 149.5(1)° for N10–Cd–O22. The four donor atoms N1, O31, O32, O41 form a equatorial plane with maximal distance from their best meanplane of 0.130(2) Å for N1, Cd being 0.353(2) Å outside of this plane. The degree of deviation from an ideal octahedron is appreciable with angles in the equatorial plane ranging from 54.06(9)° to 126.5(1)°. The Cd—N bond lengths are very close to each other but not equivalent within 3 e.s.d. [mean: 2.343(3) Å] and comparable with distances found in other phenanthroline Cd complex [4]. The distances between Cd and the oxygen atoms are: d(Cd—O41) = 2.301(3) Å for the DMF; d(Cd—O31) = 2.404(3).Å and d(Cd—O32) = 2.396(3) Å for L2, comparable with those found in analogous Cd complex [5]; d(Cd—O22) = 2.204(3).Å for L1, similar to distance found in bis(salicylato)(2,2'-bipyridyl)(dimethylformamide)cadmium(II)] for a monodentate mode [6]. Beside that, there is a very longer distance (d(Cd—O21) = 2.960(3) Å) giving a coordination of the type 6.+.1. The bond lengths and angles in the ligands are normal. The monodentate salicylato ligand shows a planar ring p1 (O21O23/C21-C27) with a maximum deviation of 0.039(3) Å for C22 atom and Cd being 0.360(4) Å outside of this plane. In contrary, the ring p2 (O31-O33/C31-C37) is far to the planarity with a maximum deviation of 0.167(3) Å for O31 atom and Cd being 0.109(3) Å outside of this plane; this last low value is in agreement with the bidentate mode of L2. The dihedral angle between p1 and p2 is 83.13(5)°. There are two intramolecular hydrogen bonds: O23–H23···O21 [2.544(5) Å, 148°] and O33–H33···O31 [2.542(4) Å, 147°]. The planes C5-C6/C11-C14 and N1/C2C4/C13-C14 of phenanthroline ligand are --stacked in pairs, through inversion centre at (1⁄2 0 1⁄2) with an average spacing of 3.406(5) Å. The crystalline cohesion is ensured by many van der Waals contacts, the shortest being 3.080(2) Å. Z. Kristallogr. NCS 224 (2009) 673-675 / DOI 10.1524/ncrs.2009.0296 673 © by Oldenbourg Wissenschaftsverlag, München

C12H22Br3N3O3 ,m onoclinic, P121/a 1( no. 14), a =1 1.932(2) A, b =1 0.091(2) A, c =1 5.514(3) A, * =1 05.19(2)°, V =1 802.7 A 3 , Z =4 , Rgt(F) =0 .038, wRref(F 2 ) =0 .114, T =2 93 K.

C28H22CdN206, monoclinic, Pl\ln (no. 14), a = 11.505(4) Â, b = 16.787(7) Â, c = 13.457(4) Â,/3 = 106.69(2)°, V = 2489.5 Â, Ζ = 4, Rgt(F) = 0.039, wR^F) = 0.112, Τ =293 Κ. Source of material The salicylatocadmium(II) [Cd(Sal)2] was prepared by reaction of Cd(NC>3)2 · 4H20 with NaSal after neutralizing HSal with a NaOH solution. An amount of 0.387 g of Cd(Sal)2 (1 mmole) and 0.210 g of neocuproine (1 mmole) were dissolved in 20 ml of methanol. The solution was stirred at 50 °C under reflux conditions for 2 hours to give the complex. Single crystals were obtained by slow evaporation of this solution. Discussion In previous work, we have synthesized and structurally characterized the ternary bis(3,5-diisopropylsalicylato)(2,9-dimethyll,10-phenanthroline)zinc complex in an effort to examine their anticonvulsivant properties [1]. Since zinc and cadmium belong to the same group 12 of the Periodic System of elements, following this work, recently we described the crystal structure of bis(3,5-diisopropylsalicylato)(2,9-dimethyl-l,10-phenanthroline)cadmium(II) complex [2] as an extension of an ongoing crystal structure investigation of non-steroidal antiinflammatory drug zinc carboxylate complexes. In the title crystal structure, the Cd atom is surrounded by two bidentate salicylate anionic (sal) ligands via atoms 01 ,02 (L1 ) or O i l , 012 (L2) and one bidentate 2,9-dimethyl-l,10-phenanthroline (neocuproine) ligand coordinated via atoms N21 and N30 (L3). The complex exhibits a highly irregular octahedral environment of the Cd atom, with apical positions occupied by Ol 1 andN21 withOl 1-Cd-N21 angle of 140.6(1)°. The fourdonor atoms Ol, 02,012, N30 form a basal plane with a maximal distance from best mean plane of 0.075(2) Â for 02 and Cd being 0.213(2) Â apart this plane. The degree of deviation from an ideal octahedron is appreciable with angles in the basal plane ranging from 53.9(1)° to 109.3(1)°. The distances Cd—N21 (2.279(3) Â) and Cd—N30 (2.312(3) Â) are in good agreement with those observed in bis(3,5-diisopropylsalicylato)(2,9dimethyl-l,10-phenanthroline)cadmium(II) [2]. Three of the four Cd—O bond lengths range from 2.225(3) Â to 2.350(3) Â which correspond to those found in other Cd complexes [3,4]. The fourth relatively long Cd—-Ol (2.517(4) Â) distance may indicate that the coordination mode of the carboxylato group of the LI salicylato ligand is indeed a hybrid between monodentate and bidentate with the latter contribution being predominant. The chelation of Cd by the salicylato ligands (LI or L2) leads to planar rings pi (01/Cl/02/Cd) and p2 (Ol 1/C11/ 012/Cd) with the maximum deviation is 0.033(3) À for C1 atom and a dihedral angle between planes pi and p2 of 85.7(1)°. L2 bidentate ligand is near to planarity with a maximum deviation of the corresponding mean plane of0.075(3) Â for Ol 1 atom and Cd being 0.232(4) Â apart this plane contrary to LI ligand which is far to the planari ty with maximum deviation of 0.187(3) À for 02 atom and Cd being 0.385(4) Â apart this plane. These values confirm the hybrid character of the chelation for LI. Internal hydrogen bonding interaction are 0 3 H 3 0 1 (2.590(6) Â, 147°) and 013-H13-011 (2.571(5) Â, 146°). The crystal packing of the complex is governed by numerous C-Η—O interactions (the most important being C16-H16-02': 3.312(9) Â, 142°; C24-H24—012": 3.406(5) Â, 150° with symmetry codes i: -Jc+3/2,y-l/2,3/2-z; ii: 2-x,2-y,2-z) and two C-H-Cg (π-ring) interactions (H23 Cgl : 2.61 À; C23-H23-Cgl : 145°; H4—Cg2': 2.95 Â; C4-H4-Cg2: 165°; with Cgl and Cg2 centroid of rings p3 (C2/C7) and p4 (C12/C17) respectively; iii: l-x, -y-z and iv: l+x,y¿). ' Correspondence author (e-mail: pascale.lemoine@parisdescartes.fr) 144 Cd(C7Hs03)2(Cl4Hl2N2) Table 1. Data collection and handling. Crystal: colorless parallelepiped. size 0.16 χ 0.18 χ 0.25 mm Wavelength: Mo Ka radiation (0.71073 Â) ft9.24 cm" 1 Diffractometer, scan mode: Enraf-Nonius CAD4, ω/θ 2θηαχ. 49.96" NOlUWd, Nf/ i i /W,«: 8709,4365 Criterion for /obs, N(hki)ρ: /obs > 2 a(lobs), 3100 N(param)nfaxA'· 334 Programs: SIR92 [5], SHELXL-97 [6] CAMERON [7], WinGX [8] Table 2. Atomic coordinates and displacement parameters (in A). Atom Site X y ζ í/uo H(3) 4c 0.3344 0.8303 0.7207 0.134 H(4) 4c 0.0380 0.8519 0.6394 0.116 H(5) 4c -0.0580 0.9734 0.6065 0.141 Table 2. Continued. Atom Site χ y ζ UISo H(6) 4c 0.0497 1.0896 0.6219 0.117 H(7) 4c 0.2602 1.0873 0.6756 0.092 H(13) 4e 0.6376 0.8490 0.4864 0.126 H(14) 4c 0.7817 0.7121 0.3958 0.134 H(15) 4c 0.9343 0.6365 0.4952 0.157 H(16) 4c 0.9991 0.6487 0.6719 0.145 H(17) 4c 0.9126 0.7460 0.7544 0.112 H(23) 4c 0.8717 0.9998 1.1560 0.080 H(24) 4c 1.0045 1.0968 1.1424 0.082 H(25) 4c 1.0716 1.1963 1.0294 0.086 H(26) 4c 1.0568 1.2474 0.8732 0.087 H(27) 4e 0.9479 1.2513 0.6795 0.082 H(28) 4c 0.7964 1.2019 0.5420 0.079 H(35A) 4c 0.6178 0.9513 1.0036 0.130 H(35B) 4c 0.7246 0.9006 1.0737 0.130 H(35C) 4c 0.6879 0.8910 0.9528 0.130 H(36A) 4c 0.6642 1.0386 0.5080 0.110 H(36B) 4c 0.6116 1.1248 0.4829 0.110 H(36C) 4c 0.5689 1.0711 0.5610 0.110 Table 3. Atomic coordinates and displacement parameters (in Â). Atom Site X y ζ Un t/22 ί/33 Un Un t/23 Cd 4c 0.65318(2) 0.97540(2) 0.75493(2) 0.0408(2) 0.0550(2) 0.0589(2) -0.0061(1) 0.0042(1) -0.0062(1) CHD 4c 0.4649(3) 0.9010(2) 0.7595(3) 0.060(2) 0.096(3) 0.089(2) 0.019(2) 0.015(2) 0.015(2) C(l) 4c 0.4100(4) 0.9644(3) 0.7260(3) 0.048(2) 0.076(3) 0.052(2) 0.000(2) 0.008(2) -0.008(2) 0(2) 4c 0.4662(3) 1.0250(2) 0.7162(3) 0.051(2) 0.075(2) 0.120(3) -0.010(2) 0.020(2) -0.017(2) C(2) 4« 0.2749(4) 0.9666(3) 0.6938(3) 0.045(2) 0.079(3) 0.046(2) -0.005(2) 0.011(2) -0.001(2) 0(3) 4c 0.2605(4) 0.8251(3) 0.7007(4) 0.119(3) 0.092(3) 0.131(4) -0.014(3) 0.049(3) 0.004(3) C(3) 4c 0.2080(5) 0.8975(3) 0.6823(4) 0.072(3) 0.088(4) 0.065(3) -0.014(3) 0.023(2) 0.000(3) C(4) 4c 0.0827(5) 0.8988(5) 0.6482(4) 0.065(3) 0.146(6) 0.079(4) -0.037(4) 0.021(3) -0.015(4) C(5) 4c 0.0263(5) 0.9714(6) 0.6276(5) 0.050(3) 0.23(1) 0.067(4) -0.001(5) 0.012(3) 0.000(5) C(6) 4c 0.0906(5) 1.0414(5) 0.6373(4) 0.074(3) 0.143(6) 0.072(3) 0.041(4) 0.015(3) 0.020(4) C(7) 4c 0.2159(4) 1.0403(3) 0.6698(4) 0.061(3) 0.101(4) 0.068(3) 0.023(3) 0.017(2) 0.013(3) C( l l ) 4c 0.7414(3) 0.8515(2) 0.6707(4) 0.046(2) 0.046(2) 0.078(3) -0.011(2) 0.016(2) -0.002(2) OUD 4c 0.6611(3) 0.8977(2) 0.6140(2) 0.069(2) 0.059(2) 0.067(2) 0.013(1) 0.005(2) -0.004(1) 0(12) 4c 0.7757(3) 0.8618(2) 0.7665(2) 0.062(2) 0.068(2) 0.068(2) -0.002(2) 0.003(2) -0.003(2) 0(13) 4c 0.6640(4) 0.8168(2) 0.4525(3) 0.142(4) 0.084(3) 0.087(3) 0.006(3) 0.032(3) -0.008(2) C(12) 4c 0.7933(4) 0.7881(2) 0.6203(4) 0.055(2) 0.044(2) 0.095(3) -0.007(2) 0.032(2) 0.002(2) C(13) 4c 0.7544(5) 0.7765(3) 0.5150(5) 0.086(3) 0.050(3) 0.107(4) -0.008(2) 0.048(3) -0.007(3) C(14) 4c 0.8078(7) 0.7192(4) 0.4673(6) 0.132(6) 0.081(4) 0.151(6) -0.017(4) 0.084(5) -0.030(4) C(15) 4c 0.8978(8) 0.6742(4) 0.5270(9) 0.132(7) 0.070(4) 0.23(1) 0.003(4) 0.114(8) -0.013(6) C(16) 4c 0.9380(6) 0.6818(4) 0.6332(8) 0.082(4) 0.067(4) 0.230(9) 0.014(3) 0.071(6) 0.034(5) C(17) 4e 0.8864(4) 0.7397(3) 0.6828(6) 0.055(3) 0.055(3) 0.176(6) 0.005(2) 0.044(3) 0.020(3) N(21) 4c 0.7755(3) 1.0211(2) 0.9091(2) 0.040(2) 0.058(2) 0.050(2) -0.001(1) 0.006(1) -0.001(2) C(22) 4c 0.7827(4) 0.9917(3) 1.0025(3) 0.053(2) 0.072(3) 0.054(2) 0.000(2) 0.012(2) 0.001(2) C(23) 4c 0.8684(4) 1.0208(3) 1.0912(3) 0.058(3) 0.088(3) 0.049(2) 0.005(2) 0.006(2) 0.000(2) C(24) 4c 0.9461(4) 1.0790(3) 1.0834<3) 0.053(2) 0.091(3) 0.054(3) 0.000(2) 0.001(2) -0.017(2) C(25) 4c 1.0137(4) 1.1757(3) 0.9719(4) 0.053(2) 0.078(3) 0.077(3) -0.021(2) 0.009(2) -0.027(3) C(26) 4c 1.0046(4) 1.2066(3) 0.8795(4) 0.063(3) 0.067(3) 0.088(4) -0.025(2) 0.023(2) -0.020(3) C(27) 4c 0.8985(4) 1.2100(3) 0.6895(4) 0.074(3) 0.056(2) 0.081(3) -0.012(2) 0.032(3) -0.002(2) C(28) 4c 0.8092(4) 1.1803(3) 0.6079(4) 0.078(3) 0.056(3) 0.063(3) 0.002(2) 0.020(2) 0.005(2) C(29) 4c 0.7371(4) 1.1173(3) 0.6237(3) 0.057(2) 0.055(2) 0.052(2) 0.005(2) 0.010(2) -0.001(2) N(30) 4c 0.7535(3) 1.0848(2) 0.7153(2) 0.042(2) 0.049(2) 0.053(2) 0.000(1) 0.006(1) -0.002(2) C(31) 4c 0.8403(3) 1.1146(2) 0.7987(3) 0.042(2) 0.044(2) 0.055(2) 0.000(2) 0.012(2) -0.011(2) C(32) 4c 0.9151(4) 1.1777(2) 0.7889(3) 0.053(2) 0.051(2) 0.073(3) -0.007(2) 0.021(2) -0.011(2) C(33) 4c 0.9390(3) 1.1127(3) 0.9868(3) 0.043(2) 0.064(3) 0.056(2) -0.002(2) 0.006(2) -0.017(2) C(34) 4c 0.8516(3) 1.0815(2) 0.9002(3) 0.038(2) 0.049(2) 0.056(2) 0.001(2) 0.009(2) -0.009(2) C(35) 4c 0.6956(5) 0.9280(4) 1.0087(4) 0.074(3) 0.110(4) 0.072(3) -0.020(3) 0.015(2) 0.019(3) C(36) 4c 0.6364(4) 1.0851(3) 0.5361(3) 0.077(3) 0.075(3) 0.055(3) -0.005(3) 0.000(2) 0.003(2) C d ( C 7 H 5 0 3 ) 2 ( C i 4 H i 2 N 2 ) 1 4 5

A very short and efficient synthesis of protected derivatives of APTO and AETD, the complex polyhydroxylated beta-amino acid residues present in microsclerodermins C, D, and E, is described. The targets are obtained in only five steps, in 23% and 16% overall yields, respectively. The key transformation involves the completely diastereoselective two-carbon homologation of appropriately selected intermediate chiral sulfinimines.

In the title compound, [MnCl2(C3H7NO2)2], the MnII ion is bound to two Cl atoms and to four O atoms from two lactamide molecules which act as bidentate ligands, giving rise to a highly distorted octahedral coordination geometry. The axial positions are occupied by one Cl atom and one O (hydroxy) atom. The values of the cis bond angles at the Mn atom are in the range 72.33 (5)–100.17 (6)°. Of the two possible coordination modes (N,O- or O,O-bidentate) in metal complexes with lactamide or its derivatives described in the literature, the title compound exhibits the O,O-bidentate mode. In the crystal structure, monomeric manganese(II) complexes are linked by several N—H...Cl, O—H...Cl and O—H...O hydrogen bonds, generating a three-dimensional network.

Triazoles from "click chemistry" are convenient ligands for the formation of platinum complexes bearing combined triazole-amine or triazole-carboxylate moieties. Striking differences in the chelation modes are observed between the two series. One of the triazole-amine platinum complexes exhibits selective cytotoxicity against breast cancer cells lines. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

In the title compound, [ZnBr2(C11H12N2O2)2], the Zn(II) ion is coordinated by two Br atoms and two O atoms from two 4-hydroxyantipyrine molecules via the carbonyl O atoms, which act as monodentate ligands, giving rise to a distorted tetrahedral geometry. The values of the bond angles at the Zn atom are in the range 99.4 (1) to 113.2 (1)°. The presence of O—H⋯O and O—H⋯Br intramolecular hydrogen bonds can explain the difference between the two Zn—O [1.961 (3)/2.015 (3) Å] and the two Zn—Br [2.350 (1)/2.378 (1) Å] bond lengths. The crystal structure is governed by C—H⋯O, C—H⋯Br and Zn—Br⋯Cg(π-ring) interactions.

In the title compound, [MnCl(2)(C(3)H(7)NO(2))(2)], the Mn(II) ion is bound to two Cl atoms and to four O atoms from two lacta-mide mol-ecules which act as bidentate ligands, giving rise to a highly distorted octa-hedral coordination geometry. The axial positions are occupied by one Cl atom and one O (hydr-oxy) atom. The values of the cis bond angles at the Mn atom are in the range 72.33 (5)-100.17 (6)°. Of the two possible coordination modes (N,O- or O,O-bidentate) in metal complexes with lacta-mide or its derivatives described in the literature, the title compound exhibits the O,O-bidentate mode. In the crystal structure, monomeric manganese(II) complexes are linked by several N-H⋯Cl, O-H⋯Cl and O-H⋯O hydrogen bonds, generating a three-dimensional network.

C29H27NO8S, monoclinic, P12(1)/n1 (no. 14), a = 12.751(1) angstrom, b = 12.825(1) angstrom, c = 17.800(1) angstrom, beta = 111.51(1)degrees, V = 2708.2 angstrom(3), Z = 4, R-gt(F) = 0.057, WRref(F-2) = 0.177, T = 293 K.