Crystal structure of bis ( salicylato ) ( neocuproin ) cadmium ( II ) , C d ( C 7 H 5 0 3 ) 2 ( C l 4 H 1 2 N 2 )

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