616 Ζ. Kristallogr. NCS 224 (2009) 616-618 / DOI 10.1524/ncrs.2009.0271 © by Oldenbourg Wissenschaftsverlag, München

Crystal structure of bis[diaquaisomcotinatosamarium(III)]-/¿- isomcotinato-[düsomcotinatocopper(II)], CuSiihCCelLiNChMHiO^

Yi-Fang Deng, Xue Nie, Chun-Hua Zhang and Dai-Zhi Kuang*

Key Laboratory of Functional Organometallic Materials, Hengyang Normal University, Department of Chemistry and Materials Science, Hengyang, Hunan 421008, P. R. China

Received August 19,2009, accepted and available on-line September 18,2009; CCDC no. 1267/2742

Abstract Discussion C4gH4oCuNg02oSm2, monoclinic, P2\/n (no. 14), In the past few years, more extensive attention had been paid to a = 9.5218(9) Â, b = 15.037(1) Â, c = 18.285(2) Â, the research on the chemistry of the heterometallic lanthanide- 3 β = 93.822(1)°, V = 2612.2 Â , Ζ = 2, Rgl(F) = 0.021, transition metal complexes [1-3]. Isonicotinic acid is a good lin- wRk^F2) = 0.049, T= 293 K. ear bridging ligand with oxygen and nitrogen donors on opposite sides. Source of material In the crystal of the title compound, the Cu11 center is four- A mixture of CuO (1.0 mmol, 0.082 g), SŒL2O3 (0.5 mmol, coordinated by two O atoms from two different isonicotinate an- 0.180 g), isonicotinic acid (2.0 mmol, 0.248 g), H20 (10 mL, ions, two Ν atoms from the other two isonicotinate molecules. 0.55 mmol) and two drops of acetic acid, with the pH value of Thus the Cu11 ion has a distorted square coordination. The Smm about 2.0, was sealed in a 25 ml capacity Teflon-lined reaction center is eight-coordinated by six O atoms from five different vessel at 160 °C for 5 days, the reaction mixture was cooled to isonicotinate anion and two O atoms from two water molecules. room temperature over a period of 48 h. The product was col- So the Sm111 ion has a square antiprismatic environment. The ad- lected by filtration, washed with H2O and air-dried. Blue block- jacent Cu-Sm centers are bridged by the tridentate isonicotinate shaped crystals suitable for X-ray analysis were obtained. ligands, forming a one-dimensional chain structure. The water molecules are hydrogen bonded to the Ν atoms of the pyridyl Experimental details groups of the ligands, which link the complex into a three- H atoms bonded to C atoms were placed geometrically and dimensional framework. treated as riding, with d(C—H) = 0.93 Â and IWH) = 1.2 Ueq(C). The water H atoms found from difference Fourier maps were included in the refinements with restraints for d(0—H) = 0.829 - 0.833 À and i/iso(H) = 1.5 Ueq(0).

* Correspondence author (e-mail: yifang7124@ 163.com) CuSm2(C6H4N02)8(H20)4 617

Table 1. Data collection and handling. Table 2. Continued.

Crystal: blue block, size 0.27 χ 0.30 χ 0.40 mm Atom Site χ ν ; (Λ» Wavelength: Mo Ka radiation (0.71073 Â) 1 μ· 27.08 cm" H(4) Ae 0.2050 1.2589 0.2189 0.050 Diffractometer, scan mode: Broker SMART CCD, φ/ω H(5) Ae 0.0914 1.3015 0.3201 0.061 20ma*: 51° H(7) Ae 0.4656 1.1504 0.3518 0.055 M/lfc/Veasured, N(hkl)unique: 18387,4853 H(8) Ae 0.4216 1.1283 0.2282 0.038 Criterion for lobs, N(hkl)ρ: /obs > 2 allobsl, 4222 H(10) Ae 0.6913 0.9242 0.2439 0.049 N(param)^r¡nv¡: 359 H(ll) Ae 0.7197 0.9507 0.3669 0.069 Programs: SHELXS-97 [4], SHELXL-97 [5], H(13) Ae -0.0508 0.6921 0.0004 0.028 SHELXTL [6] H(14) Ae 0.0676 0.8252 0.0027 0.028 H(16) Ae 0.4305 0.6889 0.0072 0.029 H(17) Ae 0.3018 0.5594 0.0074 0.027 H(19) Ae -0.5995 0.7038 -0.2288 0.049 H(20) Ae -0.4856 0.6926 -0.1148 0.038 Table 2. Atomic coordinates and displacement parameters (in Â2). H(22) Ae -0.2191 0.5207 -0.1994 0.050 H(23) Ae -0.3379 0.5410 -0.3118 0.064 Atom Site χ y ζ i/i» H(1W) Ae 0.0757 1.0919 -0.1202 0.043 H(2W) Ae 0.0301 1.0314 -0.0715 0.043 H(l) Ae -0.2213 1.1456 0.2656 0.069 H(3W) Ae 0.3208 1.2307 -0.1068 0.045 H(2) Ae -0.1151 1.0949 0.1648 0.056 H(4W) Ae 0.2738 1.2729 -0.0473 0.045

Table 3. Atomic coordinates and displacement parameters (in Â2).

Atom Site X y ζ Vu Un t/33 Un Í/13 Un

Sm(l) Ae 0.30355(1) 1.084800(9) -0.000640(7) 0.01495(9) 0.01529(9) 0.01549(8) -0.00210(6) 0.00169(5) -0.00087(5) Cu(l) 2b 0 Vi 0 0.0205(3) 0.0153(3) 0.0264(3) -0.0064(2) -0.0071(2) 0.0056(2) O(l) Ae 0.1022(2) 1.0699(1) 0.0832(1) 0.025(1) 0.027(1) 0.025(1) -0.0042(9) 0.0061(9) -0.0054(9) 0(2) Ae 0.2241(2) 1.1940(1) 0.0893(1) 0.039(1) 0.023(1) 0.035(1) -0.007(1) 0.019(1) -0.0044(9) 0(3) Ae 0.4104(2) 1.0342(2) 0.1113(1) 0.039(2) 0.066(2) 0.026(1) 0.009(1) -0.008(1) 0.004(1) 0(4) Ae 0.6048(3) 0.9525(2) 0.1123(1) 0.055(2) 0.051(2) 0.027(1) 0.013(1) 0.016(1) -0.007(1) 0(5) Ae 0.2714(2) 0.9288(1) -0.0040(1) 0.037(1) 0.018(1) 0.058(2) -0.006(1) -0.002(1) 0.001(1) 0(6) Ae 0.4704(2) 0.8532(2) -0.0098(1) 0.021(1) 0.035(1) 0.080(2) -0.013(1) 0.004(1) 0.002(1) 0(7) Ae -0.1420(2) 0.5537(1) -0.0714(1) 0.027(1) 0.027(1) 0.028(1) -0.002(1) -0.0083(9) 0.0054(9) 0(8) Ae -0.3139(2) 0.6213(2) -0.0144(1) 0.048(2) 0.036(1) 0.027(1) 0.001(1) -0.002(1) -0.002(1) N(l) Ae -0.0769(4) 1.2279(2) 0.3032(2) 0.064(2) 0.044(2) 0.044(2) -0.006(2) 0.031(2) -0.011(2) N(2) Ae 0.5926(3) 1.0505(3) 0.3727(2) 0.046(2) 0.088(3) 0.022(2) -0.010(2) -0.003(1) -0.009(2) N(3) Ae 0.1135(2) 0.6129(2) 0.0024(1) 0.021(1) 0.016(1) 0.021(1) -0.004(1) -0.001(1) 0.0023(9) N(4) Ae -0.4825(3) 0.6230(2) -0.2816(2) 0.049(2) 0.046(2) 0.037(2) 0.009(2) -0.020(1) -0.007(1) C(l) Ae -0.1334(4) 1.1683(3) 0.2564(2) 0.049(2) 0.062(3) 0.067(3) -0.017(2) 0.040(2) -0.023(2) C(2) Ae -0.0711(4) 1.1377(3) 0.1950(2) 0.037(2) 0.050(2) 0.054(2) -0.014(2) 0.021(2) -0.023(2) C(3) Ae 0.0576(3) 1.1721(2) 0.1798(2) 0.028(2) 0.026(2) 0.025(2) 0.003(1) 0.008(1) -0.002(1) C(4) Ae 0.1180(4) 1.2343(2) 0.2275(2) 0.045(2) 0.043(2) 0.041(2) -0.013(2) 0.019(2) -0.011(2) C(5) Ae 0.0485(4) 1.2599(3) 0.2882(2) 0.065(3) 0.045(2) 0.044(2) -0.013(2) 0.020(2) -0.018(2) C(6) Ae 0.1329(3) 1.1432(2) 0.1133(2) 0.020(2) 0.026(2) 0.022(2) 0.004(1) 0.002(1) 0.003(1) C(7) Ae 0.5089(4) 1.1027(3) 0.3300(2) 0.057(3) 0.050(2) 0.034(2) -0.007(2) 0.014(2) -0.016(2) C(8) Ae 0.4824(4) 1.0906(2) 0.2553(2) 0.034(2) 0.034(2) 0.027(2) 0.005(2) 0.007(1) -0.001(1) C(9) Ae 0.5483(3) 1.0211(2) 0.2221(2) 0.021(2) 0.029(2) 0.018(1) -0.003(1) 0.002(1) 0.001(1) C(10) Ae 0.6410(4) 0.9697(3) 0.2647(2) 0.040(2) 0.054(2) 0.028(2) 0.015(2) 0.003(2) 0.005(2) C(ll) Ae 0.6578(4) 0.9867(3) 0.3388(2) 0.046(2) 0.100(4) 0.025(2) 0.018(2) -0.004(2) 0.011(2) C(12) Ae 0.5193(3) 1.0016(2) 0.1418(2) 0.028(2) 0.028(2) 0.020(2) -0.007(1) 0.003(1) 0.003(1) C(13) Ae 0.0470(3) 0.6917(2) 0.0015(2) 0.018(2) 0.023(2) 0.029(2) -0.002(1) -0.001(1) 0.001(1) C(14) Ae 0.1172(3) 0.7720(2) 0.0021(2) 0.021(2) 0.017(2) 0.031(2) 0.001(1) 0.000(1) 0.000(1) C(15) Ae 0.2621(3) 0.7722(2) 0.0017(1) 0.022(2) 0.021(2) 0.019(1) -0.008(1) -0.001(1) -0.001(1) C(16) Ae 0.3327(3) 0.6910(2) 0.0051(2) 0.017(2) 0.024(2) 0.032(2) -0.004(1) 0.002(1) 0.001(1) C(17) Ae 0.2545(3) 0.6135(2) 0.0052(2) 0.022(2) 0.018(2) 0.028(2) 0.000(1) -0.001(1) 0.002(1) C(18) Ae 0.3420(3) 0.8586(2) -0.0039(2) 0.027(2) 0.022(2) 0.027(2) -0.009(1) -0.002(1) 0.000(1) C(19) Ae -0.5216(3) 0.6665(2) -0.2229(2) 0.028(2) 0.045(2) 0.047(2) 0.010(2) -0.010(2) 0.002(2) C(20) Ae -0.4541(3) 0.6600(2) -0.1538(2) 0.027(2) 0.037(2) 0.032(2) 0.004(2) -0.001(1) -0.000(1) C(21) Ae -0.3387(3) 0.6041(2) -0.1436(2) 0.025(2) 0.023(2) 0.029(2) -0.003(1) -0.006(1) 0.002(1) C(22) Ae -0.2961(4) 0.5588(2) -0.2040(2) 0.046(2) 0.042(2) 0.036(2) 0.018(2) -0.012(2) -0.012(2) C(23) Ae -0.3693(4) 0.5708(3) -0.2715(2) 0.062(3) 0.057(3) 0.038(2) 0.022(2) -0.020(2) -0.023(2) C(24) Ae -0.2594(3) 0.5932(2) -0.0693(2) 0.026(2) 0.016(2) 0.029(2) -0.006(1) -0.006(1) 0.004(1) 0(9) Ae 0.0897(2) 1.0706(1) -0.0783(1) 0.025(1) 0.034(1) 0.025(1) -0.010(1) -0.0081(9) 0.0053(9) O(10) Ae 0.2777(2) 1.2248(1) -0.0692(1) 0.041(1) 0.022(1) 0.028(1) 0.002(1) 0.013(1) 0.0045(9) 618 CuSltl2(C6H4N02)8(H20)4

Acknowledgment. This work was supported by the Construct Program of the Key Discipline in Hunan Province and Hengyang Bureau of Science and Technology (grant no. 2009KJ29). References

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