Z. Kristallogr. NCS 223 (2008) 437-438 / DOI 10.1524/ncrs.2008.0191
437
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Crystal structure of catena-bis(imidazole)bis($2-succinato)copper(II), Cu(C3N2H4)2(C4H5O4)2 Bo HuI, Jing-Zhong Chen*,I, Hong ChenI and Zhi-Feng LiII I II
China University of Geosciences, Faculty of Material Science and Chemical Engineering, Hubei, Wuhan 430074, P. R. China Jiangxi University of Science and Technology, School of Materials & Chemical Engineering, Ganzhou, Jiangxi 341000, P. R. China
Received May 28, 2008, accepted and available on-line September 28, 2008; CCDC no. 1267/2382
adipato ligands bridging complex [Cu(C3N2H4)2(C6H9O4)2] [1,2]. The polymeric chains [Cu(C3N2H4)2(C4H5O4)4/2] with 14 membered rings display strong intrachain O−H···hydrogen bonds between the coordinating hydroxyl O3 and uncoordinating carboxylate O2 atoms with d(O···O) = 2.554 Å. The interchain N2−H2A···O2 hydrogen bonding interactions play an important role in assembling the ribbon-like chains into open 3D frameworks. Table 1. Data collection and handling. Crystal:
Abstract C14H18CuN4O8, monoclinic, P121/c1 (no. 14), a = 8.405(1) Å, b = 12.683(2) Å, c = 8.031(1) Å, 0 = 91.203(2)°, V = 855.9 Å3, Z = 2, Rgt(F) = 0.041, wRref(F2) = 0.145, T = 295 K. Source of material Dropwise addition of 1 mol/l NaOH solution (6.0 ml) to a stirred aqueous solution of CuCl2 · 2H2O (0.426 g, 2.50 mmol) in 5.0 ml H2O produced pale blue precipitate Cu(OH)2 · xH2O, which was then centrifugated and washed with double-distilled water until no Cl− anions were detected. The precipitate was subsequently added to a stirred solution of 0.295 g (2.50 mmol) succinic acid and 0.170 g (2.50 mmol) imidazole in 50.0 ml CH3OH/H2O (1:1, v/v). The mixture was further stirred for ca. one hour. After insoluble solid was filtered off, the blue filtrate was kept still at room temperature and blue crystals were formed by slow evaporation for several weeks. Discussion The crystal structure of the title compound consists of hydrogen succinato-bridged ribbon-like polymeric chains in terms of [Cu(C3N2H4)2 (C4H5O4)4/2] extending infinitely along [001]. The coordination sphere around Cu atoms is elongated octahedral, two imidazole nitrogen atoms and two carboxylate oxygen being at equatorial positions and two hydroxyl oxygen atoms at the axial positions with the equatorial Cu—N and Cu—O bond lengths of 1.974(3) Å and 1.983(3) Å, respectively, and the axial Cu—O bond lengths of 2.694(3) Å. Obviously, the larger axial Cu—O bond distances are indicative for Jahn-Teller distortion due to d9configuration. The hydrogen succinate anions function as a bis-monodentate bridging ligand with the hydroxyl oxygen O3 atom unexpectedly bonded to Cu atom besides the carboxylate oxygen O1. The present bridging fashion of the hydrogen succinate anions is similar to that observed in hydrogen
Wavelength: ': Diffractometer, scan mode: 2#max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
blue column, size 0.103 × 0.112 × 0.315 mm Mo K2 radiation (0.71073 Å) 13.30 cm−1 Bruker SMART APEXII CCD, +/3 54.3° 4784, 1842 Iobs > 2 "(Iobs), 1461 125 SHELXS-97 [3], SHELXL-97 [4], SHELXTL [5]
Table 2. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
y
z
Uiso
H(1A) H(2B) H(3A) H(2A) H(6A) H(6B) H(7A) H(7B) H(3B)
4e 4e 4e 4e 4e 4e 4e 4e 4e
0.4962 0.2521 0.1397 0.0378 0.8697 0.9120 0.6194 0.6778 0.7446
0.7314 0.8316 0.5578 0.7192 0.6728 0.5526 0.6282 0.5111 0.6283
0.1696 0.2120 0.0078 0.1131 0.4011 0.3994 0.5155 0.5289 0.8913
0.049 0.054 0.040 0.047 0.034 0.034 0.044 0.044 0.036
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* Correspondence author (e-mail:
[email protected])
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438
Cu(C3N2H4)2(C4H5O4)2
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
y
z
U11
U22
U33
Cu N(1) C(1) C(2) C(3) N(2) O(1) O(2) C(5) C(6) C(7) C(8) O(3) O(4)
2d 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
½ 0.3548(3) 0.3938(4) 0.2594(5) 0.1992(4) 0.1372(3) 0.6347(3) 0.8024(3) 0.7479(3) 0.8250(4) 0.7126(4) 0.7866(4) 0.6798(3) 0.9278(3)
½ 0.6138(2) 0.7091(3) 0.7645(3) 0.6131(3) 0.7032(2) 0.5276(2) 0.6482(2) 0.5922(2) 0.6026(3) 0.5840(3) 0.6071(2) 0.6280(2) 0.6070(2)
0 0.0679(3) 0.1415(4) 0.1662(5) 0.0528(4) 0.1111(3) 0.2009(3) 0.1055(2) 0.2195(3) 0.3901(3) 0.5315(3) 0.6987(3) 0.8135(2) 0.7281(3)
0.0214(3) 0.028(1) 0.037(2) 0.054(2) 0.026(2) 0.028(2) 0.032(1) 0.037(1) 0.020(1) 0.025(2) 0.030(2) 0.029(2) 0.029(1) 0.027(1)
0.0255(3) 0.028(1) 0.034(2) 0.034(2) 0.036(2) 0.052(2) 0.033(1) 0.045(1) 0.030(2) 0.041(2) 0.060(2) 0.031(2) 0.044(1) 0.064(2)
0.0235(3) 0.027(1) 0.050(2) 0.047(2) 0.038(2) 0.037(1) 0.023(1) 0.019(1) 0.018(1) 0.018(1) 0.020(1) 0.020(1) 0.018(1) 0.024(1)
U12 0.0005(2) 0.003(1) 0.001(2) 0.011(2) −0.002(1) 0.015(1) −0.003(1) −0.007(1) 0.005(1) −0.003(1) −0.009(2) −0.005(1) −0.003(1) 0.001(1)
U13 −0.0062(2) −0.004(1) −0.013(2) −0.001(2) −0.003(1) 0.002(1) −0.012(1) −0.0046(9) −0.002(1) −0.004(1) −0.003(1) −0.003(1) −0.0019(9) −0.0058(9)
U23 −0.0054(2) −0.004(1) −0.016(2) −0.016(2) −0.004(1) −0.001(1) −0.0035(9) −0.0016(9) −0.006(1) −0.003(1) −0.007(1) 0.001(1) −0.0014(9) −0.004(1)
Acknowledgments. The authors gratefully acknowledge the financial support of Grant-in-Aid for Scientific Research (B) (no. 14340161) from The Ministry of Education, Culture, Sports, Science and Technology (MEXT).
References 1. Suresh, E.; Bhadbhade, M. M.: Metal-2,3-Dicarboxylate Complexes. II. catena-Poly[bis(imidazole-N3)copper(II)-diadipato(1−)-O1:O6;O6:O1] . Acta Crystallogr. C53 (1997). 422-425. 2. Ying, E. B.; Zheng, Y. Q.; Zhang, H. J.: Syntheses, crystal structures and properties of two Cu(II) coordination polymers: Cu(C3N2H4)2(HL)2 and Cu(C3N2H4)2L with C3N2H4 = imidazole, H2L = adipic acid. J. Mol. Struct. 693 (2004). 73-80.
3. Sheldrick, G. M.: SHELXS-97. Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997. 4. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997. 5. Sheldrick, G. M.: SHELXTL. Structure Determination Software Suite. Version 6.14. Bruker AXS, Madison, Wisconsin, USA 2000.
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