Syntheses, Structure, and Properties of the Dimer Cu(DMAP)4(ClO4)2 (DMAP = 4-N, N-Dimethylaminopyridine)

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The rational design and synthesis of discrete coordination architectures or polymeric coordination networks has received much attention recently, and hydrogen bonding and p-p stacking interactions are often employed in their construction. In this text, a strongly hydrogen-bonded dimer of the Cu(II) of 4-N, N-dimethylaminopyridine (DMAP), Cu(DMAP)4(ClO4)2, was synthesized and characterized by single crystal X-ray diffraction, UV-Vis and IR spectroscopy. X-ray analysis indicates that this compound is a dimer structure and the coordination geometries around the two Cu(II) centers could be described as distorted octahedrons. In addition, the ClO4- anions are involved in hydrogen bonding connecting the dimeric units to give a three dimensional infinite network. The extension of this work to a similar type of supramolecular systems may be fundamental to the study of the bonding interactions present in the solid state.

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Edited by:

Rongming Wang, Ying Wu and Xiaofeng Wu

Pages:

296-300

DOI:

10.4028/www.scientific.net/MSF.688.296

Citation:

L. Wang and D. P. Sun, "Syntheses, Structure, and Properties of the Dimer Cu(DMAP)4(ClO4)2 (DMAP = 4-N, N-Dimethylaminopyridine)", Materials Science Forum, Vol. 688, pp. 296-300, 2011

Online since:

June 2011

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[1] 429 Temperature (K) 291 m (mm–1).

836 Crystal system Triclinic F (000) 1564 Space group P Reflections collected 17753 a (Ǻ).

[11] 0552(14) Reflections unique (Rint) 12096 (0. 063) b (Ǻ).

[16] 752(2) Reflections observed [I > 2s (I)] 3882 c (Ǻ).

[20] 296(3) Parameters 917 α (˚).

[97] 139(2) Final R indices [I > 2s (I)] R1 = 0. 0517, wR2 = 0. 0832 β (˚) 104. 219(2) Goodness–of–fit on F2.

716 γ (˚) 102. 670(2) ê/e·Å–3 (max, min).

26 / -0. 27 V (Ǻ3) 3491. 2(8) R1=S||Fo|-|Fc||/S|Fo|, wR2=[S[w(Fo2-Fc2)2]/Sw(Fo2)2]1/2 Table 2. Selected bond distances (Å) and bond angles (o) Cu1-N1.

[1] 985(4) Cu1-O1.

[2] 672(4) Cu2-N15.

[2] 007(4) Cu1-N5.

[1] 992(4) Cu1-O5.

[2] 831(5) Cu2-N11.

[2] 009(4) Cu1-N3.

[2] 006(4) Cu2-N13.

[1] 994(4) Cu2-O13.

[2] 580(17) Cu1-N7.

[2] 009(4) Cu2-N9.

[1] 996(4) Cu2-O9.

[2] 735(4) N1-Cu1-N5 169. 9(2) N1-Cu1-O5.

[84] 49(17) N15-Cu2-N11 168. 6(2) N1-Cu1-N3.

[92] 5(2) N5-Cu1-O5.

[85] 50(17) N13-Cu2-O13.

[84] 2(4) N5-Cu1-N3.

[88] 28(19) N3-Cu1-O5.

[88] 1(2) N9-Cu2-O13.

[87] 0(4) N1-Cu1-N7.

[89] 45(18) N7-Cu1-O5 104. 6(2) N15-Cu2-O13.

[99] 9(5) N5-Cu1-N7.

[92] 04(19) O1-Cu1-O5 167. 17(16) N11-Cu2-O13.

[91] 4(5) N3-Cu1-N7 167. 3(2) N13-Cu2-N9 171. 24(19) N13-Cu2-O9.

[98] 32(16) N1-Cu1-O1.

[87] 88(17) N13-Cu2-N15.

[88] 74(18) N9-Cu2-O9.

[90] 45(16) N5-Cu1-O1 102. 17(16) N9-Cu2-N15.

[92] 61(18) N15-Cu2-O9.

[81] 97(16) N3-Cu1-O1.

[81] 94(17) N13-Cu2-N11.

[91] 14(17) N11-Cu2-O9.

[86] 81(16) N7-Cu1-O1.

[85] 57(16) N9-Cu2-N11.

[89] 24(16) O13-Cu2-O9 176. 9(4) Table 3 hydrogen bonding parameters (Å, o) in the title compound D–H…A D–H H…A D…A ÐDHA Sym. trans C12–H12…O6.

93.

[2] 60.

[3] 49(1) 162 O19–H19…O5.

93.

[2] 36.

[3] 09(1) 136 C21–H21B…O3.

96.

[2] 59.

[3] 49(1) 156 -1+x, y, z C21–H21C…O12.

96.

[2] 51.

[3] 41(1) 155 -1+x, y, z C27–H27A…O11.

96.

[2] 57.

[3] 44(1) 150 1-x, 1-y, 1-z C36–H36…O9.

93.

[2] 54.

[3] 15(1) 123 C42–H42C…O2.

96.

[2] 49.

[3] 33(1) 146 1+x, y, z C49–H49C…O7.

96.

[2] 58.

[3] 35(2) 137 1+x, -1+y, z C50–H50…O11.

93.

[2] 59.

[3] 35(1) 140 Results and discussion IR Spectra and UV-vis Spectra. Peaks at 1624, 1545, 1441, 1391, 1227, 1369, and 804 cm-1 present in the compound can be assigned for the C=C and C=N ring stretching vibrations. Peaks are also observed at 766 cm-1 for C-H stretching, strong band that appeared at 1093 cm-1 correspond to the characteristic absorption of perchlorate anions In addition, UV–vis spectra of the compound in methanol solution was recorded. Compared with the free DMAP ligand at 245 nm in our experiment, the UV–vis spectra of complexe show new MLCT bands around 383 nm and a red shift absorption at 260 nm for intra-ring p–p transition of aromatic rings in DMAP ligand after the metal ion complexation. Crystal Structure of Cu(DMAP)4(ClO4)2 The title compound is composed of two dimeric neutral Cu(DMAP)4(ClO4)2 entities The mononuclear units are linked together by extensive hydrogen bonds, leading to the topology of a three dimensional framework. The asymmetric unit consists of two independent centrosymmetric Cu(DMAP)4(ClO4)2 molecules, hereafter referred to as molecules A and B. Relevant bond lengths and angles are listed in Table 2. As illustrated in Fig. 1, the geometry around Cu(II) of each Cu(DMAP)4(ClO4)2 fragment shows the typical Jahn-Teller distortion of an elongated octahedral coordination. The equatorial plane is defined by four pyridine nitrogen atoms from four different DMAP ligands. Four nitrogen atoms from four different DMAP ligands constitute the basal plane with the bond lengths 1. 985(4)–2. 009(4) Å for Cu–N contacts, while the apical position is occupied by two oxygen atoms of the two perchlorate anions with a longer bond length of 2. 578(5)-2. 830(7) Å. Fig. 1 Thermal Ellipsoid Plot (ORTEP) diagram (30% thermal probability) of the molecular structure of the compound with the atom-numbering schem As shown in Fig. 2 and Table 3, intramolecular and intermolecular hydrogen bonding interactions are observed in the Cu(DMAP)4(ClO4)2 dimers and they are believed to be responsible for the arrangement of molecules in their crystal packing. Fig. 2 View of H-bonding interactions in the crystal packing of the compound Conclusion A dimeric copper(II) complex with 4-N, N-dimethylaminopyridine ligand has been synthesized and structurally characterized and its geometric parameters, electronic structure and spectroscopic property were investigated by combining X-ray crystallography and spectroscopy. The hydrogen bonding interactions play important roles in forming a three dimensional infinite network. References.

DOI: 10.4028/www.scientific.net/msf.688.296

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