Cluster based copper(II)-azide polymer: Synthesis, structure and ...

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S. Saha et al. / Polyhedron 29 (2010) 3342–3348 3345Table 3Selected bond distances (Å) and angles (°) for complex 1.Cu1–N1 1.972(5) N5–N6 1.149(7)Cu1–N4 1.973(4) N7–N8 1.199(7)Cu1–N7 1.992(6) N8–N9 1.116(9)Cu1–N10 2.030(4) N10–N11 1.266(6)Cu1–N10_b 2.437(4) N11–N12 1.117(9)Cu2–N7 1.987(5)Cu2–N10 2.018(4)Cu2–N13 2.002(4)Cu2–N14 1.997(5)Cu2–N6_a 2.465(6)Cu2–N1_b 2.744(5)N1–N2 1.192(7)N2–N3 1.156(8)N4–N5 1.201(6)N1–Cu1–N4 95.57(19) N1–N2–N3 177.6(6)N1–Cu1–N7 166.2(2) Cu1–N4–N5 120.5(3)N1–Cu1–N10 92.55(18) N4–N5–N6 176.1(5)N1–Cu1–N10_b 90.92(16) Cu2_a–N6–N5 133.2(4)N4–Cu1–N7 93.5(2) Cu1–N7–Cu2 102.1(3)N4–Cu1–N10 171.63(17) Cu1–N7–N8 124.4(4)N4–Cu1–N10_b 94.88(15) Cu2–N7–N8 131.6(4)N7–Cu1–N10 78.89(18) N7–N8–N9 178.8(7)N7–Cu1–N10_b 98.6(2) Cu1–N10–Cu2 99.70(17)N10–Cu1–N10_b 82.93(15) Cu1–N10–N11 119.7(3)N7–Cu2–N10 79.3(2) Cu1–N10–Cu1_b 97.07(16)N7–Cu2–N13 174.9(2) Cu2–N10–N11 123.8(3)N7–Cu2–N14 97.8(2) Cu1_b–N10–Cu2 97.42(15)N6_a–Cu2–N7 97.4(2) Cu1_b–N10–N11 114.0(3)N1_b–Cu2–N7 92.3(2) N10–N11–N12 175.9(6)N10–Cu2–N13 96.57(17) Cu2–N13–C1 109.1(4)N10–Cu2–N14 173.49(18) Cu2–N14–C2 107.7(4)N6_a–Cu2–N10 98.25(19) Cu2–N13–H13B 110.00N1_b–Cu2–N10 81.57(15) C1–N13–H13A 110.00N13–Cu2–N14 85.99(19) Cu2–N13–H13A 110.00N6_a–Cu2–N13 86.02(18) H13A–N13–H13B 108.00N1_b–Cu2–N13 84.20(15) C1–N13–H13B 110.00N6_a–Cu2–N14 87.9(2) Cu2–N14–H14B 110.00N1_b–Cu2–N14 92.76(17) Cu2–N14–H14A 110.00N1_b–Cu2–N6_a 170.13(17)Cu1–N1–N2 121.1(4)Cu1–N1–Cu2_b 89.26(17)Cu2_b–N1–N2 126.3(4)Fig. 2. Packing arrangement of polymeric chains in 1.a =1 x, y, 1 z; b =2 x, y, 1 z.notation) between these groups joins parallel polymeric chainsalong crystallographic c-axis. One of the amino groups (N14 nitrogen)of the chelating ethylene diamine ligand takes part in thiscentrosymmetric cyclic hydrogen bonding pattern where both ofits protons are attached to N3 terminal nitrogen atoms of end-onbridging azides from adjacent polymeric chains. The other aminogroup (N13 nitrogen) also forms strong bifurcated hydrogen bondsdonating H13A protons simultaneously to N4 of end-to-end bridgingazide and N12 of end-on bridging azide, respectively. The otherproton (H13B) is also donated to the same N4 nitrogen but with adifferent symmetry location (x, 1+y, z) on a different polymericchain. This establishes supramolecular connection between adjacentpolymeric chains of Cu 4 clusters along the crystallographicb-axis. Thus the overall packing is the result of a hydrogen-bondedsupramolecular assembly of 1D polymeric chains of Cu 4 clusterswhose compact arrangement is facilitated by –NH 2 group assistedhydrogen bonding among these chains in other two crystallographicdirections. This hydrogen bonding pattern is responsiblefor the respective optimal alignment of the azide ions which, inturn, fixes the geometrical angle parameters of the magnetic exchangepathway.3.3. Magnetic propertiesv M T versus T data for 1 are shown in Fig. 4. The v M T product of 1at 300 K is 1.82 cm 3 mol 1 K, close to the value expected for fourFig. 3. Hydrogen bonding between amine and azide groups in 1.non-interacting S = 1/2 ions (g = 2.2). This shows a slow decreaseupon cooling down to 100 K, below which temperature the decreaseaccelerates, reaching a value of 0.33 cm 3 mol 1 K at 2 K. Thisbehaviour suggests the interplay of weak antiferromagnetic interactions.M versus H measurements at 2 K show no signs of saturationup to 5.5 T, indicating the presence of exchange coupling overan extended magnetic system.Based on the crystal structure of 1, we may view the complex asa series of centrosymmetric defective double cubanes (Fig. 5). Fromthis analysis, a rigorous interpretation of the magnetic behaviour of1 would require the consideration of four exchange pathways,namely J 1 = J Cu1Cu2 = J Cu1 0 Cu2 0, J 2 = J Cu1Cu2 0 = J Cu1 Cu2, J 0 3 = J Cu1Cu1 0 andJ 4 = J Cu1Cu2 00 = J Cu1 00 Cu2 (Fig. 5). Since a polymeric structure with such
3346 S. Saha et al. / Polyhedron 29 (2010) 3342–3348Table 4Hydrogen bond parameters (Å, °).D–HA D–H (Å) HA (Å) DA (Å)
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