Table S1 Selected bond lengths [Å] and angles [ ] for complexes 1 8. Complex 1. Complex 2. Complex 3. Complex 4. Complex 5.
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1 Table S1 Selected bond lengths [Å] and angles [ ] for complexes 1 8. Complex 1 Zn(1) O(1) 1.969(2) Zn(1) O(5) 1.989(3) Zn(1) O(6) 1.930(3) Zn(1) O(4) a 1.954(4) Zn(1) O(3) a 2.519(25) O(6) Zn(1) O(4) a (11) O(6) Zn(1) O(1) (11) O(4) a Zn(1) O(1) (11) O(6) Zn(1) O(5) 99.27(12) O(4) a Zn(1) O(5) (10) O(1) Zn(1) O(5) (11) Complex 2 Zn(1) O(1) 1.992(9) Zn(1) O(1) a 1.992(9) Zn(1) N(2) 2.051(5) Zn(1) N(2) a 2.051(5) O(1) Zn(1) O(1) a 142.9(6) O(1) Zn(1) N(2) a 106.4(3) O(1) a Zn(1) N(2) 94.6(4) O(1) Zn(1) N(2) 94.6(4) O(1) a Zn(1) N(2) 106.4(3) N(2) a Zn(1) N(2) 110.4(4) Complex 3 Zn(1) O(1) 1.968(2) Zn(1) O(3) a 1.949(2) Zn(1) N(3) 2.010(3) Zn(1) N(4) 2.085(3) Zn(2) O(7) 1.950(2) Zn(2) O(5) b 1.955(3) Zn(2) N(5) 2.094(3) Zn(2) N(6) 2.009(3) O(3) a Zn(1) O(1) (10) O(3) a Zn(1) N(3) (11) O(1) Zn(1) N(3) (11) O(3) a Zn(1) N(4) (11) O(1) Zn(1) N(4) 94.46(11) N(3) Zn(1) N(4) (10) O(7) Zn(2) O(5) b (10) O(7) Zn(2) N(6) (11) O(5) b Zn(2) N(6) (11) O(7) Zn(2) N(5) (11) O(5) b Zn(2) N(5) 94.75(11) N(6) Zn(2) N(5) 99.22(10) Complex 4 Cu(1) O(2) 1.955(2) Cu(1) O(4) a (19) Cu(1) O(5) 2.310(2) Cu(1) N(1) 2.017(2) Cu(1) N(2) 2.012(2) O(4) a Cu(1) O(2) 90.79(9) O(4) a Cu(1) N(2) 95.31(9) O(2) Cu(1) N(2) (9) O(4) a Cu(1) N(1) (8) O(2) Cu(1) N(1) 92.94(9) N(2) Cu(1) N(1) 80.92(9) O(4) a Cu(1) O(5) 86.53(9) O(2) Cu(1) O(5) 85.71(9) N(2) Cu(1) O(5) 95.68(9) N(1) Cu(1) O(5) 96.38(9) Complex 5 Cu(1) O(3) (17) Cu(1) O(6) (18) Cu(1) N(3) a 2.011(2) Cu(1) N(4) (19) Cu(1) O(5) (18) O(3) Cu(1) O(6) (8) O(3) Cu(1) N(3) a 92.74(8) O(6) Cu(1) N(3) a 87.21(8) O(3) Cu(1) N(4) 90.55(8) O(6) Cu(1) N(4) 88.92(8) N(3) a Cu(1) N(4) (8) O(3) Cu(1) O(5) 83.43(7) O(6) Cu(1) O(5) (8) N(3) a Cu(1) O(5) 89.23(7) N(4) Cu(1) O(5) 97.28(7) Complex 6
2 Cu(1) O(1) b 1.970(5) Cu(1) O(4) 1.974(5) Cu(1) N(1) 1.987(6) Cu(1) N(2) 1.992(5) Cu(1) O(3) 2.329(5) Cu(1) O(2) b (55) O(1) b Cu(1) O(4) 159.0(2) O(1) b Cu(1) N(1) 91.6(2) O(4) Cu(1) N(1) 91.9(2) O(1) b Cu(1) N(2) 92.45(19) O(4) Cu(1) N(2) 84.88(19) N(1) Cu(1) N(2) 175.6(2) O(1) b Cu(1) O(3) (18) O(4) Cu(1) O(3) 99.27(18) N(1) Cu(1) O(3) 87.0(2) N(2) Cu(1) O(3) 90.4(2) Complex 7 Cd(1) O(1) a 2.339(6) Cd(1) O(1) b 2.592(6) Cd(1) N(4) d 2.327(7) Cd(1) O(3) c 2.229(6) Cd(1) S(1) 2.635(3) Cd(1) S(2) d 2.798(4) Cd(2) O(2) a 2.250(6) Cd(2) N(1) 2.370(9) Cd(2) N(2) 2.393(9) Cd(2) N(3) 2.407(7) Cd(2) S(2) 2.623(3) Cd(2) S(1) 2.693(3) O(3) c Cd(1) N(4) d 128.8(3) O(3) c Cd(1) O(1) a 79.4(2) N(4) d Cd(1) O(1) a 147.5(2) O(3) c Cd(1) O(1) b 150.3(2) N(4) d Cd(1) O(1) b 80.9(2) O(1) a Cd(1) O(1) b 72.0(2) O(3) c Cd(1) S(1) 98.66(19) N(4) d Cd(1) S(1) 92.5(2) O(1) a Cd(1) S(1) 99.40(18) O(1) b Cd(1) S(1) 78.74(16) O(3) c Cd(1) S(2) d (19) N(4) d Cd(1) S(2) d 60.4(2) O(1) a Cd(1) S(2) d (18) O(1) b Cd(1) S(2) d 89.44(17) S(1) Cd(1) S(2) d (9) O(2) a Cd(2) N(1) 159.4(3) O(2) a Cd(2) N(2) 87.4(3) N(1) Cd(2) N(2) 72.1(3) O(2) a Cd(2) N(3) 89.6(3) N(1) Cd(2) N(3) 86.2(3) N(2) Cd(2) N(3) 83.8(3) O(2) a Cd(2) S(2) 93.58(19) N(1) Cd(2) S(2) 92.9(2) N(2) Cd(2) S(2) 102.2(2) N(3) Cd(2) S(2) (19) O(2) a Cd(2) S(1) (19) N(1) Cd(2) S(1) 89.0(2) N(2) Cd(2) S(1) 141.9(2) N(3) Cd(2) S(1) 61.75(19) S(2) Cd(2) S(1) (10) Complex 8 Cd(1) O(1) 2.236(6) Cd(1) N(2) 2.292(6) Cd(1) O(3) b 2.303(5) Cd(1) N(1) a 2.339(6) Cd(1) O(4) c 2.614(5) Cd(1) O(2) (7) Cd(1) O(4) b 2.356(5) O(1) Cd(1) N(2) 94.8(2) O(1) Cd(1) O(3) b 147.1(2) N(2) Cd(1) O(3) b 90.2(2) O(1) Cd(1) N(1) a 86.9(2) N(2) Cd(1) N(1) a 178.2(2) O(3) b Cd(1) N(1) a 88.5(2) O(1) Cd(1) O(4) c 84.2(2) N(2) Cd(1) O(4) c 89.6(2) O(3) b Cd(1) O(4) c (19) N(1) a Cd(1) O(4) c 90.2(2) O(1) Cd(1) O(4) b (19) N(2) Cd(1) O(4) b 90.86(19) O(3) b Cd(1) O(4) b 52.30(17) N(1) a Cd(1) O(4) b 87.4(2) O(4) c Cd(1) O(4) b 76.15(18) [a] Symmetry codes: For 1: a x, -1+y, z; For 2: a -x+1,y,-z+3/2; For 3: a -x+5/2,y-1/2,-z+1/2; b -x-5/2,y-1/2,-z+1/2; For 4: a -x-1,-y,-z; For 5: a x, y-1, z; For 6: b -x+3/2,y-1/2,-z+3/2; For 7: a 2-x, -y, 1-z; b x-1,y,z; c -x+1,-y,-z; d -x+1,-y,-z+1; For 8: a x+1/2,y+1/2,z; b x+1/2,-y+3/2,z-1/2; c -x+1,y,-z+3/2.
3 Table S2 Hydrogen-bonding geometries for compounds 1, 4 and 5. D H A D H (Å) H A (Å) D A (Å) D H A ( ) Complex 1 O(5) H(5B) O(2) (4) 155 O(6) H(6A) O(1)# (3) 147 O(6) H(6B) O(3)# (3) 142 O(5) H(5A) N(1)# (4) 177 Complex 4 O(6) H(6A) O(3)# (4) 171 O(6) H(6B) N(3) (4) 162 Complex 5 O(5) H(5A) O(2)# (3) 166 O(5) H(5B) O(1)# (2) 168 O(6) H(6A) O(7)# (3) 176 O(6) H(6B) O(1)# (2) 161 O(7) H(7A) N(2) (3) 164 O(7) H(7B) O(2)# (2) 175 For 1: #1 1+x, y, z, #2 1/2+x, 1/2-y, -z, #3 1-x, -1/2+y, 1/2-z. For 4: #1 -x, -y, -z; #2 1+x, 1+y, z. For 5: #1 x, y, - 1+z; #2 -x, -y, 1-z, #3 1-x, 1-y, 1-z, #4 1-x, -y, 1-z, #5, -x, 1-y, 2-z. Table S3 S S bond lengths [Å] and C S S C torsion angles [ ], the dihedral angles of the two pyridyl rings [ ] in the cpds 2- ligands. Complexes S S distance (Å) C S S C torsion angle( ) Dihedral angle of the two pyridyl rings ( )
4 Supplementary Material (ESI) for CrystEngComm Figure S1 The regular 3D framework in 1. Figure S2 The chiral single-chain structure linking by only the M-or the P-form of the cpds2ligands in 2.
5 Figure S3 Polymeric sheets encapsulated free water molecules in 2. Figure S4 Perspective and space-filling views of the 1D tubular channel in 3.
6 Supplementary Material (ESI) for CrystEngComm Figure S5 Representation showing the infinite channels filled with water molecules and bpe ligands. Figure S6 The 3D crystal packing diagram in 4.
7 Supplementary Material (ESI) for CrystEngComm Figure S7 Perspective view of the twelve-member ring formed by hydrogen bonding in 5. (A: x, -1+y, z; B: -x, 1-y, -z; C: -x, 1-y, 1-z; D: x, -1+y, 1+z) Figure S8 The 3D supramolecular network directed by interlayer π-π stacking interactions in 5. Figure S9 Schematic view of the net topology of 6.
8 Supplementary Material (ESI) for CrystEngComm Figure S10 A representation of the stacking of the 2D networks in 7. Figure S11 The 1D quadrate strap by the linkage between bpe ligands and bimetallic Cd(II) units. Figure S12 The 3D microporous framework encapsulating free water molecules. Figure S13 TGA curves of complexes 1 8.
9 (1) (2) (3) (4) (5) (6) (7) (8) Figure S14 (1) Comparison of XRPD patterns of the simulated pattern and the as-synthesized in compound 1; (2) in compound 2; (4) in compound 4; (5) in compound 5; (7) in compound 7; (3) Comparison of XRPD patterns of the simulated pattern, the as-synthesized and the desolvated
10 products in compound 3; (6) Comparison of XRPD patterns of the simulated pattern, the as-synthesized and the desolvated products in compound 6; (8) Comparison of XRPD patterns of the simulated pattern, the as-synthesized and the desolvated products in compound 8.
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ΖΕΡΔΑΛΗΣ ΣΩΤΗΡΙΟΣ ΤΟ ΟΥΤΙ ΣΤΗ ΒΕΡΟΙΑ (1922-ΣΗΜΕΡΑ) ΘΕΣΣΑΛΟΝΙΚΗ 2005 1
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metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 = 91.155 (4) = 108.148 (4) = 111.344 (3) V = 894.09 (7) Å 3 Z =1 Mo K radiation = 17.13 mm 1 T = 295 K 0.41