Tuning of the charge in octahedral ferric complexes based on pyridoxal-N-substituted thiosemicarbazone ligands

Abstract

Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe S1 2.2222(19). . yes Fe S2 2.205(2). . yes Fe O1 1.884(5). . yes Fe O3 1.962(5). . yes Fe N1 1.926(5). . yes C12A C13B 1.64(2). . no C12A C12B 0.85(2). . no C12A C13A 1.38(2). . no C12A C16B 1.79(2). . no C12A C16A 1.46(2). . no C12B C13A 1.64(2). . no C12B C13B 1.37(2). . no C12B C16B 1.509(19). . no C12B C16A 1.75(2). . no C13A C13B 0.95(2). . no C14 C17 1.480(10). . no C14 C15 1.413(11). . no C16A C16B 1.10(3). . no C1 H1 0.95. . no C4 H4 0.95. . no C7 H7 0.99. . no C7 H7' 0.99. . no C8 H8 0.98. . no C8 H8' 0.98. . no C8 H8" 0.98. . no C10 H10 0.95. . no C13A H132 1.42. . no C13A H131 0.95. . no C13B H131 1.44. . no C13B H132 0.95. . no C16A H161' 0.99. . no C16A H161 0.99. . no C16A H42 1.41. . no C16B H162 0.99. . no C16B H162' 0.99. . no C16B H161' 0.55. . no C17 H17 0.98. . no C17 H17' 0.98. . no C17 H17" 0.98. . no Fe S2 C18 94.6(3). .. yes O5 S3 O6 109.1(3) 2_555. 2_555 yes O6 S3 O6 110.4(3). . 2_555 yes O5 S3 O6 109.0(3) 2_555. . yes O5 S3 O6 109.1(3). .. yes O5 S3 O5 110.1(3). . 2_555 yes O5 S3 O6 109.0(3). . 2_555 yes Fe O1 C6 125.5(4). .. yes Fe O3 C15 125.9(5). .. yes O4B O4A C16A 24.1(9). .. yes C16A O4B C16B 50(2). .. yes O4A O4B C16B 78.3(10). .. yes O4A O4B C16A 57.9(19). .. yes C7 O2 H21 100(7). .. no C16A O4A H41 109. .. no O4B O4A H41 117. .. no C16B O4B H161' 19. .. no C16A O4B H161' 68. .. no C16A O4B H42 134. .. no O4A O4B H161 107. .. no O4A O4B H42 168. .. no O4A O4B H161' 93. .. no C16A O4B H161 92. .. no H42 O4B H161 75. .. no C16B O4B H161 132. .. no H161' O4B H161 138. .. no C16B O4B H42 110. .. no H161' O4B H42 93. .. no H31 O7 H31' 139(14). .. no H33 O9 H33' 85(18). .. no H35 O11 H35' 143(17). .. no N3 N1 C1 114.3(5). .. yes Fe N1 N3 120.4(4). .. yes Fe N1 C1 125.3(5). .. yes C4 N2 C5 125.2(7). .. yes N1 N3 C9 113.7(5). .. yes Fe N5 N7 120.2(4). .. yes Fe N5 C10 125.7(5). .. yes N7 N5 C10 113.8(5). .. yes C13A N6A C13B 37.3(9). .. yes C13A N6A C14 124.7(12). .. yes C13B N6A C14 109.2(11). .. yes N6B N6A C13B 60.1(15). .. yes N6B N6A C14 74.2(16). .. yes N6B N6A C13A 97.4(18). .. yes N6A N6B C14 76.6(16). .. yes C13A N6B C13B 36.7(9). .. yes N6A N6B C13B 94.0(18). .. yes C13B N6B C14 123.8(13). .. yes C13A N6B C14 109.4(11). .. yes N6A N6B C13A 57.2(15). .. yes N5 N7 C18 113.6(5). .. yes C5 N2 H22 131(9). .. no C4 N2 H22 103(9). .. no H24 N4 H24' 120(12). .. no C9 N4 H24 111(8). .. no C9 N4 H24' 113(8). .. no C13B N6A H61 120. .. no N6B N6A H62 46. .. no C13A N6A H61 118. .. no N6B N6A H61 99. .. no C14 N6A H61 118. .. no C14 N6A H62 97. .. no C13B N6A H62 88. .. no H61 N6A H62 53. .. no C13A N6A H62 116. .. no N6A N6B H62 100. .. no N6A N6B H61 47. .. no C...

Unusual Magneto‐Structural Features of the Halo‐Substituted Materials [FeIII(5‐X‐salMeen)2]Y: a Cooperative [HS‐HS]↔[HS‐LS] Spin Transition

“…The room temperature values of χ M T for 1 – 4 , which occur in the range 4.06–4.28 cm 3 K mol −1 , are consistent with the spin‐only value for HS iron(III) (χ M T ≈4.38 cm 3 K mol −1 ). They also concur with literature values in the range 3.80–4.50 cm 3 K mol −1 for closely related ferric spin‐crossover materials; although some of these reported values are somewhat low . The spin conversion in 1 – 4 , evidenced by the decrease in the values of χ M T with temperature, culminates in a plateau with a width of 115 K (140‐25 K) for 2 – 4 and 85 K (110‐25 K) for 1 .…”

“…They also concurw ithl itera- ture values in the range 3.80-4.50 cm 3 Kmol À1 for closely related ferric spin-crossover materials; [1-20, 24, 29, 34, 35, 45, 46, 48-51] although some of these reported values are somewhat low. [12,[14][15][16]49] [24] and the closely related saltrienc omplexes [Fe III L]PF 6 (H 2 L = H 2 -5-iPr-saltrieno rH 2 -5-tBu-saltrien), [52] which unfortunately were not crystallographically elucidated.…”

“…X-band EPR spectroscopy revealed that all the complexes [Fe III (5-X-salMeen) 2 ]ClO 4 (1-4) are fully LS in frozen methanol solution at liquid nitrogen temperature and their EPR spectra are virtually indistinguishable from one another (see Experimental Sectioni nS upporting Information). LS Fe III EPR spectra tend to be either rhombic [28,35,42,49,53,60,62] or axial. [19,27,49,53,58] Those of complexes 1-4,r epresented by the spectrum of [Fe III (5-Cl-salMeen) 2 ]ClO 4 (2)[ Figure 11 b: g ?…”

Synthesis and characterisation of Fe(III) and Co(III) complexes of thiazole-containing thiosemicarbazone ligands

“…[9][10][11] Thiosemicarbazonebased ligands have been used to generate interesting complexes with a range of potential applications, however one area that appeals to us is their use in Fe(III) spincrossover (SCO) systems. [12][13][14][15][16][17] Most examples of thiosemicarbazone-based SCO active complexes use simple thiosemicarbazides and salicylaldehyde (SA) derivatives (e.g. Hthsa, Hth5Clsa and Hth5Brsa, Fig.…”

Complexes of pyridoxal thiosemicarbazones formed with vanadium(IV/V) and copper(II): Solution equilibrium and structure

“…Bis-ligand complexes are formed with e.g. Fe III [23], Co III [24] and Ni II [25], when an octahedral coordination mode is preferred. In case of Cu II mainly mono-ligand complexes were described [11,26,27] sometimes in dimerized form [13].…”