Molybdenum(VI) complexes of branched ligands with [N,O,O,O] and [O,O,O] donor sets. The crystal and molecular structures of [MoO2{HOC2H4N(C2H4)O2}], [(n-C4H9)4N]2[Mo2O4{(O2NCCH2O)3}2]·202NC(CH2OH)3, [(n-C4H9)4N][Mo2O5{(HO2CCH2N)(CH2CO2)2}2]·H2O and [n-C4H9)4N][Mo3O6(OCH3{(CH3OCH2O)3}2]

Abstract Reactions in methanol of [TBA] 2 [Mo 2 O 7 ] with the appropriate branched polyhydroxylic and polycarboxylic ligands yielded the complexes [MoO 2 {(HOC 2 H 4 N(C 2 H 4 O) 2 }] ( 3 ), [TBA] 2 [Mo 2 O 4 {(O 2 NC(CH 2 O) 3 } 2 ]·2O 2 NC(CH 2 OH) 3 ( 4 ), [TBA] 2 [Mo 2 O 5 {(HO 2 CCH 2 N(CH 2 CO 2 ) 2 } 2 ]·H 2 O ( 5 ) and [TBA][Mo 3 O 6 (OCH 3 ){(CH 3 CCH 2 O) 3 } 2 ] ( 6 ) [where TBA = ( n -C 4 H 9 ) 4 N]. The deprotonation of 3 yields [Et 3 NH][MoO 2 {(N(C 2 H) 4 O) 3 }] ( 3a ), while 4 was found to aggregate with additional molybdate to give [TBA][Mo 3 O 6 (OCH 3 ){(O 2 NCCH 2 O) 3 } 2 ] ( 4a ) and [MO 4 O 8 ,(OCH 3 )2{(O 2 NCCH 2 O) 3 } 2 ] ( 4b ). The structural interrelationship of this series of polymolybdate coordination compounds is discussed in terms of simple aggregation processes. Crystal data: 3 , monoclinic P 2 1 / n , a = 10.688(2), b = 7.559(3), c = 11.386(7) β,A = 99.62(1)°, V = 905.2(5) A 3 , Z = 4, D calc , = 2.02 g cm −3 ; 1786 reflections, R = 0.0406. 4 , triclinic P 1 , a = 10.965(2), b = 11.850(3), c = 13.247(3) A, α= 84.72(1), β = 89.52(2), γ = 66.95(2)°, V = 1576.4(7) A 3 , Z = 1, D calc = 1.40 g cm −3 ; 4718 reflections, R = 0.0389. 5 , monoclinic P 2 1 , a = 10.735(2), b = 13.404(6), c = 19.257(6) A, β = 90.61(2)°, V = 2770.9(16) A 3, Z = 2, D calc = 1.36 g cm −3 ; 3212 reflections, R = 0.0380. 6 , monoclinic P 2 1 / n , a = 10.908(2), b = 25.674(5), c = 13.059(2) A, β= 96.35(2)°, V = 3635.6(12) A 3 , Z = 4, D calc = 1.62 g cm −3 ; 3143 reflections, R = 0.0490.