Guanidinium Ion as a Symmetrical Template in the Formation of Cubic Hydrogen-Bonded Borate Networks with the Boracite Topology

Reaction between boric acid and guanidinium salts in methanolic solution at room temperature in the presence of various bases and anions gives well-formed solvated crystals of composition {[B(OCH3)4]3[C(NH2)3]4}+X-. The products in which X- = Cl- and PF6- are characterized by single-crystal X-ray diffraction. The tetramethoxyborate and guanidinium components form a highly symmetrical (cubic) hydrogen-bonded 3D network having the “boracite topology” [i.e., the (63)(6284) topology]. Highly disordered solvent molecules and anions occupy methyl-surfaced cavities and channels that represent more than 30% of the space

Guanidinium Ion as a Symmetrical Template in the Formation of Cubic Hydrogen-Bonded Borate Networks with the Boracite Topology

Reaction between boric acid and guanidinium salts in methanolic solution at room temperature in the presence of various bases and anions gives well-formed solvated crystals of composition {[B(OCH3)4]3[C(NH2)3]4}+X-. The products in which X- = Cl- and PF6- are characterized by single-crystal X-ray diffraction. The tetramethoxyborate and guanidinium components form a highly symmetrical (cubic) hydrogen-bonded 3D network having the “boracite topology” [i.e., the (63)(6284) topology]. Highly disordered solvent molecules and anions occupy methyl-surfaced cavities and channels that represent more than 30% of the space

Cu(SO₃)₄^7-: A Readily Accessible Building Block for New Coordination Polymers

The combination of Cu(II) with excess sodium sulfite or a mixture of sodium sulfite and sodium hydrogensulfite produces a colorless solution consistent with the reduction of Cu(II) to Cu(I). The addition of divalent metal ions such as Mn2+, Co2+, Ni2+ and Zn2+ to such solutions, leads to the generation of coordination networks in which the divalent metal ions link together anions of formula Cu(SO3)47−. This symmetrical anion consists of a tetrahedrally coordinated Cu(I) center bound to the sulfur atoms of four sulfite anionic ligands. Isostructural 1D coordination polymers of composition Na3{[CuI(SO3)4][ZnII(H2O)2]2}·H2O and Na3{[CuI(SO3)4][CoII(H2O)2]2}·H2O, isostructural 2D coordination polymers of composition [Na4(H2O)17][Ni(H2O)6]2{[Cu(SO3)4]2[Ni(H2O)2]3} and [Na4(H2O)17][Co(H2O)6]2{[Cu(SO3)4]2[Co(H2O)2]3}, and a 3D coordination polymer of composition Na(H2O)6{[CuI(SO3)4][MnII(H2O)2]3} are reported

Guanidinium Ion as a Symmetrical Template in the Formation of Cubic Hydrogen-Bonded Borate Networks with the Boracite Topology

Reaction between boric acid and guanidinium salts in methanolic solution at room temperature in the presence of various bases and anions gives well-formed solvated crystals of composition {[B(OCH3)4]3[C(NH2)3]4}+X-. The products in which X- = Cl- and PF6- are characterized by single-crystal X-ray diffraction. The tetramethoxyborate and guanidinium components form a highly symmetrical (cubic) hydrogen-bonded 3D network having the “boracite topology” [i.e., the (63)(6284) topology]. Highly disordered solvent molecules and anions occupy methyl-surfaced cavities and channels that represent more than 30% of the space

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands

Serendipity and Design in the Generation of New Coordination Polymers: An Extensive Series of Highly Symmetrical Guanidinium-Templated, Carbonate-Based Networks with the Sodalite Topology

The serendipitous discovery of a 3D [Cu(CO3)22-]n network with the topology of the 4264 sodalite net in [Cu6(CO3)12(CH6N3)8]·K4·8H2O paved the way for the deliberate engineering of an extensive series of structurally related guanidinium-templated metal carbonates of composition [M6(CO3)12(CH6N3)8]Na3[N(CH3)4]·xH2O, where the divalent metal M in the framework may be Mg, Mn, Fe, Co, Ni, Cu, Zn, or Cd. A closely related crystalline material with a [Ca(CO3)22-]n sodalite-like framework, but containing K+ rather than Na+, of composition [Ca6(CO3)12(CH6N3)8]K3[N(CH3)4]·3H2O was also isolated. All of these compounds were obtained under the simplest possible conditions from aqueous solution at room temperature, and their structures were determined by single-crystal X-ray diffraction. Pairs of guanidinium cations are associated with the hexagonal windows of the sodalite cages, alkali-metal cations are associated with their square windows, and N(CH3)4+ ions are located at their centers. Structures fall into two classes depending on the metal, MII, in the framework. One type, the BC type (Im3̄m), comprising the compounds for which M2+ = Ca2+, Mn2+, Cu2+, and Cd2+, has a body-centered cubic unit cell, while the second type, the FC type (Fd3̄c), for which M2+ = Mg2+, Fe2+, Co2+, Ni2+, and Zn2+, has a face-centered cubic unit cell with edges on the order of twice those of the BC structural type. The metal M in the BC structures has four close carbonate oxygen donors and four other more distant ones, while M in the FC structures has an octahedral environment consisting of two bidentate chelating carbonate ligands and two cis monodentate carbonate ligands