The respectively yellow and red coordination polymers 2

The coordination polymers  ∞2[(CuCN)2(μ‐2 Mepyz)],  ∞3[CuCN(μ‐2 Mepyz)] and  ∞3[CuCN(μ‐4 Mepym)] (1–3) (2 Mepyz = 2‐methylpyrazine; 4 Mepym = 4‐methylpyrimidine) may be prepared by self‐assembly in acetonitrile solution at 100 °C (1, 3) or without solvent at 20 °C (2). All three contain  ∞1[CuCN] chains that are bridged by the bidentate aromatic ligands into sheets in 1 and 3 D frameworks in 2 and 3. Reaction of CuSCN with these heterocyclic diazines at 100 °C leads to formation of the lamellar coordination polymers  ∞2[(CuSCN)(μ‐2 Mepyz)] (4) and  ∞2[CuSCN · (4 Mepym‐κN1)] (5), which contain respectively  ∞1[CuSCN] chains and trans‐trans fused  ∞2[CuSCN] sheets as substructures. The presence of an asymmetric substitution pattern in 2 Mepyz and 4 Mepym induces the adoption of a chiral structure by 2 and 5 (space groups P212121 and P1).

Non-centrosymmetric one-to three-dimensional CuSCN-based coordination polymers with substituted pyrazine or pyrimidine spacer ligands can be prepared by self-assembly in acetonitrile solution at 100°C. Both 1 I [CuSCN(2 NCpyz) 2 ] (1) (2 NCpyz = 2-cyanopyrazine) and 1 I [CuSCN(4 HOpym) 2 ] (3) (4 HOpym = 4-hydroxypyrimidine) contain single zigzag CuSCN chains as their central backbone and crystallise in polar space groups (monoclinic Cm and orthorhombic Ama2). In 2 I [(CuSCN) 2 (l-2 Mepyz)] (2) (2 Mepyz = 2-methylpyrazine), 1 I [(CuSCN) 2 ] staircase double chains are connected by bridging 2 Mepyz ligands to afford a lamellar polymer (triclinic P 1). Whereas 2 I [CuSCN(5 Brpym)] (4) (5 Brpym = 5-bromopyrimidine) with its honeycomb 2 I [CuSCN] layers is chiral (monoclinic P2 1 ), both 3 D polymers 3 I [(CuSCN) 2 (l-pym)] (5) and 3 I [(CuSCN) 3 (l-4 Mepym)] (6) (4 Mepym = 4-methylpyrimidine) contain polar coordination networks (orthorhombic Fdd2 and monoclinic Pc). The CuSCN framework in (5) consists of thiocyanate bridged 1 I [CuS] chains, that in 6 of interlocked 2 I [CuSCN] and 2 I [Cu 2 S(SCN)] sheets. Nichtzentrosymmetrische Koordinationspolymere mit CuSCN und substituierten Pyrazin-und Pyrimidinliganden Inhaltsu È bersicht. Nichtzentrosymmetrische ein-bis drei-dimensionale Koordinationspolymere mit CuSCN und substituierten Pyrazin-oder Pyrimidinliganden ko È nnen durch Selbstorganisation in Acetonitrillo È sung bei 100°C dargestellt werden. Sowohl 1 I [CuSCN(2NCpyz)] (1) (2 NCpyz = 2-Cyanopyrazin) als auch 1 I [CuSCN(4 HOpym) 2 ] (3) (4 HOpym = 4-Hydroxypyrimidin) enthalten einfache zickzackartige CuSCN-Ketten als zentrales Ru È ckgrat und kristallisieren in polaren Raumgruppen (monoklin Cm bzw. orthorhombisch Ama2). In 2 I [(CuSCN) 2 (l-2 Mepyz)] (2) (2 Mepyz = 2-Methylpyrazin), erzeugt die Verknu È pfung von treppenartigen Doppelketten 1 I [(CuSCN) 2 ] durch 2 Mepyz-Bru È ckenliganden ein schichtartiges Polymer (triklin P 1). Wa È hrend 2 I [CuSCN(5 Brpym)] (4) (5 Brpym = 5-Bromopyrimidine) mit seinen wabenartigen Schichten 2 I [CuSCN] chiral (monoklin P2 1 ) ist, weisen die dreidimensionalen Polymere 3 I [(CuSCN) 2 (l-pym)] (5) and 3 I [(CuSCN) 3 (l-4 Mepym)] (6) (4 Mepym = 4-Methylpyrimidin) polare Koordinationsnetzwerke (orthorhombisch Fdd2 bzw. monoklin Pc) auf. Das CuSCN-Geru È st von 5 besteht aus SCN-verbru È ckten 1 I [CuS]-Ketten, das von 6 aus miteinander verbundenen 2 I [CuSCN]-und 2 I [Cu 2 S(SCN)]-Schichten.

Treatment of an acetonitrile solution of CuCN with methylcycloarsoxane (CH 3 AsO) n at 110°C affords the coordination polymer 3 ϱ [CuCN{cyclo-(CH 3 AsO) 4 }] (1), in which infinite CuCN zigzag chains are linked by µ-As 1 ,As 3 cyclotetramers (CH 3 AsO) 4 into an open 3-D framework. Under similar solvothermal conditions, reaction of CuSCN with (CH 3 AsO) n in the presence of KSCN leads to metal-mediated ring expansion of the cycloarsoxane to yield the complex 1 ϱ [{K[cyclo-(CH 3 AsO) 5 ] 2 }Cu(NCS) 2 ] (2). This contains discrete [Cu(NCS-κN) 2 {cyclo-(CH 3 AsO) 5 κAs} 2 ] Ϫ anions that bridge κ 10 O coordinated potassium 709 cations into infinite chains. In contrast, the structure directing role of the [K(1,7DT18C6) 2 ] ϩ sandwich building units for the solvothermal product 3 ϱ [{K(1,7DT18C6) 2 }Cu 6 (CN) 7 ] (3) (1,7DT18C6 ϭ 1,7dithia-18-crown-6) leads to formation of an open 3 ϱ [{Cu 6 (CN) 7 } Ϫ ] framework. Individual [K(1,7DT18C6) 2 ] ϩ moieties bridge Cu Atoms in a µ-S 1 ,S 7 mode and are encapsulated within the large [Cu 26 (CN) 28 ] 2Ϫ cages of the cyanocuprate(I) network.

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