2-Aminopyrimidine(2AP)-succinic acid (SA) 1:1 cocrystal, C4HsN3.C4H604, Mr=213.19, = = 13.426 ( monoclinic, P21/n, a 5.045 (4), b 5), c = 15.148 (5)/1,, fl = 95.45 (5) °, V= 1021 (2) A 3~ Z= 4, Dx = 1.39 g cm -3,

We have synthesized [Pt(CN-iso-C 3 H 7 ) 4 ][M(CN) 4 ] (M ) Pt, Pd) and studied their reversible hydration and sorption properties with UV-vis, FT-IR spectroscopy, and X-ray diffraction. Powder diffraction studies show that anhydrous [Pt(CN-iso-C 3 H 7 ) 4 ][Pt(CN) 4 ] and [Pt(CN-iso-C 3 H 7 ) 4 ][Pd(CN) 4 ] crystallize in a tetragonal space group with nearly identical lattice constants. Gravimetric studies reveal that variable guest-host stoichiometries occur when solid [Pt(CN-iso-C 3 H 7 ) 4 ][Pt(CN) 4 ] sorbs the guest at room temperature from the gas phase [water, 12.1(1) molecules per formula unit, chloroform 6.0(1), methanol 8.0(1), and trifluoroethanol 4.1(1)]; these sorption processes are reversible. The unit cell distances in the tetragonal ab-plane expand dramatically when the solvent guests are sorbed, but changes along the c-axis (the M-M direction) are minimal. Crystallization of [Pt(CN-iso-C 3 H 7 ) 4 ][Pt(CN) 4 ] from water gives monoclinic crystals of a hexadecahydrate [Pt(CN-iso-C 3 H 7 ) 4 ][Pt(CN) 4 ]‚16H 2 O. This salt consists of alternating cation/anion chains along b with an average Pt-Pt distance of b/2 ) 3.1521(1) Å. The sixteen water molecules per formula weight interlace neighboring chains via H-bonding with each other and the CNions of the Pt(CN) 4 2units. The shifts in the UV-vis and IR spectra that occur when solvent guests are sorbed by the double complex salts are discussed in terms of the lattice expansions that are observed. A mechanism for the lattice expansions that accompany the sorption of guest molecules is proposed.

A new synthetic procedure developed recently in our laboratories has made possible the synthesis of variety of new complexes of CuCN with diamines. Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. This procedure also provides an alternative pathway to a novel diamine complex reported by us previously, (CuCN)(3)(HMTA)(2) (1) (where HMTA = hexamethylenetetramine). The other diamine ligands used were 1,4-diazabicyclo[2.2.2]octane (dabco), 1,4-dimethylpiperazine (dmpip), piperazine (pip), 1,4-butanediamine (butda), N,N,N',N'-tetramethylethylenediamine (tetmen), and N-phenylpiperazine (phpip). Complex2, Cu(2)(CN)(3)(dabco-H), crystallizes in the hexagonal space group P6(3) with unit cell dimensions a = 8.174(3) Å, c = 8.083(4) Å, and Z = 2. Complex 3, (CuCN)(2)(dmpip), crystallizes in the monoclinic space group C2/m with unit cell dimensions a = 8.812(3) Å, b = 9.631(2) Å, c = 7.266(3) Å, beta = 113.40(3) degrees, and Z = 2. Complex 4, (CuCN)(2)(pip), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 9.439(3) Å, b = 10.561(2) Å, c = 8.870(3) Å, beta = 98.32(3) degrees, and Z = 4. Complex 5, Cu(2)(CN)(3)(pip-H), crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 20.573(9) Å, b = 8.354(2) Å, c = 15.989(6) Å, beta = 133.70(3) degrees, and Z = 8. Complex 6, (CuCN)(2)(butda), crystallizes in the monoclinic space group P2(1)/c with unit cell dimensions a = 10.456(2) Å, b = 5.550(1) Å, c = 8.669(3) Å, beta = 106.80(2) degrees, and Z = 2. Complex 7, (CuCN)(2)(tetmen), crystallizes in the orthorhombic space group Cmc2(1) with unit cell dimensions a = 11.889(4) Å, b = 33.380(8) Å, c = 9.012(3) Å, and Z = 12. Complex 8, (CuCN)(phpip), crystallizes in the monoclinic space group P2(1)/cwith unit cell dimensions a = 17.8819(3) Å, b = 6.9190(1) Å, c = 8.6972(1) Å, beta = 96.720(1) degrees, and Z = 4.

The continuous absorption spectra for gaseous Cl2, Br2, BrCl, IC1, and IBr between 220 and 600 µ are reported. The experimental data have been fitted to theoretical curves of the type suggested by Sulzer and Wieland. The parameters for these curves are given.

The syntheses and crystal structures of the first cyanide, sulfur mixed ligand copper(I) complexes are reported. The first complex of the family was discovered when (CuCN)(3)(C(6)H(12)N(4))(2) (1) (C(6)H(12)N(4) = hexamethylenetetramine) was treated with aqueous thiourea. The sulfur ligands include thiourea (tu), 1,3-dimethyl-2-thiourea (dmtu), 1,3-diethyl-2-thiourea (detu), 1,1,3,3-tetramethyl-2-thiourea (tmtu), and 2-imidazolidinethione (N,N'-ethylenethiourea, etu). Synthesis was effected by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. Complex 2, (CuCN)(2)(tu)(3)(H(2)O), crystallizes in the triclinic space group P&onemacr;with unit cell dimensions a = 7.696(5) Å, b = 9.346(2) Å, c = 10.772(2) Å, alpha = 106.53(2) degrees, beta = 91.11(4) degrees, gamma = 98.42(3) degrees, and Z = 2. Complex 3, (CuCN)(3)(dmtu)(2), crystallizes in the monoclinic space group Cc with unit cell dimensions a = 10.082(3) Å, b = 14.984(5) Å, c = 11.413(3) Å, beta = 104.50(2) degrees, and Z = 4. Complex 4, (CuCN)(2)(detu)(H(2)O), crystallizes in the monoclinic space group P2(1)/n with unit cell dimensions a = 7.969(5) Å, b = 11.559(4) Å, c = 13.736(5) Å, beta = 100.48(4) degrees, and Z = 4. Complex 5, (CuCN)(tmtu) (polymorph a), crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell dimensions a = 8.653(1) Å, b = 9.426(1) Å, c = 11.620(3) Å, and Z = 4. Complex 6, (CuCN)(tmtu) (polymorph b), which has the same connectivity as 5, crystallizes in the triclinic space group P&onemacr; with unit cell dimensions a = 9.660(4) Å, b = 14.202(4) Å, c = 16.03(1) Å, alpha = 101.68(5) degrees, beta = 107.08(6) degrees, gamma = 70.07(2) degrees, and Z = 8. The difference between the polymorphs is that 5 has a zig-zag chain with a repeat unit of two while 6 has a 4-fold helix. Complex 7, (CuCN)(2)(etu), crystallizes in the monoclinic space group P2(1)( )()with unit cell dimensions a = 3.994(2) Å, b = 13.886(3) Å, c = 7.556(1) Å, beta = 97.07(2) degrees, and Z = 2.

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Crystal Data for [M 2 (dimen) 4 ](Y) 2 salts. [Rh 2 (dimen) 4 ](TFPB) 2 : C 1 12 H 9 B 2 F 4 8 N 8 Rh 2 , M = 2693.40, orange irregular crystal (0.60 x 0.50 x 0.30 mm), triclinic, space group P 1 (No. 2), a = 13.287 (3) A, b = 13.792 (6) A, c = 17.953 (7) A, a = 86.90 (3)0, 0 = 89.44 (3)0, y= 69.76 (3)o, V = 3082 (4) A3, Pcalc = 1.451 g cm-3 , Z = 1; 20max = 43.90; 7940 reflections (7539 unique, Rint = 0.037), T = 24.0 oC, 3729 observations (338 parameters) converged to R = 0.093 (Rw = 0.106). [Rh 2 (dimen) 4 1[B(C 6 Hs) 4 1 2 : C 9 6 H 1 12 B 2 N 8 Rh 2 , M = 1605.428, red prism (0.30 x 0.33 x 0.41 mm), space group Pbca (No. 61), a = 19.390 (5) A, b = 29.492 (7) A, c = 30.970 (7) A,V= 17710 (7) A3, Pcalc = 1.204 g cm-3 , Z= 8; 26max = 40,00; 16793 reflections (7821 unique, Rint = 0.03 1), T = 23.0 oC, 7817 observations (505 parameters) converged to R = 0.104 (R, = 0.080). [Ir 2 (dimen) 4 1(PF 6) 2 : C 4 8 H 7 2 F 1 2 Ir 2 N 8 P 2 , M = 1435.53, dark prism (0.45 x 0.75 x 0.08 mm), triclinic, space group P 1 (No. 2), a = 13.605 (8) A, b = 14.196 (4) A, c = 9.464 (7) A, a = 94.96 (4)0, 0 = 104.21 (5)0, Y = 61.83 (3)O, V= 1561 (3) A3, Pcalc = 1.527 g cm-3 , Z= 1; 20max = 52.00; 6497 reflections (6045 unique, Rint = 0.048), T = 24.0 oC, 3520 observations (194 parameters) converged to R = 0.073 (Rw = 0.075). [1r 2 (dimen) 4 1(TFPB) 2 : C 1 12 H 9 6 B 2 F 4 8 Ir 2 N 8 , M = 2872.03, purple plate (0.30 x 0.25 x 0.05 mm), triclinic, space group P 1 (No. 2), a = 13.110 (5) A, b = 13.513 (3) A, c = 17.770 (4) A, a = 87.61 (2)0, P = 90.43 (2)0, y 70.10 (2)0, V= 2970 (3) A3, Pcalc = 1.606 g cm-3 , Z= 1; 26max = 32.00; 3211 reflections (2893 unique, Rit = 0.066), T=-101.0 oC, 1976 observations (330 parameters) converged to R = 0.079 (R, = 0.067). [Ir 2 (dimen) 4 1[B(C 6 Hs) 4)1 2 : C 9 6 H 1 12 B 2 Lr 2 N 8 , M = 1784.05, black prism (0.240 x 0.140 x 0.130 mm), orthorhombic, space group Pbca (No. 61), a = 19.32 (1) A, b = 29.45 (1) A, c = 30.92 (3) A, V= 17600 (33) A3, Pcalc = 1.346 g cm-3 , Z = 8; 20max = 43.90; 10753 reflections (all unique), T =-101.0 oC, 4771 observations (359 parameters) converged to R = 0.061 (Rw = 0.062).