Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. II. Some Adducts of Group 2 Salts With Pyridine

1996 ◽  
Vol 49 (1) ◽  
pp. 35 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Metal Atom ◽  
Room Temperature ◽  
Site Symmetry ◽  
Nitrogen Base ◽  
Coordination Environment ◽  
X Ray ◽  
Pyridine Nitrogen ◽  
The Subject ◽  
Group 2 ◽  
A Site

Recrystallization of Group 2 halides from pyridine ( py ) solution has yielded, in a number of cases, crystalline adducts MX2.npy which have been the subject of room-temperature single-crystal X-ray structural characterization. MgBr2.6py (1) is orthorhombic, Ccca, a 11.575(2), b 14.999(4), c 17.292(2) Ǻ, Z = 4; conventional R on [F] for No = 752 'observed' (I > 3σ(I)) reflections was 0.043. The compound is formulated as [( py )4MgBr2].2py, the metal atom on a site of 222 symmetry having a trans-X2MN4 coordination environment. With CaCl2, a 1:2 adduct (2) is formed, orthorhombic, Fdd2, a 33.83(1), b 18.143(2), c 3.981(7) Ǻ, Z = 8 f.u ., R 0.040 for No 451; the complex is an infinite polymer along c, [( py )2CaCl2](∞ ׀ ∞), the…CaCl2CaCl2Ca…spine having six-coordinate, octahedral calcium environments in which the pyridine nitrogen atoms are bound trans to either side, with the calcium site symmetry being 2. With SrBr2, a 1:5 adduct (3) is found, mononuclear, [( py )5SrBr2], with the metal atom in a pentagonal bipyramidal coordination environment (orthorhombic, Pcab , a 18.611(5), b 17.768(7), c 17.411(7) Ǻ, Z = 8; R 0.060 for No 949). With BaI2, a 1:6 adduct (4) is obtained, [( py )6BaI2], the eight-coordinate barium atom lying on a crystallographic 2 axis in a monoclinic C2/c cell, Z = 4, a 18.311(2), b 9.960(3), c l8.856(8) Ǻ, β 99.28(3)° (R 0.031 for No 2279), with the iodide atoms occupying a pair of B sites in one of the trapezoidal planes of a quasi-dodecahedral array. [(2-mpy)2MgBr2] (5), 2-mpy=2-methylpyridine, is of interest, offering a four-coordinate N2MgBr2 array (triclinic, Pī, a 8.046(3), b 8.873(3), c 11.475(1) Ǻ, α 86.25(2), β 78.82(5), γ 67.88(5)°, Z = 2; R 0.069 for No 2091), while [( py )6/(4-mpy)6Ba(O2ClO2)2] (6) and (7), perhaps surprisingly, are isomorphous with (4), with O,O'-bidentate perchlorates replacing iodide in the coordination sphere (R 0.031 and 0.052 for No 2401 and 2204 respectively). With 3,5-dmpy (3,5-dimethylpyridine), strontium iodide yields a trans-six- rather than seven-coordinate adduct, [(3,5-dmpy)4SrI2] (8), the molecule conforming to crystallographic 4/m symmetry in the tetragonal space group I4/m, a 9.808(4), c 17.196(8) Ǻ, Z = 2; R 0.066 for No 608.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. IX. Some Complexes of Group 2 Metal Halides With 2,2':6',2"-Terpyridine

1996 ◽  
Vol 49 (1) ◽  
pp. 137 ◽  
Author(s):  
BW Skelton ◽  
AF Waters ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Nitrogen Base ◽  
Space Group ◽  
Trigonal Symmetry ◽  
X Ray ◽  
Space Groups ◽  
Structure Determinations ◽  
Group 2 ◽  
A Site

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of MX2.ntpy stoichiometry of salts of Group 2 metals, MX2, with 2,2':6',2"-terpyridine ( tpy ). ' Homoleptic' adducts, [M( tpy )3] X2, are found in space groups with trigonal symmetry, with M located on a site of at least 3 symmetry, the structures being derivative of the P 62c array found in [ Pb ( tpy )3] (ClO4)2, but with variations in anion and cation stackings . [M( tpy )3] I2.~1.7MeOH, M = Ca (1), Sr (2), are trigonal , P3c1, a ≈ 13, c ≈ 15.3 Ǻ, Z = 2 f.u., conventional R on ׀ F ׀ being 0.050, 0.086 for No 894, 865 independent 'observed' (I > 3σ(I)) reflections respectively. [ Sr ( tpy )3] Br2.2MeOH (3), although similar, is modelled in space group P3c1, a 13.040(4), c 15.13(1) Ǻ, Z = 2 f.u ., R 0.041 for No 447. [( tpy )2BaI2] (4) is monoclinic, P 21/c, a 10.812(4), b 16.740(5), c 17.458(4) Ǻ, β 109.39(2)°, Z = 4 f.u ., R 0.042 for No 3256. [( tpy )2Ba(O2ClO2)2] (5) is triclinic, Pī , a 14.220(4), b 11.212(2), c 10.511(2) Ǻ, α 65.66(2), β 87.32(2), γ 88.92(2)°, Z = 2 f.u ., R 0.029 for No 4676.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. I. Some Adducts of Group 2 Halides With Acetonitrile

1996 ◽  
Vol 49 (1) ◽  
pp. 27 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Coordination Sphere ◽  
Molecular Species ◽  
Room Temperature ◽  
Linear Array ◽  
Nitrogen Base ◽  
X Ray ◽  
Unusual Combination ◽  
Anionic Species ◽  
Group 2 ◽  
O 352

Recrystallization of anhydrous Group 2 halides from anhydrous acetonitrile has yielded, in a number of cases, adducts MX2.nMeCN suitable for characterization by room-temperature single-crystal X-ray studies, which revealed novel stereochemical types. Magnesium(II) bromide yields a trisolvate, ionic with disproportionated ligand arrays, as [Mg(NCMe)6][MgBr4] (1), an unusual combination of homoleptic cationic and anionic species. Crystals are triclinic, Pī , a 19.129(1), b l6.870(8), c 8.737(7) Ǻ,α 83.96(3), β 87.93(4), γ 65.24(2)�, Z=4 f.u .; R was 0.068 for N o 3181 'observed' (I > 3σ(I)) reflections. Mg-N are 2.12(2)-2.18(2) Ǻ, and Mg-Br are 2.452(7)-2.481(6) Ǻ. Calcium(II) bromide, by contrast, yields a disolvate , an infinite polymer, with the two MeCN ligands trans in a quasi-octahedral coordination sphere, and the polymer comprising a ... Ca(μ-Br)2Ca(μ-Br)2... linear array. Crystals of 1:2 CaBr2/MeCN (2) are orthorhombic, Pbam , a l4.252(3), b 8.539(2), c 4.2088(6) Ǻ, Z=2 f.u .; R 0.043 for N o 352. Ca-N is 2.46(1) Ǻ, and Ca-Br 2.8765(9) Ǻ. CaI2 and SrI2 yield pentasolvates as neutral, molecular species [( MeCN )5MX2] (3) and (4), with the halides trans in a pentagonal bipyramidal coordination sphere. They are isomorphous . orthorhombic, Pcab , a ≈ 18.4, b ≈ 14.6, c ≈ 14.3 Ǻ, Z = 8 f.u .; R were 0.042 and 0.059 for N o 2297 and 1489 respectively. Ca-I are 3.132(2), 3.116(2) Ǻ and Sr -I are 3.265(3), 3.238(3) Ǻ, while Ca-N are (range) 2.518(8)-2.566(8) Ǻ and Sr -N 2.68(2)-2.73(2) Ǻ.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. VII. Some Complexes of Group 2 Metal Halides With Aromatic N,N'-Bidentate Ligands

1996 ◽  
Vol 49 (1) ◽  
pp. 99 ◽  
Author(s):  
BW Skelton ◽  
AF Waters ◽  
AH White
Keyword(s):  
Room Temperature ◽  
The Novel ◽  
Bidentate Ligands ◽  
Nitrogen Base ◽  
One Dimensional ◽  
X Ray ◽  
L System ◽  
L Systems ◽  
Group 2 ◽  
Structural Characterizations

Syntheses and room-temperature single-crystal X-ray structural characterizations are recorded for a number of adducts of Group 2 halides with the aromatic N,N′- bidentate ligands L = 2,2'-bipyridine ( bpy ) and 1,10-phenanthroline ( phen ). One adduct of 1 : 1 MX2/L stoichiometry is recorded: [( bpy )Ca(μ-Br)(4/2)](∞ ׀ ∞) (1) is monoclinic, C 2/c, a l7.102(5), b 9.845(1), c 7.600(2) Ǻ, β 107.65(2)°, Z = 4 f.u .; conventional R on #1472; F ׀ at convergence was 0.057 for No 817 independent 'observed' ( I > 3σ(I)) reflections, the compound being a one-dimensional polymer… CaL (μ-Br)2CaL(μ-Br)2…, with six-coordinate calcium, cis-CaN2(μ-Br)4, on a twofold axis. 1 : 2 MX2/L systems have been described for two types of array: [( bpy )2CaI2] (2), orthorhombic, Pnca, a 16.914(4), b 13.80(1), c 9.290(4) Ǻ, Z = 4 f.u .; R 0.039 for No 1738, is discrete mononuclear, containing cis-CaN4I2 six-coordinate calcium, whereas the barium analogue is an infinite one-dimensional polymer, [( bpy )2Ba(μ-I)(4/2)](∞׀ ∞) (3), triclinic, Pī, a 11.318(2), b 11.078(2), c 9.206(4) Ǻ, α 80.87(2), β 77.52(2), γ 87.53(1)°, Z = 2 f.u .; R 0.032 for No 4154, with eight-coordinate (N2)2Ba(μ-I)4. The perchlorate analogue, [( bpy )2Ba(μ-OClO2O)(4/2)](∞ ׀ ∞) (4), although of similar stoichiometry, has a trans-rather than a cis-linked chain; it is monoclinic, P 21/c, a 6.606(2), b 18.661(7), c 19.440(8) Ǻ, β 109.45(4)°, Z = 4 f.u .; R 0.044 for No 4060, with μ-I replaced by O,O'-ClO4 bridging units and eight-coordinate barium, (N2)2BaO4. The 1 : 3 MX2/L system is represented (as its hemi( bipyridine ) 'solvate') by mononuclear [( bpy )3SrI2].0.5bpy (5), monoclinic, P 21/c, a 20.834(8), b 9.735(4), c 18.460(7) Ǻ, β 114.87(3)°, Z = 4 f.u .; R 0.039 for No 3711, containing eight-coordinate strontium, [(N2)3SrI2]; there is also an isomorphous calcium/ perchlorate analogue [( bpy )3Ca(OClO3)2].0.5bpy (6), a 21.413(6), b 9.813(4), c 18.659(2) Ǻ, β 115.67(2)°, R 0.057 for No 3090, in which unidentate O-ClO4 ligands replace the iodine about the metal atom. A 1 : 4 adduct is obtained with CaI2/phen; ionic [Ca( phen )4] I2 (7), triclinic, Pī , a 14.703(3), b 13.292(3), c 11.38(1) Ǻ, α 92.78(4), β 96.15(4), γ 105.22(2)°, Z = 2 f.u ., R 0.053 for No 3658, contains eight-coordinate Ca(N2)4 arrays, while the novel 1 : 5 adduct [ Ba ( phen )4] I2.MeCN (8) is triclinic, Pī , a 12.170(6), b 13.760(7), c 18 254(8) Ǻ, α 77.05(9), ,β 71.96(4), γ 70.83(9)°, Z = 2 f.u ., R 0.040 for No 4447, containing 10-coordinate barium, [ Ba (N2)5]. A 1 : 4 adduct formed with BaBr2 is [ BrBa( phen )4] Br.MeOH (9), triclinic, Pī , a 17.748(4), b 17.418(2), c 15.535(7) Ǻ, α 91.63(2), β 100.53(3), γ 115.39(1)°, Z = 4 f.u ., R 0.062 for No 4092, containing nine-coordinate barium, [ BrBa (N2)4].

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. VI. Mixed Oligodentate-Aliphatic-Base/Oxygen Ligand Adducts

1996 ◽  
Vol 49 (1) ◽  
pp. 87 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Mixed Ligand ◽  
Metal Salts ◽  
Precise Description ◽  
Nitrogen Base ◽  
X Ray ◽  
Oxygen Ligand ◽  
Group 2 ◽  
Ligand Species

In the course of synthesizing oligodentate aliphatic nitrogen base adducts of Group 2 metal salts, a number of mixed- ligand species have been isolated with oxygen ligands , and characterized by room-temperature single-crystal X-ray studies. BaCl2.4en.H2O ≡[(en)4Ba(OH2)] Cl2 (1) is monoclinic, P 21/c, a 9.456(4), b 14.953(6), c 14.82(1) Ǻ, β 100.78(6)°, Z = 4 f.u ., R 0.043 for No 1862 independent 'observed' (I > 3σ(I)) diffractometer reflections. Ba -N range between 2.900(9) and 2.97(1) Ǻ, and Ba-O is 2.779(8) Ǻ in the nine-coordinate BaN8O environment. CaCl2.2dien.H2O ≡ [( dien )2Ca(OH2) Cl ] Cl (2) is monoclinic, P 21/c, a 10.808(4), b 11.999(4), c 15.71(1) Ǻ, β 123.58(4)°, Z = 4 f.u ., R 0.050 for No 3134; CaBr2.2dien.2H2O ≡ [( dien )2Ca(OH2)2] Br2 (3) is monoclinic, P 21/c, a 18.001(3), b 11.983(6), c 21.562(5) Ǻ, β 124.97(2)°, Z = 8 f.u ., R 0.045 for No 2858; CaBr2.2dien.2MeOH ≡ [( dien )2Ca( HOMe )2] Br2 (4) is orthorhombic, P212121, a 16.620(8), b 12.78(1), c 9.765(4) Ǻ, Z = 4 f.u ., R 0.073 for No 878. In (2)-(4), the cation configurations are similar, being of the form [L2Ca( dien )2], L (L') being the unidentate ligand, with the eight-coordinate calcium environments [L2Ca(N3)2] in a common isomeric configuration, the two ligands L being cis in an array of quasi-2 symmetry. Ca- Cl in (2) is 2.834(1) Ǻ; Ca-N generally range between 2.52(5) and 2.64(1) Ǻ; Ca-O(H2O) is 2.418(2) in (2), 2.434(7)-2.496(7) Ǻ in (3), while Ca-O( MeOH ) in (4) are 2.43(2) and 2.43(2) Ǻ. [Mg(HOMe)6] I2.2tmeda (5) ( tmeda = Me2N(CH2)2NMe2), orthorhombic, Pbca, a 23.423(8), b 15.306(4), c 9.345(1) Ǻ, Z = 4 f.u ., R 0.052 for No 1928, provides a usefully precise description for the centrosymmetric cation, Mg-O being 2.069(4), 2.080(4), 2.096(5) Ǻ, with Mg-O-C 128.4(4) l28.9(4), l29.7(4)°. [( tmeda )SrI2 ( HOMe )3].½tmeda (6), monoclinic, P 21/c, a 7.730(1), b 35.493(9), c 11.081(2) Ǻ, β 126.49(1)°, R 0.042 for No 3161, has a seven-coordinate, quasi-pentagonal bipyramidal SrN2I2O3 array about the metal with trans-iodines.

The Rare Earth(III) Nitrate Dimethyl Sulfoxide Adducts [( dmso )nLn(O2NO)3]

1996 ◽  
Vol 49 (9) ◽  
pp. 997 ◽  
Author(s):  
LI Semenova ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Rare Earth ◽  
Single Crystal ◽  
Dimethyl Sulfoxide ◽  
Metal Atom ◽  
Metal Ion ◽  
Room Temperature ◽  
X Ray ◽  
The Subject ◽  
Ion Radius ◽  
The Rare Earth

Adducts [( dmso )nLn(O2NO)3], obtained by the crystallizatior , of lanthanoid (III) nitrate ( Ln (NO3)3.-xH2O) with excess dimethyl sulfoxide (' dmso ') in methanol or ethanol, have been the subject of a series of room-temperature single-crystal X-ray studies, defining more clearly the manner in which stoichiometry and structure systematically vary with change in metal ion radius. All complexes studied are mononuclear, the metal ion being complexed by three bidentate nitrate ligands and a number of dmso ligands , four for La-Sm and three beyond. The array La- Sm is monoclinic C2/c, a ≈ 14.9, b ≈ 15.5, c ≈ 15.5 Ǻ, β ≈ 108.4°, Z = 4 f.u .; the metal atom is disposed on a crystallographic 2 axis, which also passes through one of the nitrate groups. The series Eu -Tm (inclusive also of Y) is monoclinic, P21/n, a ≈ 11.5, b ≈ 12.7, c ≈ 13.6 Ǻ, β ≈ 100°, Z = 4 f.u ., while Yb and Lu are also monoclinic, P21/c, a ≈ 10.0, b ≈ 12.6, c ≈ 16 Ǻ, β ≈ 100.6°, Z = 4 f.u.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. III. Some Mixed-Ligand Complexes With Pyridine Base and Oxygen Donors

1996 ◽  
Vol 49 (1) ◽  
pp. 47 ◽  
Author(s):  
DL Kepert ◽  
BW Skelton ◽  
AF Waters ◽  
AH White
Keyword(s):  
Room Temperature ◽  
Preceding Paper ◽  
Mixed Ligand ◽  
Water Molecules ◽  
Two Dimensional ◽  
Nitrogen Base ◽  
X Ray ◽  
Pyridine Base ◽  
Group 2 ◽  
Oxygen Donors

In association with the report of a number of homoleptic pyridine base adducts of Group 2 salts in the preceding paper, a number of mixed-ligand compounds have been synthesized and characterized by room-temperature single-crystal X-ray studies. MgI2.2H2O.6py ≡ [trans-( py )4Mg(OH2)2]I2.2py (1) is monoclinic, P21/c, a 10.47(1), b 10.0400(8), c 32.77(1) Ǻ, β 92.34(6)°, Z = 4; R was 0.053 for No = 2990 independent, observed (I > 3σ(I)) diffractometer reflections. Mg-O are 2.063(8) and 2.061(8), Mg-N ranging between 2.19(1) and 2.23(1) Ǻ. MgI2.4H2O.8(3,5-dmpy)≡[trans-(3,5-dmpy)2Mg(OH2)4]I2.6(3,5-dmpy) (2) is orthorhombic, Pcab , a 22.203(6), b 17.023(8), c 16.548(7) Ǻ, Z = 4 f.u .; R 0.045 for N o 2457. Mg-O are 2.026(5) and 2.082(5), and Mg-N 2.267(6) Ǻ in the centrosymmetric cation, with which the aggregate of anions and solvent form a discrete hydrogen-bonded cluster. CaBr2.2H2O.4(2-mpy) ≡ [trans-CaBr2(OH2).2(2-mpy)2].2(2-mpy) (3) is monoclinic, P 21/c, a 7.076(1), b 9.329(3), c 21.957(2) Ǻ, β 98.34(1)°, Z = 2 f.u .; R 0.076 for No 1599; Ca-Br, N, O are 2.840(1), 2.56(1), 2.355(6) Ǻ respectively; its 3-mpy counterpart (4) has a very similar cell but with b and c transposed; R was 0.047 for No 2116, and Ca-Br, N, O 2.8902(6), 2.500(5), 2.344(3) Ǻ. Sr (ClO4)2.3py.dmf ≡ [ Sr (O2ClO2)2( py )3(O- dmf )] (5) is monoclinic, P21, a 8.814(2), b 16.985(7), c 9.499(1) Ǻ, β 114.97(1)°, Z = 2; R 0.047 for No 1717. The strontium is eight-coordinate: Sr -O(ClO4) are 2.644(8)-2.69(1), Sr-N 2.64(1)-2.69(1), Sr -O( dmf ) 2.417(9) Ǻ. The other two compounds, Ba (ClO4)2.H2O.L (L = py (6), 3-mpy (7)), are two-dimensional polymers, linked by bridging perchlorate ions and water molecules. Compound (6) is orthorhombic, Pnna , a 24.098(3), b 10.444(1), c 4.871(3) Ǻ, Z = 4 f.u ., R 0.025 for N o 688: the barium is 11-coordinate Ba (O(H2O))2(O(ClO4))8N with m symmetry, Ba -N 2.889(7), Ba-O(H2O)2.943(4), Ba-O(ClO4) 2.844(6)-2.942(5) Ǻ. Compound (7) is monoclinic, P 21/c, a 7.421(4), b 24.479(8), c 7.293(7) Ǻ, β 104.80(6)°, Z = 4 f.u ., R 0.041 for N o 2033; the barium is nine-coordinate Ba (O(H2O))2(O(ClO4))6N, Ba-N 2.839(7), Ba -O(H2O) 2.791(5), 3.049(5), Ba-O(ClO4) 2.753(6)-2.936(6) Ǻ.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. V. Some Complexes With 3-Azapentane-1,5-diamine

1996 ◽  
Vol 49 (1) ◽  
pp. 73 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Tridentate Ligands ◽  
Nitrogen Base ◽  
Space Group ◽  
X Ray ◽  
Group 2 ◽  
Probable Space ◽  
Structural Characterizations

Syntheses and room-temperature single-crystal X-ray structural characterizations are recorded for an array of adducts of H2N(CN2)2NH(CH2)2NH2, ' dien ', with salts of Group 2 elements, MX2.n( dien ).[Mg( dien )2] Cl2 (1) is monoclinic, P 21/c, a 11.326(6), b 10.928(5), c 12.636(6) Ǻ, β 92.74(4)°, Z = 4 f.u .; R was 0.047 for No 1726 independent 'observed' (I > 3σ(I)) diffractometer reflections. [Mg( dien )2] Br2 (2) is monoclinic, P 21/c, a 9.541(7), b 14.55(1), c 11.894(8) Ǻ, β 100.42(5)°, Z = 4 f.u ., R 0.054 for No 1778. [Mg( dien )2] I2 (3) is isomorphous , a 9.969(2), b 14.907(2), c 12.300(3) Ǻ, β 100.02(2)°, R 0.039 for No 3180. In all three complexes, the two tridentate ligands are disposed mer in a six-coordinate MgN6 environment, the trans Mg-N(central) distances being somewhat shorter (2.161 (4)-2.181(9)Ǻ) than Mg-N(distal) (2.215(8)-2.249(4)Ǻ). [Ba(dien)3] Cl2 (4a) is orthorhombic, Pnaa , a 19.309(2), b 13.545(2), c 8.872(2)Ǻ, Z = 4 f.u ., R 0.055 for No 1070; the methanol disolvate (4b) is monoclinic, P 21/c, a 16.807(8), b 8.764(5), c 19.493(4) Ǻ, β 102.39(3)°, Z = 4 f.u ., R 0.11 for No 2613. A family of derivative structures (5)-(8), [M( dien )3] X2, M, X = Sr , Br (5), Sr , I(6), Ba , Br (7), Ba , I(8), have cells of half the volume (a ≈ 13.8, b ≈ 9, c ≈ 9.8 Ǻ), probable space group P21212, R 0.050, 0.061, 0.034, 0.037 for No 549, 914, 1044, 1801 respectively, with the cations disposed about crystallographic 2 axes with one disordered ligand . [ Ba( dien )3](ClO4)2 (9) is rhombohedral , R3c, a 10.240(2), c 45.19(1) Ǻ (hexagonal setting), Z = 6 f.u ., R 0.054 for No 508. Like (4)-(8), the barium environment is nine-coordinate with the three tridentate ligands here� disposed about a 3 axis through the metal.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. IV. Some Complexes of Group 2 Halides With Ethane-1,2-diamine

1996 ◽  
Vol 49 (1) ◽  
pp. 61 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Single Crystal ◽  
Room Temperature ◽  
Metal Salts ◽  
Nitrogen Base ◽  
X Ray ◽  
Structure Determinations ◽  
Group 2

Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of ethane-1,2-diamine (en) with Group 2 metal salts, MX2.n(en). [Mg(en)3] Br2.MeOH (1) is monoclinic, P 21/c, a 9.067(5), b 15.161(4), c 14.839(8) Ǻ, β 121.86(5)°, Z = 4 f.u .; R was 0.070 for No 1226 independent 'observed' (I > 3σ(I)) diffractometer reflections; [Mg(en)3] I2.MeOH (2) is triclinic, Pī , a 11.500(2), b 9.527(6), c 8.825(4) Ǻ, α 106.30(4), β 100.57(3), γ 90.28(4)°, Z = 2 f.u .; R 0.045 for No 3562. In (1) and (2), (Mg-N) are 2.20 and 2.19 Ǻ. [Ca(en)4]Br2 (3) is orthorhombic, Fddd , a 28.54(1), b 15.863(7), c 8.927(9) Ǻ, Z = 8 f.u .; Ca-N are 2.608(7) and 2.556(8) Ǻ. [ Sr (en)4] Cl2.2MeOH (4) is also orthorhombic, Fddd , a 26.627(8), b 15.388(4), c 11.313(4) Ǻ, Z = 8 f.u .; R 0.059 for No 535. [ Sr (en)4] Br2.2en (5) is tetragonal, I 41/a, a 9.215(7), c 27.678(3) Ǻ, Z = 4 f.u ., R 0.044 for No 657. [ Sr (en)4]I2.MeOH (6) is tetragonal, I41/amd, a 9.389(1), c 28.78(1) Ǻ, Z = 4. f.u ., R 0.040 for No 10. In (4), (5) and (6), Sr -N are 2.728(7), 2.718(7); 2.720(7), 2.703(7) and 2.75(2), 2.72(7) Ǻ. [ ClBa (en)3(en)(2/2)](∞ ׀ ∞) Cl (≡ BaCl2.4en) (7) is monoclinic, P 21, a 8.666(3), b 9.063(10), c 12.655(5) Ǻ, β 108.13(3)°, Z = 2 f.u ., R 0.048 for No 1479. In (1) and (2), magnesium is six-coordinate [Mg(N,N'- bidentate )3]; (3)-(6), calcium and strontium are eight-coordinate [M(N,N'- bidentate )4]; in (7), barium is nine-coordinate, one of the en ligands being bridging so that the complex is a single-stranded polymer generated by the 21 screw. Ba-Cl is 3.419(5) Ǻ, Ba -N bidentate en-N are 2.91(2)-2.97(3) Ǻ, and Ba -N monodentate en-N 2.92(1), 3.15(1) Ǻ.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. X. Some Mixed-Ligand Complexes of Group 2 Metal Halides With 2,2':6',2"-Terpyridine and Oxygen Donors

1996 ◽  
Vol 49 (1) ◽  
pp. 147 ◽  
Author(s):  
AF Waters ◽  
AH White
Keyword(s):  
Room Temperature ◽  
Mixed Ligand ◽  
The Other ◽  
Metal Halides ◽  
Nitrogen Base ◽  
X Ray ◽  
Group 2 ◽  
Oxygen Donors ◽  
Centrosymmetric Dimers ◽  
Structural Characterizations

Room-temperature single-crystal X-ray structural characterizations are recorded for a variety of adducts of Group 2 metal halides with 2,2':6',2?-terpyridine ( tpy ) from various hydroxylic solvents. [Mg( tpy )2][Mg( tpy )(OH2)3] Br4.PriOH (1) is triclinic, Pī, a 19.352(6), b 12.852(5), c 11.463(3) Ǻ, α 110.95(3), β 99.04(2), γ 98.81(3)°, Z = 2 f.u .; conventional R on ׀ F ׀ at convergence was 0.056 for No 4398 independent 'observed' (I > 3σ(I)) reflections. In the [Mg( tpy )2]2+ ion, Mg-N(central; distal) are 2.099(9), 2.09(1); 2.152(9)-2.212(8) Ǻ, while in [Mg( tpy )(OH2)3]2+, Mg-N(central; distal) are 2.139(7); 2.206(9), 2.222(9) Ǻ, while Mg-O trans to these are 2.042(6); 2.082(9), 2.097(8) Ǻ. [Mg( tpy )(OH2)2( MeOH )] Cl2 (2) is triclinic, Pī, a 14.049(7), b 8.354(4), c 8.301(2) Ǻ, α 74.25(3), β 73.05(3), γ 80.37(4)°, Z = 2 f.u., R 0.064 for No 2417. In the cation, Mg-N(central; distal) are 2.125(4); 2.203(4), 2.218(4) Ǻ; Mg-O( MeOH ) is trans to Mg-N(central), being 2.013(4) Ǻ; Mg-O(OH2) are 2.067(4) and 2.063(4) Ǻ. [CaCl2( tpy )( dmf )2 (3) ( dmf = N,N- dimethylformamide ) is monoclinic, C2/c, a 23.27(2), b 11.225(6), c 16.517(8) Ǻ, β 109.56(5)°, Z = 4 centrosymmetric dimers, R 0.061 for No 985. The calcium atoms are linked by a pair of μ-chlorines, CaCl2Ca, and are seven-coordinate, N3Ca(μ-Cl )4 being broadly coplanar in the equatorial plane of a pentagonal bipyramidal array, with the other chlorine and the dmf oxygen trans and axial.

Structural Systematics of Rare Earth Complexes. XIX (Hydrated) 1 : 2 Mononuclear Adducts of Lanthanoid(III) Chlorides with 2,2′-Bipyridine and 1,10-Phenanthroline

1999 ◽  
Vol 52 (6) ◽  
pp. 571 ◽  
Author(s):  
Lioubov I. Semenova ◽  
Allan H. White
Keyword(s):  
Rare Earth ◽  
Single Crystal ◽  
Metal Atom ◽  
Room Temperature ◽  
Rare Earth Complexes ◽  
Coordination Environment ◽  
X Ray ◽  
Structure Determinations

Room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of hydrated lanthanoid(III) trichlorides with 2,2′-bipyridine (‘bpy’) and 1,10-phenanthroline (‘phen’), crystallized from water, methanol or ethanol solutions, containing mononuclear arrays with 1 : 2 Ln/bpy or phen stoichiometry. LaCl3/phen/H2O(1 : 3 : 9), [(phen)2La(OH2)5]Cl3.phen.4H2O, although of overall 1 : 3 LaCl3/phen stoichiometry, has a lattice phen; it is orthorhombic, Pnna, a 19·947(7), b 16·457(5), c 12·213(2) Å, Z = 4; conventional R on |F| was 0·030 for No 2567 ‘observed’ (I >3σ(I)) diffractometer reflections. LaCl3/phen/H2O/MeOH (1 : 2 : 6 : 1), [(phen)2La(OH2)5]Cl3.H2O.MeOH, is triclinic, P 1, a 19·060(3), b 9·252(3), c 8·994(3) Å, α 69·33(3), β 86·81(2), γ 89·66(2)°, Z = 2, R 0·037 for No 5452. LaCl3/bpy/H2O (1 : 2 : 6), [(bpy)2La(OH2)4Cl]Cl2.2H2O, is monoclinic, P 21/c, a 19·389(3), b 9·071(1), c 16·873(2) Å, β 114·10(1)°, Z = 4, R 0·029 for No 4699. All three of these complexes have a nine-coordinate [(N,N′-bidentate)2La(unidentate)5] coordination environment with quasi-2 symmetry; that of the remaining compounds following is eight-coordinate [(N,N′-bidentate)2Ln(unidentate)4]. LuCl3/phen/H2O (1 : 2 : 6), [(phen)2Lu(OH2)4]Cl3.2H2O, is monoclinic, C 2/c, a 11·045(7), b 17·660(6), c 14·474(9) Å, β 92·82(5)°, Z = 4, R 0·042 for No 1695, the Lu lying on a crystallographic 2 -axis. Crystals of LnCl3/phen/H2O(1 : 2 : 4), [(phen)2Ln(OH2)3Cl]Cl2.H2O (Ln = Dy, Er, Y), are triclinic, P 1, a≈ 12·6, b ≈ 10·5, c ≈ 10·4 Å, α ≈ 93·3, β ≈ 109·3, γ ≈ 96·8°, Z = 2, R 0·030, 0·040, 0·052 for No 4221, 5100, 2690 respectively. PrCl3/bpy/H2O/EtOH (1 : 2 : 1 : 0·5), [(bpy)2Pr(OH2)Cl3].½EtOH, is triclinic, P 1, a 13·331(3), b 10·734(2), c 9·758(2) Å, α 63·67(2), β 78·99(2), γ 71·24(2)°, Z = 2, R 0·033 for No 4596, while [(bpy)2Pr(OH2)2Cl2]Cl is monoclinic, C 2/c, a 15·921(15), b 11·314(8), c 14·114(8) Å, β 116·70(6)°, Z = 4, R 0·041 for No 2269. ErCl3/bpy/H2O(1 : 2 : 2 (also)), [(bpy)2Er(OH2)2Cl2]Cl, is cubic, I 23, a 26·032(4) Å, Z = 24, R 0·066 for No 1644. Crystals of LnCl3/phen/H2O/MeOH (1 : 2 : 1 : 1), [(phen)2Ln(OH2)Cl3].MeOH (Ln = La, Pr, Nd, Eu), are monoclinic, P 21/a, a ≈ 13·2, b ≈ 10·7, c ≈ 18·5 Å, β ≈ 102·1°, Z = 4, R 0·054, 0·032, 0·040, 0·054 for No 2872, 4792, 3179, 2847 respectively. LnCl3/bpy/H2O/EtOH (1 : 2 : 1 : 1), [(bpy)2Ln(OH2)Cl3].EtOH (Ln = Nd, Eu), are triclinic, P 1, a ≈ 11·3, b ≈ 10·9, c ≈ 10·4 Å, α ≈ 75·5, β ≈ 89·8, γ ≈ 78·0°, Z = 2, R 0·044, 0·056 for No 4979, 3596 respectively. LaCl3/bpy/EtOH (1 : 2 : 0·5) is binuclear [(bpy)2Cl2La(µ-Cl)2LaCl2(bpy)2].EtOH, monoclinic, P 21/c, a 9·6878(2), b 17·5696(3), c 16·1341(2) Å, β 123·10(1)°, Z = 2, R 0·033 for No 4256. A totally unsolvated array is found for YbCl3/bpy (1 : 2), [(bpy)2YbCl3], monoclinic, P 21/c, a 15·065(8), b 8·598(4), c 16·92(1) Å, β 112·46(5)°, Z = 4, R 0·032 for No 3548, in which, alone, the metal atom is seven-coordinate.

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