Structural investigation of dibromobis(benzimidazole)Zn(II) complex

The molecular structure of the title complex [ZnBr₂(C₇H₆N₂)₂] was investigated by X-ray diffraction and IR spectroscopy methods. Molecules of zinc(II) complex crystallize in the triclinic crystal system with cell constants a=7.526(2) Å, b=7.8971(8) Å, c=13.431(1) Å, Z=2 and V=791.3(2) Å³. In the molecular structure, the Zn atom is coordinated tetrahedrally by two Br⁻ anions and two benzimidazole ligands. Intramolecular steric repulsions between Br⁻ anions and benzimidazole groups have been caused to cis configuration around the central metal atom.     

Structural and theoretical studies of Xe(OChF5)2 and [XeOChF5][AsF6] (Ch = Se, Te)

The XeOSeF₅⁺ cation has been synthesized for the first time and characterized in solution by ¹⁹F, ⁷⁷Se and ¹²⁹Xe NMR spectroscopy and in the solid state by X-ray crystallography and Raman spectroscopy with AsF₆⁻ as its counter anion. The X-ray crystal structures of the tellurium analogue and of the Xe(OChF₅)₂ derivatives have also been determined: [XeOChF₅][AsF₆] crystallize in tetragonal systems, P4/n, a=6.1356(1) Å, c=13.8232(2) Å, V=520.383(14) Å³, Z=2 and R₁=0.0453 at −60°C (Te) and a=6.1195(7) Å, c=13.0315(2) Å, V=488.01(8) Å³, Z=2 and R₁=0.0730 at −113°C (Se); Xe(OTeF₅)₂ crystallizes in a monoclinic system, P2₁/c, a=10.289(2) Å, b=9.605(2) Å, c=10.478(2) Å, β=106.599(4)°, V=992.3(3) Å³, Z=4 and R₁=0.0680 at −127°C; Xe(OSeF₅)₂ crystallizes in a triclinic system, , a=8.3859(6) Å, c=12.0355(13) Å, V=732.98(11) Å³, Z=3 and R₁=0.0504 at −45°C. The energy minimized geometries and vibrational frequencies of the XeOChF₅⁺ cations and Xe(OChF₅)₂ were calculated using density functional theory, allowing for definitive assignments of their experimental vibrational spectra.     

Equilibrium diagram of KPO3–Y(PO3)3 system, chemical preparation and characterization of KY(PO3)4

Microdifferential thermal analysis (μ-DTA), X-ray diffraction (XRD) and infrared (IR) spectroscopy were used for the first time to investigate the liquidus and solidus relations in the KPO₃–Y(PO₃)₃ system. The only compound observed within the system was KY(PO₃)₄ melting incongruently at 1033 K. An eutectic appears at 13.5 mol% Y(PO₃)₃ at 935 K, the peritectic occurs at 1033 K and the phase transition for potassium polyphosphate KPO₃ was observed at 725 K. Three monoclinic allotropic phases of the single crystals were obtained. KY(PO₃)₄ polyphosphate has the P2₁ space group with lattice parameters: a=7.183(4) Å, b=8.351(6) Å, c=7.983(3) Å, β=91.75(3)° and Z=2 is isostructural with KNd(PO₃)₄. The second allotropic form of KY(PO₃)₄ belongs to the P2₁/n space group with lattice parameters: a=10.835(3) Å, b=9.003(2) Å, c=10.314(1) Å, β=106.09(7)° and Z=4 and is isostructural with TlNd(PO₃)₄. The IR absorption spectra of the two forms show a chain polyphosphates structure. The last modification of KYP₄O₁₂ crystallizes in the C2/c space group with lattice parameters: a=7.825(3) Å, b=12.537(4) Å, c=10.584(2) Å, β=110.22(7)° and Z=4 is isostructural with RbNdP₄O₁₂ and contains cyclic anions. The methods of chemical preparations, the determination of crystallographic data and IR spectra for these compounds are reported.     

Structural and spectroscopic properties of Hexamethylenetetramine cobalt(II) complex: [Co(NCS)2(hmt)2(H2O)2][Co(NCS)2(H2O)4] (H2O)

Synthesis, structure, spectroscopy and thermal properties of complex [Co(NCS)₂(hmt)₂(H₂O)₂][Co(NCS)₂(H₂O)₄] (H₂O) (I), assembled by hexamethylenetetramine and octahedral Co(II) metal ions, are reported. Crystal data for I: F_w 387.34, a=9.020(8), b=12.887(9), c=7.95(1) Å, =96.73(4), β=115.36(5), γ=94.16(4)°, V=820(1) Å³, Z=2, space group=P−1, T=173 K, λ(Mo-K)=0.71070 Å, ρ_calc=1.718567 g cm⁻³, μ=17.44 cm⁻¹, R=0.088, R_w=0.148. An interesting two-dimensional network is assembled via hydrogen bonds through coordinated and free water molecules. The d–d transition energy levels of Co(II) ion are determined by UV–vis spectroscopy and calculated by ligand field theory. The calculated results agree well with experiment ones.     

Crystal structure of a novel Hg(II) complex, [Hg(tri-2-furylphosphine)2(tri-2-furylphosphinoxide)3] [ClO4]2

The Hg(II) complex [Hg(TFP)₂(OTFP)₃][ClO₄]₂ with TFP=tri-2-furyl-phosphine and OTFP=tri-2-furylphosphinoxide has been prepared and characterised. It crystallises in the hexagonal P6₃/m space group with Z=2, a=13.308(3), c=21.092 (4) Å, V=3235(1) Å³. The structure of the complex cation consists of independent molecules with Hg pentacoordinated in exact trigonal bipyramidal geometry.     

Hydrothermal synthesis and structure of one-dimensional Co(dien)2(VO3)3·(H2O) (dien=diethylenetriamine)

One-dimensional Co(dien)₂(VO₃)₃·(H₂O) was prepared from the hydrothermal reaction of NH₄VO₃, Co₂O₃, diethylenetriamine (dien) and H₂O at 130 °C. The compound crystallizes in the monoclinic system, space group P2₁/c with a=16.1581(6) Å, b=8.7006(3) Å, c=13.9893(4) Å, β=103.1483(11)°, V=1915.13(11) Å³, Z=4, and R₁=0.0268 for 3060 observed reflections. Single crystal X-ray diffraction revealed that the structure is composed of infinite one-dimensional chains formed by corner-sharing VO₄ tetrahedra with Co(dien)³⁺ complex cations and crystallization water molecules occupying the interchain positions, which are held together to a three-dimensional network via extensive hydrogen-bonding interactions. The compound, with a new zig-zag conformation of metavanadate chains, is the first example of vanadium oxides incorporating trivalent transition metal coordination groups. Other characterizations by elemental analysis, IR and thermal analysis are also described.     

Structural, spectral and thermal properties of a polymeric nickel(II) complex containing two-dimensional network

The structure of the complex [Ni(hmt)(NCS)₂(H₂O)₂]_n, assembled by hexamethylenetetramine (hmt) and octahedral Ni(II), is reported. Crystal data: Fw 351.07, a=9.885(10) Å, b=12.06(1) Å, c=12.505(8) Å, β=114.41(4)°, V=1357(1) ų, Z=4, space group=C2/c, T=173 K, λ(Mo−K)=0.71070 Å, ρ_calc=1.718 gcm⁻¹, μ=17.44 cm⁻¹, R=0.099, Rw=0.145. The tetrahedral assembling template effect of the hmt molecule is completed by two coordination bonds and two hydrogen interactions. The UV–vis absorption spectrum of this complex [Ni(hmt)(NCS)₂(H₂O)₂]_n with a two-dimensional network is determined in the range of 5000–35000 cm⁻¹ at room temperature. The observed spectrum is discussed and explained perfectly by the scaling radial theory proposed by us. The two-dimensional structure has no apparent effects on the d–d transitions of the central Ni(II) ion. The IR spectrum and the GT curve of the complex were also measured and clearly reflect its structural properties.     

Syntheses and crystal structures of 1,2:5,6:9,10:13,14:17,18:21,22-hexabenzo-3,7,11,15,19,23-hexadehydro[24]annulene (HBC), 1,2:5,6:9,10:13,14-tetrabenzo-3,7,11,15-tetradehydro[16]annulene (QBC) and a tetracobalt complex of QBC. The first example of a transition metal complex of QBC

1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15-tetradehydro[16]annulene, or tetrabenzocyclyne (QBC) and 1,2:5,6:9,10:13,14:17,18:21,22-hexabenzo-3,7,11,15,19,23-hexadehydro[24]annulene (HBC) have been structurally characterized by X-ray. crystallography. QBC crystallizes in two different space groups; P2₁/c with a = 10.652(3) Å, b = 10.624(2) Å, c = 19.549(4) Å, β = 93.83(2)°, V = 2207.4(8) ų, and Z = 4 and P4₁2₁2 with a = 9.330(1) Å, c = 25.497(8) Å, V = 2219.6(12) Å, and Z = 4. HBC crystallizes in monoclinic P2₁/n with a = 14.763(3) Å, b = 10.296(2) Å, c = 22.057(4) Å, β = 108.61(3), V = 3177.4(11) ų, T = 133 K, and Z = 4. Reaction of QBC with dicobaltoctacarbonyl has produced a tetracobalt complex which has been characterized by X-ray crystallography. This complex crystallizes in monoclinic P2₁/c with a = 14.699(3) Å, b = 17.188(3) Å, c = 17.254(3) Å, β = 112.63(3)°, V = 4023.5(13) ų, and Z = 4. Only two of the four C---C triple bonds of QBC bind to dicobalthexacarbonyl moieties even when excess dicobaltoctacarbonyl is used.     

Hydrothermal synthesis and crystal structure of a novel three-dimensional mixed-valence iron coordination polymer [Fe2FeO2(IN)2(ox)] (IN=isonicotinate, OX=oxalate)

A novel three-dimensional (3D) mixed-valence iron coordination polymer [Fe₂^IIIFe^IIO₂(IN)₂(ox)] (IN=isonicotinate, OX=oxalate) (1) has been hydrothermally synthesized by using two different anionic ligands and characterized by elemental analysis, IR spectrum, electron spin resonance (ESR), X-ray photoelectron spectrum (XPS), thermogravimetric analysis (TGA) and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic, space group P2(1)/c with a=5.8774(7) Å, b=18.528(2) Å, c=7.7117(9) Å, V=817.69(17) Å³, Z=2, and R₁=0.0321 (wR₂=0.0777). The Fe(II) and Fe(III) centers in 1 both exhibit a distorted octahedral coordination geometry and are bridged by the IN and oxalate groups into a covalently bonded 3D metal–organic network. TGA showed that the 3D network possesses a good stability up to 291 °C.     

Hydrogenmaleato bridged supramolecular double chains via π–π stacking interactions: syntheses, crystal structures and magnetic properties of ∞[Cu(phen)X(HL)2/2] with X=Cl (1), NO3 (2) and H2L=maleic acid

Two novel hydrogen maleato (HL) bridged Cu(II) complexes _∞¹[Cu(phen)Cl(HL)_2/2] 1 and _∞¹[Cu(phen)(NO₃)(HL)_2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl₂·2H₂O and Cu(NO₃)₂·3H₂O, respectively, in CH₃OH/H₂O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P2₁/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, D_calc=1.720 g/cm³ and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, D_calc=1.734 g/cm³. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χ_m(T−θ)=0.414 cm³ mol⁻¹ K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively.     

Structural and spectral studies of N-2-(pyridyl)-, N-2-(3-, 4-, 5-, and 6-picolyl)- and N-2-(4,6-lutidyl)-N′-2-thiomethoxyphenylthioureas

Structures of the following compounds have been obtained: N-(2-pyridyl)-N′-2-thiomethoxyphenylthiourea, PyTu2SMe, monoclinic, P2₁/c, a=11.905(3), b=4.7660(8), c=23,532(6) Å, β=95.993(8)°, V=1327.9(5) ų and Z=4; N-2-(3-picolyl)-N′-2-thiomethoxyphenyl-thiourea, 3PicTu2SeMe, monoclinic, C2/c, a=22.870(5), b=7.564(1), c=16.941(4) Å, β=98.300(6)°, V=2899.9(9) ų and Z=8; N-2-(4-picolyl)-N′-2-thiomethoxyphenylthiourea, 4PicTu2SMe, monoclinic P2₁/a, a=9.44(5), b=18.18(7), c=8.376(12) Å, β=91.62(5)°, V=1437(1) ų and Z=4; N-2-(5-picolyl)-N′-2-thiomethoxyphenylthiourea, 5PicTu2SMe, monoclinic, C2/c, a=21.807(2), b=7.5940(9), c=17.500(2) Å, β=93.267(6)°, V=2893.3(5) ų and Z=8; N-2-(6-picolyl)-N′-2-thiomethoxyphenylthiourea, 6PicTu2SMe, monoclinic, P2₁/c, a=8.499(4), b=7.819(2), c=22.291(8) Å, β=90.73(3)°, V=1481.2(9) ų and Z=4 and N-2-(4,6-lutidyl)-N′-2-thiomethoxyphenyl-thiourea, 4,6LutTu2SMe, monoclinic, P2₁/c, a=11.621(1), b=9.324(1), c=14.604(1) Å, β=96.378(4)°, V=1572.4(2) ų and Z=4. Comparisons with other N-2-pyridyl-N′-arylthioureas having substituents in the 2-position of the aryl ring are included.     

Synthesis and crystal structure of two novel nickel (imidazole) complexes having hydrogen-bonded networks

Two nickel (imidazole) complexes, Ni(im)₆Cl₂·4H₂O (1) and Ni(im)₆(NO₃)₂ (2) (im=imidazole) have been synthesized and characterized by elemental analysis, IR, UV, TG and single crystal X-ray diffraction. 1 crystallizes in the triclinic space group P-1 with a=8.800(6) Å, b=9.081(6) Å, c=10.565(7) Å, =75.058(9)°, β=83.143(8)°, γ=61.722(8)°, V=718.3(8) Å³, Z=1 and R₁ (wR₂)=0.0469 (0.1497). 2 crystallizes in the trigonal space group R-3 with a=12.370(6) Å, b=12.370(6) Å, c=14.782(14) Å, =90.00°, β=90.00°, γ=120.00°, V=1959(2) Å³, Z=3 and R₁ (wR₂)=0.0358 (0.0955). 1 and 2 exhibit different supramolecular network due to their different counter anions and different hydrogen bonding connection. In compound 1, [Ni(im)₆]²⁺ cation and counter anions Cl⁻ alternatively array in an ABAB fashion via N–HCl hydrogen bonding. In compound 2, the plane of each NO₃²⁻ is almost parallel and each NO₃²⁻ connect three different [Ni(im)₆]²⁺ cations via N–HO hydrogen bonding.     

Structure analysis and the standard molar enthalpy of formation of a coordination polymer [Co(TO)2Cl2]n (TO = 1,2,4-triazole-5-one)

A coordination polymer was synthesized by the reaction of CoCl₂ with 1,2,4-triazole-5-one (TO) and charaterized by means of IR and TG–DTG. Single-crystal structure analysis showed that the complex crystallized in the monoclinic space group C2/c: a = 23.105(9) Å, b = 3.5683(2) Å, c = 13.589(6) Å,  = 90°, β = 124.038(4)°, γ = 90°, V = 928.4(7) Å³, Z = 4. The standard molar enthalpy of formation of the complex was determined to be (−1034.28 ± 0.95) kJ mol⁻¹.     

Structures of 3,3′-dicarbometoxy-2,2′-bipyridine complexes with silver(I) and copper(II) cations

The structures of 3,3′-dicarbometoxy-2,2′-bipyridine (dcmbpy) complexes with copper(II) and silver(I) cations have been determined using single crystal X-ray-diffraction. The crystals of Cu(dcmbpy)Cl₂ are monoclinic, C2/c, a = 16.966(3), b = 18.373(3), c = 13.154(2) Å, β = 126.543(3)°. The crystals of Ag(dcmbpy)NO₃ · H₂O are also monoclinic, C2/c, a = 16.7547(13), b = 11.0922(9), c = 18.7789(18) Å, β = 100.228(7)°. The results have been compared with the literature data on the complexes of dcmbpy and its precursors: 2,2′-bipyridine (bpy) and 3,3′-dicarboxy-2,2′-bipyridine (dcbpy). Two types of complexes of 3,3′-carboxy derivatives of bpy are distinguished: (1) with metal atom bonded to two N atoms of the same molecule and (2) with metal atom bonded to two N atoms of two different molecules. The Cu(dcmbpy)Cl₂ complex belongs to the first type, whereas Ag(dcmbpy)NO₃ · H₂O belongs to the second type.     

Crystal and molecular structures of two europium(III) nitrate complexes with triphenylphosphine oxide

The X-ray structures of the complexes Eu(NO₃)(Ph₃PO)₃(acetone)₂ (A) (Ph₃PO = triphenylphosphine oxide) and Eu(NO₃)₃(Ph₃PO)₂(ethanol) (B) have been solved by the heavy-atom method, by using the three-dimensional Patterson-Fourier synthesis. The crystals are both monoclinic and belong to the space group P2₁/n, with Z = 4. The cell dimensions are: a = 27.825(4) Å, b = 19.422(4) Å, c = 11.238(2) Å, β = 94.9(3)° for A; and a = 22.193(4) Å, b = 10.866(2) Å, c = 17.101(3) Å, β = 105.6(3)° for B. In both complexes the europium(III) ion is ennea-coordinated to three chelate nitrate groups and three oxygens of the Ph₃PO ligands for A and two of the Ph₃PO and one of the ethanol for B. The acetone molecules of A are outside the coordination sphere of the metal and disordered.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

The organic ligands as template: the synthesis, structures and properties of a series of the layered structure rare-earth coordination polymers

A series of new 2D-layered structural rare-earth coordination polymers with the general formal [Ln(C₈H₄O₅)(H₂O)₅]·(H₂O)·(C₈H₄O₅)_1/2 (Ln=Eu for (1); Gd for (2); Tb for (3); Dy for (4); and Er for (5)) have been yielded by hydrothermal synthesis. The coordination polymers crystallize in monoclinic space group C/2c with a=19.838(16), b=10.529(8), c=17.752(14) Å, β=107.503(14)° for (1), with a=19.823(7), b=10.552(4), c=17.762(6) Å, β=107.443(6)° for (2), with a=19.770(4), b=10.519(2), c=17.698(4) Å, β=107.52(3)° for (3), with a=19.632(2), b=10.492(2), c=17.617(3) Å, β=107.470(12)° for (4), with a=19.648(7), b=10.480(3), c=17.598(6) Å, β=107.502(6)° for (5), respectively. And the metal ions (Ln³⁺) are located in nine-member coordination environment. The carboxyl groups from 5-hydroxyisophthalate chelate the metal ions to form 1D helical cation chains. It is interesting that these helical cation chains are arranged to form 2D anion–cation layers by the uncoordinated ligands' anions as template. And the luminescence properties of the rare-earth ions are studied in the paper.     

Cation–anion interactions in triphenyl telluronium salts. The crystal structures of (Ph3Te)2[MCl6] (M=Pt, Ir), (Ph3Te)[AuCl4], and (Ph3Te)(NO3)·HNO3

Triphenyltelluronium hexachloroplatinate (1), hexachloroiridate (2), tetrachloroaurate (3), and tetrachloroplatinate (4) were prepared from Ph₃TeCl and potassium salts of the corresponding anions. Upon recrystallization of 4 from concentrated nitric acid, K₂[PtCl₆] and (Ph₃Te)(NO₃)·HNO₃ (5) were obtained. The crystal structures of 1–3 and 5 are reported. Compounds 1 and 2 are isostructural. They are triclinic, P , Z=2 (the asymmetric unit contains two formula units). Compound 1: a=10.7535(2), b=17.2060(1), c=21.4700(3) Å, =78.9731(7), β=77.8650(4), γ=78.8369(4)°. Compound 2: a=10.7484(2), b=17.1955(2), c=21.4744(2) Å, =78.834(1), β=77.649(1), γ=78.781(1)°. Compound 3 is monoclinic, P2₁/c, Z=4, a=8.432(2), b=14.037(3), c=17.306(3) Å, β=93.70(3)°. Compound 5 is monoclinic. P2₁/n, Z=4, a=9.572(2), b=14.050(3), c=13.556(3) Å, β=90.76(3)°. The primary bonding in the Ph₃Te⁺ cation in each salt is a trigonal AX₃E pyramid with Te---C bond lengths in the range 2.095(8)–2.14(2) Å and the bond angles 94.1(6)–100.9(5)°. The weak TeCl (1–3) and TeO (5) secondary interactions expand the coordination sphere. In 1 and 2 the cation shows a trigonal bipyramidal AX₃YE coordination with one primary Te---C bond and the shortest secondary TeCl contact in axial positions and the two other Te---C bonds and the lone-pair in equatorial positions. The cation in 3 shows a distorted octahedral AX₃Y₃E environment and that in 5 is a more complex AX₃Y₃Y′₂ arrangement. In both latter salts the structure is a complicated three-dimensional network of cations and anions.     

Structures of propionaldehyde, butyraldehyde, and pivalaldehyde complexes of the chiral rhenium fragment [(η-C5H5)Re(NO)(PPh3)]

The crystal structures of propionaldehyde complex (RS,SR)-(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₃)]⁺ PF₆⁻ (1b⁺ PF₆^s−; monoclinic, P2₁/c (No. 14), a = 10.166 (1) Å, b = 18.316(1) Å, c = 14.872(2) Å, β = 100.51(1)°, Z = 4) and butyraldehyde complex (RS,SR)-[(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHCH₂CH₂CH₃)]⁺ PF₆⁻ (1c⁺PF₆⁻; monoclinic, P2₁/a (No. 14), a = 14.851(1) Å, b = 18.623(3) Å, c = 10.026(2) Å, β = 102.95(1)°, Z = 4) have been determined at 22°C and −125°C, respectively. These exhibit C O bond lengths (1.35(1), 1.338(5) Å) that are intermediate between those of propionaldehyde (1.209(4) Å) and 1-propanol (1.41 Å). Other geometric features are analyzed. Reaction of [(η⁵-C₅H₅)Re(NO)(PPh₃)(ClCH₂Cl)]⁺ BF₄⁻ and pivalaldehyde gives [(η⁵-C₅H₅)Re(NO)(PPh₃)(η²-O=CHC(CH₃)₃)]⁺BF₄⁻ (81%), the spectroscopic properties of which establish a π C O binding mode.     

Novel coordination of a hydroxamic acid : Crystal structures of bis(glycinohydroxamoto)nickel(II) and tris(glycinohydroxamoto)cobalt(III)

The structures of two glycinohydroxamoto (GHA) complexes of Ni(II) and Co(III) have been determined by single-crystal X-ray diffraction methods. The crystals of Ni(GHA)₂ are monoclinic with a = 5.360(1), b = 7.315(4), c = 10.194(4) Å, β = 96.57(3), Z = 2, and space group P2₁/c. The crystals of Co(GHA)₃•1/2 H₂O are monoclinic with a = 22.467(19), b = 8.041(4), c = 13.700(11) Å, β = 116.01(7), Z = 8, and space group C2/c. The values of the final residuals R for Ni(GHA)₂ and Co(GHA)₃•1/2 H₂O are 0.0275 and 0.032, respectvely. The molecular structures of Ni(GHA)₂ and Co(GHA)₃ consist of a square planar and an octahedral coordination, respectively, with the glycinohydroxamato (NH₂CH₂CONOH⁻) ligands coordinating to the metal ion via the N (amino) and the N (NOH⁻). These two complexes are the first well-established cases of coordination of the NHO⁻ group of a hydroxamic acid to a transition metal via the nitrogen atom.