Evaluation of the individual hydrogen bonding energies in N-methylacetamide chains

The individual hydrogen bonding energies in N-methylacetamide chains were evaluated at the MP2/6-31+G** level including BSSE correction and at the B3LYP/6-311++G(3df,2pd) level including BSSE and van der Waals correction. The calculation results indicate that compared with MP2 results, B3LYP calculations without van der Waals correction underestimate the individual hydrogen bonding energies about 5.4 kJ mol^?1 for both the terminal and central hydrogen bonds, whereas B3LYP calculations with van der Waals correction produce almost the same individual hydrogen bonding energies as MP2 does for those terminal hydrogen bonds, but still underestimate the individual hydrogen bonding energies about 2.5 kJ mol^?1 for the hydrogen bonds near the center. Our calculation results show that the individual hydrogen bonding energy becomes more negative (more attractive) as the chain becomes longer and that the hydrogen bonds close to the interior of the chain are stronger than those near the ends. The weakest individual hydrogen bonding energy is about ?29.0 kJ mol^?1 found in the dimer, whereas with the growth of the N-methylacetamide chain the individual hydrogen bonding energy was estimated to be as large as ?62.5 kJ mol^?1 found in the N-methylacetamide decamer, showing that there is a significant hydrogen bond cooperative effect in N-methylacetamide chains. The natural bond orbital analysis indicates that a stronger hydrogen bond corresponds to a larger positive charge for the H atom and a larger negative charge for the O atom in the N-H?O=C bond, corresponds to a stronger second-order stabilization energy between the oxygen lone pair and the N-H antibonding orbital, and corresponds to more charge transfer between the hydrogen bonded donor and acceptor molecules.     

Low-Barrier Hydrogen Bonds in Negative Thermal Expansion Material H3[Co(CN)6]

The covalent nature of the low-barrier N−H−N hydrogen bonds in the negative thermal expansion material H₃[Co(CN)₆] has been established by using a combination of X-ray and neutron diffraction electron density analysis and theoretical calculations. This finding explains why negative thermal expansion can occur in a material not commonly considered to be built from rigid linkers. The pertinent hydrogen atom is located symmetrically between two nitrogen atoms in a double-well potential with hydrogen above the barrier for proton transfer, thus forming a low-barrier hydrogen bond. Hydrogen is covalently bonded to the two nitrogen atoms, which is the first experimentally confirmed covalent hydrogen bond in a network structure. Source function calculations established that the present N−H−N hydrogen bond follows the trends observed for negatively charge-assisted hydrogen bonds and low-barrier hydrogen bonds previously established for O−H−O hydrogen bonds. The bonding between the cobalt and cyanide ligands was found to be a typical donor–acceptor bond involving a high-field ligand and a transition metal in a low-spin configuration.     

Density functional theory and topological analysis on the hydrogen bonding interactions in cysteine‐thymine complexes

Hydrogen bonding interactions between amino acids and nucleic acid bases constitute the most important interactions responsible for the specificity of protein binding. In this study, complexes formed by hydrogen bonding interactions between cysteine and thymine have been studied by density functional theory. The relevant geometries, energies, and IR characteristics of hydrogen bonds (H‐bonds) have been systematically investigated. The quantum theory of atoms in molecule and natural bond orbital analysis have also been applied to understand the nature of the hydrogen bonding interactions in complexes. More than 10 kinds of H‐bonds including intra‐ and intermolecular H‐bonds have been found in complexes. Most of intermolecular H‐bonds involve O (or N) atom as H‐acceptor, whereas the H‐bonds involving C or S atom usually are weaker than other ones. Both the strength of H‐bonds and the structural deformation are responsible for the stability of complexes. Because of the serious deformation, the complex involving the strongest H‐bond is not the most stable structures. Relationships between H‐bond length (ΔR_X‐H), frequency shifts (Δv), and the electron density (ρ_b) and its Laplace (?²ρ_b) at bond critical points have also been investigated. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Cover Feature: An Exploration of the Hydrogen Bond Donor Ability of Ammonia (ChemPhysChem 20/2023)

Ammonia is an important molecule due to its wide use in the fertiliser industry. It is also used in aminolysis reactions. Theoretical studies of the reaction mechanism predict that in reactive complexes and transition states, ammonia acts as a hydrogen bond donor forming N−H⋅⋅⋅O hydrogen bond. Experimental reports of N−H⋅⋅⋅O hydrogen bond, where ammonia acts as a hydrogen bond donor are scarce. Herein, the hydrogen bond donor ability of ammonia is investigated with three chalcogen atoms i. e. O, S, and Se using matrix isolation infrared spectroscopy and electronic structure calculations. In addition, the chalcogen bond acceptor ability of ammonia has also been investigated. The hydrogen bond acceptor molecules used here are O(CH₃)₂, S(CH₃)₂, and Se(CH₃)₂. The formation of the 1 : 1 complex has been monitored in the N−H symmetric and anti-symmetric stretching modes of ammonia. The nature of the complex has been delineated using Atoms in Molecules analysis, Natural Bond Orbital analysis, and Energy Decomposition Analysis. This work presents the first comparison of the hydrogen bond donor ability of ammonia with O, S, and Se.     

Determination of the structure of cellulose II.

The structure of regenerated cellulose is shown by x-ray diffraction to be comprised of an array of antiparallel chain molecules. The determination was based on the intensity data from rayon fibers and utilized rigid-body least-squares refinement techniques. The unit cell is monoclinic with space group P2(1) and dimensions a = 8.01 A, b = 9.04 A, c = 10.36 A (fiber axis), and gamma = 117.1 degrees. Models containing chains with the same sense (parallel) or alternating sense (antiparallel) were refined against the intensity data. The only acceptable model contains antiparallel chains. The -CH2OH groups of the corner chain are oriented near to the gt position while those of the center chain are near to the tg position. Both chains possess an O3-H-O5' intramolecular hydrogen bond, and the center chain also has an O2'-H-O6 intramolecular bond. Intermolecular hydrogen bonding occurs along the 020 planes (o6-h-o2 bonds for the corner chains and O6-H-O3 bonds for the center chains) and also along the 110 planes with a hydrogen bond between the O2-H of the corner chain and the O2' of the center chain. This center-corner chain hydrogen bonding is a major difference between the native and regenerated structures and may account for the stability of the latter form.     

5‐Amino‐2,4,6‐tribromoisophthalic acid: the MAD triangle for experimental phasing

The title compound, C₈H₄Br₃NO₄, shows an extensive hydrogen‐bond network. In the crystal structure, molecules are linked into chains by COO—H...O bonds, and pairs of chains are connected by additional COO—H...O bonds. This chain bundle shows stacking interactions and weak N—H...O hydrogen bonds with adjacent chain bundles. The three Br atoms present in the molecule form an equilateral triangle. This can be easily identified in the heavy‐atom substructure when this compound is used as a heavy‐atom derivative for experimental phasing of macromolecules. The title compound crystallizes as a nonmerohedral twin.     

Density functional complete study of hydrogen bonding between the water molecule and the hydroxyl radical (H2O · HO)

The hydrogen bonding complexes formed between the H₂O and OH radical have been completely investigated for the first time in this study using density functional theory (DFT). A larger basis set 6‐311++G(2d,2p) has been employed in conjunction with a hybrid density functional method, namely, UB3LYP/6‐311++G(2d,2p). The two degenerate components of the OH radical ²Π ground electronic state give rise to independent states upon interaction with the water molecule, with hydrogen bonding occurring between the oxygen atom of H₂O and the hydrogen atom of the OH radical. Another hydrogen bond occurs between one of the H atoms of H₂O and the O atom of the OH radical. The extensive calculation reveals that there is still more hydrogen bonding form found first in this investigation, in which two or three hydrogen bonds occur at the same time. The optimized geometry parameter and interaction energy for various isomers at the present level of theory was estimated. The infrared (IR) spectrum frequencies, IR intensities, and vibrational frequency shifts are reported. The estimates of the H₂O · OH complex's vibrational modes and predicted IR spectra for these structures are also made. It should be noted that a total of 10 stationary points have been confirmed to be genuine minima and transition states on the potential energy hypersurface of the H₂O · HO system. Among them, four genuine minima were located. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

A theory of molecules in molecules IV. Application to the Hydrogen Bonding Interaction in NH3 · H2O

The theory of molecules in molecules introduced in previous articles is applied to study the hydrogen bonding interaction between an ammonia molecule as proton acceptor and a water molecule as proton donor. The localized orbitals which are assumed to be least affected by the formation of the hydrogen bond are transferred unaltered from calculations on the fragments NH₃ and H₂O, the remaining orbitals are recalculated. A projection operator is used to obtain orthogonality to the transferred orbitals. Additional approximations have been introduced in order to be able to save computational time. These approximations can be justified and are seen to lead to binding energies and bond lengths which are in satisfactory agreement with the SCF values. The point charge approximation for the calculation of the interaction energy between the two sets of transferred localized orbitals is, however, not applicable in this case. An energy analysis of the effect of the hydrogen bond on the localized orbitals of the two fragments is given.     

Structures,vibrational frequencies,topologies, and energies of hydrogen bonds in cysteine‐formaldehyde complexes

The hydrogen bonding interactions between cysteine (Cys) and formaldehyde (FA) were studied with density functional theory regarding their geometries, energies, vibrational frequencies, and topological features of the electron density. The quantum theory of atoms in molecules and natural bond orbital analyses were employed to elucidate the interaction characteristics in the Cys‐FA complexes. The intramolecular hydrogen bonds (H‐bonds) formed between the hydroxyl and the N atom of cysteine moiety in some Cys‐FA complexes were strengthened because of the cooperativity. Most of intermolecular H‐bonds involve the O atom of cysteine/FA moiety as proton acceptors, while the strongest H‐bond involves the O atom of FA moiety as proton acceptor, which indicates that FA would rather accept proton than providing one. The H‐bonds formed between the CH group of FA and the S atom of cysteine in some complexes are so weak that no hydrogen bonding interactions exist among them. In most of complexes, the orbital interaction of H‐bond is predominant during the formation of complex. The electron density (ρ_b) and its Laplace (?²ρ_b) at the bond critical point significantly correlate with the H‐bond parameter δR, while a linearly relationship between the second‐perturbation energy E(2) and ρ_b has been found as well. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

A novel tubular hydrogen‐bond pattern in a new diazaphosphole oxide: a combination of X‐ray crystallography and theoretical study of hydrogen bonds

In the structure of 2‐(4‐chloroanilino)‐1,3,2λ⁴‐diazaphosphol‐2‐one, C₁₂H₁₁ClN₃OP, each molecule is connected with four neighbouring molecules through (N—H)₂…O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R ³₃(12) and R ₄³(14) hydrogen‐bond ring motifs, combined with a C (4) chain motif. The hole constructed in the tubular architecture includes a 12‐atom arrangement (three P, three N, three O and three H atoms) belonging to three adjacent molecules hydrogen bonded to each other. One of the N—H groups of the diazaphosphole ring, not co‐operating in classical hydrogen bonding, takes part in an N—H…π interaction. This interaction occurs within the tubular array and does not change the dimension of the hydrogen‐bond pattern. The energies of the N—H…O and N—H…π hydrogen bonds were studied by NBO (natural bond orbital) analysis, using the experimental hydrogen‐bonded cluster of molecules as the input file for the chemical calculations. In the ¹H NMR experiment, the nitrogen‐bound proton of the diazaphosphole ring has a high value of 17.2 Hz for the ²J _H–P coupling constant.     

A Combined Experimental and Theoretical Electron Density Study of Intra‐ and Intermolecular Interactions in Thiourea S,S‐Dioxide

The thiourea S,S‐dioxide molecule is recognized as a zwitterion with a high dipole moment and an unusually long C? S bond. The molecule has a most interesting set of intermolecular interactions in the crystalline state—a relatively strong O???H? N hydrogen bond and very weak intermolecular C???S and N???O interactions. The molecule has C_s symmetry, and each oxygen atom is hydrogen‐bonded to two hydrogen atoms with O???H? N distances of 2.837 and 2.826 Å and angles of 176.61 and 158.38°. The electron density distribution is obtained both from Xray diffraction data at 110 K and from a periodic density functional theory (DFT) calculation. Bond characterization is made in terms of the analysis of topological properties. The covalent characters of the C? N, N? H, C? S, and S? O bonds are apparent, and the agreement on the topological properties between experiment and theory is adequate. The features of the Laplacian distributions, bond paths, and atomic domains are comparable. In a systematic approach, DFT calculations are performed based on a monomer, a dimer, a heptamer, and a crystal to see the effect on the electron density distribution due to the intermolecular interactions. The dipole moment of the molecule is enhanced in the solid state. The typical values of ρ_b and H_b of the hydrogen bonds and weak intermolecular C???S and N???O interactions are given. All the interactions are verified by the location of the bond critical point and its associated topological properties. The isovalue surface of Laplacian charge density and the detailed atomic graph around each atomic site reveal the shape of the valence‐shell charge concentration and provide a reasonable interpretation of the bonding of each atom.     

Comparison between Hydrogen and Halogen Bonds in Complexes of 6-OX-Fulvene with Pnicogen and Chalcogen Electron Donors

Quantum chemical calculations are applied to complexes of 6-OX-fulvene (X=H, Cl, Br, I) with ZH₃/H₂Y (Z=N, P, As, Sb; Y=O, S, Se, Te) to study the competition between the hydrogen bond and the halogen bond. The H-bond weakens as the base atom grows in size and the associated negative electrostatic potential on the Lewis base atom diminishes. The pattern for the halogen bonds is more complicated. In most cases, the halogen bond is stronger for the heavier halogen atom, and pnicogen electron donors are more strongly bound than chalcogen. Halogen bonds to chalcogen atoms strengthen in the order O<S<Se<Te, whereas the pattern is murkier for the pnicogen donors. In terms of competition, most halogen bonds to pnicogen donors are stronger than their H-bond analogues, but there is no clear pattern with respect to chalcogen donors. O prefers a H-bond, while halogen bonds are favored by Te. For S and Se, I-bonds are strongest, followed Br, H, and Cl-bonds in that order.     

The new three‐dimensional supramolecule bis{μ‐2‐[(4‐hydroxybenzoyl)hydrazonomethyl]phenolato}bis[aquacopper(II)] dinitrate

In the title centrosymmetric binuclear complex, [Cu₂(C₁₄H₁₁N₂O₃)₂(H₂O)₂](NO₃)₂, the two metal centres are bridged by the phenolate O atoms of the ligand, forming a Cu₂O₂ quadrangle. Each Cu atom has a distorted square‐pyramidal geometry, with the basal donor atoms coming from the O,N,O′‐tridentate ligand and a symmetry‐related phenolate O atom. The more weakly bound apical donor O atom is supplied by a coordinated water molecule. When a further weak Cu...O interaction with the 4‐hydroxy O atom of a neighbouring cation is considered, the extended coordination sphere of the Cu atom can be described as distorted octahedral. This interaction leads to two‐dimensional layers, which extend parallel to the (100) direction. The two‐dimensional polymeric structure contrasts with other reported structures involving salicylaldehyde benzoylhydrazone ligands, which are usually discrete mono‐ or dinuclear Cu complexes. The nitrate anions are involved in a three‐dimensional hydrogen‐bonding network, featuring intermolecular N—H...O and O—H...O hydrogen bonds.     

Hydrogen bonding on accessible surfaces of cellulose from various sources and relationship to order within crystalline regions

Celluloses from a variety of common sources were analyzed for availabilities of O(2)H, O(3)H, and O(6)H in order to estimate the extent of hydrogen bonding on accessible fibrillar surfaces. Celluloses from flax, ramie, sisal, and wood (both cellulose I and II from wood) together with liquid NH₃-swollen cotton and NaOH-swollen cotton (cellulose II) had relative availabilities similar to those of native cotton. Celluloses from Valonia centricosa and in rayon samples stood apart from each other and from the “cotton family.” The difference between Valonia and cotton celluloses appears to result, in addition to the accepted smaller, less perfect crystallites in cotton, from an O(2)H hydrogen bond which is likely the intramolecular bond between O(2)H and O(6′)H that is present in Valonia and absent in cotton. Rayon samples also showed evidence of similar bonds involving O(2)H on accessible surfaces. Since the regenerated rayons had relative availabilities different from those of mercerized cotton and wood cellulose samples, it is proposed that chain packing arrangements are not the same in these two types of cellulose II.     

The double H‐atom acceptability of the P=O group in new XP(O)(NHCH2C6H4‐2‐Cl)2 phosphoramidates [X = C6H5O– and CF3C(O)NH–]: a database analysis of compounds having a P(O)(NHR) group

In the hydrogen‐bond patterns of phenyl bis(2‐chlorobenzylamido)phosphinate, C₂₀H₁₉Cl₂N₂O₂P, (I), and N,N′‐bis(2‐chlorobenzyl)‐N′′‐(2,2,2‐trifluoroacetyl)phosphoric triamide, C₁₆H₁₅Cl₂F₃N₃O₂P, (II), the O atoms of the related phosphoryl groups act as double H‐atom acceptors, so that the P=O...(H—N)₂ hydrogen bond in (I) and the P=O...(H—N_amide)₂ and C=O...H—N_C(O)NHP(O) hydrogen bonds in (II) are responsible for the aggregation of the molecules in the crystal packing. The presence of a double H‐atom acceptor centre is a result of the involvement of a greater number of H‐atom donor sites with a smaller number of H‐atom acceptor sites in the hydrogen‐bonding interactions. This article also reviews structures having a P(O)NH group, with the aim of finding similar three‐centre hydrogen bonds in the packing of phosphoramidate compounds. This analysis shows that the factors affecting the preference of the above‐mentioned O atom to act as a double H‐atom acceptor are: (i) a higher number of H‐atom donor sites relative to H‐atom acceptor centres in molecules with P(=O)(NH)₃, (N)P(=O)(NH)₂, C(=O)NHP(=O)(NH)₂ and (NH)₂P(=O)OP(=O)(NH)₂ groups, and (ii) the remarkable H‐atom acceptability of this atom relative to the other acceptor centre(s) in molecules containing an OP(=O)(NH)₂ group, with the explanation that the N atom bound to the P atom in almost all of the structures found does not take part in hydrogen bonding as an acceptor. Moreover, the differences in the H‐atom acceptability of the phosphoryl O atom relative to the O atom of the alkoxy or phenoxy groups in amidophosphoric acid esters may be illustrated by considering the molecular packing of compounds having (O)₂P(=O)(NH) and (O)P(=O)(NH)(N)groups, in which the unique N—H unit in the above‐mentioned molecules almost always selects the phosphoryl O atom as a partner in forming hydrogen‐bond interactions. The P atoms in (I) and (II) are in tetrahedral coordination environments, and the phosphoryl and carbonyl groups in (II) are anti with respect to each other (the P and C groups are separated by one N atom). In the crystal structures of (I) and (II), adjacent molecules are linked via the above‐mentioned hydrogen bonds into a linear arrangement parallel to [100] in both cases, in (I) by forming R₂²(8) rings and in (II) through a combination of R₂²(10) and R₂¹(6) rings.     

Specific hydration effects on oxo-thio triazepine derivatives

The specific hydration of 2,7-dimethyl-1,2,4-triazepine oxo-thio derivatives by one water molecule has been investigated at the B3LYP/6-311++G(3df,2p)//B3LYP/6-311+G(d,p) level of theory. The existence of different hydrogen bond (HB) donor and acceptor centers in these molecules led to different kinds of hydrogen bonds (CH-O, OH-S, NH-O, OH-N, and OH-O) and different kinds of complexes. Among them, the most stable structures correspond to complexes where the heteroatom X or Y at positions 3 and 5 behaves as HB acceptor and the hydrogen atom associated with the nitrogen atom at position 4 as HB donor. In accordance with previous studies, it has been shown that the thiocarbonyl group forms stronger HBs than the carbonyl group because the sulfur atom is a better HB acceptor than the oxygen one. With the help of the AIM (atoms in molecules) theory and ELF (electron localization function) analysis, it has been shown that, in the case of 3O5O, 3S5O, and 3S5S, the most basic site is the heteroatom at position 3, while in 3O5S species the most basic center is the sulfur atom.     

Theoretical Study on the Hydrogen Bonding Interactions in Complexes of 5‐Hydroxytryptamine with Water

The energies, geometries and harmonic vibrational frequencies of 1:1 5‐hydroxytryptamine‐water (5‐HT‐H₂O) complexes are studied at the MP2/6‐311++G(d,p) level. Natural bond orbital (NBO), quantum theory of atoms in molecules (QTAIM) analyses and the localized molecular orbital energy decomposition analysis (LMO‐EDA) were performed to explore the nature of the hydrogen‐bonding interactions in these complexes. Various types of hydrogen bonds (H‐bonds) are formed in these 5‐HT‐H₂O complexes. The intermolecular C4H5^5‐HT···O^w H‐bond in HTW3 is strengthened due to the cooperativity, whereas no such cooperativity is found in the other 5‐HT‐H₂O complexes. H‐bond in which nitrogen atom of amino in 5‐HT acted as proton donors was stronger than other H‐bonds. Our researches show that the hydrogen bonding interaction plays a vital role on the relative stabilities of 5‐HT‐H₂O complexes.     

Structures and energetics of hydrated oxygen anion clusters

Hydration of the atomic oxygen radical anion is studied with computational electronic structure methods, considering (O(-))(H(2)O)(n) clusters and related proton-transferred (OH(-))(OH)(H(2)O)(n)(-)(1) clusters having n = 1-5. A total of 67 distinct local-minimum structures having various interesting hydrogen bonding motifs are obtained and analyzed. On the basis of the most stable form of each type, (O(-))(H(2)O)(n)) clusters are energetically favored, although for n > or = 3, there is considerable overlap in energy between other members of the (O(-))(H(2)O)(n) family and various members of the (OH(-))(OH)(H(2)O)(n)(-)(1) family. In the lower-energy (O(-))(H(2)O)(n) clusters, the hydrogen bonding arrangement about the oxygen anion center tends to be planar, leaving the oxygen anion p-like orbital containing the unpaired electron uninvolved in hydrogen bonding with any water molecule. In (OH(-))(OH)(H(2)O)(n)(-)(1) clusters, on the other hand, nonplanar arrangements are the rule about the anionic oxygen center that accepts hydrogen bonds. No instances are found of OH(-) acting as a hydrogen bond donor. Those OH bonds that form hydrogen bonds to an anionic O(-) or OH(-) center are significantly stretched from their equilibrium value in isolated water or hydroxyl. A quantitative inverse correlation is established for all hydrogen bonds between the amount of the OH bond stretch and the distance to the other oxygen involved in the hydrogen bond.     

Intra- and intermolecular hydrogen bonding in formohydroxamic acid complexes with water and ammonia: infrared matrix isolation and theoretical study

The complexes of formohydroxamic acid with water and ammonia have been studied using FTIR matrix isolation spectroscopy and MP2 calculations with a 6-311++G(2d,2p) basis set. The analysis of the experimental spectra of the HCONHOH/H₂O(NH₃)/Ar matrixes indicates formation of strongly hydrogen-bonded complexes in which the NH group of formohydroxamic acid acts as a proton donor toward the oxygen atom of water or the nitrogen atom of ammonia. The NH stretching vibration of formohydroxamic acid exhibits 150 cm⁻¹ red shift in the complex with water and 443 cm⁻¹ red shift in the complex with ammonia as compared to the NH stretch of the HCONHOH monomer. The theoretical calculations indicate stability of five isomers for the water complex and three isomers for the ammonia complex. The most stable are the cyclic structures in which the water or ammonia molecules are inserted within the intramolecular hydrogen bond of the formohydroxamic acid molecule and act as proton donors for the CO group and proton acceptors for the OH group of the formohydroxamic acid molecule. In spite of their stability the cyclic structures have not been observed in the matrixes which indicates high energy barrier for their formation, the reaction of complex formation is under kinetic and not thermodynamic control.     

Structural and magnetic properties of vanadyl dichloride solvates: from molecular units to extended hydrogen-bonded solids

The preparation, structural characterization and magnetic properties of three solvent adducts of VOCl(2), trans-VOCl(2)(THF)(2)(H(2)O) (1), trans-VOCl(2)(H(2)O)(2).2Et(2)O (2) and cis-VOCl(2)(MeOH)(3) (3) are described. In these solids, hydrogen bonding among the inorganic complexes is the critical determinant of the formation of extended magnetic networks. Compound forms one-dimensional double chains where alternating monomers from the two branches of the chain are hydrogen bonded via the V-Cl ... H-O-V network (with an axial water molecule and equatorial chloride ions). Magnetic studies indicate no interaction among the vanadyl centers. The paramagnetism of 1 is consistent with the extension of the network from the hydrogen donor site of the axial water, which is orthogonal to the d(xy) magnetic orbital. Compound 2 forms one-dimensional chains with water molecules of adjacent monomers held together by hydrogen bonds to ether molecules (V-O-H ... O(ether) ... H -O-V). The chain network radiates only through the equatorial plane of the complex where the water molecules are located. The presence of the intervening solvent molecule between hydrogen bonds of the primary coordination sphere magnetically insulates metal centers and compound is also a simple paramagnet. Removal of the solvent turns on the magnetic interaction and neighboring spin centers couple antiferromagnetically. Compound 3 forms a layered structure via V-Cl ... H-O-V hydrogen bonding, where all the hydrogen donor sites participate in the formation of the network. The vanadyl spin centers, at distances of 5.5 and 6.5 A from each other, couple antiferromagnetically (J/k=-0.7 K). Thus, magnetic coupling among metal centers is achieved when the hydrogen bond network directly radiates from the coordination plane containing the magnetic orbital. These results further support the utility of hydrogen bond as a viable design element in the construction of low dimensional, magnetic solids.