Inversion Center Research Articles

Synthesis, crystal structure and Hirshfeld analysis of N-ethyl-2-{3-methyl-2-[(2Z)-pent-2-en-1-yl]cyclo-pent-2-en-1-yl-idene}hydrazinecarbo-thio-amide.

The title compound (C14H23N3S, common name: cis-jasmone 4-ethyl-thio-semicarbazone) was synthesized by the equimolar reaction of cis-jasmone and 4-ethyl-thio-semicarbazide in ethanol facilitated by acid catalysis. There is one crystallographically independent mol-ecule in the asymmetric unit, which shows disorder of the terminal ethyl group of the jasmone carbon chain [site-occupancy ratio = 0.911 (5):0.089 (5)]. The thio-semicarbazone entity [N-N-C(=S)-N] is approximately planar, with the maximum deviation of the mean plane through the N/N/C/S/N atoms being 0.0331 (8) Å, while the maximum deviation of the mean plane through the five-membered ring of the jasmone fragment amounts to -0.0337 (8) Å. The dihedral angle between the two planes is 4.98 (7)°. The mol-ecule is not planar due to this structural feature and the sp 3-hybridized atoms of the jasmone carbon chain. Additionally, one H⋯N intra-molecular inter-action is observed, with graph-set motif S(5). In the crystal, the mol-ecules are connected through pairs of H⋯S inter-actions with R 2 2(8) and R 2 1(7) graph-set motifs into centrosymmetric dimers. The dimers are further connected by H⋯N inter-actions with graph-set motif R 2 2(12), which are related by an inversion centre, forming a mono-periodic hydrogen-bonded ribbon parallel to the b-axis. The crystal structure and the supra-molecular assembly of the title compound are compared with four known cis-jasmone thio-semicarbazone derivatives (two crystalline modifications of the non-substituted form, the 4-methyl and the 4-phenyl derivatives). A Hirshfeld surface analysis indicates that the major contributions for the crystal cohesion are from H⋯H (70.7%), H⋯S/S⋯H (13.5%), H⋯C/C⋯H (8.8%), and H⋯N/N⋯H (6.6%) inter-faces (only the disordered atoms with the highest s.o.f. were considered for the evaluation).

Skyrmion lattice in centrosymmetric magnets with local Dzyaloshinsky–Moriya interaction

It is common for the local inversion symmetry to break in crystals, even though the whole crystal has global inversion symmetry. This local inversion symmetry breaking allows for a local Dzyaloshinsky–Moriya interaction (DMI) in magnetic crystals. Here we show that the local DMI can stabilize a skyrmion as a metastable excitation or as a skyrmion crystal in equilibrium. We consider the crystal structure with layered structure as an example, where local inversion is violated in each layer but a global inversion center exists in the middle of the two layers. These skyrmions come in pairs that are related by inversion symmetry. The two skyrmions with opposite helicity in a pair form a bound state. We study the properties of a skyrmion pair in the ferromagnetic background and determine the equilibrium phase diagram, where a robust lattice of skyrmion pairs is stabilized. Our results point to a new direction to search for the skyrmion lattice in centrosymmetric magnets.

Piezoelectric characteristics of doped β-Ga2O3 monolayer: a first-principles study

Two-dimensional (2D) piezoelectric materials have been widely concerned because of their important applications in nano-piezoelectric generators. Finding two-dimensional materials with large piezoelectric effects is still a great challenge. In this work, the inversion center of the β-Ga2O3 monolayer was broken by substitutional doping. Not only the in-plane piezoelectric effect but also the uncommon out-of-plane piezoelectric effect is induced in the doped β-Ga2O3 monolayer. In addition, we analyzed the cause of the piezoelectric effects from their electronic properties. The values of out-of-plane (in-plane) piezoelectric coefficient for Cu-doped and Al-doped β-Ga2O3 reach −4.04 (3.95) pm/V and −2.91 (0.37) pm/V, respectively. The results are comparable with those of the commonly used bulk piezoelectric materials such as α-quartz (d11 = 2.3 pm V−1), AlN (d33 = 5.1 pm V−1), and GaN (d33 = 3.1 pm V−1), even though they are both two-dimensional structures. Our study shows a great potential application of doped β-Ga2O3 monolayer in micro and nano-electromechanical devices such as smart wearables, sensors, energy converters, and micro energy collectors.

Synthesis, crystal structure and characterization of two new cobalt(II) metal–organic frameworks with 1,4-bis((1h-imidazol-1-yl)methyl) benzene and 1,3,5-tris[(1h-imidazol-1-yl)methyl]benzene ligands

Two novel CoII metal–organic frameworks {[Co(BIMB)2(H2O)2](SO4)·EG·3 H2O}n (I) and {[Co(TIMB)2](SiF6)}n (II) were hydrothermally synthesized by corresponding metal salt with organic ligands 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (TIMB) or 1,4-bis((1H-imidazol-1-yl)methyl)benzene (BIMB). Crystal structural analysis reveals that they exhibit varied structures. Compound I contains two crystallographically unique CoII centers, each lying on an inversion center and having a slightly distorted octahedral environment. The BIMB ligands link the CoII cations to generate a three-dimensional porous framework with a 4-connected uninodal (65.8) topology. Compound II exhibits a two-dimensional sheeted metal-organic structure running parallel to the (0 0 1) plane, in which TIMB ligands join Co2+ centers having a six-coordinated octahedral structure. In the solid state, adjacent sheets are further bridged by guest SiF6 - anions via C–H…F hydrogen-bonding interactions, giving rise to a three-dimensional supramolecular network structure with a 2-nodal (3-c)2(6-c) net. The topological analysis suggests that the point Schläfli symbol of compound II is (43)2(46.66.83). In addition, their thermal stabilities have also been investigated.

Syntheses, characterizations and crystal structures of two Ni(II) complexes [Ni2(neoc)4(H2O)(CO3)](NO3)2·3H2O and [Ni(bapa)2](NO3)2·H2O and magnetic properties of the carbonato complex

By the reaction of nickel(II) nitrate hexahydrate with 2,9-dimethyl-1,10-phenanthroline (neoc) and bis(3-aminopropyl)amine (bapa) two novel complexes were isolated, namely [Ni2(neoc)4(H2O)(CO3)](NO3)2·3H2O (1) and [Ni(bapa)2](NO3)2·H2O (2). Both structures are ionic and comprise hexacoordinated Ni(II) central atoms. Complex 1 is built up of dinuclear [Ni2(neoc)4(H2O)(CO3)]2+ complex cation, nitrate anions and water solvate molecules. The dinuclear complex cation is centrosymmetric and the two Ni(II) atoms are linked by a μ3-bridging-chelating carbonato ligand which, due to the presence of an inversion centre, exhibits two orientations with equal probability. The coordination sphere of Ni(II) atom is heteroleptic with an N4O2 donor set formed by two chelating neoc ligands and two O-donor atoms from bridging carbonato and aqua ligands. The carbonato ligand was formed by transformation of absorbed carbon dioxide from air (single crystals) or from dry ice (bulk sample). The crystal structure of 2 is formed by [Ni(bapa)2]2+ complex cation, nitrate anions and water solvate molecule. The coordination sphere of Ni(II) atom in 2 is homoleptic with N6 donor set. Both bapa ligands act as double chelating 3 N-donor ligands and are coordinated in mer-fashion. The study of the magnetic response of 1 in the temperature range 1.8–300 K revealed that the system can be considered as a system of antiferromagnetic S = 1 spin dimers with exchange interaction J/hc = -13.86 cm−1 (J/kB = -19.96 K) and axial single-ion anisotropy D/hc = -4.94 cm−1 (D/kB = -7.12 K). The experimental magnetic results were corroborated by ab initio and DFT calculations.

Synthesis and crystal structure of tetra-methyl (E)-4,4'-(ethene-1,2-di-yl)bis-(5-nitro-benzene-1,2-di-carboxyl-ate).

The title compound, C22H18N2O12, was obtained as a by-product during the planned synthesis of 1,2-bis-(2-nitro-4,5-dimethyl phthalate)ethane by oxidative dimerization starting from dimethyl-4-methyl-5-nitro phthalate. To identify this compound unambiguously, a single-crystal structure analysis was performed. The asymmetric unit consists of half a mol-ecule that is located at a centre of inversion. As a result of symmetry restrictions, the mol-ecule shows an E configuration around the double bond. Both phenyl rings are coplanar, whereas the nitro and the two methyl ester groups are rotated out of the ring plane by 32.6 (1), 56.5 (2) and 49.5 (2)°, respectively. In the crystal, mol-ecules are connected into chains extending parallel to the a axis by pairs of C-H⋯O hydrogen bonds that are connected into a tri-periodic network by additional C-H⋯O hydrogen-bonding inter-actions.

Trans-Di-bromido-tetra-kis-(5-methyl-1H-pyrazole-κN2)manganese(II).

The title compound, trans-di-bromido-tetra-kis-(5-methyl-1H-pyrazole-κN 2)manganese(II), [MnBr2(C4H6N2)4] or [Mn(3-MePzH)4Br2] (1) crystallizes in the triclinic P space group with the cell parameters a = 7.6288 (3), b = 8.7530 (4), c = 9.3794 (4) Å and α = 90.707 (4), β = 106.138 (4), γ = 114.285 (5)°, V = 542.62 (5) Å3, T = 120 K. The asymmetric unit contains only half the mol-ecule with the manganese atom is situated on a crystallographic inversion center. The 3-MePzH ligands are present in an AABB type manner with two methyl groups pointing up and the other two down. The supra-molecular architecture is characterized by several inter-molecular C-H⋯N, N-H⋯Br, and C-H⋯π inter-actions. Earlier, a polymorphic structure of [Mn(3-MePzH)4Br2] (2) with a similar geometry and also an AABB arrangement for the pyrazole ligands was described [Reedijk et al. (1971 ▸). Inorg. Chem. 10, 2594-2599; a = 8.802 (6), b = 9.695 (5), c = 7.613 (8) Å and α = 105.12 (4), β = 114.98 (4), γ = 92.90 (3)°, V = 558.826 (5) Å3, T = 295 K]. A varying supra-molecular pattern was reported, with the structure of 1 featuring a herringbone type pattern while that of structure 2 shows a pillared network type of arrangement along the a axis. A nickel complex [Ni(3-MePzH)4Br2] isomorphic to 1 and the analogous chloro derivatives of FeII, CoII and CuII are also known.

Synthesis, characterization, antimicrobial and anti-biofilm studies of Ni(II) complex with Schiff base derived from 2-thiophene carboxaldehyde and phenyl acetic hydrazide

Schiff base titled (Z)-2-phenyl-N'-(thiophen-2-ylmethylene)acetohydrazide (HL) and its Ni (II) complex were obtained by the condensation of 2-thiophene carboxaldehyde and phenyl acetic hydrazide. The ligand (HL) was characterized using elemental analysis, Fourier transform infrared (FTIR), proton nuclear magnetic resonance (1HNMR ), Ultraviolet–visible (UV–Vis.) spectroscopy, and Liquid chromatography–mass spectrometry (LC/MS) methods. Elemental analysis, FTIR, UV–Vis, and X-ray single crystal studies were used to elucidate the structure of the [NiL2] complex. The brown single crystal structure of the Ni(II) complex was elucidated by X-ray diffraction technique, and the complex structure was found to crystallize in a triclinic crystal system with P1¯ space group. With symmetries of 1-x, 1-y, and -z and -x, 1-y, and 1-z, the nickel atoms in the asymmetric unit are positioned on an inversion centre. It was determined that the antimicrobial activity of the newly synthesized HL and [NiL2] compounds was high on clinically important strains and had low minimal inhibitory concentration (MIC) values. In addition, the anti-biofilm activity of the compounds showed 45.14 % and 42.28 % biofilm inhibition, respectively, on the E. coli ATCC 25,922 strain at a concentration of 100 µg/ml, whereas it showed 56.36 % and 42.28 % inhibition, respectively, on the P. aeruginosa ATCC 278533 strain showed an inhibitory effect.

Bis[S-octyl 3-(2-methyl-propyl-idene)di-thio-carb-az-ato-κ2N3,S]nickel(II).

The central NiII atom in the title complex, [Ni(C13H25N2S2)2], is located on an inversion center and adopts a roughly square-planar coordination environment defined by two chelating N,S donor sets of two symmetry-related ligands in a trans configuration. The Ni-N and Ni-S bond lenghts are 1.9193 (14) and 2.1788 (5) Å, respectively, with a chelating N-Ni-S bond angle of 86.05 (4)°. These data are compared with those measured for similar di-thio-carbazato ligands that bear n-octyl or n-hexyl alkyl chains. Slight differences are observed with respect to the phenyl-ethyl-idene derivative where the ligands are bound cis relative to one another.

A new paddle wheel type Cu(II) complex with photoluminescence and photocatalytic properties

A paddle wheel-shaped complex formulated [Cu2(piv)4(CH3OH)2]·1.5(CH3OH)·0.5(H2O) (1) has been synthesized by a reaction of Cu(NO3)2·3H2O with pivalic acid. The structure of the complex is characterized by FTIR, elemental analysis and single X-ray crystallography. The crystal structure demonstrates that complex exhibits a paddle wheel type configuration. The asymmetric unit of 1 is composed of a half molecule due to the existence of an inversion center between the two Cu(II) centers. The oxygen atoms of the pivalate serve as bridging ligands, and the two methanol molecules occupy the axial position. Each pivalate ion has syn-, syn- coordination mode and its geometry may be described as square pyramidal. The complex works well as a photocatalyst, breaking down methylene blue (MB) by 78.26% after 120 minutes of 30 W ultraviolet light exposure. The optimized photocatalytic parameters were as follows; catalyst loading = 40 mg, primary concentration of MB = 15 mg/L, temperature = 323K, and pH = 8. The reaction kinetics were best demonstrated by a pseudo-first-order kinetic model followed by a rate constant of 0.00715 min–1. The reuse of the catalyst over five photocatalytic runs suggested its excellent sustainability and recyclability. Hydroxyl radicals and superoxide anions were found to be active participants in the catalytic reaction, as investigated by scavenging studies. These findings contributed to a deeper understanding of the mechanistic aspects of the photocatalytic reaction. Theoretical investigation is well support to experimental work.

Shpol’skii effect: new interpretation for the nature of the spectral multiplet structure and Bethe-splitting

New approach to the interpretation of the multiplet structure in the Shpol’skii spectra based on the symmetry consideration of the impurity molecule and crystal matrix is proposed. The reasons and peculiarities of doublet structure formation in the spectra of molecules without inversion center and highly symmetric molecules are considered. It is shown that the structure of electron density distribution in the naphthalene molecule causes a doubly degenerate of the electronic level of its ground state. The calculated data are compared with the experimental results. The main research stages and directions in the field of narrow-line spectroscopy of organic molecules are marked.

Synthesis and crystal structure of diisothiocyanatotetrakis(4-methylpyridine N-oxide)cobalt(II) and diisothiocyanatotris(4-methylpyridine N-oxide)cobalt(II) showing two different metal coordination polyhedra

The reaction of Co(NCS)2 with 4-methylpyridine N-oxide (C6H7NO) leads to the formation of two compounds, namely, tetrakis(4-methylpyridine N-oxide-κO)bis(thiocyanato-κN)cobalt(II), [Co(NCS)2(C6H7NO)4] (1), and tris(4-methylpyridine N-oxide-κO)bis(thiocyanato-κN)cobalt(II), [Co(NCS)2(C6H7NO)3] (2). The asymmetric unit of 1 consists of one CoII cation located on a centre of inversion, as well as one thiocyanate anion and two 4-methylpyridine N-oxide coligands in general positions. The CoII cations are octahedrally coordinated by two terminal N-bonding thiocyanate anions in trans positions and four 4-methylpyridine N-oxide ligands. In the extended structure, these complexes are linked by C—H...O and C—H...S interactions. In compound 2, two crystallographically independent complexes are present, which occupy general positions. In each of these complexes, the CoII cations are coordinated in a trigonal–bipyramidal manner by two terminal N-bonding thiocyanate anions in axial positions and by three 4-methylpyridine N-oxide ligands in equatorial positions. In the crystal, these complex molecules are linked by C—H...S interactions. For compound 2, a nonmerohedral twin refinement was performed. Powder X-ray diffraction (PXRD) reveals that 2 was nearly obtained as a pure phase, which is not possible for compound 1. Differential thermoanalysis and thermogravimetry data (DTA–TG) show that compound 2 start to decompose at about 518 K.

Synthesis and structure of trans-bis-(4-amino-3-nitro-benzoato-κO)bis-(4-amino-3-nitro-benzoic acid-κO)di-aqua-manganese(II) dihydrate.

The manganese title complex, [Mn(C7H5N2O4)2(C7H6N2O4)2(H2O)2]·2H2O, is one of the first 4-amino 3-nitro-benzoic acid (4 A3NBA) monoligand metal complexes to be synthesized. It crystallizes in the centrosymmetric monoclinic space group P21/n with the complex mol-ecules located on inversion centers. Four 4 A3NBA ligand mol-ecules are monodentately coordinated by the Mn2+ ion through the carb-oxy-lic oxygen atoms while the other two positions of the inner coordination sphere are occupied by water mol-ecules, giving rise to a distorted octa-hedron, and two water mol-ecules are in the outer coordination sphere. There are two intra-molecular hydrogen bonds in the complex mol-ecule. The first is of the common N-H⋯O=N type, while the second is a rarely occurring very strong hydrogen bond in which a common proton is shared by two uncoordinated oxygen atoms of neighboring carboxyl-ate groups. In the crystal, an intricate system of inter-molecular hydrogen bonds links the complex mol-ecules into a three-dimensional-network.

ISODISTROTLaMTeO6 (M = Ga3+ and Mn3+): the critical role of electronic configuration and cation ordering in crystal structures.

In this work, PbSb2O6-type oxides LaMTeO6 (M = Ga3+ and Mn3+) were synthesized and structurally characterized by Rietveld refinements against high-resolution X-ray powder diffraction data. The Ga3+/Te6+ partial ordering within the honeycomb-like two-dimensional [GaTeO6]3- anionic layer leads to the loss of the inversion center between Ga3+ and Te6+; however the inversion center on the 3̄-roto-inversion axis is preserved, thereby resulting in a 2-fold PbSb2O6-type superstructure by doubling the c-axis associated with a structural symmetry descending from the original P3̄1m to P3̄1c symmetry. In contrast, LaMnTeO6 (P21/c) adopts a monoclinically distorted 4-fold superstructure with lattice dimensions of a ≈ aH, b ≈ √3aH, c ≈ 2cH, where aH and cH represent the lattice parameters of trigonal PbSb2O6. The formation of this P21/c-superstructure is attributed to the combination of complete Mn3+/Te6+ ordering and the first-order Jahn-Teller distortion of Mn3+ with the electronic configuration of d4. Such a monoclinic distortion can effectively lift the Mn3+ spin moments arranged on the triangular sublattice, resulting in a sharp peak for antiferromagnetic transition, which is in stark contrast to subtle magnetic transitions for PbSb2O6-type tellurates AMn(VI)TeO6 (A = alkaline earth and Pb2+) and LnCrTeO6 (Ln = rare earth) with higher structural symmetry. Our findings highlight that the electronic configuration effects of M-cations play a critical role in controlling the structure symmetry of LaMTeO6, providing a strategy to fine-tune the crystal structures and physical properties.

Optical bistability in topological layered structure and its application in photonic neural network

Optical bistable state exhibits its great potential applications in photonic integrated circuit and photonic neural network. However, the traditional optical bistable state will be influenced by the system disorders, which are not suitable for application. In this work, we investigate the topological bistable states in a layered structure with center inversion symmetry consisting of alternating layers of high index material TiO<sub>2</sub> and low index material SiO<sub>2</sub>. In the topological mode, the electric field is highly localized in the inversion center of the layered structure (also known as the interface) and exponentially decays into the bulk. Thus, when the nonlinear permittivity is strategically introduced into those layers, nonlinear phenomena such as the bistable state appears. The finite element numerical simulations reveal that the optimal bistable state appears when the layer period is 5 with a threshold power around 1.2 W/m. Benefiting from the topological characteristics, such a bistable state persists when random perturbations are introduced into the layer thickness and refractive index. Finally, we apply the bistable states to a photonic neural network. The bistable function shows prediction accuracy similar to the classic activation function ReLu and sigmoid in various learning tasks. These results provide a novel method for inserting highly robust optical bistable states from topological layered structure into photonic neural network.

ON THE MAXIMUM CIRCULAR INVERSES OF MAXIMUM CIRCLES

In this study, the inverses of maximum circles under the maximum circular inversion are examined. The maximum circular inversion is observed to transform maximum circles to curves consisting of parabolic arcs, line segments, and sometimes rays. It is seen that the image curve occurs in different shapes depending on the relative positions of the inversion circle and the maximum circle. While the images of maximum circles not passing through the inversion center are closed curves, the images of those passing through the inversion center are not closed. Inverse curves have been studied by considering the radii of the maximum circles and the positions of the lines joining their centers and the center of maximum inversion. Classifications of the inverses of maximum circles are presented.

Bis[1,3-bis-(2,4,6-tri-methyl-phen-yl)imidazolium] bis(μ-cis-1,2-di-phenyl-ethene-1,2-di-thiol-ato-κ2S,S':κS)bis-[(cis-1,2-di-phenyl-ethene-1,2-di-thiol-ato-κ2S,S')iron(III)] di-methyl-formamide disolvate.

The mol-ecular structure of the solvated title salt, (C21H25N2)2[Fe2(C14H10S2)4]·2C3H7NO reveals that the anion is situated on a crystallographic inversion center in the triclinic space group P . The title compound crystallizes utilizing a network of weak π-stacking inter-actions of phenyl rings pertaining to the di-thiol-ene unit. Moreover, the acidic imidazolium H atoms [N-C(H)-N] display non-classical hydrogen-bonding inter-actions of the C-H⋯O type to the oxygen atoms of the N,N-dimethyl formamide solvent, and hydrogen atoms on the backbone of imidazolium rings display weak C-H⋯S inter-actions with the di-thiol-ene sulfur atoms.

Electric Tuning of Vortex Ratchet Effect in NbSe2.

Inversion symmetry breaking has played an important role in recent discoveries of nonreciprocal charge transport. Niobium diselenide, for example, lacks an inversion center in the monolayer form and can host prominent nonreciprocal transport property. Here, however, we observe a nonreciprocal transport signal in the second-harmonic channel of bulk-like NbSe2, in which inversion symmetry of the lattice seems preserved. The second-harmonic signal occurs along different in-plane current orientations and appears not only in the vortex-liquid regime but also even in the superconducting fluctuation regime without an applied magnetic field. By adding a direct current (DC) bias, we quantify the symmetry breaking effect in the vortex-liquid regime. The DC bias also suggests that the rectification effect at the contacts may account for the seemingly nonreciprocal transport at zero magnetic field. Our results demonstrate that DC biasing is a useful knob for addressing nonreciprocal charge transport in a wide range of materials.

Enantiomorph conversion in single crystals of the Weyl semimetal CoSi

Chiral intermetallic phases may show unusual chemical and physical properties with nontrivial structure-property relationship. It is therefore of particular interest to study the structural conversion between domains of different handedness. Here, the atomic decoration of the enantiomorph exchange area within single crystal of the Weyl semimetal CoSi is determined by a combination of atomic-resolution scanning transmission electron microscopy imaging, single crystal X-ray diffraction and quantum chemical analysis of atomic interactions. Two-atomic [CoSi] units are shown to be the bonding base for the FeSi-type structure and may be considered as ‘pseudo-molecules’, thinking of molecular organic crystals. Tiny reorganisation of atomic interactions within these units results in the appearance of sequence ‘faults’ in the structure pattern i.e. in a different structural motif in the enantiomorph exchange area, which – contrary to the A and B enantiomorphs of CoSi – contains an inversion centre and allows a local enantiomorph ‘conversion’. Due to the special features of atomic interactions, the reorganisation of multi-atomic bonds leads to slightly higher total energy. This appears within one and the same grain which is prepared by the short distance chemical vapor transport.

Nonlinear and Emissive {[MIII(CN)6]3-···Polyresorcinol} (M = Fe, Co, Cr) Cocrystals Exhibiting an Ultralow Frequency Raman Response.

Optically active functional noncentrosymmetric architectures might be achieved through the combination of molecules with inscribed optical responses and species of dedicated tectonic character. Herein, we present the new series of noncentrosymmetric cocrystal salt solvates (PPh4)3[M(CN)6](L)n·msolv (M = Cr(III), Fe(III), Co(III); L = polyresorcinol coformers, multiple hydrogen bond donors: 3,3',5,5'-tetrahydroxy-1,19-biphenyl, DiR, n = 2, or 5'-(3,5-dihydroxyphenyl)-3,3″,5,5″-tetrahydroxy-1,19:3',1″-terphenyl, TriRB, n = 1) denoted as MDiR and MTriRB, respectively. The hydrogen-bonded subnetworks {[M(CN)6]3-;Ln}∞ of dmp, neb, or dia topology are formed through structural matching between building blocks within supramolecular cis-bis(chelate)-like {[M(CN)6]3-;(H2L)2(HL)2} or tris(chelate)-like {[M(CN)6]3-;(H2L)3} fragments. The quantum-chemical analysis demonstrates the mixed electrostatic and covalent character of these interactions, with their strength clearly enhanced due to the negative charge of the hydrogen bond acceptor metal complex. The corresponding interaction energy is also dependent on the geometry of the contact and size matching of its components, rotational degree of freedom and extent of the π-electron system of the coformer, and overall fit to the molecular surroundings. Symmetry of the crystal lattices is correlated with the local symmetry of coformers and {complex;(coformer)n} hydrogen-bonded motifs characterized by the absence of the inversion center and mirror plane. All compounds reveal second-harmonic generation activity and photoluminescence diversified by individual UV-vis spectral characteristics of the components, and interesting low-frequency Raman scattering spectra within the subterahertz spectroscopic domain. Vibrational (infrared/Raman), UV-vis electronic absorption (experimental and calculated), and 57Fe Mössbauer spectra together with electrospray ionization mass spectrometry (ESI-MS) data are provided for the complete description of our systems.