High-temperature heat capacity and thermodynamic properties of Pb<Subscript>4</Subscript>V<Subscript>2</Subscript>O<Subscript>9</Subscript> and Pb<Subscript>8</Subscript>V<Subscript>2</Subscript>O<Subscript>13</Subscript>

The molar heat capacity of Pb₄V₂O₉ and Pb₈V₂O₁₃ in the temperature range 350–1000 K was measured by differential scanning calorimetry. It was determined that the plot C_p = f(T) for Pb₈V₂O₁₃ has an extremum within the range 416–516 K, which is due to a phase transition. A correlation was found between the heat capacity and composition of oxides in the PbO–V₂O₅ system. The data obtained allowed one to predict the specific heat capacity value for Pb(VO₃)₂.     

Synthesis,structure, and properties of M<Subscript>3</Subscript>VO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> (M = Rb,Cs)

Vanadium(V) complexes of general composition M₃VO₂(SO₄)₂ (M = Rb, Cs) were synthesized by a solid-state route. The individuality of the synthesized compounds was proved by X-ray and neutron diffraction, vibrational spectroscopy, and microscopic analysis. The X-ray diffraction patterns of M₃VO₂(SO₄)₂ were indexed to fit the monoclinic system (space group P2/c, Z = 4) with the following unit cell parameters: a = 11.6487(2) Å, b = 8.4469(2) Å, c = 12.1110(2) Å, β = 109.483(1)°, V = 1123.43 ų (Rb); a = 12.0546(3) Å b = 8.7706(2) Å, c = 12.6496(3) Å, β = 109.843(2)°, V = 1257.99 ų (Cs). In the crystal structure of M₃VO₂(SO₄)₂, [VO₂(SO₄)₂]^3? complex anions can be discerned in which the vanadium atom is surrounded by five oxygen atoms: two oxygen atoms form short terminal V–O bonds, and three oxygen atoms are from the two sulfato groups, one of which acts as a monodentate ligand and the other acts as a bidentate chelating ligand.     

The thermodynamic properties of the [(Me<Subscript>3</Subscript>Si)<Subscript>7</Subscript>C<Subscript>60</Subscript>]<Subscript>2</Subscript> fullerene complex

The temperature dependence of the heat capacity C _p ^o of the [(Me₃Si)₇C₆₀]₂ fullerene complex was measured for the first time using precision adiabatic vacuum calorimetry over the temperature range 6.7–340 K and high-accuracy differential scanning calorimetry at 320–635 K. For the most part, the error in the C _p ^o values was about ±0.5%. An irreversible endothermic effect caused by the splitting of the dimeric bond between fullerene fragments and the thermal decomposition of the complex was observed at 448–570 K. The thermodynamic characteristics of this transformation were calculated and analyzed. Multifractal analysis of the low-temperature (T < 50 K) heat capacity was performed, and conclusions were drawn concerning the character of the heterodynamicity of the structure. The experimental data obtained were used to calculate the standard thermodynamic functions C _p ^o (T), H ^o (T) ? H ^o (0), S ^o (T) ? S ^o (0), and G ^o (T) ? H ^o (0) over the temperature range from T → 0 to 445 K and estimate the standard entropy of formation of the compound from simple substances at 298.15 K. The standard thermodynamic properties of [(Me₃Si)₇C₆₀]₂ are compared with those of the (C₆₀)₂ dimer, the [(η⁶-Ph₂)₂Cr]⁺[C₆₀]^?? fulleride, and the initial C₆₀ fullerene.     

Synthesis and crystal structure of ternary molybdate compound K<Subscript>5</Subscript>Pb<Subscript>0.5</Subscript>Hf<Subscript>1.5</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>6</Subscript>

Single crystals of triple molybdate of composition 5:1:3 K₅Pb_0.5Hf_1.5(MoO₄)₆ have been grown and their crystal structure has been solved from X-ray diffraction data (an automated diffractometer X8 APEX, MoK _α -radiation, 2173 F(hkl), R = 0.0321). Trigonal unit cell parameters are: a = b = 10.739(2) Å, c = 37.933(9) Å; V = 3789(1) ų, Z = 6, ρ_calc = 4.014 g/cm³, space group \(R\bar 3\). Three-dimensional mixed framework of the structure is formed by two types of MoO₄ tetrahedra and Pb and Hf octahedra linking via common O-vertices. Potassium atoms of three types occupy large vacancies in the framework.     

K<Subscript>3</Subscript>VO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Formation conditions,crystal structure,and physicochemical properties

Potassium oxosulfatovanadate(V) K₃VO₂(SO₄)₂ has been obtained by solid-phase synthesis from K₂SO₄, K₂S₂O₇, and V₂O₅ (2: 1: 1), and its formation conditions, crystal structure, and physiochemical properties have been studied. The conversions of K₃VO₂(SO₄)₂ in contact with potassium vanadates and other potassium oxosulfatovanadates(V) are considered in terms of phase relations in the K₂O-V₂O₅-SO₃ system, which models the active component of vanadium catalysts for sulfur dioxide oxidation into sulfur trioxide. The X-ray diffraction pattern of K₃VO₂(SO₄)₂ is indexed in the monoclinic system (space group P2₁) with unit cell parameters of a = 10.0408(1) Å, b = 7.2312(1) Å, c = 7.3821(1) Å, β = 104.457(1)°, Z = 2, and V = 519.02 ų. The crystal structure of K₃VO₂(SO₄)₂ is built from [VO₂(SO₄)₂]^3? complex anions, in which the vanadium atom is in an octahedral oxygen environment formed by two terminal oxygen atoms (V-O(6) = 1.605(7) Å, V-O(10) = 1.619(7) Å and four oxygen atoms of the two chelating sulfate anions. The vibrational spectra of K₃VO₂(SO₄)₂ are analyzed using these structural data.     

Synthesis,structure, and properties of V<Subscript>2</Subscript>O<Subscript>3</Subscript>(XO<Subscript>4</Subscript>)<Subscript>2</Subscript> (X = S,Se)

Compounds described as V₂O₃(XO₄)₂, where X = S or Se, were prepared from vanadium(V) oxide mixtures with concentrated sulfuric and selenic acids. The physicochemical properties of the products were studied; for V₂O₃(SeO₄)₂, the crystal structure was determined by powder X-ray diffraction and neutron diffraction, and its key differences from the structure of V₂O₃(SO₄)₂ were identified. V₂O₃(SeO₄)₂ crystallizes in the monoclinic system with the unit cell parameters a = 15.3831(2)Å, b = 5.54096(5)Å, c = 9.71644(7)Å, β = 111.886(1)°, V = 768.51ų, space group C2/c (no. 15).     

X-ray diffraction and thermodynamic characteristics for tellurite of the composition Li<Subscript>2</Subscript>CeTeO<Subscript>5</Subscript>

Tellurite of the composition Li₂CeTeO₅ is synthesized by solid-phase method from cerium(IV) and tellurium(IV) oxides and lithium carbonate. The type of syngony, the unit cell parameters, and the compound’s X-ray and pycnometry densities are determined via X-ray diffraction analysis. The isobaric heat capacity of lithium–cerium tellurite is studied by means of dynamic calorimetry in the temperature range of 298.15–673 K; the results serve as the basis for deriving C _p ^° ~ f(T) dependency equations and determining the compound’s thermodynamic functions. λ-shaped anomalous effects, due probably to Type II phase transitions, are found on the C _p ^° ~ f(T) dependence.     

Synthesis and structure of [UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>){CONH<Subscript>2</Subscript>N(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>}<Subscript>2</Subscript>]

The single crystals of [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] were synthesized and studied by X-ray diffraction. The crystals are monoclinic, a = 7.461(2) Å, b = 8.828(2) Å, c = 11.756(2) Å, β = 107.21(3)°, space group Pc, Z = 2, R = 2.94%. The structure comprises infinite chains [UO₂(C₂O₄){CONH₂N(CH₃)₂}₂] extended along [001] and corresponding to the AT¹¹M ₂ ¹ crystallochemical group (A = UO ₂ ²⁺ , T¹¹ = C₂O ₄ ^2? , M¹ = N,N-CONH₂N(CH₃)₂) of uranyl complexes. The chains are connected into a three-dimensional framework by hydrogen bonds involving the oxygen atoms of oxalate and uranyl ions and the N,N-dimethylcarbamide methyl groups.     

Orientational disorder in crystal structures of (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>ZrF<Subscript>7</Subscript> and (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

Crystal structures of (NH₄)₃ZrF₇ (I) and (NH₄)₃NbOF₆ (II) are refined by X-ray diffraction at room temperature. The compounds are isostructural and belong to the structural type of elpasolite: space group F23; a(I) = 9.4185(3) Å, a(II) = 9.3371(5) Å; V(I) = 835.50(5) ų, V(II) = 814.02(8) ų; Z = 4; R(I) = 0.0145, and R(II) = 0.0138. The refinement of the structures in the space group Fm3m yields abnormally short X-X distances in the pentagonal bipyramid MX₇ (X = F, O). The oxygen atom in II is identified by Nb-X distances and occupies one of the axial vertices of the bipyramid. The Nb atom in II is statistically distributed over the position 24f, while Zr in I resides in the symmetry center. The pentagonal bipyramid MX₇ has six independent orientations in I and twelve in II. One of three crystallographically independent ammonium groups of the structures is disordered over six or twelve equivalent orientations.     

Synthesis and crystal structure of a 1D coordination polymer [Cd(NITpPy)<Subscript>2</Subscript>(N(CN)<Subscript>2</Subscript>)<Subscript>2</Subscript>)]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A novel one-dimensional chain complex [Cd(NITpPy)₂(N(CN)₂)₂)] _n (NITpPy = 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) has been synthesized and characterized structurally. It crystallizes in the triclinic space group P \(\bar 1\) with a = 7.1742(13), b = 9.4913(17), c = 13.208(2) Å, α = 71.020(2)°, β=87.308(2)°, γ = 70.503(2)°, V = 799.8(3) ų, C₂₈H₃₂CdN₁₂O₄, Mr = 713.06, Z = 1, ρ _c = 1.48 g/cm³, μ(MoK _α) = 0.736 mm^?1, F(000) = 364, R = 0.0275 and wR = 0.0605 for 2702 observed reflections with I > 2σ(I). The crystal structure consists of infinite chains of [Cd(NITpPy)₂(N(CN)₂)₂)] units linked by dicyanamide anions [N(CN)₂]^?. Each Cd²⁺ ion is six-coordinated with the geometry of a distorted octahedron.     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Low-temperature heat capacity and high-temperature thermal behavior of sodium lutetium molybdate phosphate Na<Subscript>2</Subscript>Lu(MoO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)

The low-temperature heat capacity of Na₂Lu (MoO₄)(PO₄) was measured by adiabatic calorimetry in the range of 7.47–345.74 K. The experimental data were used to calculate the thermodynamic functions of Na₂Lu (MoO₄)(PO₄). At 298.15 K, the following values were obtained: C _p ⁰ (298.15 K) = 237.7 ± 0.1 J/(K mol), S ⁰(298.15 K) = 278.1 ± 0.8 J/(K mol), H ⁰(298.15 K) ? H ⁰ (0 K) = 42330 ± 20 J/mol, and Φ⁰(298.15 K) = 136.1 ± 0. 3 J/(K mol). A heat capacity anomaly was found in the range of 10-67 K with a maximum at T _tr = 39.18 K. The entropy and enthalpy of transition are ΔS = 12.39 ± 0.75 J/(K mol) and ΔH = 403 ± 16 J/mol. The thermal investigation of sodium lutetium molybdate phosphate in the high-temperature range (623–1223 K) was performed using differential scanning calorimetry. It was found that during melting in the range of 1030–1200 K, Na₂Lu(MoO₄)(PO₄) degrades to simpler compounds; the degradation scenario is verified by X-ray powder diffraction.     

Crystal structures of [Zn(SALIMP)(CH<Subscript>3</Subscript>CO<Subscript>2</Subscript>)]<Subscript>2</Subscript> and [Cu(SALIMP)Cl] with 2-[[(2-pyridinylmethyl) imino]methyl]phenol (HSALIMP) as a ligand

Two complexes [Zn(SALIMP)(CH₃CO₂)]₂ (1) and [Cu(SALIMP)Cl] (2) are obtained by the reactions of zinc(II) and copper(II) salts with a tridentate Schiff base ligand 2-[[(2-pyridinylmethyl) imino]methyl]phenol (HSALIMP). Their structure is determined by single crystal X-ray diffraction. Data for complex 1: C₃₀H₂₈N₄O₆Zn₂, CCDC number: 668213, M _r = 671.3, monoclinic, C2/c, with a = 34.670(5) Å, b = 15.266(2) Å, c = 23.464(4) Å, β = 114.045(2)°, V = 11341(3) ų, Z = 16, F(000) = 5504, GOOF(F ²) = 0.894, the final R = 0.0520 and wR = 0.1272 for 10515 observed reflections with I > 2σ(I); complex 2: C₁₃H₁₂N₂OClCu, CCDC number: 668211, M _r = 311.24, triclinic, P-1, with a = 7.4050(8) Å, b = 10.2369(11) Å, c = 16.2873(17) Å, α = 87.728(2)°, β = 87.818(2)°, γ = 78.279(2)°, V = 1207.4(2) ų, Z = 4, F(000) = 632, GOOF(F ²) = 1.077, the final R = 0.0326 and wR = 0.0381 for 4209 observed reflections with I > 2σ(I).     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-[Re<Subscript>6</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>2</Subscript>L<Subscript>4</Subscript>] complexes,L = pyridine or 4-methylpyridine

The structures of three novel octahedral rhenium cluster compounds [Re₆S₈(CN)₂(py)₄]·H₂O (1), [Re₆S₈(CN)₂(4-Mepy)₄] (2), [Re₆S₈(CN)₂(4-Mepy)₄]·4-Mepy (3) (py = pyridine, 4-Mepy = 4-methylpyridine) are determined by X-ray crystallography. Crystal data are: C2/m space group, a = 14.813(1) Å, b = 14.772(1) Å, c = 9.2122(6) Å, β = 119.085(2)°, V = 1761.7(2) ų, d _x = 3.318 g/cm³, R = 0.0585 (1); I4₁/amd space group, a = 16.0018(3) Å, c = 14.7186(5) Å, V = 3768.81(16) ų, d _x = 3.169 g/cm³, R = 0.0489 (2); P2₁/c space group, a = 9.0452(4) Å, b = 15.8065(7) Å, c = 15.2951(6) Å, β = 103.700(2)°, V = 2124.57(16) ų, d _x = 2.957 g/cm³, R = 0.0245 (3). Molecular cluster complexes interact via π-π stacking affording 3D frameworks in 1 and 2 and chains in 3.     

Crystal structure and properties of [M(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl](NO<Subscript>3</Subscript>)<Subscript>2</Subscript>, (M = Ir,Rh, Ru)

The crystal structures of compounds from the series [M(NH₃)₅Cl](NO₃)₂, (M = Ir, Rh, Ru) were described. The compounds crystallized in the tetragonal crystal system, space group I4, Z = 2. Crystal data for [Ir(NH₃)₅Cl](NO₃)₂ (I): a = 7.6061(1) Å, b = 7.6061(1) Å, c = 10.4039(2) Å, V = 601.894(16) ų, ρ_calc = 2.410 g/cm³, R = 0.0087; [Rh(NH₃)₅Cl](NO₃)₂ (II): a = 7.5858(5) Å, b = 7.5858(5) Å, c = 10.41357(7) Å, V = 599.24(7) ų, ρ_calc = 1.926 g/cm³, R = 0.0255; [Ru(NH₃)₅Cl](NO₃)₂ (III): a = 7.5811(6) Å, b = 7.5811(6) Å, c = 10.5352(14) Å, V = 605.49(11) ų, ρ_calc = 1.896 g/cm³, R = 0.0266. The compounds were defined by IR spectroscopy and XRPA and thermal analyses.     

Organometallic coordination polymers based on silver carboxylates: [AgCF<Subscript>3</Subscript>CO<Subscript>2</Subscript>(2,3-Et<Subscript>2</Subscript>Pyz)] and [AgCF<Subscript>3</Subscript>CO<Subscript>2</Subscript>(Bpeta)]

Coordination polymers [AgCF₃CO₂(2,3-Et₂Pyz)](I)(2,3-Et₂Pyz-C₈H₁₂N₂) and [AgCF₃CO₂(Bpeta)] (II) (Bpeta is 4′4-bipyridylethane, C₁₂H₁₂N₂) are synthesized. Their structures are determined. The crystals of compound I are monoclinic, space group P2(1)/n, a = 7.185(1), b = 14.754(1), c = 12.317(1)Å, β = 97.09(1)°, V = 1295.7(2) ų, ρ_calcd = 1.831 g/cm³, Z = 4. Structure I consists of infinite chains of doubled polymeric chains joined by silver carboxylate dimers [[Ag₂(CF₃CO₂)₂(Et₂Pyz)₂]_∞. The coordination polyhedron of Ag⁺ is a distorted tetrahedron. The crystals of compound II are orthorhombic, space group Pbca, a = 13.555(3), b = 13.991(3), c = 16.449(3) Å, V = 3119.5(11) ų, ρ_calcd = 1.725 g/cm³, Z = 8. Doubled polymeric chains with the Ag…Ag bond (3.16 Å) are also formed in structure II. Supramolecular layers are formed in the structure due to the weak π-π-stacking interaction between the aromatic groups of chains. The CF₃CO ₂ ^? anion is weakly bound to Ag⁺ (Ag-O_avg 2.790 Å).     

Organic-inorganic hybrid perovskite (C<Subscript>6</Subscript>H<Subscript>5</Subscript>(CH<Subscript>2</Subscript>)<Subscript>2</Subscript>NH<Subscript>3</Subscript>)<Subscript>2</Subscript>CdCl<Subscript>4</Subscript>: Synthesis,structural and thermal properties

The present research work reports the study on crystal structure, vibrational spectroscopy and thermal analysis of organic-inorganic hybrid compound (C₆H₅(CH₂)₂NH₃)₂CdCl₄. Single crystals of bis(phenethylammonium)tetrachlorocadmate (C₆H₅(CH₂)₂NH₃)₂CdCl₄ (PEA–Cd) were obtained by diffusion at room temperature. This compound crystallizes in the orthorhombic space group C2cb with unit cell parameters a = 7.4444(2) Å, b = 38.8965(3) Å, c = 7.3737(2) Å and Z = 4. Single crystal structure has been solved and refined to R = 0.036 and wR = 0.092. The structure consists of an extended [CdCl₄]^2– network and two [C₆H₅(CH₂)₂NH₃]⁺ cations to form a two-dimensional perovskite system. The infrared (IR) spectrum of the title compound was recorded at room temperature. Differential scanning calorimetry (DSC) was used to investigate the phase transition; this compound exhibits a reversible single solid-solid phase transition.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Low-temperature heat capacity of sodium erbium molybdophosphate Na<Subscript>2</Subscript>Er(MoO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)

Adiabatic calorimetry is used to measure the low-temperature heat capacity of Na₂Er(MoO₄)(PO₄)from 6.41 to 347.87 K. Experimental data are used to calculate the thermodynamic functions of Na₂Er(MoO₄)(PO₄), which at 298.15 K are as follows: C _p ⁰ (298.15 K) = 243,3 ± 0.4 J/(K mol), S ⁰(298.15 K) = 312.8 ± 0.8 J/(K mol), H ⁰(298.15 K) ? H ⁰(0 K) = 45280 ± 90 J/mol, and Φ⁰(298.15 K) = 136.1 ± 0.3 J/(K mol). A diffuse heat-capacity anomaly associated with splitting of the Stark levels (Schottky anomaly) is discovered in the low-temperature region.     

Structure of arsenic 8-mercaptoquinolinate: Synthesis and crystal structure of arsenic 4-methoxy-8-mercaptoquinolinate As[C<Subscript>9</Subscript>H<Subscript>5</Subscript>(OCH<Subscript>3</Subscript>)NS]<Subscript>3</Subscript>

Arsenic 4-methoxy-8-mercaptoquinolinate As[C₉H₅(4-OCH₃)NS]₃ (I) was synthesized and studied by X-ray diffraction. Crystals are trigonal: space group R3, a = b = 13.9867(4) Å, c = 12.4991(5) Å, γ = 120°, V = 2117.58(12) ų, ρ = 1.519 g/cm³, Z = 3. An arsenic atom in the crystal structure occupies a special position on axis 3. The structural unit of the crystal (neutral complex I) has symmetry C3. 4-Methoxy-8-mercaptoquinoline acts as a bidentate (N,S-) ligand. The coordination polyhedron of the arsenic atom is a symmetric octahedron (3S + 3N) or, with allowance for the lone electron pair, ψ-one-capped octahedron (3S + 3N + E). Bond lengths are as follows: As-S, 2.3179(7)Å; As…N 2.688(3) Å. The geometries of coordination polyhedra of arsenic atoms are compared in the crystal structures of As(C₉H₆NS)₃, As[C₉H₅(2-CH₃)NS]₃, and As[C₉H₅(4-CH₃)NS]₃.