Crystal structure of (3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocen-2-yl) carboxylic acid and its bis-[W(CO)5] complex·0.5C5H12: Conformation of 1,1′-diphosphaferrocenes

The structures of (3,3,4,4-tetramethyl-1,1-diphosphaferrocen-2-yl)carboxylic acid (1) and its bis-[W(CO)₅] pentane solvate complex (2) have been determined by X-ray analysis. The compound 1 crystallizes in the monoclinic P2₁ /n space group with Z = 4; a = 7.8404(9), b = 14.9441(16), c = 11.7730(14) Å, = 92.773(10)°, V = 1377.8(3) ų, and D_calc = 1.553 g cm^–3. The compound 2 crystallizes in the triclinic space group with two complex molecules and one pentane molecule in the unit cell. Cell parameters: a = 10.7070(2), b = 12.577(2), c = 13.239(3) Å, = 84.00(2), = 77.58(1), = 66.06(1)°, V = 1591.0(5) ų, and D_calc = 2.100 g cm^–3 .The fully eclipsed conformation of the phospholyl rings with P···P secondary bonding of 3.353(1) Å is observed in 1 and a partially eclipsed conformation is found in 2. The 10 possible conformations of 1,1-diphosphaferrocenes were described as the function of conformational parameter and observed geometry of the phospholyl rings.⁷ We suppose that the earlier conclusions concerning the destabilizing nature of 1,1-diphosphaferrocene conformations with < 100° cannot be considered as general. The mode of W – P coordination, the structural changes of 1 by W(CO)₅ coordination, the structural effect of phospholyl rings substitution by the –COOH group, and hydrogen bonds are analyzed.     

C−Cl...π(Ar)...Cl−C,Cl...Cl and other interactions in the structures of two 6-substituted-2,4-bis(trichloromethyl)-1,3-benzdioxin's: (I) 6-carboxymethyl; (II) 6-propionyl,an antimethanogenesis food additive

C₁₂H₃Cl₆O₄, (I),M _r=428.91, triclinic, ,a=9.197(1),b=9.336(2),c=9.830(1) Å, =79.29(1), =83.33(1), =85.38(1)°,V=822.16,Z=2,D _x=1.73 Mg m^–3,F(000)=428, (MoK)=0.71069 Å, =10.62 cm^–1, room temperature, finalR=0.033 for 2573 unique counter reflections withF _o>4(F _o). C₁₃H₁₀Cl₆O₃, (II),M _r=426.94, triclinic, ,a=9.374(2),b=9.503(1),c=9.888(4) Å, =79.26(2), =82.10(3), =84.43(1)°,V=854.88,Z=2,D _c=1.66 Mg m^–3,F(000)=428, =0.71069 Å, =10.17 cm^–1, room temperature, finalR=0.030 for 2609 unique counter reflections withF _o>4(F _o). Compounds I and II are isostructural. Centrosymmetric dimers are formed by hydrogen bonds from the two methine hydrogen atoms to the carbonyl oxygen atom. The dimers are linked by Cl...(Ar)...Cl, Cl...O and Cl...Cl interactions to form a three-dimensional pattern. The geometry associated with these interactions is discussed in terms of the electrophile: nucleophile model.     

Structural characterization of Elisabatin B and Elisabatin C

X-ray structures of Elisabatin B (1) and Elisabatin C (2) have been determined. Crystal data for 1: Triclinic, P (No. 2), a = 7.528(2) Å, b = 9.404(2) Å, c = 11.414(2) Å, = 75.363(3)°, = 86.668(4)°, = 89.683(4)°, and Z = 2. Crystal data for 2: Monoclinic, P2₁/c (No. 14), a = 8.242(2) Å, b = 14.870(2) Å, c = 13.060(2) Å, = 101.458(3)°, and Z = 4. Both compounds are highly unsaturated leading to extended aromatic conjugation. They show different intermolecular O–HO hydrogen bonds, via which 1 forms dimers, and 2 zig-zag polymeric chains.     

Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Cyclohexanone inclusion compounds of related multipedal hosts

The structures of the cyclohexanone inclusion compounds of (1) hexakis (3-hydroxy-3, 3-diphenyl-2-propynyl) benzene (H1) (triclinic, P1¯, a = 8.957(4), b = 16.69(1), c = 17.201(4) Å, = 93.82(3), = 97.61(3), and = 93.13(5)°); (2) 1,2,3,5,6,7-hexakis(3-hydroxy-3,3-diphenyl-2-propynyl)naphthalene (H2) (monoclinic, P2₁/n, a = 9.444(5), b = 18.353(5), c = 31.59(1) Å, and = 92.18(3)°) and (3) tetra(3-hydroxy-3,3-diphenyl-2-propynyl)ethylene (H3) (triclinic, P1¯, a = 14.208(2), b = 14.710(4), c = 17.915(2) Å, = 91.06(1), = 89.98(1), and = 110.60(2)°) have been determined. A second cyclohexanone inclusion compound with H1 with a different host to guest ratio (4: triclinic, P1¯, a = 9.512(2), b = 15.327(3),c = 16.151(3) Å, = 114.89(2), = 95.19(2), and = 102.67(2)°) was obtained from a 50:50 molar solution of cyclohexanone and 1,4-dioxane, which confirms the selectivity of this host for compounds with carbonyl functional groups. The thermal analysis results of all these cyclohexanone inclusion compounds are reported.     

Structures and nonlinear optical properties of polar 2-amino-1,2,3-triazolequinone derivatives

A series of phenyldialkylamine, dimethoxyphenyl, and nitrothiophene derivatives of 2-amino-1,2,3-triazolequinones was characterized by NMR, IR, mass spectroscopy, cyclic voltammetry, and chemical analyses. The solvatochromic procedure was used to evaluate the potential of nine compounds for nonlinear optical applications, and the possible failure of this model is discussed. The crystal structures of seven compounds were determined: (4) P2₁/c, a = 15.430(3) Å, b = 7.633(2) Å, c = 15.940(3) Å, = 105.19(3)° (5) P2₁/c, a = 20.201(2) Å, b = 9.6579(9) Å , c = 18.517(2) Å, = 95.907(2)° (6) P-1, a = 7.769(2) Å, b = 8.515(3) Å, c = 17.312(5) Å, = 89.347(7)°, = 83.219(6)°, = 86.001(7)° (7) P-1, a = 8.1365(7) Å, b = 8.9605(8) Å, c = 11.630(1) Å, = 79.553(2)°, = 75.048(2)°, = 82.080(2)° (8) P-1, a = 8.298(3) Å, b = 9.720(3) Å, c = 10.033(3) Å, = 84.803(6)°, = 83.735(6)°, = 77.659(5)° (10) P2₁/n, a = 8.4300(7) Å, b = 13.980(1) Å, c = 13.975(1) Å, = 106.590(2)° (12) P2₁/n, a = 7.715(2) Å, b = 14.206(3) Å, c = 12.758(3) Å, = 91.016(5)°.     

N-Arylmaleimide derivatives

Nine phenyl substituted N-phenylmaleimide monomers for photopolymerization studies have been characterized by x-ray crystallography. Structures for N-(2-t-butylphenyl)maleimide (1), P2₁/n, a = 10.197(3) Å, b = 11.904(4) Å, c = 10.496(5) Å, = 100.61(3)° N-(2-trifluoromethylphenyl)maleimide (2), P2₁/c, a = 11.763(8) Å, b = 10.699(9) Å, c = 8.284(5) Å, = 90.02(5)° N-(2,6-diisopropylphenyl)maleimide hemibenzene solvate (3), Pc, a = 16.747(6) Å, b = 8.552(3) Å, c = 12.899(4) Å, = 105.08(3)° N-(2,6-diisopropylphenyl) maleimide (unsolvated) (4), C2/c, a = 28.146(10) Å, b = 8.434(4) Å, c = 12.881(4) Å, = 92.20(4)° N-(2-bromo-3,5-bis(trifluoromethyl)phenyl) maleimide (5), P2₁/n, a = 8.7115(16) Å, b = 16.125(3) Å, c = 9.6707(19) Å, = 99.757(15)° N-(2-phenylphenyl)maleimide (6), P2₁/n, a = 8.519(4) Å, b = 13.742(5) Å, c = 11.147(4) Å, = 92.25(3)° N-(4-methoxyphenyl)maleimide (7), P2₁/n, a = 9.320(3) Å, b = 6.621(2) Å, c = 16.059(6) Å, = 99.58(3)° N-(2-trifluoromethylphenyl)-2-methylmaleimide (8), Fdd2, a = 43.362(12) Å, b = 8.202(2) Å, c = 12.720(4) Å and N-(2-trifluoromethylphenyl)-2-methanosuccinimide (9), Cc, a = 7.708(2) Å, b = 22.191(9) Å, c = 7.137(2) Å, = 115.76(2)° are described. Molecules with bulky 2-substituents show larger rotations between the mean phenyl and maleimide ring planes, and varying degrees of distortion to the imide group.     

Syntheses and structural characterization of two novel α-diketone bisacylhydrazones

Benzil bis(3,4,5-trimethoxybenzohydrazone) (I) and 3,3-dimethoxybenzil bis(benzohydrazone) (II) were synthesized by condensation, acid catalyzed, of the proper -diketone and the corresponding hydrazide. Compound I crystallizes in the monoclinic system, space group P2₁/n, with a = 11.464(2), b = 21.098(4), c = 13.837(2) Å, = 109.50(1)° V = 3154.8(9) ų and D _c = 1.319 g/cm³ for Z = 4. Compound II crystallizes in the triclinic system, space group P , with a = 11.106(3), b = 11.728(10), c = 10.656(5) Å, = 91.86(2), = 92.68(3), = 110.00(2)° V = 1301.1(7) ų and D _c = 1.293 g/cm³ for Z = 2.     

Synthesis and structure of a new hybrid vanadium arsenate: [VO<Subscript>2</Subscript>(phen)]<Subscript>2</Subscript>(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)⋅H<Subscript>3</Subscript>O

A new hybrid vanadium arsenate [VO₂(phen)]₂(H₂AsO₄)H₃O 1 (phen = 1,10-phenanthroline) was synthesized under hydrothermal reaction conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis (TGA), IR and elemental analyses. Crystal data for 1: monoclinic, P2₁/n, a = 9.175(2) Å, b = 18.638(5) Å, c = 14.482(4) Å, = 102.333(3), V = 2419(1) ų, Z = 4. Compound 1 is composed of discrete tricyclic (VO₂)₂(H₂AsO₄) cluster decorated with two phen ligands. The discrete arsenic–vanadium clusters are extended into three-dimensional supramolecular arrays via – stacking interactions of phen groups.     

Synthesis and crystal structure of bis(2,2′-bipyridyl)mononitritozinc(II) perchlorate. An example of a six-coordinate cis-octahedral ZnN4O2 chromophore

The crystal structure of bis(2,2-bipyridyl)mononitritozinc(II) perchlorate, [Zn(bipy)₂ (ONO)][ClO₄] (1) has been determined. The complex is monoclinic, with a = 10.9195(4) Å, b = 12.2320(5) Å, c = 16.5477(8) Å, = 105.6150(10), P2₁/n space group, with final R1 = 0.0657 and wR2 = 0.1630. The complex involves a [Zn(bipy)₂ (ONO)]⁺ cation and a [ClO₄]^– anion. The ZnN₄O₂ chromophore is six-coordinate, with a cis-distortion of the two oxygens of the nitrite, O(1) and O(2), at distances 2.216(5) and 2.197(5) Å from the zinc (Zn– O _mean = 2.206(5) Å, O = 0.019(5) Å) and two out of plane Zn–N bonds, Zn–N(2) and Zn–N(3), at 2.129(4) and 2.135(4) Å (Zn–n _mean/out = 2.132(4) Å, n _2,3 = 0.006(4) Å). The two inplane nitrogens, N(1) and N(4), at distances Zn–N(1) = 2.090(4) and Zn–N(4) = 2.085(4) Å (Zn–n _mean/in = 2.087(4) Å, n _1,4 = 0.005(4) Å) are greater than 2.0 Å, but slightly shorter than the axial bonds. The inplane angles ₁, ₂, and ₃ in 1 have values 150.33(18), 108.98(17), and 99.73(18) respectively. The stereochemistry is cis-distorted octahedral, with an ₃ = 99.37(18), which is lower than ₃ = 103.4(1) observed in [Zn(bipy)₂(ONO)][NO₃] (5). Comparison with the corresponding [Cu(bipy)₂(ONO)][Y] complexes suggested that the cis-distortion of the CuN₄O₂ chromophore in the copper(II) series does not originate in the Jahn–Teller or pseudo-Jahn–Teller effect.     

Nonpreorganized neutral acyclic anion receptors: Structural investigations of N,N′-diphenyl-1, 3-benzenedisulfonamide and N,N′bis(4-t-butylphenyl)-1, 3-benzenedisulfonamide

The structure of N,N-diphenyl-1,3-benzenedisulfonamide (1) was determined by single crystal X-ray diffraction. It crystallizes in P2₁/n with cell dimensions: a = 11.8390(6) Å, b = 12.3950(10) Å, c = 12.1184(10) Å, = 94.388(6)°, and V = 1773.1(2) ų. Its di-t-butyl derivative, N,N-bis(4-t-butylphenyl)-1,3-benzenedisulfonamide (2), was prepared and structurally characterized as two solvated structures. Both crystallize in P with cell dimensions: 2 CF₃CH₂OH, a = 9.469(2) Å, b = 10.0039(18) Å, c = 16.385(3) Å, = 85.561(16)°, = 83.035(18)°, = 72.459(16), and V = 1467.7(5) ų; 2 ClCH₂CH₂Cl, a = 9.559(2) Å, b = 9.8125(12) Å, c = 17.100(6) Å, = 82.495(19)°, = 83.47(2)°, = 70.100(15), and V = 1491.1(6) ų. The structures exhibit hydrogen-bonding, and are evaluated in terms of preorganization for anion binding.     

Short H· · ·H distances in norbornene derivatives

A short H···H intramolecular interaction was reported previously for an anhydride of syn-sesquinorbornene. The synthesis and structure of a such an anhydride with an additional five-membered dithiole ring has been investigated. While hydrogen atom positions are not accurately located, the 1.62 Å separation indicates this molecule is a candidate for the shortest H···H interaction. Two cycloadducts of norbornadiene, which literature suggests might exhibit additional short interactions, are reported also; however, the isomers with minimal intramolecular interactions are the isolated products. C₂₂H₂₀O₃S₂, 3, crystallizes in P with a = 10.881(4), b = 13.712(8), C = 6.548(8) Å, = 101.32(6), = 107.49(5), = 90.49(4)°, D _calc = 1.445 g cm^–3, and Z = 2, C₂₁H₂₀O₄Cl₈, 5, in P2₁/n with a = 8.168(2), b = 13.488(4), c = 23.500(6) Å, = 94.72(2)°, D _calc = 1.597 g cm^–3, and Z = 4, C₂₁H₂₈O₄, 6, in P> with a = 12.667(2), b = 12.792(2), c = 12.540(2) Å, = 113.51(1), = 98.18(1), = 74.39(1)°, D _calc = 1.276 g cm^–3, and Z = 4.     

A structural study on gallium and indium β-diketonates

In an attempt to prepare pentacoordinate chlorobis(-diketonato) gallium(III) and indium(III) complexes only the corresponding tris-products, Ga(PhCOCHCOPh)₃ (1), Ga(^tBuCOCHCO^tBu)₃ (1a), and In(PhCOCHCOPh)₃ (2), could be isolated. The crystal and molecular structures of 1 and 2 were determined. Both the complexes were found to have triclinc crystal system, with P1 space group. Cell parameters: 1 – a = 9.913(3) Å, b = 10.534(6) Å, c = 18.05(2) Å, = 93.86(5)°, = 94.40(4)°, = 106.58(4)°, V = 1805(2) ų, z = 2; 2 – a = 10.507(3) Å, b = 11.448(3) Å, c = 16.322(4) Å, = 107.38(2)°, = 97.38(2)°, = 102.23(2)°, V = 1792(1) ų, z = 2.     

Structure and properties of potential nonlinear optical materials

The synthesis, structure and properties of four ferrocene derivatives of 2-amino-1,2,3-triazole are reported. Solvatochromism is used as a screening process to assess the potential nonlinear optical behavior of these compounds. In general, this technique involves a number of assumptions, which may not be valid for organometallic complexes. Compound 3 crystallizes in space group P-1 with cell dimensions a = 5.771(2), b = 19.048(5), c = 19.343(5) Å and = 61.104(4), = 88.410(5), = 89.858(5)°; compound 5 crystallizes in space group P2₁/c with cell dimensions a = 12.545(2), b = 13.308(2), c = 20.513(4) Å and = 104.035(3)°; compound 9 crystallizes in space group P2₁/n with cell dimensions a = 12.599(4), b = 14.734(4), c = 13.619(5) Å, and = 107.63(2); compound 11 crystallizes in space group P-1 with cell dimensions a = 7.638(3), b = 9.619(4), c = 12.692(5) Å and = 77.588(7), = 78.416(7), = 71.357(7).     

Crystal structures of diphosphinated group 6 Fischer alkoxy carbenes

The crystal structures of four diphosphinated Group 6 Fischer alkoxy carbenes with the compositions fac-(dppe)(CO)₃M–C(OR)(R) (R = Me, R = Et, M = Cr, 1; R = Ph, R = Me, M = Cr, 2; R = Me, R = Me, M = W, 3; R/OR = 3-methyl-2-oxacyclopentylidenyl, M = Cr, 4) have been determined at 243 K. Compound 1 crystallizes in the monoclinic system, space group P2₁/c with a = 11.2243(11) Å, b = 18.5998(18) Å, c = 15.1260(15) Å, = 107.056(4), V = 3019.0(5) ų, and Z = 4. Compound 2 crystallizes in the monoclinic system, space group P2₁/c with a = 11.8102(9) Å, b = 18.3152(14) Å, c = 15.0262(12) Å, = 93.753(3), V = 3243.3(4) ų, and Z = 4. Compound 3 crystallizes in the monoclinic system, space group P2₁/c with a = 11.3458(6) Å, b = 18.5772(9) Å, c = 15.3883(8) Å, = 108.576(6), V = 3074.5(3) ų, and Z = 4. Compound 4 crystallizes in the orthorhombic system, space group Pna2₁ with a = 22.6509(14) Å, b = 9.8118(6) Å, c = 13.7507(8) Å, V = 3056.0(3) ų, and Z = 4. Steric repulsions with the dppe ligand favor a conformation with the alkoxy moiety directed toward the dppe backbone, in an E geometry, in 1–4.     

Study of the sulfur atom as hydrogen bond acceptor in N(2)-pyridylmethyl-N′-arylthioureas

The hydrogen acceptor capability of the sulfur atom in the biologically relevant N-2-pyridylmethyl-N-arilthioureas was explored. N-2-Pyridylmethyl thioreas were selected to avoid the formation of intramolecular six-membered hydrogen-bonded ring. The compounds studied were N-2-pyridylmethyl-N-phenylthiourea (1), N-2-pyridylmethyl-N-2-methoxythiourea (2), N-2-pyridylmethyl-N-4-methoxyphenylthiourea (3), and N-2-pyridylmethyl-N-4-bromophenylthiourea (4). 1 crystallizes in the monoclinic space group P2₁/c, with a = 7.419(1) Å, b = 18.437(2) Å, c = 9.656(1) Å, = 106.277(6)°, V = 1267.8(3) ų, Z = 4. 2 crystallizes in the monoclinic space group P2₁/c, with a = 8.064(2) Å, b = 18.382(7) Å, c = 9.865(5) Å, = 97.81(3)°, V = 1448.8(11) ų, Z = 4. 3 crystallizes in the monoclinic space group P2₁/c, with a = 11.472(1) Å, b = 13.520(1) Å, c = 10.088(1) Å, = 112.60(1)°, V = 1444.5(2) ų, Z = 4. 4 crystallizes in the triclinic space group P-1, with a = 4.583(3) Å, b = 10.263(3) Å, c = 14.396(3) Å, = 77.92(2)°, = 88.55(4)°, = 80.02(4)°, V = 652.1(5) ų, Z = 2. Both thiourea N–H groups form intermolecular hydrogen bonds, one with the thione sulfur atom and the other with the pyridine nitrogen atom but the H-bonding schemes are not the same maybe due to the flexibility of the molecules.     

Crystal structure of tolazoline hydrochloride

The title compound (C₁₀H₁₂N₂ HC1,M _r =196.7) crystallizes in the monoclinic space groupP2₁/c witha=8.997(1),b=9.665(1) andc=12.290(1) Å,=104.41(1)°,V=1035·1 ų,D _x =1.262 g·cm^–3 forZ=4,=29.4 cm^–1, (CuK)=1.54178 Å,F(000)=416. FinalR=0.051 (R _w =0.063) for 1937 reflections collected on a diffractometer. The structure was solved by direct methods. The two N atoms of the imidazoline ring are equivalent due to protonation and they participate in N-HCl hydrogen bonds which join the molecules into infinite chains. The imidazoline ring is approximately planar and is oriented perpendicular to the plane of the benzene ring. The separations of the two N atoms from the center of the aromatic ring are 4.691(3) and 4.598(3) Å, close to the values found in the crystal structures of clonidinelike agents.     

Molecular structure of 1-phenyl-1-dimethylamino-4,4-bis(trimethylsilyl)-2-aza-3λ3-phosphabutadiene-1,3

The crystal and molecular structure of 1-phenyl-1-dimethylamino-4,4-bis(trimethylsilyl)-2-aza-3³-phosphabutadiene-1,3, Me₂N(Ph)C=N—P=C(SiMe₃)₂ (1), has been determined. Crystal data: triclinic, P1¯, a = 8.975(4), b = 10.001(5), c = 12.440(6) Å, = 79.04(4), = 77.98(4), = 73.07(4)°, V = 1034.7 ų, Z = 2, and D _c = 1.08 g cm^–3. The main geometrical parameters of 1 as well as ab initio (HF/6-31+G**) calculations of the model systems show no clear evidence of high efficiency of the (C=N)— (P=C) conjugation.     

Structural studies of N(4)-substituted thiosemicarbazones prepared from 4-formylantipyrine and a thiourea derived from 4-aminoantipyrine

Reaction of 4-formylantipyrine with N(4)-dimethylthiosemicarbazide and 3-piperidylthiosemicarbazide produces the N(4)-dimethylthiosemicarbazone (1), and the 3-piperidyl-thiosemicarbazone (2), respectively. Compound 1 is triclinic, space group P-1 with a = 6.329(1) Å, b = 11.699(1) Å, c = 11.943(1) Å, = 65.83(1)°, = 80.83(1)°, = 84.90(1)°, and V = 796.1(1) ų with Z = 2, for D _calc = 1.324 g/cm³. Compound 2 is triclinic, space group P-1 with a = 6.784(1) Å, b = 10.485(2) Å, c = 13.462(3) Å, = 102.05(2)°, = 98.61(2)°, = 101.32(2)°, and V = 899.8(5) ų with Z = 2, for D _calc = 1.319 g/cm³. Reaction of 4-aminoantipyrine with phenyl isothiocyanate produced N-antipyrine-N-phenylthiourea (3). Compound 3 is monoclinic, space group P2₁/n with a = 6.863(7) Å, b = 15.361(3) Å, c = 16.332(5) Å, = 90.35(6)°, and V = 1720.7(18) ų with Z = 4, for D _calc = 1.306 g/cm³. Compounds 1 and 2 have intermolecular hydrogen bonding between the carbonyl oxygen of the antipyrine moiety and the NH hydrogen of the thiosemicarbazone moiety. In 3 the two unique molecules are held together as a dimer by interactions of the two thiourea NH's and the antipyrine moiety's\break oxygen.     

Meisenheimer complex from picric acid and diisopropylcarbodiimide

Reaction of picric acid with diisopropylcarbodiimide produces a pale yellow 1:1 adduct N-(2,4,6-trinitrophenyl)-N,N-di(isopropyl)urea (5) and a 1:2 adduct fluorescent red zwitterionic Meisenheimer complex (6) as approximately N,N,N-tri(isopropyl)-4-oxo-6-(isopropyliminio)-2-s-(2H)triazinespiro-1-2,4,6-trinitro cyclohexadienylide. Crystals of (5) are triclinic, P-1 (#2), with a = 10.444(13) Å, b = 15.47(2) Å, c = 17.74(2) Å, = 110.43(9)°, = 99.85(10)°, = 92.78(10)°, V = 2629(6) ų for Z = 6 (three molecules per asymmetric unit). Crystals of (6) are orthorhombic, Pna2₁ (#33), with a = 24.12(4), b = 9.011(19) Å, c = 10.87(2) Å, V = 2362(8) ų for Z = 4. Nitro groups in the Meisenheimer complex are twisted 2–8° from the mean formerly aryl ring plane; in (5), nitro groups are twisted out of the aryl plane by 11–62°. In the Meisenheimer complex, cationic charge is distributed over an iminium/guanidinium group; anion charge is distributed over the cyclohexadienide ring and attached nitro groups.