Home Physical Sciences Preparation and crystal structure of a cationic olefin polymerization precatalyst: (1,7-bis(2,6–dichlorophenyl)-1,7-di-aza-4-oxo-heptan-1,4,7-triyl)dimethyl zirconium(IV), C18H20Cl4N2OZr
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Preparation and crystal structure of a cationic olefin polymerization precatalyst: (1,7-bis(2,6–dichlorophenyl)-1,7-di-aza-4-oxo-heptan-1,4,7-triyl)dimethyl zirconium(IV), C18H20Cl4N2OZr

  • Peter J. Bonitatibus ORCID logo EMAIL logo and Guido J. Reiss
Published/Copyright: November 6, 2020
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Zeitschrift für Kristallographie - New Crystal Structures
From the journal Zeitschrift für Kristallographie - New Crystal Structures Volume 236 Issue 1

Abstract

C18H20Cl4N2OZr, monoclinic, Pnma (no. 62), a = 12.457(3) Å, b = 22.806(8) Å, c = 7.398(2) Å, V = 2101.7(11) Å3, Z = 4, Rgt(F) = 0.0291, wRref(F2) = 0.0685, T = 110 K.

CCDC no.: 2036254

The molecular structure is shown in the Figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Colorless plate
Size:0.50 × 0.30 × 0.10 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:1.04 mm−1
Diffractometer, scan mode:Siemens P4, ω
θmax, completeness:23.0°, 94%
N(hkl)measured, N(hkl)unique, Rint:3537, 1404, 0.048
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 1174
N(param)refined:139
Programs:XSCANS [1], SHELX [2], [3], [4], Diamond [5]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Zr0.74304 (4)0.7500000.68161 (7)0.0302 (2)
Cl10.63067 (8)0.61740 (4)0.99885 (14)0.0474 (3)
Cl20.85483 (9)0.61215 (5)0.37369 (14)0.0529 (3)
O0.5856 (3)0.7500000.5144 (4)0.0312 (8)
N0.6935 (2)0.66376 (11)0.6302 (4)0.0318 (7)
C10.7687 (6)0.7500000.9815 (9)0.0440 (15)
H110.805 (3)0.7816 (12)1.013 (5)0.064 (14)*
H120.705 (3)0.7500001.037 (9)0.09 (3)*
C20.9116 (5)0.7500000.5820 (11)0.0499 (16)
H210.948 (3)0.7160 (11)0.605 (5)0.060 (13)*
H220.914 (5)0.7500000.461 (3)0.08 (3)*
C30.5669 (3)0.69755 (14)0.4115 (5)0.0394 (9)
H3A0.6122800.6967700.3049610.047*
H3B0.4924960.6952850.3737110.047*
C40.5940 (3)0.64784 (15)0.5352 (5)0.0400 (10)
H4A0.5364130.6415470.6212260.048*
H4B0.6043830.6120780.4664230.048*
C50.7530 (3)0.61610 (13)0.6965 (5)0.0309 (8)
C60.7366 (3)0.59144 (14)0.8692 (5)0.0332 (9)
C70.7987 (3)0.54664 (14)0.9378 (6)0.0414 (10)
H70.7855590.5319231.0529180.050*
C80.8802 (3)0.52399 (15)0.8342 (6)0.0475 (11)
H80.9236210.4943710.8802850.057*
C90.8979 (3)0.54501 (15)0.6619 (6)0.0444 (11)
H90.9523120.5291650.5910220.053*
C100.8348 (3)0.58951 (14)0.5956 (5)0.0343 (9)

Source of material

Synthesis of the title complex [NONCl]ZrMe2, was carried out by reaction of the tridentate H2[NONCI] ligand [(2,6-Cl2C6H3NHCH2CH2)2O] with tetrakis(dimethylamide)zirconium(IV) to form [NONCI]Zr(NMe2)2 initially, followed by stepwise conversion from [NONCI]Zr(NMe2)2 to [NONCI]ZrCl2 with subsequent methylation to form [NONCI]ZrMe2 (structure pictured in the Figure). Synthesis of the ligand involved reaction of the lithium anilide (protected with a trimethylsilyl group) [6] with commercially available diethylene glycol di(p-toluenesulfonate) in THF, followed by hydrolysis with aqueous HCl. Synthesis of all compounds required to produce [NONCI]ZrMe2 are described below.

2,6-Dichloro(trimethylsilyl)aniline: 5.0 g (30.86 mmol) of 2,6-dichloroaniline was dissolved in 100 mL of a 70:30 mixture of THF:Et2O. Potassium hydride (1.24 g, 30.92 mmol) was added in small portions at room temperature under N2 with stirring, so as to keep bubbling to a minimum. With each addition of solid KH bubbling occurred, and more KH was added only when the solution homogenized. After 2 h of stirring, the resulting light orange-yellow solution of anilide was treated with chlorotrimethylsilane (3.35 g, 30.84 mmol). Upon addition, the color was discharged to originate a cloudy white suspension. After 2 h, all volatiles were removed and the product was extracted with 60 mL of pentane and filtered through a pad of celite. A light-yellow/colorless oil-liquid was isolated (80.6%) upon removal of pentane. 1H NMR (300 MHz, CDCl3): d 7.20 (d, 2, Hm), 6.65 (t, 1, Hp), 4.01 (br s, 1, NH), 0.318 (s, 9, Si(CH3)3).

H2[NONCl] ligand [(2,6–Cl2C6H3NHCH2CH2)2O]: 2.22 g (9.48 mmol) of 2,6-dichloro(trimethylsilyl)aniline was dissolved in 100 mL of THF. This was set to chill for 90 min at −20 °C. n-BuLi (3.80 mL, 9.5 mmol) was added dropwise as a 2.5 M solution in hexanes over 10 min with stirring under N2. This was allowed to stir for hours originating a deep-orange homogeneous solution of lithium anilide at room temperature. The reaction was again set to chill for 45 min at −20 °C, and then treated with solid diethylene glycol di(p-toluenesulfonate) over a 7-min period in small portions (4.74 mmol). This reaction was allowed to stir for 3 days. Next, the homogeneous mixture was taken to dryness, and the resulting orange microcrystalline solid was stirred for 60 min in 100 mL of pentane. A very light-yellow solution was obtained upon filtration through a celite pad. All volatiles were removed to obtain an almost colorless oil which completely solidified to a white solid. The white solid was treated with 40 mL of a 3 N HCl solution after dissolution with 100 mL of Et2O. Hydrolysis proceeded overnight with stirring at 40 °C. The reaction was then quenched with 60 mL of 3 N KOH (until slightly basic). The organic phase was separated and the aqueous layer extracted with another 50 mL of Et2O. The organics were combined, washed twice with distilled water (until neutral), dried over MgSO4, and filtered. This compound was isolated as a light-orange oil (80%), which solidified over the course of a fortnight upon Et2O removal. FAB-MS: positive ion (M+H)+, measured (calc'd.): 393.0106 ± 0.0012 (393.009499), 1H NMR (300 MHz, CDCl3): d 7.23 (d, 4, Hm), 6.79 (t, 2, Hp), 4.51 (br s, 2, NH), 3.61 (t, 4, OCH2), 3.55 (t, 4, NHCH2).

[NONCI]Zr(NMe2)2: H2[NONCI] was dissolved in 15 mL of pentane (0.48 g, 1.22 mmol). To this was added as a 5 mL pentane solution, Zr(NMe2)4 (0.33 g, 1.22 mmol). This was allowed to stir overnight, filtered through a bed of celite, and concentrated in vacuo to a yellow solid (0.61 g, 88%). This reaction has been scaled up to 1.5 g of H2[NONCI]. 1H NMR (300 MHz, C6D6): d 7.11 (d, 4, Hm), 6.316 (t, 2, Hp), 3.55 (t, 4, OCH2), 3.48 (t, 4, NCH2), 2.88 (s, 12, NMe2).

[NONCI]ZrCl2: [NONCI]Zr(NMe2)2 was dissolved in 40 mL of Et2O (0.61 g, 1.07 mmol) to originate a light-yellow solution. To this was added neat chlorotrimethylsilane (2.31 g, 21.26 mmol) at room temperature under N2 with vigorous stirring. After 60 min, the reaction was only slightly turbid, so the mixture was allowed to stir overnight. All volatiles were removed in vacuo to yield the compound as a fine off-white powder (0.53 g, 90%). In some cases, the product was washed with pentane. 1H NMR (300 MHz, C6D6): d 6.93 (d, 4, Hm), 6.28 (t, 2, Hp), 3.57 (t, 4, OCH2), 3.38 (t, 4, NCH2); 1H NMR (300 MHz, toluene-d8): d 6.90 (d, 4, Hm), 6.28 (t, 2, Hp), 3.62 (t, 4, OCH2), 3.37 (t, 4, NCH2).

[NONCI]ZrMe2: [NONCI]ZrCl2 was suspended in 20 mL of Et2O (0.50 g, 0.91 mmol). This was set to chill at −20 °C for 30 min after which 0.5 mL of a 3.7 M solution of MeMgBr in Et2O (also at −20 °C) was added via syringe. The white suspension appeared to homogenize to a light-yellow solution upon addition of the Grignard reagent. This was set to stir at room temperature for 10 min until the reaction gave deposition of brown solids. At this point, 5 mL of dioxane were added which initiated the precipitation of a fine white powder. After stirring for an additional 20 min, all volatiles were removed in vacuo. The product was extracted using 40 mL of toluene, filtered through a pad of celite, and concentrated to dryness to yield the compound as a pale-white solid (0.326 g, 70%). Crystals suitable for X-ray diffraction were obtained overnight from a concentrated toluene solution sitting at −20 °C. Anal.: found (calc’d.): C: 41.96 (42.11)%, H: 4.04 (3.93)%, N: 5.37 (5.46)%, Cl: 27.69 (27.62)%; 1H NMR (300 MHz, C6D6): d 7.081 (d, 4, Hm), 6.371 (t, 2, Hp), 3.479 (t, 4, OCH2), 3.35 (t, 4, NCH2), 0.67 (s, 6, CH3).

Experimental details

Coordinates of hydrogen atoms of the methyl groups were refined with a restrained C–H distance and individually refined Uiso parameters. All other H atoms were included using the standard riding models of the SHELX system [3] with constrained Uiso parameters (Uiso = 1.2Ueq(C)). The data collection which dates back many years was accidentally interrupted. Thus, the completeness is only 94% in the choosen Ewald sphere, but we still achieved a data to parameter ratio of 10:1.

Comparing the title structure containing the 2,6-dichlorophenyl moiety with the structure of the analogous literature known 2,6-dimethylphenyl derivative, an isomorphous structural relation (same space group type, and indeed almost the same coordinates) is present, if the methyl group is seen as a pseudo atom.

Furthermore in contrast to the literature known 2,6-dimethylphenyl derivative [6], for the title structure, we were able to show that the two methyl groups exactly fulfill the crystallographically imposed mirror symmetry (see the Figure) of the space group Pnma.

Comment

The title complex, [NONCI]ZrMe2, was obtained in 70% colorless crystalline yield from toluene and thoroughly characterized by means of X-ray diffraction and bulk analyses. The asymmetric unit of the title structure contains one half of the title complex (see the Figure), located on a mirror plane. Thus, the atoms Zr, O, C1, and C2 and one hydrogen atom of each methyl group (C1, C2) occupy the 4c Wyckoff site (transparent, red plane in the Figure). This X-ray study confirmed that the structure contains axial amido groups and a highly distorted trigonal bipyramidal geometry of zirconium(IV) with a N–Zr–N′ angle of 139.5(2)° (see the Figure). The Zr–C1 and Zr–C2 bond lengths, 2.225(7) and 2.242(6) Å respectively, are very close to being statistically equivalent, while the O–Zr–C1 and O–Zr–C2 angles, 130.4(2)° and 128.4(2)° respectively, are statistically distinct. On the NMR time scale (solution NMR), no structure lower than C2v symmetry was detected.

A Cambridge Structural Database [7] search shows closely related examples, namely the bis(2,6-dimethylphenyl derivative, [NONMe]ZrMe2, [6] as well as the N,N-bis(2-(2,6-dichloroanilino)ethyl)-N-methylamine-N,N′,N″ derivative, [NNNCI]ZrMe2 [8]. While all three dimethylzirconium(IV) complexes are structurally very similar (near identical), they display different reactivity. Both [NONMe]ZrMe2 and [NONCI]ZrMe2 can be activated with one equivalent of [HNMe2Ph][B(C6F5)4] to form [(NONE)Zr(Me)(NMe2Ph)][B(C6F5)4] where E = Me or Cl, however the former is substitutionally inert (with respect to NMe2Ph exchange) relative to the latter title complex [6]. Activation of [NONCI]ZrMe2 in bromobenzene at 0 °C generated a catalyst for the cationic polymerization of 1-hexene to poly(1-hexene) and shows some semblance to the rather highly active and more stable catalyst [NNNCI]ZrMe2 reported previously [8].

Corresponding author: Peter J. Bonitatibus, Jr., Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute Cogswell Laboratory, 110 8th Street, Troy, NY12180-3590, USA, E-mail:

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

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Received: 2020-09-18
Accepted: 2020-10-12
Published Online: 2020-11-06
Published in Print: 2021-01-26

© 2020 Peter J. Bonitatibus and Guido J. Reiss, published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  64. Crystal structure of (1aS,1a1S,2S)-4a-butoxy-1a,1a1,2,4a,5,6-hexahydro-1H-cyclobuta[de]naphthalen-2-yl-4-nitrobenzoate, C22H25NO5
  65. Crystal structure of carbonyl(2-oxopyridin-1(2H)-olato-k2O,O′)(triphenylarsine-κAs)rhodium(I), C24H19AsNO3Rh
  66. Crystal structure of catena-poly[triqua-bis(μ2-4-carboxy-2-(1H-tetrazol-1-yl)-1H-imidazole-5-carboxylato-k3N,O:O′)barium(II)] tetrahydrate, C14H14BaN12O15
  67. Crystal structure of (E)-3′,6′-bis(ethylamino)-2-((quinoxalin-2-ylmethylene)amino)spiro[isoindoline-1,9′-xanthen]-3-one, C35H32N6O2
  68. Crystal structure of diaqua-bis(μ2-5-chloro-salicylato-κ3O,O′:O′)-bis(5-chloro-salicylato-κ2O,O′)-bis(1,10-phenanthroline-κ2N,N′) dilead(II) – water (1/2), C52H36C14N4O14Pb2·2(H2O)
  69. Crystal structure of (E)-2-(4-ethoxycarbonyl-3,5-dimethyl-2-(pyrrole-2-ylmethyleneamino)-3′,6′-dihydroxylspiro[isoindoline-1,9′-xanthen]-3-one-methanol (1/1), C31H29N3O7
  70. The crystal structure of 5H-dibenzo[b,e]azepine-6,11-dione, C14H9NO2
  71. Crystal structure of (E)-2-(4-fluoro-2-(trifluoromethyl)benzylidene)-7-methoxy-3,4-dihydronaphthalen-1(2H)-one, C19H14F4O2
  72. The crystal structure of N-(2-methoxy-4,5-bis[phenylselanyl]phenyl)picolinamide, C25H20N2O2Se2
  73. The crystal structure of (E)-2-(5-bromo-2-hydroxybenzylidene)-N-phenylhydrazine-1- carboxamide monohydrate, C14H14BrN3O3
  74. Crystal structure of fac-tricarbonyl-(nitrato-k1O)-bis(pyridine-κN)-rhenium, C13H10O6N3Re
  75. Crystal structure of (E)-2-(((1H-pyrrol-2-yl)methylene)amino)-3′,6′-dihydroxyspiro[isoindoline-1,9′-xanthen]-3-one — methanol (1/2), C27H25N3O6
  76. The crystal structure of 4-amino-N′-(4-aminobenzoyl)benzohydrazide monohydrate, C14H16N4O3
  77. Crystal structure of bis(amino(carbamothioylamino)methaniminium) 5-hydroxyisophthalate monohydrate, C12H20N8O6S2
  78. The crystal structure of 2-(chloromethyl)pyridine, C6H6ClN
  79. The crystal structure of 1-bromo-4-iodo-benzene, C6H4BrI
  80. The crystal structure of 2,6-dimethyl-4-nitro-phenol, C8H9NO3
  81. The crystal structure of 3-chloropropionic acid, C3H5ClO2
  82. The crystal structure of 2-(2-methoxyphenyl)acetic acid, C9H10O3
https://doi.org/10.1515/ncrs-2020-0464
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Articles in the same Issue

  1. Frontmatter
  2. New Crystal Structures
  3. The crystal structure of 3-oxo-urs-12-en-28-oic acid, C30H46O3·1/6H2O
  4. The crystal structure of (3S,12R,20R,24R)-3,12-diacetyl-20,24-epoxy-dammarane-3,12,25–triol–ethyl acetate (4/1), C34H56O6⋅ 0.25(C4H8O2)
  5. A new polymorph of tetrakis(dimethylammonium) catena-poly[tetrakis(μ2-sulfato-κ2O:O′)dizinc(II)], Zn2C8H32N4O16S4
  6. Crystal structure of 10-oxysophoridine, C15H22N2O2
  7. The crystal structure of (5R,8R,9R,10R,12R,13R,14R)-12-hydroxy-4,4,8,10,14-pentamethyl-17-((R)-2,6,6-trimethyltetrahydro-2H-pyran-2-yl)tetradecahydro-3H-cyclopenta[a]phenanthrene-3,6(2H)-dione, C30H48O4
  8. Synthesis, crystal structure and optical property of 1,6-bis(p-tolylthio)pyrene, C30H22S2
  9. The crystal structure of hexakis(2-(pyridin-2-ylamino)pyridin-1-ium) decavanadate(V) dihydrate, C60H64N18O30V10
  10. Preparation and crystal structure of a cationic olefin polymerization precatalyst: (1,7-bis(2,6–dichlorophenyl)-1,7-di-aza-4-oxo-heptan-1,4,7-triyl)dimethyl zirconium(IV), C18H20Cl4N2OZr
  11. The crystal structure of fac-tricarbonyl(4,4-dimethyl-2,2-dipyridyl-κ2N,N′)- (pyrazole-κN)rhenium(I) nitrate, C18H16O3N4Re
  12. Synthesis and crystal structure of hexaaquacopper(II) 2,5-dicarboxyterephthalate, C10H16O14Cu
  13. The crystal structure of (8R,10R,12R,14R)- 12-hydroxy-16-(5-(2-hydroxypropan-2-yl)-2-methyltetrahydrofuran-2-yl)- 4,4,8,10,14-pentamethyltetradecahydro-3H- cyclopenta[a]phenanthrene-3,6(2H)-dione, C30H48O5
  14. Structure of the mixed crystal (S)-(6-(bromo/chloro)-2-methoxy-2,6-dihydroquinolin-3-yl)(phenyl)methanol, C17H14Br0.5Cl0.5NO2
  15. The crystal structure of trans-tetraaqua-bis(4-acetylphenoxyacetato-κ1O)manganese(II), C20H26O12Mn
  16. Crystal structure of (E)-2-(4-fluoro-3-(trifluoromethyl)benzylidene)-7-methoxy-3,4-dihydronaphthalen-1(2H)-one, C19H14F4O2
  17. Crystal structure of DL-α-(methylaminomethyl)benzyl alcohol, C9H13NO
  18. The crystal structure of dipentaerthritol hexanitrate, C10H16N6O19
  19. Crystal structure of N,N-diphenylformamide, C13H11NO
  20. Crystal structure of (E)-2-(3,5-bis(trifluoromethyl)benzylidene)-7-methoxy-3,4-dihydronaphthalen- 1(2H)-one, C20H14F6O2
  21. Crystal structure of ortho-methoxy benzaldehyde, C8H8O2 – a second polymorph and deposition of 3D coordinates
  22. Crystal structure of catena-poly[diaqua-bis(μ2-2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propanoato-κ2O:O')-(2-(4-(2,4,4-trimethylpentan-2-yl)phenoxy)propanoato-κ2O,O')yttrium(III)], C51H79O11Y
  23. Crystal structure of benzylthiouronium chloride, C8H11ClN2S
  24. Synthesis and crystal structure of tert-butyl (2′R,3R,3′R,4a′R,9a′S)-1-acetyl-5-chloro-3″-methyl-2,5″,9′-trioxo-1″-phenyl-1″,4a′,5″,9a′-tetrahydro-1′H,3′H,9′H-dispiro[indoline-3,4′-xanthene-2′,4″-pyrazole]-3′-carboxylate, C36H32ClN3O7
  25. Crystal structure of 2-hydroxy-4-methoxy benzaldehyde, C8H8O3
  26. Crystal structure of poly[diaqua-(m3-3′,5′-dicarboxy-[1,1′-biphenyl]-3,4-dicarboxylato-K4O,O′:O″:O‴) cadmium(II)], C16H11O10Cd
  27. Crystal structure of {tetraaqua-bis(1-(4-hydroxy-2-oxotetrahydrofuran-3-yl)-2-((4aS,6R,8aS)-6-hydroxy-5-(hydroxymethyl)-5,8a-dimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-sulfonato-k2O,O') calcium(II)}-{triaqua-bis(1-(4-hydroxy-2-oxotetrahydrofuran-3-yl)-2-((4aS,6R,8aS)-6-hydroxy-5-(hydroxymethyl)-5,8a-dimethyl-2-methylenedecahydronaphthalen-1-yl)ethane-1-sulfonato-k2O,O') calcium(II)} – water – acetone (1/1/8/2)
  28. Synthesis and crystal structure of bis{2-bromo-6-((E)-((4-((E)-1-(methoxy-imino)ethyl)phenyl)imino)methyl)phenolato- κ2N,O}zinc(II)-methanol(1/2), C65H60Br4N8O9Zn2
  29. Crystal structure of benzenesulphonic acid
  30. Crystal structure of N-benzyl-N-nicotinoyl-nicotine amide C19H15N3O2
  31. Crystal structure of poly[aqua(μ3-2,4-diamino-benzenesulfonato-κ4N:N′,O:O′)silver(I)], C12H18O8N4S2Ag2
  32. Crystal structure of 1,4-bis(methylpyridinium benzene) bis(1,2-dicyanoethene-1,2-dithiolato-κ2S:S)nickel(II), C26H18N6NiS4
  33. Crystal structure of the Cu(II) complex chlorido-(6-oxo-2-phenyl-1,6-dihydropyrimidine-4-carboxylato-k2N,O)-(phenanthroline-k2N,N')copper(II), C23H15ClCuN4O3
  34. Crystal structure of phenarsazine chloride acetic acid solvate, C14H13AsClNO2
  35. Crystal structure of poly[aqua-(μ2-3,3′,4,5′-biphenyl tetracarboxylate- κ3O,O′:O′′) -(μ2-4,4′-bis(pyrid-4-yl)biphenyl-κ2N:N′)zinc(II)], C27H18NO9Zn
  36. Crystal structure of catena-poly[(μ2-3-amino-benzenedisulfonato-κ2N:O)-bis (3-methyl-isoquinoline-κN)silver(I)], C26H24N3O3SAg
  37. Crystal structure of 2-((4-Aminophenyl)thio)acetic acid, C8H9NO2S
  38. Crystal structure of phenarsazine chloride dimethylsulfoxide solvate, C14H15AsClNOS
  39. Synthesis and crystal structure of 2-azido-N-phenylacetamide, C8H8N4O
  40. Crystal structure of chlorido{hydridotris[3-phenyl-5-methylpyrazol-1-yl-κN3]borato}copper(II), C30H28BClCuN6
  41. Crystal structure of benzanthrone – a redetermination for correct molecular geometry and localization of hydrogen atoms
  42. Crystal structure of 4-bromobenzaldehyde – complete redetermination at 200 K, C7H5BrO
  43. Crystal structure and spectroscopic properties of chlorido{hydridotris[3-,5-dimethylpyrazol-1-yl-κN3]borato}(3-,5-dimethylpyrazol-1-yl-κN)copper(II), C20H30BClCuN8
  44. The crystal structure of 4-((2-hydroxynaphthalen-1-yl)(pyrrolidin-1-yl)methyl)benzonitrile, C22H20N2O
  45. Crystal structure of 4-ethyl-3-phenylisoquinolin-1(2H)-one, C17H15NO
  46. Crystal structure of (tricyclohexylphosphane-κP)-[(Z)-N-(3-fluorophenyl)-O-methylthiocarbamato-k1S]gold(I), C26H40AuFNOPS
  47. Crystal structure of (3S,8R,10R,12R,14R)-12-hydroxy-4,4,8,10,14-pentamethyl-17-((R)-2,6,6-trimethyltetrahydro-2H-pyran-2-yl) hexadecahydro-1H-cyclopenta[a]phenanthren-3-yl acetate, C32H54O4
  48. The crystal structure of 2-[(S)-1-(naphthalen-1-yl)ethyl]-2,3,7,7a- tetrahydro-3a,6-epoxyisoindol-1(6H)-one, C19H20NO2
  49. Crystal structure of {hydridotris[3-(t-butyl)-5-isopropylpyrazol-1-yl-κN3]borato}thallium(I), C30H52BN6Tl
  50. Synthesis and crystal structure of 1-octyl-3-phenylquinoxalin-2(1H)-one, C22H26N2O
  51. The crystal structure of 2,6-difluorophenol, C6H4F2O
  52. 4-(9H-Fluoren-9-yl)-4-methylmorpholin-4-ium bromide, C18H20BrNO
  53. The crystal structure of 2,4-dimethylimidazole monohydrate, C5H10N2O
  54. The crystal structure of 1,2-dimethylimidazole, C5H8N2
  55. The crystal structure of 3-ammonio-4-aminobenzoate, C7H8N2O2 – a second polymorph
  56. The crystal structure of 4-hydroxy-2,5-bis(1-methyl-1H-imidazol-3-ium-2-ylthio)-3,6-dioxocyclohexa-1,4-dienolate chloride monohydrate, C14H15N4O5S2Cl
  57. The crystal structure of butyrylferrocene, C14H16FeO
  58. The crystal structure of bi-1,1′-cyclopentane-1,1′-diol, C10H18O2
  59. The crystal structure of 2-iso-propylimidazole, C6H10N2
  60. The crystal structure of aqua-tris (1,3-diphenylpropane-1,3-dionato-κ2O,O′)-lanthanum(III), C45H35LaO7
  61. Crystal structure of (3E,5E)-3,5-bis-4-methoxy-3-(trifluoromethyl)benzylidene)-1-methylpiperidin-4-one, C24H21F6NO3
  62. The crystal structure of 3,5-dichloro-6-diazo-2,4-dinitrocyclohexa-2,4-dien-1-one, C6Cl2N4O5
  63. Crystal structure of carbonyl(2-methylquinolin-8-olato-κ2N,O)(triphenylarsine-κAs)rhodium(I), C29H23AsNO2Rh
  64. Crystal structure of (1aS,1a1S,2S)-4a-butoxy-1a,1a1,2,4a,5,6-hexahydro-1H-cyclobuta[de]naphthalen-2-yl-4-nitrobenzoate, C22H25NO5
  65. Crystal structure of carbonyl(2-oxopyridin-1(2H)-olato-k2O,O′)(triphenylarsine-κAs)rhodium(I), C24H19AsNO3Rh
  66. Crystal structure of catena-poly[triqua-bis(μ2-4-carboxy-2-(1H-tetrazol-1-yl)-1H-imidazole-5-carboxylato-k3N,O:O′)barium(II)] tetrahydrate, C14H14BaN12O15
  67. Crystal structure of (E)-3′,6′-bis(ethylamino)-2-((quinoxalin-2-ylmethylene)amino)spiro[isoindoline-1,9′-xanthen]-3-one, C35H32N6O2
  68. Crystal structure of diaqua-bis(μ2-5-chloro-salicylato-κ3O,O′:O′)-bis(5-chloro-salicylato-κ2O,O′)-bis(1,10-phenanthroline-κ2N,N′) dilead(II) – water (1/2), C52H36C14N4O14Pb2·2(H2O)
  69. Crystal structure of (E)-2-(4-ethoxycarbonyl-3,5-dimethyl-2-(pyrrole-2-ylmethyleneamino)-3′,6′-dihydroxylspiro[isoindoline-1,9′-xanthen]-3-one-methanol (1/1), C31H29N3O7
  70. The crystal structure of 5H-dibenzo[b,e]azepine-6,11-dione, C14H9NO2
  71. Crystal structure of (E)-2-(4-fluoro-2-(trifluoromethyl)benzylidene)-7-methoxy-3,4-dihydronaphthalen-1(2H)-one, C19H14F4O2
  72. The crystal structure of N-(2-methoxy-4,5-bis[phenylselanyl]phenyl)picolinamide, C25H20N2O2Se2
  73. The crystal structure of (E)-2-(5-bromo-2-hydroxybenzylidene)-N-phenylhydrazine-1- carboxamide monohydrate, C14H14BrN3O3
  74. Crystal structure of fac-tricarbonyl-(nitrato-k1O)-bis(pyridine-κN)-rhenium, C13H10O6N3Re
  75. Crystal structure of (E)-2-(((1H-pyrrol-2-yl)methylene)amino)-3′,6′-dihydroxyspiro[isoindoline-1,9′-xanthen]-3-one — methanol (1/2), C27H25N3O6
  76. The crystal structure of 4-amino-N′-(4-aminobenzoyl)benzohydrazide monohydrate, C14H16N4O3
  77. Crystal structure of bis(amino(carbamothioylamino)methaniminium) 5-hydroxyisophthalate monohydrate, C12H20N8O6S2
  78. The crystal structure of 2-(chloromethyl)pyridine, C6H6ClN
  79. The crystal structure of 1-bromo-4-iodo-benzene, C6H4BrI
  80. The crystal structure of 2,6-dimethyl-4-nitro-phenol, C8H9NO3
  81. The crystal structure of 3-chloropropionic acid, C3H5ClO2
  82. The crystal structure of 2-(2-methoxyphenyl)acetic acid, C9H10O3
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