Home Crystal structure of (2,2′-bipyridine-κ2N,N′)bis(tri(p-tolyl)phosphine-κP)copper(I) tetrafluoroborate – 4,4′-bipyridine (2/1), C57H54BCuF4N3P2
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Crystal structure of (2,2′-bipyridine-κ2N,N′)bis(tri(p-tolyl)phosphine-κP)copper(I) tetrafluoroborate – 4,4′-bipyridine (2/1), C57H54BCuF4N3P2

  • Atif Fazal and Mohammed Fettouhi EMAIL logo
Published/Copyright: October 22, 2018

Abstract

C57H54BCuF4N3P2, monoclinic, P21/c (no. 14), a = 11.6379(12) Å, b = 20.173(2) Å, c = 21.786(2) Å, β = 97.270(2)°, V = 5073.5(9) Å3, Z = 4, Rgt(F) = 0.0440, wRref(F2) = 0.1283, T = 298(2) K.

CCDC no.: 1868161

The title crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow block
Size:0.45 × 0.41 × 0.13 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.55 mm−1
Diffractometer, scan mode:Bruker Smart Apex, ω
θmax, completeness:28.3°, >99%
N(hkl)measured, N(hkl)unique, Rint:68883, 12618, 0.034
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 9340
N(param)refined:619
Programs:Bruker [1], SHELX [2], [3] , ORTEP-3 [4]
Table 2:

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

AtomxyzUiso*/Ueq
Cu10.31019(2)0.17359(2)0.30655(2)0.04038(8)
P10.40244(4)0.07880(2)0.28757(2)0.04044(12)
P20.35092(4)0.27533(2)0.26976(2)0.03982(12)
N10.13427(14)0.16312(9)0.31270(8)0.0467(4)
N20.30615(15)0.19118(9)0.40105(8)0.0467(4)
N30.0906(3)0.12847(15)0.10686(13)0.0965(8)
C10.05284(19)0.14369(12)0.26713(12)0.0583(6)
H10.07320.13900.22740.070*
C2−0.0598(2)0.13043(15)0.27666(15)0.0747(7)
H2−0.11420.11700.24410.090*
C3−0.0899(2)0.13743(18)0.33465(17)0.0860(9)
H3−0.16510.12820.34230.103*
C4−0.0084(2)0.15819(16)0.38192(14)0.0754(8)
H4−0.02840.16410.42160.090*
C50.10479(18)0.17038(11)0.36989(11)0.0509(5)
C60.1983(2)0.19208(11)0.41748(10)0.0519(5)
C70.1784(3)0.21398(15)0.47600(12)0.0750(8)
H70.10380.21470.48700.090*
C80.2703(3)0.23441(17)0.51687(13)0.0874(9)
H80.25830.24950.55590.105*
C90.3797(3)0.23270(14)0.50071(12)0.0742(7)
H90.44290.24570.52850.089*
C100.3943(2)0.21127(12)0.44223(10)0.0568(5)
H100.46860.21070.43090.068*
C110.36297(17)0.33243(9)0.33542(9)0.0434(4)
C120.2613(2)0.34618(12)0.36057(11)0.0568(5)
H120.19100.33050.34090.068*
C130.2635(2)0.38271(14)0.41405(12)0.0660(6)
H130.19430.39200.42950.079*
C140.3661(3)0.40577(13)0.44509(12)0.0678(7)
C150.3665(4)0.4417(2)0.50639(15)0.1074(12)
H15A0.32010.48110.50020.161*
H15B0.44450.45360.52230.161*
H15C0.33510.41320.53540.161*
C160.4664(2)0.39174(14)0.42040(13)0.0738(7)
H160.53670.40650.44080.089*
C170.4657(2)0.35624(12)0.36605(12)0.0606(6)
H170.53480.34840.35010.073*
C180.48577(16)0.28184(9)0.23616(9)0.0416(4)
C190.58540(17)0.25400(11)0.26848(10)0.0485(5)
H190.58250.23570.30740.058*
C200.68801(18)0.25346(12)0.24303(11)0.0556(5)
H200.75400.23580.26580.067*
C210.69525(18)0.27848(12)0.18449(11)0.0538(5)
C220.8072(2)0.27672(17)0.15651(14)0.0774(8)
H22A0.83880.32060.15620.116*
H22B0.79270.26030.11490.116*
H22C0.86130.24810.18060.116*
C230.5961(2)0.30533(12)0.15245(11)0.0559(5)
H230.59870.32230.11300.067*
C240.49330(18)0.30754(11)0.17769(10)0.0505(5)
H240.42820.32650.15530.061*
C250.24615(16)0.31756(10)0.21361(9)0.0423(4)
C260.2472(2)0.38630(11)0.20758(12)0.0580(6)
H260.30000.41130.23370.070*
C270.1708(2)0.41782(13)0.16322(12)0.0661(6)
H270.17400.46370.15950.079*
C280.08981(19)0.38252(14)0.12429(11)0.0591(6)
C290.0057(3)0.41757(18)0.07659(14)0.0902(10)
H29A0.04790.44160.04870.135*
H29B−0.04070.44780.09700.135*
H29C−0.04360.38550.05380.135*
C300.08862(19)0.31453(13)0.13068(10)0.0558(5)
H300.03500.28980.10490.067*
C310.16556(17)0.28195(11)0.17466(10)0.0483(5)
H310.16280.23600.17790.058*
C320.50357(17)0.08219(9)0.23037(9)0.0428(4)
C330.4813(2)0.12347(11)0.17944(10)0.0536(5)
H330.41480.14950.17460.064*
C340.5582(3)0.12615(13)0.13556(11)0.0660(7)
H340.54250.15440.10180.079*
C350.6571(2)0.08797(13)0.14077(12)0.0639(6)
C360.7418(3)0.09246(19)0.09379(16)0.1024(12)
H36A0.80290.12270.10840.154*
H36B0.70240.10810.05510.154*
H36C0.77390.04940.08800.154*
C370.6778(2)0.04665(14)0.19106(13)0.0662(7)
H370.74330.01980.19520.079*
C380.60356(19)0.04420(12)0.23552(11)0.0558(5)
H380.62080.01660.26960.067*
C390.49272(17)0.04555(10)0.35511(9)0.0432(4)
C400.5746(2)0.08653(11)0.38746(11)0.0560(5)
H400.58090.13020.37460.067*
C410.6470(2)0.06409(13)0.43827(12)0.0620(6)
H410.70110.09280.45900.074*
C420.6402(2)−0.00061(12)0.45877(11)0.0579(5)
C430.7186(3)−0.02565(16)0.51455(13)0.0818(8)
H43A0.6732−0.04850.54180.123*
H43B0.75760.01110.53600.123*
H43C0.7748−0.05550.50130.123*
C440.5581(2)−0.04128(12)0.42694(11)0.0629(6)
H440.5514−0.08470.44030.076*
C450.4853(2)−0.01936(11)0.37569(11)0.0558(5)
H450.4313−0.04820.35500.067*
C460.30730(16)0.00959(9)0.26085(9)0.0432(4)
C470.32909(18)−0.03313(11)0.21393(11)0.0546(5)
H470.3971−0.02870.19600.065*
C480.2503(2)−0.08254(12)0.19335(12)0.0602(6)
H480.2667−0.11090.16190.072*
C490.14848(19)−0.09035(12)0.21853(12)0.0597(6)
C500.0597(3)−0.14192(16)0.19323(17)0.0892(10)
H50A−0.0040−0.12040.16880.134*
H50B0.0321−0.16500.22700.134*
H50C0.0950−0.17290.16790.134*
C510.1284(2)−0.04872(13)0.26654(12)0.0632(6)
H510.0612−0.05390.28500.076*
C520.20673(19)0.00054(11)0.28754(11)0.0537(5)
H520.19150.02780.32000.064*
C530.1228(4)0.0662(2)0.11584(17)0.1288(17)
H530.17160.05620.15180.155*
C540.0899(3)0.01523(16)0.07624(14)0.1021(12)
H540.1156−0.02760.08600.122*
C550.0190(2)0.02697(12)0.02230(10)0.0539(5)
C56−0.0144(2)0.09166(13)0.01201(12)0.0640(6)
H56−0.06210.1032−0.02390.077*
C570.0231(3)0.13953(14)0.05529(15)0.0780(8)
H57−0.00150.18290.04710.094*
B10.2432(3)0.7557(2)0.03899(16)0.0771(9)
F10.14482(19)0.73022(15)0.00891(10)0.1298(9)
F20.2320(3)0.82102(13)0.05247(15)0.1592(12)
F30.3280(2)0.75118(19)0.00178(13)0.1644(12)
F40.2783(2)0.72219(12)0.09161(10)0.1270(8)

Source of material

The complex was obtained as an unexpected product during the synthesis of a bimetallic mixed-ligand binuclear complex including the bridging 4,4′-bipyridine ligand. Stoichiometric amounts with the ratio (2/2/2/1) respectively of 2,2′-bipyridine, [Cu(CH3CN)4]BF4, the phosphine and 4,4′-bipyridine were reacted in dichloromethane for 12 h. Evaporation of the solvent yielded a yellow powder that was recrystallized from dimethylformamide, affording quality crystals of the title compound.

Experimental details

All hydrogen atoms were placed in calculated positions using a riding model with C—H distances of 0.93 Å (sp2 carbon atoms), or 0.96 Å (sp3 carbon atoms). The isotropic displacement parameters were Uiso(H) = 1.5Ueq(C) for the methyl atoms and Uiso(H) = 1.2UUeq(C) for all other atoms.

Some residual density peaks near the BF4 ion suggest the presence of a minor disorder.

Comment

Diimine copper(I) complexes are an important and versatile class of molecules. They have found wide applications in diverse areas such as light emitting devices (LEDs), trace metal analysis, metal signaling, design of optical devices, molecular sensing and catalytic application in carbon-carbon bond formation reactions [5], [6]. Herein, we report on the crystal structure of a cocrystal containing a mixed-ligand copper(I) compound. The compound crystallizes with half uncoordinated 4,4′-bipyridine per complex formula. The copper(I) ion is bonded to the two nitrogen atoms of the chelating 2,2′-bipyridine ligand and the phosphorus atoms of two tri(p-tolyl)phosphine ligands. The geometry around the metal ion is distorted tetrahedral. The 2,2′-bipyridine bite angle, N1—Cu—N2, is 79.00(7)°, the P—Cu—P angle is 125.08(2)° and the N—Cu—P angles are in the range (103.00(5)°–114.89(5)°). The Cu—N and Cu—P bond distances are similar to those reported for the triphenylphosphine and tricyclohexylphosphine analogous copper(I) complexes [7], [8]. Intermolecular weak, non-classical CH⋯N hydrogen bonding interactions take place between the uncoordinated 4,4′-bipyridine and metal complex through 2,2′-bipyridine (C1⋯N3: 3.587(4) Å) as well as one tri(p-tolyl)phosphine ligand (C31⋯N3: 3.494(4) Å), generating a supra-molecular structure. Interestingly, the first H-bonding interaction likely contributes to the non-coplanarity of the two pyridyl rings of 2,2′-bipyridine with a twisting of the pyridyl ring (N1,C1—C5) and a resulting dihedral angle of 11.74(9)° between the two pyridyl rings.

Acknowledgements

The authors gratefully acknowledge the support of CRP and King Fahd University of Petroleum & Minerals (KFUPM), Dhahran, Saudi Arabia.

References

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Received: 2018-07-15
Accepted: 2018-09-30
Published Online: 2018-10-22
Published in Print: 2018-12-19

©2018 Atif Fazal et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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  45. Crystal structure of catena-poly[dichlorido-(μ2-1,5-dimethyl-2-phenyl-4-((pyridin-4-ylmethylene)amino)-1,2-dihydro-3H-pyrazol-3-one-κ2N:O)cobalt(II)] – methanol (1/1), C18H20Cl2CoN4O2
  46. Crystal structure of poly[diaqua-bis(μ2-1-(4-(1H-imidazol-1-yl)benzyl)-1H-1,2,4-triazole-κ2N:N′)manganese(II)]bis(2-carboxybenzoate) dihydrate, MnC40H40N10O12
  47. The crystal structure of 4-((3,4-dichlorobenzylidene)amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one, C18H15Cl2N3O
  48. Crystal structure of bis(2-methoxy-6-((2-(pyrimidin-2-yl)hydrazono)methyl)phenolato-κ3N,N′,O)iron(III) perchlorate, C24H22N8O8ClFe
  49. The crystal structure of 2-[4-hydroxy-3-methoxyphenyl]-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl, C14H19N2O4
  50. Crystal structure of diaqua-bis(3,3-dimethylacrylato-κ2O,O′)zinc(II), C10H18ZnO6
  51. Crystal structure of dichloro-tetrakis[(E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol-κN]cadmium (II), C60H74CdCl6N12O4
  52. Crystal structure of (20R)-20,25-epoxy-dammaran-3,12-dione, C30H48O3
  53. Crystal structure of (E)-3′,6′-bis(ethylamino)-2′,7′-dimethyl-2-((pyridin-2-ylmethylene)amino)spiro[isoindoline-1,9′-xanthen]-3-one, C32H31N5O2
  54. The crystal structure of 2-(4-fluorophenyl)-1,3,4-oxadiazole, C8H5FN2O
  55. Crystal structure of (2,2′-bipyridine-κ2N,N′)bis(tri(p-tolyl)phosphine-κP)copper(I) tetrafluoroborate – 4,4′-bipyridine (2/1), C57H54BCuF4N3P2
  56. The crystal structure of 2,6-dimethyl-3,5-dinitrocyclohexa-2,5-diene-1,4-dione, C8H6N2O6
  57. The crystal structure of 2,3-dimethyl-1,4-dinitrobenzene – a Z′ = 4 structure, C8H8N2O4
  58. Crystal structure of [(1,2-η)-1,2,3,4,5-pentamethyl-cyclopenta-2,4-dien-1-yl] (1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-κ6N2,O4) rubidium (I), [Rb(diaza-18-crown-6)]Cp*, C22H41N2O4Rb
  59. Crystal structure of 2-(4-fluorophenyl)-N-phenyl-2-(phenylamino)ethanesulfonamide – toluene (1/0.5), C23.5H23FN2O2S
  60. Crystal structure of pyrene-4-aldehyde, C17H10O
  61. Crystal structure of 2-(furan-2-yl)-5-methyl-1,3-dioxane-5-carboxylic acid, C10H12O5
  62. Crystal structure of 2-(4-chlorophenyl)-3-phenyl-1,8-naphthyridine, C20H13N2Cl
  63. Crystal structure and photochromism of 1-(2-ethyl-5-formylthiophen-3yl)-2-(2-cyano-1,5-dimethyl-4-pyrrl)-3,3,4,4,5,5-hexafluorocyclopent-1-ene, C19H14F6N2OS
  64. Crystal structure of 2-(4-bromophenyl)-1,3-dimethyl-1H-perimidin-3-ium iodide, C19H16BrIN2
  65. Crystal structure of 2-(4-(dimethylamino)phenyl)-10-methylacridin-9(10H)-one, C22H20N2O
  66. Crystal structure of 4-(acetoxymethyl)-6-(3-acetyl-3-(4-fluorophenyl)thioureido)cyclohex-4-ene-1,2,3-triyl triacetate, C24H26FN2O9S
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