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Synthesis and X-ray diffraction data for dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI) (C12H8N2MoBr2O2)

Published online by Cambridge University Press:  17 February 2016

H. A. Camargo ,
J. A. Henao  and
N. J. Castellanos
H. A. Camargo*
Affiliation:
Grupo de Investigación en Nuevos Materiales y Energías Alternativas (GINMEA), Universidad Santo Tomás, Facultad de Química Ambiental, Campus Universitario Floridablanca, Santander, Colombia
J. A. Henao
Affiliation:
Grupo de Investigación en Química Estructural (GIQUE). Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga – Colombia
N. J. Castellanos
Affiliation:
Estado Sólido y Catálisis Ambiental (ESCA), Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Carrera 30 No. 45-03, Bogotá, Colombia
*
a)Author to whom correspondence should be addressed. Electronic mail: hernando.camargo@mail.ustabuca.edu.co
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Abstract

The dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI) complex (C12H8N2MoBr2O2) was prepared from molybdic acid and 1,10-phenanthroline using hydrobromic acid as solvent. The molybdenum complex solid was separated by filtration and washed with ethyl ether. The X-ray powder diffraction pattern for the title compound was analyzed and found to crystallizes in monoclinic system, space group P21/c (No14) with refined unit-cell parameters a = 12.036 (1), b = 9.819 (1), c = 12.671 (2) Å, and β = 110.44° (1). The volume of the unit cell is V = 1403.2 (3) Å3.

Keywords

dioxomolybdenum complexX-ray powder diffractionoxygen atom transfer
Type
New Diffraction Data
Information
Powder Diffraction , Volume 31 , Issue 1 , March 2016 , pp. 66 - 70
Copyright
Copyright © International Centre for Diffraction Data 2016 

I. INTRODUCTION

1,10-Phenanthroline represents one of the most representative bidentate chelating ligands in coordination chemistry (Accorsi et al., Reference Accorsi, Listorti, Yoosaf and Armaroli2009). Its versatility, manifested in the ability to be functionalized in different positions has expanded its coordination compounds in new applications in areas such as medicine (Ganeshpandian et al., Reference Ganeshpandian, Ramakrishnan, Palaniandavar, Suresh, Riyasdeen and Akbarsha2014; Inci et al., Reference İnci, Aydın, Yılmaz, Gençkal, Vatan, Çinkılıç and Zorlu2015), electronics devices (Kurtz et al., Reference Kurtz, Dhakal, Hulme, Nichol and Felton2015), sensors (Kaur and Alreja, Reference Kaur and Alreja2015), and new materials to oxidation (Yang et al., Reference Yang, Wang, Liu, Wang, Chai and Lei2015) or degradation of organic compounds (Abolhosseini et al., Reference Abolhosseini, Mahjoub, Eslami-Moghadam and Fakhri2014). Structurally, the main difference with the common 2,2′-bipyridine ligand is imposed by the rigid center ring in which the two nitrogen atoms are always held in juxtaposition, increasing the formation rates of bidentate coordination complex (Sammes and Yahioglu, Reference Sammes and Yahioglu1994). Among the innumerable metal complexes with 1,10-phenanthroline ligand and phenanthroline derivates ligand, ruthenium (II) (Heidary et al., Reference Heidary, Howerton and Glazer2014), copper (II) (Liu et al., Reference Liu, Pan, Liu and Chen2014), nickel (Cai et al., Reference Cai, Liu and Zhou2013), and iridium (Kwon et al., Reference Kwon, Sunesh and Choe2015) metals are certainly the most widely used. We have reported, over the years, the synthesis of several molybdenum complexes with bidentate chelating ligands such as bipyridyl (Páez et al., Reference Páez, Castellanos, Martínez, Ziarelli, Agrifoglio, Páez-Mozo and Arzoumanian2008, Reference Páez, Lozada, Castellanos, Martínez, Ziarelli, Agrifoglio, Páez-Mozo and Arzoumanian2009) and bis-pyrazolyl (Castellanos et al., Reference Castellanos, Martínez, Páez-Mozo, Ziarelli and Arzoumanian2012) ligands and studied, under homogeneous and heterogeneous conditions, their properties as oxygen atom transfer agents (Arzoumanian et al., Reference Arzoumanian, Castellanos, Martínez, Páez-Mozo and Ziarelli2010). In a previous work, we have reported the powder diffraction data of a related molybdenum complex (Camargo et al., Reference Camargo, Castellanos, Rosas and Henao2014). Currently, our interest focuses on the study of the electron density effect of different bidentate ligands in oxygen atom transfer processes catalyzed by dioxo-molybdenum entity. In this work, we report the synthesis, molecular characterization [Fourier transform infrared (FTIR), nuclear magnetic resonance (NMR)], and X-ray powder diffraction (XRPD) data for the compound dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI) newly synthesized (Figure 1).

Figure 1. Synthesis of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

II. EXPERIMENTAL

A. Synthesis

All materials were commercial and were used without further purification unless otherwise noted. All solvents were thoroughly degassed prior to use. Acetonitrile was distilled and kept under argon. Molybdic acid (H2MoO4.H2O, 5 g) was dissolved in the minimum volume (ca. 25 ml) of warm concentrated (46%) hydrobromic acid and the mixture was slowly stirred at 25 °C for 1 h. 1,10-Phenanthroline monohydrate (C12H8N2.H2O, 5, 50 g) was added in the solution to obtain a yellow solid. The product was separated by filtration, washed with diethyl ether (3 × 100 ml) and recrystallized from acetone (yield 82%). The molecular characterization was carried out with ultraviolet–visible (UV–Vis) spectroscopy which showed two absorption bands at 270 and 350 nm. Infrared spectrometry showed stretching vibrations; ν: 1650 (C=N); 1434 (C=C); 940, 895 (Mo=O); and NMR on protons (1H NMR, 400 MHz, dimethyl sulfoxide (DMSO)) showed δ (ppm) = 8.15 (d-d, 2H), 7.51 (d-d, 2H), 7.02 (s, 2H), 6.82 (d-d, 2H).

B. Powder data collection

A small portion of the title compound was gently ground in an agata mortar and sieved to a grain size <38 µm. The specimen was mounted on a polymethyl methacrylate specimen holder. The XRPD pattern was recorded with a D8 ADVANCE BRUKER diffractometer operating in DaVinci geometry equipped with an X-ray tube (CuK α radiation: λ = 1.5406 Å, 40 kV, and 30 mA) using a nickel filter and a one-dimensional LynxEye detector. A receiving slit (RS) of 0.6 mm and primary and secondary soller slits (SS) of 2.5° were used. The scan range was 5°–70°2θ with a step size of 0.015 26° and a count time of 2 s per step. Powder data were collected at room temperature (298 K).

Powder analytical software was used to remove the background (Sonneveld and Visser, Reference Sonneveld and Visser1975), to smooth the pattern (Saviztky and Golay, Reference Saviztky and Golay1964), and to eliminate the Kα 2 component from each reflection (Rachinger, Reference Rachinger1948). The second derivative method was used to determine the position and intensities of the diffraction maxima from each reflection.

III. RESULTS AND DISCUSSION

The X-ray powder pattern of the compound dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI) is shown in Figure 2. The XRPD data for the compound are given in Table I. All reflections were indexed successfully using the DICVOL06 program (Boultif and Louër, Reference Boultif and Loüer2004) in a monoclinic unit cell. An absolute error of 0.03° (2θ), was assigned to all the peak positions used in the indexing of the pattern. The space group, P21/c (No. 14), estimated by the program CHEKCELL (Laugier and Bochu, Reference Laugier and Bochu2002) was compatible with the systematic absences and with the crystal density. The lattice parameters of the compound (2) were refined with the program NBS*AIDS83 software (Miguell et al., Reference Miguell, Hubberd and Stalick1981). Its crystal data, X-ray density and figures of merit M20 (de Wolff, Reference de Wolff1968) and F20 (Smith and Snyder, Reference Smith and Snyder1979) of the compound under study are compiled in Table II.

Figure 2. Powder X-ray diffraction pattern of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

Table I. X-ray Powder Diffraction data of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

Table II. Parameters obtained by XRPD for the compound dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

SUPPLEMENTARY MATERIAL

To view supplementary material for this article, please visit http://dx.doi.org/10.1017/S0885715615000949.

ACKNOWLEDGEMENTS

The authors thank Centro de Investigaciones of Universidad Santo Tomás (Bucaramanga-Colombia) for their support with the project approved in the VII internal call of research projects and the Laboratorio de Rayos-X PTG, Vicerrectoría de Investigación y Extensión of Universidad Industrial de Santander (Bucaramanga-Colombia) for data collection.

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Figure 0

Figure 1. Synthesis of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

Figure 1

Figure 2. Powder X-ray diffraction pattern of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

Figure 2

Table I. X-ray Powder Diffraction data of dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

Figure 3

Table II. Parameters obtained by XRPD for the compound dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI).

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