Oxovanadium(IV) and Dioxouranium(VI) Complexes of Azo Dyes

This article was downloaded by: [University of Chicago Library] On: 11 November 2014, At: 19:02 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lsrt19 Oxovanadium(IV) and Dioxouranium(VI) Complexes of Azo Dyes Mandalika S. Sastry a , Udai P. Singh a , Ranjana Ghose a & Animesh K. Ghose a a Department of Chemistry, Faculty of Science , Banaras Hindu University , Varanasi, 221005, India Published online: 23 Sep 2006. To cite this article: Mandalika S. Sastry , Udai P. Singh , Ranjana Ghose & Animesh K. Ghose (1991) Oxovanadium(IV) and Dioxouranium(VI) Complexes of Azo Dyes, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 21:1, 73-88, DOI: 10.1080/15533179108020166 To link to this article: http://dx.doi.org/10.1080/15533179108020166 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. 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CHEM., 21(1), 73-88 (1991) OXOVANADIUM( IV) AND DIOXOURANIUM(V1) COMPLEXES OF A20 DYES Mandalika S. Sastry, Udai P. Singh, Ranjana Chose and Animesh K. Chose* apa r tmen t of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi-221005, India ABSTRACT Oxovanadium( IV) and dioxouranium (VI) complexes of l-(Z-pyridylazo)-2-naphthol (PAN) and 4-(2-pyridylazo) resorcinol (PAR) have been prepared and character ised by elemental analyses, various physico-chemical methods and magnetic measurements. The I.R. observations suggest t h a t PAN is coordinated through oxygen and (pyridine) nitrogen, whereas PAR i s coordinated through (pyridine) nitrogen and the ortho-hydroxyl group. The spectral-studies suggest t h a t oxovanadium(1V) complexes have the coomiination number f i v e and dioxouranium(V1) complexes have the coordination number s i x f o r the cations. 73 Copyright 0 1991 by Marcel Dekker. Inc. D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 74 SASTRY ET AL. O N 0 O N 0 PAR PAN Figure 1 INTRODUCTION Azo compounds are widely used i n industry as t e x t i l e As a r e s u l t they can become environmental po l lu tan ts dyes. through discharge of the contents of p la t ing baths from tex t i le works i n to r ivers , spec ia l ly i f not t r e a t e d by the ac t ive sludge process, as has been observed i n c e r t a i n cases' * '. 4-(2-pyridylazo) resorcinol (PAR) (FIG. 4 ) &re hetero- cyc l ic dyes, which generally a c t a s t r i d e n t a t e l igand i n metal complexes but i n some cases, t h e i r bidentate behaviour has a l so been observed394. I-( 2-Fyridylazo)-2-naphthol (8-PAN) and Although considerable a t t en t ion has been given t o metal complexes of azo compounds, ma idy with regard t o the metal-azo bond and its proper tie^^^, the simple complexes of PAN and PAR w i t h oxovanadium(1V) and dioxouranium (VI) have not previously been i so l a t ed i n the s o l i d s t a t e . This prompted the au thors t o report t he synthesis and charac te r i sa t ion s t u d i e s of PAM and PAR complexes w i t h oxovanadiur ( I V ) and dioxouraniiui (VI). D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 TWO COMPLEXES OF AZO DYES 75 EXPERIMENTAL Prepara t ion of oxovanadium ( IV) comgLZLe2 Vanadyl su lpha te (1 mmole, 0.1809 g) d isso lved i n minimum amount of water was added t o 40 - S O mL e t h a n o l i c so lu t ion . Containing sodium s a l t o f PAN o r PAR (1 mmole, O.?713g o r 0.2552g). P+P r e a c t i o n mixture 0 8 s re f luxed f o r about 1 6 h r s and t h e p r e c i p i t a t i o n o f t h e complex was i n i t i a t e d by adding ethanol-water mixture (70:30 r a t i o ) . The complex was f i l t e r e d , washed s e v e r a l times with an e-1 banol--water mixture (70:30 r a t i o ) , f i n a l l y with e t h e r and d r i e d a t about 50°C. Preparat ion o f dioxouranium (VI) cornpleEe5 Uranyl n i t r a t e (1 mmole, 0.5024 g) w a s ref luxed with 1 mmole (0.2713 g o r 0.2552 g ) sodium form of PAN o r PAR i n - 50mL of et.hano1 f o r about 1 6 h r s . The react ion mixture was evaporaled t o a f o u t one-third o f t h e o r i g i n a l volume and t h e complex was p r e c i p i t a t e d by adding a ethanol-water mixture (70:30 r a t i o ) . The p r e c i p i t a t e d complex w a s f i l t e r e d , washed s e v e r a l times with 70:30 r a t i o ethanol-water mixture, f i n a l l y with e t h e r and d r i e d a t about 5 0 O C . Elemental a n a l y s i s I n t h e complexes vanadium and uranium were determined by volumetry9 and gravimetry”, r e s p e c t i v e l y , D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 76 SASTRY ET AL. a f t e r decomposing the complexes i n cortcentrated n i t r i c acid. Carbon, hydrogen and ni t rogen were analysed using a Perkin-Elmer model 240C elemental analyser. Physical e a s u rements The molar conductance i n DMSO w a s measured on a LBR/B type conductivity meter. The I R spec t r a of t he l igands and t h e i r complexes in Nujol mull were recorded i n the 4000-200 cm-' range using a Perkin-Elmer 783 Spectrophotometer. The e l ec t ron ic spec t ra of the complexes i n C2H50H w e r e recorded on a Perkin-Elmer Lambda - 3 (200 - 900 nm) Spectrophotometer. Room temperature (294.2 K ) magnetic measurements were made using a Faraday magnetic s u s c e p t i b i l i t y balance. ESR Spectra of oxovanadium( IV) complexes i n powder fom, were recorded on an X-band varian-11 ESR Spectrometer a t room temperature using Coppinger's r ad ica l a s reference. Powder X-ray d i f f r ac t ion pa t t e rn were recorded by a Phi l ips X-ray D i f f ractometer FWI 710 using CuKa radiat ion. RESULTS AND DISCUSSION The complexes were synthesized by mixing equimolecular so lu t ions of t h e l igands and me ta l l i c s a l t s . The formed complexes have general formulae D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 TA BL E I A n al yt ic al D at a an d O th er P h ys ic al P ro p er ti es o f th e C om pl ex es M .P . M ol ar M ag ne ti c Y ie ld ('C ) (o hm -l cr n2 mo le -' ) (B .M .) Co mp le x C ol ou r Fo un d (C al cd .) 96 M C H N co n d u ct iv it y m om en t % I vo (P AN 12 Da rk v io le t 11 .9 6 63 .8 1 3. 51 14 .8 7 [C ~H ~~ N~ O~ VI u0 2 (P A N ) 2 B ro w ni gh r ed 30 .9 2 46 .8 5 2. 66 11 .0 2 [ C 30 H2 0N 60 4U 1 VO (P AR 12 Da rk v io le t 13 .4 3 53 31 7 3. 26 16 .8 9 [ C 22 H1 sN6'5'] uo 2 (P A R ) 2 B ro w ni sh r ed 34 .1 5 37 .7 1 2. 22 12 .1 2 CC zzH 16 Nr , 0 ,d (3 4. 07 ) (3 7. 80 ) (2 .2 9) ( 12 .0 2) >3 00 0, 14 9 d ia m ag n et ic 7 0 (1 1. 89 ) (6 30 95 ) (3 .5 5) (1 4. 92 ) 23 0- 24 0 0. 16 8 1. 29 65 (3 1. 07 ) (4 6. 99 ) (2 .6 1) (1 0. 96 ) 28 0- 28 5 0. 05 di am ag ne ti c 90 (1 3. 51 ) (5 3. 29 ) (3 .2 3) (1 6. 95 ) >3 00 0. 18 6 1. 53 85 PA N = 1- (2 -p yr id yl az o) -2 -n ap ht ho l; PA R - 4-( 2- p yr id yl az o) r es or ci n ol . D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 78 SASTRY ET A L . of ML2, where N = U 0 2 o r VO and L-PAN o r PAR (Table I ) and can be represented with equations, VOS04 + 2 NaL ---> VOL2 + Na2SOq U0,(N03)2+ 2 NaL -+ U02L2 + 2NaN03 The oxovanadium(1V) complexes are dark v i o l e t whereas the dioxouranium(V1) complexes a r e brownish red. All complexes o f PAN are soluble i n common organic so lvents but t h e PAR complexes are so luble only i n nitrobenzene, pyridine, e thanol , DMF and DKSO. PAR compounds do not m e l t up t o 300’C whereas PAN complexes m e l t i n between 230 - 265 OC. In f r a red spectra Some important i n f r a red bands 8911-13 of l igands and t h e i r complexes a r e given i n Table 11, The IR spectrum of f r ee PANq4 exh ib i t s vC=N a t 1620 cm”, vC=O a t 1605 cm” and vN=N a t 1450 c m - l . The ?lC=N and ? C = O bands o f PAN s h i f t t o t he lower frequency region upon complexation suggesting the pa r t i c ipa t ion of the he te rocycl ic ni t rogen and phenolic oxygen atom i n coordination. The v N = N band of P h i does not show any subs t an t i a l s h i f t upon complexation, which excludes t h e p o s s i b i l i t y o f azonitrogen coordination with the metal ions. D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 TA BL E I1 So me I m po rt an t In fr ar ed B an ds o f L ig an ds a nd i ts C om pl ex es Vi br at io n PA N V O (P A N 2 V o, (P A N )2 PA R VO (P A R ) vo ,( P 'w 2 -, -- vc =c VC =N V C P O V C =N V N = N vc -0 , vc -N v c-r i V C -C IH 6C -0 , 6C -N , 6C -H vc -o 6 C- €I (p yr id ir ie r in g) VV =O VO =U =O VM -N V M -G - 16 20 m 16 05 r n - 14 50 s - - 12 30 m 12 00 s 98 8 m - - - I ... - 15 75 m 15 55 w - 14 50 s - - 13 00 r n 12 80 m 98 5 w S6 5 rn 51 0 w 40 0 m 44 5 m 30 0 m -.. - - 15 90 m 15 70 w - 14 50 s - - 12 15 w 11 85 w 97 0 w 90 0 s 52 0 m 39 8 w 44 2 m 30 0 w - - 16 25 m 15 55 m - - 15 70 w 15 52 rn 13 70 s 13 24 rn 12 66 w - 52 10 r n - - - - - - 16 00 m 15 62 w - - 15 50 m 15 34 w 13 75 s 13 20 r n 12 66 w 12 35 m - - - 53 5 m 53 0 m 41 2 m 30 0 m - 16 00 w 15 78 m - - 15 55 w 15 26 rn 13 72 s 13 12 w 12 74 m 12 30 m - - - - 866 s 52 2 rn 37 5 w 43 0 m 31 6 w D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 80 SASTRY ET AL. In the spectrum of f r e e PAR” bands appear a t 1025, 1595 cm” and 1570, 1552 cm-I a t t r i b u t a b l e t o t h e ?)C=C and YC=N vibra t ions , respect ively. The IR spec t r a of t he complexes show s h i f t i n g i n these bands, ind ica t ing the l inkage o f metal ions w i t h t he pyridine nitrogen. The band due t o t h e N-N s t r e t ch ing mode remains almost unchanged i n the metal complexes, which excludes the involvement o f t he azo-group i n coordination. A broad band due t o vO-H t h a t appears i n the spectrum of f r e e sodium sa l t of FA2 a t 3250 cm-’ remains unchanged i n the spec t ra o f t he complexes. S h i f t s a r e also observed f o r the vC-0 and VC-N bands (1324 cm-I). ass ignable t o 6C-0, 6C-M and 6C-H, s h i f t s t o higher frequency suggesting the complexation of metal ions w i t h the ortho-oxygen group o f PAR, whereas the band a t 1266 cm-’ due t o vC-OH is unaffected i n t h e A medium band a t 1210 cm-’, complexes. A narmw band of medium i n t e n s i t y appearing i n the range 985250 cm-I i n the complexes may be a t t r i b u t e d t o vY=O v ib ra t ion . The s t rong bands loca ted i n the region 900-3.30 cm-’ f o r dioxouranium(V1) have been a t t r i b u t e d t o the? w3 ( a s p ) of t h e O=U=O group The vM-N bands appear i n the 530 - 510 cm’l and 435 - 320 c m whereas the dioxouranium(V1) complexes show these bands 15 16-18 -1 regions in t he spec t ra o f oxovanadium(1V) complexes, D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 TWO COMPLEXES OF A 2 0 DYES 81 i n 522 -510 cm-’ and 410 - 350 cm-’ regions 19-21. bands appearing i n the regions 455 -445 cm-’ and 310 - 300 cm-’ i n oxovanadium(1V) complexes and in the 450-43) cm-I and 320 - 300 cm” regions i n dioxouranium(V1) complexes have been assigned t o vM-0 vibrat ions 22-24. of two bands f o r M-N and M-0 suggest t h a t both the l igands bind t o t h e oxovanadium and dioxouranium i n the c i s - form of sterochemical arrangement The me presence On the basis of above I R spec t r a l s tud ie s it may be suggested t h a t PAN and PAR behave as bidentate l igands because PAN binds through i ts oxygen and heterocycl ic ni t rogen atom whereas PAR involves pyridine nitrogen and ortho-hydmxyl group i n coordination, and giving t h e ca t ion coordination number f i v e and six in oxovanadium and dioxouranium complexes respectively. Mametic data The magnetic moments obtained f o r oxovanadium (IV) complexes f a l l i n the mnge 1.29 - 1.53 B.M. These are less than the sp in-only value f o r oxovanadium(1V) complexes when the o r b i t a l contr ibut ion is completely quenched. l i t e r a tu re25 that most of the oxovanadium( IV) complexes of the bidentate dibasic Schiff bases containing ON0 o r ONS donor atoms exhiblit subnoma1 magnetic moments. The subnomal magnetic moments of the present oxova- But it is reported i n the D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 82 SASTRY ET AL. TABLE I11 X-Ray Data of Complexes ~~~~ ~ ~~~ ~~ Powder 20 d values Relative Qobs QCa1 h k l P a t t e r n intensity Line 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 1 2 3 4 5 6 7 8 9 10 11.329 12.589 13.279 15.675 16.800 17.417 18.038 19.142 20.019 20 . 670 21,452 22.573 23.827 24.150 26.259 27.101 27. €40 31 379 34.217 35.829 44.430 5.926 6.793 11.877 14.563 15.796 17.879 18.644 19.026 22.551 22 . 882 7.8101 7.031 5 6.6676 5 , 6533 5,0916 4.9176 4.6366 4.4352 4.2970 4.1420 3.9389 3.7343 3.685 1 3 3938 3 2902 3 . 2045 2.8507 2 . 6205 2.5062 2.0390 5 2772 173 89 104 168 103 105 75 103 74 160 71 90 132 128 90 335 93 121 64 37 49 14.9132 1400 13.0126 214 7.4511 146 6.0824 323 5.6101 347 4.9609 59 4 . 7592 199 4.6644 127 3.9427 73 3 . 8864 95 0.0163 0.0163 0.0202 0.0202 0.0224 0.0224 0.0312 0.0326 0.0359 0.0365 0.0385 0.0387 0.0413 0.@404 0.0465 0.0448 0.0508 0.0528 0.0541 0.0550 0.0582 0.0567 0.0644 0.0652 0,0717 0.0713 0.0736 0.0730 0.0868 0.0854 0.0923 0.0932 0.0973 0.0978 0,1230 0.1212 0.1456 0.1467 0.1592 0.1568 0,2405 0.2420 0.0044 0.0044 0.0059 0.0059 0.0180 0.0180 0.0270 0.0264 0.0517 0.0308 .0.0406 0,0413 0.0459 0.0456 0.0643 0.0633 0 . 0662 0.0662 0.0441 0.0448 I00 010 00 1 200 110 101 0 20 002 210 20 1 1 20 400 30 1 220 410 230 600 060 900 007 029 100 010 00 1 600 700 0 70 202 540 5 70 760 D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 TWO COMPLEXES OF A 2 0 DYES 83 TABLE I11 (contd.. . . I Powder 20 d values Relative Qobs Qcal hkl P a t t e r n intens it y Line 12 13 14 15 16 17 18 19 20 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 23.905 25.523 26.231 27.541 28.448 29.963 30.545 35 -615 39.423 27.925 12.285 12.831 15.312 16.691 18.007 20.751 22.467 25 . 642 25.856 26.607 31.815 35.401 36.187 37.326 38.264 42.384 50.702 52.466 33. 922 3.7224 3.4899 3 0 3973 3.2386 3.1950 3.1374 2.9821 2.9266 2.5208 2.2856 7.2043 6.8992 5 . 7864 5.3115 4.9261 4 . 2805 3.9573 3.4740 3.4457 3.3501 2.8126 2.6426 2,5355 2.4822 2.4091 2.3521 2.1325 1.8@05 1,7440 105 240 129 100 90 101 90 44 64 96 48 163 77 110 I10 53 66 104 327 56 123 70 56 36 56 54 42 36 36 0.0721 0.0720 0.0821 0 -0838 0.0866 0.0868 0.0957 0.0956 0.0979 0.0984 0.1015 0.1018 0.1124 0.1116 0.1167 0.1164 0.1573 0,1568 0.1914 0.1915 0.0192 0.0192 0.0210 0.0210 0,0298 0.0288 0.0354 0.0354 0.0412 0.0402 0.0545 0.0546 0.0638 0.0642 0,0828 0.0834 0.0842 0.0840 0.0891 0.0882 0.1264 0.1266 0.1431 0.1416 0.1555 0.1554 0.1623 0.1608 0,1723 0,1728 0.1807 0.1800 0.2199 0.2184 0.3084 0.3072 0.3267 0.3282 GO4 024 980 004 604 025 904 605 707 05 9 100 101 004 103 111 113 105 115 106 007 117 226 221 216 300 302 226 31 8 41 1 Am0 rphous D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 a4 SASTRY ET A L . nadium(1V) complexes may be due to the exis tence of exchange in t e rac t ions i n the complexes. A l l t he dioxouranium (VI) complexes a r e diamagnetic. E lec t ronic spec t ra The e l ec t ron ic spec t ra of oxovanadium(1V) complexes i n C2%OH show d-d t r a n s i t i o n maxima a t 470nm, 550m and 620nm i n VO-FAN complexes and a t 345 nm, 560nm and 670nm i n VO-PAR complexes corresponding t o 2B2 --+ ‘El, 2B2 --+ ‘B1 and 2B2 --+ ‘A1 t r a n s i t i o n s respectively. be s t a t e d t h a t the geometry is l i k e l y t o be f i ve - coordinate . Thus, it may 26-32 Electron sp in resonance spectra The ESR spectra o f oxovanadium(1V) complexes i n powder form show a s ing le band centered a t g=1.961 f o r t he VO-PAN and a t 1.986 f o r the VO-PAR complex. The appearance of the s igna l as a narrow l i n e of the VO-PAN and VO-PAR complexes suggests s t rong exchange in t e rac t ion between the complex molecules 33 . X-Rav powder d i f f r a c t i o n s tud ie s Table I11 shows X-ray d i f f r a c t i o n data of the complexes. The indexing pattern34 y i e l d s the l a t t i c e constants a = 7.81, b = 7.03 and c = 6.67 A f o r VO -PAN; 0 D ow nl oa de d by [ U ni ve rs ity o f C hi ca go L ib ra ry ] at 1 9: 03 1 1 N ov em be r 20 14 THO COMPLEXES OF A 2 0 DYES 85 vo L2 u02l-2 W h e r e L = PAN o r PAR Figure 2 a = 14.19, b = 13.01 and c = 7.45 1 f o r U 0 2 -PAN; a = b = 7.20 and c = 23.57 A f o r the VO-PAR complex ind ic s t ing orthorhombic symmetry f o r VO -PAN, U02-PAN and te t ragonal symmetry f o r t he VO-PAR complex. 0 Although it is reported that PAN and PAR behaves as t r i d e n t a t e ligands3, t h i s work proves t h e probabi l i ty of these te rdenta te l igands t o act as bidenta te l igands , which is supported by the works already published 4,14 . 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