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Preparation of a novel uranyl-o-sulfamidobenzoate complex: its crystal and molecular structure at 150 K
www.elsevier.nl/locate/ica Inorganica Chimica Acta 309 (2000) 163– 165
Note
Preparation of a novel uranyl-o-sulfamidobenzoate complex: its crystal and molecular structure at 150 K Andrei S. Batsanov a, Clair Bilton a, Robert M.K. Deng b, Keith B. Dillon a,*, Judith A.K. Howard a, Harriet Okatch-Nkala b a b
Chemistry Department, Uni6ersity of Durham, South Road, Durham, DH1 3LE, UK Chemistry Department, Uni6ersity of Botswana, Pri6ate Bag 0022 Gaborone, Botswana Received 29 May 2000; accepted 17 July 2000
Abstract The reaction of saccharinate ions with uranyl nitrate hexahydrate (2:1) has led to the opening of five-membered heterocyclic rings, and the formation of a novel uranyl complex of o-sulfamidobenzoate. This has been confirmed by determination of its crystal and molecular structure at 150 K. © 2000 Elsevier Science B.V. All rights reserved. Keywords: Crystal structures; Molecular structures; Uranyl complexes; o-Sulfamidobenzoate complexes; Saccharinate ions
1. Introduction
2. Results and discussion
In previous papers, we have summarised published work on the crystal structures of transition metal complexes of 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide (saccharinate), particularly those with additional bidentate ligands such as 2,2%-bipyridine (bipy) or 1,10phenanthroline (phen) present [1,2]. The crystal structures of the complexes [M(sac)2(H2O)4]·2H2O have been ascertained for divalent ions of V [3], Cr [4], Mn [5], Fe [6], Co [6], Ni [6], Cu [6,7], Zn [8] and Cd [8], but there have been no structural reports for analogous uranyl complexes. In the present work we reacted saccharinate anion (as its sodium salt) with uranyl nitrate hexahydrate in an aqueous solution, and obtained a new uranyl complex; this has been shown by X-ray crystallography at 150 K to have a novel ring-opened catena structure.
From a 2:1 reaction of sodium saccharinate and uranyl nitrate hexahydrate, a yellow crystalline solid was isolated, which analysed well as [UO2(sac)2]·4H2O (Section 3). Crystal structure determination at 150 K indicated, however, that both of the five-membered heterocyclic rings had opened by scission of the CN bond, and that the ligand coordinates to the uranyl ion via the carboxylic oxygen of the carboxyl group thus formed (Fig. 1 and Table 1). One of the o-sulfamidobenzoate ligands is unidentate, while the second carboxyl group bridges two uranium atoms, symmetrically related via the a glide plane. The complex crystallises in a catena-structure, with distorted pentagonal bipyramidal coordination of the metal. All seven ligands are oxygen atoms, the two double bonds of the uranyl group being mutually trans in the axial positions, with two water molecules and three carboxyl oxygens in the equatorial plane. There are two intramolecular hydrogen bonding contacts, as shown in Fig. 1, between a hydrogen on N(1) and O(14), at an N···O distance of 2.87(2) A, , and between a hydrogen on N(2) and O(24) of the unidentate sulfamidobenzoate ligand, at an N···O
* Corresponding author. Tel.: + 44-191-374 2000; fax: + 44-191384 4737.
0020-1693/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 0 - 1 6 9 3 ( 0 0 ) 0 0 2 4 6 - 2
A.S. Batsano6 et al. / Inorganica Chimica Acta 309 (2000) 163–165
164
distance of 2.82(2) A, . There are also several possible intermolecular H-bonding interactions, between N(1)H(11N)···O(11%) (NO distance 2.92(2) A, ), O(3)H(O31)···O(24%) (OO distance 2.60(2) A, ), O(3)H(O31)···O(2%) (2.96(2) A, ), O(4)H(O41)···O(21%) (2.87(2) A, ), and O(4)H(O42)···O(1%) (2.66(2) A, ); the last of these is shown in Fig. 1. The overall analytical composition is identical to that of [UO2(sac)2]·4H2O. Ring-opening reactions of saccharinates, with scission of the NC bond, are known to occur with nucleophiles [9]. The ring is also hydrolysed under strongly acidic conditions and on heating in water, but this results in additional rupture of the NS bond [9]. It is not clear why the five-membered rings were opened in this reaction. No strong nucleophiles were present, and although gentle heating took place to reduce the solvent volume and induce crystallisation (Section 3), this was similar to the methodology used to prepare other saccharinate complexes, where ring-opening did not occur. The identical starting material (sodium saccharinate) was used in each case [1,2]. Nevertheless this interesting and novel structure adds a new chapter to uranyl and saccharinate chemistry.
Fig. 1. X-ray structure of complex 1, showing the catena-structure and hydrogen bonds. Atoms generated by the symmetry operation x+ 1/2, 1 −y, z are primed, by the x − 1/2, 1 − y, z operation are double-primed. Table 1 Selected bond distances (A, ) and angles (°) UO(1) UO(2) UO(3) UO(4)
1.78(l) 1.78(l) 2.415(8) 2.45(l)
UO(13) UO(14%) UO(23)
2.38(l) 2.40(l) 2.36(l)
O(2)UO(1) O(l)UO(3) O(l)UO(4) O(l)UO(13) O(l)UO(14%) O(l)UO(23) O(2)UO(3) O(2)UO(4)
178.0(5) 91.0(4) 94.3(4) 89.4(4) 92.2(4) 85.9(4) 88.4(4) 87.2(4)
O(2)UO(13) O(2)UO(14%) O(2)UO(23) O(13)UO(14%) O(23)UO(3) O(14%)UO(3) O(23)UO(4) O(13)UO(4)
90.1(4) 85.8(4) 95.7(4) 73.1(3) 75.0(3) 72.1(3) 73.1(3) 67.4(3)
3. Experimental
3.1. Synthesis of the complex Uranyl nitrate hexahydrate (3.000 g, 5.98 mmol) was dissolved in 50 cm3 of water, and added to a solution of sodium saccharinate (2.450 g, 11.94 mmol) in 50 cm3 of water. The resulting bright yellow solution was gently heated, with stirring, until the volume was reduced to 15 cm3. The mixture was allowed to stand for 9 days, and the yellow crystals which formed were separated, washed with cold water and dried. Found: C, 23.67, H, 2.25, N, 3.96. C14H16N2O12S2U requires: C, 23.80, H, 2.28, N, 3.97%. Microanalyses were performed by the microanalytical services of the Department of Chemistry, University of Durham.
3.2. X-ray crystal structure determination The single-crystal diffraction data from a yellow crystal (0.4× 0.14× 0.02 mm) were collected on a SMART 1K CCD area detector (graphite-monochromated Mo Ka radiation, u( = 0.71073 A, ) at T= 150 K. Crystal data: C14H16N2O12S2U, M= 706.44, orthorhombic, space group Pca21 (no. 29), a= 7.999(8), b= 8.260(7), c= 29.761(6) A, , U= 1966(3) A, 3, Z= 4, Dcalc =2.39 g cm − 3, v= 8.54 mm − 1. Four sets of scans, each set at different and/or 2q angles, nominally covered a hemisphere of reciprocal space, giving 9862 reflections with 2q5 54.5°, of which 3940 were unique. A semi-empirical absorption correction [10] based on the intensities of Laue equivalents, reduced Rint from 0.099 to 0.058 (maximum and minimum transmission factors 0.46 and 0.29). The crystal proved to be a racemic twin with essentially equal contributions of components. The structure was solved by the Patterson method and refined by least squares against F 2 of all data using SHELX-97 software [11] (U and S atoms anisotropic, C, O and N isotropic, H riding in idealised positions, 141 refined parameters) to R=0.049 (for 3529 data with F 2 ] |(F 2)) and wR(F 2)= 0.126.
4. Supplementary material Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 144825. Copies of this information may be obtained free of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: + 44-1223-336033; e-mail: deposit@ ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
A.S. Batsano6 et al. / Inorganica Chimica Acta 309 (2000) 163–165
Acknowledgements J.A.K.H. thanks the Royal Society for a Leverhulme Trust Senior Research Fellowship, while C.B. thanks the EPSRC for financial support.
References [1] K.B. Dillon, C. Bilton, J.A.K. Howard, V.J. Hoy, R.M.K. Deng, D.T. Sethatho, Acta Crystallogr., Sect. C 55 (1999) 330. [2] R.M.K. Deng, C. Bilton, K.B. Dillon, J.A.K. Howard, Acta Crystallogr., Sect. C 56 (2000) 142. [3] F.A. Cotton, L.R. Falvello, R. Llusar, E. Libby, C.A. Murillo, W. Schwotzer, Inorg. Chem. 25 (1986) 3423.
.
165
[4] F.A. Cotton, G.E. Lewis, C.A. Murillo, W. Schwotzer, G. Valle, Inorg. Chem. 23 (1984) 4038. [5] B. Kamenar, G. Jovanovski, Cryst. Struct. Commun. 11 (1982) 251. [6] S.Z. Haider, K.M.A. Malik, K.J. Ahmed, H. Hess, H. Riffel, M.B. Hursthouse, Inorg. Chim. Acta 72 (1983) 21. [7] K.J. Ahmed, A. Habib, S.Z. Haider, K.M.A. Malik, M.B. Hursthouse, Inorg. Chim. Acta 56 (1981) L37. [8] S.Z. Haider, K.M.A. Malik, S. Das, M.B. Hursthouse, Acta Crystallogr., Sect. C 40 (1984) 1147. [9] M. Hettler, Adv. Heterocycl. Chem. 15 (1973) 233. [10] G.M. Sheldrick, SADABS: Program for Scaling and Correction of Area Detector Data, University of Go¨ttingen, Go¨ttingen, Germany, 1998. [11] G.M. Sheldrick, SHELX-97, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
Note
Preparation of a novel uranyl-o-sulfamidobenzoate complex: its crystal and molecular structure at 150 K Andrei S. Batsanov a, Clair Bilton a, Robert M.K. Deng b, Keith B. Dillon a,*, Judith A.K. Howard a, Harriet Okatch-Nkala b a b
Chemistry Department, Uni6ersity of Durham, South Road, Durham, DH1 3LE, UK Chemistry Department, Uni6ersity of Botswana, Pri6ate Bag 0022 Gaborone, Botswana Received 29 May 2000; accepted 17 July 2000
Abstract The reaction of saccharinate ions with uranyl nitrate hexahydrate (2:1) has led to the opening of five-membered heterocyclic rings, and the formation of a novel uranyl complex of o-sulfamidobenzoate. This has been confirmed by determination of its crystal and molecular structure at 150 K. © 2000 Elsevier Science B.V. All rights reserved. Keywords: Crystal structures; Molecular structures; Uranyl complexes; o-Sulfamidobenzoate complexes; Saccharinate ions
1. Introduction
2. Results and discussion
In previous papers, we have summarised published work on the crystal structures of transition metal complexes of 1,2-benzisothiazol-3(2H)-onate 1,1-dioxide (saccharinate), particularly those with additional bidentate ligands such as 2,2%-bipyridine (bipy) or 1,10phenanthroline (phen) present [1,2]. The crystal structures of the complexes [M(sac)2(H2O)4]·2H2O have been ascertained for divalent ions of V [3], Cr [4], Mn [5], Fe [6], Co [6], Ni [6], Cu [6,7], Zn [8] and Cd [8], but there have been no structural reports for analogous uranyl complexes. In the present work we reacted saccharinate anion (as its sodium salt) with uranyl nitrate hexahydrate in an aqueous solution, and obtained a new uranyl complex; this has been shown by X-ray crystallography at 150 K to have a novel ring-opened catena structure.
From a 2:1 reaction of sodium saccharinate and uranyl nitrate hexahydrate, a yellow crystalline solid was isolated, which analysed well as [UO2(sac)2]·4H2O (Section 3). Crystal structure determination at 150 K indicated, however, that both of the five-membered heterocyclic rings had opened by scission of the CN bond, and that the ligand coordinates to the uranyl ion via the carboxylic oxygen of the carboxyl group thus formed (Fig. 1 and Table 1). One of the o-sulfamidobenzoate ligands is unidentate, while the second carboxyl group bridges two uranium atoms, symmetrically related via the a glide plane. The complex crystallises in a catena-structure, with distorted pentagonal bipyramidal coordination of the metal. All seven ligands are oxygen atoms, the two double bonds of the uranyl group being mutually trans in the axial positions, with two water molecules and three carboxyl oxygens in the equatorial plane. There are two intramolecular hydrogen bonding contacts, as shown in Fig. 1, between a hydrogen on N(1) and O(14), at an N···O distance of 2.87(2) A, , and between a hydrogen on N(2) and O(24) of the unidentate sulfamidobenzoate ligand, at an N···O
* Corresponding author. Tel.: + 44-191-374 2000; fax: + 44-191384 4737.
0020-1693/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 0 - 1 6 9 3 ( 0 0 ) 0 0 2 4 6 - 2
A.S. Batsano6 et al. / Inorganica Chimica Acta 309 (2000) 163–165
164
distance of 2.82(2) A, . There are also several possible intermolecular H-bonding interactions, between N(1)H(11N)···O(11%) (NO distance 2.92(2) A, ), O(3)H(O31)···O(24%) (OO distance 2.60(2) A, ), O(3)H(O31)···O(2%) (2.96(2) A, ), O(4)H(O41)···O(21%) (2.87(2) A, ), and O(4)H(O42)···O(1%) (2.66(2) A, ); the last of these is shown in Fig. 1. The overall analytical composition is identical to that of [UO2(sac)2]·4H2O. Ring-opening reactions of saccharinates, with scission of the NC bond, are known to occur with nucleophiles [9]. The ring is also hydrolysed under strongly acidic conditions and on heating in water, but this results in additional rupture of the NS bond [9]. It is not clear why the five-membered rings were opened in this reaction. No strong nucleophiles were present, and although gentle heating took place to reduce the solvent volume and induce crystallisation (Section 3), this was similar to the methodology used to prepare other saccharinate complexes, where ring-opening did not occur. The identical starting material (sodium saccharinate) was used in each case [1,2]. Nevertheless this interesting and novel structure adds a new chapter to uranyl and saccharinate chemistry.
Fig. 1. X-ray structure of complex 1, showing the catena-structure and hydrogen bonds. Atoms generated by the symmetry operation x+ 1/2, 1 −y, z are primed, by the x − 1/2, 1 − y, z operation are double-primed. Table 1 Selected bond distances (A, ) and angles (°) UO(1) UO(2) UO(3) UO(4)
1.78(l) 1.78(l) 2.415(8) 2.45(l)
UO(13) UO(14%) UO(23)
2.38(l) 2.40(l) 2.36(l)
O(2)UO(1) O(l)UO(3) O(l)UO(4) O(l)UO(13) O(l)UO(14%) O(l)UO(23) O(2)UO(3) O(2)UO(4)
178.0(5) 91.0(4) 94.3(4) 89.4(4) 92.2(4) 85.9(4) 88.4(4) 87.2(4)
O(2)UO(13) O(2)UO(14%) O(2)UO(23) O(13)UO(14%) O(23)UO(3) O(14%)UO(3) O(23)UO(4) O(13)UO(4)
90.1(4) 85.8(4) 95.7(4) 73.1(3) 75.0(3) 72.1(3) 73.1(3) 67.4(3)
3. Experimental
3.1. Synthesis of the complex Uranyl nitrate hexahydrate (3.000 g, 5.98 mmol) was dissolved in 50 cm3 of water, and added to a solution of sodium saccharinate (2.450 g, 11.94 mmol) in 50 cm3 of water. The resulting bright yellow solution was gently heated, with stirring, until the volume was reduced to 15 cm3. The mixture was allowed to stand for 9 days, and the yellow crystals which formed were separated, washed with cold water and dried. Found: C, 23.67, H, 2.25, N, 3.96. C14H16N2O12S2U requires: C, 23.80, H, 2.28, N, 3.97%. Microanalyses were performed by the microanalytical services of the Department of Chemistry, University of Durham.
3.2. X-ray crystal structure determination The single-crystal diffraction data from a yellow crystal (0.4× 0.14× 0.02 mm) were collected on a SMART 1K CCD area detector (graphite-monochromated Mo Ka radiation, u( = 0.71073 A, ) at T= 150 K. Crystal data: C14H16N2O12S2U, M= 706.44, orthorhombic, space group Pca21 (no. 29), a= 7.999(8), b= 8.260(7), c= 29.761(6) A, , U= 1966(3) A, 3, Z= 4, Dcalc =2.39 g cm − 3, v= 8.54 mm − 1. Four sets of scans, each set at different and/or 2q angles, nominally covered a hemisphere of reciprocal space, giving 9862 reflections with 2q5 54.5°, of which 3940 were unique. A semi-empirical absorption correction [10] based on the intensities of Laue equivalents, reduced Rint from 0.099 to 0.058 (maximum and minimum transmission factors 0.46 and 0.29). The crystal proved to be a racemic twin with essentially equal contributions of components. The structure was solved by the Patterson method and refined by least squares against F 2 of all data using SHELX-97 software [11] (U and S atoms anisotropic, C, O and N isotropic, H riding in idealised positions, 141 refined parameters) to R=0.049 (for 3529 data with F 2 ] |(F 2)) and wR(F 2)= 0.126.
4. Supplementary material Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 144825. Copies of this information may be obtained free of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: + 44-1223-336033; e-mail: deposit@ ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
A.S. Batsano6 et al. / Inorganica Chimica Acta 309 (2000) 163–165
Acknowledgements J.A.K.H. thanks the Royal Society for a Leverhulme Trust Senior Research Fellowship, while C.B. thanks the EPSRC for financial support.
References [1] K.B. Dillon, C. Bilton, J.A.K. Howard, V.J. Hoy, R.M.K. Deng, D.T. Sethatho, Acta Crystallogr., Sect. C 55 (1999) 330. [2] R.M.K. Deng, C. Bilton, K.B. Dillon, J.A.K. Howard, Acta Crystallogr., Sect. C 56 (2000) 142. [3] F.A. Cotton, L.R. Falvello, R. Llusar, E. Libby, C.A. Murillo, W. Schwotzer, Inorg. Chem. 25 (1986) 3423.
.
165
[4] F.A. Cotton, G.E. Lewis, C.A. Murillo, W. Schwotzer, G. Valle, Inorg. Chem. 23 (1984) 4038. [5] B. Kamenar, G. Jovanovski, Cryst. Struct. Commun. 11 (1982) 251. [6] S.Z. Haider, K.M.A. Malik, K.J. Ahmed, H. Hess, H. Riffel, M.B. Hursthouse, Inorg. Chim. Acta 72 (1983) 21. [7] K.J. Ahmed, A. Habib, S.Z. Haider, K.M.A. Malik, M.B. Hursthouse, Inorg. Chim. Acta 56 (1981) L37. [8] S.Z. Haider, K.M.A. Malik, S. Das, M.B. Hursthouse, Acta Crystallogr., Sect. C 40 (1984) 1147. [9] M. Hettler, Adv. Heterocycl. Chem. 15 (1973) 233. [10] G.M. Sheldrick, SADABS: Program for Scaling and Correction of Area Detector Data, University of Go¨ttingen, Go¨ttingen, Germany, 1998. [11] G.M. Sheldrick, SHELX-97, University of Go¨ttingen, Go¨ttingen, Germany, 1997.