Scientific paper
Supramolecular Potential of Vanadium ß-Diketonate and Picolinate Compounds and The First One-dimensional Oxidovanadium(IV) Complex
with ß-Diketonate Ligand
Tanja Kole{a-Dobravc, Anton Meden and Franc Perdih*
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ve~na pot 113, P. O. Box 537, SI-1000 Ljubljana, Slovenia, and CO EN-FIST, Trg Osvobodilne fronte 13, SI-1000 Ljubljana, Slovenia
* Corresponding author: E-mail: franc.perdih@fkkt.uni-lj.si
Received: 22-09-2014
Dedicated to the memory of Prof. Dr. Jurij V. Brencic
Abstract
Three vanadium compounds with ß-diketonato or picolinato ligands were prepared and structurally characterized. In compounds [VO(tfpb)2]^ (1) (tfpb = 4,4,4-trifluoro-1-phenylbutane-1,3-dionate) and [VO(acac)2(2-pyridone)] (2) the coordination of vanadium atom is octahedral and in the compound Hpy[VO2(pic)Cl] (3) the central atom is pentacoor-dinated. X-Ray crystallographic studies reveal infinite chain formation with the V=O-V=O interactions in 1, while 2 and 3 are mononuclear compounds. Centrosymmetric hydrogen-bonded dimers are formed in 2 via N-H—O interactions due to the 2-pyridone ligand. In 3 the Hpy+ cation is hydrogen bonded to the complex anion and crystal structure is further stabilized by n—n and C-H-O interactions.
Keywords: ß-Diketonates, Picolinates, Vanadium, Crystal structure, K---K interaction
1. Introduction
The coordination chemistry of vanadium complexes with various N-, O- and S-donor chelating ligands has received considerable attention due to their interesting properties and applications. Vanadium compounds, among them also ß-diketonates and picolinates, are intensively studied for medical applications, they possess insulin enhancing activity,1 anticarcinogenic, antiproliferative, antiparasitic (Chagas disease) and other effects.2-4 The interactions of vanadium compounds with blood transport proteins have also been studied.5 Additionally, vanadium complexes are used as catalysts in oxidation reactions,6 ionic liquids7 and as precursors in metal-organic chemical vapor deposition.8 Since the discovery of MIL-26 and MIL-47 at the beginning of the last decade9 the field of vanadium metal-organic frameworks started to grow consi-derably.10 MOF materials can be constructed by covalent and/or non-covalent bonds. The acetylacetonato (acac) and picolinato (pic) ligands were selected in this research as prototypical ligands still widely studied for medical ap-
plications and also enabling the study of weak interactions. We were interested in the formation of non-covalent forces in these systems such as classical hydrogen bonds as well as C-H-O/n and n-n interactions since they have been demonstrated as important tools for assembling molecules in crystal lattices.11,12 Furthermore, the fluorinated ß-diketonato ligand 4,4,4-trifluoro-1-phenylbutane-1,3-dionate (tfpb) was selected since it is not symmetric and possesses the phenyl group enabling not only the formation of тс—тс and C-H - n interactions, but also C-H - F, F - F and C-F - n interactions13 and also because no crystal structures of VO2+ compounds with tfpb were reported so far. We were also interested if the use of fluorinated ß-diketonates would facilitate the polymer formation via V=O -V=O interactions in oxidovanadium(IV) compounds, since the introduction of fluorine atom to the li-gand enhances the acid character of the central metal atom and the increase of the coordination number can occur.
The molecular and crystal structures of [VO(tfpb)2]^ (1), [VO(acac)(2-pyridone)] (2) and Hpy[VO2(pic)Cl] (3) are presented and their geometries are discussed. This
study provides an insight into the influence of different types of ligands on the crystal architecture, hydrogen-bond formation and ж—ж interactions.
2. Experimental
2. 1. Materials and Characterization
Reagents and chemicals were obtained as reagent grade from commercial sources and were used as purchased without any further purification. VO(acac)2 was prepared according to a literature procedure.14 Infrared (IR) spectra (4000-600 cm-1) of the samples were recorded using a Perkin-Elmer Spectrum 100, equipped with a Spe-cac Golden Gate Diamond ATR as a solid sample support. Elemental (C, H, N) analyses were obtained using a Perkin-Elmer 2400 Series II CHNS/O Elemental Analyzer.
2. 2. Synthesis
Compound 1 (prepared by a modified procedure3a): 4,4,4-trifluoro-1-phenylbutane-1,3-dione (432 mg, 2.00 mmol) was dissolved in methanol (2 mL). After addition of NaCH3COO 3H2O (272 mg, 2.00 mmol) in water (2 mL), the mixture was stirred for 5 min and then added dropwise to the solution of VOSO4 5H2O (253 mg, 1.00 mmol) in water (3 mL). A light brown precipitate occur-
red. The mixture was stirred at 70 °C for additional 5 min. The precipitate was filtered off and dried. Yield: 380 mg, 76%. Crystals suitable for X-ray analysis were obtained either from ethanol/toluene solution of the product or from organic layer obtained after extraction of reaction mixture with chloroform (2 x 4 mL) and addition of toluene (2 mL). In both cases after a few days of slow evaporation of solvents yellow needles were grown from the solution. IR (ATR, cm-1): 1597s, 1572m, 1547w, 1538w, 1455m, 1321m, 1311w, 1293s, 1255m, 1181m, 1139s, 1095w, 1076w, 946w, 888s, 807m, 768m, 722m, 692m, 656m, 601m. CHN elemental analysis calculated for C20F6H12O5V (%): C 48.31, H 2.43; found: C 48.24, H 2.32.
Compound 2: VO(acac)2 (66 mg, 0.25 mmol) was dissolved in warm chloroform (5 mL) and 2-pyridone (24 mg, 0.25 mmol) was added. The reaction mixture was stirred for 10 min and then allowed to stand at room temperature. Green crystals suitable for X-ray analysis were obtained after slow evaporation of the solvent. Yield: 36 mg, 55%. IR (ATR, cm-1): 3088w, 2918w, 1647m, 1571m, 1520s, 1429m, 1383m, 1363s, 1279m, 1241m, 1168m, 1018m, 972s, 931m, 787s, 781m, 768m, 738m, 679m, 606m.
Compound 3: Ammonium metavanadate (59 mg, 0.50 mmol) was suspended in water (3 mL) and picolinic acid (62 mg, 0.50 mmol) was added. The mixture was stir-
Table 1. Crystallographic and refinement data for 1a, 1b, 2 and 3.
Parameter	[VO(tfpb)2]	[VO(tfpb)2]	[VO(acac)2(2-pyridone)]	Hpy[VO2(pic)Cl]
	(1a)	(1b)	(2) 2	(3)
Mr	497.24	497.24	360.25	320.60
T (K)	150(2)	293(2)	293(2)	293(2)
Crystal system	Orthorhombic	Orthorhombic	Triclinic	Monoclinic
Space group	Ccc2	Ccc2	P-1	P21/c
a (À)	16.4708(7)	16.7507(10)	7.5066(3)	10.15709(3)
b (À)	16.8106(8)	16.8587(14)	10.6366(6)	9.9246(4)
c (À)	7.5120(4)	7.5561(6)	10.7430(5)	13.4691(4)
« (°)	90.00	90.00	88.063(3)	90.00
ß(°)	90.00	90.00	75.206(3)	115.553(2)
r(°)	90.00	90.00	85.574(3)	90.00
Volume (À3)	2079.95(17)	2133.8 (3)	826.78(7)	1274.85(7)
Z	4	4	2	4
Dcalc(Mg/m3)	1.588	1.548	1.447	1.670
^ (mm 1)	4.772	0.545	0.629	0.998
F(000)	996	996	374	648
Crystal size (mm)	0.20 x 0.02 x 0.02	0.25 x 0.05 x 0.05	0.20 x 0.10 x 0.08	0.20 x 0.07 x 0.05
Reflections collected	3131	5510	6608	5461
Reflections unique (Rint)	1576 (0.0203)	1929 (0.0402)	3673 (0.0355)	2893 (0.0217)
Parameters	241	234	212	174
R, wR2 [I>2o(/)]a	0.0393, 0.1007	0.0533, 0.1139	0.0472, 0.1200	0.0375, 0.0937
R, wR2 (all data)b	0.0468, 0.1087	0.0808, 0.1295	0.0645, 0.1340	0.0552, 0.1047
GOF, Sc	1.059, 1.091	1.104, 1.123	1.077	1.042
Max/min Ар (e/ À3)	0.180/-0.199	0.132/-0.187	0.308/-0.366	0.230/-0.319
a R = X||Fo| - |Fc||/£|FJ. b wR2 = {X[w(Fo2 - Fc2)2]/E[w(Fo2)2]}1/2. c S = {X[(Fo2 - Fc2)2]/(n/p)}1/2 where n is the number of reflections and p is the total number of parameters refined.
red for one minute and then pyridine (79 mg, 1.00 mmol), concentrated hydrochloric acid (0.5 mL) and methanol (5 mL) were added. Yellow solution was stirred for an additional hour at room temperature and then filtered. After few days of slow evaporation of solvents, green crystals concomitantly with a few colorless crystals of NH4Cl were grown from the solution. They were filtered, washed with water and methanol, and dried. Yield: 107 mg, 67%. IR (ATR, cm-1): 3080w, 3062w, 2813br, 1685s, 1637w, 1606m, 1536w, 1485m, 1447w, 1374w, 1340s, 1289m, 1240w, 1202w, 1162m, 1049m, 946m, 924s, 908m, 857m, 754s, 740m, 709m, 676s, 650m, 607w.
2. 3. X-ray Crystallography
Single crystal X-ray diffraction data were collected at room temperature with an Agilent Technologies SuperNova Dual diffractometer with an Atlas detector (1a, 1b) and a Nonius Kappa CCD diffractometer (2, 3) using monobromated Mo-£a radiation (X = 0.71073 À) (1a, 2, 3) or Cu-£a radiation (X = 1.54184 À) (1b). The data were processed using CrysAlis Pro15 (1a, 1b) or DENZO16 (2, 3). The structures were solved by direct methods implemented in SHELXS17 (1b), SIR-9718 (2, 3) and SIR-200419 (1a) and refined by a full-matrix least-squares procedure based on F2 with SHELXL-97.17 All the non-hydrogen atoms were refined anisotropically. All H atoms were initially located in a difference Fourier maps and then treated as riding atoms in geometrically idealized positions. In 1a C4-C10 atoms were refined with FLAT restrain. V atom, O atoms and C7-C10 atoms of phenyl group are disordered over two positions in the ratio
0.57:0.43, and the CF3 group is disordered over two positions in the ratio 0.53:0.47. C-F and V=O bond distances were restrained by SADI instruction, and ISOR restraint was used in refinement of fluorine, O1A, and O1B atoms. In 1b V atom, O atoms, CF3 group, and phenyl group are disordered over two positions in the same ratios as in 1a. The fluorine atoms were fitted into regular tetrahedron using SADI instruction for C-F and F-F distances. F1A and F1B were additionally refined using ISOR restrain. The crystallographic data are listed in Table 1. Due to severe disorder the structure was also solved in the monoclinic P21/c and in the orthorhombic Cccm space group, however, no improvement regarding the disordered part was achieved. For comparison, at the completion of the refinement the tf-factor for 1a (150 K) was 0.0393 for Ccc2 and 0.0505 for Cccm.
3. Results and Discussion
3. 1. Literature Data and Possible Geometry for Bischelated VO2+ Complexes of ß-Diketonates
The crystallographic evidence reveals that bis(dike-tonate) complexes of oxidovanadium(IV) [VO(diketona-te)2] display a square-pyramidal geometry with two ß-di-ketonates in the equatorial position and an oxido ligand in the axial position (Scheme 1).20 In the case of non-symmetric ß-diketonates cis (A)21 and trans (B)3a22 iso-mers are possible. However, the central metal atom is in such cases coordinatively unsaturated. The completion of
Scheme 1
the coordination sphere can be achieved by adduct formation, in most cases by small neutral O- or N-donating li-gands, leading to [VO(diketonate)2L] species with ligand L in trans position to VO2+ moiety.23 In such octahedral species the non-symmetric ß-diketonates bound to the central metal atom in equatorial position could still form cis (C)3a and trans isomers (D). Additionally, the ligand L may lie not only in the axial position (trans to the VO2+ moiety), but also in equatorial position (cis to the VO2+ moiety) (E).24 In none of these cases infinite structures are obtained, instead only discrete molecules are formed. In order to overcome this problem, we have to be aware that the supramolecular frameworks in the case of diketonates can be typically achieved using functionalized diketones or by the introduction of additional neutral ligands linking the metal centers thus enabling further connectivity.25 On the other hand, in the case of oxidovanadium(IV) bis(di-ketonates) the third approach to form infinite covalently bound structures is possible due to V=O-V=O interactions (F). The crystallographic evidence of such interaction is scarce, mostly polymeric oxidovanadium(IV) Schiff base compounds have been reported.26,27 In CSD no analogous polymeric crystal structures have been reported on ß-diketonates. In the last decades it has been established that the introduction of fluorine atom into organic framework of the ligand enhances the acid character of the central metal atom and a stronger binding to the additional ligands can therefore occur.28 The increase in the coordination number from five to six can also be achieved as, for example, in the case of many copper ß-diketonato complexes.28 It can be thus expected, that the enhanced acid character of vanadium center due to fluorinated ß-diketo-nates could facilitate the polymer formation via V=O—V=O interactions.
3. 2. Synthesis and Characterization of
Bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato)oxidovanadium(IV) (1a, 1b)
Compound 1 was prepared from VOSO45H2O and 4,4,4-trifluoro-1-phenylbutane-1,3-dione by a modified procedure published by Sgarbossa et al.3a Yellow needles of rather moderate quality but still suitable for X-ray analyses were obtained from ethanol/toluene or chloroform/toluene solutions at room temperature after a few days of standing on air. The IR spectrum of 1 fits well with the previously published3a with a strong band at 889 cm-1, which is according to the literature characteristic V=O stretching band for polymeric •V=O-V=O - linear chain structures with distorted octahedral geometry.26
This observation is in accordance with results of the single crystal analysis. Two different crystals were analyzed by single crystal X-ray diffraction at 150 K (1a) and at room temperature (1b). Cell parameters at both temperatures are quite similar with the exception of axis a, that is elongated at higher temperature (~17%, 0.28 À). Crystal
Figure 1. Structure of 1a with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. Disorder is presented by dashed lines.
structures were refined in orthorhombic Ccc2 space group and show the presence of one-dimensional polymeric structure.
Structures 1a and 1b are very similar. Selected bond distances and angles of 1a are summarized in Table 2, data of room temperature measurement 1b can be found in Supplementary material. Asymmetric unit of 1a contains one half of the bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato)oxidovanadium(IV) complex with the VO2+ moiety on a twofold axis. Vanadium center has distorted octahedral geometry with carbonyl oxygen atoms of two bi-dentate tfpb ligands in the equatorial plane and with oxido atoms in axial positions (Figure 1). The first oxido atom is doubly bound to vanadium center, while the second is a part of the adjacent VO2+ moiety. Each oxido atom is therefore also a bridging atom to the next vanadium center enabling •V=O-V=O- interactions and causing the formation of one-dimensional coordination polymer.
The structure of 1a shows a great crystallographic disorder over two positions. The VO2+ moiety, carbonyl oxygen atoms and phenyl ring occupy two opposite positions with distinct refined occupation ratio of 0.57:0.43, while an easily rotatable CF3 group is disordered with the ratio 0.53:0.47. Both positions of the disordered complex give the same, only inverted, polymeric structure. To simplify, only the major part will be discussed briefly. Bond distance of V=O double bond is 1.601(11) À and bond distance of V-O interaction is 2.155(11) À. Vanadium is shifted 0.31 À out of the basal plane generated by the equatorial oxygen atoms. Tfpb ligand is bound to vanadium in a bidentate manner with the chelate angle 88.3(2)° and V-O bond distances 1.985(5) and 1.982(5) À. Angles between O1 and equatorial oxygen atoms are 99.3(2) and 98.5(2)°. Polymeric chain is stabilized by weak rc -rc stacking interactions with the centroid-to-centroid distance between phenyl rings of 4.215(8) À (Figure 2).
Table 2. Selected bond distances and angles for 1a.
Distance	(A)		
V1A-O1A	1.601(11)	V1B-O1B	1.609(13)
V1A-O2A	1.985(5)	V1B-O2B	1.989(7)
V1A-O3A	1.982(5)	V1B-O3B	1.990(6)
V1A-O1Aii	2.155(11)	V1B-O1Biii	2.147(13)
Angle	(°)		
O1A-V1A-O1Aii	180.000(4)	O1B-V1B-O1Bm	180.000(2)
O1A-V1A-O2A	99.3(2)	O1B-V1B-O2B	97.7(3)
O1A-V1A-O3A	98.5(2)	O1B-V1B-O3B	99.0(3)
O2A-V1A-O2Ai	161.4(5)	O2B-V1B-O2Bi	164.6(6)
O2A-V1A-O3A	88.3(2)	O2B-V1B-O3B	89.7(3)
O2A-V1A-O3Ai	88.9(2)	O2B-V1B-O3Bi	87.9(3)
O3A-V1A-O3Ai	162.9(4)	O3B-V1B-O3Bi	162.1(5)
O1An-V1A-O2A	80.7(2)	O1Biii-V1B-O2B	82.3(3)
O1An-V1A-O3A	81.5(2)	O1Biii -V1B-O3B	v81.0(3)
Symmetry codes: (i) -x, -y, z; (ii) -x, y, z - /; (iii) -x, y, z + /.
Figure 2. Coordination polymer of 1a. For clarity only one orientation of the coordination polymer chain without a minor part of the disorder is presented. Stabilization by ГС---ГС stacking interactions is indicated by dashed lines (symmetry codes: (i) x, -y, z + /; (ii) x,
-y, z - /).
3. 3. Synthesis and Characterization of Bis(acetylacetonato)(2-pyridone) oxidovanadium(IV) (2)
Compound 2 was prepared by mixing VO(acac)2 with 2-pyridone in 1:1 ratio in warm chloroform and crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent at room temperature. In IR spectrum of 2 a stretching vibration of the VO2+ moiety is observed as a strong band at 972 cm-1. A band at 1635 cm-1 in the free 2-pyridone corresponding to C=O vibration is shifted to 1647 cm-1 upon coordination. This vibration confirms the presence of the lactam form of 2-pyridone in compound 2. Vibrations near 2918 cm-1 suggest the involvement of the O-H group in the hydrogen bonding.
Compound 2 crystallizes as green prisms in the triclinic P-1 space group. Selected bond distances and
Figure 3. The asymmetric unit of 2 showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability
level.
Table 3. Selected bond distances and angles for 2.
Distance	(A)				
V1-O1	1.588(2)	V1-	O4		1.9828(18)
V1-O2	1.9830(17)	V1-	O5		1.9886(17)
V1-O3	1.9891(17)	V1-	-O6		2.515(2)
Angle	(°)				
O1-V1-O2	100.14(10)	O2	-V1-	O5	160.66(8)
O1-V1-O3	99.74(10)	O3	-V1-	O4	160.09(8)
O1-V1-O4	100.16(10)	O3	-V1-	O5	88.56(7)
O1-V1-O5	99.18(10)	O4-V1-		O5	88.84(7)
O2-V1-O3	88.86(7)	O1	-V1-	O6	174.65(9)
O2-V1-O4	87.10(7)				
angles of 2 are summarized in Table 3. The vanadium atom in compound 2 is octahedrally coordinated (Fig. 3) with four oxygen atoms of two chelating acac ligands with V-O distances 1.983-1.989 À in a basal plane and the vanadium atom lying 0.34 À above this plane. Bite angles O-V-O are ~88.8°, while O-V-O in trans posi-
Figure 4. The 2D network parallel to the bc plane in 2 formed by weak C-H-O interactions (symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y + 2, -z + 1; (iii) -x + 1, -y + 1, -z).
tions are ~160°. The V=O double bond length is 1.588(2) À and the V-O(pyridone) is 2.515(2) À. This distance is rather long; however, similar contacts in the range from 2.46 even up to 2.58 À were found in CSD.29 Even though the carbonyl oxygen of the 2-pyrido-ne ligand is coordinated to the vanadium center, it can still act as a hydrogen bond acceptor facilitating the formation of centrosymmetric hydrogen-bonded dimers via N1-H1-O6(-x + 1, -y + 1, -z + 1) interactions (Fig. 4, Table 4). Hydrogen-bonded dimers are further stabilized by weak C15-H15-O5(-x + 1, -y + 1, -z + 1) interactions and 2D framework is achieved by weak C13-H13-O2(-x + 1, -y + 1, -z) and C10-H10A-O3(-x + 1, -y + 2, -z + 1) interactions (Fig. 4).
3. 4. Literature Data and Structures for VO2+ Complexes of Monochelated Picolinates and Chlorido Compounds
The crystallographic evidence on bischelated pico-linato complexes of VO2+ has been discussed earlier.5a30 When examining the known monopicolinate complexes of dioxidovanadium(V), VO2(picolinate), we found only four structures and all display a trigonal bipyramidal geometry with a chelating picolinato or quinoline-2-carboxy-lato ligand and an additional monodentate ligand.31 Structures with chlorido ligand bonded to VO2+ are also not numerous, as only five entries in CSD could be found. All of these compounds were prepared under the inert atmosphere since V-Cl bond can be easily hydroly-zed. Compounds [VO2Cl(py)2]32 33 and [VO2Cl(O-py)2]33 possess trigonal bipiramidal and PPh3Me[VO2Cl2]34 te-trahedral geometry.
3. 5. Synthesis and Characterization of Pyridinium Chlorido(pyridin-2-carboxylato-jV,0)dioxidovanadate(V) (3)
Compound 3 was prepared from ammonium metava-nadate and picolinic acid with the addition of pyridine and hydrochloric acid. Small cubic crystals of a side product NH4Cl with similar solubility were present despite many attempts of washing and recrystallization of the compound 3. Anyway, we managed to isolate some single crystals suitable for X-ray analysis. In IR spectrum of 3 bands for aromatic C-H vibrations are present at 3080 and 3062 cm-1,
Table 4. Hydrogen bonds for 2 [À and °]
D-H-A	d(D-H)	d(H-A)	d(D-A)	<(DHA)	Symmetry transformation for acceptors
N1-H1-O6	0.86	2.02	2.884(2)	177	-x + 1, -y + 1, -z + 1
C10- H10A-O3	0.96	2.57	3.367(4)	140	-x + 1, -y + 2, -z + 1
C13-H13-O2	0.93	2.55	3.426(4)	158	-x + 1 , -y + 1 , -z
C15-H15-O5	0.93	2.46	3.249(4)	142	-x + 1 , -y + 1 , -z + 1
as well as asymmetric and symmetric vibrations of COO-group at 1685 and 1340 cm-1. The difference between asymmetric and symmetric stretching vibrations (A = vas -vs) of 345 cm1 is in accordance with the monodentate coordination of the COO- group to the VO2+ moiety. Stretching vibrations of the VO2+ group are observed as a medium band at 946 cm-1 and a strong band at 924 cm-1.
Compound 3 crystallizes as green prisms in the monoclinic P21/c space group. Selected bond distances and angles of 3 are summarized in Table 5. Asymmetric unit of 3 consists of vanadium(V) complex anion and pyridinium cation as its counter ion (Fig. 5). Vanadium(V) metal center is pentacoordinated. The distortion of a trigonal bip-yramid can be best described by the structural parameter т (0 for an ideal square pyramid and 1 for an ideal trigonal bipyramid),35 which in this case has the value of 0.44. This value would imply the presence of distorted square pyramid geometry; however, visual inspection would suggest distorted trigonal bipyramidal geometry. Although the trigonality index т is a well established structural parameter some of the reported examples show that т is not always a reliable guidance.36 This seems to be the case for compounds in which one metal-ligand bond is elonga-ted,36 as is the case in 3. Reason for this is that the parame-
Table 5. Selected bond distances and angles for 3.
Distance	(A)			
V1-O1	1.6124(18)	V1-	-N1	2.125(2)
V1-O2	1.6276(18)	V1-	-Cl1	2.3308(8)
V1-O3	2.0347(15)			
Angle	(°)			
O1-V1-O2	108.41(10)	O3	-V1-N1	75.17(7)
O1-V1-O3	117.23(9)	O1	-V1-Cl1	100.32(7)
O2-V1-O3	132.76(9)	O2	-V1-Cl1	99.37(7)
O1-V1-N1	93.36(9)	O3	-V1-Cl1	84.42(5)
O2-V1-N1	91.19(9)	N1-	-V1-Cl1	159.03(6)
Figure 5. The asymmetric unit of 3 with atom labels. Ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonds.
ter т is based solely on the two largest X-M-X angles, and does not account for the distortion of the geometry due to bond elongations.
Pyridin-2-carboxylato (picolinato) ligand is bound to vanadium in a bidentate manner through nitrogen and car-boxylato oxygen atoms with the chelate angle 75.17(7)°. The angle between N1 and Cl1 atoms is 159.03(6)°, angles between oxygen atoms are 108.41(10)-132.76(9)°, while angles between N1 or Cl1 and oxygen atoms are 84.42(5)-100.32(7)°. The V-Cl distance is 2.3308(8) À, and the V=O double bond lengths are 1.6124(18) and 1.6276(18) À. These lengths are in the same range as in the other dioxidovanadates(V), but slightly shorter as in octahedral bis(picolinato)dioxovanadate(V) complex.37
Crystal structure of 3 is stabilized by hydrogen bonds, ж—ж stacking interactions and weak C-H -O/Cl interactions listed in Table 6. Hydrogen bonds are formed between the pairs of a pyridinium cation and a complex vanadate anion. N2-H2 group of the pyridinium cation is hydrogen-bonded to the carboxylate O3, as well as to the chlorido Cl1 atom in the same anion. Hydrogen-bonded pairs are connected into infinite chains parallel to the b axis (Fig. 6) due to ж—ж stacking interactions between picolinato (ring centroid Cg2) and pyridinium rings or between two adjacent pyridinium rings (ring centroid Cg3) with the centroid-to-centroid distances 3.5886(17) and 4.008(2) À, respectively. Further stabilization is enabled by weak hydrogen interactions between pyridinium C-H and O1, O4 and Cl1 atoms spreading in all three dimensions (Fig. 7).
Table 6. Hydrogen bonds for 3 [À and °]
D-H-A	d(D-H)	d(H-A)	d(D-A)	<(DHA)	Symmetry transformation for acceptors
N2-H2-O3	0.86	2.07	2.872 (3)	154	x, y, z
N2-H2-CU	0.86	2.72	3.357 (2)	132	x, y, z
C7-H7-O4	0.93	2.55	3.347(3)	144	x, -y + У , z - У
C8-H8-CU	0.93	2.70	3.620(4)	171	-x + 1, y - У, -z + У
C9-H9-O1	0.93	2.60	3.357(4)	139	-x + 1, -y, -z + 1
C10-H10-O1	0.93	2.42	3.193(3)	141	x + 1, -y + У, z + У
C11-H11-O4	0.93	2.40	3.222(4)	148	x, y, z
Figure 6. Twisted infinite chains formed by the combination of hydrogen bonds and re-re stacking interactions in 3 forming infinite chain along b axis. Dashed lines indicate hydrogen bonds, and dotted lines indicate centroid-to-centroid distances (symmetry codes: (i) —x + 1, -y + 1, -z + 1; (ii) -x + 1, —y, —z + 1).
Figure 7. 3D network formed by weak hydrogen bonds in 3. Dashed lines indicate weak C-H---O interactions (symmetry codes: (i) x, -y + /, z - / (ii) -x + 1, y - '/2, -z + '/2; (iii) -x + 1, -y, -z + 1).
fluorinated ß-diketonato ligand tfpb enhances the acid character of the vanadium atom and the additional interaction with the adjacent oxidovanadium(IV) group occurs. Compound [VO(acac)(2-pyridone)] (2) has an octahedral structure with the 2-pyridone ligand in trans position to VO2+ group. Even though the carbonyl oxygen of the 2-pyridone ligand is coordinated to the vanadium center, it can still act as a hydrogen bond acceptor facilitating the formation of centrosymmetric hydrogen-bonded dimers via N-H - O interactions with the adjacent molecule. In compound Hpy[VO2(pic)Cl] (3) the metal center is pentacoordinated with one picolinato and one chlorido ligand coordinated to the dioxidovanadium(V) moiety, and the Hpy+ cation is hydrogen bonded to the complex anion. The crystal structure is stabilized by ж—ж and C-H - O interactions. This study provides an insight on the influence of different types of ligands on the molecular structure and crystal architecture. Such cases are valuable examples that can help to understand the covalent and non-covalent factors governing the supramolecular aggregation important for crystal engineering and crystal structure prediction.
5. Supplementary Material
CCDC 1024846-1024849 (1a-3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Cry-stallographic Data Centre via www.ccdc.cam.ac.uk/da-ta_request/cif.
4. Conclusion
Three vanadium compounds with ß-diketonato or pi-colinato ligands were prepared and structurally characterized. Compound [VO(tfpb)2]^ (1) represents the first X-ray structure of an oxidovanadium(IV) ß-diketonate with infinite chain formed by the V=O-V=O interactions. The
6. Acknowledgment
The authors thank the Ministry of Education, Science and Sport of the Republic of Slovenia and the Slovenian Research Agency for financial support (P1-0230-0175) as well as the EN-FIST Centre of Excellence, Trg Osvobodilne fronte 13, 1000 Ljubljana, Slovenia for use of the Supernova diffractometer.
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Povzetek
Pripravili in strukturno okarakterizirali smo tri vanadijeve spojine z yö-diketonato in picolinato ligandi. V spojinah [VO(tfpb)2]^ (1) (tfpb = 4,4,4-trifluoro-1-fenilbutan-1,3-dionat) in [VO(acac)2(2-piridon)] (2) je koordinacija vanadije-vega atoma oktaedrična, v spojini Hpy[VO2(pic)Cl] (3) je centralni atom pentakoordiniran. Rentgenska strukturna analiza razkriva tvorbo neskončne verige preko V=O-V=O vezi v 1, medtem ko sta 2 in 3 enojedrni spojini. V 2 se preko N-H—O vezi s pomočjo koordiniranega 2-piridona tvorijo centrosimetrični dimeri. V 3 je Hpy+ kation preko vodikovih vezi vezan na kompleksni anion, kristalna struktura pa je dodatno stabilizirana s K---K in C-H—O interakcijami.
Supplementary material
Supramolecular Potential of Vanadium jff-Diketonate and Picolinate Compounds and The First One-dimensional Oxidovanadium(IV) Complex with jff-Diketonate Ligand
Tanja Koleša-Dobravc, Anton Meden, Franc Perdih*
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, P. O. Box 537, SI-1000 Ljubljana, Slovenia, and CO EN-FIST, Trg Osvobodilne fronte 13, SI-1000 Ljubljana, Slovenia
Fig. S1. The molecule of 1b showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level. The disorder of CF3 groups is indicated by dashed lines, minor part of disordered vanadyl moiety and phenyl ring is omitted for clarity (symmetry codes: (i) -x, -y, z; (ii) -x, y, z - V).
Table S1. Selected bond distances and angles for 1b.
о
Distance
(Ä)
V1A-O1A V1A-O2A V1A-O3A V1A-O1Ai
ii
1.54(2) 1.970(10) 1.992(9) 2.23(2)
V1B-O1B V1B-O2B V1B-O3B V1B-O1B
iii
1.54(3) 2.007(17) 1.984(14) 2.24(3)
Angle
(°)
O1A-V1A-O1A11
O1A-V1A-O2A
O1A-V1A-O3A
O2A-V1A-O2Ai
O2A-V1A-O3A
O2A-V1A-O3Ai
O3A-V1A-O3Ai
O1Aii-V1A-O2A
O1Aii-V1A-O3A
ii
98.5(4)
97.2(4)
163.1(8)
89.1(5)
88.7(5)
165.7(8)
81.5(4)
82.8(4)
180.000(1)
O1B-V1B-O1B111 180.000(4)
O1B-V1B-O2B	100.3(6)
O1B-V1B-O3B	101.7(6)
O2B-V1B-O2B1	159.4(12)
O2B-V1B-O3B	88.5(7)
O2B-V1B-O3B1	87.4(6)
O3B-V1B-O3B1	156.6(12)
O1B111-V1B-O2B	78.3(6)
O1B111 -V1B-O3B	79.7(6)
Symmetry codes: (i) -x, -y, z; (ii) -x, y, z - V; (iii) -x, y, z + V.