Transition metal coordination compounds with the ... - Springer Link

Journal of Crystallographic and Spectroscopic Research, Vol. 18, No. 2, 1988

Transition metal coordination compounds with the dithiooxalate ligand. Synthesis, spectroscopic studies, crystal structure, and bonding of (CsI-IsNH)2[Ni(82C202)2] P. ROMi~N,* C. BAO, and J. M. GUTIt~RREZ-ZORRILLA Departamento de Quimica Inorgdnica, Universidad del Pals Vasco Apartado 644, 48080 Bilbao, Spain

A. VEGAS lnstituto de Qufmica lnorgdnica "Elhuyar, "' CSIC, Serrano 113 28006 Madrid, Spain

(Received August 9, 1987; revised November 23, 1987)

Abstract Several new compounds belonging to the family of bis(dithiooxalato)nickelate(II) complex anion with the general formula (BH)2[Ni(S2C202)E] , where B = pyridine, 3-methylpyridine, 3-ethylpyridine, 4-methylpyridine, and 4-ethylpyridine (hereafter abbreviated as PYNIDT, M3NIDT, E3NIDT, M4NIDT, and E4NIDT, respectively) have been prepared. PYNIDT, M3NIDT, and E3NIDT are isostructural between them and different from the two other compounds, M4NIDT and E4NIDT, which are also isostructural. All of these compounds crystallize in the monoclinic system, space group P2~/n with Z = 2. Crystal parameters for PYNIDT are: a = 5.793(3), b = 14.280(5), c = 11.222(3) A,, /3 = 97.29(4) ~ V = 920.8(9) ~3, F(000) = 468, Dx = 1.66, Do = 1.65(1) Mg m -a, R = 0.048, and Rw = 0.057 for 1236 observed reflections. The IR and UV-V spectra show that the organic bases are protonated and the anion presents the well-known spectrum for the bis(dithiooxalato)nickelate(II) anions. Thermogravimetric studies indicate that the compounds are anhydrous. The structure solution of PYNIDT confirms that this compound contains discrete quasi-planar complex [Ni($2C202)2] 2- anions and (CsHsNH) + 207 0277-8068/88/0400-0207506.00/0

9 1988 Plenum Publishing Corporation

208

Roman et al.

planar cations linked through hydrogen bonds. The structure stacks into layers where the ions are associated into cation 9 9 9 anion 9 9 9cation entities through bifurcated hydrogen bonds.

Introduction

The synthesis and the crystal structure of alkaline, alkaline-earth, Zn, and transition metals salts of the anion [Ni($2C202)2] 2- have been reported previously (Frasse et al., 1985; Gleizes et al., 1979, 1980, 1981, 1984; Gleizes and Galy, 1979; Gleizes and Verdaguer, 1984; Maury and Gleizes, 1980; Trombe et al., 1984, 1985). This paper deals with the synthesis, chemical characterization, spectroscopic studies, and the crystal data of pyridinium and some n-alkylpyridinium bis(dithiooxalato)nickelate(II) new complexes, and the crystal structure and bonding of pyridinium salt. The structure is discussed in terms of comparison with those of the alkylpyridinium complexes. This work forms part of a series of studies on bis(dithiooxalato)metalate(II) of protonated organic bases aimed at a better understanding of the structural features of the implied ions. The first contributions to this subject have been published recently (Enjalbert etal., 1985; Trombe et al., 1985). PYNIDT was isolated during an aqueous solution study of the formation of pyridinium and n-alkylpyridinium bis(dithiooxalato)nickelate(II). The compound is a black crystalline solid. It is insoluble in all nonpolar solvents and soluble in polar solvents. It is stable in air, light, and X-ray exposure.

Experimental

Synthesis

PYNIDT, M3NIDT, E3NIDT, M4NIDT, and E4NIDT compounds were obtained by mixing potassium bis(dithiooxalato)nickelate(II) with the perchlorate of the protonated organic bases in concentrated aqueous solution according to the methods of Robinson and Jones (1912) and Cox et al. (1935): 2 (BH)C104 + Kz[Ni(S2C202) 2] -'* (BH)2[Ni(S2C202) 2] + 2 KC104

(1)

where B = pyridine, 3-methylpyridine, 3-ethylpyridine, 4-methylpyridine, and 4-ethylpyridine. Potassium perchlorate precipitates and is eliminated by filtration. On evaporation of the solutions, black prismatic needles as single crystals appear. They are filtered, washed with EtOH and Et20, and finally dried in air. Formulas and content of C, H, N, and Ni (%) are listed in Table 1.

Structure of

(CsHsNH)2[Ni(S2C202)2]

209

Decomposition studies Thermogravimetric analyses were performed on a Perkin-Elmer TGS-2 instrument at a heating rate of 5~ in dinitrogen under atmospheric pressure.

Spectroscopic studies Infrared spectra were recorded on a Perkin-Elmer 1430 spectrophotometer (4000-250 cm-l). Solid compounds were mixed with potassium bromide and pressed into colorless disks. Ultraviolet and visible spectra were recorded on a Shimadzu UV 260 spectrophotometer operating in the region 200-650 nm. Samples were dissolved in water and 1-cm silica cells were used.

Density measurements Densities were measured by the method of Archimedes (Rom~in and Guti6rrez-Zorrilla, 1985) in a mixture of CCI4/CHBr3.

X-ray data collection The single crystals were mounted on an Enraf-Nonius CAD-4 computercontrolled four-circle X-ray diffractometer, and data were collected at 295 K (Mo Kot, k = 0.71069 ,~). The cell parameters of the compounds were determined by least-squares fit of 25 Bragg angles measured for both positive and negative 0 values. Table 2 lists the crystallographic data of the compounds. Three of the compounds are isostructural among them (PYNIDT, M3NIDT, and E3NIDT), and the compounds M4NIDT and FANIDT are also isostructural between them, showing different parameters. The crystal of PYNIDT selected for the crystal solution was a prismatic single crystal of dimensions 0.33 • 0.10 • 0.10 mm. During data collection, two references were monitored to check drifts in electronics, radiation damage, variations in X-ray tube intensity, crystal stability, and counter response. No Table 1. Formulasand content of C, N, H, and Ni(%) Found (Calcd.) % Compound

Formula

C

H

N

Ni

PYNIDT M3NIDT E3NIDT M4NIDT E4NIDT

(CsHsNH)2[Ni(S2C202)2] (C6H7NH)2[Ni(SEC202)2I (C7H9NH)2[Ni(S2C202)2] (C6HTNH)2[Ni(S2C202)2] (C7H9HN)2[Ni(S2C202)2]

36.6 (36.6) 39.5 (39.4) 42.0 (42.0) 39.3 (39.4) 42.1 (42.0)

2.6 (2.6) 3.2 (3.3) 4.0 (3.9) 3.4 (3.3) 4.1 (3.9)

6.1 (6.0) 5.7 (5.8) 5.5 (5.4) 5.8 (5.8) 5.3 (5.4)

12.7 (12.8) 12.1 (12.1) 11.3 (11.4) 12.0 (12.1) 11.4 (11.4)

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R o m a n et al.

Table 2. Crystallographic data for the complexes Compound Molecular weight Space group a(A) b c a (deg) 13 3' V (.~3) Z Do(Mg m -3) Dx

PYNIDT 459.23 P2 ~/n 5.793(3) 14.280(5) 11.222(3) 90 97.29(4) 90 920.8(9) 2 1.65(1) 1.66

M3NIDT 487.28 P2 ~/n 6.046(8) 14.474(5) 11.698(9) 90 101.21(6) 90 1004(1) 2 1.61(2) 1.61

E3NIDT 515.33 P21/n 5.854(2) 15.465(6) 12.399(5) 90 99.97(6) 90 1105(3) 2 1.56(2) 1.55

M4NIDT 487.28 P2 ~/n 7.151(3) 12.776(3) 11.254(5) 90 98.82(2) 90 1016(3) 2 1.58(2) 1.59

E4NIDT 515.33 P21/n 7.766(4) 13.312(5) 11.687(2) 90 104.65(3) 90 1164(2) 2 1.48(2) 1.47

crystal decay was o b s e r v e d during the data collection process. Table 3 summarizes the data c o l l e c t i o n and final refinements o f the crystal structure.

Structure determination and refinement A total o f 1236 reflections with I > 3a(I) was classified as o b s e r v e d and used for the structure refinement. T h e intensities w e r e corrected for Lorentz and polarization effects. Scattering factors for neutral atoms w e r e taken f r o m the International Tables for X-ray Crystallography ( C r o m e r and W a b e r , 1974). T h e position o f the nickel a t o m was located on a Patterson map, the r e m a i n i n g Table 3. Data collection and refinement conditions for PYNIDT Temperature (K) Radiation h(Mo Ks) (A) Monochromatization Detector window Scan mode Maximum Bragg angle (0) Scan amplitude Scan speed Controls Reflections Periodicity Recorded reflections Observed reflections [1 > 3a(1)] Refined parameters R Rw s (e/A_3)

(A/O')max

Data collection 295 0.71069 graphite oriented height = 4 mm; width = 4mm

w/20 30 A0 = A0o + B tan 0; A0o = 1~ B = 0.35 3~ Intensity Orientation (0 2 -6), (0 4 -6) (0 2 -6), (0 4 -6) 7200 s 100 reflections Conditions for refinement 2755 1236 139 0.048 0.057 0.955 0.093

211

Structure of (CsHsNH)2[Ni(S2C202)2] Table 4. Atomiccoordinates and isotropic thermal parameters (x

10 4

for non-H atoms, and

• 102 for H atoms) (~2) for PYNIDT Atom

x/a

y/b

z/c

Ueqa

Ni S(1) S(2) C(I) C(2) O(1) 0(2) N C(3) C(4) C(5) C(6) C(7)

0.0000 0.2160(3) 0.1766(3) 0.4065(10) 0.3930(11) 0.5598(10) 0.5315(9) 0.8952( 11) 0.9975(14) 1.1833(19) 1.2561(21) 1.1418(15) 0.9637(15)

0.0000 0.0521(1) 0.0876(1) 0.1280(5) 0.1455(5) 0.1719(4) 0.2010(4) 0.2922(4) 0.3112(5) 0.3714(8) 0.4095(8) 0.3875(6) 0.3273(5)

0.0000 -0.1313(1) 0.1429(1) -0.0552(5) 0.0796(5) -0.1007(4) 0.1332(4) 0.0086(5) -0.0871 (6) -0.0761(9) 0.0351(10) 0.1324(8) 0.1168(7)

330(3) 457(5) 419(5) 399(19) 392(18) 609(18) 579(17) 459(18) 515(24) 852(39) 938(45) 645(29) 541(24)

H H(3) H(4) H(5) H(6) H(7)

0.791(13) 0.935(13) 1.252(15) 1.354(24) 1.193(15) 0.865(10)

0.257(5) 0.280(5) 0.385(6) 0.446(10) 0.410(6) 0.310(4)

0.002(6) -0.161(7) -0.142(8) 0.050(12) 0.216(8) 0.178(5)

U~ 1(2) 3(2) 4(2) 10(5) 4(2) 1(1)

aThermal parameters for non-H atoms as U~q = (1/3) ~[Uoa*a*aiaj cos(al, aj)]. bThermal parameters for H atoms as: U = exp [-8r2U(sin 0/X)2]. atoms of the structure being located on successive Fourier syntheses. Isotropic refinement was carried out by full-matrix least-squares analysis. An empirical absorption correction (/~ = 15.14 cm - t ) was applied after isotropic refinement (Walker and Stuart, 1983). A difference Fourier synthesis revealed the positions of all H atoms according to the expected geometrical grounds. A weighting scheme was employed to obtain fiat dependence in (wA2F) vs. (Fo) and vs. (sin 0/X) (Martinez-Ripoll and Cano, 1975). The discrepancy indices R = 0.048 and R w = 0.057 were obtained at the last cycles of the refinement. The greater part of the calculations was carried out using the XRAY 76 System (Stewart, 1976) running on a V A X 11/750 computer. Final atomic coordinates are given in Table 4.

R e s u l t s and discussion

TGA and DTG studies Table 5 lists the temperature interval (~ the number of steps, and the weight loss (%) for all the compounds. All of them are anhydrous. The corn-

212

R o m a n et al.

Table 5. Temperature interval (~

Compound

Steps

PYNIDT

T~ -

1 2 1 2 1 2 3 1 2 1 2

M3NIDT E3NIDT

M4NIDT E4NIDT

the number of steps, and weight loss (%) for the complexes Tf (~

% Weight loss

E % Weight loss

79.34 4.23 54.28 25.38 53.66 29.70 4.52 81.85 2.96 83.49 3.04

79.34 83.57 54.28 79.66 53.66 83.36 87.88 81.85 84.81 83.49 86.53

33-339 339-591 24-242 242-599 33-218 218-348 348-594 23-418 418-599 26-410 410-599

pounds present two decomposition steps, except the E3NIDT compound which shows three. The residue of all of the compounds at 600~ was identified by X-ray powder diffraction as a mixture of nickel sulfurs (NiaS2 and NiS). UV-V and IR spectra

The [Ni($2C202)2] 2- anion has been characterized in the 340-1600 c m - l region. Vibration frequencies of the complex anion and their description in different compounds are given in the literature (Coucouvanis et al, 1973; Pons et al., 1980) and are in good agreement with the studied complexes (Table 6), which have been compared with the Kz[Ni(S2C202)2] represented as K2NIDT. At ca. 1600 cm -1 a strong band appears which can be attributed to the anion (Coucouvanis et al., 1973) and to the alkylpyridinium cations. We have assigned this band to the protonated base, but this strong band is formed by both contributions. The infrared spectra of the pyridinium and alkylpyridinium cations have been characterized in the 800-3200 cm -1 region (Cook, 1961; Petrov et al., 1969). The characteristic and very strong bands of the pyridinium cations were Table 6. Vibration frequencies (cm-i) of the [Ni($2C202)2] 2- anion in different compounds and their description PYNIDT 368s 410m 450w 535w 880w 949s 1090vs 1575vs

M3NIDT

E3NIDT

365s 415m 470w 530w

360s 415m 500w 575w

949m 1090vs 1560s

948s 1087s 1575vs

M4NIDT

FANIDT

365vs 409m 475m 525m 875w 947vs 1090vs 1590vs

360vs 414m 445s 535s 875s 945s 1090s 1595vs

K2NIDT

Assignment

349vs

us (Ni-S) ua (Ni-S) ua (C-S) ~s (C-S) ~(C-O) + pa (C-S) + + v(C=S) u(C=C) + ~,(C-S) u(C=O)

614w 910m 1059vs 1588vs

Structure of (CsHsNH)2[Ni(SzC2Oz)zl

213

obtained between 1480 and 1640 cm -~ (Romfin et al., 1986, 1987). There are only slight differences among the IR spectra of the five studied compounds. The UV-V spectra of the compounds exhibit four bands, three of them due to the anion in the visible region and the other one corresponding to the cation in the ultraviolet region. The broad absorption band, which appears in the UV region for all the compounds, is in the range k = 254.6-261.6 nm and e = 4510-7850, and may be due to the 7r* ~ n and 7r* '-- 7r transitions. The complexes exhibit a second characteristic band (X = 289.0-308.8 nm, e = 3560-5780) which is smoothly displaced as a function of the nature and position of the alkyl radicals in the ring. The two other bands can be identified by )~ = 488.8-499.8 nm, e = 19801370 and ~ = 547.8-566.2 nm, e = 390-400, respectively.

Description of the structure of P YNIDT The structure solution confirms that the PYNIDT complex contains [Ni($2C202)2] 2- quasi-planar anions and (CsHsNH) + planar cations with atom labelling (Fig. 1). There is an extensive array of hydrogen bonds formed in the crystal. These hydrogen bonds plus the electrostatic interactions account for the adopted molecular structure. The molecular dimensions of the anion and cation are in excellent agreement with previous determinations. Figure 2 shows the crystal structure projection onto the (1 0 0) plane of the PYNIDT complex. The anions are located in two different levels (z = 0 and z = 89 In each level the anions are linked by a bifurcated hydrogen bond through the two oxygen atoms of the anion and the hydrogen atoms of the pyridinium nitrogen with a 9 9 .c-a-c-c-a-c. 9 9 sequence (where a = anion and c = cation). The angle between cation and anion planes is equal to 3.0 ~ and the mean plan which contains both is parallel to the plan (1 3 0). Anions and cations stack into layers following the same 9 9 .c-a-c-c-a-c. 9 9 sequence as in the M4NIDT compound (Enjalbert et al., 1985). The normal to the mean plan of the anion [Ni($2C202)2] 2 - forms an angle of 50.6 ~ with the b axis. The nickel atom is coordinated to two dithiooxalate ligands trough the sulfur atoms located at the corners of a quasi-square parallelogram. The plane of coordination of the nickel atom and the two sulfur atoms with the O-C-C-O plane is 9.5 ~ The Ni(82C202)2] 2- anion is centrosymmetric and the nickel atom lies in a special position in the unit cell. The medium plane of the pyridinium cation deviates 7.8 ~ from the planarity. Table 7 lists the relevant bond lengths and angles for the PYNIDT complex and the most representative ones for the M4NIDT (Enjalbert et al., 1985). The PYNIDT compound has a laminar structure where each sheet is built up by parallel chains of ions linking through a bifurcated hydrogen bond between them. The closest-approach distances that are suitably oriented to permit hydrogen contacts between anion oxygen atoms and pyridinium nitrogen or carbon

Table 7. Bond lengths (A) and angles (deg) for the PYNIDT and the M4NIDT complexes Bond

PYNIDT

M4NIDT

Ni-S(1) Ni-S(2) S(1)-C(1) S(2)-C(2) C(1)-C(2) C(1)-O(1) C(2)-O(2)

2.181(2) 2.183(2) 1.698(6) 1.728(7) 1.545(9) 1.248(9) 1.229(8)

2.177(1) 2.182(1) 1.725(5) 1.713(5) 1.530(7) 1.226(6) 1.227(6)

Angle

PYNIDT

M4NIDT

Ni-S(1)-C(1) S(1)-C(1)-C(2) C(1)-C(2)-S(2) C(2)-S(2)-Ni S(2)-Ni-S(1) O(1)-C(1)-S(1) O(1)-C(I)-C(2) O(2)-C(2)-C(1) S(2)-C(2)-O(2)

105.7(2) 119.1(5) 117.0(4) 105.6(2) 92.6(1) 124.5(5) 116.5(5) 118.2(6) 124.7(5)

105.3(2) 117.7(3) 118.7(4) 105.0(2) 92.7(1) 123.9(4) 118.4(4) 117.4(4) 123.9(4)

Bond

PYNIDT

M4NIDT

N-C(3) C(3)-C(4) C(4)-C(5) C(5)-C(6) C(6)-C(7) N-C(7) N-H C(3)-H(3) C(4)-H(4) C(5)-H(5) C(6)-H(6) C(7)-H(7)

1.320(10) 1.371(14) 1.376(15) 1.383(15) 1.337(12) 1.326(9) 0.79(8) 0.97(7) 0.90(9) 0.77(14) 1.00(9) 0.98(6)

1.327(6) 1.370(7) 1.391(7) 1.384(7) 1.366(7) 1.338(7) 0.78(7) 0.96(6) 0.90(8) 0.78(10) 1.01(7) 0.99(5)

Angle

PYNIDT

M4NIDT

N-C(3)-C(4) C(3)-C(4)-C(5) C(4)-C(5)-C(6) C(5)-C(6)-C(7) C(6)-N-C(7) C(7)-N-C(3)

119.0(7) 118.0(9) 120.0(9) 118.8(9) 119.9(7) 123.7(7)

119.9(5) 119.2(4) 118.9(4) 119.7(5) 119.5(5) 122.7(4)

atoms (Taylor and Kennard, 1982; Roman et al., 1986; 1987) are listed in Table 8.

Acknowledgments The authors are thankful to the U.E.I. de Cristalografia, Instituto Rocasolano, CSIC (Madrid), for providing the facilities for X-ray data collection

Structure of (CsHsNH)2[Ni(S2C202)2]

215

S(2)

~1

~.

~

~V

s(]) (a)

H(5) H(4) H(6) C( ) % C(7) H(7)/

H(3) N(II

(b) Fig. 1. Atom labelling of: (a) bis(dithiooxalato)nickelate(II) anion; (b) pyridinium cation.

216

R oma n et aL

o o

"~

71 ~

217

Structure of (CsHsNH)z[Ni(S2C202)z] Table 8. Hydrogen contacts Bond type

X-H

N-H. 9 9O(1) N-H. 9 90(2) C(3)-H(3) 9 - - O(1) C(6)-H(6) 9 9 .O(1) C(7)-H(7) 9 9 9O(2)

0.79(8) 0.79(8) 0.97(7) 1.00(9) 0.98(7)

X-'.O

H.--O

2.762(8) 2.973(8) 3.17(1) 3.21(1) 3.11(1)

2.05(7) 2.37(8) 2.46(8) 2.57(9) 2.49(6)

zX-H'''O 151 (7) 135(7) 130(2) 121(6) 121(4)

a n d t h e u s e o f t h e V A X 1 1 / 7 5 0 c o m p u t e r . T h a n k s also are d u e to Prof. M . M a r t i n e z - R i p o l l f o r h e l p f u l d i s c u s s i o n s . T w o o f t h e a u t h o r s (P. R. a n d J. M . G.-Z.) acknowledge financial assistance by Iberduero, S.A.

References Cook, D. (1961) Can. J. Chem. 39, 2009. Coucouvanis, D., Baezinger, N. C., and Johnson, S. M. (1973) J. Am. Chem. Soc. 95, 3875. Cox, E. G., Wardlaw, W., and Webster, K. C. (1935) J. Chem. Soc. 1475. Cromer, D. T., and Waber, J. T. (1974) International Tables for X-ray Crystallography, J. A. Ibers, and W. C. Hamilton, eds. (Kynoch Press: Birmingham, England), Vol. IV, Table 2.2A, pp. 72ff. Enjalbert, R., Gleizes, A., Trombe, J.-C., Guti6rrez-Campo, M. L., and Rom~in, P. (1985) J. Mol. Struct. 131, 1. Frasse, C., Trombe, J.-C., Gleizes, A., and Galy, G. (1985) C. R. Acad. Sci. Paris 300, 403. Gleizes, A., and Galy, J. (1979) J. Solid State Chem. 30, 23. Gleizes, A., and Verdaguer, M. (1984) J. Am. Chem. Soc. 106, 3727. Gleizes, A., Clery, F., Bruniquel, M. F., and Cassoux, P. (1979) Inorg. Chim. Acta 37, 19. Gleizes, A., Maury, F., and Galy, J. (1980) Inorg. Chem. 19, 2074. Gleizes, A., Maury, F., Cassoux, P., and Galy, J. (1981) Z. Kristallogr. 155, 293. Gleizes, A., Maury, F., and Galy, J. (1984) Nouv. J. Chim. 8, 521. Martfnez-Ripoll, M., and Cano F. H. (1975) PESOS, program for the automatic treatment of weighting schemes for least-squares refinement, Instituto Rocasolano, CSIC, Serrano 119, 28006 Madrid, Spain. Maury, F., and Gleizes, A. (1980) Inorg. Chim. Acta 41, 185. Petrov, K. I., Rubtsov, M. V., Sinitsyn, N. M., and Travkin, V. F. (1969) Zh. Neorg. Khim. 14, 3230. Pons, J. N., Roger, J., and Stem, M. (1980) Rev. Chim. Miner. 17, 497. Robinson, C. S., and Jones, H. O. (1912) J. Chem. Soc. 101, 62. Romfin, P., and Guti6rrez-Zorrilla, J. M. (1985) J. Chem. Educ. 62, 167. Rom~in, P., Guti6rrez-Zorrilla, J. M., Martinez-Ripoll, M., and Garc/a-Blanco, S. (1986) Transition Met. Chem. 11, 143. Romfin, P., Guti6rrez-Zorrilla, J. M., Martinez-Ripoll, M., and Garc/a-Blanco, S. (1987) J. Crystallogr. Spectrosc. Res. 17, 109. Stewart, J. M. (1976) The XRAY76 System, Tech. Rept. TR-446, Computer Science Center, University of Maryland, College Park, Maryland. Taylor, R., and Kennard, O. (1982) J. Am. Chem. Soc. 104, 5063. Trombe, J.-C., Gleizes, A., and Galy, J. (1984) lnorg. Chim. Acta 87, 23. Trombe, J.-C., Gleizes, A., and Galy, J. (1985) C. R. Acad. Sci. Paris 300, 5. Walker, N., and Stuart, D. (1983) Acta Crystallogr. A 39, 158. Structure factor data have been deposited with the British Library, Boston Spa, Wetherby, West Yorkshire, UK, as supplementary publication No. 63071 (14 pages).