Inorg. Chem. 1983, 22, 1897-1902
1897
Contribution from the Consiglio Nazionale delle Ricerche of Italy, Istituto di Chimica Generale e Inorganica, University of Sassari, 07100 Sassari, Italy, Istituto di Chimica Generale e Inorganica e Centro del CNR, University of Milano, 20133 Milano, Italy, and Istituto di Chimica Generale e Inorganica, University of Modena, 41 100 Modena, Italy
Relation between Structures and Spectroscopic Properties of Group 2B Metal [M(chelate)X2]Complexes (X = C1, Br, I). Crystal and Molecular Structure of [H2NCH2(CH3)2CCH2NH2]MX2 Complexes (M = Zn, X = C1, Br; M = Cd, X = Br) F R A N C 0 CARIATI,Ia GIANFRANCO CIANI,lb LED1 MENABUE," GIAN CARLO PELLACANI,*lC GLORIA RASSU,la and A N G E L 0 SIRONIlb
Received July 14, 1982 The synthesis and structural and spectroscopic characterization of a series of d10metal(I1) compounds of the type [M(dmpd)X,] X = C1, Br, I) are described. The different (M = Zn(II), Cd(II), Hg(I1); dmpd = 2,2-dimethylpropane-1,3-diamine; spectroscopic properties, which divide the complexes into two classes, are discussed and unambiguously assigned only on the basis of the knowledge of the crystal structure of compounds representative of each class. Therefore, the crystal structures of [Zn(dmpd)C12](I), [Zn(dmpd)Br2] (II), and [Cd(dmpd)Brz] (111) are determined from three-dimensional single-crystal X-ray data. The complexes are monoclinic, space groups P2,/m for I and I1 and P2 for 111, with two formula units in cells of the following dimensions: a = 6.014 (1) A, b = 7.724 (1) A, c = 10.483 (1) and 0 = 91.32O for I; a = 6.234 (2) A, b = 7.968 (2) A, c = 10.628 (2) A, and = 91-81" for 11; a = 11.288 (2) A, b = 5.893 (1) A, c = 7.622(1) A, and p = 92.72' for 111. The structures have been refined to R = 0.024, 0.036, and 0.025 for I, 11, and 111, respectively. The complexes I and I1 are isomorphous and isostructural. In these complexes the zinc atom is tetrahedrally surrounded by two halogen and two nitrogen atoms. The only difference between these complexes is the strength of hydrogen-bonding interactions. In the complex 111 the cadmium atom is octahedrally surrounded by four bromine atoms and two nitrogen atoms of a dmpd molecule. The octahedral moieties are linked in infinite chains by bromine bridges. In all the compounds the dmpd molecule acts as a chelating ligand, giving a six-membered chelate ring in a partially flattened chair conformation.
A,
Introduction The dl0 metal(I1)-halide adducts are rather interesting. They show a variety of coordination numbers and geometries, closely dependent on many factors, among which are interactions due to crystal-packing and hydrogen-bonding forces as well as metal ion and halide dimensiom2 For these reasons, one must be very cautious in assigning the complex stereochemistry in the absence of structural data. Nevertheless, the majority of conclusions on the structures proposed are based largely on infrared evidence. We therefore undertook a systematic investigation of the structural and spectroscopic properties of a series of MX,L (M = Zn(II), Cd(II), Hg(I1); X = C1, Br, I) complexes, where L is 2,2-dimethylpropane1,3-diamine (hereafter abbreviated as dmpd). Recently some complexes of dmpd with ~ o p p e r ( I 1 )and ~ p l a t i n ~ m ( I 1 )ions ~ have been investigated. The crystal structures of [C u ( dmpd) 2( C104)2] and [Pt (dmpd) (malonate)]4a show distorted-tetragonal-bipyramidal and squareplanar metal coordination, respectively. In both cases, the ligand forms a six-membered chelate ring having a "flattened" chair conformation. Further interest in the systems investigated here derives from a biological point of view, since it has been demonstrated that compounds with NH2 groups of aliphatic amines show a significant antitumor activity as found for [Pt(dmpd)(malonate)] .4a Experimental Section All chemicals were reagent grade and used as received. 2,2-Di-
methylpropane-l,3-diaminewas kindly supplied by BASF. Reparation of the Complexes. (i) [M(dmpd)X2] (M = Zn, Cd, Hg; X = Cl, Br, I) Complexes. These complexes were obtained by mixing the MX, salt and dmpd in methanol with a metal to ligand 1:l molar ratio. The compounds were recrystallized from methanol. Their deuterated analogues were prepared by recrystallization of the (1) (a) University of Sassari. (b) University of Milano. (c) University of Modena. (2) (a) Dean, P.A. W. Prog. Inorg. Chem. 1978, 24, 109 and references cited therein. (b) Tuck, D. G. Rev. Inorg. Chem. 1979, 1, 209 and references cited therein. (3) Battaglia, L. P.; Bonamartini Corradi, A.; Marcotrigiano, G.; Menabue, L.; Pellacani, G. C. J. Chem. SOC.,Dalton Trans. 1981, 8. (4) (a) Kralingen, C. G.; Reedijk, J.; Spek, A. L.Inorg. Chem. 1980, 19, 1481. (b) Appleton, T. G.; Hall, J. R. Ibid. 1970, 9, 1800. 0020-1669/83/1322-1897$01.50/0
compounds in tetradeuteriomethanol and deuterium oxide. Zn(dmpd)Cl,. Anal. Calcd for CSH14ClzN2Zn:C, 25.16; H, 5.91; N, 11.75. Found: C, 25.01; H, 5.91; N, 11.47. Mp 264 "C. Zn(dmpd)Br2. Anal. Calcd for C5H14Br2N,Zn:C, 18.33; H, 4.31; N, 8.56. Found: C, 18.18; H, 4.38; N, 8.37. Mp 246 "C. Zn(dmpd)Iz. Anal. Calcd for CSHI4I2N2Zn:C, 14.24; H, 3.35; N, 6.65. Found: C, 14.34; H, 3.37; N, 6.37. Mp 274 "C. Cd(dmpd)ClP Anal. Calcd for CSH14CdC12N,:C, 21.02; H, 4.94; N, 9.81. Found: C, 19.92; H, 4.88; N, 9.87. Mp >300 "C. Cd(dmpd)Brz. Anal. Calcd for C5HI4Br2CdN2:C, 16.03; H, 3.77; N, 7.48. Found: C, 16.10; H, 3.75; N, 7.53. Mp 257 OC. Cd(dmpd)Iz. Anal. Calcd for CSH14CdI,N,: C, 12.81; H, 3.01; N , 5.98. Found: C, 12.83; H, 2.98; N , 5.92. Mp 204 OC. Hg(dmpd)Clz. Anal. Calcd for C5H14C12HgN2:C, 16.06; H, 3.78; N, 7.50. Found: C, 16.10; H, 3.85; N, 7.52. Mp 200 "C. Hg(dmpd)Brz. Anal. Calcd for CSH14Br2HgN2:C, 12.97; H, 3.05; N, 6.06. Found: C, 13.00; H, 3.07; N, 6.06. Mp 186 "C. Hg(dmpd)I,. Anal. Calcd for CSHI4IZHgN2:C, 10.78; H, 2.54; N, 5.03. Found: C, 10.85; H, 2.53; N, 5.05. Mp 154 "C. (ii) [MX4XdmpdH2](M = Zn, X = C1, Br; M = Cd, X = Br; M = Hg, X = I) Complexes. These complexes were obtained by adding 5 mmol of MX2 to an aqueous solution of HX containing 5 mmol of dmpd. A precipitate was obtained that was then filtered and dried under vacuum. [ZnClJdmpdH,]. Anal. Calcd for CSHI6Cl4N2Zn:C, 19.27; H, 5.18; N, 8.99. Found: C, 19.24; H, 5.25; N, 9.08. Mp 275 OC. [ZnBr41dmpdHz]. Anal. Calcd for CSHI6Br4N2Zn:C, 12.26; H, 3.29; N, 5.72. Found: C, 12.23; H, 3.25; N, 5.78. Mp 286 "C. [CdBr41dmpdHz]. Anal. Calcd for C5H16Br4CdN2:C, 11.19; H, 3.01; N, 5.22. Found: C, 10.78; H, 3.01; N, 4.98. Mp 265 "C. [H&IdmpdHz]. Anal. Calcd for C5HI6I4HgN,: C, 7.38; H, 1.98; N, 3.45. Found: C, 7.54; H, 2.21; N, 3.52. Mp 278 OC. Physical Measurements. Infrared spectra were recorded on a Beckman 4250 spectrophotometer as Nujol mulls or KBr pellets in range (no difference was observed among spectra the 300-4000-~m-~ obtained by these two different methods) and a Perkin-Elmer 180 spectrophotometer as Nujol mulls on polythene, as support, in the 100-5OO-cm-' range. Raman spectra were recorded on solid samples with a Coderg PHO spectrophotometer equipped with an argon laser. Nitrogen, carbon, and hydrogen were analyzed with a Carlo-Erba elemental analyzer. X-ray Data Collection, Structure Determination, and Refinement. The refined cell constants and other relevant crystal data for the three compounds [Zn(dmpd)C12] (I), [Zn(dmpd)Br,] (11), and [Cd(dmpd)Br2] (111) are presented in Table I, together with details of intensity measurements. The intensity data for compounds I and 111 were collected on an Enraf-Nonius CAD-4 diffractometer, while the
0 1983 American Chemical Society
Cariati et al.
1898 Inorganic Chemistry, Vol. 22, No. 13, I983 Table I. Details of Data Collection and Structures for the Three Comuounds
formula mol wt cryst syst space group a, A b, A c,
a
R , deg v, A 3 Z
Pcalcd, g cm'3 abs coeff w(Mo K 4 , cm-' cryst size, mm
Zn(dmpd)Cl,
Zn(dmpd)Br,
(1)
(11)
C H ,,C12 N, Zn 238.5 monoclinic P2,/m (No. 11) 6.014 (1) 7.724 (1) 10.483 (1) 91.32 (1) 486.8 2 1.63 30.8
C ,H 1 4 Br ,N, Zn 3 27.4 monoclinic P2,/m (No. 11) 6.234 (2) 7.968 (2) 10.628 (2) 91.8 1 (3) 5 27.7 2 2.06 98.3
C, H ,Br ,CdN, 374.4 monoclinic P2, (No. 4) 11.288 (2) 5.893 (1) 7.622 (1) 92.72 (1) 506.2 2 2.46 99.1
0.12 X0.35 X 0.38 Mo Kor
0.10 X0.13 X 0.38 Mo K a
scan 1.2
scan 1.1 + 0.347 tan 0 3.3
0.04 X 0.28 X 0.30 radiation (A, A) Mo Kor (0.71073) scan type w scan scan width, deg 1.2 + 0.347 tan 0 max scan speed, 4.0 deg/min data collection 3 < s < 2 6 range, deg part of the +h,k,l sphere no. of unique 1027 data no. of data used 867 (I > 30) in the refinements cryst decay no decay max and min 1.00-0.67 transmission fact or s weighting fudge 0.04 factor R 0 .O 24 0.032 Rw
(W
2.4
X = Br
2.212 (1) 2.290 (1) 2.018 (1) 1.494 (4) 1.544 (4) 1.513 (7) 1.538 (7)
2.350 (1) 2.418 (1) 2.024 (4) 1.484 (6) 1.528 (7) 1.524 (12) 1.520 (11)
X(l)-Zn-X(2) X(1)-Zn-N X(2)-ZnyN N-Zn-N1 Zn-N-C(1) N C ( 1K ( 2 ) C(l)-C(2)-C(l)i C(1)-C(2)-C(3) C(l)-C(2)-C(4) C(3)-C(2)-C(4)
108.2 (1) 122.0 (1) 104.3 (1) 93.6 (2) 112.6 (2) 114.3 (3) 113.0 (4) 111.3 (3) 106.1 (3) 108.9 (5)
107.8 (1) 122.5 (1) 104.2 (1) 93.0 (2) 112.4 (3) 115.1 ( 5 ) 112.7 (5) 111.4 (4) 106.6 (4) 107.7 (7)
Related position for i : x, '1, - y , z.
a
w
x=c1 Zn-X(l) Zn-X(2) Zn-N N-C(l) C(l)-C(2) C(2)-C(3) C(2)-C(4)
Cd(dmpd)Br,
w
3.5
