Structure of (8-amino-5,7-dichloroquinoline)dinitratocopper(II), [Cu(NO3)2(C9H6Cl2N2)]

46 Acta Cryst. (1985). C41, 46-47 Structure of (8-Amino-5,7-dlchloroqulnollne)dlnitratocopper(II), [Cu(NOa)2(C9H6CI2N2)] BY X. SOLANS AND M. FONT-ALTABA Departamento de Cristalograf:a y Mineralog:a, Universidad de Barcelona, Gran Via 585, 08007-Barcelona, Spain AND M. IZQUIERDO AND J. CASABO Departamento de Qu:mica Inorganica, Universidad Autonoma de Barcelona, Bellaterra (Barcelona), Spain (Received 9 May 1984; accepted 18 September 1984) Abstract. M r = 400.62, monoclinic, C2/c, a = 20.901 (5), b=7.439 (2), c= 18.708 (4) A, fl= 114.59(3) ° , V=2645(2)A 3, Z--8, Dx=2.01 Mg m -a, F(000) = 1592, 2(Mo Ka) = 0.71069 A, p(MoKa) = 2.152 mm -~, room temperature, R = 0.016, R w = 0.021 for 1132 observed reflections. The Cu atom displays a distorted octahedral coordination, being linked to four O atoms of two NO a groups and two N atoms of the aminoquinoline. The different hybridization states of the N atoms produce variations in equatorial Cu-O bond distances, while the apical Cu-O lengths are larger than the equatorial lengths: Cu-Oeq 1.990 (2), 2.039 (3) A; Cu-Oax 2.488 (3), 2.473 (3) A. Introduction. The title compound was synthesized in the Department of Inorganic Chemistry of the Universidad Autonoma de Barcelona, as a first step in attempts to obtain p-NO 3 bridges between Cu 2+ ions. Crystal structure analysis was carried out in order to elucidate the position of the nitro groups and determine the geometry of the complex. Discussion. Final atomic parameters are in Table 1" and selected bond lengths and angles in Table 2. The atom numbering is shown in Fig. 1. The Cu 2+ ion is surrounded by two N atoms of the aminoquinoline group and four O atoms of two nitro groups in a distorted octahedral shape. N(1), N(11), O(14), O(18) are in a roughly equatorial plane [deviations from the mean plane are: Cu 0.041 (3), N(1) -0.141 (4), N(11) 0.118 (4), O(14) 0.111 (4) and O(18) -0.130 (4)A], while O(17) and 0(20) occupy the axial sites [deviations of these atoms from the mean equatorial plane are -1.948(4) and 1.743 (4)A]. The axial * Lists of structure factors, anisotropic thermal parameters and bond lengths and angles in the ligands have been deposited with the British Library Lending Division as Supplementary Publication No. SUP 39748 (8 pp.). Copies may be obtained through The Executive Secretary, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England. Table 1. Atomic coordinates (x 104,for Cu x 105) and Experimental. D m not determined. Crystal 0.15 x 0.15 x 0.1 mm. Philips PW1100 diffractometer, monochromatized Mo Kct radiation. Cell parameters from 25 Cu N(1) reflections (6 _ 0 _< 9°). co-scan technique, scan width c(2) 1 °, scan speed 0.03 ° s -1. 1265 intensities (0_<25°), c(3) hkl = -24/22, 0/8, 0/22; 1132 with I > 2.5a(/). Three c(4) - C(5) standard reflections every 2 h; no significant variation c(6) of intensity. Lp, absorption (SHELX76, Sheldrick, c(7) c(8) 1976) corrections, max. and min. transmission factors c(9) 0.75 and 0-64. Cu atom from Patterson synthesis, c(10) remaining atoms from weighted F o synthesis. FullN(II) Cl(12) matrix least-squares refinement (SHELX76); anisoCI(I3) tropic thermal parameters, H atoms not considered; 0(14) ZwllFol--IFcll 2 minimized; w=cr-2(Fo), f f ' andf" N(I5) O(16) from International Tables for X-ray Crystallography o(17) (1974). (A/tr)max = -0.08 [UI~ of N(11)]. Pmax and Pmi. O(18) on final AF synthesis 0.2eA -3 and -0.3 eA -3. N(19) O(20) VAX-VM780 and IBM4341 computers. 0(21) equivalent &otropic thermal parameters (A 2) 8 2 * * Beq = gTr ~Uija i a dai.aj. x y z 15189 (2) 78235 (7) 21761 (3) 660 (1) 7507 (3) 1207 (2) 49 (2) 6862 (6) 1127 (3) -512 (2) 6635 (5) 413 (3) -461 (2) 7201 (7) -258 (3) 184 (2) 7953 (5) -211 (2) 316 (2) 8422 (5) -844 (3) 964 (2) 9132 (6) -747 (3) 1494 (2) 9194 (5) 7 (3) 1399 (2) 8685 (6) 653 (2) 739 (2) 7983 (5) 552 (2) 1906 (2) 8828 (5) 1444 (2) -352 (1) 8312 (2) -1777 (1) 2294 (1) 10096 (2) I14 (I) 1077 (1) 7003 (4) 2878 (2) 1246 (2) 5390 (5) 2996 (2) 1068 (2) 4494 (5) 3444 (2) 1564 (2) 4680 (4) 2625 (2) 2477 (1) 7751 (4) 3111 (2) 2550 (2) 9385 (5) 3348 (2) 2078 (1) 10392 (4) 3071 (2) 3111 (1) 9771 (5) 3958 (2) neq 3.19 (8) 2-3(1) 3.7 (2) 3.5 (2) 3.9 (2) 2.9 (2) 3.5 (2) 3.8 (2) 2.9 (2) 2.9 (2) 2-5 (2) 3-0(1) 5.3 (2) 5.8 (2) 3.2(1) 3.7(1) 5.1 (3) 5.1 (3) 4.1 (1) 3.5(I) 4.2 (3) 4-4 (3) 0108-2701/85/010046-02501.50 © 1985 International Union of Crystallography X. SOLANS, M. FONT-ALTABA, M. IZQUIERDO AND J. CASAB0 47 Table 2. Bond distances (A) and angles (°)for the Cu coordination sphere Cu-N(l) 1.963 (3) Cu-O(18) 2.039 (3) Cu--N(11) 2.002 (4) Cu-O(20) 2.488 (3) Cu-O(14) 1.990 (2) Cu-O(17) 2.473 (3) N(11)-Cu-N(l) 83.5 (1) O(18)-Cu-O(14) 89.2 (1) O(14)-Cu-N(1) 94.4 (l) O(18)-Cu-O(17) 78.4 (1) O(14)-Cu-N(l l) 175.1 (1) O(20)-Cu-N(1) 134.9 (1) O(17)-Cu-N(1) 95.2 (l) O(20)-Cu-N(11) 87.9 (1) O(17)-Cu-N(I 1) 128.0 (1) O(20)-Cu-O(14) 90.5 (1) O(17)-Cu-O(14) 56.5 (1) O(20)-Cu-O(17) 123.8 (1) O(18)-Cu-N(I) 169.4 (1) O(20)-Cu-O(18) 54.9 (1) O(18)-Cu-N(11) 93.7 (I) Cu-O distances [mean value 2.480 (7)] are larger than the equatorial distances [mean 2.014 (24) A]. The Cu-N(1) bond distance [1.963 (3)A] is similar to those obtained in other compounds [weighted mean of literature values 1.96 (1)A (Palenik, 1964; Hoy & Morris, 1967; Williams & Wallwork, 1967], while it is shorter than the Cu-N(ll) bond distance [2.002 (4)A] due to the sp 2 character of N(1); this produces a lengthening of the Cu-O bond distance opposite to N(1). This work was sponsored by a grant from the Universidad de B arcelona. o,1/ N(15)c~¢ 0(21) /~0(14) L"-CI(13) C1(12)L~ Fig. 1. A view of the complex with the numbering of the atoms. References HoY, T. C. & MORRIS, R. H. (1967). Acta Cryst. 22, 476-482. International Tables for X-ray Crystallography (1974). Vol. IV. Birmingham: Kynoch Press. PALENm, G. J. (1964). Acta Cryst. 17, 687-693. SrtELDRICK, G. M. (1976). SHELX76. A program for crystal structure determination. Univ. of Cambridge, England. WILLIAMS, R. M. & WALLWORK, J. C. (1967). Acta Cryst. 23, 448-455. Acta Cryst. (1985). C41, 47-52 Triply Bridged Thiolate Complexes of Oxotungstate(V): Structures of Tetraphenylphosphonium #-Chloro-bis~-phenylthiolato)-bis[dichlorooxotungstate(V)] (I), [Ph 4 P ][CI 20 W~- CI)~-S C6H 5 )2W OC12], and T etraphenylarsonium fl-C hloro-bis- ~-p-tolylthiolato)-bis[dichlorooxotungstate(V)] (II), [Ph4As][CI2OW(#-CI)- {#-S(p-C6H4CH3)}2WOCI 2] BY JOANNE M. BALL, P. MICHAEL BOORMAN,* KELLY J. MOYNIHAN AND JOHN F. RICHARDSON Department of Chemistry, The University of Calgary, Calgary, Alberta, Canada T2N 1N4 (Received 22 May 1984; accepted 18 September 1984) Abstract. (I): Mr=1134.71, triclinic, Pi, a= 10.8421 (8), b= 11.242(1), c= 16.491 (1)A, a= 98.384(7), fl=98.119(6), 7= 100.267(7) ° , V= 1927.6 (4) A 3, Z = 2, D m = 1.94 (1), D x = 1.955 gcm -3, F(000) = 1084, /t(Mo Kct) = 68.30 cm -~, ~. = 0.71069 A, T= 295 (1) K, R = 0.036 for 6066 unique reflections. (II): Mr= 1206.71, tet- * Author to whom correspondence should be addressed. 0108-2701/85/010047-06501.50 ragonal, P~,, a= 16.173 (1), c=7.8566 (8)A, V= 2055.1 (3) A 3, z= 2, D m = 1.94 (1), Dx= 1.950 gcm -3, F(000) = 1152, /t(Mo Kcx) = 72.13 cm -~, T= 295 (1) K, R = 0.049 for 1430 unique reflections. The anions consist of a greatly distorted confacial bioctahedral framework in which there is a weakly bound #-CI atom trans to two terminal O atoms. The R groups (phenyl, p-tolyl) on the bridging thiolato ligands adopt the relatively unusual axial-axial configuration. © 1985 International Union of Crystallography