Mar 30, 1981 - Centro di Studio per la Strutturistica Diffrattomettrica del CNR, via M. d'Azeglio 85, 43 100 ... 32.72 (4) A, fl= 96.6 (2) ° , U= 4284 A 3, Z = 4, D x =.
607
Acta Cryst. (1982). B38, 607-609
Bis(isothioeyanato)tetrakis(4-methylpyridine)niekel(ll)--o-Xylene (1:2)* BY JANUSZ LIPKOWSKI
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01 224 Warszawa, Poland AND GIOVANNI D. ANDREErrI
Centro di Studio per la Strutturistica Diffrattomettrica del CNR, via M. d'Azeglio 85, 43 100 Parma, Italy (Received 30 March 1981 ; accepted 24 June 1981 )
Abstract. C26H28N6NiS 2. 2C8H~0, M r = 759.7, monoclinic, P2L/c, a = 11.48 (1), b = 11.49 (2), c = 32.72 (4) A, f l = 96.6 (2) ° , U = 4284 A 3, Z = 4, D x = 1.178 Mg m -a, F(000) = 1608, g(Cu Ka) = 1.71 mm -l. The structure consists of discrete, propellershaped Ni(4-MePy)4(NCS) 2 molecules and two symmetrically independent sets of o-xylene molecules one of which shows some positional disorder. The structure was refined to R = 0.098 for 1242 observed reflections with most atoms refined isotropically. Introduction. Ni(4-MePy)4(NCS) 2 on contact with xylene isomers produces clathrate-type compounds (Schaeffer, Dorsey, Skinner & Christian, 1957). The clathrates are usually of tetragonal symmetry with a 1:I guest/host molar ratio (Lipkowski, Suwifiska, Andreetti & Stadnicka, 1981), but o-xylene of an appropriate purity yields a different crystalline phase (Starzewski & Lipkowski, 1979) with a 2:1 guest/host molar ratio. Formation of this compound is 'orthoselective' instead of 'para-selective' as is usually observed for samples of the above-mentioned tetragonal clathrates (Starzewski & Lipkowski, 1979). It thus seemed of interest to determine the structure of the title compound. Crystals of a size suitable for X-ray analysis were produced by crystallization of the Ni(4-MePy)4(NCS)2 host complex from solutions in o-xylene: slow cooling of the solution saturated at 333 K gave large, deep-blue clathrate crystals. A crystal 0.35 × 0.30 × 0.25 mm was mounted along a. To prevent deterioration in air (desorption of the guest component), it was mounted inside a Lindemann-glass capillary tube with a small amount of the mother liquor. 3009 independent reflections were measured up to 0 = 35 ° on a Siemens AED computer-controlled three-circle diffractometer with filtered Cu Ka radiation. The o,r--20 and five-points techniques (Hoppe, * Clathrate Inclusion Compounds of Bis(isothiocyanato)tetrakis(4-methylpyridine)nickel(II). IV. Part III: Lipkowski, Sgarabotto & Andreetti (1982). 0567-7408/82/020607-03501.00
1969) were used. 1242 reflections having I _> 2a(I) were used in the structure analysis. Lorentz and polarization corrections were applied but no correction for absorption was made. The structure was solved by direct methods with M U L T A N (Main, Woolfson, Lessinger, Germain & Declercq, 1974). Subsequent electron-density calculations revealed the positions of all the non-H atoms of the host complex and of one guest molecule (A). Interpretation of the electron-density distribution over the other guest molecule (B) presented problems. Disorder has finally been assumed as the reason for that. The assumption that the o-xylene B occupies two different positions, B 1 and B 2, enabled the structure to be refined. The small number of observed reflections supports the concept of some disorder in the structure. In view of this, only a rather limited set of parameters was refined. Anisotropic thermal parameters were assigned only to the atoms of the Ni(NCS)2 subunit. The o-xylene molecules were refined as rigid groups, molecules B~ and B 2 with idealized geometry (regular hexagon for the aromatic ring), while the geometry of molecule A was refined in the final cycles. H atoms were placed in calculated positions. The final R was 0.098. The site-occupation factors (s.o.f.'s) for the two positions of guest molecule B refined to 0.62 for B~ and 0.38 for B 2. The maximum residual electron density in the final difference map was 0.37 e A -3. The refinement calculations were performed with S H E L X (Sheldrick, 1975).
Discussion. The final atomic parameters for the non-H atoms are listed in Table 1.t Bond lengths and selected bond angles within the host complex are shown in Fig. 1. 5"Lists of structure factors have been deposited with the British Library Lending Division as Supplementary Publication No. SUP 36258 (9 pp.). Copies may be obtained through The Executive Secretary, International Union of Crystallography, 5 Abbey Square, Chester CH 1 2HU, England. © 1982 International Union of Crystallography
608
C26HzsN6NiS2 • 2C8H lo
Table 1. Fractional coordinates (× 10 4) and thermal parameters (× 10 3) for the non-H atoms with e.s.d.'s in parentheses Ni N(1) N(2) N(3) N(4) N(5) N(6) S(I) S(2) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) C(24) C(25) C(26)
x
y
z
U (A 2)
-1441 (4) -1827 (20) -1100 (24) 222 (19) -655 (19) -3086 (18) -2178 (20) -2420 (9) -1242 (10) -2080 (29) -1121 (29) 1130 (26) 2206 (29) 2375 (27) 1441 (26) 387 (27) 3561 (28) - 5 (25) 627 (26) 566 (26) -61 (25) -721 (26) 1284 (25) -3737 (24) -4847 (29) -5340 (26) -4731 (27) -3626 (26) -6585 (28) -1575 (30) -1986 (25) -2907 (26) -3581 (29) -3103 (25) -3386 (29)
6851 (4) 6962 (23) 6779 (23) 6131 (18) 8545 (20) 7564 (18) 5097 (20) 6923 (9) 6637 (11) 6947 (27) 6688 (27) 6248 (23) 5795 (26) 5004 (26) 4852 (26) 5397 (25) 4454 (31) 8802 (29) 9864 (27) 10655(28) 10324 (29) 9308 (28) 11793 (27) 7229 (25) 7614 (27) 8443 (27) 8805 (27) 8381 (26) 8901 (31) 4319 (30) 3130 (31) 2906 (27) 3700 (28) 4855 (28) 1631 (28)
8757 (1) 8124 (8) 9385 (8) 8699 (7) 8763 (7) 8828 (7) 8736 (7) 7281 (3) 10224 (3) 7784 (11) 9726 (11) 8968 (9) 8969 (10) 8656 (9) 8357 (10) 8380 (9) 8626 (11) 8445 (10) 8463 (10) 8790 (10) 9104 (10) 9085 (10) 8804 (9) 9133 (9) 9175 (10) 8922 (9) 8605 (9) 8574 (9) 8940 (10) 8987 (10) 8944 (9) 8682 (9) 8427 (10) 8478 (9) 8634 (I0)
* * * 74 (7) 86 (8) 74 (7) 80 (7) * * * * 77 (9) 93 (10) 87 (10) 88 (10) 90 (10) 133 (13) 92 (I 1) 91 (10) 95 (11) 98 (11) 93 (10) 106 (10) 82 (10) 99 (11) 86 (10) 91 (10) 90 (I0) 135 (13) 109 (11) 92 (9) 87 (10) 105 (11) 83 (10) 135 (13)
Table 1 (cont.) y
Z
U (A2)
Position B v s.o.f. -- 0.38 E.s.d.'s (x 10+)(25)
(29)
(9)
(7)
C(27) C(28) C(29) C(30) C(31) C(32) C(39) C(40)
8746 7735 6666 6610 7621 8689 7561 9773
2317 2295 2405 2537 2558 2448 2699 2471
94 187 132 98 134 126 143 156
X
1307 630 1152 2352 3028 2506 4313 3234
* Anisotropic temperature factors with e.s.d.'s
U22
Ui i
Ni N(I) N(2) S(I) S(2) C(1) C(2)
U33
116 (4) 52 (3) III (20) 54 (17) 153 (24) 33 (17) 206 (11) 98 (8) 216 (12) 209 (13) 174 (33) 29 (20) 149 (29) 13 (20)
1.51
C(5)
c,:,y "-% 1,,//1'7
(3)
(6)
C(43) C(44) C(45) C(46) C(47) C(48) C(49) C(50)
7454 8563 9501 9344 8178 7274 7925 6064
-1 -34 60 217 258 145 429 227
114 123 109 115 107 110 163 162
(21)
(6)
(7)
8220 9413 10017 9425 8232 7629 7599 6351
2630 2553 2427 2377 2455 2581 2402 2664
152 119 174 135 101 155 216 179
2111 1703 2458 3591 4033 3251 5281 3797
.~/.s(21
c,%. ~c(7, .y. C(10)/~-~C(9)
\138
141/ COt,) ~
N(3) ?~C(2)
Z11(
~ % / , ~ t 2 )CC (21)( 2 1 ~ C1.45 N C(22)
y
k,..N(4)214(2) /
c(11)\
/-
137\
/,.38 U
J
/1.37
¢/
C(12}" - - ~139 ' 7 - ~ C( 1 3 ~ N ( 1 }
13y
N(6L/
:!210(2)
k~3t ~23) C(26)
C ( 2 5 ~ (144 24)
~/"co) 136/ ~ 3 7 "S(1)
137
N(1) - NJ - N(2) N(1) - Ni - N(3)
1780 (10)" 9 1 5 (9)
C(16)
N(1)- Ni - N(4}
8 9 8 (9)
C(17)"
N(1) - Ni - N(5}
8 9 7 (9)
1 53
N(1) - Ni - N(6)
89 3 1
