Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100000160/ja1012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100000160/ja1012Isup2.hkl |
CCDC reference: 144614
To a 30 ml aqueous solution containing CdCl2·2.5H2O (1.45 g, 5 mmol) and KSCN (2.91 g, 10 mmol), aniline (1.9 ml, 20 mmol) was added; the pH of the solution was adjusted to 9 by adding 2-aminoethanol and citric acid. After a small amount of the precipitate was filtered off, the aqueous solution was allowed to stand in a refrigerator at 278 K. After a few weeks, pale yellow crystals were obtained.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cd(CNS)2(C6H7N)2] | F(000) = 412 |
Mr = 414.81 | Dx = 1.635 Mg m−3 Dm = 1.64 Mg m−3 Dm measured by flotation in mesitylene-bromoform |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.1132 (13) Å | Cell parameters from 39 reflections |
b = 5.8547 (6) Å | θ = 4.7–12.5° |
c = 13.1706 (13) Å | µ = 1.54 mm−1 |
β = 100.466 (9)° | T = 293 K |
V = 842.68 (16) Å3 | Block, pale yellow |
Z = 2 | 0.40 × 0.31 × 0.22 mm |
Siemens P4 diffractometer | 1616 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 27.5°, θmin = 1.9° |
2θ/ω scans | h = −1→14 |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | k = −1→7 |
Tmin = 0.510, Tmax = 0.712 | l = −17→17 |
2664 measured reflections | 3 standard reflections every 97 reflections |
1943 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0289P)2 + 0.222P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1943 reflections | Δρmax = 0.25 e Å−3 |
98 parameters | Δρmin = −0.47 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0317 (14) |
[Cd(CNS)2(C6H7N)2] | V = 842.68 (16) Å3 |
Mr = 414.81 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1132 (13) Å | µ = 1.54 mm−1 |
b = 5.8547 (6) Å | T = 293 K |
c = 13.1706 (13) Å | 0.40 × 0.31 × 0.22 mm |
β = 100.466 (9)° |
Siemens P4 diffractometer | 1616 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.021 |
Tmin = 0.510, Tmax = 0.712 | 3 standard reflections every 97 reflections |
2664 measured reflections | intensity decay: none |
1943 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.25 e Å−3 |
1943 reflections | Δρmin = −0.47 e Å−3 |
98 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. All non-H atoms were refined anisotropically. All hydrogen atoms were fixed at their calculated positions with the isotropic displacement parameters. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.0000 | 0.5000 | 0.5000 | 0.04603 (11) | |
S1 | −0.10627 (8) | 0.74326 (10) | 0.63889 (5) | 0.0663 (2) | |
C1 | −0.0890 (2) | 1.0014 (3) | 0.59413 (18) | 0.0442 (5) | |
N1 | −0.0779 (2) | 1.1809 (3) | 0.56386 (16) | 0.0564 (5) | |
N10 | −0.1773 (2) | 0.5709 (4) | 0.37581 (16) | 0.0563 (5) | |
H10A | −0.2129 | 0.6990 | 0.3939 | 0.068* | |
H10B | −0.1545 | 0.5978 | 0.3147 | 0.068* | |
C11 | −0.2668 (2) | 0.3916 (5) | 0.36198 (18) | 0.0528 (6) | |
C12 | −0.2635 (2) | 0.2250 (5) | 0.2885 (2) | 0.0607 (6) | |
H12A | −0.2048 | 0.2314 | 0.2464 | 0.073* | |
C13 | −0.3465 (3) | 0.0503 (6) | 0.2777 (3) | 0.0742 (8) | |
H13A | −0.3443 | −0.0611 | 0.2277 | 0.089* | |
C14 | −0.4337 (3) | 0.0375 (6) | 0.3403 (4) | 0.0826 (10) | |
H14A | −0.4897 | −0.0821 | 0.3331 | 0.099* | |
C15 | −0.4362 (3) | 0.2026 (7) | 0.4122 (3) | 0.0835 (10) | |
H15A | −0.4949 | 0.1958 | 0.4543 | 0.100* | |
C16 | −0.3526 (3) | 0.3819 (6) | 0.4243 (2) | 0.0680 (7) | |
H16A | −0.3550 | 0.4935 | 0.4742 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.06856 (18) | 0.02665 (14) | 0.04478 (15) | −0.00455 (10) | 0.01534 (10) | 0.00278 (8) |
S1 | 0.1231 (6) | 0.0290 (3) | 0.0606 (3) | −0.0041 (3) | 0.0535 (4) | 0.0022 (3) |
C1 | 0.0662 (13) | 0.0304 (11) | 0.0400 (10) | −0.0033 (10) | 0.0203 (9) | −0.0043 (8) |
N1 | 0.0834 (14) | 0.0314 (10) | 0.0610 (12) | −0.0019 (10) | 0.0301 (11) | 0.0038 (9) |
N10 | 0.0726 (14) | 0.0475 (11) | 0.0507 (11) | 0.0015 (11) | 0.0160 (10) | 0.0094 (10) |
C11 | 0.0567 (14) | 0.0506 (15) | 0.0516 (12) | 0.0068 (12) | 0.0113 (10) | 0.0105 (11) |
C12 | 0.0597 (14) | 0.0618 (17) | 0.0613 (14) | 0.0038 (13) | 0.0130 (11) | −0.0025 (13) |
C13 | 0.0692 (18) | 0.0599 (17) | 0.089 (2) | 0.0040 (15) | 0.0015 (16) | −0.0072 (16) |
C14 | 0.0660 (18) | 0.065 (2) | 0.114 (3) | −0.0063 (15) | 0.0080 (19) | 0.0123 (19) |
C15 | 0.0694 (18) | 0.086 (2) | 0.103 (2) | 0.0017 (17) | 0.0379 (18) | 0.022 (2) |
C16 | 0.0792 (18) | 0.0639 (19) | 0.0667 (16) | 0.0106 (16) | 0.0289 (14) | 0.0056 (14) |
Cd1—N1i | 2.283 (2) | C11—C16 | 1.368 (3) |
Cd1—N1ii | 2.283 (2) | C11—C12 | 1.379 (4) |
Cd1—N10 | 2.358 (2) | C12—C13 | 1.368 (4) |
Cd1—N10iii | 2.358 (2) | C12—H12A | 0.9300 |
Cd1—S1iii | 2.7485 (6) | C13—C14 | 1.384 (6) |
Cd1—S1 | 2.7485 (6) | C13—H13A | 0.9300 |
S1—C1 | 1.646 (2) | C14—C15 | 1.358 (5) |
C1—N1 | 1.139 (3) | C14—H14A | 0.9300 |
N1—Cd1iv | 2.2830 (19) | C15—C16 | 1.391 (4) |
N10—C11 | 1.434 (4) | C15—H15A | 0.9300 |
N10—H10A | 0.9000 | C16—H16A | 0.9300 |
N10—H10B | 0.9000 | ||
N1i—Cd1—N1ii | 180.0 | C11—N10—H10B | 108.4 |
N1i—Cd1—N10 | 94.27 (8) | Cd1—N10—H10B | 108.4 |
N1ii—Cd1—N10 | 85.73 (8) | H10A—N10—H10B | 107.4 |
N1i—Cd1—N10iii | 85.73 (8) | C16—C11—C12 | 120.1 (3) |
N1ii—Cd1—N10iii | 94.27 (8) | C16—C11—N10 | 119.8 (3) |
N10—Cd1—N10iii | 180.0 | C12—C11—N10 | 120.0 (2) |
N1i—Cd1—S1iii | 93.37 (5) | C13—C12—C11 | 119.9 (3) |
N1ii—Cd1—S1iii | 86.63 (5) | C13—C12—H12A | 120.0 |
N10—Cd1—S1iii | 92.04 (6) | C11—C12—H12A | 120.0 |
N10iii—Cd1—S1iii | 87.96 (6) | C12—C13—C14 | 120.7 (3) |
N1i—Cd1—S1 | 86.63 (5) | C12—C13—H13A | 119.7 |
N1ii—Cd1—S1 | 93.37 (5) | C14—C13—H13A | 119.7 |
N10—Cd1—S1 | 87.96 (6) | C15—C14—C13 | 118.8 (3) |
N10iii—Cd1—S1 | 92.04 (6) | C15—C14—H14A | 120.6 |
S1iii—Cd1—S1 | 180.000 (18) | C13—C14—H14A | 120.6 |
C1—S1—Cd1 | 98.36 (8) | C14—C15—C16 | 121.3 (3) |
N1—C1—S1 | 179.2 (2) | C14—C15—H15A | 119.3 |
C1—N1—Cd1iv | 163.1 (2) | C16—C15—H15A | 119.3 |
C11—N10—Cd1 | 115.59 (16) | C11—C16—C15 | 119.1 (3) |
C11—N10—H10A | 108.4 | C11—C16—H16A | 120.4 |
Cd1—N10—H10A | 108.4 | C15—C16—H16A | 120.4 |
N1i—Cd1—S1—C1 | −168.68 (11) | S1—Cd1—N10—C11 | −96.85 (17) |
N1ii—Cd1—S1—C1 | 11.32 (11) | Cd1—N10—C11—C16 | 86.1 (3) |
N10—Cd1—S1—C1 | −74.28 (12) | Cd1—N10—C11—C12 | −91.5 (2) |
N10iii—Cd1—S1—C1 | 105.72 (12) | C16—C11—C12—C13 | 0.3 (4) |
S1iii—Cd1—S1—C1 | 50 (100) | N10—C11—C12—C13 | 178.0 (3) |
Cd1—S1—C1—N1 | 169 (100) | C11—C12—C13—C14 | −0.5 (5) |
S1—C1—N1—Cd1iv | 148 (24) | C12—C13—C14—C15 | 0.5 (5) |
N1i—Cd1—N10—C11 | −10.38 (18) | C13—C14—C15—C16 | −0.4 (5) |
N1ii—Cd1—N10—C11 | 169.62 (18) | C12—C11—C16—C15 | −0.2 (4) |
N10iii—Cd1—N10—C11 | 156 (100) | N10—C11—C16—C15 | −177.9 (3) |
S1iii—Cd1—N10—C11 | 83.15 (17) | C14—C15—C16—C11 | 0.3 (5) |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+2, −z+1; (iii) −x, −y+1, −z+1; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cd(CNS)2(C6H7N)2] |
Mr | 414.81 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.1132 (13), 5.8547 (6), 13.1706 (13) |
β (°) | 100.466 (9) |
V (Å3) | 842.68 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.40 × 0.31 × 0.22 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.510, 0.712 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2664, 1943, 1616 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.068, 1.05 |
No. of reflections | 1943 |
No. of parameters | 98 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.47 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Siemens, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Cd1—N1i | 2.283 (2) | C11—C16 | 1.368 (3) |
Cd1—N10 | 2.358 (2) | C11—C12 | 1.379 (4) |
Cd1—S1 | 2.7485 (6) | C12—C13 | 1.368 (4) |
S1—C1 | 1.646 (2) | C13—C14 | 1.384 (6) |
C1—N1 | 1.139 (3) | C14—C15 | 1.358 (5) |
N10—C11 | 1.434 (4) | C15—C16 | 1.391 (4) |
N1i—Cd1—N10 | 94.27 (8) | C16—C11—N10 | 119.8 (3) |
N1i—Cd1—S1 | 86.63 (5) | C12—C11—N10 | 120.0 (2) |
N10—Cd1—S1 | 87.96 (6) | C13—C12—C11 | 119.9 (3) |
C1—S1—Cd1 | 98.36 (8) | C12—C13—C14 | 120.7 (3) |
N1—C1—S1 | 179.2 (2) | C15—C14—C13 | 118.8 (3) |
C1—N1—Cd1ii | 163.1 (2) | C14—C15—C16 | 121.3 (3) |
C11—N10—Cd1 | 115.59 (16) | C11—C16—C15 | 119.1 (3) |
C16—C11—C12 | 120.1 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
The supramolecular architecture of multi-dimensional networks has become of great interest recently. It has been reported that these networks may have electronic, magnetic, optical, or catalytic applications (Batten & Robson, 1998; Dunbar & Heintz, 1997). For designing infinite inorganic-organic frameworks, we and others (Kim et al., 1999; Cortes et al., 1997; Demunno et al., 1997) have used various pseudohalide ions, such as CN-, OCN-, SCN-, SeCN-, CNO- and N3-, and complementary organic ligands. Due to the terminal and bridging bonding properties, multi-dimensional framework structures linking one metal atom M to another metal atom M' alternately could be built by using pseudohalide ions (Wells, 1984). As an extension of the study, we have introduced the thiocyanate and aniline as complementary ligands. We here report the one-dimensional inorganic-organic composite coordination polymeric structure of the compound [Cd(SCN)2(C6H5NH2)2], (I). \sch
As shown in Figs. 1 and 2, each cadmium(II) atom lies on an inversion centre and is hexacoordinated by the two thiocyanate sulfur atoms, two isothiocyanate nitrogen atoms, and two aniline nitrogen atoms. The pairs of the same kinds of ligands are all in trans-configurations. The coordination environment of the central cadmium(II) atom adopts a distorted octahedral geometry. The bond length of Cd—SSCN is longer than that of Cd—NNCS in the corresponding cation [2.7485 (6) versus 2.283 (2) Å]. The bond length of Cd—NNCS is shorter than that of Cd—Naniline [2.283 (2) versus 2.358 (2) Å]. The variations in the Cd—S—CSCN and Cd—N—CNCS bond angles are all within the reported range (Wells, 1984). The bond lengths and angles of the SCN and aniline ligands of (I) are unexceptional and similar to those reported in the literature (Zukerman-Schpector et al., 1988).
As shown in Fig. 2, the octahedral Cd centres run in parallel to the b axis and are doubly bridged with neighbouring Cd centres by the SCN and NCS ligands to form an eight-membered ring with a repeating unit of Cd—S—C—N—Cd—S—C—N– and a centre of inversion in the centre of the ring. Thus, (I) forms a one-dimensional infinite polymeric linear chain structure. In comparison with other similar systems, the coordination geometry and crystal structure of (I) is very different. In the crystal structure of cadmium dithiocyanate itself, the cadmium atom is six-coordinated by four sulfur and two trans-nitrogen atoms (Cannas et al., 1976a). Treatment with an amine such as tetramethylethylenediamine furnishes an adduct in which adjacent cadmium atoms are bridged by a pair of NCS/SCN bridges (Zukerman-Schpector et al., 1988). 1,2,4-Triazole can be used for the purpose of forming the [Cd(NCS)2]n chains (Haasnoot et al., 1983; Biagini Cingi et al., 1986). On the other hand, with 2,2'-bipyridine, the resulting complex exists as a monomer and the bridges are absent (Rodesiler et al., 1984). When a triamine is used, the resulting complex has the cadmium atom bonded by five nitrogen atoms (Cannas et al., 1976b). These observations indicate that the crystal structure of the thiocyanate complexes is significantly affected by the bonding properties of the thiocyanate group and the skeleton of the organic ligand.