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New complexes containing the 1,4-bis­(pyridazin-4-yl)­benzene ligand, namely diaqua­tetra­kis­[1,4-bis­(pyridazin-4-yl)­benzene-[kappa]N2]cadmium(II) hexa­iodido­dicadmate(II), [Cd(C14H10N4)4(H2O)2][Cd2I6], (I), and poly[[[mu]-1,4-bis­(pyridazin-4-yl)benzene-[kappa]2N2:N2']bis­([mu]-thio­cyanato-[kappa]2N:S)­cadmium(II)], [Cd(NCS)2(C14H10N4)]n, (II), demonstrate the adaptability of the coordination geometries towards the demands of slipped [pi]-[pi] stacking inter­actions between the extended organic ligands. In (I), the discrete cationic [Cd-N = 2.408 (3) and 2.413 (3) Å] and anionic [Cd-I = 2.709 (2)-3.1201 (14) Å] entities are situated across centres of inversion. The cations associate via complementary O-H...N2' hydrogen bonding [O...N = 2.748 (4) and 2.765 (4) Å] and extensive triple [pi]-[pi] stacking inter­actions between pairs of pyridazine and phenyl­ene rings [centroid-centroid distances (CCD) = 3.782 (4)-4.286 (3) Å] to yield two-dimensional square nets. The [Cd2I6]2- anions reside in channels generated by packing of successive nets. In (II), the CdII cation lies on a centre of inversion and the ligand is situated across a centre of inversion. A two-dimensional coordination array is formed by crosslinking of linear [Cd([mu]-NCS)2]n chains [Cd-N = 2.3004 (14) Å and Cd-S = 2.7804 (5) Å] with N2:N2'-bident­ate organic bridges [Cd-N = 2.3893 (12) Å], which generate [pi]-[pi] stacks by double-slipped inter­actions between phenyl­ene and pyridazine rings [CCD = 3.721 (2) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113002801/tp3018sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002801/tp3018Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002801/tp3018IIsup3.hkl
Contains datablock II

CCDC references: 934551; 934552

Comment top

Slipped ππ stacking interactions represent a common type of supramolecular force for the structure of coordination compounds incorporating heteroaromatic ligands (Janiak, 2000). Extension of the aromatic linkage has a pronounced impact on the coordination architecture (Khlobystov et al., 2001), while leading to stabilization of a pattern favouring parallel alignment of the organic modules with multiple ππ or C—H···π interactions (Domasevitch et al., 2002). The role of such weaker bonding (and its reliability as a special design tool) becomes even more appreciable when considering flexible coordination systems readily adaptable to the needs of interaromatic stacking (Roesky & Andruh, 2003). In this view, the coordination geometries adopted by CdII cations and electron-deficient and low-basic pyridazine (pKa 2.24 for the parent pyridazine versus pKa 5.25 for pyridine) are of special interest for providing a clear structural response to subtle changes in chemical composition and for the evaluation of weaker interactions. The dual behaviour of pyridazine (pdz), as either a short bridge or a monodentate pyridine-like donor, is especially sensitive to the latter. The combination of µ-pdz and double halogenide bridges that is relevant for one-dimensional [CdX2(pdz)] (X = Cl or Br; Pazderski et al., 2004) becomes unfavourable for bifunctional 4,4'-bipyridazine (bpdz; Domasevitch et al., 2012). In this case, the interplay of coordination and weak interactions dominates the double pyridine-like coordination of the ligand within the [CdX2(bpdz)] (X = Cl or Br) array in a similar manner to the 4,4'-bipyridine analogues (Hu et al., 2003). However, the mismatch of the ππ stacking and [Cd(µ-X)2] chain geometries results in the formation of a pattern related to the [CdX2(pdz)] prototype (Domasevitch et al., 2012). An even more illustrative situation may be anticipated for extended bipyridazine tectons, exhibiting much stronger ππ stacking, when combined with the related one-dimensional scaffolds [Cd(µ-X)2] (X = I or NCS; Englert, 2010). The long µ-X bridges maintain a period of more than 4.1 Å, which is incompatible with the close interactions of the axially coordinated ligands. Therefore, claims for the densest ππ stacking may only be fulfilled with a partial reorganization of the inorganic substructure, allowing evaluation of the supramolecular stabilizing effects. In this context, we have prepared two complexes based on the extended 1,4-bis(pyridazin-4-yl)benzene ligand (bpph), viz. [Cd(bpph)4(H2O)2][Cd2I6], (I), and [Cd(µ-NCS)2(µ-bpph)]n, (II), and report their structures here.

Complex (I) adopts a structure comprising discrete [Cd(bpph)4(H2O)2]2+ cations and [Cd2I6]2- anions, both of which are situated across inversion centres (Fig. 1). This type of binuclear anion (formed by two distorted [CdI4] tetrahedra sharing one common edge) is very characteristic for Cd–iodide systems (Svensson et al., 1998). In the case of (I), the CdII cations of the iodocadmate are equally disordered over two closely separated positions (Cd2A and Cd2B) on both axial sides of the I1/I2/I3 plane (Fig. 1). This behaviour is determined by the packing mode of the anions, which are situated in the channels of the structure and stack with almost identical interplanar distances adopted by parallel I1/I2/I3 faces within the anion [3.3769 (4) Å; symmetry code: -x + 1, -y + 1, -z + 1] and between neighbouring anions [3.2763 (4) Å; symmetry code: -x, -y + 1, -z + 1]. Since successive anions within the chain are related by translation along the a axis, each such stack is defined by either the Cd2A or Cd2B positions.

In the complex cation, the Cd1 cation lies on an inversion centre and has a distorted octahedral geometry, with four N atoms of organic ligands in the equatorial plane [Cd1—N = 2.408 (3)–2.413 (3) Å] and two aqua ligands in the axial positions [Cd1—O1 = 2.257 (2) Å]. This geometry is similar to that observed for CdII complexes with pyridine N-atom donors, for example bis(pyridin-4-yl)amine [Cd—N = 2.322 and 2.331 Å; Krishnan et al., 2007] and N,N'-bis(pyridin-3-yl)urea [Cd—N = 2.309–2.367 Å; Kumar et al., 2007], while slightly longer Cd—N bonds in the present case may indicate the weaker donor ability of pyridazine. It is worth noting that only one of the four N-donor atoms present in the ligand is coordinated to the metal cation.

The noncoordinated pyridazine group acts as an acceptor in O—H···N hydrogen bonding, providing further supramolecular organization of the system. In this view, the [Cd(bpph)4(H2O)2]2+ cations represent a very illustrative case: the numbers of H-atom donor (four OH) and acceptor (four pdz) sites are equal and therefore the building blocks are self-complementary. The combined interconnection of the available donor and acceptor sites [O···N = 2.748 (4) and 2.765 (4) Å; Table 2] yields a two-dimensional square net parallel to the (110) plane. This structure exhibits extensive slipped ππ interactions that occur between pairs of pdz rings, with typical ranges of centroid-to-centroid separations [3.782 (4)—3.978 (3) Å] and slippage angles [24.0 (2)–28.4 (2)°; Table 3] (Janiak, 2000), and dictates a parallel alignment of the long polyaromatic molecules (Fig. 2). Weak C—H···N hydrogen bonding between pairs of cis-positioned pyridazines [C15···N1i = 3.120 (4) Å; C15H···N1i = 141°; symmetry code: (i) -x + 2, -y, -z] is also beneficial for the generation of the ππ stack. It reduces the steric interactions between the coordinated pdz rings and allows a degree of flattening of the Cd(pdz)4 fragment [the dihedral angle formed by the N5/N6/C15–C18 and CdN4 planes is 32.017 (13)°].

Extensively slipped ππ stacking is a possible reason for the behaviour of bpph as a monodentate ligand and for the relatively simple organization of the entire coordination system. In particular, the combination of µ-pyridazine and iodide bridges (observed in a Cd iodide complex with prototypical tetradentate 4,4'-bipyridazine; Domasevitch et al., 2012) in the present case becomes less favorable in view of the greater role of the ππ interactions, while the one-dimensional motif involving Cd(µ-I)2 (Cd···Cd > 4.1 Å) can also not support effective stacking interactions between the axial N-aromatic ligands (Hu et al., 2003). As a result, the polymeric Cd–iodide linkage is eliminated altogether, with the formation of discrete Cd–organic cations and iodocadmate anions (Figs. 2 and 3).

The packing of the hydrogen-bonded square nets generates channels along the a axis, with dimensions of ca 8 × 6 Å, well suited to accommodating the [Cd2I6]2- counterions. The orientation of these anions inside the bpph channels is governed by a set of very weak C—H···I interactions, as shown in Fig. 2. In total, seven unique contacts of this type are observed, with C···I distances in the range 3.656–4.075 Å (Table 2). These values are similar to those of contacts described previously (Ferguson et al., 1994; Glidewell et al., 1994), although comparable examples of C—H···I hydrogen bonding are relatively rare. The present system is important and demonstrates a clear discrimination of the binding sites, which follows a common pattern for convenient hydrogen bonding: the prefered acceptor is atom I3 (four contacts), which is terminal and is the most underbonded and electronegative. At the same time, five out of the seven contacts present are maintained by pyridazine CH groups, which are the most polarized and acidic.

In (II), the CdII cation lies on an inversion centre and the organic ligand is situated across an inversion centre (Fig. 4). The structure exhibits typical N-heteroaryl-ligand Cd/NCS coordination motifs in the form of a one-dimensional chain, along the a axis, of octahedral CdII catons doubly bridged by N:S-bidentate thiocyanate links [Cd1—N3 = 2.3004 (14) Å and Cd1—S1 = 2.7804 (9) Å] and accommodating pairs of pyridazine donors at the axial positions [Cd1—N2 = 2.3893 (12) Å] (Fig. 4). A similar coordination geometry, with a slightly shorter Cd—S bond [2.737 (3) Å], is reported for the [Cd(NCS)2(4,4'-bipy)]n complex (4,4'-bipy is 4,4'-bypyridine; Pan et al., 1999).

At first glance, this motif cannot be favourable for the long polyaromatic bpph linkers since the translation period of the inorganic chain [Cd···Cd = 5.9018 (6) Å, parameter a of the unit cell] is incompatible with any ππ stacking interactions between adjacent ligands. This geometry mismatch is relevant for the closely related Cd/NCS complex with 2,5-bis(pyridin-3-yl)-1,3,4-thiadiazole (Niu et al., 2008), where it results in the replacement of every second organic link by a pair of stacked monodentate ligands. The same pattern is also seen in a complex with nicotinic acid (Yang et al., 2001). However, N2-coordination of the pyridazine is responsible for the inclined orientation of the ligand towards the plane of the [Cd(NCS)2]n scaffold, which favours the formation of slipped ππ stacking utilizing two of the three aromatic rings (Fig. 5). In this way, the stacking pattern exists in the form of centrosymmetric pdz/p-C6H4/pdz sandwiches, with centroid-to-centroid distances of 3.721 (2) Å, interplanar distances of 3.614 (2) Å and slippage angles of 13.77 (8)°. Additional stabilization of the present ligand/scaffold orientation is given by weak C1—H1···N3 hydrogen bonding [C1···N3 = 3.287 (2) Å; Fig. 5].

The bpph ligands of (II), acting as a simple bitopic bridge, link the CdII cations of adjacent one-dimensional [Cd(NCS)2]n chains [symmetry code: x + 1, y - 1, z + 1] at a distance 14.12 Å, resulting in a two-dimensional network parallel to the (011) plane (Fig. 5). The N2:N2'-coordination mode of the ligand is formally equivalent to its N2-coordination and hydrogen bonding in (I) and has a precedent in the structure of [CuBr2(bpph)]n, which exhibits triple-stacking interactions between the organic molecules (Degtyarenko, Solntsev, Rusanov et al., 2008 or Degtyarenko, Solntsev, Krautscheid et al., 2008 ?). These coordination layers pack one on the top of another via extensive weak C—H···S hydrogen bonding (Fig. 6). The most notable interaction of this type is between C3—H3 and atom S1vii [C3···S1vii = 3.7683 (15) Å and C3—H3···S1vii = 164°; symmetry code: (vii) x - 1, y, z + 1], which is similar to the interactions of the N,S-coordinated thiocyanate group reported in the CdII complex with nicotinic acid (C···S = 3.692 Å and H···S = 2.82 Å; Yang et al., 2001). Another kind of weak interlayer interaction is C—H···N hydrogen bonding arranging the pdz rings into centrosymmetric `dimers' (C4···N1vi; see Table 5 for details]. These dimers are a characteristic supramolecular motif dominating the structure of pyridazine itself [C···N = 3.506 (3) Å; Blake & Rankin, 1991] and were also observed in the structure of bpph [C···N = 3.399 (3) Å; Degtyarenko, Solntsev, Rusanov et al., 2008].

In conclusion, the present system demonstrates the adaptability of the coordination geometry to accommodate the demands imposed by stacking of long aromatic ligands, such as 1,4-bis(pyridazin-4-yl)benzene. This is a crucial factor in the Cd–iodide system. However, in combination with the relatively robust coordination substructure (e.g. [Cd(µ-NCS)2]n), the special and peculiar role of the interligand stacking may be considered for designing and fine-tuning the metrics of the coordination layer.

Related literature top

For related literature, see: Blake & Rankin (1991); Degtyarenko, Solntsev, Krautscheid, Rusanov, Chernega & Domasevitch (2008); Degtyarenko, Solntsev, Rusanov, Chernega & Domasevitch (2008); Domasevitch et al. (2002, 2012); Englert (2010); Ferguson et al. (1994); Glidewell et al. (1994); Hu et al. (2003); Janiak (2000); Khlobystov et al. (2001); Krishnan et al. (2007); Kumar et al. (2007); Niu et al. (2008); Pan et al. (1999); Pazderski (2004); Roesky & Andruh (2003); Svensson et al. (1998); Yang et al. (2001).

Experimental top

1,4-Bis(pyridazin-4-yl)benzene, bpph, was prepared according to the procedure of Degtyarenko, Solntsev, Krautscheid et al. (2008). For the synthesis of (I), a solution of CdI2 (18.3 mg, 0.05 mmol) in methanol (3 ml) was added to a solution of bpph (11.7 mg, 0.05 mmol) in the same solvent (3 ml). Slow evaporation of the solution over a period of 2 d gave yellow prismatic crystals of the product (yield 21 mg, 80%). Complex (II) was synthesized using the hydrothermal method. A mixture of Cd(NCS)2 (11.4 mg, 0.05 mmol), bpph (11.7 mg, 0.05 mmol) and water (5 ml) in a Teflon vessel was placed in a steel autoclave, heated at 434 K for 20 h, and then cooled to room temperature over a period of 48 h. The yellow prisms of (II) (yield 16 mg, 70%) were filtered off and dried in air.

Refinement top

All H atoms were located from difference maps and then refined as riding, with O—H = 0.85 Å or C—H = 0.94 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). In (I), the CdII cation of the iodocadmate anion is disordered over two closely separated [0.572 (2) Å] positions. The refinement of partial occupancy factors led to values of 0.487 (19) and 0.513 (19), and therefore the subsequent calculations were based on equal contributions from the disorder components. They were refined freely without any geometry or thermal-motion restraints.

Computing details top

Data collection: APEX2 (Bruker, 2008) for (I); IPDS Software (Stoe & Cie, 2000) for (II). Cell refinement: SAINT (Bruker, 2008) for (I); IPDS Software (Stoe & Cie, 2000) for (II). Data reduction: SAINT (Bruker, 2008) for (I); IPDS Software (Stoe & Cie, 2000) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing (a) discrete [Cd(bpph)4(H2O)2]2+ cations and (b) [Cd2I6]2- anions, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. The aromatic rings labelled AF provide the key to the intermolecular interactions listed in Table 3. N atoms are shaded grey. Note the disordered mode of the CdII cations within the iodocadmate linkage in part (b), denoted by open and solid bonds. [Symmetry codes: (i) -x + 2, -y, -z; (ii) -x + 1, -y + 1, -z + 1; (iii) -x, -y + 1, -z + 1.]
[Figure 2] Fig. 2. A fragment of the structure of (I), showing the formation of a square network via O—H···N hydrogen bonding and slipped ππ stacking between the metal–organic cations. C-bound H atoms have been omitted for clarity, N atoms are shaded grey and dashed lines indicate hydrogen bonding. [Symmetry code: (iv) x + 1, y - 1, z.]
[Figure 3] Fig. 3. A projection of the structure of (I) onto the ab plane, showing the packing of successive supramolecular layers and the location of bulk [Cd2I6]2- anions (in a polyhedral representation). C-bound H atoms have been omitted for clarity. (See Figs. 1 and 2 for symmetry codes.)
[Figure 4] Fig. 4. The structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. N atoms are shaded grey. [Symmetry codes: (i) -x, -y + 2, -z; (ii) x - 1, y, z; (iii) -x + 1, -y + 2, -z; (iv) -x + 1, -y + 1, -z + 1.]
[Figure 5] Fig. 5. A view of the two-dimensional coordination sheet in the structure of (II), showing the formation of [Cd(NCS)2]n polymeric chains along the a axis and their interconnection by the organic bridges. Note the double-slipped ππ stacking (indicated by thin lines) between the latter and the generation of pdz···C6H4···pdz sandwiches. [Symmetry codes: (v) x + 1, y, z; (viii) x + 1, y - 1, z + 1.]
[Figure 6] Fig. 6. A projection of the structure of (II) onto the bc plane, showing the packing of the coordination layers (indicated with grey stripes), double pdz/pdz hydrogen bonding and multiple interlayer C—H···S interactions between sterically accessible S atoms. These interactions are indicated by dashed lines. [Symmetry codes: (vi) -x - 1, -y + 2, -z + 1; (vii) x - 1, y, z + 1.]
(I) Diaquatetrakis[1,4-bis(pyridazin-4-yl)benzene-κN2]cadmium(II) hexaiodidodicadmate(II) top
Crystal data top
[Cd(C14H10N4)4(H2O)2][Cd2I6]Z = 1
Mr = 2071.67F(000) = 970
Triclinic, P1Dx = 2.209 Mg m3
a = 8.0710 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.0867 (5) ÅCell parameters from 18145 reflections
c = 15.2422 (7) Åθ = 1.4–26.4°
α = 81.885 (2)°µ = 4.04 mm1
β = 81.742 (3)°T = 213 K
γ = 79.870 (2)°Prism, yellow
V = 1557.26 (11) Å30.20 × 0.19 × 0.16 mm
Data collection top
Bruker APEXII area-detector
diffractometer
6320 independent reflections
Radiation source: fine-focus sealed tube4886 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω scansθmax = 26.4°, θmin = 1.4°
Absorption correction: numerical
face-indexed (SADABS; Bruker, 2008)
h = 99
Tmin = 0.499, Tmax = 0.564k = 1616
18145 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.022P)2 + 0.7356P]
where P = (Fo2 + 2Fc2)/3
6320 reflections(Δ/σ)max = 0.001
385 parametersΔρmax = 1.04 e Å3
0 restraintsΔρmin = 0.93 e Å3
Crystal data top
[Cd(C14H10N4)4(H2O)2][Cd2I6]γ = 79.870 (2)°
Mr = 2071.67V = 1557.26 (11) Å3
Triclinic, P1Z = 1
a = 8.0710 (3) ÅMo Kα radiation
b = 13.0867 (5) ŵ = 4.04 mm1
c = 15.2422 (7) ÅT = 213 K
α = 81.885 (2)°0.20 × 0.19 × 0.16 mm
β = 81.742 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer
6320 independent reflections
Absorption correction: numerical
face-indexed (SADABS; Bruker, 2008)
4886 reflections with I > 2σ(I)
Tmin = 0.499, Tmax = 0.564Rint = 0.030
18145 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.061H-atom parameters constrained
S = 1.02Δρmax = 1.04 e Å3
6320 reflectionsΔρmin = 0.93 e Å3
385 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd11.00000.00000.00000.02707 (10)
Cd2A0.3046 (2)0.46357 (17)0.46770 (16)0.0573 (4)0.50
Cd2B0.2488 (2)0.48662 (17)0.45048 (16)0.0528 (4)0.50
I10.08549 (3)0.43341 (2)0.619573 (19)0.04554 (9)
I20.38460 (3)0.66554 (2)0.44533 (2)0.04999 (9)
I30.38632 (4)0.37457 (2)0.31392 (2)0.04989 (9)
O11.2106 (3)0.05672 (18)0.05284 (16)0.0354 (6)
H1W1.28860.00710.06750.053*
H2W1.17590.09040.09750.053*
N10.8956 (4)0.1811 (2)0.1537 (2)0.0355 (8)
N20.9210 (4)0.1763 (2)0.0680 (2)0.0331 (7)
N30.4760 (4)0.9057 (3)0.1966 (2)0.0417 (8)
N40.4601 (4)0.9010 (2)0.1111 (2)0.0385 (8)
N50.6741 (4)0.1186 (2)0.1163 (2)0.0334 (7)
N60.8112 (4)0.0462 (2)0.13112 (19)0.0289 (7)
N71.0058 (4)0.2434 (3)0.8036 (2)0.0387 (8)
N80.8869 (4)0.1572 (2)0.7958 (2)0.0375 (8)
C10.8873 (4)0.2617 (3)0.0270 (3)0.0318 (9)
H10.90720.25560.03290.038*
C20.8235 (4)0.3605 (3)0.0681 (3)0.0302 (8)
C30.7996 (5)0.3650 (3)0.1559 (3)0.0374 (9)
H30.75840.42870.18830.045*
C40.8377 (5)0.2734 (3)0.1959 (3)0.0363 (9)
H40.82160.27700.25620.044*
C50.5265 (4)0.8167 (3)0.0725 (3)0.0339 (9)
H50.51370.81710.01210.041*
C60.6151 (4)0.7265 (3)0.1159 (3)0.0307 (9)
C70.6285 (5)0.7315 (3)0.2038 (3)0.0411 (10)
H70.68330.67410.23880.049*
C80.5591 (5)0.8234 (3)0.2394 (3)0.0471 (11)
H80.57290.82690.29910.057*
C90.7798 (4)0.4536 (3)0.0189 (3)0.0310 (9)
C100.7936 (5)0.5533 (3)0.0643 (3)0.0371 (9)
H100.83790.56080.12490.045*
C110.7421 (5)0.6402 (3)0.0197 (3)0.0375 (9)
H110.75120.70670.05080.045*
C120.6778 (4)0.6322 (3)0.0690 (3)0.0298 (8)
C130.6691 (5)0.5331 (3)0.1150 (3)0.0408 (10)
H130.62930.52560.17620.049*
C140.7193 (5)0.4456 (3)0.0704 (3)0.0420 (10)
H140.71190.37910.10190.050*
C150.8386 (4)0.0075 (3)0.2134 (2)0.0293 (8)
H150.93560.04290.22090.035*
C160.7340 (4)0.0359 (3)0.2902 (2)0.0264 (8)
C170.5966 (4)0.1110 (3)0.2748 (3)0.0327 (9)
H170.52030.13610.32250.039*
C180.5730 (5)0.1492 (3)0.1872 (3)0.0365 (9)
H180.47820.20070.17740.044*
C190.8426 (4)0.1163 (3)0.7170 (3)0.0328 (9)
H190.75990.05590.71480.039*
C200.9090 (4)0.1555 (3)0.6363 (2)0.0269 (8)
C211.0288 (5)0.2432 (3)0.6460 (3)0.0390 (10)
H211.08120.27580.59570.047*
C221.0722 (5)0.2837 (3)0.7297 (3)0.0435 (10)
H221.15480.34390.73420.052*
C230.7719 (4)0.0130 (3)0.3803 (2)0.0285 (8)
C240.7275 (5)0.0407 (3)0.4550 (3)0.0337 (9)
H240.66790.10930.44880.040*
C250.7689 (5)0.0043 (3)0.5377 (2)0.0342 (9)
H250.73870.03420.58670.041*
C260.8549 (4)0.1061 (3)0.5498 (2)0.0290 (8)
C270.8953 (5)0.1609 (3)0.4752 (3)0.0415 (10)
H270.95130.23040.48170.050*
C280.8548 (5)0.1150 (3)0.3929 (3)0.0407 (10)
H280.88390.15360.34380.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0360 (2)0.02320 (19)0.0192 (2)0.00151 (16)0.00280 (17)0.00154 (15)
Cd2A0.0673 (12)0.0524 (9)0.0485 (9)0.0122 (8)0.0175 (7)0.0151 (6)
Cd2B0.0519 (9)0.0564 (10)0.0502 (9)0.0135 (7)0.0121 (6)0.0193 (7)
I10.03864 (15)0.05538 (18)0.03680 (17)0.00085 (13)0.00263 (13)0.00401 (14)
I20.04687 (17)0.04602 (17)0.0560 (2)0.01024 (13)0.00167 (14)0.00683 (15)
I30.05963 (19)0.04255 (17)0.04205 (19)0.00439 (14)0.00069 (14)0.00915 (14)
O10.0384 (14)0.0337 (14)0.0326 (16)0.0043 (12)0.0057 (12)0.0100 (12)
N10.0402 (18)0.0326 (18)0.0292 (19)0.0010 (15)0.0001 (15)0.0012 (15)
N20.0383 (18)0.0271 (16)0.0300 (19)0.0003 (14)0.0037 (15)0.0023 (14)
N30.046 (2)0.039 (2)0.041 (2)0.0069 (16)0.0056 (18)0.0095 (17)
N40.0397 (19)0.0302 (17)0.045 (2)0.0005 (15)0.0091 (17)0.0058 (16)
N50.0337 (17)0.0361 (18)0.0287 (19)0.0007 (15)0.0071 (15)0.0018 (15)
N60.0315 (16)0.0332 (17)0.0219 (17)0.0036 (14)0.0022 (14)0.0057 (14)
N70.049 (2)0.0411 (19)0.0257 (19)0.0056 (17)0.0068 (16)0.0011 (16)
N80.0430 (19)0.0435 (19)0.0259 (19)0.0046 (16)0.0046 (16)0.0060 (16)
C10.036 (2)0.028 (2)0.029 (2)0.0008 (17)0.0044 (18)0.0017 (17)
C20.032 (2)0.0246 (19)0.031 (2)0.0023 (16)0.0028 (17)0.0025 (17)
C30.045 (2)0.029 (2)0.031 (2)0.0016 (18)0.0017 (19)0.0082 (18)
C40.044 (2)0.036 (2)0.026 (2)0.0007 (19)0.0071 (19)0.0011 (18)
C50.036 (2)0.033 (2)0.033 (2)0.0035 (18)0.0078 (18)0.0026 (18)
C60.031 (2)0.028 (2)0.033 (2)0.0044 (16)0.0059 (17)0.0011 (17)
C70.050 (3)0.035 (2)0.038 (3)0.000 (2)0.017 (2)0.0010 (19)
C80.062 (3)0.047 (3)0.037 (3)0.012 (2)0.013 (2)0.010 (2)
C90.031 (2)0.0275 (19)0.032 (2)0.0006 (16)0.0059 (18)0.0017 (17)
C100.048 (2)0.030 (2)0.029 (2)0.0037 (18)0.0008 (19)0.0023 (18)
C110.046 (2)0.025 (2)0.039 (3)0.0078 (18)0.001 (2)0.0044 (18)
C120.032 (2)0.0262 (19)0.030 (2)0.0020 (16)0.0093 (17)0.0023 (17)
C130.058 (3)0.034 (2)0.024 (2)0.001 (2)0.002 (2)0.0008 (18)
C140.056 (3)0.026 (2)0.038 (3)0.0003 (19)0.001 (2)0.0072 (18)
C150.0290 (19)0.032 (2)0.026 (2)0.0002 (16)0.0013 (17)0.0084 (17)
C160.0297 (19)0.0251 (18)0.024 (2)0.0029 (16)0.0014 (16)0.0042 (16)
C170.034 (2)0.034 (2)0.027 (2)0.0017 (17)0.0012 (17)0.0072 (17)
C180.033 (2)0.038 (2)0.034 (2)0.0059 (18)0.0086 (19)0.0024 (19)
C190.033 (2)0.035 (2)0.030 (2)0.0028 (17)0.0048 (18)0.0042 (18)
C200.0286 (19)0.0305 (19)0.023 (2)0.0091 (16)0.0009 (16)0.0038 (16)
C210.047 (2)0.039 (2)0.027 (2)0.0071 (19)0.0021 (19)0.0084 (19)
C220.047 (2)0.041 (2)0.038 (3)0.005 (2)0.007 (2)0.002 (2)
C230.032 (2)0.030 (2)0.022 (2)0.0047 (16)0.0004 (16)0.0036 (16)
C240.039 (2)0.028 (2)0.030 (2)0.0029 (17)0.0023 (18)0.0055 (17)
C250.046 (2)0.033 (2)0.023 (2)0.0002 (18)0.0013 (18)0.0112 (17)
C260.035 (2)0.0287 (19)0.023 (2)0.0059 (17)0.0027 (17)0.0022 (16)
C270.057 (3)0.029 (2)0.036 (3)0.0098 (19)0.013 (2)0.0085 (19)
C280.060 (3)0.035 (2)0.027 (2)0.005 (2)0.010 (2)0.0103 (18)
Geometric parameters (Å, º) top
Cd1—O12.257 (2)C6—C121.489 (5)
Cd1—O1i2.257 (2)C7—C81.384 (5)
Cd1—N2i2.408 (3)C7—H70.9400
Cd1—N22.408 (3)C8—H80.9400
Cd1—N6i2.413 (3)C9—C141.374 (5)
Cd1—N62.413 (3)C9—C101.403 (5)
Cd2A—Cd2B0.572 (2)C10—C111.378 (5)
Cd2A—I32.710 (2)C10—H100.9400
Cd2A—I12.730 (2)C11—C121.373 (5)
Cd2A—I22.793 (2)C11—H110.9400
Cd2A—I2ii3.1201 (14)C12—C131.393 (5)
Cd2B—I32.709 (2)C13—C141.384 (5)
Cd2B—I22.741 (2)C13—H130.9400
Cd2B—I12.776 (2)C14—H140.9400
Cd2B—I1iii3.0058 (14)C15—C161.397 (5)
O1—H1W0.8500C15—H150.9400
O1—H2W0.8500C16—C171.370 (5)
N1—C41.327 (4)C16—C231.481 (5)
N1—N21.341 (4)C17—C181.386 (5)
N2—C11.326 (4)C17—H170.9400
N3—C81.308 (5)C18—H180.9400
N3—N41.338 (4)C19—C201.398 (5)
N4—C51.318 (4)C19—H190.9400
N5—C181.322 (5)C20—C211.370 (5)
N5—N61.347 (4)C20—C261.475 (5)
N6—C151.318 (4)C21—C221.380 (5)
N7—C221.314 (5)C21—H210.9400
N7—N81.349 (4)C22—H220.9400
N8—C191.316 (4)C23—C281.384 (5)
C1—C21.399 (5)C23—C241.393 (5)
C1—H10.9400C24—C251.374 (5)
C2—C31.371 (5)C24—H240.9400
C2—C91.484 (5)C25—C261.390 (5)
C3—C41.388 (5)C25—H250.9400
C3—H30.9400C26—C271.397 (5)
C4—H40.9400C27—C281.372 (5)
C5—C61.401 (5)C27—H270.9400
C5—H50.9400C28—H280.9400
C6—C71.370 (5)
O1—Cd1—O1i180.00 (14)N3—C8—C7125.0 (4)
O1—Cd1—N2i92.37 (9)N3—C8—H8117.5
O1i—Cd1—N2i87.63 (9)C7—C8—H8117.5
O1—Cd1—N287.63 (9)C14—C9—C10118.3 (3)
O1i—Cd1—N292.37 (9)C14—C9—C2121.6 (3)
N2i—Cd1—N2180.0 (2)C10—C9—C2120.0 (3)
O1—Cd1—N6i90.40 (9)C11—C10—C9119.9 (4)
O1i—Cd1—N6i89.60 (9)C11—C10—H10120.1
N2i—Cd1—N6i87.90 (10)C9—C10—H10120.1
N2—Cd1—N6i92.10 (10)C12—C11—C10121.7 (3)
O1—Cd1—N689.60 (9)C12—C11—H11119.2
O1i—Cd1—N690.40 (9)C10—C11—H11119.2
N2i—Cd1—N692.10 (10)C11—C12—C13118.6 (3)
N2—Cd1—N687.90 (10)C11—C12—C6121.6 (3)
N6i—Cd1—N6180.00 (16)C13—C12—C6119.8 (3)
I3—Cd2A—I1135.22 (10)C14—C13—C12119.9 (4)
I3—Cd2A—I2111.29 (8)C14—C13—H13120.0
I1—Cd2A—I2110.39 (8)C12—C13—H13120.0
I3—Cd2A—I2ii93.89 (6)C9—C14—C13121.6 (4)
I1—Cd2A—I2ii93.22 (6)C9—C14—H14119.2
I2—Cd2A—I2ii101.58 (6)C13—C14—H14119.2
I3—Cd2B—I2112.91 (9)N6—C15—C16124.8 (3)
I3—Cd2B—I1132.97 (9)N6—C15—H15117.6
I2—Cd2B—I1110.57 (8)C16—C15—H15117.6
I3—Cd2B—I1iii96.04 (6)C17—C16—C15114.7 (3)
I2—Cd2B—I1iii102.86 (6)C17—C16—C23123.9 (3)
I1—Cd2B—I1iii91.01 (6)C15—C16—C23121.4 (3)
Cd1—O1—H1W112.4C16—C17—C18118.4 (3)
Cd1—O1—H2W113.0C16—C17—H17120.8
H1W—O1—H2W108.3C18—C17—H17120.8
C4—N1—N2118.3 (3)N5—C18—C17124.8 (3)
C1—N2—N1120.4 (3)N5—C18—H18117.6
C1—N2—Cd1126.3 (2)C17—C18—H18117.6
N1—N2—Cd1112.9 (2)N8—C19—C20125.1 (3)
C8—N3—N4117.2 (3)N8—C19—H19117.5
C5—N4—N3120.8 (3)C20—C19—H19117.5
C18—N5—N6117.1 (3)C21—C20—C19113.4 (3)
C15—N6—N5120.3 (3)C21—C20—C26123.8 (3)
C15—N6—Cd1123.9 (2)C19—C20—C26122.8 (3)
N5—N6—Cd1115.8 (2)C20—C21—C22119.8 (4)
C22—N7—N8117.0 (3)C20—C21—H21120.1
C19—N8—N7120.5 (3)C22—C21—H21120.1
N2—C1—C2123.5 (3)N7—C22—C21124.3 (4)
N2—C1—H1118.3N7—C22—H22117.9
C2—C1—H1118.3C21—C22—H22117.9
C3—C2—C1115.7 (3)C28—C23—C24117.5 (3)
C3—C2—C9122.3 (3)C28—C23—C16120.5 (3)
C1—C2—C9122.0 (3)C24—C23—C16122.1 (3)
C2—C3—C4118.6 (3)C25—C24—C23121.5 (3)
C2—C3—H3120.7C25—C24—H24119.3
C4—C3—H3120.7C23—C24—H24119.3
N1—C4—C3123.5 (4)C24—C25—C26120.9 (3)
N1—C4—H4118.2C24—C25—H25119.5
C3—C4—H4118.2C26—C25—H25119.5
N4—C5—C6124.0 (4)C25—C26—C27117.6 (3)
N4—C5—H5118.0C25—C26—C20122.6 (3)
C6—C5—H5118.0C27—C26—C20119.8 (3)
C7—C6—C5114.7 (3)C28—C27—C26121.1 (3)
C7—C6—C12124.5 (3)C28—C27—H27119.4
C5—C6—C12120.6 (3)C26—C27—H27119.4
C6—C7—C8118.2 (4)C27—C28—C23121.5 (3)
C6—C7—H7120.9C27—C28—H28119.3
C8—C7—H7120.9C23—C28—H28119.3
I3—Cd2B—I1—Cd2Biii99.21 (10)C14—C9—C10—C112.0 (6)
I2—Cd2B—I1—Cd2Biii104.15 (7)C2—C9—C10—C11175.6 (3)
I1iii—Cd2B—I1—Cd2Biii0.0C9—C10—C11—C120.4 (6)
I3—Cd2A—I2—Cd2Aii98.86 (8)C10—C11—C12—C131.7 (6)
I1—Cd2A—I2—Cd2Aii97.89 (8)C10—C11—C12—C6177.2 (3)
I2ii—Cd2A—I2—Cd2Aii0.0C7—C6—C12—C11146.0 (4)
C4—N1—N2—C10.6 (5)C5—C6—C12—C1138.0 (5)
C4—N1—N2—Cd1174.4 (3)C7—C6—C12—C1335.2 (6)
O1—Cd1—N2—C154.1 (3)C5—C6—C12—C13140.9 (4)
O1i—Cd1—N2—C1125.9 (3)C11—C12—C13—C142.2 (6)
N6i—Cd1—N2—C1144.5 (3)C6—C12—C13—C14176.7 (3)
N6—Cd1—N2—C135.5 (3)C10—C9—C14—C131.4 (6)
O1—Cd1—N2—N1132.5 (2)C2—C9—C14—C13176.1 (3)
O1i—Cd1—N2—N147.5 (2)C12—C13—C14—C90.6 (6)
N6i—Cd1—N2—N142.1 (2)N5—N6—C15—C160.0 (5)
N6—Cd1—N2—N1137.9 (2)Cd1—N6—C15—C16177.7 (3)
C8—N3—N4—C50.2 (5)N6—C15—C16—C171.2 (5)
C18—N5—N6—C151.2 (5)N6—C15—C16—C23178.7 (3)
C18—N5—N6—Cd1176.7 (3)C15—C16—C17—C181.2 (5)
O1—Cd1—N6—C1558.7 (3)C23—C16—C17—C18178.7 (3)
O1i—Cd1—N6—C15121.3 (3)N6—N5—C18—C171.1 (6)
N2i—Cd1—N6—C1533.6 (3)C16—C17—C18—N50.1 (6)
N2—Cd1—N6—C15146.4 (3)N7—N8—C19—C200.5 (6)
O1—Cd1—N6—N5119.0 (2)N8—C19—C20—C210.2 (5)
O1i—Cd1—N6—N561.0 (2)N8—C19—C20—C26179.8 (3)
N2i—Cd1—N6—N5148.6 (2)C19—C20—C21—C220.1 (5)
N2—Cd1—N6—N531.4 (2)C26—C20—C21—C22179.6 (4)
C22—N7—N8—C190.6 (5)N8—N7—C22—C210.4 (6)
N1—N2—C1—C20.4 (5)C20—C21—C22—N70.0 (7)
Cd1—N2—C1—C2172.5 (3)C17—C16—C23—C28149.5 (4)
N2—C1—C2—C31.1 (5)C15—C16—C23—C2830.4 (5)
N2—C1—C2—C9177.1 (3)C17—C16—C23—C2430.9 (5)
C1—C2—C3—C40.7 (5)C15—C16—C23—C24149.2 (4)
C9—C2—C3—C4177.5 (3)C28—C23—C24—C252.0 (6)
N2—N1—C4—C31.0 (6)C16—C23—C24—C25177.6 (3)
C2—C3—C4—N10.3 (6)C23—C24—C25—C260.9 (6)
N3—N4—C5—C60.9 (6)C24—C25—C26—C270.8 (6)
N4—C5—C6—C70.1 (5)C24—C25—C26—C20176.9 (3)
N4—C5—C6—C12176.5 (3)C21—C20—C26—C25162.6 (4)
C5—C6—C7—C81.6 (6)C19—C20—C26—C2517.0 (5)
C12—C6—C7—C8177.8 (3)C21—C20—C26—C2715.0 (6)
N4—N3—C8—C71.4 (6)C19—C20—C26—C27165.4 (4)
C6—C7—C8—N32.4 (7)C25—C26—C27—C281.3 (6)
C3—C2—C9—C14145.7 (4)C20—C26—C27—C28176.4 (4)
C1—C2—C9—C1432.4 (5)C26—C27—C28—C230.2 (6)
C3—C2—C9—C1031.8 (5)C24—C23—C28—C271.5 (6)
C1—C2—C9—C10150.1 (4)C16—C23—C28—C27178.2 (4)
Symmetry codes: (i) x+2, y, z; (ii) x+1, y+1, z+1; (iii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N4iv0.851.902.748 (4)174
O1—H2W···N8v0.851.922.765 (4)174
C1—H1···N7v0.942.663.597 (5)174
C15—H15···N1i0.942.333.120 (4)141
C3—H3···I3vi0.943.144.073 (4)173
C7—H7···I1ii0.943.083.953 (4)155
C13—H13···I30.943.344.075 (4)137
C17—H17···I30.943.113.655 (4)119
C18—H18···I30.943.223.729 (4)116
C21—H21···I2iv0.943.174.041 (4)155
C27—H27···I1vii0.943.334.004 (4)130
Symmetry codes: (i) x+2, y, z; (ii) x+1, y+1, z+1; (iv) x+1, y1, z; (v) x+2, y, z+1; (vi) x+1, y+1, z; (vii) x+1, y, z+1.
(II) Poly[[µ-1,4-bis(pyridazin-4-yl)benzene-κ2N2:N2']bis(µ-thiocyanato-κ2N:S)cadmium(II)] top
Crystal data top
[Cd(NCS)2(C14H10N4)]Z = 1
Mr = 462.82F(000) = 228
Triclinic, P1Dx = 1.902 Mg m3
a = 5.9018 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.6619 (9) ÅCell parameters from 4656 reflections
c = 9.2433 (10) Åθ = 2.3–28.7°
α = 88.980 (12)°µ = 1.62 mm1
β = 75.434 (11)°T = 213 K
γ = 87.049 (12)°Prism, yellow
V = 404.00 (8) Å30.22 × 0.21 × 0.18 mm
Data collection top
Stoe IPDS
diffractometer
2084 independent reflections
Radiation source: fine-focus sealed tube2001 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ϕ oscillation scansθmax = 28.7°, θmin = 2.3°
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
h = 77
Tmin = 0.717, Tmax = 0.759k = 1010
4656 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0359P)2]
where P = (Fo2 + 2Fc2)/3
2084 reflections(Δ/σ)max < 0.001
115 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.64 e Å3
Crystal data top
[Cd(NCS)2(C14H10N4)]γ = 87.049 (12)°
Mr = 462.82V = 404.00 (8) Å3
Triclinic, P1Z = 1
a = 5.9018 (6) ÅMo Kα radiation
b = 7.6619 (9) ŵ = 1.62 mm1
c = 9.2433 (10) ÅT = 213 K
α = 88.980 (12)°0.22 × 0.21 × 0.18 mm
β = 75.434 (11)°
Data collection top
Stoe IPDS
diffractometer
2084 independent reflections
Absorption correction: numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
2001 reflections with I > 2σ(I)
Tmin = 0.717, Tmax = 0.759Rint = 0.024
4656 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.048H-atom parameters constrained
S = 1.04Δρmax = 0.39 e Å3
2084 reflectionsΔρmin = 0.64 e Å3
115 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.00001.00000.00000.02294 (6)
S10.78837 (6)0.69895 (5)0.05077 (4)0.02727 (9)
N10.2199 (2)0.93227 (17)0.34860 (14)0.0242 (2)
N20.0184 (2)0.89156 (17)0.24645 (13)0.0234 (2)
N30.3573 (2)0.8507 (2)0.07795 (16)0.0309 (3)
C10.1508 (2)0.79239 (19)0.28360 (16)0.0239 (3)
H10.28960.76780.20940.029*
C20.1333 (2)0.72252 (17)0.42723 (15)0.0190 (2)
C30.0738 (2)0.76561 (18)0.53186 (15)0.0212 (2)
H30.09960.72490.63090.025*
C40.2431 (2)0.87072 (19)0.48660 (16)0.0230 (3)
H40.38310.90010.55840.028*
C50.4953 (2)0.52484 (19)0.35120 (15)0.0219 (3)
H50.49330.54160.25050.026*
C60.3232 (2)0.60956 (17)0.46355 (14)0.0186 (2)
C70.3307 (2)0.58394 (19)0.61293 (15)0.0215 (3)
H70.21710.64090.68950.026*
C80.5364 (2)0.78950 (19)0.06813 (15)0.0226 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.01768 (8)0.03368 (9)0.01738 (8)0.00555 (5)0.00598 (5)0.00522 (5)
S10.02072 (16)0.03266 (19)0.02838 (19)0.00495 (13)0.00755 (13)0.00348 (15)
N10.0216 (5)0.0279 (6)0.0230 (6)0.0037 (4)0.0066 (4)0.0029 (5)
N20.0225 (5)0.0282 (6)0.0197 (5)0.0036 (4)0.0068 (4)0.0050 (5)
N30.0228 (6)0.0410 (8)0.0289 (6)0.0061 (5)0.0077 (5)0.0029 (6)
C10.0231 (6)0.0298 (7)0.0174 (6)0.0052 (5)0.0045 (5)0.0054 (5)
C20.0200 (6)0.0203 (6)0.0177 (6)0.0009 (4)0.0070 (4)0.0035 (5)
C30.0213 (6)0.0243 (6)0.0178 (6)0.0008 (5)0.0050 (5)0.0046 (5)
C40.0198 (6)0.0249 (6)0.0231 (6)0.0018 (5)0.0042 (5)0.0021 (5)
C50.0230 (6)0.0282 (7)0.0146 (5)0.0027 (5)0.0060 (4)0.0039 (5)
C60.0190 (5)0.0203 (6)0.0169 (6)0.0006 (4)0.0058 (4)0.0040 (5)
C70.0212 (6)0.0268 (6)0.0154 (6)0.0048 (5)0.0039 (4)0.0005 (5)
C80.0207 (6)0.0294 (7)0.0168 (6)0.0004 (5)0.0035 (4)0.0000 (5)
Geometric parameters (Å, º) top
Cd1—N32.3004 (14)C1—H10.9400
Cd1—N3i2.3004 (14)C2—C31.3836 (18)
Cd1—N2i2.3893 (12)C2—C61.4821 (17)
Cd1—N22.3893 (12)C3—C41.3917 (19)
Cd1—S1ii2.7804 (5)C3—H30.9400
Cd1—S1iii2.7804 (5)C4—H40.9400
S1—C81.6520 (14)C5—C7iv1.3898 (18)
N1—C41.3288 (18)C5—C61.3989 (19)
N1—N21.3456 (17)C5—H50.9400
N2—C11.3329 (17)C6—C71.4027 (18)
N3—C81.158 (2)C7—C5iv1.3898 (18)
C1—C21.4041 (18)C7—H70.9400
N3—Cd1—N3i180.0N2—C1—H1118.1
N3—Cd1—N2i91.97 (5)C2—C1—H1118.1
N3i—Cd1—N2i88.03 (5)C3—C2—C1115.30 (12)
N3—Cd1—N288.03 (5)C3—C2—C6122.49 (12)
N3i—Cd1—N291.97 (5)C1—C2—C6122.21 (12)
N2i—Cd1—N2180.0C2—C3—C4118.27 (12)
N3—Cd1—S1ii88.36 (4)C2—C3—H3120.9
N3i—Cd1—S1ii91.64 (4)C4—C3—H3120.9
N2i—Cd1—S1ii92.24 (3)N1—C4—C3124.30 (13)
N2—Cd1—S1ii87.76 (3)N1—C4—H4117.8
N3—Cd1—S1iii91.64 (4)C3—C4—H4117.8
N3i—Cd1—S1iii88.36 (4)C7iv—C5—C6120.60 (12)
N2i—Cd1—S1iii87.76 (3)C7iv—C5—H5119.7
N2—Cd1—S1iii92.24 (3)C6—C5—H5119.7
S1ii—Cd1—S1iii180.0C5—C6—C7118.77 (12)
C8—S1—Cd1v98.66 (6)C5—C6—C2121.20 (12)
C4—N1—N2117.73 (12)C7—C6—C2120.03 (12)
C1—N2—N1120.63 (12)C5iv—C7—C6120.63 (12)
C1—N2—Cd1124.27 (9)C5iv—C7—H7119.7
N1—N2—Cd1115.05 (8)C6—C7—H7119.7
C8—N3—Cd1156.76 (12)N3—C8—S1178.57 (14)
N2—C1—C2123.75 (13)
C4—N1—N2—C10.2 (2)Cd1—N2—C1—C2176.84 (11)
C4—N1—N2—Cd1177.89 (10)N2—C1—C2—C30.9 (2)
N3—Cd1—N2—C12.31 (12)N2—C1—C2—C6178.65 (14)
N3i—Cd1—N2—C1177.69 (12)C1—C2—C3—C40.4 (2)
S1ii—Cd1—N2—C190.75 (12)C6—C2—C3—C4179.18 (13)
S1iii—Cd1—N2—C189.25 (12)N2—N1—C4—C30.7 (2)
N3—Cd1—N2—N1175.32 (10)C2—C3—C4—N10.4 (2)
N3i—Cd1—N2—N14.68 (10)C7iv—C5—C6—C70.6 (2)
S1ii—Cd1—N2—N186.88 (10)C7iv—C5—C6—C2178.50 (13)
S1iii—Cd1—N2—N193.12 (10)C3—C2—C6—C5160.30 (14)
N2i—Cd1—N3—C8148.9 (3)C1—C2—C6—C519.3 (2)
N2—Cd1—N3—C831.1 (3)C3—C2—C6—C718.8 (2)
S1ii—Cd1—N3—C8118.9 (3)C1—C2—C6—C7161.67 (14)
S1iii—Cd1—N3—C861.1 (3)C5—C6—C7—C5iv0.6 (2)
N1—N2—C1—C20.7 (2)C2—C6—C7—C5iv178.51 (13)
Symmetry codes: (i) x, y+2, z; (ii) x1, y, z; (iii) x+1, y+2, z; (iv) x+1, y+1, z+1; (v) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N30.942.653.287 (2)125
C4—H4···N1vi0.942.573.4357 (19)154
C3—H3···S1vii0.942.853.7683 (15)164
C5—H5···S10.943.153.9249 (14)141
C7—H7···S1vii0.943.043.9354 (15)160
Symmetry codes: (vi) x1, y+2, z+1; (vii) x1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cd(C14H10N4)4(H2O)2][Cd2I6][Cd(NCS)2(C14H10N4)]
Mr2071.67462.82
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)213213
a, b, c (Å)8.0710 (3), 13.0867 (5), 15.2422 (7)5.9018 (6), 7.6619 (9), 9.2433 (10)
α, β, γ (°)81.885 (2), 81.742 (3), 79.870 (2)88.980 (12), 75.434 (11), 87.049 (12)
V3)1557.26 (11)404.00 (8)
Z11
Radiation typeMo KαMo Kα
µ (mm1)4.041.62
Crystal size (mm)0.20 × 0.19 × 0.160.22 × 0.21 × 0.18
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Stoe IPDS
diffractometer
Absorption correctionNumerical
face-indexed (SADABS; Bruker, 2008)
Numerical
[X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
Tmin, Tmax0.499, 0.5640.717, 0.759
No. of measured, independent and
observed [I > 2σ(I)] reflections
18145, 6320, 4886 4656, 2084, 2001
Rint0.0300.024
(sin θ/λ)max1)0.6250.676
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.061, 1.02 0.019, 0.048, 1.04
No. of reflections63202084
No. of parameters385115
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.04, 0.930.39, 0.64

Computer programs: APEX2 (Bruker, 2008), IPDS Software (Stoe & Cie, 2000), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).

Selected geometric parameters (Å, º) for (I) top
Cd1—O12.257 (2)Cd2A—I2i3.1201 (14)
Cd1—N22.408 (3)Cd2B—I32.709 (2)
Cd1—N62.413 (3)Cd2B—I22.741 (2)
Cd2A—I32.710 (2)Cd2B—I12.776 (2)
Cd2A—I12.730 (2)Cd2B—I1ii3.0058 (14)
Cd2A—I22.793 (2)
O1—Cd1—N2iii92.37 (9)I3—Cd2A—I2i93.89 (6)
O1—Cd1—N287.63 (9)I1—Cd2A—I2i93.22 (6)
O1—Cd1—N6iii90.40 (9)I2—Cd2A—I2i101.58 (6)
N2—Cd1—N6iii92.10 (10)I3—Cd2B—I2112.91 (9)
O1—Cd1—N689.60 (9)I3—Cd2B—I1132.97 (9)
N2—Cd1—N687.90 (10)I2—Cd2B—I1110.57 (8)
I3—Cd2A—I1135.22 (10)I3—Cd2B—I1ii96.04 (6)
I3—Cd2A—I2111.29 (8)I2—Cd2B—I1ii102.86 (6)
I1—Cd2A—I2110.39 (8)I1—Cd2B—I1ii91.01 (6)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x+2, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···N4iv0.851.902.748 (4)174
O1—H2W···N8v0.851.922.765 (4)174
C1—H1···N7v0.942.663.597 (5)174
C15—H15···N1iii0.942.333.120 (4)141
C3—H3···I3vi0.943.144.073 (4)173
C7—H7···I1i0.943.083.953 (4)155
C13—H13···I30.943.344.075 (4)137
C17—H17···I30.943.113.655 (4)119
C18—H18···I30.943.223.729 (4)116
C21—H21···I2iv0.943.174.041 (4)155
C27—H27···I1vii0.943.334.004 (4)130
Symmetry codes: (i) x+1, y+1, z+1; (iii) x+2, y, z; (iv) x+1, y1, z; (v) x+2, y, z+1; (vi) x+1, y+1, z; (vii) x+1, y, z+1.
ππ contacts (Å, °) for (I) top
Group 1/group 2TypeCCD (Å)IPD (Å)IPA (°)SA (°)
Ring A/ring CviLayer3.826 (3)3.365 (3)11.26 (14)28.4 (2)
Ring D/ring FvLayer3.782 (4)3.454 (3)15.06 (18)24.0 (2)
Ring B/ring BviLayer4.268 (3)4.036 (3)019.0 (2)
Ring B/ring BviiInterlayer4.286 (3)3.793 (3)027.8 (2)
Ring E/ring EvLayer3.978 (3)3.539 (3)027.2 (2)
Notes: rings AF are labelled according to Fig. 1. CCD is the centroid-to-centroid distance, IPD is the interplanar distance (distance from one plane to the neighbouring centroid), IPA is the interplanar angle and SA is the slippage angle (angle subtended by the intercentroid vector to the plane normal); for details, see Janiak (2000). Symmetry codes: (v) -x + 2, -y, -z + 1; (vi) -x + 1, -y + 1, -z; (vii) -x + 2, -y + 1, -z.
Selected geometric parameters (Å, º) for (II) top
Cd1—N32.3004 (14)Cd1—S1i2.7804 (5)
Cd1—N22.3893 (12)
N3—Cd1—N2ii91.97 (5)N2—Cd1—S1i87.76 (3)
N3—Cd1—N288.03 (5)N3—Cd1—S1iii91.64 (4)
N3ii—Cd1—N291.97 (5)N2—Cd1—S1iii92.24 (3)
Symmetry codes: (i) x1, y, z; (ii) x, y+2, z; (iii) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C1—H1···N30.942.653.287 (2)125
C4—H4···N1iv0.942.573.4357 (19)154
C3—H3···S1v0.942.853.7683 (15)164
C5—H5···S10.943.153.9249 (14)141
C7—H7···S1v0.943.043.9354 (15)160
Symmetry codes: (iv) x1, y+2, z+1; (v) x1, y, z+1.
 

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