1. Chemical context
The ditopic ligand 4,4′-bipyridyl is ubiquitous in coordination chemistry, usually providing bridges between metal centres to generate coordination polymers. While bidentate bridging is normally observed in the structural chemistry of zinc(II) bis(N,N′-dialkyldithiocarbamate)s, these more often than not lead to binuclear species of the general formula [Zn(S2CNRR′)2]2(4,4′-bipyridyl) as first observed in the archetypal compound [Zn(S2CNEt2)2]2(4,4′-bipyridyl) (Zemskova et al., 1994) and in other compounds relevant to the present study, such as {Zn[S2CN(R)CH2CH2OH]2}2(4,4′-bipyridyl) for R = Me, Et and CH2CH2OH (Benson et al., 2007). The exceptional structure is that of Zn[S2CN(n-Pr)2]2(4,4′-bipyridyl), which features a relatively rare monodentate coordination mode for the 4,4′-bipyridyl molecule (Klevtsova et al., 2001). The analogous chemistry for cadmium(II) bis(N,N′-dialkyldithiocarbamate)s is considerably less explored with the only example in the Cambridge Structural Database (Groom et al., 2016) being a linear coordination polymer in the crystal of {Cd[S2CN(CH2Ph)2]2(4,4′-bipyridyl)}n (Fan et al., 2007). The difference in chemistry between zinc and cadmium dithiocarbamates can be rationalized in terms of the larger size of cadmium versus zinc but, also in terms of the reduced Lewis acidity of the zinc atom owing to the strong chelation mode of the dithiocarbamate ligand. This is also true for cadmium whereby unusual coordination modes are found for related pyridyl-containing molecules that might otherwise be expected to be bridging. This is discussed further below in Database survey. In the present report, the crystal and molecular structures of two compounds, formulated as Zn[S2CN(i-Pr)CH2CH2OH]2(4,4′-bipyridyl)·0.5(4,4′-bipyridyl) (I) and the cadmium analogue (II), are described, i.e. featuring monodentate and non-coordinating 4,4′-bipyridine molecules.
2. Structural commentary
The molecular structure of the constituents of (I) are shown in Fig. 1a and selected geometric parameters are collected in Table 1. The asymmetric unit comprises an entire molecule of Zn[S2CN(i-Pr)CH2CH2OH]2(4,4′-bipyridyl) and half a molecule of 4,4′-bipyridine, the latter being disposed about a centre of inversion. The zinc atom is coordinated by two dithiocarbamate ligands that form disparate Zn—S bond lengths. This is seen in the values of Δ(Zn—S) = Zn—Slong − Zn—Sshort, which compute to 0.19 and 0.23 Å for the S1- and S3-dithiocarbamate ligands, respectively. The fifth position in the coordination geometry is occupied by a pyridyl-N atom. Based on the value of τ (Addison et al., 1984), which equals to 0.0 and 1.0 for ideal square-pyramidal and trigonal–bipyramidal geometries, respectively, it is possible to assign a coordination geometry based on the NS4 donor set. In (I), τ = 0.64 indicating a highly distorted coordination geometry but, one approximating a trigonal bipyramid. In this description, the less tightly bound S2 and S4 atoms define the axial positions, Table 1. The coordinated 4,4′-bipyridyl molecule is non-planar with the dihedral angle between the two residues being 28.12 (14)°.
Zn—N3 | 2.077 (2) | C1—S1 | 1.733 (3) | Zn—S1 | 2.3540 (10) | C1—S2 | 1.715 (3) | Zn—S2 | 2.5366 (9) | C7—S3 | 1.735 (3) | Zn—S3 | 2.3541 (9) | C7—S4 | 1.714 (3) | Zn—S4 | 2.5904 (9) | | | | | | | S1—Zn—S3 | 124.19 (3) | S2—Zn—S4 | 162.87 (3) | | |
| Figure 1 The molecular structures of the constituents of (a) (I) and (b) (II) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. For each of (I) and (II), the 4,4′-bipyridine molecule has been expanded to show the entire molecule; unlabelled atoms are related by the symmetry operation −x, 2 − y, −z. |
Crystals of (II) are isostructural to those of (I), Fig. 1b and Table 2. Some differences in molecular geometry are apparent, most notably in the degree of symmetry in the Cd—S bond lengths, i.e. Δ(Cd—S) = 0.09 and 0.11 Å for the S1- and S3-dithiocarbamate ligands, respectively. This is reflected in the narrower ranges in the C—S bond lengths in (II) cf. (I), Tables 1 and 2. The value of τ = 0.67 suggests a coordination geometry marginally closer to trigonal bipyramidal in (II) than for (I). The dihedral angle between the two rings comprising the coordinated 4,4′-bipyridyl molecule is 28.86 (7)°.
Cd—N3 | 2.3011 (11) | C1—S1 | 1.7310 (12) | Cd—S1 | 2.5547 (3) | C1—S2 | 1.7218 (12) | Cd—S2 | 2.6500 (3) | C7—S3 | 1.7328 (13) | Cd—S3 | 2.5620 (4) | C7—S4 | 1.7257 (13) | Cd—S4 | 2.6696 (4) | | | | | | | S1—Cd—S3 | 125.725 (11) | S2—Cd—S4 | 165.865 (11) | | |
3. Supramolecular features
The molecular packing of (I) comprises conventional hydrogen bonding as well as a number of weaker, non-covalent interactions, Table 3. The presence of hydroxy-O—H⋯O(hydroxy) hydrogen bonds leads to the formation of a centrosymmetric, 28-membered {⋯HOC2NCSZnSCNC2O}2 synthon. This ring contains two additional hydroxy-O—H H atoms and these form hydroxy-O—H⋯N(pyridyl) hydrogen bonds with the non-coordinating end of the monodentate 4,4′-bipyridyl molecules. This network of hydrogen bonds leads to the formation of a two-dimensional array lying parallel to (100), Fig. 2a. These layers are connected into double-layers via methine-C—H⋯S and π–π interactions involving the coordinated pyridyl ring [inter-centroid distance between the (N3/C13–C17) and (N3/C13–C17)i rings = 3.6246 (18) Å and angle of inclination = 0.46 (13)° for symmetry code (i): −x, y, − z]. The double-layers are connected into a three-dimensional architecture via 4,4′-bipyridyl-C—H⋯O(hydroxy) interactions, involving an H atom from the non-coordinating ring of the coordinated 4,4′-bipyridyl molecule. This architecture defines channels parallel to the c axis in which residue the non-coordinating 4,4′-bipyridine molecules. The closest interaction between the host and guests are of the type pyridine-C—H⋯π(Zn/S3/S4/C7), i.e. C—H⋯π(chelate ring), a supramolecular synthon gaining prominence in the structural chemistry of metal-containing species (Tiekink, 2017), especially for dithiocarbamates (Tiekink & Zukerman-Schpector, 2011) owing to the ability of the dithiocarbamate ligand to form strong chelating interactions (see above).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | O1—H1O⋯N4i | 0.83 (2) | 1.88 (2) | 2.7085 (15) | 176 (1) | O2—H2O⋯O1ii | 0.83 (1) | 1.89 (1) | 2.7162 (14) | 173 (2) | C4—H4⋯S2iii | 1.00 | 2.68 | 3.5395 (14) | 144 | C22—H22⋯O2iv | 0.95 | 2.40 | 3.3473 (17) | 174 | C26—H26⋯Cg1v | 0.95 | 3.00 | 3.776 (3) | 140 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) x, y+1, z. | |
| Figure 2 Molecular packing in (I): (a) view of two-dimensional supramolecular array sustained by hydroxy-O—H⋯O(hydroxy) and hydroxy-O–H⋯N(pyridyl) hydrogen bonding with all but the acidic H atoms removed and (b) a view of the unit-cell contents in projection down the c axis, with the non-coordinating 4,4′-bipyridine molecules in one channel highlighted in space-filling mode. The O—H⋯O, O—H⋯N, C—H⋯O, C—H⋯S and π–π interactions are shown as orange, blue, pink, sea-blue and purple dashed lines, respectively. |
The molecular packing for isostructural (II) follows that just described for (I), Table 4. However, in this case, the putative pyridyl-C—H⋯π(Cd/S3/S4/C7) interaction is just beyond the sum of the van der Waals radii for this type of contact (Spek, 2009).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | O1—H1O⋯N4i | 0.85 (2) | 1.85 (2) | 2.697 (3) | 179 (3) | O2—H2O⋯O1ii | 0.84 (2) | 1.88 (2) | 2.718 (3) | 176 (4) | C4—H4⋯S2iii | 1.00 | 2.67 | 3.515 (3) | 142 | C22—H22⋯O2iv | 0.95 | 2.36 | 3.300 (3) | 170 | C26—H26⋯Cg1v | 0.95 | 3.04 | 3.7943 (15) | 138 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) x, y+1, z. | |
4. Database survey
As mentioned in the Chemical context, ditopic ligands such as 4,4′-bipyridyl are normally observed providing bridges between metal centres. Thus, the structures of (I) and (II) are doubly curious as not only is the 4,4′-bipyridyl ligand coordinating in a monodentate fashion, there is a non-coordinating 4,4′-bipyridine molecule in the crystal. Recent reports confirm these interesting observations with related bipyridyl-type molecules of both the zinc(II) and, especially, cadmium(II) dithiocarbamates. Thus, just as for the 4,4′-bipyridyl structures mentioned in the Chemical context, i.e. [Zn(S2CNEt2)2]2(4,4′-bipyridyl) (Zemskova et al., 1994) and Zn[S2CN(n-Pr)2]2(4,4′-bipyridyl) (Klevtsova et al., 2001), with the anticipated bidentate, bridging and non-anticipated terminal coordination, respectively, similar chemistry occurs for the ditopic ligand with an ethylene space, i.e. trans-bis(4-pyridyl)ethylene (bpe) where structures of both bridging, i.e. [Zn(S2CNEt2)2]2(bpe) (Arman et al., 2009), and terminal, i.e. Zn[S2CN(n-Pr)2]2(bpe) (Lai & Tiekink, 2003), coordination modes are known. Very recently, terminal coordination was found for 4-pyridinealdazine in the structure of Zn[S2CN(Me)CH2CH2OH2]2(4-pyridinealdazine) (Broker et al., 2017). In the realm of cadmium dithiocarbamates, the potentially bridging ligand just mentioned occurs in the structure of Cd[S2CN(n-Pr)CH2CH2OH2]2(4-pyridinealdazine)2 with both being terminally bound (Broker & Tiekink, 2011). The ditopic ligand bpe was mentioned above. In the case of cadmium dithiocarbamates, a bidentate, bridging mode is seen in the crystal of [Cd(S2CNEt2)2(bpe)]n (Chai et al., 2003). However, in another example both bridging and terminal modes, in a 1:2 ratio, are seen in the structure of Cd[S2CN(i-Pr)CH2CH2OH2]2(bpe)3 (Jotani et al., 2016). The occurrence of unusual coordination modes for these bipyridyl-type ligands indicate additional factors are coming into play, often a competition between hydrogen bonding and M←N donor interactions but, not always as seen in the structure of Zn[S2CN(n-Pr)2]2(4,4′-bipyridyl) (Klevtsova et al., 2001).
5. Synthesis and crystallization
All chemicals and solvents were used as purchased without purification·The melting point was determined using an Krüss KSP1N melting point meter. The IR spectra were obtained by the attenuated total reflectance (ATR) technique on a Perkin Elmer RX1 FTIR spectrophotometer from 4000 to 400 cm−1. 1H and 13C NMR spectra were recorded at room temperature in DMSO-d6 solution on a Bruker Avance 400MHz NMR spectrometer.
Synthesis of (I): 4,4′-bipyridine (1.79 mmol, 0.28 g) in ethanol (25 ml) was added dropwise to bis(N-2-hydroxyethyl,N-isopropyldithiocarbamato)zinc(II) (1.21 mmol, 0.51 g) in ethanol (25 ml). The resulting mixture was stirred for 0.5 h follow by filtration. After a week of slow evaporation of the filtrate, yellow blocks precipitated (yield: 0.698 g, 88%; m.p. 445.6 K). IR (cm−1): 1467 (m) [ν(C—N)], 1175 (m) [ν(C—S)] cm−1. 1H NMR: δ 8.78–7.83 (m, 12H, aromatic H), 5.14 (sept, 2H, NCH, 6.63 Hz), 4.90 (t, 2H, OH, 5.38 Hz), 3.78–3.64 (m, 8H, NCH2CH2O), 1.18 (d, 12H, CH3, 6.72 Hz). 13C NMR: δ 204.15 (CS2), 150.53, 144.65, 121.58 (aromatic-C), 58.21 (CH2O), 55.53 (NCH2), 49.80 (NCH), 19.88 (CH3).
Synthesis of (II): 4,4′-bipyridine (1.61 mmol, 0.25 g) in ethanol (25 ml) was added dropwise to bis(N-2-hydroxyethyl,N-isopropyldithiocarbamato)cadmium(II) (1.07 mmol, 0.50 g) in ethanol (25 ml). The resulting mixture was stirred for 0.5 h follow by filtration. A week of slow evaporation of the filtrate yielded yellow blocks (yield: 0.652 g, 87%; m.p. 438.7 K). IR (cm−1): 1467 (m) [ν(C—N)], 1174 (m) [ν(C—S)] cm−1. 1H NMR: δ 8.79–7.80 (m, 12H, aromatic H), 5.22 (sept, 2H, NCH, 6.63 Hz), 4.84 (t, 2H, OH, 5.52 Hz), 3.80–3.64 (m, 8H, NCH2CH2O), 1.17 (d, 12H, CH3, 6.72 Hz). 13C NMR: δ 205.29 (CS2), 150.57, 144.46, 121.41 (aromatic-C), 58.26 (CH2O), 56.62 (NCH2), 50.47 (NCH), 19.91 (CH3).
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 5. For each of (I) and (II), carbon-bound H atoms were placed in calculated positions (C—H = 0.95–1.00 Å) and were included in the refinement in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The O-bound H atoms were located in difference-Fourier maps but were refined with a distance restraint of O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O). For (I), owing to poor agreement, two reflections, i.e. (0 0 6) and (27 3 4), were omitted from the final cycles of refinement. For (II), one reflection, i.e. ( 7 7), was omitted for the same reason.
| (I) | (II) | Crystal data | Chemical formula | [Zn(C6H12NOS2)2(C10H8N2)]·0.5C10H8N2 | [Cd(C6H12NOS2)2(C10H8N2)]·0.5C10H8N2 | Mr | 656.22 | 703.25 | Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Temperature (K) | 100 | 100 | a, b, c (Å) | 22.418 (5), 11.501 (2), 25.094 (5) | 22.7028 (12), 11.5950 (6), 24.8196 (13) | β (°) | 105.50 (3) | 103.385 (1) | V (Å3) | 6235 (2) | 6356.0 (6) | Z | 8 | 8 | Radiation type | Mo Kα | Mo Kα | μ (mm−1) | 1.09 | 0.98 | Crystal size (mm) | 0.30 × 0.20 × 0.20 | 0.04 × 0.04 × 0.03 | | Data collection | Diffractometer | Bruker SMART APEX CCD | Bruker SMART APEX CCD | Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Tmin, Tmax | 0.968, 0.979 | 0.962, 0.971 | No. of measured, independent and observed [I > 2σ(I)] reflections | 31204, 7738, 5204 | 41284, 7847, 7204 | Rint | 0.082 | 0.023 | (sin θ/λ)max (Å−1) | 0.667 | 0.667 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.096, 1.00 | 0.019, 0.049, 0.99 | No. of reflections | 7738 | 7847 | No. of parameters | 358 | 358 | No. of restraints | 2 | 2 | H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | Δρmax, Δρmin (e Å−3) | 0.48, −0.46 | 0.46, −0.24 | Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) and publCIF (Westrip, 2010). | |
Supporting information
For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
(4,4'-Bipyridyl-
κN)bis[
N-(2-hydroxyethyl)-
N-isopropyldithiocarbamato-
κ2S,
S']zinc(II)–4,4'-bipyridyl (2/1) (I)
top Crystal data top [Zn(C6H12NOS2)2(C10H8N2)]·0.5C10H8N2 | F(000) = 2744 |
Mr = 656.22 | Dx = 1.398 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.418 (5) Å | Cell parameters from 3045 reflections |
b = 11.501 (2) Å | θ = 2.3–25.2° |
c = 25.094 (5) Å | µ = 1.09 mm−1 |
β = 105.50 (3)° | T = 100 K |
V = 6235 (2) Å3 | Block, yellow |
Z = 8 | 0.30 × 0.20 × 0.20 mm |
Data collection top Bruker SMART APEX CCD diffractometer | 7738 independent reflections |
Radiation source: fine-focus sealed tube | 5204 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
ω scans | θmax = 28.3°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −27→29 |
Tmin = 0.968, Tmax = 0.979 | k = −15→15 |
31204 measured reflections | l = −33→33 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
7738 reflections | Δρmax = 0.48 e Å−3 |
358 parameters | Δρmin = −0.46 e Å−3 |
2 restraints | |
Special details top Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn | 0.05280 (2) | 0.31725 (3) | 0.16518 (2) | 0.01632 (9) | |
S1 | −0.04838 (3) | 0.24709 (6) | 0.12760 (3) | 0.01626 (15) | |
S2 | 0.00828 (3) | 0.43350 (6) | 0.07767 (3) | 0.01723 (15) | |
S3 | 0.14139 (3) | 0.24004 (6) | 0.14471 (3) | 0.01887 (16) | |
S4 | 0.09136 (3) | 0.14774 (6) | 0.23371 (3) | 0.01927 (16) | |
O1 | −0.20135 (9) | 0.08393 (16) | 0.01233 (8) | 0.0200 (4) | |
H1O | −0.1869 (13) | 0.034 (2) | 0.0372 (9) | 0.030* | |
O2 | 0.25910 (9) | −0.01819 (18) | 0.09286 (8) | 0.0250 (5) | |
H2O | 0.2425 (14) | −0.036 (3) | 0.0599 (6) | 0.038* | |
N1 | −0.10592 (10) | 0.35160 (18) | 0.03253 (9) | 0.0138 (5) | |
N2 | 0.18772 (10) | 0.05318 (19) | 0.20497 (9) | 0.0162 (5) | |
N3 | 0.06894 (10) | 0.45571 (18) | 0.22034 (9) | 0.0147 (5) | |
N4 | 0.15344 (12) | 0.9270 (2) | 0.40786 (10) | 0.0240 (6) | |
N5 | 0.02413 (12) | 0.7932 (2) | 0.11006 (10) | 0.0260 (6) | |
C1 | −0.05450 (12) | 0.3457 (2) | 0.07419 (11) | 0.0140 (5) | |
C2 | −0.15890 (12) | 0.2760 (2) | 0.03229 (11) | 0.0157 (6) | |
H2A | −0.1974 | 0.3119 | 0.0093 | 0.019* | |
H2B | −0.1630 | 0.2682 | 0.0704 | 0.019* | |
C3 | −0.15066 (13) | 0.1563 (2) | 0.00952 (11) | 0.0180 (6) | |
H3A | −0.1488 | 0.1632 | −0.0293 | 0.022* | |
H3B | −0.1114 | 0.1214 | 0.0314 | 0.022* | |
C4 | −0.11249 (13) | 0.4398 (2) | −0.01199 (11) | 0.0183 (6) | |
H4 | −0.0699 | 0.4635 | −0.0129 | 0.022* | |
C5 | −0.14485 (14) | 0.5472 (2) | 0.00182 (13) | 0.0280 (7) | |
H5A | −0.1490 | 0.6049 | −0.0277 | 0.042* | |
H5B | −0.1860 | 0.5258 | 0.0052 | 0.042* | |
H5C | −0.1204 | 0.5802 | 0.0369 | 0.042* | |
C6 | −0.14513 (14) | 0.3914 (3) | −0.06898 (11) | 0.0265 (7) | |
H6A | −0.1484 | 0.4524 | −0.0969 | 0.040* | |
H6B | −0.1213 | 0.3259 | −0.0776 | 0.040* | |
H6C | −0.1867 | 0.3647 | −0.0691 | 0.040* | |
C7 | 0.14472 (13) | 0.1375 (2) | 0.19613 (11) | 0.0167 (6) | |
C8 | 0.23385 (12) | 0.0495 (2) | 0.17274 (11) | 0.0185 (6) | |
H8A | 0.2719 | 0.0110 | 0.1950 | 0.022* | |
H8B | 0.2448 | 0.1300 | 0.1650 | 0.022* | |
C9 | 0.21025 (13) | −0.0148 (3) | 0.11867 (11) | 0.0208 (6) | |
H9A | 0.1976 | −0.0947 | 0.1255 | 0.025* | |
H9B | 0.1740 | 0.0259 | 0.0947 | 0.025* | |
C10 | 0.19577 (13) | −0.0287 (2) | 0.25202 (11) | 0.0216 (6) | |
H10 | 0.1560 | −0.0303 | 0.2629 | 0.026* | |
C11 | 0.24603 (15) | 0.0160 (3) | 0.30141 (12) | 0.0342 (8) | |
H11A | 0.2511 | −0.0384 | 0.3324 | 0.051* | |
H11B | 0.2852 | 0.0227 | 0.2912 | 0.051* | |
H11C | 0.2341 | 0.0925 | 0.3124 | 0.051* | |
C12 | 0.20898 (15) | −0.1525 (2) | 0.23619 (13) | 0.0294 (7) | |
H12A | 0.2140 | −0.2037 | 0.2683 | 0.044* | |
H12B | 0.1744 | −0.1801 | 0.2061 | 0.044* | |
H12C | 0.2471 | −0.1532 | 0.2241 | 0.044* | |
C13 | 0.06136 (13) | 0.5664 (2) | 0.20303 (11) | 0.0190 (6) | |
H13 | 0.0458 | 0.5809 | 0.1645 | 0.023* | |
C14 | 0.07504 (12) | 0.6604 (2) | 0.23849 (11) | 0.0182 (6) | |
H14 | 0.0692 | 0.7373 | 0.2242 | 0.022* | |
C15 | 0.09742 (12) | 0.6424 (2) | 0.29521 (11) | 0.0158 (6) | |
C16 | 0.10366 (12) | 0.5272 (2) | 0.31327 (11) | 0.0165 (6) | |
H16 | 0.1175 | 0.5102 | 0.3517 | 0.020* | |
C17 | 0.08975 (12) | 0.4380 (2) | 0.27525 (11) | 0.0169 (6) | |
H17 | 0.0951 | 0.3602 | 0.2884 | 0.020* | |
C18 | 0.11560 (13) | 0.7408 (2) | 0.33461 (11) | 0.0172 (6) | |
C19 | 0.08885 (13) | 0.8507 (2) | 0.32338 (12) | 0.0208 (6) | |
H19 | 0.0571 | 0.8641 | 0.2903 | 0.025* | |
C20 | 0.10898 (14) | 0.9398 (2) | 0.36078 (12) | 0.0235 (7) | |
H20 | 0.0902 | 1.0141 | 0.3526 | 0.028* | |
C21 | 0.17857 (14) | 0.8211 (2) | 0.41830 (12) | 0.0251 (7) | |
H21 | 0.2101 | 0.8102 | 0.4517 | 0.030* | |
C22 | 0.16164 (13) | 0.7269 (2) | 0.38367 (11) | 0.0192 (6) | |
H22 | 0.1811 | 0.6536 | 0.3932 | 0.023* | |
C23 | −0.00233 (15) | 0.7643 (2) | 0.05770 (13) | 0.0277 (7) | |
H23 | −0.0148 | 0.6858 | 0.0501 | 0.033* | |
C24 | −0.01294 (14) | 0.8414 (2) | 0.01340 (12) | 0.0256 (7) | |
H24 | −0.0318 | 0.8151 | −0.0231 | 0.031* | |
C25 | 0.00438 (12) | 0.9574 (2) | 0.02306 (11) | 0.0152 (6) | |
C26 | 0.03155 (13) | 0.9879 (2) | 0.07766 (11) | 0.0218 (6) | |
H26 | 0.0444 | 1.0658 | 0.0868 | 0.026* | |
C27 | 0.03987 (14) | 0.9051 (3) | 0.11860 (12) | 0.0260 (7) | |
H27 | 0.0581 | 0.9292 | 0.1556 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.01770 (18) | 0.01443 (16) | 0.01542 (16) | −0.00168 (14) | 0.00199 (13) | −0.00196 (13) |
S1 | 0.0195 (4) | 0.0144 (3) | 0.0137 (3) | −0.0037 (3) | 0.0024 (3) | 0.0018 (3) |
S2 | 0.0190 (4) | 0.0162 (3) | 0.0149 (3) | −0.0062 (3) | 0.0019 (3) | 0.0018 (3) |
S3 | 0.0212 (4) | 0.0169 (3) | 0.0191 (4) | −0.0009 (3) | 0.0062 (3) | 0.0018 (3) |
S4 | 0.0232 (4) | 0.0183 (3) | 0.0172 (4) | 0.0032 (3) | 0.0071 (3) | 0.0019 (3) |
O1 | 0.0201 (11) | 0.0164 (10) | 0.0207 (11) | −0.0046 (8) | 0.0006 (9) | 0.0059 (8) |
O2 | 0.0193 (11) | 0.0349 (12) | 0.0216 (11) | −0.0052 (9) | 0.0066 (9) | −0.0113 (10) |
N1 | 0.0157 (12) | 0.0126 (11) | 0.0126 (11) | −0.0023 (9) | 0.0031 (9) | 0.0012 (8) |
N2 | 0.0159 (12) | 0.0178 (12) | 0.0139 (11) | 0.0007 (10) | 0.0020 (9) | −0.0006 (9) |
N3 | 0.0134 (12) | 0.0159 (11) | 0.0134 (11) | −0.0017 (9) | 0.0010 (9) | −0.0001 (9) |
N4 | 0.0313 (15) | 0.0186 (12) | 0.0204 (13) | 0.0010 (11) | 0.0039 (11) | −0.0049 (10) |
N5 | 0.0279 (15) | 0.0205 (13) | 0.0284 (14) | 0.0004 (11) | 0.0055 (12) | 0.0037 (11) |
C1 | 0.0161 (14) | 0.0120 (12) | 0.0146 (13) | −0.0001 (11) | 0.0050 (11) | −0.0028 (10) |
C2 | 0.0113 (14) | 0.0175 (13) | 0.0176 (14) | −0.0014 (11) | 0.0025 (11) | 0.0039 (11) |
C3 | 0.0165 (15) | 0.0202 (14) | 0.0163 (14) | −0.0059 (11) | 0.0026 (11) | −0.0010 (11) |
C4 | 0.0195 (15) | 0.0186 (14) | 0.0150 (14) | −0.0025 (12) | 0.0014 (11) | 0.0064 (11) |
C5 | 0.0345 (19) | 0.0170 (15) | 0.0354 (18) | 0.0029 (13) | 0.0142 (15) | 0.0076 (13) |
C6 | 0.0271 (18) | 0.0318 (17) | 0.0162 (15) | −0.0034 (14) | −0.0020 (13) | 0.0073 (13) |
C7 | 0.0175 (15) | 0.0154 (13) | 0.0147 (14) | −0.0044 (11) | 0.0003 (11) | −0.0047 (10) |
C8 | 0.0153 (15) | 0.0213 (14) | 0.0189 (14) | −0.0005 (12) | 0.0044 (12) | −0.0045 (11) |
C9 | 0.0166 (15) | 0.0242 (15) | 0.0216 (15) | −0.0037 (12) | 0.0047 (12) | −0.0049 (12) |
C10 | 0.0215 (16) | 0.0227 (15) | 0.0200 (15) | 0.0053 (13) | 0.0046 (12) | 0.0054 (12) |
C11 | 0.039 (2) | 0.0365 (19) | 0.0228 (17) | 0.0076 (16) | 0.0007 (15) | 0.0012 (14) |
C12 | 0.0344 (19) | 0.0234 (16) | 0.0299 (18) | 0.0057 (14) | 0.0076 (15) | 0.0068 (13) |
C13 | 0.0201 (15) | 0.0198 (14) | 0.0143 (14) | 0.0016 (12) | −0.0002 (12) | 0.0007 (11) |
C14 | 0.0198 (15) | 0.0136 (13) | 0.0195 (14) | 0.0014 (11) | 0.0022 (12) | −0.0002 (11) |
C15 | 0.0115 (14) | 0.0179 (14) | 0.0181 (14) | 0.0011 (11) | 0.0042 (11) | −0.0021 (11) |
C16 | 0.0193 (15) | 0.0183 (14) | 0.0115 (13) | −0.0017 (12) | 0.0035 (11) | −0.0010 (11) |
C17 | 0.0191 (15) | 0.0138 (13) | 0.0179 (14) | −0.0003 (11) | 0.0050 (12) | 0.0010 (11) |
C18 | 0.0200 (16) | 0.0154 (13) | 0.0172 (14) | −0.0008 (11) | 0.0067 (12) | −0.0008 (11) |
C19 | 0.0212 (16) | 0.0180 (14) | 0.0206 (15) | 0.0032 (12) | 0.0012 (12) | −0.0015 (11) |
C20 | 0.0289 (17) | 0.0160 (14) | 0.0250 (16) | 0.0019 (13) | 0.0065 (13) | −0.0040 (12) |
C21 | 0.0324 (18) | 0.0223 (15) | 0.0161 (14) | 0.0017 (14) | −0.0013 (13) | −0.0025 (12) |
C22 | 0.0239 (16) | 0.0163 (14) | 0.0166 (14) | 0.0008 (12) | 0.0042 (12) | −0.0023 (11) |
C23 | 0.0342 (19) | 0.0154 (14) | 0.0330 (18) | −0.0033 (13) | 0.0077 (15) | −0.0007 (13) |
C24 | 0.0342 (19) | 0.0179 (15) | 0.0233 (16) | −0.0031 (13) | 0.0051 (14) | −0.0013 (12) |
C25 | 0.0120 (14) | 0.0135 (13) | 0.0203 (14) | 0.0026 (11) | 0.0049 (11) | 0.0014 (11) |
C26 | 0.0270 (17) | 0.0109 (13) | 0.0255 (16) | −0.0030 (12) | 0.0035 (13) | −0.0013 (11) |
C27 | 0.0295 (18) | 0.0244 (16) | 0.0208 (16) | −0.0003 (14) | 0.0009 (13) | −0.0022 (13) |
Geometric parameters (Å, º) top Zn—N3 | 2.077 (2) | C8—H8A | 0.9900 |
Zn—S1 | 2.3540 (10) | C8—H8B | 0.9900 |
Zn—S2 | 2.5366 (9) | C9—H9A | 0.9900 |
Zn—S3 | 2.3541 (9) | C9—H9B | 0.9900 |
Zn—S4 | 2.5904 (9) | C10—C11 | 1.525 (4) |
C1—S1 | 1.733 (3) | C10—C12 | 1.529 (4) |
C1—S2 | 1.715 (3) | C10—H10 | 1.0000 |
C7—S3 | 1.735 (3) | C11—H11A | 0.9800 |
C7—S4 | 1.714 (3) | C11—H11B | 0.9800 |
O1—C3 | 1.426 (3) | C11—H11C | 0.9800 |
O1—H1O | 0.843 (10) | C12—H12A | 0.9800 |
O2—C9 | 1.414 (3) | C12—H12B | 0.9800 |
O2—H2O | 0.837 (10) | C12—H12C | 0.9800 |
N1—C1 | 1.335 (3) | C13—C14 | 1.381 (4) |
N1—C2 | 1.471 (3) | C13—H13 | 0.9500 |
N1—C4 | 1.486 (3) | C14—C15 | 1.392 (4) |
N2—C7 | 1.343 (3) | C14—H14 | 0.9500 |
N2—C8 | 1.474 (3) | C15—C16 | 1.396 (4) |
N2—C10 | 1.483 (3) | C15—C18 | 1.486 (4) |
N3—C13 | 1.341 (3) | C16—C17 | 1.378 (4) |
N3—C17 | 1.347 (3) | C16—H16 | 0.9500 |
N4—C20 | 1.335 (4) | C17—H17 | 0.9500 |
N4—C21 | 1.338 (3) | C18—C22 | 1.388 (4) |
N5—C23 | 1.331 (4) | C18—C19 | 1.395 (4) |
N5—C27 | 1.337 (4) | C19—C20 | 1.381 (4) |
C2—C3 | 1.520 (4) | C19—H19 | 0.9500 |
C2—H2A | 0.9900 | C20—H20 | 0.9500 |
C2—H2B | 0.9900 | C21—C22 | 1.377 (4) |
C3—H3A | 0.9900 | C21—H21 | 0.9500 |
C3—H3B | 0.9900 | C22—H22 | 0.9500 |
C4—C5 | 1.519 (4) | C23—C24 | 1.391 (4) |
C4—C6 | 1.527 (4) | C23—H23 | 0.9500 |
C4—H4 | 1.0000 | C24—C25 | 1.393 (4) |
C5—H5A | 0.9800 | C24—H24 | 0.9500 |
C5—H5B | 0.9800 | C25—C26 | 1.388 (4) |
C5—H5C | 0.9800 | C25—C25i | 1.489 (5) |
C6—H6A | 0.9800 | C26—C27 | 1.377 (4) |
C6—H6B | 0.9800 | C26—H26 | 0.9500 |
C6—H6C | 0.9800 | C27—H27 | 0.9500 |
C8—C9 | 1.512 (4) | | |
| | | |
N3—Zn—S1 | 120.49 (7) | O2—C9—C8 | 107.2 (2) |
N3—Zn—S3 | 115.32 (7) | O2—C9—H9A | 110.3 |
S1—Zn—S3 | 124.19 (3) | C8—C9—H9A | 110.3 |
N3—Zn—S2 | 97.53 (6) | O2—C9—H9B | 110.3 |
S1—Zn—S2 | 73.73 (3) | C8—C9—H9B | 110.3 |
S3—Zn—S2 | 99.76 (3) | H9A—C9—H9B | 108.5 |
N3—Zn—S4 | 99.60 (6) | N2—C10—C11 | 109.8 (2) |
S1—Zn—S4 | 97.06 (3) | N2—C10—C12 | 112.1 (2) |
S3—Zn—S4 | 73.12 (3) | C11—C10—C12 | 111.9 (2) |
S2—Zn—S4 | 162.87 (3) | N2—C10—H10 | 107.6 |
C1—S1—Zn | 87.38 (9) | C11—C10—H10 | 107.6 |
C1—S2—Zn | 82.03 (9) | C12—C10—H10 | 107.6 |
C7—S3—Zn | 88.01 (10) | C10—C11—H11A | 109.5 |
C7—S4—Zn | 81.07 (10) | C10—C11—H11B | 109.5 |
C3—O1—H1O | 106 (2) | H11A—C11—H11B | 109.5 |
C9—O2—H2O | 105 (2) | C10—C11—H11C | 109.5 |
C1—N1—C2 | 120.0 (2) | H11A—C11—H11C | 109.5 |
C1—N1—C4 | 121.0 (2) | H11B—C11—H11C | 109.5 |
C2—N1—C4 | 118.8 (2) | C10—C12—H12A | 109.5 |
C7—N2—C8 | 120.5 (2) | C10—C12—H12B | 109.5 |
C7—N2—C10 | 121.3 (2) | H12A—C12—H12B | 109.5 |
C8—N2—C10 | 117.7 (2) | C10—C12—H12C | 109.5 |
C13—N3—C17 | 117.0 (2) | H12A—C12—H12C | 109.5 |
C13—N3—Zn | 121.84 (18) | H12B—C12—H12C | 109.5 |
C17—N3—Zn | 121.11 (17) | N3—C13—C14 | 123.2 (2) |
C20—N4—C21 | 116.7 (2) | N3—C13—H13 | 118.4 |
C23—N5—C27 | 115.3 (3) | C14—C13—H13 | 118.4 |
N1—C1—S2 | 122.3 (2) | C13—C14—C15 | 120.0 (2) |
N1—C1—S1 | 120.8 (2) | C13—C14—H14 | 120.0 |
S2—C1—S1 | 116.84 (15) | C15—C14—H14 | 120.0 |
N1—C2—C3 | 111.0 (2) | C14—C15—C16 | 116.8 (2) |
N1—C2—H2A | 109.4 | C14—C15—C18 | 121.8 (2) |
C3—C2—H2A | 109.4 | C16—C15—C18 | 121.4 (2) |
N1—C2—H2B | 109.4 | C17—C16—C15 | 119.8 (2) |
C3—C2—H2B | 109.4 | C17—C16—H16 | 120.1 |
H2A—C2—H2B | 108.0 | C15—C16—H16 | 120.1 |
O1—C3—C2 | 109.4 (2) | N3—C17—C16 | 123.2 (2) |
O1—C3—H3A | 109.8 | N3—C17—H17 | 118.4 |
C2—C3—H3A | 109.8 | C16—C17—H17 | 118.4 |
O1—C3—H3B | 109.8 | C22—C18—C19 | 117.4 (2) |
C2—C3—H3B | 109.8 | C22—C18—C15 | 120.6 (2) |
H3A—C3—H3B | 108.2 | C19—C18—C15 | 121.9 (2) |
N1—C4—C5 | 109.9 (2) | C20—C19—C18 | 119.4 (3) |
N1—C4—C6 | 112.4 (2) | C20—C19—H19 | 120.3 |
C5—C4—C6 | 111.8 (2) | C18—C19—H19 | 120.3 |
N1—C4—H4 | 107.5 | N4—C20—C19 | 123.4 (3) |
C5—C4—H4 | 107.5 | N4—C20—H20 | 118.3 |
C6—C4—H4 | 107.5 | C19—C20—H20 | 118.3 |
C4—C5—H5A | 109.5 | N4—C21—C22 | 124.2 (3) |
C4—C5—H5B | 109.5 | N4—C21—H21 | 117.9 |
H5A—C5—H5B | 109.5 | C22—C21—H21 | 117.9 |
C4—C5—H5C | 109.5 | C21—C22—C18 | 118.9 (3) |
H5A—C5—H5C | 109.5 | C21—C22—H22 | 120.6 |
H5B—C5—H5C | 109.5 | C18—C22—H22 | 120.6 |
C4—C6—H6A | 109.5 | N5—C23—C24 | 124.5 (3) |
C4—C6—H6B | 109.5 | N5—C23—H23 | 117.8 |
H6A—C6—H6B | 109.5 | C24—C23—H23 | 117.8 |
C4—C6—H6C | 109.5 | C23—C24—C25 | 119.4 (3) |
H6A—C6—H6C | 109.5 | C23—C24—H24 | 120.3 |
H6B—C6—H6C | 109.5 | C25—C24—H24 | 120.3 |
N2—C7—S4 | 122.3 (2) | C26—C25—C24 | 116.3 (2) |
N2—C7—S3 | 120.0 (2) | C26—C25—C25i | 122.2 (3) |
S4—C7—S3 | 117.69 (16) | C24—C25—C25i | 121.5 (3) |
N2—C8—C9 | 112.2 (2) | C27—C26—C25 | 119.9 (3) |
N2—C8—H8A | 109.2 | C27—C26—H26 | 120.1 |
C9—C8—H8A | 109.2 | C25—C26—H26 | 120.1 |
N2—C8—H8B | 109.2 | N5—C27—C26 | 124.7 (3) |
C9—C8—H8B | 109.2 | N5—C27—H27 | 117.7 |
H8A—C8—H8B | 107.9 | C26—C27—H27 | 117.7 |
| | | |
C2—N1—C1—S2 | −178.61 (19) | C17—N3—C13—C14 | 1.4 (4) |
C4—N1—C1—S2 | −3.1 (3) | Zn—N3—C13—C14 | −176.2 (2) |
C2—N1—C1—S1 | 1.6 (3) | N3—C13—C14—C15 | −0.5 (4) |
C4—N1—C1—S1 | 177.10 (19) | C13—C14—C15—C16 | −1.3 (4) |
Zn—S2—C1—N1 | −178.6 (2) | C13—C14—C15—C18 | 177.0 (3) |
Zn—S2—C1—S1 | 1.23 (13) | C14—C15—C16—C17 | 2.1 (4) |
Zn—S1—C1—N1 | 178.5 (2) | C18—C15—C16—C17 | −176.2 (3) |
Zn—S1—C1—S2 | −1.31 (14) | C13—N3—C17—C16 | −0.5 (4) |
C1—N1—C2—C3 | −83.1 (3) | Zn—N3—C17—C16 | 177.1 (2) |
C4—N1—C2—C3 | 101.3 (3) | C15—C16—C17—N3 | −1.2 (4) |
N1—C2—C3—O1 | 177.3 (2) | C14—C15—C18—C22 | −150.2 (3) |
C1—N1—C4—C5 | −93.7 (3) | C16—C15—C18—C22 | 28.0 (4) |
C2—N1—C4—C5 | 81.8 (3) | C14—C15—C18—C19 | 27.9 (4) |
C1—N1—C4—C6 | 141.0 (3) | C16—C15—C18—C19 | −153.9 (3) |
C2—N1—C4—C6 | −43.5 (3) | C22—C18—C19—C20 | 0.2 (4) |
C8—N2—C7—S4 | −178.27 (18) | C15—C18—C19—C20 | −178.0 (3) |
C10—N2—C7—S4 | −6.7 (3) | C21—N4—C20—C19 | −0.4 (4) |
C8—N2—C7—S3 | 2.4 (3) | C18—C19—C20—N4 | 0.2 (5) |
C10—N2—C7—S3 | 173.96 (19) | C20—N4—C21—C22 | 0.4 (5) |
Zn—S4—C7—N2 | −176.4 (2) | N4—C21—C22—C18 | −0.1 (5) |
Zn—S4—C7—S3 | 2.93 (13) | C19—C18—C22—C21 | −0.2 (4) |
Zn—S3—C7—N2 | 176.2 (2) | C15—C18—C22—C21 | 177.9 (3) |
Zn—S3—C7—S4 | −3.19 (14) | C27—N5—C23—C24 | 1.1 (5) |
C7—N2—C8—C9 | −86.4 (3) | N5—C23—C24—C25 | −0.4 (5) |
C10—N2—C8—C9 | 101.7 (3) | C23—C24—C25—C26 | −0.1 (4) |
N2—C8—C9—O2 | −176.9 (2) | C23—C24—C25—C25i | 178.3 (3) |
C7—N2—C10—C11 | −94.0 (3) | C24—C25—C26—C27 | −0.1 (4) |
C8—N2—C10—C11 | 77.8 (3) | C25i—C25—C26—C27 | −178.5 (3) |
C7—N2—C10—C12 | 140.9 (3) | C23—N5—C27—C26 | −1.3 (5) |
C8—N2—C10—C12 | −47.3 (3) | C25—C26—C27—N5 | 0.8 (5) |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) topCg1 is the centroid of the Cd/S3/S4/C7 chelate ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N4ii | 0.85 (2) | 1.85 (2) | 2.697 (3) | 179 (3) |
O2—H2O···O1iii | 0.84 (2) | 1.88 (2) | 2.718 (3) | 176 (4) |
C4—H4···S2iv | 1.00 | 2.67 | 3.515 (3) | 142 |
C22—H22···O2v | 0.95 | 2.36 | 3.300 (3) | 170 |
C26—H26···Cg1vi | 0.95 | 3.04 | 3.7943 (15) | 138 |
Symmetry codes: (ii) −x, y−1, −z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+3/2, z; (v) x, −y, z−1/2; (vi) x, y+1, z. |
(4,4'-Bipyridyl-
κN)bis(
N-2-hydroxyethyl-
N-isopropyldithiocarbamato-
κ2S,
S')cadmium(II)–4,4'-bipyridyl (2/1) (II)
top Crystal data top [Cd(C6H12NOS2)2(C10H8N2)]·0.5C10H8N2 | F(000) = 2888 |
Mr = 703.25 | Dx = 1.470 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.7028 (12) Å | Cell parameters from 24754 reflections |
b = 11.5950 (6) Å | θ = 2.2–28.3° |
c = 24.8196 (13) Å | µ = 0.98 mm−1 |
β = 103.385 (1)° | T = 100 K |
V = 6356.0 (6) Å3 | Block, yellow |
Z = 8 | 0.04 × 0.04 × 0.03 mm |
Data collection top Bruker SMART APEX CCD diffractometer | 7847 independent reflections |
Radiation source: fine-focus sealed tube | 7204 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 28.3°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −30→30 |
Tmin = 0.962, Tmax = 0.971 | k = −15→15 |
41284 measured reflections | l = −33→33 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.019 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | w = 1/[σ2(Fo2) + (0.0249P)2 + 6.291P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
7847 reflections | Δρmax = 0.46 e Å−3 |
358 parameters | Δρmin = −0.24 e Å−3 |
2 restraints | |
Special details top Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd | 0.04996 (2) | 0.31263 (2) | 0.16486 (2) | 0.01723 (3) | |
S1 | −0.05744 (2) | 0.24286 (3) | 0.12217 (2) | 0.01723 (6) | |
S2 | 0.00085 (2) | 0.43727 (3) | 0.07636 (2) | 0.01907 (7) | |
S3 | 0.14726 (2) | 0.23031 (3) | 0.14448 (2) | 0.02008 (7) | |
S4 | 0.09406 (2) | 0.14429 (3) | 0.23619 (2) | 0.02109 (7) | |
O1 | −0.20171 (4) | 0.08734 (8) | 0.00837 (4) | 0.02070 (19) | |
H1O | −0.1878 (8) | 0.0408 (13) | 0.0337 (6) | 0.031* | |
O2 | 0.26295 (4) | −0.02139 (9) | 0.09436 (4) | 0.0253 (2) | |
H2O | 0.2468 (8) | −0.0409 (17) | 0.0620 (5) | 0.038* | |
N1 | −0.10858 (5) | 0.35363 (9) | 0.02905 (4) | 0.0151 (2) | |
N2 | 0.19087 (5) | 0.05102 (10) | 0.20849 (4) | 0.0180 (2) | |
N3 | 0.06811 (5) | 0.46557 (9) | 0.22553 (4) | 0.0166 (2) | |
N4 | 0.15540 (6) | 0.92852 (10) | 0.41323 (5) | 0.0257 (2) | |
N5 | 0.02716 (6) | 0.79642 (11) | 0.11132 (6) | 0.0294 (3) | |
C1 | −0.05999 (5) | 0.34592 (10) | 0.07123 (5) | 0.0146 (2) | |
C2 | −0.16139 (5) | 0.27871 (11) | 0.02738 (5) | 0.0169 (2) | |
H2A | −0.1980 | 0.3156 | 0.0045 | 0.020* | |
H2B | −0.1676 | 0.2693 | 0.0653 | 0.020* | |
C3 | −0.15277 (6) | 0.16054 (11) | 0.00341 (5) | 0.0189 (2) | |
H3A | −0.1516 | 0.1683 | −0.0360 | 0.023* | |
H3B | −0.1139 | 0.1266 | 0.0237 | 0.023* | |
C4 | −0.11285 (6) | 0.44310 (11) | −0.01475 (5) | 0.0187 (2) | |
H4 | −0.0706 | 0.4674 | −0.0149 | 0.022* | |
C5 | −0.14574 (7) | 0.54876 (13) | −0.00028 (7) | 0.0298 (3) | |
H5A | −0.1484 | 0.6072 | −0.0293 | 0.045* | |
H5B | −0.1866 | 0.5269 | 0.0025 | 0.045* | |
H5C | −0.1234 | 0.5803 | 0.0352 | 0.045* | |
C6 | −0.14156 (7) | 0.39715 (14) | −0.07228 (6) | 0.0269 (3) | |
H6A | −0.1434 | 0.4589 | −0.0996 | 0.040* | |
H6B | −0.1172 | 0.3332 | −0.0811 | 0.040* | |
H6C | −0.1826 | 0.3698 | −0.0732 | 0.040* | |
C7 | 0.14824 (6) | 0.13339 (11) | 0.19783 (5) | 0.0176 (2) | |
C8 | 0.23758 (6) | 0.04441 (12) | 0.17638 (5) | 0.0198 (3) | |
H8A | 0.2740 | 0.0063 | 0.1990 | 0.024* | |
H8B | 0.2491 | 0.1234 | 0.1677 | 0.024* | |
C9 | 0.21556 (6) | −0.02239 (12) | 0.12279 (6) | 0.0216 (3) | |
H9A | 0.2055 | −0.1027 | 0.1309 | 0.026* | |
H9B | 0.1788 | 0.0143 | 0.0999 | 0.026* | |
C10 | 0.19723 (6) | −0.02799 (12) | 0.25659 (6) | 0.0235 (3) | |
H10 | 0.1579 | −0.0276 | 0.2682 | 0.028* | |
C11 | 0.24587 (8) | 0.01794 (16) | 0.30508 (6) | 0.0369 (4) | |
H11A | 0.2500 | −0.0343 | 0.3368 | 0.055* | |
H11B | 0.2846 | 0.0229 | 0.2941 | 0.055* | |
H11C | 0.2342 | 0.0948 | 0.3154 | 0.055* | |
C12 | 0.20978 (7) | −0.15172 (13) | 0.24188 (7) | 0.0302 (3) | |
H12A | 0.2136 | −0.2008 | 0.2747 | 0.045* | |
H12B | 0.1763 | −0.1796 | 0.2124 | 0.045* | |
H12C | 0.2475 | −0.1544 | 0.2291 | 0.045* | |
C13 | 0.06012 (6) | 0.57559 (11) | 0.20834 (5) | 0.0184 (2) | |
H13 | 0.0437 | 0.5903 | 0.1702 | 0.022* | |
C14 | 0.07479 (6) | 0.66804 (11) | 0.24394 (5) | 0.0182 (2) | |
H14 | 0.0688 | 0.7446 | 0.2301 | 0.022* | |
C15 | 0.09848 (5) | 0.64880 (11) | 0.30033 (5) | 0.0153 (2) | |
C16 | 0.10526 (6) | 0.53450 (11) | 0.31809 (5) | 0.0168 (2) | |
H16 | 0.1201 | 0.5173 | 0.3562 | 0.020* | |
C17 | 0.09027 (6) | 0.44634 (11) | 0.27985 (5) | 0.0172 (2) | |
H17 | 0.0959 | 0.3689 | 0.2925 | 0.021* | |
C18 | 0.11718 (6) | 0.74550 (11) | 0.33969 (5) | 0.0167 (2) | |
C19 | 0.08995 (6) | 0.85379 (12) | 0.33087 (6) | 0.0226 (3) | |
H19 | 0.0577 | 0.8671 | 0.2995 | 0.027* | |
C20 | 0.11034 (7) | 0.94170 (12) | 0.36829 (6) | 0.0263 (3) | |
H20 | 0.0914 | 1.0150 | 0.3617 | 0.032* | |
C21 | 0.18115 (7) | 0.82418 (12) | 0.42167 (6) | 0.0241 (3) | |
H21 | 0.2131 | 0.8134 | 0.4535 | 0.029* | |
C22 | 0.16396 (6) | 0.73140 (11) | 0.38674 (5) | 0.0196 (2) | |
H22 | 0.1837 | 0.6590 | 0.3946 | 0.024* | |
C23 | −0.00188 (8) | 0.76757 (13) | 0.05982 (7) | 0.0323 (3) | |
H23 | −0.0154 | 0.6902 | 0.0533 | 0.039* | |
C24 | −0.01356 (7) | 0.84325 (12) | 0.01538 (6) | 0.0288 (3) | |
H24 | −0.0343 | 0.8172 | −0.0203 | 0.035* | |
C25 | 0.00530 (6) | 0.95788 (11) | 0.02321 (5) | 0.0188 (2) | |
C26 | 0.03523 (7) | 0.98828 (12) | 0.07680 (6) | 0.0258 (3) | |
H26 | 0.0490 | 1.0651 | 0.0848 | 0.031* | |
C27 | 0.04485 (7) | 0.90635 (13) | 0.11837 (7) | 0.0299 (3) | |
H27 | 0.0655 | 0.9299 | 0.1545 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd | 0.01892 (5) | 0.01605 (5) | 0.01519 (5) | −0.00140 (3) | 0.00083 (3) | −0.00184 (3) |
S1 | 0.02100 (15) | 0.01453 (14) | 0.01510 (14) | −0.00512 (11) | 0.00201 (11) | 0.00145 (11) |
S2 | 0.02016 (15) | 0.01946 (15) | 0.01593 (14) | −0.00819 (12) | 0.00078 (11) | 0.00279 (11) |
S3 | 0.02200 (15) | 0.02007 (15) | 0.01891 (15) | −0.00138 (12) | 0.00624 (12) | 0.00193 (12) |
S4 | 0.02419 (16) | 0.02194 (16) | 0.01883 (15) | 0.00403 (12) | 0.00847 (12) | 0.00277 (12) |
O1 | 0.0189 (4) | 0.0182 (4) | 0.0216 (5) | −0.0049 (4) | −0.0023 (4) | 0.0050 (4) |
O2 | 0.0196 (5) | 0.0355 (6) | 0.0214 (5) | −0.0060 (4) | 0.0062 (4) | −0.0109 (4) |
N1 | 0.0155 (5) | 0.0150 (5) | 0.0151 (5) | −0.0024 (4) | 0.0041 (4) | 0.0010 (4) |
N2 | 0.0174 (5) | 0.0204 (5) | 0.0158 (5) | −0.0001 (4) | 0.0028 (4) | −0.0006 (4) |
N3 | 0.0167 (5) | 0.0170 (5) | 0.0150 (5) | −0.0016 (4) | 0.0016 (4) | −0.0009 (4) |
N4 | 0.0340 (7) | 0.0196 (6) | 0.0230 (6) | −0.0005 (5) | 0.0057 (5) | −0.0054 (5) |
N5 | 0.0313 (7) | 0.0235 (6) | 0.0328 (7) | 0.0015 (5) | 0.0061 (5) | 0.0050 (5) |
C1 | 0.0170 (6) | 0.0129 (5) | 0.0146 (5) | −0.0020 (4) | 0.0052 (4) | −0.0016 (4) |
C2 | 0.0135 (5) | 0.0172 (6) | 0.0198 (6) | −0.0028 (4) | 0.0036 (5) | 0.0001 (5) |
C3 | 0.0172 (6) | 0.0188 (6) | 0.0192 (6) | −0.0040 (5) | 0.0015 (5) | −0.0023 (5) |
C4 | 0.0186 (6) | 0.0207 (6) | 0.0167 (6) | −0.0018 (5) | 0.0036 (5) | 0.0054 (5) |
C5 | 0.0379 (8) | 0.0205 (7) | 0.0345 (8) | 0.0032 (6) | 0.0156 (7) | 0.0084 (6) |
C6 | 0.0281 (7) | 0.0324 (8) | 0.0175 (6) | −0.0029 (6) | −0.0002 (5) | 0.0056 (6) |
C7 | 0.0188 (6) | 0.0182 (6) | 0.0146 (5) | −0.0037 (5) | 0.0014 (4) | −0.0033 (5) |
C8 | 0.0168 (6) | 0.0228 (6) | 0.0197 (6) | −0.0019 (5) | 0.0038 (5) | −0.0047 (5) |
C9 | 0.0192 (6) | 0.0248 (7) | 0.0211 (6) | −0.0047 (5) | 0.0055 (5) | −0.0067 (5) |
C10 | 0.0236 (7) | 0.0269 (7) | 0.0191 (6) | 0.0044 (5) | 0.0031 (5) | 0.0046 (5) |
C11 | 0.0408 (9) | 0.0442 (10) | 0.0199 (7) | 0.0038 (8) | −0.0047 (6) | 0.0004 (7) |
C12 | 0.0320 (8) | 0.0254 (7) | 0.0336 (8) | 0.0054 (6) | 0.0087 (6) | 0.0083 (6) |
C13 | 0.0188 (6) | 0.0203 (6) | 0.0149 (6) | 0.0009 (5) | 0.0013 (5) | 0.0010 (5) |
C14 | 0.0192 (6) | 0.0159 (6) | 0.0182 (6) | 0.0024 (5) | 0.0018 (5) | 0.0019 (5) |
C15 | 0.0131 (5) | 0.0164 (6) | 0.0160 (6) | 0.0000 (4) | 0.0028 (4) | −0.0020 (4) |
C16 | 0.0175 (6) | 0.0187 (6) | 0.0136 (5) | −0.0006 (5) | 0.0026 (4) | 0.0011 (4) |
C17 | 0.0184 (6) | 0.0158 (6) | 0.0166 (6) | −0.0018 (5) | 0.0025 (5) | 0.0015 (5) |
C18 | 0.0187 (6) | 0.0158 (6) | 0.0164 (6) | −0.0008 (5) | 0.0055 (5) | −0.0009 (5) |
C19 | 0.0254 (7) | 0.0199 (6) | 0.0213 (6) | 0.0050 (5) | 0.0032 (5) | −0.0009 (5) |
C20 | 0.0337 (8) | 0.0170 (6) | 0.0273 (7) | 0.0053 (6) | 0.0055 (6) | −0.0029 (5) |
C21 | 0.0283 (7) | 0.0224 (7) | 0.0188 (6) | −0.0006 (5) | −0.0005 (5) | −0.0034 (5) |
C22 | 0.0228 (6) | 0.0166 (6) | 0.0188 (6) | 0.0019 (5) | 0.0036 (5) | −0.0012 (5) |
C23 | 0.0436 (9) | 0.0152 (6) | 0.0365 (8) | −0.0051 (6) | 0.0062 (7) | 0.0002 (6) |
C24 | 0.0392 (8) | 0.0171 (6) | 0.0284 (7) | −0.0059 (6) | 0.0045 (6) | −0.0032 (6) |
C25 | 0.0169 (6) | 0.0146 (6) | 0.0256 (7) | 0.0011 (5) | 0.0067 (5) | −0.0018 (5) |
C26 | 0.0272 (7) | 0.0182 (6) | 0.0291 (7) | −0.0026 (5) | 0.0010 (6) | −0.0026 (5) |
C27 | 0.0328 (8) | 0.0253 (7) | 0.0284 (7) | −0.0006 (6) | 0.0003 (6) | 0.0005 (6) |
Geometric parameters (Å, º) top Cd—N3 | 2.3011 (11) | C8—H8A | 0.9900 |
Cd—S1 | 2.5547 (3) | C8—H8B | 0.9900 |
Cd—S2 | 2.6500 (3) | C9—H9A | 0.9900 |
Cd—S3 | 2.5620 (4) | C9—H9B | 0.9900 |
Cd—S4 | 2.6696 (4) | C10—C12 | 1.523 (2) |
C1—S1 | 1.7310 (12) | C10—C11 | 1.528 (2) |
C1—S2 | 1.7218 (12) | C10—H10 | 1.0000 |
C7—S3 | 1.7328 (13) | C11—H11A | 0.9800 |
C7—S4 | 1.7257 (13) | C11—H11B | 0.9800 |
O1—C3 | 1.4259 (15) | C11—H11C | 0.9800 |
O1—H1O | 0.833 (9) | C12—H12A | 0.9800 |
O2—C9 | 1.4168 (16) | C12—H12B | 0.9800 |
O2—H2O | 0.832 (9) | C12—H12C | 0.9800 |
N1—C1 | 1.3364 (16) | C13—C14 | 1.3801 (18) |
N1—C2 | 1.4733 (15) | C13—H13 | 0.9500 |
N1—C4 | 1.4895 (16) | C14—C15 | 1.3960 (17) |
N2—C7 | 1.3416 (17) | C14—H14 | 0.9500 |
N2—C8 | 1.4688 (16) | C15—C16 | 1.3940 (17) |
N2—C10 | 1.4851 (17) | C15—C18 | 1.4832 (17) |
N3—C13 | 1.3441 (16) | C16—C17 | 1.3827 (17) |
N3—C17 | 1.3441 (16) | C16—H16 | 0.9500 |
N4—C20 | 1.3363 (19) | C17—H17 | 0.9500 |
N4—C21 | 1.3389 (18) | C18—C19 | 1.3942 (18) |
N5—C27 | 1.3356 (19) | C18—C22 | 1.3944 (18) |
N5—C23 | 1.338 (2) | C19—C20 | 1.3846 (19) |
C2—C3 | 1.5242 (18) | C19—H19 | 0.9500 |
C2—H2A | 0.9900 | C20—H20 | 0.9500 |
C2—H2B | 0.9900 | C21—C22 | 1.3801 (18) |
C3—H3A | 0.9900 | C21—H21 | 0.9500 |
C3—H3B | 0.9900 | C22—H22 | 0.9500 |
C4—C5 | 1.520 (2) | C23—C24 | 1.386 (2) |
C4—C6 | 1.5220 (19) | C23—H23 | 0.9500 |
C4—H4 | 1.0000 | C24—C25 | 1.3960 (18) |
C5—H5A | 0.9800 | C24—H24 | 0.9500 |
C5—H5B | 0.9800 | C25—C26 | 1.3917 (19) |
C5—H5C | 0.9800 | C25—C25i | 1.487 (3) |
C6—H6A | 0.9800 | C26—C27 | 1.382 (2) |
C6—H6B | 0.9800 | C26—H26 | 0.9500 |
C6—H6C | 0.9800 | C27—H27 | 0.9500 |
C8—C9 | 1.5202 (18) | | |
| | | |
N3—Cd—S1 | 121.64 (3) | O2—C9—C8 | 107.32 (10) |
N3—Cd—S3 | 112.61 (3) | O2—C9—H9A | 110.3 |
S1—Cd—S3 | 125.725 (11) | C8—C9—H9A | 110.3 |
N3—Cd—S2 | 95.71 (3) | O2—C9—H9B | 110.3 |
S1—Cd—S2 | 69.571 (10) | C8—C9—H9B | 110.3 |
S3—Cd—S2 | 104.839 (11) | H9A—C9—H9B | 108.5 |
N3—Cd—S4 | 98.43 (3) | N2—C10—C12 | 112.15 (11) |
S1—Cd—S4 | 102.645 (11) | N2—C10—C11 | 109.64 (12) |
S3—Cd—S4 | 69.533 (10) | C12—C10—C11 | 112.07 (13) |
S2—Cd—S4 | 165.865 (11) | N2—C10—H10 | 107.6 |
C1—S1—Cd | 87.22 (4) | C12—C10—H10 | 107.6 |
C1—S2—Cd | 84.39 (4) | C11—C10—H10 | 107.6 |
C7—S3—Cd | 87.13 (4) | C10—C11—H11A | 109.5 |
C7—S4—Cd | 83.88 (5) | C10—C11—H11B | 109.5 |
C3—O1—H1O | 106.5 (13) | H11A—C11—H11B | 109.5 |
C9—O2—H2O | 105.2 (13) | C10—C11—H11C | 109.5 |
C1—N1—C2 | 120.10 (10) | H11A—C11—H11C | 109.5 |
C1—N1—C4 | 121.37 (10) | H11B—C11—H11C | 109.5 |
C2—N1—C4 | 118.36 (10) | C10—C12—H12A | 109.5 |
C7—N2—C8 | 120.56 (11) | C10—C12—H12B | 109.5 |
C7—N2—C10 | 121.95 (11) | H12A—C12—H12B | 109.5 |
C8—N2—C10 | 117.13 (11) | C10—C12—H12C | 109.5 |
C13—N3—C17 | 117.88 (11) | H12A—C12—H12C | 109.5 |
C13—N3—Cd | 122.21 (8) | H12B—C12—H12C | 109.5 |
C17—N3—Cd | 119.83 (8) | N3—C13—C14 | 122.62 (12) |
C20—N4—C21 | 117.14 (12) | N3—C13—H13 | 118.7 |
C27—N5—C23 | 115.51 (13) | C14—C13—H13 | 118.7 |
N1—C1—S2 | 121.29 (9) | C13—C14—C15 | 119.85 (12) |
N1—C1—S1 | 120.01 (9) | C13—C14—H14 | 120.1 |
S2—C1—S1 | 118.69 (7) | C15—C14—H14 | 120.1 |
N1—C2—C3 | 111.34 (10) | C16—C15—C14 | 117.23 (11) |
N1—C2—H2A | 109.4 | C16—C15—C18 | 121.11 (11) |
C3—C2—H2A | 109.4 | C14—C15—C18 | 121.64 (11) |
N1—C2—H2B | 109.4 | C17—C16—C15 | 119.62 (11) |
C3—C2—H2B | 109.4 | C17—C16—H16 | 120.2 |
H2A—C2—H2B | 108.0 | C15—C16—H16 | 120.2 |
O1—C3—C2 | 109.17 (10) | N3—C17—C16 | 122.77 (12) |
O1—C3—H3A | 109.8 | N3—C17—H17 | 118.6 |
C2—C3—H3A | 109.8 | C16—C17—H17 | 118.6 |
O1—C3—H3B | 109.8 | C19—C18—C22 | 117.47 (12) |
C2—C3—H3B | 109.8 | C19—C18—C15 | 121.90 (12) |
H3A—C3—H3B | 108.3 | C22—C18—C15 | 120.62 (11) |
N1—C4—C5 | 109.96 (11) | C20—C19—C18 | 119.37 (13) |
N1—C4—C6 | 112.47 (11) | C20—C19—H19 | 120.3 |
C5—C4—C6 | 112.12 (12) | C18—C19—H19 | 120.3 |
N1—C4—H4 | 107.3 | N4—C20—C19 | 123.24 (13) |
C5—C4—H4 | 107.3 | N4—C20—H20 | 118.4 |
C6—C4—H4 | 107.3 | C19—C20—H20 | 118.4 |
C4—C5—H5A | 109.5 | N4—C21—C22 | 123.81 (13) |
C4—C5—H5B | 109.5 | N4—C21—H21 | 118.1 |
H5A—C5—H5B | 109.5 | C22—C21—H21 | 118.1 |
C4—C5—H5C | 109.5 | C21—C22—C18 | 118.98 (12) |
H5A—C5—H5C | 109.5 | C21—C22—H22 | 120.5 |
H5B—C5—H5C | 109.5 | C18—C22—H22 | 120.5 |
C4—C6—H6A | 109.5 | N5—C23—C24 | 124.26 (14) |
C4—C6—H6B | 109.5 | N5—C23—H23 | 117.9 |
H6A—C6—H6B | 109.5 | C24—C23—H23 | 117.9 |
C4—C6—H6C | 109.5 | C23—C24—C25 | 119.73 (14) |
H6A—C6—H6C | 109.5 | C23—C24—H24 | 120.1 |
H6B—C6—H6C | 109.5 | C25—C24—H24 | 120.1 |
N2—C7—S4 | 121.13 (10) | C26—C25—C24 | 116.13 (13) |
N2—C7—S3 | 119.58 (10) | C26—C25—C25i | 121.98 (15) |
S4—C7—S3 | 119.30 (8) | C24—C25—C25i | 121.88 (15) |
N2—C8—C9 | 111.65 (10) | C27—C26—C25 | 119.81 (13) |
N2—C8—H8A | 109.3 | C27—C26—H26 | 120.1 |
C9—C8—H8A | 109.3 | C25—C26—H26 | 120.1 |
N2—C8—H8B | 109.3 | N5—C27—C26 | 124.56 (14) |
C9—C8—H8B | 109.3 | N5—C27—H27 | 117.7 |
H8A—C8—H8B | 108.0 | C26—C27—H27 | 117.7 |
| | | |
C2—N1—C1—S2 | −176.55 (9) | C17—N3—C13—C14 | 1.25 (19) |
C4—N1—C1—S2 | −1.29 (16) | Cd—N3—C13—C14 | −175.45 (10) |
C2—N1—C1—S1 | 3.28 (16) | N3—C13—C14—C15 | −0.6 (2) |
C4—N1—C1—S1 | 178.54 (9) | C13—C14—C15—C16 | −1.00 (19) |
Cd—S2—C1—N1 | −176.80 (10) | C13—C14—C15—C18 | 177.49 (12) |
Cd—S2—C1—S1 | 3.36 (6) | C14—C15—C16—C17 | 1.82 (18) |
Cd—S1—C1—N1 | 176.69 (10) | C18—C15—C16—C17 | −176.68 (12) |
Cd—S1—C1—S2 | −3.48 (7) | C13—N3—C17—C16 | −0.37 (19) |
C1—N1—C2—C3 | −83.28 (14) | Cd—N3—C17—C16 | 176.41 (9) |
C4—N1—C2—C3 | 101.32 (13) | C15—C16—C17—N3 | −1.19 (19) |
N1—C2—C3—O1 | 173.57 (10) | C16—C15—C18—C19 | −152.60 (13) |
C1—N1—C4—C5 | −93.77 (14) | C14—C15—C18—C19 | 28.96 (19) |
C2—N1—C4—C5 | 81.57 (14) | C16—C15—C18—C22 | 28.66 (18) |
C1—N1—C4—C6 | 140.52 (12) | C14—C15—C18—C22 | −149.77 (13) |
C2—N1—C4—C6 | −44.15 (15) | C22—C18—C19—C20 | 0.4 (2) |
C8—N2—C7—S4 | −178.55 (9) | C15—C18—C19—C20 | −178.33 (13) |
C10—N2—C7—S4 | −5.59 (17) | C21—N4—C20—C19 | −0.3 (2) |
C8—N2—C7—S3 | 1.70 (16) | C18—C19—C20—N4 | −0.1 (2) |
C10—N2—C7—S3 | 174.65 (10) | C20—N4—C21—C22 | 0.3 (2) |
Cd—S4—C7—N2 | −176.04 (10) | N4—C21—C22—C18 | 0.1 (2) |
Cd—S4—C7—S3 | 3.71 (7) | C19—C18—C22—C21 | −0.45 (19) |
Cd—S3—C7—N2 | 175.91 (10) | C15—C18—C22—C21 | 178.35 (12) |
Cd—S3—C7—S4 | −3.85 (7) | C27—N5—C23—C24 | 0.4 (2) |
C7—N2—C8—C9 | −84.72 (15) | N5—C23—C24—C25 | −0.2 (3) |
C10—N2—C8—C9 | 102.00 (13) | C23—C24—C25—C26 | −0.1 (2) |
N2—C8—C9—O2 | 178.55 (11) | C23—C24—C25—C25i | 179.10 (16) |
C7—N2—C10—C12 | 138.65 (13) | C24—C25—C26—C27 | 0.3 (2) |
C8—N2—C10—C12 | −48.17 (16) | C25i—C25—C26—C27 | −178.94 (16) |
C7—N2—C10—C11 | −96.19 (15) | C23—N5—C27—C26 | −0.2 (2) |
C8—N2—C10—C11 | 76.99 (15) | C25—C26—C27—N5 | −0.1 (2) |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) topCg1 is the centroid of the Zn/S3/S4/C7 chelate ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N4ii | 0.83 (2) | 1.88 (2) | 2.7085 (15) | 176 (1) |
O2—H2O···O1iii | 0.83 (1) | 1.89 (1) | 2.7162 (14) | 173 (2) |
C4—H4···S2iv | 1.00 | 2.68 | 3.5395 (14) | 144 |
C22—H22···O2v | 0.95 | 2.40 | 3.3473 (17) | 174 |
C26—H26···Cg1vi | 0.95 | 3.00 | 3.776 (3) | 140 |
Symmetry codes: (ii) −x, y−1, −z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y+3/2, z; (v) x, −y, z−1/2; (vi) x, y+1, z. |
Acknowledgements
Sunway University is thanked for support of biological and crystal engineering studies of metal dithiocarbamates.
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science
Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2009). Acta Cryst. E65, m1472–m1473. Web of Science CSD CrossRef IUCr Journals
Benson, R. E., Ellis, C. A., Lewis, C. E. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 930–941. Web of Science CSD CrossRef CAS
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Broker, G. A., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 1458–1464. Web of Science CSD CrossRef IUCr Journals
Broker, G. A. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m320–m321. Web of Science CSD CrossRef CAS IUCr Journals
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Chai, J., Lai, C. S., Yan, J. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 249–250. Web of Science CSD CrossRef CAS
Fan, J., Wei, F.-X., Zhang, W.-G., Yin, X., Lai, C.-S. & Tiekink, E. R. T. (2007). Acta Chim. Sinica, 65, 2014–2018. CAS
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Jotani, M. M., Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1700–1709. Web of Science CSD CrossRef IUCr Journals
Klevtsova, R. F., Glinskaya, L. A., Berus, E. I. & Larionov, S. V. (2001). J. Struct. Chem. 42, 639–647. Web of Science CSD CrossRef CAS
Lai, C. S. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 251–252. Web of Science CSD CrossRef CAS
Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals
Tiekink, E. R. T. (2017). Coord. Chem. Rev. 345, 209–228. Web of Science CrossRef CAS
Tiekink, E. R. T. & Zukerman-Schpector, J. (2011). Chem. Commun. 47, 6623–6625. Web of Science CrossRef CAS
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals
Zemskova, S. M., Glinskaya, L. A., Durasov, V. B., Klevtsova, R. F. & Larionov, S. V. (1994). J. Struct. Chem. 34, 794–802. CrossRef
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
ISSN: 2056-9890
Open
access