1. Chemical context
The title ligand, N,N′,N′′,N′′′-[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(N-methylaniline) (L), whose synthesis and crystal structure have been described in the preceding publication (Tesouro Vallina & Stoeckli-Evans, 2020), is a new tetrakis-substituted pyrazine derivative. It was designed to study its coordination behaviour with transition metals (Tesouro Vallina, 2001). The reaction of the ligand with CdI2 and ZnCl2 lead to the formation of the title mononuclear complexes I and II. Herein, we describe their syntheses, molecular and crystal structures and the analyses of their Hirshfeld surfaces.
2. Structural commentary
The molecular structure of the cadmium(II) complex, Cd(L)I2 (I), of the ligand N,N′,N′′,N′′′-[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(N-methylaniline) (L), is illustrated in Fig. 1. Selected geometrical parameters are given in Table 1. The complex possesses twofold rotation symmetry, with the twofold axis bisecting the cadmium atom, Cd1, and the nitrogen atoms N1 and N4 of the pyrazine ring. The ligand coordinates in a mono-tridentate manner and the cadmium atom has a fivefold CdN3I2 coordination environment with a distorted shape (see Fig. 2a). The τ5 parameter for the fivefold coordination of atom Cd1 is 0.14 (τ5 = 0 for a perfect square-pyramidal geometry and = 1 for a trigonal–pyramidal geometry; Addison et al., 1984).
Cd1—N1 | 2.295 (3) | Cd1—I1 | 2.7038 (3) | Cd1—N2 | 2.599 (3) | | | | | | | N1—Cd1—N2 | 69.65 (6) | N2—Cd1—I1i | 95.35 (6) | N2i—Cd1—N2 | 139.31 (12) | N2—Cd1—I1 | 101.29 (6) | N1—Cd1—I1 | 114.551 (10) | I1i—Cd1—I1 | 130.90 (2) | Symmetry code: (i) . | |
| Figure 1 A view of the molecular structure of complex I, with atom labelling [symmetry code (i): −x + , y, −z]. Displacement ellipsoids are drawn at the 30% probability level. The intramolecular C—H⋯π interactions are shown as dashed red arrows (Table 2). |
| Figure 2 A comparison of the coordination spheres of (a) the cadmium atom in complex I [symmetry code (i): −x + , y, −z], and (b) the zinc atom in complex II. |
A search of the Cambridge Structural Database (CSD, Version 5.41, last update November 2019; Groom et al., 2016) for a CdN3I2 coordination environment involving a pyrazine N atom yielded only one relevant structure, the CdI2 mononuclear complex of the ligand 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine (TPPZ), viz. complex (2,3,5,6-tetrakis(pyridin-2-yl)pyrazine)bis(iodo)cadmium(II) (GAHRIT; Saghatforoush, 2015). Here the τ5 parameter for the cadmium atom is 0.04. The Cd—Npz bond length is ca 2.388 Å compared to 2.295 (3) Å in I, while the Cd—I bond lengths are ca 2.741 and 2.727 Å compared to 2.7038 (3) Å in I. The N-methylaniline groups on the non-coordinated side of the ligand are linked by intramolecular C—H⋯π interactions (Fig. 1 and Table 2).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | C18—H18C⋯Cg5i | 0.97 | 2.95 | 3.896 (5) | 165 | C17—H17⋯I1ii | 0.94 | 3.09 | 3.907 (4) | 147 | Cd1—I1⋯Cgiii | 2.70 (1) | 3.96 (1) | 6.5131 (12) | 155 (1) | Cd1—I1⋯Cg3iv | 2.70 (1) | 3.96 (1) | 6.5131 (12) | 155 (1) | Symmetry codes: (i) ; (ii) ; (iii) -x+1, -y, -z; (iv) . | |
The molecular structure of the zinc(II) complex, Zn(L)Cl2·0.6(CH2Cl2) (II), is illustrated in Fig. 3. It crystallized as a partial dichloromethane solvate. Selected geometrical parameters are given in Table 3. The ligand L coordinates in a mono-tridentate manner and the zinc atom, Zn1, has a fivefold ZnN3Cl2 coordination environment with a distorted shape (see Fig. 2b). The τ5 parameter for atom Zn1 is 0.30.
Zn1—N1 | 2.057 (3) | Zn1—Cl1 | 2.2251 (10) | Zn1—N2 | 2.385 (3) | Zn1—Cl2 | 2.2425 (11) | Zn1—N5 | 2.413 (3) | | | | | | | N1—Zn1—N2 | 75.02 (12) | Cl1—Zn1—N2 | 98.12 (8) | N1—Zn1—N5 | 74.23 (12) | Cl2—Zn1—N2 | 95.70 (9) | N2—Zn1—N5 | 149.21 (11) | Cl1—Zn1—N5 | 93.02 (7) | N1—Zn1—Cl1 | 114.15 (9) | Cl2—Zn1—N5 | 98.34 (8) | N1—Zn1—Cl2 | 114.68 (9) | Cl1—Zn1—Cl2 | 131.14 (4) | | |
| Figure 3 A view of the molecular structure of compound II, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. For clarity, H atoms have been omitted. |
A search of the CSD for a ZnN3Cl2 coordination environment involving a pyrazine N atom yielded five relevant structures, which again involve the ligand TPPZ. They include two polymorphs of the mononuclear complex dichloro-[2,3,5,6-tetrakis(2-pyridyl)pyrazine-N,N′,N′′]zinc(II): a monoclinic polymorph (WAGPOJ; Graf et al., 1993) and a triclinic polymorph (WAGPOJ01; Saljooghi & Fatemi, 2011). There are two structures of the binuclear complex [μ2-2,3,5,6-tetrakis(2-pyridyl)pyrazine]tetrachlorodizinc(II): one hydrated (DOMHOD; Trivedi et al., 2009), the other not (PAPCER; Hong et al., 2017), and finally, the unusual polynuclear complex octakis(μ2-chloro)bis[μ2-2,3,5,6-tetrakis(2-pyridyl)pyrazine]dodecachlorotetraaquadecazinc (WIBVOS; Graf & Stoeckli-Evans, 1994). For these five structures, the τ5 parameter for the zinc atoms varies from 0.08 in WAGPOJ to 0.36 in WAGPOJ01. The latter is similar to the value of 0.30 for II. The Zn—Npz bond lengths vary from ca 2.141 to 2.200 Å compared to 2.057 (3) Å in II, while the Zn—Cl bond lengths vary from ca 2.232 to 2.343 Å compared to 2.2251 (10) and 2.2425 (11) Å in II.
The conformation of the ligand L differs in the two complexes (Fig. 4). The orientation of the phenyl rings with respect to the pyrazine ring and to each other is slightly different, and the various dihedral angles are compared in Table 5. It can be seen that the most significant difference, of 20.9 (2)°, involves the orientation of ring D (ring Bi in I) with respect to ring E (ring Ci in I).
Dihedral angle (°) | Ia | II | Δ(I - II)° | A to B | 41.9 (2) | 35.5 (2) | > 6.4 | A to C | 86.1 (2) | 87.5 (3) | < 1.4 | A to D | 41.9 (2) | 34.9 (2) | > 7.0 | A to E | 86.1 (2) | 74.4 (2) | > 11.7 | B to C | 54.0 (2) | 53.7 (3) | > 0.3 | B to D | 38.0 (2) | 26.9 (2) | > 11.1 | B to E | 63.4 (2) | 71.9 (2) | < 8.5 | C to D | 63.4 (2) | 58.5 (3) | > 4.9 | C to E | 24.9 (2) | 18.3 (3) | > 6.6 | D to E | 54.0 (2) | 74.9 (2) | < 20.9 | Note: (a) D = Bi, E = Ci; symmetry code: (i) −x + , y, −z. | |
| Figure 4 A comparison of the conformation of the ligand L in complexes I and II. For complex I, which possesses twofold rotation symmetry, ring D = Bi, and ring E = Ci [symmetry code: (i) −x + , y, −z]. |
3. Supramolecular features
A partial view of the crystal packing of I is shown in Fig. 5. Molecules are linked by weak C—H⋯I contacts, forming ribbons propagating along [100]; see Table 2. There are Cd—I⋯π(pyrazine) contacts present, consolidating the chains propagating along the a-axis direction (Fig. 6a and Table 2). This situation is similar to that observed in the crystal of the CdI2 complex of TPPZ (GAHRIT; Saghatforoush, 2015). There, the I⋯centroid(pyrazine ring) distance is 3.699 (1) Å with a Cd—I⋯centroid angle of 175.92 (12)°, compared to 3.9593 (12) Å and 155.19 (3)° in complex I (Fig. 6a and Table 2).
| Figure 5 A view normal to plane (011) of the crystal packing of complex I. The weak C—H⋯I interactions are shown as dashed lines (Table 2). |
| Figure 6 (a) A partial view along the c axis of the crystal packing of I, showing the Cd—I⋯π(pyrazine) interactions (Table 2; dashed red arrows), (b) a partial view along the a axis of the crystal packing of II, showing the Zn—Cl⋯π(pyrazine) interactions (Table 4; dashed red arrows). For clarity, the dichloromethane molecule has been omitted. |
In the crystal of II, molecules are linked by a series of C—H⋯π interactions, forming layers lying parallel to the (11) plane; see Fig. 7 and Table 4. The dichloromethane molecules are linked across a center of symmetry with a short Cl4⋯Cl4(−x, −y, −z + 2) contact of 3.045 (5) Å and do not participate in any significant intermolecular interactions with the complex molecule. There are Zn—Cl⋯π(pyrazine) contacts present, which link inversion-related molecules, forming dimers (Fig. 6b and Table 5). This arrangement is similar to that observed in the crystal structure of the ZnCl2 complex of TPPZ (PAPCER; Hong et al., 2017). This compound crystallized with two independent molecules in the asymmetric unit. There, the Cl⋯centroid(pyrazine ring) distances are ca 3.087 and 3.167 Å, with the corresponding Zn—Cl⋯centroid angles being ca 152.62 and 141.76°. In the crystal structure of WIBVOS, a similar interaction is present with a Cl⋯centroid(pyrazine ring) distance of ca 3.987 Å and a Zn—Cl⋯centroid angle of ca. 170.96°. In complex II, the corresponding Cl⋯centroid(pyrazine ring) distance and Zn—Cl⋯centroid angle are 3.683 (2) Å and 155.96 (6)°, respectively (Table 4).
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | C6—H6⋯Cg7i | 0.94 | 2.88 | 3.814 (6) | 177 | C11—H11B⋯Cg5ii | 0.98 | 2.90 | 3.540 (5) | 124 | C26—H26⋯Cg3iii | 0.94 | 2.95 | 3.544 (5) | 122 | Zn1—Cl2⋯Cg3iv | 2.24 (1) | 3.68 (1) | 5.8035 (19) | 156 (1) | Symmetry codes: (i) x-1, y-1, z; (ii) -x+1, -y, -z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y, -z+1. | |
| Figure 7 A view along the a axis of the crystal packing of compound II. The various C—H⋯π interactions (Table 4; blue, red and green) are shown as dashed lines. The dichloromethane molecule has been omitted, and only the H atoms (blue, red and green) involved in the C—H⋯π interactions have been included. |
4. Hirshfeld surface analysis and two-dimensional fingerprint plots
The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007) were performed with CrystalExplorer17 (Turner et al., 2017). The Hirshfeld surfaces are colour-mapped with the normalized contact distance, dnorm, ranging from red (distances shorter than the sum of the van der Waals radii) through white to blue (distances longer than the sum of the van der Waals radii). A summary of the short intermolecular contacts in the crystal structures of I and II is given in Table 6.
Contact | Length | Length − vdW | Symmetry operation | I | | | | C11⋯C12 | 3.278 | −0.122 | − x, − − y, − − z | C12⋯H11A | 2.805 | −0.095 | − x, − − y, − − z | I1⋯H17 | 3.087 | −0.093 | − + x, −y, z | N3⋯H11B | 2.671 | −0.079 | − x, − − y, − − z | N3⋯C11 | 3.234 | −0.016 | − x, − − y, − − z | | | | | II | | | | Cl4⋯Cl4 | 3.045 | −0.455 | -x, −y, 2 − z | C6⋯H40B | 2.758 | −0.142 | -x, −y, 1 − z | C30⋯H3B | 2.779 | −0.121 | 1 − x, −y, 1 − z | H23B⋯H23B | 2.287 | −0.113 | 1 − x, 1 − y, 1 − z | H6⋯C36 | 2.798 | −0.102 | −1 + x, −1 + y, z | Cl1⋯H33 | 2.854 | −0.096 | −1 + x, y, z | H6⋯C37 | 2.858 | −0.042 | −1 + x, −1 + y, z | H3B⋯H30A | 2.359 | −0.041 | 1 − x, −y, 1 − z | H10B⋯H26 | 2.382 | −0.018 | 1 − x, 1 − y, 1 − z | Note: (a) distances were calculated using Mercury (Macrae et al., 2008). | |
For complex I, the Hirshfeld surface (HS) mapped over dnorm, and the two-dimensional fingerprint plots are given in Fig. 8. The red spots on the HS (Fig. 8a) correspond to the I⋯H contacts, which give a pair of spikes in the fingerprint plot (Fig. 8b) at de + di ≃ 3.0 Å, contributing 14.2% to the HS. The H⋯H contacts contribute 63.4% and the C⋯H contacts 18.0%. Any other atom–atom contacts contributed less than 2% and have not been included here.
| Figure 8 (a) The Hirshfeld surface of complex I, mapped over dnorm, in the colour range −0.0713 to 1.5380 a.u., (b) the full two-dimensional fingerprint plot for complex I, and fingerprint plots delineated into H⋯H, C⋯H/H⋯C and I⋯H/H⋯I contacts. |
For compound II, the Hirshfeld surface mapped over dnorm, is shown in Fig. 9a, and that for the complex itself and the solvent molecule in Figs. 9b and 9c, respectively. The faint red spots correspond to the Cl⋯H contacts in the crystal. These give a pair of spikes in the fingerprint plots, at de + di ≃ 2.7 Å, contributing 22.7%, in the compound (Fig. 10a) and at de + di ≃ 2.7 Å, contributing 18.1%, in the complex (Fig. 10b). For the solvent molecule, a single sharp spike is observed (de + di ≃ 2.8 Å) with a contribution of 59.6% to the HS (Fig. 10c). The H⋯H contacts contribute 55.1, 59.4 and 25.2% to the Hirshfeld surfaces of the compound, the complex and the solvent molecule, respectively, while the C⋯H contributions are 17.7, 18.8 and 6.8%, respectively. Any other atom–atom contacts contributed less than 2% and have not been included here.
| Figure 9 (a) The Hirshfeld surface of compound II, mapped over dnorm, in the colour range −0.2597 to 1.5438 a.u., (b) the Hirshfeld surface of complex II, mapped over dnorm, in the colour range −0.0933 to 1.5453 a.u., (c) the Hirshfeld surface of the solvent molecule, mapped over dnorm, in the colour range −0.2602 to 1.4344 a.u.. |
| Figure 10 (a) The full two-dimensional fingerprint plot for compound II, and fingerprint plots delineated into H⋯H, Cl⋯H/H⋯Cl, C⋯H/H⋯C and Cl⋯C/C⋯Cl contacts, (b) the full two-dimensional fingerprint plot for complex II, and fingerprint plots delineated into H⋯H, C⋯H/H⋯C and Cl⋯H/H⋯Cl contacts, (c) the full two-dimensional fingerprint plot for the solvent molecule and fingerprint plots delineated into Cl⋯H/H⋯Cl, H⋯H, C⋯H/H⋯C, Cl⋯Cl and Cl⋯C/C⋯Cl contacts. |
5. Synthesis and crystallization
The synthesis and crystal structure of the ligand, N,N′,N′′,N′′′-[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(N-methylaniline) L, have been described in the preceding publication (Tesouro Vallina & Stoeckli-Evans, 2020).
Synthesis of the complex [Cd(L)I2] (I):
About 10 ml of a very dilute CH2Cl2 solution of ligand L were introduced into a glass tube and layered with ca 2 ml of MeOH as a buffer zone. Then, 10 ml of a dilute methanolic solution of CdI2 were added slowly to avoid possible mixing. The glass tube was sealed and left at room temperature. The colour of the interphase changed immediately to deep yellow and in hours to green. After a few days, green rod-like crystals were formed. IR (KBr pellet, cm−1): 2922 (m), 1599 (vs), 1507 (s), 1497 (s), 1173 (m), 1120 (m), 751 (s), 694 (s). No elemental analytical data are available.
Synthesis of the complex [Zn(L)Cl2]·0.6(CH2Cl2) (II):
To a solution of ZnCl2 (0.1 mmol, 0.014 g) in 5 ml of MeOH, a solution of L (0.05 mmol, 0.028 g, 5 ml CH2Cl2) was added. The solution was stirred at RT for 2 h without any significant colour change. The clear light-green solution obtained was filtered to avoid any impurity and allowed to evaporate slowly. After a few days, yellow rod-like crystals were obtained. IR (KBr pellet, cm−1): 1599 (vs), 1507 (s), 1451 (m), 1363 (s), 1257 (m), 1171 (m), 1033 (m), 920 (m), 746 (s), 691 (s). Analysis for [Zn(C36H40N6)Cl2]·0.6CH2Cl2 (743.99 g mol−1): calculated C 60.50, H 5.68, N 11.65%; found C 60.66, H 5.78, N 11.93%.
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 7. The C-bound H atoms were included in calculated positions and treated as riding on their parent C atom: C—H = 0.94–0.98 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.
| I | II | Crystal data | Chemical formula | [CdI2(C36H40N6)] | [ZnCl2(C36H40N6)]·0.6CH2Cl2 | Mr | 922.94 | 743.99 | Crystal system, space group | Monoclinic, I2/a | Triclinic, P | Temperature (K) | 223 | 223 | a, b, c (Å) | 12.8370 (7), 20.1241 (14), 15.2568 (9) | 11.9196 (8), 12.1208 (8), 13.919 (1) | α, β, γ (°) | 90, 110.871 (6), 90 | 98.222 (8), 100.313 (8), 107.580 (7) | V (Å3) | 3682.7 (4) | 1843.9 (2) | Z | 4 | 2 | Radiation type | Mo Kα | Mo Kα | μ (mm−1) | 2.30 | 0.93 | Crystal size (mm) | 0.40 × 0.10 × 0.10 | 0.30 × 0.10 × 0.10 | | Data collection | Diffractometer | STOE IPDS 1 | STOE IPDS 1 | Absorption correction | Multi-scan (MULABS; Spek, 2020) | Multi-scan (MULABS; Spek, 2020) | Tmin, Tmax | 0.961, 1.000 | 0.983, 1.000 | No. of measured, independent and observed [I > 2σ(I)] reflections | 14308, 3566, 2549 | 14512, 6654, 3490 | Rint | 0.031 | 0.054 | (sin θ/λ)max (Å−1) | 0.615 | 0.615 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.072, 0.95 | 0.043, 0.117, 0.79 | No. of reflections | 3566 | 6654 | No. of parameters | 207 | 437 | H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | Δρmax, Δρmin (e Å−3) | 1.15, −0.88 | 0.75, −0.35 | Computer programs: EXPOSE, CELL and INTEGRATE in IPDS-I (Stoe & Cie, 2004), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2020), SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010). | |
With the STOE IPDS I, a one-circle diffractometer, for the triclinic system often only 93% of the Ewald sphere is accessible. Hence, for compound II the _diffrn_reflns_Laue_measured_fraction_full of 0.939 is below the required minimum of 0.95. For II, a small number of low-angle reflections, either in the shadow of the beam-stop or with bad agreement, were omitted during the final cycles of refinement.
Supporting information
For both structures, data collection: EXPOSE in IPDS-I (Stoe & Cie, 2004); cell refinement: CELL in IPDS-I (Stoe & Cie, 2004); data reduction: INTEGRATE in IPDS-I (Stoe & Cie, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008). Software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010) for (I); SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010) for (II).
Diiodido{
N,
N',
N'',
N'''-[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(
N-methylaniline)-
κ3N2,
N1,
N6}cadmium(II) (I)
top Crystal data top [CdI2(C36H40N6)] | F(000) = 1808 |
Mr = 922.94 | Dx = 1.665 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8370 (7) Å | Cell parameters from 5000 reflections |
b = 20.1241 (14) Å | θ = 1.7–26.1° |
c = 15.2568 (9) Å | µ = 2.30 mm−1 |
β = 110.871 (6)° | T = 223 K |
V = 3682.7 (4) Å3 | Rod, green |
Z = 4 | 0.40 × 0.10 × 0.10 mm |
Data collection top STOE IPDS 1 diffractometer | 3566 independent reflections |
Radiation source: fine-focus sealed tube | 2549 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.031 |
φ rotation scans | θmax = 25.9°, θmin = 2.0° |
Absorption correction: multi-scan (MULABS; Spek, 2009) | h = −15→15 |
Tmin = 0.961, Tmax = 1.000 | k = −24→24 |
14308 measured reflections | l = −18→18 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0409P)2] where P = (Fo2 + 2Fc2)/3 |
3566 reflections | (Δ/σ)max = 0.001 |
207 parameters | Δρmax = 1.15 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
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 | |
Cd1 | 0.750000 | 0.06345 (2) | 0.000000 | 0.04883 (11) | |
I1 | 0.55787 (2) | 0.11927 (2) | −0.00131 (2) | 0.07922 (12) | |
N1 | 0.750000 | −0.05058 (17) | 0.000000 | 0.0399 (8) | |
N2 | 0.6906 (2) | 0.01854 (14) | −0.17053 (17) | 0.0460 (6) | |
N3 | 0.7067 (3) | −0.26232 (15) | −0.15731 (19) | 0.0545 (7) | |
N4 | 0.750000 | −0.18660 (18) | 0.000000 | 0.0423 (8) | |
C1 | 0.7472 (2) | −0.08374 (16) | −0.0768 (2) | 0.0410 (7) | |
C2 | 0.7432 (3) | −0.15288 (16) | −0.0772 (2) | 0.0417 (7) | |
C3 | 0.7572 (3) | −0.04292 (16) | −0.1562 (2) | 0.0476 (8) | |
H3A | 0.835630 | −0.031459 | −0.142427 | 0.057* | |
H3B | 0.731715 | −0.069302 | −0.213986 | 0.057* | |
C4 | 0.7161 (3) | 0.06601 (18) | −0.2319 (2) | 0.0513 (8) | |
C5 | 0.7873 (3) | 0.0528 (2) | −0.2792 (3) | 0.0655 (10) | |
H5 | 0.820979 | 0.010810 | −0.273599 | 0.079* | |
C6 | 0.8096 (4) | 0.1012 (2) | −0.3351 (3) | 0.0838 (14) | |
H6 | 0.858370 | 0.091568 | −0.367010 | 0.101* | |
C7 | 0.7617 (4) | 0.1625 (3) | −0.3441 (4) | 0.0881 (14) | |
H7 | 0.777532 | 0.195179 | −0.381596 | 0.106* | |
C8 | 0.6897 (4) | 0.1759 (2) | −0.2974 (3) | 0.0835 (13) | |
H8 | 0.655115 | 0.217760 | −0.304226 | 0.100* | |
C9 | 0.6677 (3) | 0.1284 (2) | −0.2406 (3) | 0.0674 (11) | |
H9 | 0.619914 | 0.138442 | −0.207941 | 0.081* | |
C10 | 0.5702 (3) | 0.0017 (2) | −0.2061 (2) | 0.0591 (9) | |
H10A | 0.550377 | −0.019190 | −0.267217 | 0.089* | |
H10B | 0.526719 | 0.041903 | −0.211542 | 0.089* | |
H10C | 0.554820 | −0.028697 | −0.162881 | 0.089* | |
C11 | 0.7299 (3) | −0.19289 (17) | −0.1643 (2) | 0.0528 (8) | |
H11A | 0.669076 | −0.173622 | −0.217143 | 0.063* | |
H11B | 0.798405 | −0.188947 | −0.178391 | 0.063* | |
C12 | 0.7924 (3) | −0.30691 (18) | −0.1149 (2) | 0.0564 (9) | |
C13 | 0.7708 (5) | −0.3737 (2) | −0.1026 (3) | 0.0763 (13) | |
H13 | 0.696946 | −0.389104 | −0.121410 | 0.092* | |
C14 | 0.8600 (6) | −0.4174 (2) | −0.0619 (4) | 0.0975 (17) | |
H14 | 0.844606 | −0.462330 | −0.054507 | 0.117* | |
C15 | 0.9680 (6) | −0.3971 (3) | −0.0330 (4) | 0.1016 (18) | |
H15 | 1.026535 | −0.427029 | −0.004708 | 0.122* | |
C16 | 0.9892 (4) | −0.3321 (3) | −0.0459 (3) | 0.0862 (14) | |
H16 | 1.063444 | −0.317367 | −0.027305 | 0.103* | |
C17 | 0.9041 (4) | −0.2880 (2) | −0.0856 (3) | 0.0664 (10) | |
H17 | 0.921527 | −0.243502 | −0.093253 | 0.080* | |
C18 | 0.5935 (4) | −0.2794 (2) | −0.1693 (3) | 0.0777 (12) | |
H18A | 0.569896 | −0.317068 | −0.211386 | 0.117* | |
H18B | 0.545221 | −0.241751 | −0.195689 | 0.117* | |
H18C | 0.589042 | −0.290749 | −0.108965 | 0.117* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.03359 (17) | 0.0483 (2) | 0.0628 (2) | 0.000 | 0.01500 (15) | 0.000 |
I1 | 0.04735 (16) | 0.0918 (2) | 0.0946 (2) | 0.02423 (13) | 0.02050 (14) | −0.00291 (16) |
N1 | 0.0377 (19) | 0.043 (2) | 0.0401 (19) | 0.000 | 0.0151 (15) | 0.000 |
N2 | 0.0346 (13) | 0.0559 (16) | 0.0469 (14) | 0.0013 (12) | 0.0136 (11) | 0.0099 (12) |
N3 | 0.0613 (18) | 0.0577 (18) | 0.0493 (16) | −0.0119 (15) | 0.0254 (14) | −0.0097 (14) |
N4 | 0.049 (2) | 0.044 (2) | 0.0371 (19) | 0.000 | 0.0191 (16) | 0.000 |
C1 | 0.0357 (15) | 0.0541 (19) | 0.0358 (15) | 0.0012 (14) | 0.0157 (12) | 0.0024 (14) |
C2 | 0.0398 (16) | 0.0521 (19) | 0.0373 (16) | 0.0012 (14) | 0.0187 (13) | −0.0003 (14) |
C3 | 0.0478 (18) | 0.0541 (19) | 0.0444 (17) | 0.0018 (15) | 0.0209 (14) | 0.0078 (14) |
C4 | 0.0404 (17) | 0.059 (2) | 0.0513 (18) | −0.0002 (15) | 0.0118 (14) | 0.0126 (16) |
C5 | 0.057 (2) | 0.076 (3) | 0.071 (2) | 0.0077 (19) | 0.0325 (19) | 0.024 (2) |
C6 | 0.074 (3) | 0.098 (3) | 0.093 (3) | 0.013 (3) | 0.046 (3) | 0.040 (3) |
C7 | 0.075 (3) | 0.094 (3) | 0.099 (3) | 0.003 (3) | 0.036 (3) | 0.045 (3) |
C8 | 0.071 (3) | 0.070 (3) | 0.104 (3) | 0.010 (2) | 0.025 (3) | 0.033 (3) |
C9 | 0.052 (2) | 0.068 (2) | 0.081 (3) | 0.0093 (18) | 0.023 (2) | 0.021 (2) |
C10 | 0.0371 (18) | 0.077 (3) | 0.058 (2) | −0.0061 (17) | 0.0104 (15) | 0.0104 (18) |
C11 | 0.068 (2) | 0.056 (2) | 0.0398 (17) | −0.0015 (17) | 0.0263 (16) | −0.0037 (15) |
C12 | 0.080 (3) | 0.055 (2) | 0.0427 (18) | −0.0036 (19) | 0.0322 (18) | −0.0075 (15) |
C13 | 0.113 (4) | 0.060 (3) | 0.064 (2) | −0.011 (2) | 0.041 (3) | −0.009 (2) |
C14 | 0.161 (6) | 0.059 (3) | 0.084 (3) | 0.018 (3) | 0.058 (4) | 0.005 (2) |
C15 | 0.126 (5) | 0.101 (5) | 0.088 (4) | 0.042 (4) | 0.051 (4) | 0.004 (3) |
C16 | 0.084 (3) | 0.107 (4) | 0.074 (3) | 0.021 (3) | 0.035 (2) | −0.008 (3) |
C17 | 0.076 (3) | 0.072 (3) | 0.058 (2) | 0.002 (2) | 0.032 (2) | −0.0091 (19) |
C18 | 0.070 (3) | 0.094 (3) | 0.072 (3) | −0.023 (2) | 0.029 (2) | −0.011 (2) |
Geometric parameters (Å, º) top Cd1—N1 | 2.295 (3) | C6—H6 | 0.9400 |
Cd1—N2i | 2.599 (3) | C7—C8 | 1.380 (7) |
Cd1—N2 | 2.599 (3) | C7—H7 | 0.9400 |
Cd1—I1i | 2.7038 (3) | C8—C9 | 1.386 (6) |
Cd1—I1 | 2.7038 (3) | C8—H8 | 0.9400 |
N1—C1 | 1.338 (3) | C9—H9 | 0.9400 |
N1—C1i | 1.338 (3) | C10—H10A | 0.9700 |
N2—C4 | 1.454 (4) | C10—H10B | 0.9700 |
N2—C3 | 1.475 (4) | C10—H10C | 0.9700 |
N2—C10 | 1.484 (4) | C11—H11A | 0.9800 |
N3—C12 | 1.388 (5) | C11—H11B | 0.9800 |
N3—C11 | 1.440 (4) | C12—C17 | 1.394 (6) |
N3—C18 | 1.440 (5) | C12—C13 | 1.398 (5) |
N4—C2 | 1.335 (4) | C13—C14 | 1.402 (7) |
N4—C2i | 1.335 (4) | C13—H13 | 0.9400 |
C1—C2 | 1.392 (5) | C14—C15 | 1.360 (9) |
C1—C3 | 1.506 (4) | C14—H14 | 0.9400 |
C2—C11 | 1.511 (4) | C15—C16 | 1.364 (8) |
C3—H3A | 0.9800 | C15—H15 | 0.9400 |
C3—H3B | 0.9800 | C16—C17 | 1.370 (6) |
C4—C5 | 1.376 (5) | C16—H16 | 0.9400 |
C4—C9 | 1.386 (5) | C17—H17 | 0.9400 |
C5—C6 | 1.390 (5) | C18—H18A | 0.9700 |
C5—H5 | 0.9400 | C18—H18B | 0.9700 |
C6—C7 | 1.363 (7) | C18—H18C | 0.9700 |
| | | |
N1—Cd1—N2i | 69.65 (6) | C6—C7—H7 | 120.5 |
N1—Cd1—N2 | 69.65 (6) | C8—C7—H7 | 120.5 |
N2i—Cd1—N2 | 139.31 (12) | C7—C8—C9 | 120.7 (4) |
N1—Cd1—I1i | 114.551 (10) | C7—C8—H8 | 119.6 |
N2i—Cd1—I1i | 101.29 (6) | C9—C8—H8 | 119.6 |
N1—Cd1—I1 | 114.551 (10) | C8—C9—C4 | 120.1 (4) |
N2i—Cd1—I1 | 95.35 (6) | C8—C9—H9 | 120.0 |
N2—Cd1—I1i | 95.35 (6) | C4—C9—H9 | 120.0 |
N2—Cd1—I1 | 101.29 (6) | N2—C10—H10A | 109.5 |
I1i—Cd1—I1 | 130.90 (2) | N2—C10—H10B | 109.5 |
C1—N1—C1i | 120.2 (4) | H10A—C10—H10B | 109.5 |
C1—N1—Cd1 | 119.92 (19) | N2—C10—H10C | 109.5 |
C1i—N1—Cd1 | 119.92 (19) | H10A—C10—H10C | 109.5 |
C4—N2—C3 | 113.3 (3) | H10B—C10—H10C | 109.5 |
C4—N2—C10 | 111.0 (2) | N3—C11—C2 | 114.4 (3) |
C3—N2—C10 | 109.6 (3) | N3—C11—H11A | 108.7 |
C4—N2—Cd1 | 111.3 (2) | C2—C11—H11A | 108.7 |
C3—N2—Cd1 | 101.28 (17) | N3—C11—H11B | 108.7 |
C10—N2—Cd1 | 110.0 (2) | C2—C11—H11B | 108.7 |
C12—N3—C11 | 120.8 (3) | H11A—C11—H11B | 107.6 |
C12—N3—C18 | 120.1 (3) | N3—C12—C17 | 121.8 (3) |
C11—N3—C18 | 116.6 (3) | N3—C12—C13 | 121.4 (4) |
C2—N4—C2i | 118.9 (4) | C17—C12—C13 | 116.8 (4) |
N1—C1—C2 | 119.5 (3) | C12—C13—C14 | 119.6 (5) |
N1—C1—C3 | 116.7 (3) | C12—C13—H13 | 120.2 |
C2—C1—C3 | 123.7 (3) | C14—C13—H13 | 120.2 |
N4—C2—C1 | 120.9 (3) | C15—C14—C13 | 122.1 (5) |
N4—C2—C11 | 117.2 (3) | C15—C14—H14 | 118.9 |
C1—C2—C11 | 121.9 (3) | C13—C14—H14 | 118.9 |
N2—C3—C1 | 111.4 (3) | C14—C15—C16 | 118.4 (5) |
N2—C3—H3A | 109.3 | C14—C15—H15 | 120.8 |
C1—C3—H3A | 109.3 | C16—C15—H15 | 120.8 |
N2—C3—H3B | 109.3 | C15—C16—C17 | 121.0 (5) |
C1—C3—H3B | 109.3 | C15—C16—H16 | 119.5 |
H3A—C3—H3B | 108.0 | C17—C16—H16 | 119.5 |
C5—C4—C9 | 118.9 (3) | C16—C17—C12 | 122.1 (4) |
C5—C4—N2 | 123.7 (3) | C16—C17—H17 | 118.9 |
C9—C4—N2 | 117.4 (3) | C12—C17—H17 | 118.9 |
C4—C5—C6 | 120.5 (4) | N3—C18—H18A | 109.5 |
C4—C5—H5 | 119.8 | N3—C18—H18B | 109.5 |
C6—C5—H5 | 119.8 | H18A—C18—H18B | 109.5 |
C7—C6—C5 | 120.7 (4) | N3—C18—H18C | 109.5 |
C7—C6—H6 | 119.6 | H18A—C18—H18C | 109.5 |
C5—C6—H6 | 119.6 | H18B—C18—H18C | 109.5 |
C6—C7—C8 | 119.1 (4) | | |
| | | |
C1i—N1—C1—C2 | 2.3 (2) | C4—C5—C6—C7 | 0.0 (7) |
Cd1—N1—C1—C2 | −177.7 (2) | C5—C6—C7—C8 | −0.5 (8) |
C1i—N1—C1—C3 | −173.3 (3) | C6—C7—C8—C9 | 1.2 (7) |
Cd1—N1—C1—C3 | 6.7 (3) | C7—C8—C9—C4 | −1.6 (7) |
C2i—N4—C2—C1 | 2.3 (2) | C5—C4—C9—C8 | 1.1 (6) |
C2i—N4—C2—C11 | −177.0 (3) | N2—C4—C9—C8 | 179.4 (4) |
N1—C1—C2—N4 | −4.7 (4) | C12—N3—C11—C2 | −82.7 (4) |
C3—C1—C2—N4 | 170.6 (3) | C18—N3—C11—C2 | 79.2 (4) |
N1—C1—C2—C11 | 174.6 (3) | N4—C2—C11—N3 | 10.3 (4) |
C3—C1—C2—C11 | −10.1 (5) | C1—C2—C11—N3 | −169.0 (3) |
C4—N2—C3—C1 | 167.5 (3) | C11—N3—C12—C17 | −6.2 (5) |
C10—N2—C3—C1 | −68.0 (3) | C18—N3—C12—C17 | −167.4 (3) |
Cd1—N2—C3—C1 | 48.2 (3) | C11—N3—C12—C13 | 176.2 (3) |
N1—C1—C3—N2 | −41.9 (4) | C18—N3—C12—C13 | 15.0 (5) |
C2—C1—C3—N2 | 142.8 (3) | N3—C12—C13—C14 | 178.1 (4) |
C3—N2—C4—C5 | 5.8 (4) | C17—C12—C13—C14 | 0.3 (6) |
C10—N2—C4—C5 | −118.0 (4) | C12—C13—C14—C15 | 0.6 (7) |
Cd1—N2—C4—C5 | 119.1 (3) | C13—C14—C15—C16 | −1.3 (8) |
C3—N2—C4—C9 | −172.4 (3) | C14—C15—C16—C17 | 1.2 (8) |
C10—N2—C4—C9 | 63.8 (4) | C15—C16—C17—C12 | −0.3 (7) |
Cd1—N2—C4—C9 | −59.1 (3) | N3—C12—C17—C16 | −178.2 (3) |
C9—C4—C5—C6 | −0.3 (6) | C13—C12—C17—C16 | −0.5 (5) |
N2—C4—C5—C6 | −178.5 (4) | | |
Symmetry code: (i) −x+3/2, y, −z. |
Hydrogen-bond geometry (Å, º) topCg3 is the centroid of the pyrazine ring N1/N4/C1/C2/C1i/C2i and Cg5 is the centroid of the C12–C17 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18C···Cg5i | 0.97 | 2.95 | 3.896 (5) | 165 |
C17—H17···I1ii | 0.94 | 3.09 | 3.907 (4) | 147 |
Cd1—I1···Cgiii | 2.70 (1) | 3.96 (1) | 6.5131 (12) | 155 (1) |
Cd1—I1···Cg3iv | 2.70 (1) | 3.96 (1) | 6.5131 (12) | 155 (1) |
Symmetry codes: (i) −x+3/2, y, −z; (ii) x+1/2, −y, z; (iii) −x+1, −y, −z; (iv) x−1/2, −y, z. |
Dichorido{
N,
N',
N'',
N'''-[pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(
N-methylaniline)-
κ3N2,
N1,
N6}zinc(II) dichloromethane 0.6-solvate (II)
top Crystal data top [ZnCl2(C36H40N6)]·0.6CH2Cl2 | Z = 2 |
Mr = 743.99 | F(000) = 774.4 |
Triclinic, P1 | Dx = 1.340 Mg m−3 |
a = 11.9196 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.1208 (8) Å | Cell parameters from 5000 reflections |
c = 13.919 (1) Å | θ = 1.7–26.1° |
α = 98.222 (8)° | µ = 0.93 mm−1 |
β = 100.313 (8)° | T = 223 K |
γ = 107.580 (7)° | Rod, yellow |
V = 1843.9 (2) Å3 | 0.30 × 0.10 × 0.10 mm |
Data collection top STOE IPDS 1 diffractometer | 6654 independent reflections |
Radiation source: fine-focus sealed tube | 3490 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.054 |
φ rotation scans | θmax = 25.9°, θmin = 2.1° |
Absorption correction: multi-scan (MULABS; Spek, 2009) | h = −14→13 |
Tmin = 0.983, Tmax = 1.000 | k = −13→14 |
14512 measured reflections | l = −17→17 |
Refinement top Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 0.79 | w = 1/[σ2(Fo2) + (0.0649P)2] where P = (Fo2 + 2Fc2)/3 |
6654 reflections | (Δ/σ)max = 0.028 |
437 parameters | Δρmax = 0.75 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
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 | Occ. (<1) |
Zn1 | 0.35680 (4) | 0.17960 (5) | 0.48236 (4) | 0.03370 (16) | |
Cl1 | 0.26266 (9) | 0.31262 (9) | 0.48265 (8) | 0.0379 (3) | |
Cl2 | 0.33732 (10) | 0.02609 (9) | 0.55847 (8) | 0.0383 (3) | |
N1 | 0.4877 (3) | 0.2055 (3) | 0.4016 (2) | 0.0294 (8) | |
N2 | 0.2552 (3) | 0.0630 (3) | 0.3191 (2) | 0.0354 (8) | |
N3 | 0.6536 (3) | 0.0643 (4) | 0.1349 (3) | 0.0463 (10) | |
N4 | 0.6673 (3) | 0.2247 (3) | 0.3005 (2) | 0.0353 (9) | |
N5 | 0.5392 (3) | 0.3173 (3) | 0.5955 (2) | 0.0297 (8) | |
N6 | 0.9012 (3) | 0.3813 (4) | 0.3867 (3) | 0.0440 (10) | |
C1 | 0.4709 (4) | 0.1232 (4) | 0.3201 (3) | 0.0309 (10) | |
C2 | 0.5649 (4) | 0.1337 (4) | 0.2698 (3) | 0.0318 (10) | |
C3 | 0.3531 (4) | 0.0225 (4) | 0.2939 (3) | 0.0370 (10) | |
H3A | 0.332467 | −0.012157 | 0.222331 | 0.044* | |
H3B | 0.361523 | −0.039048 | 0.330527 | 0.044* | |
C4 | 0.1483 (4) | −0.0309 (4) | 0.3234 (3) | 0.0380 (11) | |
C5 | 0.1318 (4) | −0.1506 (4) | 0.2941 (3) | 0.0440 (11) | |
H5 | 0.189961 | −0.173802 | 0.267030 | 0.053* | |
C6 | 0.0295 (4) | −0.2354 (5) | 0.3049 (3) | 0.0524 (13) | |
H6 | 0.020101 | −0.315972 | 0.286843 | 0.063* | |
C7 | −0.0586 (5) | −0.2035 (6) | 0.3417 (4) | 0.0615 (15) | |
H7 | −0.128003 | −0.261909 | 0.348052 | 0.074* | |
C8 | −0.0441 (4) | −0.0849 (6) | 0.3691 (4) | 0.0618 (15) | |
H8 | −0.104135 | −0.062684 | 0.393942 | 0.074* | |
C9 | 0.0583 (4) | 0.0012 (5) | 0.3603 (4) | 0.0518 (13) | |
H9 | 0.067382 | 0.081656 | 0.379134 | 0.062* | |
C10 | 0.2243 (4) | 0.1374 (4) | 0.2491 (3) | 0.0492 (12) | |
H10C | 0.195802 | 0.090689 | 0.181450 | 0.074* | |
H10B | 0.295684 | 0.204609 | 0.253252 | 0.074* | |
H10A | 0.161260 | 0.165493 | 0.267231 | 0.074* | |
C11 | 0.5545 (4) | 0.0370 (4) | 0.1832 (3) | 0.0458 (12) | |
H11A | 0.549429 | −0.035832 | 0.207651 | 0.055* | |
H11B | 0.479057 | 0.021761 | 0.133629 | 0.055* | |
C12 | 0.6568 (4) | 0.1362 (4) | 0.0662 (3) | 0.0447 (12) | |
C13 | 0.7525 (5) | 0.1612 (5) | 0.0174 (4) | 0.0666 (16) | |
H13 | 0.814974 | 0.129703 | 0.032399 | 0.080* | |
C14 | 0.7552 (7) | 0.2312 (7) | −0.0519 (5) | 0.087 (2) | |
H14 | 0.820382 | 0.246888 | −0.083057 | 0.105* | |
C15 | 0.6682 (9) | 0.2781 (6) | −0.0769 (5) | 0.098 (3) | |
H15 | 0.671980 | 0.325867 | −0.124647 | 0.117* | |
C16 | 0.5726 (7) | 0.2540 (6) | −0.0303 (4) | 0.086 (2) | |
H16 | 0.510787 | 0.285978 | −0.046768 | 0.103* | |
C17 | 0.5667 (5) | 0.1833 (5) | 0.0405 (4) | 0.0599 (14) | |
H17 | 0.500786 | 0.167545 | 0.070873 | 0.072* | |
C18 | 0.7620 (6) | 0.0419 (6) | 0.1793 (4) | 0.086 (2) | |
H18C | 0.779738 | −0.012043 | 0.130429 | 0.129* | |
H18B | 0.749440 | 0.006775 | 0.236560 | 0.129* | |
H18A | 0.829462 | 0.115809 | 0.200454 | 0.129* | |
C21 | 0.5910 (4) | 0.2969 (4) | 0.4341 (3) | 0.0288 (9) | |
C22 | 0.6828 (3) | 0.3080 (4) | 0.3814 (3) | 0.0310 (10) | |
C23 | 0.5972 (4) | 0.3833 (4) | 0.5261 (3) | 0.0324 (10) | |
H23A | 0.681896 | 0.429429 | 0.558643 | 0.039* | |
H23B | 0.555559 | 0.438161 | 0.507247 | 0.039* | |
C24 | 0.5072 (4) | 0.3885 (4) | 0.6722 (3) | 0.0317 (10) | |
C25 | 0.5468 (4) | 0.5100 (4) | 0.6919 (3) | 0.0362 (10) | |
H25 | 0.599552 | 0.551869 | 0.656583 | 0.043* | |
C26 | 0.5080 (4) | 0.5711 (4) | 0.7651 (3) | 0.0448 (12) | |
H26 | 0.533850 | 0.654230 | 0.778053 | 0.054* | |
C27 | 0.4327 (4) | 0.5106 (5) | 0.8179 (3) | 0.0487 (13) | |
H27 | 0.407923 | 0.552419 | 0.867503 | 0.058* | |
C28 | 0.3934 (4) | 0.3893 (5) | 0.7988 (3) | 0.0489 (12) | |
H28 | 0.341885 | 0.347757 | 0.835120 | 0.059* | |
C29 | 0.4302 (4) | 0.3282 (4) | 0.7255 (3) | 0.0440 (12) | |
H29 | 0.402641 | 0.245046 | 0.711871 | 0.053* | |
C30 | 0.6175 (4) | 0.2547 (4) | 0.6402 (3) | 0.0432 (12) | |
H30C | 0.693683 | 0.312083 | 0.679612 | 0.065* | |
H30B | 0.632752 | 0.203586 | 0.587463 | 0.065* | |
H30A | 0.577342 | 0.207377 | 0.682678 | 0.065* | |
C31 | 0.7994 (4) | 0.4100 (4) | 0.4112 (3) | 0.0463 (12) | |
H31A | 0.788908 | 0.473627 | 0.378260 | 0.056* | |
H31B | 0.817746 | 0.440047 | 0.483454 | 0.056* | |
C32 | 0.9419 (4) | 0.4069 (4) | 0.3029 (3) | 0.0368 (10) | |
C33 | 1.0564 (4) | 0.4040 (5) | 0.2933 (3) | 0.0509 (13) | |
H33 | 1.103887 | 0.380026 | 0.342028 | 0.061* | |
C34 | 1.0987 (5) | 0.4367 (6) | 0.2120 (4) | 0.0689 (17) | |
H34 | 1.175749 | 0.434902 | 0.207024 | 0.083* | |
C35 | 1.0337 (5) | 0.4715 (5) | 0.1385 (4) | 0.0710 (17) | |
H35 | 1.065545 | 0.495398 | 0.084821 | 0.085* | |
C36 | 0.9177 (5) | 0.4703 (5) | 0.1459 (4) | 0.0608 (14) | |
H36 | 0.869357 | 0.490972 | 0.095273 | 0.073* | |
C37 | 0.8741 (4) | 0.4395 (4) | 0.2261 (3) | 0.0480 (12) | |
H37 | 0.796333 | 0.440162 | 0.229773 | 0.058* | |
C38 | 0.9460 (5) | 0.3087 (5) | 0.4473 (4) | 0.0611 (15) | |
H38C | 0.951629 | 0.241231 | 0.404214 | 0.092* | |
H38B | 0.890860 | 0.281192 | 0.489074 | 0.092* | |
H38A | 1.025495 | 0.355234 | 0.489222 | 0.092* | |
C40 | 0.1063 (10) | 0.2516 (11) | 0.9543 (8) | 0.095 (4) | 0.6 |
H40A | 0.053445 | 0.294842 | 0.973082 | 0.114* | 0.6 |
H40B | 0.103192 | 0.249458 | 0.883154 | 0.114* | 0.6 |
Cl3 | 0.2564 (2) | 0.3346 (3) | 1.02194 (16) | 0.0912 (10) | 0.6 |
Cl4 | 0.0491 (3) | 0.1163 (3) | 0.9673 (2) | 0.1003 (10) | 0.6 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0365 (3) | 0.0345 (3) | 0.0385 (3) | 0.0163 (3) | 0.0187 (2) | 0.0121 (2) |
Cl1 | 0.0334 (6) | 0.0367 (7) | 0.0497 (6) | 0.0193 (6) | 0.0121 (5) | 0.0092 (5) |
Cl2 | 0.0485 (7) | 0.0319 (6) | 0.0394 (6) | 0.0134 (6) | 0.0156 (5) | 0.0167 (5) |
N1 | 0.032 (2) | 0.031 (2) | 0.0280 (18) | 0.0121 (19) | 0.0103 (15) | 0.0056 (15) |
N2 | 0.032 (2) | 0.033 (2) | 0.044 (2) | 0.0111 (19) | 0.0145 (16) | 0.0112 (16) |
N3 | 0.052 (2) | 0.052 (3) | 0.043 (2) | 0.023 (2) | 0.0239 (19) | 0.0053 (19) |
N4 | 0.037 (2) | 0.035 (2) | 0.036 (2) | 0.011 (2) | 0.0168 (16) | 0.0051 (17) |
N5 | 0.037 (2) | 0.029 (2) | 0.0307 (18) | 0.0164 (18) | 0.0140 (15) | 0.0092 (15) |
N6 | 0.034 (2) | 0.059 (3) | 0.046 (2) | 0.018 (2) | 0.0189 (18) | 0.0173 (19) |
C1 | 0.034 (2) | 0.028 (3) | 0.033 (2) | 0.011 (2) | 0.0123 (18) | 0.0089 (19) |
C2 | 0.037 (3) | 0.029 (3) | 0.033 (2) | 0.013 (2) | 0.0150 (19) | 0.0061 (18) |
C3 | 0.037 (3) | 0.031 (3) | 0.042 (3) | 0.010 (2) | 0.013 (2) | 0.003 (2) |
C4 | 0.032 (2) | 0.038 (3) | 0.040 (2) | 0.005 (2) | 0.0093 (19) | 0.010 (2) |
C5 | 0.044 (3) | 0.037 (3) | 0.046 (3) | 0.007 (3) | 0.011 (2) | 0.007 (2) |
C6 | 0.050 (3) | 0.043 (3) | 0.050 (3) | −0.002 (3) | 0.006 (2) | 0.009 (2) |
C7 | 0.042 (3) | 0.071 (5) | 0.055 (3) | −0.007 (3) | 0.013 (3) | 0.015 (3) |
C8 | 0.036 (3) | 0.079 (5) | 0.063 (3) | 0.007 (3) | 0.020 (2) | 0.006 (3) |
C9 | 0.038 (3) | 0.051 (3) | 0.064 (3) | 0.011 (3) | 0.019 (2) | 0.003 (3) |
C10 | 0.049 (3) | 0.048 (3) | 0.049 (3) | 0.015 (3) | 0.005 (2) | 0.019 (2) |
C11 | 0.055 (3) | 0.038 (3) | 0.044 (3) | 0.012 (3) | 0.024 (2) | −0.001 (2) |
C12 | 0.052 (3) | 0.046 (3) | 0.029 (2) | 0.011 (3) | 0.012 (2) | −0.006 (2) |
C13 | 0.060 (3) | 0.078 (5) | 0.044 (3) | −0.003 (3) | 0.024 (3) | −0.002 (3) |
C14 | 0.090 (5) | 0.095 (6) | 0.047 (4) | −0.012 (5) | 0.026 (4) | 0.002 (4) |
C15 | 0.149 (8) | 0.071 (5) | 0.036 (4) | −0.011 (5) | 0.017 (4) | 0.005 (3) |
C16 | 0.141 (7) | 0.066 (4) | 0.038 (3) | 0.042 (5) | −0.004 (4) | −0.007 (3) |
C17 | 0.080 (4) | 0.058 (4) | 0.039 (3) | 0.025 (3) | 0.014 (3) | −0.001 (2) |
C18 | 0.086 (4) | 0.122 (6) | 0.081 (4) | 0.072 (5) | 0.032 (4) | 0.023 (4) |
C21 | 0.032 (2) | 0.028 (3) | 0.028 (2) | 0.011 (2) | 0.0081 (18) | 0.0060 (18) |
C22 | 0.028 (2) | 0.032 (3) | 0.036 (2) | 0.011 (2) | 0.0136 (18) | 0.0078 (19) |
C23 | 0.033 (2) | 0.031 (3) | 0.035 (2) | 0.011 (2) | 0.0126 (19) | 0.0058 (19) |
C24 | 0.033 (2) | 0.035 (3) | 0.028 (2) | 0.015 (2) | 0.0075 (18) | 0.0027 (18) |
C25 | 0.039 (3) | 0.038 (3) | 0.034 (2) | 0.016 (2) | 0.0104 (19) | 0.006 (2) |
C26 | 0.056 (3) | 0.042 (3) | 0.038 (3) | 0.020 (3) | 0.014 (2) | −0.001 (2) |
C27 | 0.054 (3) | 0.060 (4) | 0.036 (3) | 0.029 (3) | 0.014 (2) | −0.002 (2) |
C28 | 0.053 (3) | 0.060 (4) | 0.040 (3) | 0.021 (3) | 0.023 (2) | 0.010 (2) |
C29 | 0.058 (3) | 0.040 (3) | 0.038 (3) | 0.016 (3) | 0.023 (2) | 0.006 (2) |
C30 | 0.050 (3) | 0.050 (3) | 0.039 (3) | 0.031 (3) | 0.009 (2) | 0.008 (2) |
C31 | 0.039 (3) | 0.046 (3) | 0.052 (3) | 0.008 (3) | 0.025 (2) | −0.001 (2) |
C32 | 0.031 (2) | 0.038 (3) | 0.036 (2) | 0.007 (2) | 0.0075 (19) | −0.001 (2) |
C33 | 0.039 (3) | 0.076 (4) | 0.040 (3) | 0.021 (3) | 0.015 (2) | 0.008 (2) |
C34 | 0.048 (3) | 0.105 (5) | 0.052 (3) | 0.021 (4) | 0.024 (3) | 0.007 (3) |
C35 | 0.076 (4) | 0.092 (5) | 0.041 (3) | 0.016 (4) | 0.027 (3) | 0.011 (3) |
C36 | 0.077 (4) | 0.051 (4) | 0.046 (3) | 0.012 (3) | 0.008 (3) | 0.015 (3) |
C37 | 0.043 (3) | 0.045 (3) | 0.054 (3) | 0.012 (3) | 0.011 (2) | 0.011 (2) |
C38 | 0.046 (3) | 0.082 (4) | 0.058 (3) | 0.019 (3) | 0.013 (3) | 0.030 (3) |
C40 | 0.082 (8) | 0.114 (10) | 0.084 (8) | 0.037 (8) | −0.013 (6) | 0.038 (7) |
Cl3 | 0.0444 (13) | 0.179 (3) | 0.0384 (12) | 0.0251 (17) | 0.0150 (10) | 0.0076 (15) |
Cl4 | 0.088 (2) | 0.098 (3) | 0.115 (2) | 0.043 (2) | 0.0134 (18) | 0.0124 (19) |
Geometric parameters (Å, º) top Zn1—N1 | 2.057 (3) | C15—C16 | 1.386 (10) |
Zn1—N2 | 2.385 (3) | C15—H15 | 0.9400 |
Zn1—N5 | 2.413 (3) | C16—C17 | 1.394 (8) |
Zn1—Cl1 | 2.2251 (10) | C16—H16 | 0.9400 |
Zn1—Cl2 | 2.2425 (11) | C17—H17 | 0.9400 |
N1—C21 | 1.334 (5) | C18—H18C | 0.9700 |
N1—C1 | 1.340 (5) | C18—H18B | 0.9700 |
N2—C4 | 1.446 (5) | C18—H18A | 0.9700 |
N2—C3 | 1.473 (5) | C21—C22 | 1.407 (5) |
N2—C10 | 1.491 (5) | C21—C23 | 1.509 (5) |
N3—C12 | 1.381 (6) | C22—C31 | 1.497 (6) |
N3—C18 | 1.449 (6) | C23—H23A | 0.9800 |
N3—C11 | 1.438 (5) | C23—H23B | 0.9800 |
N4—C2 | 1.325 (5) | C24—C25 | 1.373 (6) |
N4—C22 | 1.345 (5) | C24—C29 | 1.386 (6) |
N5—C24 | 1.453 (5) | C25—C26 | 1.399 (5) |
N5—C30 | 1.480 (5) | C25—H25 | 0.9400 |
N5—C23 | 1.476 (5) | C26—C27 | 1.371 (7) |
N6—C32 | 1.380 (5) | C26—H26 | 0.9400 |
N6—C31 | 1.441 (5) | C27—C28 | 1.371 (7) |
N6—C38 | 1.451 (6) | C27—H27 | 0.9400 |
C1—C2 | 1.408 (5) | C28—C29 | 1.385 (6) |
C1—C3 | 1.500 (6) | C28—H28 | 0.9400 |
C2—C11 | 1.516 (5) | C29—H29 | 0.9400 |
C3—H3A | 0.9800 | C30—H30C | 0.9700 |
C3—H3B | 0.9800 | C30—H30B | 0.9700 |
C4—C5 | 1.393 (6) | C30—H30A | 0.9700 |
C4—C9 | 1.400 (6) | C31—H31A | 0.9800 |
C5—C6 | 1.385 (6) | C31—H31B | 0.9800 |
C5—H5 | 0.9400 | C32—C37 | 1.399 (6) |
C6—C7 | 1.376 (7) | C32—C33 | 1.404 (6) |
C6—H6 | 0.9400 | C33—C34 | 1.380 (7) |
C7—C8 | 1.383 (8) | C33—H33 | 0.9400 |
C7—H7 | 0.9400 | C34—C35 | 1.365 (7) |
C8—C9 | 1.384 (7) | C34—H34 | 0.9400 |
C8—H8 | 0.9400 | C35—C36 | 1.401 (7) |
C9—H9 | 0.9400 | C35—H35 | 0.9400 |
C10—H10C | 0.9700 | C36—C37 | 1.365 (7) |
C10—H10B | 0.9700 | C36—H36 | 0.9400 |
C10—H10A | 0.9700 | C37—H37 | 0.9400 |
C11—H11A | 0.9800 | C38—H38C | 0.9700 |
C11—H11B | 0.9800 | C38—H38B | 0.9700 |
C12—C17 | 1.378 (6) | C38—H38A | 0.9700 |
C12—C13 | 1.408 (7) | C40—Cl4 | 1.625 (12) |
C13—C14 | 1.370 (9) | C40—Cl3 | 1.772 (11) |
C13—H13 | 0.9400 | C40—H40A | 0.9800 |
C14—C15 | 1.343 (9) | C40—H40B | 0.9800 |
C14—H14 | 0.9400 | | |
| | | |
N1—Zn1—N2 | 75.02 (12) | C16—C15—H15 | 121.0 |
N1—Zn1—N5 | 74.23 (12) | C17—C16—C15 | 121.2 (6) |
N2—Zn1—N5 | 149.21 (11) | C17—C16—H16 | 119.4 |
N1—Zn1—Cl1 | 114.15 (9) | C15—C16—H16 | 119.4 |
N1—Zn1—Cl2 | 114.68 (9) | C12—C17—C16 | 120.4 (6) |
Cl1—Zn1—N2 | 98.12 (8) | C12—C17—H17 | 119.8 |
Cl2—Zn1—N2 | 95.70 (9) | C16—C17—H17 | 119.8 |
Cl1—Zn1—N5 | 93.02 (7) | N3—C18—H18C | 109.5 |
Cl2—Zn1—N5 | 98.34 (8) | N3—C18—H18B | 109.5 |
Cl1—Zn1—Cl2 | 131.14 (4) | H18C—C18—H18B | 109.5 |
C21—N1—C1 | 120.8 (3) | N3—C18—H18A | 109.5 |
C21—N1—Zn1 | 120.7 (2) | H18C—C18—H18A | 109.5 |
C1—N1—Zn1 | 118.3 (3) | H18B—C18—H18A | 109.5 |
C4—N2—C3 | 114.5 (3) | N1—C21—C22 | 119.6 (3) |
C4—N2—C10 | 111.2 (3) | N1—C21—C23 | 115.2 (3) |
C3—N2—C10 | 109.9 (3) | C22—C21—C23 | 125.1 (4) |
C4—N2—Zn1 | 110.2 (2) | N4—C22—C21 | 119.8 (4) |
C3—N2—Zn1 | 99.2 (2) | N4—C22—C31 | 117.4 (3) |
C10—N2—Zn1 | 111.3 (3) | C21—C22—C31 | 122.8 (4) |
C12—N3—C18 | 120.4 (4) | N5—C23—C21 | 109.2 (3) |
C12—N3—C11 | 120.1 (4) | N5—C23—H23A | 109.8 |
C18—N3—C11 | 117.4 (4) | C21—C23—H23A | 109.8 |
C2—N4—C22 | 119.8 (3) | N5—C23—H23B | 109.8 |
C24—N5—C30 | 111.1 (3) | C21—C23—H23B | 109.8 |
C24—N5—C23 | 114.7 (3) | H23A—C23—H23B | 108.3 |
C30—N5—C23 | 109.3 (3) | C25—C24—C29 | 119.5 (4) |
C24—N5—Zn1 | 109.4 (2) | C25—C24—N5 | 123.5 (4) |
C30—N5—Zn1 | 111.1 (3) | C29—C24—N5 | 117.0 (4) |
C23—N5—Zn1 | 100.9 (2) | C24—C25—C26 | 119.4 (4) |
C32—N6—C31 | 122.1 (4) | C24—C25—H25 | 120.3 |
C32—N6—C38 | 122.1 (3) | C26—C25—H25 | 120.3 |
C31—N6—C38 | 115.2 (4) | C27—C26—C25 | 120.5 (4) |
N1—C1—C2 | 118.9 (4) | C27—C26—H26 | 119.7 |
N1—C1—C3 | 115.6 (3) | C25—C26—H26 | 119.7 |
C2—C1—C3 | 125.4 (4) | C28—C27—C26 | 120.2 (4) |
N4—C2—C1 | 120.9 (4) | C28—C27—H27 | 119.9 |
N4—C2—C11 | 118.2 (3) | C26—C27—H27 | 119.9 |
C1—C2—C11 | 120.7 (4) | C27—C28—C29 | 119.6 (4) |
N2—C3—C1 | 110.9 (3) | C27—C28—H28 | 120.2 |
N2—C3—H3A | 109.5 | C29—C28—H28 | 120.2 |
C1—C3—H3A | 109.5 | C28—C29—C24 | 120.7 (4) |
N2—C3—H3B | 109.5 | C28—C29—H29 | 119.6 |
C1—C3—H3B | 109.5 | C24—C29—H29 | 119.6 |
H3A—C3—H3B | 108.1 | N5—C30—H30C | 109.5 |
C5—C4—C9 | 118.8 (4) | N5—C30—H30B | 109.5 |
C5—C4—N2 | 123.3 (4) | H30C—C30—H30B | 109.5 |
C9—C4—N2 | 117.8 (4) | N5—C30—H30A | 109.5 |
C6—C5—C4 | 120.0 (4) | H30C—C30—H30A | 109.5 |
C6—C5—H5 | 120.0 | H30B—C30—H30A | 109.5 |
C4—C5—H5 | 120.0 | N6—C31—C22 | 114.2 (4) |
C7—C6—C5 | 121.1 (5) | N6—C31—H31A | 108.7 |
C7—C6—H6 | 119.5 | C22—C31—H31A | 108.7 |
C5—C6—H6 | 119.5 | N6—C31—H31B | 108.7 |
C6—C7—C8 | 119.4 (5) | C22—C31—H31B | 108.7 |
C6—C7—H7 | 120.3 | H31A—C31—H31B | 107.6 |
C8—C7—H7 | 120.3 | N6—C32—C37 | 122.3 (4) |
C7—C8—C9 | 120.5 (5) | N6—C32—C33 | 120.4 (4) |
C7—C8—H8 | 119.8 | C37—C32—C33 | 117.3 (4) |
C9—C8—H8 | 119.8 | C34—C33—C32 | 119.6 (5) |
C8—C9—C4 | 120.3 (5) | C34—C33—H33 | 120.2 |
C8—C9—H9 | 119.9 | C32—C33—H33 | 120.2 |
C4—C9—H9 | 119.9 | C35—C34—C33 | 122.9 (5) |
N2—C10—H10C | 109.5 | C35—C34—H34 | 118.5 |
N2—C10—H10B | 109.5 | C33—C34—H34 | 118.5 |
H10C—C10—H10B | 109.5 | C34—C35—C36 | 117.6 (5) |
N2—C10—H10A | 109.5 | C34—C35—H35 | 121.2 |
H10C—C10—H10A | 109.5 | C36—C35—H35 | 121.2 |
H10B—C10—H10A | 109.5 | C37—C36—C35 | 120.6 (5) |
N3—C11—C2 | 114.2 (4) | C37—C36—H36 | 119.7 |
N3—C11—H11A | 108.7 | C35—C36—H36 | 119.7 |
C2—C11—H11A | 108.7 | C36—C37—C32 | 121.9 (5) |
N3—C11—H11B | 108.7 | C36—C37—H37 | 119.1 |
C2—C11—H11B | 108.7 | C32—C37—H37 | 119.1 |
H11A—C11—H11B | 107.6 | N6—C38—H38C | 109.5 |
C17—C12—N3 | 122.3 (4) | N6—C38—H38B | 109.5 |
C17—C12—C13 | 117.4 (5) | H38C—C38—H38B | 109.5 |
N3—C12—C13 | 120.3 (4) | N6—C38—H38A | 109.5 |
C14—C13—C12 | 120.5 (6) | H38C—C38—H38A | 109.5 |
C14—C13—H13 | 119.8 | H38B—C38—H38A | 109.5 |
C12—C13—H13 | 119.8 | Cl4—C40—Cl3 | 118.1 (6) |
C15—C14—C13 | 122.5 (6) | Cl4—C40—H40A | 107.8 |
C15—C14—H14 | 118.8 | Cl3—C40—H40A | 107.8 |
C13—C14—H14 | 118.8 | Cl4—C40—H40B | 107.8 |
C14—C15—C16 | 118.0 (6) | Cl3—C40—H40B | 107.8 |
C14—C15—H15 | 121.0 | H40A—C40—H40B | 107.1 |
| | | |
C21—N1—C1—C2 | 0.9 (5) | C1—N1—C21—C22 | 0.8 (5) |
Zn1—N1—C1—C2 | −173.8 (3) | Zn1—N1—C21—C22 | 175.4 (3) |
C21—N1—C1—C3 | 177.6 (3) | C1—N1—C21—C23 | 179.5 (3) |
Zn1—N1—C1—C3 | 2.8 (4) | Zn1—N1—C21—C23 | −5.9 (4) |
C22—N4—C2—C1 | 0.6 (6) | C2—N4—C22—C21 | 1.2 (6) |
C22—N4—C2—C11 | −175.4 (4) | C2—N4—C22—C31 | −178.7 (4) |
N1—C1—C2—N4 | −1.7 (6) | N1—C21—C22—N4 | −1.9 (5) |
C3—C1—C2—N4 | −178.0 (4) | C23—C21—C22—N4 | 179.6 (3) |
N1—C1—C2—C11 | 174.2 (4) | N1—C21—C22—C31 | 178.0 (4) |
C3—C1—C2—C11 | −2.0 (6) | C23—C21—C22—C31 | −0.5 (6) |
C4—N2—C3—C1 | −163.3 (3) | C24—N5—C23—C21 | −162.9 (3) |
C10—N2—C3—C1 | 70.8 (4) | C30—N5—C23—C21 | 71.6 (4) |
Zn1—N2—C3—C1 | −46.0 (3) | Zn1—N5—C23—C21 | −45.5 (3) |
N1—C1—C3—N2 | 34.4 (5) | N1—C21—C23—N5 | 39.1 (4) |
C2—C1—C3—N2 | −149.2 (4) | C22—C21—C23—N5 | −142.4 (4) |
C3—N2—C4—C5 | −7.8 (6) | C30—N5—C24—C25 | 112.7 (4) |
C10—N2—C4—C5 | 117.5 (4) | C23—N5—C24—C25 | −11.8 (5) |
Zn1—N2—C4—C5 | −118.6 (4) | Zn1—N5—C24—C25 | −124.3 (3) |
C3—N2—C4—C9 | 171.3 (4) | C30—N5—C24—C29 | −68.9 (5) |
C10—N2—C4—C9 | −63.5 (5) | C23—N5—C24—C29 | 166.6 (3) |
Zn1—N2—C4—C9 | 60.4 (4) | Zn1—N5—C24—C29 | 54.1 (4) |
C9—C4—C5—C6 | −2.2 (6) | C29—C24—C25—C26 | −0.5 (6) |
N2—C4—C5—C6 | 176.9 (4) | N5—C24—C25—C26 | 177.9 (4) |
C4—C5—C6—C7 | 1.9 (7) | C24—C25—C26—C27 | 1.1 (6) |
C5—C6—C7—C8 | −0.6 (7) | C25—C26—C27—C28 | −0.8 (7) |
C6—C7—C8—C9 | −0.3 (8) | C26—C27—C28—C29 | −0.1 (7) |
C7—C8—C9—C4 | 0.0 (8) | C27—C28—C29—C24 | 0.7 (7) |
C5—C4—C9—C8 | 1.2 (7) | C25—C24—C29—C28 | −0.3 (6) |
N2—C4—C9—C8 | −177.9 (4) | N5—C24—C29—C28 | −178.9 (4) |
C12—N3—C11—C2 | −80.2 (5) | C32—N6—C31—C22 | 99.2 (5) |
C18—N3—C11—C2 | 83.5 (5) | C38—N6—C31—C22 | −72.1 (5) |
N4—C2—C11—N3 | −8.2 (6) | N4—C22—C31—N6 | −30.4 (6) |
C1—C2—C11—N3 | 175.7 (4) | C21—C22—C31—N6 | 149.7 (4) |
C18—N3—C12—C17 | −163.8 (5) | C31—N6—C32—C37 | −13.3 (7) |
C11—N3—C12—C17 | −0.6 (7) | C38—N6—C32—C37 | 157.3 (5) |
C18—N3—C12—C13 | 18.0 (7) | C31—N6—C32—C33 | 164.9 (4) |
C11—N3—C12—C13 | −178.8 (4) | C38—N6—C32—C33 | −24.5 (7) |
C17—C12—C13—C14 | 0.8 (8) | N6—C32—C33—C34 | −176.1 (5) |
N3—C12—C13—C14 | 179.1 (5) | C37—C32—C33—C34 | 2.2 (7) |
C12—C13—C14—C15 | −0.4 (10) | C32—C33—C34—C35 | −0.5 (9) |
C13—C14—C15—C16 | 0.0 (10) | C33—C34—C35—C36 | −1.8 (9) |
C14—C15—C16—C17 | 0.0 (9) | C34—C35—C36—C37 | 2.3 (9) |
N3—C12—C17—C16 | −179.1 (5) | C35—C36—C37—C32 | −0.7 (8) |
C13—C12—C17—C16 | −0.8 (7) | N6—C32—C37—C36 | 176.7 (5) |
C15—C16—C17—C12 | 0.4 (8) | C33—C32—C37—C36 | −1.6 (7) |
Hydrogen-bond geometry (Å, º) topCg3 is the centroid of the pyrazine ring N1/N4/C1/C2/C21/C22, and Cg5 and Cg7 are the centroids of rings C12–C17 and C32–C37, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cg7i | 0.94 | 2.88 | 3.814 (6) | 177 |
C11—H11B···Cg5ii | 0.98 | 2.90 | 3.540 (5) | 124 |
C26—H26···Cg3iii | 0.94 | 2.95 | 3.544 (5) | 122 |
Zn1—Cl2···Cg3iv | 2.24 (1) | 3.68 (1) | 5.8035 (19) | 156 (1) |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1. |
A comparison of the conformation of the ligand (L) in complexes I and II topThe definitions of rings A, B, C, D and E are given in Fig. 4. |
Dihedral angle (°) | Ia | II | Δ(I - II)° |
A to B | 41.9 (2) | 35.5 (2) | > 6.4 |
A to C | 86.1 (2) | 87.5 (3) | < 1.4 |
A to D | 41.9 (2) | 34.9 (2) | > 7.0 |
A to E | 86.1 (2) | 74.4 (2) | > 11.7 |
B to C | 54.0 (2) | 53.7 (3) | > 0.3 |
B to D | 38.0 (2) | 26.9 (2) | > 11.1 |
B to E | 63.4 (2) | 71.9 (2) | < 8.5 |
C to D | 63.4 (2) | 58.5 (3) | > 4.9 |
C to E | 24.9 (2) | 18.3 (3) | > 6.6 |
D to E | 54.0 (2) | 74.9 (2) | < 20.9 |
Note: (a) D = Bi, E = Ci; symmetry code: (i) -x + 3/2, y, -z. |
Summary of interatomic contacts (Å)a, shorter than the sum of the van der Waals radii, in the crystal structures of I and II topContact | Length | Length - vdW | Symmetry operation |
I | | | |
C11···C12 | 3.278 | -0.122 | 3/2 - x, -1/2 - y, -1/2 - z |
C12···H11A | 2.805 | -0.095 | 3/2 - x, -1/2 - y, -1/2 - z |
I1···H17 | 3.087 | -0.093 | -1/2 + x, -y, z |
N3···H11B | 2.671 | -0.079 | 3/2 - x, -1/2 - y, -1/2 - z |
N3···C11 | 3.234 | -0.016 | 3/2 - x, -1/2 - y, -1/2 - z |
| | | |
II | | | |
Cl4···Cl4 | 3.045 | -0.455 | -x, -y, 2 - z |
C6···H40B | 2.758 | -0.142 | -x, -y, 1 - z |
C30···H3B | 2.779 | -0.121 | 1 - x, -y, 1 - z |
H23B···H23B | 2.287 | -0.113 | 1 - x, 1 - y, 1 - z |
H6···C36 | 2.798 | -0.102 | -1 + x, -1 + y, z |
Cl1···H33 | 2.854 | -0.096 | -1 + x, y, z |
H6···C37 | 2.858 | -0.042 | -1 + x, -1 + y, z |
H3B···H30A | 2.359 | -0.041 | 1 - x, -y, 1 - z |
H10B···H26 | 2.382 | -0.018 | 1 - x, 1 - y, 1 - z |
Note: (a) distances were calculated using Mercury (Macrae et al., 2008). |
Acknowledgements
HSE is grateful to the University of Neuchâtel for their support over the years.
Funding information
Funding for this research was provided by: Swiss National Science Foundation and the University of Neuchâtel.
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