Copper(I) π-coordination compounds with allyl derivatives of azoles are an interesting subject of current research, but CuI π-complexes with other transition-metal ions incorporated in the structure have been virtually uninvestigated. The present work is directed toward the synthesis and structural characterization of the novel heterometallic CuI/FeII π-complex di-μ2-chlorido-1:2κ2Cl;2:3κ2Cl-tetrakis[μ2-5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine]-1:2κ2N4:N3;1(η2),κN4:2κN3;2:3κ2N3:N4;2κN3:3(η2),κN4-dicopper(I)iron(II) tetrachloridoferrate(II), [Cu2FeCl2(C5H7N3S2)4][FeCl4] (1). The structure of the 5-[(prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta, C5H7N3S2) ligand is also presented. The cationic substructure in 1 consists of one FeII and two CuI ions bridged by two chloride ions along with two σ,σ- and two π,σ-coordinated ligands, whereas the anionic part is built of isolated tetrahedral [FeCl4]2− ions. π-Coordination of the Pesta allyl group to the CuI ions prevents agglomeration of the inorganic Cu–Cl–Fe–Cl–Cu part into infinate chains. An energy framework computational analysis was performed for Pesta.
Supporting information
CCDC references: 2060540; 2060539
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
5-[(Prop-2-en-1-yl)sulfanyl]-1,3,4-thiadiazol-2-amine (Pesta)
top
Crystal data top
C5H7N3S2 | Z = 2 |
Mr = 173.26 | F(000) = 180 |
Triclinic, P1 | Dx = 1.499 Mg m−3 |
a = 6.088 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.826 (3) Å | Cell parameters from 2650 reflections |
c = 8.623 (3) Å | θ = 3.4–29.7° |
α = 79.80 (3)° | µ = 0.62 mm−1 |
β = 72.96 (3)° | T = 160 K |
γ = 80.62 (3)° | Block, clear colourless |
V = 383.9 (3) Å3 | 0.9 × 0.48 × 0.26 mm |
Data collection top
Kuma KM-4-CCD diffractometer | 1648 reflections with I > 2σ(I) |
ω scans | Rint = 0.037 |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by
Clark & Reid (1995)] | θmax = 29.6°, θmin = 3.4° |
Tmin = 0.218, Tmax = 0.582 | h = −6→8 |
5125 measured reflections | k = −9→10 |
1923 independent reflections | l = −11→11 |
Refinement top
Refinement on F2 | 0 restraints |
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) = 0.113 | w = 1/[σ2(Fo2) + (0.0684P)2 + 0.0481P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1923 reflections | Δρmax = 0.40 e Å−3 |
127 parameters | Δρmin = −0.30 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) |
S1 | 0.60004 (7) | 0.20729 (6) | 0.55188 (5) | 0.04715 (18) | |
S2 | 1.10748 (7) | 0.28004 (7) | 0.40186 (5) | 0.05078 (18) | |
N4 | 0.7092 (2) | 0.10329 (19) | 0.82074 (17) | 0.0432 (3) | |
N3 | 0.9071 (2) | 0.1553 (2) | 0.70667 (18) | 0.0446 (3) | |
C2 | 0.8779 (3) | 0.2125 (2) | 0.56378 (19) | 0.0383 (3) | |
N2 | 0.3220 (3) | 0.0866 (3) | 0.8432 (2) | 0.0588 (5) | |
C5 | 0.5339 (3) | 0.1237 (2) | 0.75821 (19) | 0.0397 (3) | |
C9A | 0.6565 (18) | 0.3818 (9) | 0.1493 (11) | 0.0637 (16) | 0.715 (6) |
H9AA | 0.555951 | 0.474766 | 0.199455 | 0.076* | 0.715 (6) |
H9AB | 0.605956 | 0.317994 | 0.084768 | 0.076* | 0.715 (6) |
C8A | 0.8624 (6) | 0.3420 (5) | 0.1689 (3) | 0.0565 (9) | 0.715 (6) |
H8A | 0.956270 | 0.248015 | 0.116280 | 0.068* | 0.715 (6) |
C7A | 0.9664 (5) | 0.4285 (4) | 0.2654 (3) | 0.0522 (8) | 0.715 (6) |
H7AA | 0.843221 | 0.506879 | 0.330691 | 0.063* | 0.715 (6) |
H7AB | 1.080732 | 0.502135 | 0.188683 | 0.063* | 0.715 (6) |
C7B | 1.0096 (11) | 0.3004 (8) | 0.2193 (7) | 0.0433 (18) | 0.285 (6) |
H7BA | 1.144285 | 0.314457 | 0.122215 | 0.052* | 0.285 (6) |
H7BB | 0.949535 | 0.190437 | 0.218771 | 0.052* | 0.285 (6) |
C8B | 0.8275 (13) | 0.4484 (10) | 0.2036 (8) | 0.0477 (19) | 0.285 (6) |
H8B | 0.851636 | 0.560141 | 0.219669 | 0.057* | 0.285 (6) |
C9B | 0.639 (4) | 0.436 (2) | 0.169 (2) | 0.050 (3) | 0.285 (6) |
H9BA | 0.608843 | 0.325900 | 0.152624 | 0.060* | 0.285 (6) |
H9BB | 0.529345 | 0.536054 | 0.161258 | 0.060* | 0.285 (6) |
H2A | 0.299 (4) | 0.032 (3) | 0.936 (3) | 0.062 (7)* | |
H2B | 0.212 (4) | 0.101 (3) | 0.798 (3) | 0.063 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0318 (2) | 0.0753 (3) | 0.0335 (2) | −0.0134 (2) | −0.01391 (18) | 0.00996 (19) |
S2 | 0.0317 (3) | 0.0748 (3) | 0.0421 (3) | −0.0137 (2) | −0.00866 (19) | 0.0063 (2) |
N4 | 0.0345 (7) | 0.0626 (8) | 0.0330 (7) | −0.0125 (6) | −0.0133 (5) | 0.0052 (6) |
N3 | 0.0352 (7) | 0.0624 (8) | 0.0374 (7) | −0.0133 (6) | −0.0147 (6) | 0.0047 (6) |
C2 | 0.0301 (7) | 0.0483 (8) | 0.0369 (8) | −0.0079 (6) | −0.0120 (6) | 0.0011 (6) |
N2 | 0.0350 (8) | 0.0980 (13) | 0.0391 (8) | −0.0195 (8) | −0.0139 (7) | 0.0191 (8) |
C5 | 0.0341 (8) | 0.0515 (8) | 0.0320 (7) | −0.0075 (6) | −0.0109 (6) | 0.0037 (6) |
C9A | 0.068 (4) | 0.076 (4) | 0.052 (3) | −0.018 (3) | −0.023 (3) | −0.002 (3) |
C8A | 0.0602 (19) | 0.070 (2) | 0.0375 (13) | −0.0107 (15) | −0.0111 (12) | −0.0037 (12) |
C7A | 0.0516 (15) | 0.0591 (17) | 0.0454 (14) | −0.0186 (12) | −0.0154 (12) | 0.0091 (11) |
C7B | 0.039 (3) | 0.057 (4) | 0.030 (3) | −0.007 (3) | −0.008 (2) | −0.001 (2) |
C8B | 0.057 (4) | 0.041 (4) | 0.040 (3) | −0.007 (3) | −0.010 (3) | 0.005 (2) |
C9B | 0.049 (5) | 0.060 (7) | 0.040 (5) | 0.001 (6) | −0.017 (4) | −0.003 (5) |
Geometric parameters (Å, º) top
S1—C2 | 1.7320 (18) | C9A—C8A | 1.294 (10) |
S1—C5 | 1.7347 (17) | C8A—H8A | 0.9500 |
S2—C2 | 1.7373 (18) | C8A—C7A | 1.483 (5) |
S2—C7A | 1.804 (3) | C7A—H7AA | 0.9900 |
S2—C7B | 1.813 (6) | C7A—H7AB | 0.9900 |
N4—N3 | 1.382 (2) | C7B—H7BA | 0.9900 |
N4—C5 | 1.306 (2) | C7B—H7BB | 0.9900 |
N3—C2 | 1.287 (2) | C7B—C8B | 1.484 (10) |
N2—C5 | 1.333 (2) | C8B—H8B | 0.9500 |
N2—H2A | 0.82 (2) | C8B—C9B | 1.29 (2) |
N2—H2B | 0.85 (3) | C9B—H9BA | 0.9500 |
C9A—H9AA | 0.9500 | C9B—H9BB | 0.9500 |
C9A—H9AB | 0.9500 | | |
| | | |
C2—S1—C5 | 86.90 (8) | C7A—C8A—H8A | 116.8 |
C2—S2—C7A | 103.27 (11) | S2—C7A—H7AA | 108.6 |
C2—S2—C7B | 105.6 (2) | S2—C7A—H7AB | 108.6 |
C5—N4—N3 | 112.12 (13) | C8A—C7A—S2 | 114.5 (2) |
C2—N3—N4 | 113.35 (14) | C8A—C7A—H7AA | 108.6 |
S1—C2—S2 | 125.49 (10) | C8A—C7A—H7AB | 108.6 |
N3—C2—S1 | 113.92 (13) | H7AA—C7A—H7AB | 107.6 |
N3—C2—S2 | 120.56 (13) | S2—C7B—H7BA | 108.6 |
C5—N2—H2A | 120.6 (17) | S2—C7B—H7BB | 108.6 |
C5—N2—H2B | 121.6 (16) | H7BA—C7B—H7BB | 107.6 |
H2A—N2—H2B | 117 (2) | C8B—C7B—S2 | 114.8 (5) |
N4—C5—S1 | 113.70 (13) | C8B—C7B—H7BA | 108.6 |
N4—C5—N2 | 124.04 (16) | C8B—C7B—H7BB | 108.6 |
N2—C5—S1 | 122.26 (13) | C7B—C8B—H8B | 117.8 |
H9AA—C9A—H9AB | 120.0 | C9B—C8B—C7B | 124.5 (9) |
C8A—C9A—H9AA | 120.0 | C9B—C8B—H8B | 117.8 |
C8A—C9A—H9AB | 120.0 | C8B—C9B—H9BA | 120.0 |
C9A—C8A—H8A | 116.8 | C8B—C9B—H9BB | 120.0 |
C9A—C8A—C7A | 126.5 (4) | H9BA—C9B—H9BB | 120.0 |
| | | |
S2—C7B—C8B—C9B | −131.4 (12) | C5—S1—C2—S2 | 178.70 (12) |
N4—N3—C2—S1 | −0.56 (19) | C5—S1—C2—N3 | 0.73 (14) |
N4—N3—C2—S2 | −178.65 (11) | C5—N4—N3—C2 | 0.0 (2) |
N3—N4—C5—S1 | 0.58 (18) | C9A—C8A—C7A—S2 | 132.6 (6) |
N3—N4—C5—N2 | −178.68 (18) | C7A—S2—C2—S1 | 26.03 (15) |
C2—S1—C5—N4 | −0.73 (13) | C7A—S2—C2—N3 | −156.12 (17) |
C2—S1—C5—N2 | 178.54 (17) | C7B—S2—C2—S1 | −10.7 (2) |
C2—S2—C7A—C8A | −76.7 (2) | C7B—S2—C2—N3 | 167.1 (2) |
C2—S2—C7B—C8B | 70.0 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N4i | 0.82 (2) | 2.16 (2) | 2.981 (3) | 171 (2) |
N2—H2B···N3ii | 0.85 (3) | 2.17 (3) | 3.021 (3) | 173 (2) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x−1, y, z. |
Di-µ
2-chlorido-1:2
κ2Cl;2:3
κ2Cl-tetrakis[µ
2-5-(prop-2-en-1-ylsulfanyl)-1,3,4-thiadiazol-2-amine]-1:2
κ2N4:
N3;1(
η2),
κN4:2
κN3;2:3
κ2N3:
N4;2
κN3:3(
η2),
κN4-dicopper(I)iron(II)
tetrachloridoferrate(II) (Cu2FePesta4Cl2FeCl4)
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Crystal data top
[Cu2FeCl2(C5H7N3S2)4][FeCl4] | F(000) = 2288 |
Mr = 1144.50 | Dx = 1.910 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.650 (5) Å | Cell parameters from 10912 reflections |
b = 10.686 (4) Å | θ = 3.6–29.5° |
c = 21.107 (6) Å | µ = 2.63 mm−1 |
β = 90.15 (3)° | T = 100 K |
V = 3981 (2) Å3 | Block, clear colourless |
Z = 4 | 0.77 × 0.54 × 0.38 mm |
Data collection top
Xcalibur, Atlas diffractometer | 4464 reflections with I > 2σ(I) |
Detector resolution: 10.6249 pixels mm-1 | Rint = 0.028 |
ω scans | θmax = 29.6°, θmin = 3.0° |
Absorption correction: analytical [CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by
Clark & Reid (1995)] | h = −22→24 |
Tmin = 0.278, Tmax = 0.517 | k = −14→11 |
24848 measured reflections | l = −27→25 |
5036 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.024P)2 + 6.463P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
5036 reflections | Δρmax = 0.48 e Å−3 |
253 parameters | Δρmin = −0.46 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) |
Cu1 | 0.28612 (2) | 0.46858 (2) | 0.43309 (2) | 0.01228 (6) | |
Fe1 | 0.250000 | 0.750000 | 0.500000 | 0.01189 (8) | |
Cl1 | 0.16834 (2) | 0.56946 (4) | 0.47478 (2) | 0.01415 (9) | |
Cl3 | 0.500000 | 0.32746 (6) | 0.250000 | 0.01849 (13) | |
S12 | 0.32338 (3) | 0.49050 (4) | 0.26438 (2) | 0.01882 (10) | |
Cl4 | 0.38520 (3) | 0.04634 (4) | 0.23786 (2) | 0.02448 (11) | |
S11 | 0.32564 (3) | 0.76568 (4) | 0.28434 (2) | 0.01878 (10) | |
S21 | 0.43384 (3) | 0.50338 (5) | 0.60757 (2) | 0.01901 (10) | |
Fe2 | 0.48975 (3) | 0.12003 (5) | 0.28183 (2) | 0.01396 (11) | 0.5 |
S22 | 0.43555 (3) | 0.31110 (5) | 0.49761 (2) | 0.02523 (12) | |
Cl2 | 0.46697 (5) | 0.11849 (9) | 0.38822 (4) | 0.01803 (18) | 0.5 |
N13 | 0.30632 (8) | 0.61523 (13) | 0.37695 (7) | 0.0127 (3) | |
N23 | 0.34880 (8) | 0.51057 (14) | 0.50948 (7) | 0.0138 (3) | |
N24 | 0.33239 (9) | 0.62041 (14) | 0.54255 (7) | 0.0163 (3) | |
N14 | 0.30300 (9) | 0.73474 (14) | 0.40397 (7) | 0.0147 (3) | |
N12 | 0.31204 (12) | 0.94572 (16) | 0.37281 (9) | 0.0256 (4) | |
N22 | 0.36669 (12) | 0.72123 (18) | 0.63756 (10) | 0.0308 (5) | |
C18 | 0.25837 (10) | 0.34788 (17) | 0.36174 (8) | 0.0141 (3) | |
H18 | 0.212845 | 0.390748 | 0.351368 | 0.017* | |
C19 | 0.26196 (11) | 0.28109 (17) | 0.41668 (9) | 0.0169 (4) | |
H19A | 0.307121 | 0.237755 | 0.427668 | 0.020* | |
H19B | 0.219307 | 0.277868 | 0.443991 | 0.020* | |
C12 | 0.31671 (10) | 0.61652 (17) | 0.31601 (8) | 0.0135 (3) | |
C15 | 0.31321 (11) | 0.82314 (17) | 0.36113 (9) | 0.0170 (4) | |
C22 | 0.40161 (10) | 0.44307 (17) | 0.53617 (8) | 0.0143 (3) | |
C17 | 0.32468 (11) | 0.35566 (17) | 0.31692 (9) | 0.0171 (4) | |
H17A | 0.325740 | 0.278716 | 0.290817 | 0.021* | |
H17B | 0.372025 | 0.357827 | 0.342159 | 0.021* | |
C25 | 0.37268 (11) | 0.62909 (18) | 0.59501 (9) | 0.0183 (4) | |
C27 | 0.50743 (11) | 0.2519 (2) | 0.55214 (11) | 0.0280 (5) | |
H27A | 0.540771 | 0.192701 | 0.529327 | 0.034* | |
H27B | 0.539076 | 0.322528 | 0.567109 | 0.034* | |
C28 | 0.47371 (13) | 0.1876 (2) | 0.60770 (13) | 0.0352 (6) | |
H28 | 0.444110 | 0.114682 | 0.600415 | 0.042* | |
C29 | 0.48266 (15) | 0.2262 (3) | 0.66664 (14) | 0.0433 (7) | |
H29A | 0.511977 | 0.298760 | 0.675278 | 0.052* | |
H29B | 0.459775 | 0.181345 | 0.700426 | 0.052* | |
H12A | 0.3173 (15) | 0.966 (2) | 0.4105 (13) | 0.033 (7)* | |
H22A | 0.3519 (14) | 0.788 (2) | 0.6241 (12) | 0.026 (7)* | |
H12B | 0.3271 (15) | 0.992 (3) | 0.3451 (13) | 0.031 (7)* | |
H22B | 0.3972 (14) | 0.724 (2) | 0.6670 (12) | 0.023 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01723 (11) | 0.01004 (11) | 0.00954 (11) | −0.00106 (8) | −0.00250 (8) | 0.00095 (8) |
Fe1 | 0.01503 (17) | 0.00983 (17) | 0.01077 (18) | −0.00222 (13) | −0.00428 (13) | 0.00220 (13) |
Cl1 | 0.01491 (19) | 0.0124 (2) | 0.0152 (2) | −0.00204 (15) | −0.00125 (15) | −0.00157 (16) |
Cl3 | 0.0115 (3) | 0.0137 (3) | 0.0303 (4) | 0.000 | −0.0021 (2) | 0.000 |
S12 | 0.0271 (2) | 0.0161 (2) | 0.0133 (2) | 0.00689 (18) | 0.00721 (18) | 0.00102 (17) |
Cl4 | 0.0309 (3) | 0.0170 (2) | 0.0255 (3) | −0.00892 (18) | 0.0072 (2) | 0.00316 (19) |
S11 | 0.0293 (2) | 0.0147 (2) | 0.0124 (2) | 0.00004 (18) | 0.00230 (18) | 0.00461 (17) |
S21 | 0.0227 (2) | 0.0193 (2) | 0.0150 (2) | 0.00498 (18) | −0.00919 (18) | −0.00082 (18) |
Fe2 | 0.0142 (2) | 0.0125 (2) | 0.0151 (3) | −0.00041 (18) | −0.00025 (19) | −0.0021 (2) |
S22 | 0.0218 (2) | 0.0346 (3) | 0.0193 (3) | 0.0079 (2) | −0.00085 (19) | −0.0112 (2) |
Cl2 | 0.0211 (4) | 0.0198 (4) | 0.0133 (4) | 0.0024 (3) | 0.0005 (3) | −0.0044 (3) |
N13 | 0.0135 (7) | 0.0107 (7) | 0.0139 (7) | −0.0009 (5) | −0.0016 (6) | 0.0014 (6) |
N23 | 0.0165 (7) | 0.0131 (7) | 0.0117 (7) | −0.0023 (6) | −0.0022 (6) | 0.0023 (6) |
N24 | 0.0214 (8) | 0.0116 (7) | 0.0158 (8) | −0.0013 (6) | −0.0081 (6) | −0.0001 (6) |
N14 | 0.0207 (8) | 0.0109 (7) | 0.0126 (7) | −0.0031 (6) | −0.0021 (6) | 0.0010 (6) |
N12 | 0.0488 (12) | 0.0137 (8) | 0.0142 (9) | −0.0069 (8) | 0.0035 (8) | 0.0031 (7) |
N22 | 0.0445 (12) | 0.0172 (9) | 0.0307 (11) | 0.0091 (8) | −0.0281 (9) | −0.0066 (8) |
C18 | 0.0148 (8) | 0.0129 (8) | 0.0147 (9) | 0.0003 (6) | 0.0009 (7) | −0.0043 (7) |
C19 | 0.0217 (9) | 0.0119 (8) | 0.0172 (9) | −0.0022 (7) | 0.0003 (7) | −0.0021 (7) |
C12 | 0.0130 (8) | 0.0134 (8) | 0.0140 (9) | 0.0012 (6) | −0.0002 (6) | 0.0029 (7) |
C15 | 0.0234 (9) | 0.0143 (9) | 0.0133 (9) | −0.0019 (7) | −0.0013 (7) | 0.0020 (7) |
C22 | 0.0157 (8) | 0.0178 (9) | 0.0095 (8) | −0.0019 (7) | −0.0011 (6) | 0.0027 (7) |
C17 | 0.0206 (9) | 0.0137 (9) | 0.0172 (9) | 0.0033 (7) | 0.0039 (7) | 0.0013 (7) |
C25 | 0.0224 (9) | 0.0142 (9) | 0.0182 (9) | 0.0004 (7) | −0.0091 (7) | 0.0014 (7) |
C27 | 0.0167 (9) | 0.0303 (12) | 0.0370 (13) | 0.0093 (8) | −0.0026 (8) | −0.0083 (10) |
C28 | 0.0258 (11) | 0.0183 (11) | 0.0615 (18) | 0.0040 (8) | −0.0062 (11) | 0.0146 (11) |
C29 | 0.0383 (14) | 0.0429 (15) | 0.0488 (17) | 0.0138 (11) | 0.0043 (12) | 0.0293 (13) |
Geometric parameters (Å, º) top
Cu1—Cl1 | 2.5034 (8) | N13—C12 | 1.300 (2) |
Cu1—N13 | 1.9974 (15) | N23—N24 | 1.396 (2) |
Cu1—N23 | 2.0037 (17) | N23—C22 | 1.305 (2) |
Cu1—C18 | 2.0415 (18) | N24—C25 | 1.318 (2) |
Cu1—C19 | 2.0773 (19) | N14—C15 | 1.320 (2) |
Fe1—Cl1 | 2.4655 (8) | N12—C15 | 1.333 (3) |
Fe1—Cl1i | 2.4655 (8) | N12—H12A | 0.83 (3) |
Fe1—N24i | 2.1982 (16) | N12—H12B | 0.81 (3) |
Fe1—N24 | 2.1982 (16) | N22—C25 | 1.337 (3) |
Fe1—N14i | 2.2406 (16) | N22—H22A | 0.81 (3) |
Fe1—N14 | 2.2406 (16) | N22—H22B | 0.82 (3) |
Cl3—Fe2ii | 2.3233 (11) | C18—H18 | 0.9500 |
Cl3—Fe2 | 2.3233 (11) | C18—C19 | 1.363 (3) |
S12—C12 | 1.7364 (19) | C18—C17 | 1.509 (2) |
S12—C17 | 1.8183 (19) | C19—H19A | 0.9500 |
Cl4—Fe2ii | 2.3811 (9) | C19—H19B | 0.9500 |
Cl4—Fe2 | 2.2086 (10) | C17—H17A | 0.9900 |
S11—C12 | 1.7357 (19) | C17—H17B | 0.9900 |
S11—C15 | 1.748 (2) | C27—H27A | 0.9900 |
S21—C22 | 1.7335 (19) | C27—H27B | 0.9900 |
S21—C25 | 1.743 (2) | C27—C28 | 1.485 (3) |
Fe2—Fe2ii | 1.3925 (11) | C28—H28 | 0.9500 |
Fe2—Cl2 | 2.2823 (12) | C28—C29 | 1.320 (4) |
S22—C22 | 1.7357 (19) | C29—H29A | 0.9500 |
S22—C27 | 1.824 (2) | C29—H29B | 0.9500 |
N13—N14 | 1.400 (2) | | |
| | | |
N13—Cu1—Cl1 | 91.16 (5) | N13—N14—Fe1 | 116.93 (10) |
N13—Cu1—N23 | 101.69 (6) | C15—N14—Fe1 | 128.72 (13) |
N13—Cu1—C18 | 95.79 (7) | C15—N14—N13 | 111.58 (15) |
N13—Cu1—C19 | 134.00 (7) | C15—N12—H12A | 115.6 (18) |
N23—Cu1—Cl1 | 94.48 (5) | C15—N12—H12B | 117.4 (18) |
N23—Cu1—C18 | 149.99 (7) | H12A—N12—H12B | 120 (3) |
N23—Cu1—C19 | 117.57 (7) | C25—N22—H22A | 116.0 (17) |
C18—Cu1—Cl1 | 109.48 (5) | C25—N22—H22B | 118.8 (17) |
C18—Cu1—C19 | 38.64 (7) | H22A—N22—H22B | 116 (2) |
C19—Cu1—Cl1 | 107.68 (6) | Cu1—C18—H18 | 93.8 |
Cl1i—Fe1—Cl1 | 180.0 | C19—C18—Cu1 | 72.10 (11) |
N24i—Fe1—Cl1 | 91.09 (5) | C19—C18—H18 | 119.1 |
N24—Fe1—Cl1i | 91.09 (5) | C19—C18—C17 | 121.85 (17) |
N24i—Fe1—Cl1i | 88.91 (5) | C17—C18—Cu1 | 104.04 (12) |
N24—Fe1—Cl1 | 88.91 (5) | C17—C18—H18 | 119.1 |
N24—Fe1—N24i | 180.0 | Cu1—C19—H19A | 104.9 |
N24i—Fe1—N14 | 87.34 (6) | Cu1—C19—H19B | 95.5 |
N24—Fe1—N14i | 87.34 (6) | C18—C19—Cu1 | 69.26 (11) |
N24i—Fe1—N14i | 92.66 (6) | C18—C19—H19A | 120.0 |
N24—Fe1—N14 | 92.66 (6) | C18—C19—H19B | 120.0 |
N14i—Fe1—Cl1i | 89.59 (4) | H19A—C19—H19B | 120.0 |
N14—Fe1—Cl1i | 90.41 (4) | S11—C12—S12 | 117.66 (10) |
N14—Fe1—Cl1 | 89.59 (4) | N13—C12—S12 | 128.52 (14) |
N14i—Fe1—Cl1 | 90.41 (4) | N13—C12—S11 | 113.82 (13) |
N14—Fe1—N14i | 180.00 (10) | N14—C15—S11 | 113.67 (14) |
Fe1—Cl1—Cu1 | 85.83 (3) | N14—C15—N12 | 125.04 (18) |
Fe2ii—Cl3—Fe2 | 34.88 (3) | N12—C15—S11 | 121.25 (15) |
C12—S12—C17 | 103.45 (9) | S21—C22—S22 | 126.65 (11) |
Fe2—Cl4—Fe2ii | 35.07 (3) | N23—C22—S21 | 113.71 (14) |
C12—S11—C15 | 87.35 (9) | N23—C22—S22 | 119.56 (14) |
C22—S21—C25 | 87.29 (9) | S12—C17—H17A | 108.6 |
Cl3—Fe2—Cl4ii | 101.08 (3) | S12—C17—H17B | 108.6 |
Cl4—Fe2—Cl3 | 106.51 (3) | C18—C17—S12 | 114.67 (13) |
Cl4—Fe2—Cl4ii | 125.63 (4) | C18—C17—H17A | 108.6 |
Cl4—Fe2—Cl2 | 105.17 (4) | C18—C17—H17B | 108.6 |
Fe2ii—Fe2—Cl3 | 72.560 (16) | H17A—C17—H17B | 107.6 |
Fe2ii—Fe2—Cl4ii | 65.68 (5) | N24—C25—S21 | 113.96 (14) |
Fe2ii—Fe2—Cl4 | 79.25 (5) | N24—C25—N22 | 124.95 (18) |
Fe2ii—Fe2—Cl2 | 175.07 (6) | N22—C25—S21 | 121.03 (15) |
Cl2—Fe2—Cl3 | 107.79 (3) | S22—C27—H27A | 109.1 |
Cl2—Fe2—Cl4ii | 109.58 (4) | S22—C27—H27B | 109.1 |
C22—S22—C27 | 103.07 (10) | H27A—C27—H27B | 107.9 |
N14—N13—Cu1 | 117.80 (11) | C28—C27—S22 | 112.29 (15) |
C12—N13—Cu1 | 128.41 (12) | C28—C27—H27A | 109.1 |
C12—N13—N14 | 113.56 (14) | C28—C27—H27B | 109.1 |
N24—N23—Cu1 | 118.40 (11) | C27—C28—H28 | 118.2 |
C22—N23—Cu1 | 128.01 (13) | C29—C28—C27 | 123.5 (2) |
C22—N23—N24 | 113.42 (15) | C29—C28—H28 | 118.2 |
N23—N24—Fe1 | 117.59 (11) | C28—C29—H29A | 120.0 |
C25—N24—Fe1 | 130.84 (13) | C28—C29—H29B | 120.0 |
C25—N24—N23 | 111.53 (15) | H29A—C29—H29B | 120.0 |
| | | |
Cu1—N13—N14—Fe1 | −13.63 (16) | N14—N13—C12—S11 | 1.23 (19) |
Cu1—N13—N14—C15 | −176.46 (12) | C19—C18—C17—S12 | −157.68 (15) |
Cu1—N13—C12—S12 | −5.3 (3) | C12—S12—C17—C18 | 55.41 (16) |
Cu1—N13—C12—S11 | 175.42 (9) | C12—S11—C15—N14 | −0.52 (15) |
Cu1—N23—N24—Fe1 | −8.43 (16) | C12—S11—C15—N12 | −178.44 (18) |
Cu1—N23—N24—C25 | 173.45 (13) | C12—N13—N14—Fe1 | 161.22 (12) |
Cu1—N23—C22—S21 | −171.90 (9) | C12—N13—N14—C15 | −1.6 (2) |
Cu1—N23—C22—S22 | 11.1 (2) | C15—S11—C12—S12 | −179.84 (12) |
Cu1—C18—C17—S12 | −80.25 (14) | C15—S11—C12—N13 | −0.43 (15) |
Fe1—N24—C25—S21 | −177.65 (9) | C22—S21—C25—N24 | 1.29 (15) |
Fe1—N24—C25—N22 | 5.3 (3) | C22—S21—C25—N22 | 178.51 (19) |
Fe1—N14—C15—S11 | −159.02 (9) | C22—S22—C27—C28 | 75.92 (18) |
Fe1—N14—C15—N12 | 18.8 (3) | C22—N23—N24—Fe1 | 175.99 (12) |
S22—C27—C28—C29 | −117.7 (2) | C22—N23—N24—C25 | −2.1 (2) |
N13—N14—C15—S11 | 1.3 (2) | C17—S12—C12—S11 | 172.23 (10) |
N13—N14—C15—N12 | 179.10 (19) | C17—S12—C12—N13 | −7.08 (19) |
N23—N24—C25—S21 | 0.1 (2) | C17—C18—C19—Cu1 | 95.71 (16) |
N23—N24—C25—N22 | −176.95 (19) | C25—S21—C22—S22 | 174.24 (13) |
N24—N23—C22—S21 | 3.17 (19) | C25—S21—C22—N23 | −2.53 (14) |
N24—N23—C22—S22 | −173.86 (12) | C27—S22—C22—S21 | 2.68 (15) |
N14—N13—C12—S12 | −179.44 (13) | C27—S22—C22—N23 | 179.28 (15) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N12—H12A···Cl1i | 0.83 (3) | 2.46 (3) | 3.239 (2) | 156 (2) |
N22—H22A···Cl1i | 0.81 (3) | 2.61 (3) | 3.317 (2) | 147 (2) |
N12—H12B···Cl4iii | 0.81 (3) | 2.55 (3) | 3.310 (2) | 156 (2) |
N22—H22B···Cl3iv | 0.82 (3) | 2.58 (3) | 3.378 (2) | 165 (2) |
N22—H22B···Cl4v | 0.82 (3) | 2.88 (2) | 3.279 (2) | 111.9 (19) |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1; (v) x, −y+1, z+1/2. |
Selected geometric parameters (Å, °) of Pesta and 1 topm is the mid-point of the C═C bond. |
Pesta | | | |
N3—C2 | 1.287 (2) | S2—C7A—C8A | 114.5 (2) |
N2—C5 | 1.333 (2) | S1—C2—S2 | 125.49 (10) |
N4—N3 | 1.382 (2) | S1—C2—N3 | 113.92 (13) |
| | | |
Complex 1 | | | |
Cu1—Cl1 | 2.5034 (8) | N13—Cu1—m | 115.11 (7) |
Fe1—Cl1 | 2.4655 (8) | N23—Cu1—m | 134.60 (7) |
Cu1—N13 | 1.9974 (15) | Cl1—Cu1—m | 109.72 (6) |
Cu1—N23 | 2.0037 (17) | N13—Cu1—Cl1 | 91.16 (5) |
Fe1—N14 | 2.2406 (16) | N23—Cu1—Cl1 | 94.48 (5) |
Fe1—N24 | 2.1982 (16) | N14—Fe1—Cl1 | 90.41 (4) |
Cu1—C18 | 2.0415 (18) | N24—Fe1—Cl1i | 91.09 (5) |
Cu1—ma | 1.943 (2) | C18—Cu1—C19 | 38.64 (7) |
C18—C19 | 1.363 (3) | C17—C18—C19 | 121.85 (17) |
Fe2—Cl2 | 2.2823 (12) | Cl2—Fe2—Cl3 | 107.79 (3) |
Fe2—Cl3 | 2.3233 (11) | Cl2—Fe2—Cl4 | 109.58 (4) |
Symmetry code: (i) -x+1/2, -y+3/2, -z+1. |
The most prominent molecular interaction energies (kJ mol-1) for the cluster
of molecules for Pesta (models A and B) topNo. | Na | Symmetry code | Rb | Eelec | | Epolc | | Edisc | | Erepc | | Etotc,d | |
| | | | A | B | A | B | A | B | A | B | A | B |
LI | 2 | x+1, y, z; x-1, y, z | 6.09 | -42.3 | -42.1 | -9.5 | -9.5 | -18.0 | -17.9 | 50.6 | 50.4 | -36.1 | -35.9 |
LII | 1 | -x+1, -y, -z+2 | 8.42 | -88.9 | -88.8 | -19.9 | -20.0 | -13.8 | -13.8 | 78.3 | 78.2 | -72.4 | -72.4 |
LIII | 1 | -x+1, -y+1, -z+1 | 4.88 | -2.9 | -9.6 | -1.7 | -2.4 | -23.8 | -34.1 | 13.6 | 30.6 | -16.7 | -22.7 |
LIV | 1 | -x+2, -y+1, -z+1 | 5.32 | -19.2 | -9.7 | -4.3 | -3.1 | -22.0 | -15.2 | 17.0 | 9.9 | -32.1 | -19.6 |
LV | 1 | -x+1, -y, -z+1 | 5.39 | -3.3 | 1.2 | -2.4 | -2.3 | -20.1 | -18.4 | 11.3 | 11.0 | -15.7 | -9.8 |
LVI | 1 | -x+2, -y, -z+1 | 4.23 | -10.8 | -24.0 | -4.4 | -6.9 | -27.5 | -35.1 | 23.5 | 32.4 | -24.1 | -41.1 |
LVII | 1 | -x+2, -y+1, -z | 8.97 | -4.3 | -3.5 | -0.6 | -0.6 | -13.3 | -13.7 | 11.3 | 10.5 | -9.6 | -9.6 |
LVIII | 2 | x, y, z+1 x, y, z-1 | 8.62 | -3.4 | -2.9 | -1.8 | -1.1 | -5.3 | -3.3 | 2.7 | 0.4 | -7.8 | -6.5 |
Notes: (a) N is the number of molecules involved in interactions
with the selected molecule; (b) R is the distance between
molecular centroids (mean atomic position) in Å;
(c) Eele, Epol, Edis, Erep
and Etot are the electrostatic, polarization, dispersion, repulsion
and total energies of the interactions; (d) each energy should be
multiplied by the respective conversion factor, i.e.
kele = 1.057,
kpol = 0.740,
kdis = 0.871 and
krep = 0.618,
to obtain the total energy (Etot). |