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The Zn complexes bis(acetylacetonato-κ
2O,
O′)bis{4′-[4-(methylsulfanyl)phenyl]-4,2′:6′,4′′-terpyridine-κ
N1}zinc(II), [Zn(C
5H
7O
2)
2(C
22H
17N
3S)
2], (I), and {μ-4′-[4-(methylsulfanyl)phenyl]-4,2′:6′,4′′-terpyridine-κ
2N1:
N1′′}bis[bis(acetylacetonato-κ
2O,
O′)zinc(II)], [Zn
2(C
5H
7O
2)
4(C
22H
17N
3S)], (II), are discrete entities with different nuclearities. Compound (I) consists of two centrosymmetrically related monodentate 4′-[4-(methylsulfanyl)phenyl]-4,2′:6′,4′′-terpyridine (
L1) ligands binding to one Zn
II atom sitting on an inversion centre and two centrosymmetrically related chelating acetylacetonate (acac) groups which bind
via carbonyl O-atom donors, giving an N
2O
4 octahedral environment for Zn
II. Compound (II), however, consists of a bis-monodentate
L1 ligand bridging two Zn
II atoms from two different Zn(acac)
2 fragments. Intra- and intermolecular interactions are weak, mainly of the C—H
π and π–π types, mediating similar layered structures. In contrast to related structures in the literature, sulfur-mediated nonbonding interactions in (II) do not seem to have any significant influence on the supramolecular structure.
Supporting information
CCDC references: 906559; 906560
The ligand L1 was synthesized as reported previously (Constable, Zhang,
Coronado et al., 2010). To a hot solution (using an oil bath at
337–341 K) of L1 (8.6 mg, 0.024 mmol) in MeCN (7 ml) contained in a
closed volumetric flask (25 ml) was added an excess of Zn(acac)2 (63.8 mg,
0.242 mmol). The resulting solution was heated in the oil bath for 10 h.
Block-like colourless crystals were obtained after removal of the hot solvent
and washing with MeCN (3 × 5 ml) and diethyl ether (2 × 4 ml)
(yield: 12 mg, 56.6%). Analysis calculated for C42H45N3O8SZn2: C
57.15, H 5.14, N 4.76, S 3.63%; found: C 57.32, H 5.26, N 4.63, S 3.68%.
Careful examination of the solid product identified two slightly different
kinds of crystals, the major fraction corresponding to compound (II) and a
second strictly minor fraction corresponding to compound (I). The latter
appear recurrently, though in trace amounts, during the synthesis described
above, irrespective of reaction conditions.
H atoms bonded to C were found in a difference Fourier map, but were further
idealized and refined as riding atoms [aromatic C—H = 0.93 Å, with
Uiso(H) = 1.2Ueq(C); methyl C—H = 0.97 Å, with
Uiso(H) = 1.5Ueq(C)].
For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) bis(acetylacetonato-
κ2O,
O')bis{4'-[4-(methylsulfanyl)phenyl]-
4,2':6',4''-terpyridine-
κN1}zinc(II)
top
Crystal data top
[Zn(C5H7O2)2(C22H17N3S)2] | F(000) = 2032 |
Mr = 974.47 | Dx = 1.385 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 9886 reflections |
a = 26.6479 (7) Å | θ = 3.8–28.9° |
b = 10.7706 (3) Å | µ = 0.67 mm−1 |
c = 16.4983 (5) Å | T = 295 K |
β = 99.187 (3)° | Block, colourless |
V = 4674.5 (2) Å3 | 0.26 × 0.20 × 0.12 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Gemini CCD S Ultra diffractometer | 5288 independent reflections |
Radiation source: fine-focus sealed tube | 3620 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans, thick slices | θmax = 28.9°, θmin = 3.8° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −20→35 |
Tmin = 0.83, Tmax = 0.92 | k = −14→13 |
9886 measured reflections | l = −22→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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
5288 reflections | (Δ/σ)max < 0.001 |
307 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
[Zn(C5H7O2)2(C22H17N3S)2] | V = 4674.5 (2) Å3 |
Mr = 974.47 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.6479 (7) Å | µ = 0.67 mm−1 |
b = 10.7706 (3) Å | T = 295 K |
c = 16.4983 (5) Å | 0.26 × 0.20 × 0.12 mm |
β = 99.187 (3)° | |
Data collection top
Oxford Diffraction Gemini CCD S Ultra diffractometer | 5288 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 3620 reflections with I > 2σ(I) |
Tmin = 0.83, Tmax = 0.92 | Rint = 0.017 |
9886 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
5288 reflections | Δρmin = −0.40 e Å−3 |
307 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.2500 | 0.2500 | 0.0000 | 0.03104 (10) | |
S1 | −0.22969 (2) | 0.25503 (6) | 0.20448 (5) | 0.0654 (2) | |
N1 | 0.18461 (6) | 0.33489 (14) | 0.05266 (9) | 0.0338 (4) | |
N2 | 0.05064 (6) | 0.63117 (14) | 0.11045 (10) | 0.0349 (4) | |
N3 | 0.01939 (8) | 1.08964 (18) | 0.11689 (15) | 0.0706 (6) | |
C1 | 0.14304 (7) | 0.50523 (19) | 0.10663 (13) | 0.0438 (5) | |
H1 | 0.1457 | 0.5843 | 0.1295 | 0.053* | |
C2 | 0.18550 (7) | 0.4475 (2) | 0.08669 (13) | 0.0446 (5) | |
H2 | 0.2164 | 0.4891 | 0.0975 | 0.054* | |
C3 | 0.13966 (8) | 0.27750 (17) | 0.04058 (13) | 0.0367 (5) | |
H3 | 0.1381 | 0.1983 | 0.0179 | 0.044* | |
C4 | 0.09553 (7) | 0.32755 (17) | 0.05944 (11) | 0.0339 (4) | |
H4 | 0.0654 | 0.2824 | 0.0500 | 0.041* | |
C5 | 0.09622 (7) | 0.44535 (16) | 0.09254 (11) | 0.0312 (4) | |
C6 | 0.04921 (7) | 0.50658 (17) | 0.11032 (11) | 0.0308 (4) | |
C7 | 0.00698 (7) | 0.43913 (17) | 0.12383 (11) | 0.0332 (4) | |
H7 | 0.0076 | 0.3528 | 0.1224 | 0.040* | |
C8 | −0.03643 (6) | 0.50110 (16) | 0.13962 (11) | 0.0307 (4) | |
C9 | −0.03453 (7) | 0.63055 (17) | 0.13924 (12) | 0.0362 (4) | |
H9 | −0.0625 | 0.6761 | 0.1493 | 0.043* | |
C10 | 0.00861 (7) | 0.69151 (18) | 0.12412 (12) | 0.0339 (4) | |
C11 | 0.01171 (7) | 0.82965 (17) | 0.12092 (12) | 0.0375 (5) | |
C12 | −0.02682 (12) | 0.9052 (2) | 0.1351 (3) | 0.1119 (15) | |
H12 | −0.0568 | 0.8709 | 0.1474 | 0.134* | |
C13 | −0.02166 (13) | 1.0334 (3) | 0.1314 (3) | 0.1182 (15) | |
H13 | −0.0492 | 1.0822 | 0.1398 | 0.142* | |
C14 | 0.05544 (10) | 1.0158 (2) | 0.10173 (18) | 0.0715 (8) | |
H14 | 0.0850 | 1.0523 | 0.0896 | 0.086* | |
C15 | 0.05338 (9) | 0.8878 (2) | 0.10226 (16) | 0.0563 (6) | |
H15 | 0.0806 | 0.8416 | 0.0898 | 0.068* | |
C16 | −0.08256 (7) | 0.43551 (16) | 0.15548 (11) | 0.0310 (4) | |
C17 | −0.08026 (7) | 0.32421 (17) | 0.19845 (11) | 0.0336 (4) | |
H17 | −0.0488 | 0.2879 | 0.2163 | 0.040* | |
C18 | −0.12371 (7) | 0.26613 (16) | 0.21532 (12) | 0.0363 (4) | |
H18 | −0.1211 | 0.1922 | 0.2448 | 0.044* | |
C19 | −0.17111 (7) | 0.31761 (18) | 0.18844 (12) | 0.0358 (4) | |
C20 | −0.17422 (7) | 0.42817 (19) | 0.14415 (12) | 0.0410 (5) | |
H20 | −0.2058 | 0.4633 | 0.1250 | 0.049* | |
C21 | −0.13062 (7) | 0.48542 (18) | 0.12868 (12) | 0.0382 (5) | |
H21 | −0.1333 | 0.5596 | 0.0995 | 0.046* | |
C22 | −0.21480 (9) | 0.1278 (2) | 0.27307 (14) | 0.0592 (7) | |
H22A | −0.1993 | 0.0627 | 0.2459 | 0.089* | |
H22B | −0.2454 | 0.0973 | 0.2899 | 0.089* | |
H22C | −0.1916 | 0.1547 | 0.3204 | 0.089* | |
O1A | 0.22421 (5) | 0.07433 (12) | 0.02249 (8) | 0.0365 (3) | |
O2A | 0.20393 (5) | 0.24688 (12) | −0.11169 (8) | 0.0370 (3) | |
C1A | 0.18303 (10) | −0.1193 (2) | 0.00482 (15) | 0.0593 (6) | |
H1AA | 0.2130 | −0.1697 | 0.0077 | 0.089* | |
H1AB | 0.1557 | −0.1568 | −0.0320 | 0.089* | |
H1AC | 0.1737 | −0.1124 | 0.0585 | 0.089* | |
C2A | 0.19366 (7) | 0.00850 (17) | −0.02625 (12) | 0.0358 (4) | |
C3A | 0.16957 (7) | 0.04515 (19) | −0.10402 (12) | 0.0397 (5) | |
H3A | 0.1471 | −0.0111 | −0.1331 | 0.048* | |
C4A | 0.17611 (7) | 0.15876 (19) | −0.14219 (11) | 0.0370 (5) | |
C5A | 0.14763 (8) | 0.1800 (2) | −0.22755 (13) | 0.0527 (6) | |
H5AA | 0.1342 | 0.2629 | −0.2316 | 0.079* | |
H5AB | 0.1202 | 0.1216 | −0.2387 | 0.079* | |
H5AC | 0.1703 | 0.1692 | −0.2667 | 0.079* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.02582 (16) | 0.02878 (16) | 0.03907 (18) | 0.00138 (14) | 0.00684 (12) | −0.00130 (14) |
S1 | 0.0357 (3) | 0.0678 (4) | 0.0976 (5) | −0.0049 (3) | 0.0255 (3) | 0.0256 (4) |
N1 | 0.0287 (8) | 0.0311 (8) | 0.0429 (9) | 0.0038 (7) | 0.0100 (7) | −0.0008 (7) |
N2 | 0.0294 (8) | 0.0283 (8) | 0.0481 (9) | 0.0011 (7) | 0.0099 (7) | −0.0034 (7) |
N3 | 0.0581 (13) | 0.0297 (10) | 0.126 (2) | −0.0050 (10) | 0.0202 (13) | −0.0022 (11) |
C1 | 0.0313 (10) | 0.0363 (11) | 0.0657 (14) | −0.0031 (9) | 0.0139 (10) | −0.0183 (10) |
C2 | 0.0264 (10) | 0.0452 (12) | 0.0634 (14) | −0.0027 (9) | 0.0107 (9) | −0.0156 (10) |
C3 | 0.0364 (11) | 0.0272 (10) | 0.0492 (12) | 0.0019 (8) | 0.0149 (9) | −0.0014 (8) |
C4 | 0.0278 (9) | 0.0281 (10) | 0.0480 (11) | −0.0005 (8) | 0.0125 (8) | 0.0010 (8) |
C5 | 0.0277 (9) | 0.0301 (10) | 0.0373 (10) | 0.0034 (8) | 0.0095 (8) | 0.0013 (8) |
C6 | 0.0264 (9) | 0.0295 (10) | 0.0370 (10) | 0.0017 (8) | 0.0065 (8) | −0.0013 (8) |
C7 | 0.0300 (10) | 0.0251 (9) | 0.0457 (11) | 0.0041 (8) | 0.0101 (8) | −0.0008 (8) |
C8 | 0.0247 (9) | 0.0291 (10) | 0.0385 (10) | 0.0010 (8) | 0.0058 (8) | 0.0010 (8) |
C9 | 0.0264 (9) | 0.0289 (10) | 0.0550 (12) | 0.0061 (8) | 0.0117 (9) | −0.0012 (9) |
C10 | 0.0296 (10) | 0.0264 (9) | 0.0467 (11) | 0.0026 (9) | 0.0089 (9) | −0.0014 (9) |
C11 | 0.0321 (10) | 0.0263 (10) | 0.0550 (12) | −0.0002 (9) | 0.0092 (9) | −0.0016 (9) |
C12 | 0.079 (2) | 0.0289 (13) | 0.251 (4) | −0.0045 (14) | 0.097 (3) | −0.013 (2) |
C13 | 0.087 (2) | 0.0301 (13) | 0.257 (5) | −0.0003 (15) | 0.088 (3) | −0.017 (2) |
C14 | 0.0485 (14) | 0.0383 (13) | 0.130 (2) | −0.0086 (12) | 0.0225 (15) | 0.0136 (15) |
C15 | 0.0395 (12) | 0.0360 (12) | 0.0974 (19) | 0.0035 (10) | 0.0230 (13) | 0.0088 (12) |
C16 | 0.0261 (9) | 0.0279 (9) | 0.0404 (10) | 0.0025 (8) | 0.0092 (8) | −0.0028 (8) |
C17 | 0.0282 (9) | 0.0291 (10) | 0.0431 (11) | 0.0039 (8) | 0.0046 (8) | 0.0000 (8) |
C18 | 0.0381 (11) | 0.0269 (10) | 0.0441 (11) | −0.0004 (9) | 0.0074 (9) | 0.0037 (8) |
C19 | 0.0301 (10) | 0.0354 (11) | 0.0443 (11) | −0.0022 (9) | 0.0127 (8) | −0.0015 (9) |
C20 | 0.0241 (9) | 0.0400 (11) | 0.0597 (13) | 0.0045 (9) | 0.0097 (9) | 0.0056 (10) |
C21 | 0.0315 (10) | 0.0339 (10) | 0.0504 (12) | 0.0047 (9) | 0.0102 (9) | 0.0106 (9) |
C22 | 0.0713 (16) | 0.0497 (13) | 0.0650 (15) | −0.0122 (13) | 0.0367 (13) | 0.0003 (12) |
O1A | 0.0344 (7) | 0.0313 (7) | 0.0438 (7) | 0.0009 (6) | 0.0061 (6) | −0.0001 (6) |
O2A | 0.0331 (7) | 0.0374 (7) | 0.0400 (7) | 0.0010 (7) | 0.0048 (6) | 0.0012 (6) |
C1A | 0.0687 (16) | 0.0401 (12) | 0.0701 (16) | −0.0137 (12) | 0.0140 (13) | −0.0011 (12) |
C2A | 0.0309 (10) | 0.0303 (10) | 0.0502 (12) | 0.0009 (9) | 0.0185 (9) | −0.0071 (9) |
C3A | 0.0319 (10) | 0.0418 (11) | 0.0459 (11) | −0.0060 (9) | 0.0079 (9) | −0.0102 (10) |
C4A | 0.0255 (9) | 0.0482 (12) | 0.0390 (11) | 0.0061 (9) | 0.0105 (8) | −0.0070 (10) |
C5A | 0.0404 (12) | 0.0725 (17) | 0.0439 (12) | 0.0010 (12) | 0.0023 (10) | 0.0009 (12) |
Geometric parameters (Å, º) top
Zn1—O2Ai | 2.0448 (13) | C12—C13 | 1.390 (3) |
Zn1—O2A | 2.0448 (13) | C12—H12 | 0.9300 |
Zn1—O1Ai | 2.0667 (12) | C13—H13 | 0.9300 |
Zn1—O1A | 2.0667 (12) | C14—C15 | 1.380 (3) |
Zn1—N1i | 2.2607 (14) | C14—H14 | 0.9300 |
Zn1—N1 | 2.2607 (14) | C15—H15 | 0.9300 |
S1—C19 | 1.7586 (18) | C16—C17 | 1.389 (2) |
S1—C22 | 1.781 (2) | C16—C21 | 1.394 (2) |
N1—C3 | 1.334 (2) | C17—C18 | 1.383 (2) |
N1—C2 | 1.335 (2) | C17—H17 | 0.9300 |
N2—C6 | 1.342 (2) | C18—C19 | 1.386 (3) |
N2—C10 | 1.345 (2) | C18—H18 | 0.9300 |
N3—C14 | 1.302 (3) | C19—C20 | 1.393 (3) |
N3—C13 | 1.306 (3) | C20—C21 | 1.375 (2) |
C1—C2 | 1.376 (2) | C20—H20 | 0.9300 |
C1—C5 | 1.391 (2) | C21—H21 | 0.9300 |
C1—H1 | 0.9300 | C22—H22A | 0.9600 |
C2—H2 | 0.9300 | C22—H22B | 0.9600 |
C3—C4 | 1.374 (2) | C22—H22C | 0.9600 |
C3—H3 | 0.9300 | O1A—C2A | 1.266 (2) |
C4—C5 | 1.380 (2) | O2A—C4A | 1.259 (2) |
C4—H4 | 0.9300 | C1A—C2A | 1.511 (3) |
C5—C6 | 1.486 (2) | C1A—H1AA | 0.9600 |
C6—C7 | 1.387 (2) | C1A—H1AB | 0.9600 |
C7—C8 | 1.396 (2) | C1A—H1AC | 0.9600 |
C7—H7 | 0.9300 | C2A—C3A | 1.397 (3) |
C8—C9 | 1.395 (2) | C3A—C4A | 1.400 (3) |
C8—C16 | 1.477 (2) | C3A—H3A | 0.9300 |
C9—C10 | 1.381 (2) | C4A—C5A | 1.507 (3) |
C9—H9 | 0.9300 | C5A—H5AA | 0.9600 |
C10—C11 | 1.492 (3) | C5A—H5AB | 0.9600 |
C11—C15 | 1.353 (3) | C5A—H5AC | 0.9600 |
C11—C12 | 1.359 (3) | | |
| | | |
O2Ai—Zn1—O2A | 180.00 (9) | N3—C13—C12 | 124.1 (3) |
O2Ai—Zn1—O1Ai | 88.72 (5) | N3—C13—H13 | 117.9 |
O2A—Zn1—O1Ai | 91.28 (5) | C12—C13—H13 | 117.9 |
O2Ai—Zn1—O1A | 91.28 (5) | N3—C14—C15 | 125.3 (2) |
O2A—Zn1—O1A | 88.72 (5) | N3—C14—H14 | 117.4 |
O1Ai—Zn1—O1A | 180.00 (8) | C15—C14—H14 | 117.4 |
O2Ai—Zn1—N1i | 87.95 (5) | C11—C15—C14 | 119.9 (2) |
O2A—Zn1—N1i | 92.05 (5) | C11—C15—H15 | 120.0 |
O1Ai—Zn1—N1i | 90.14 (5) | C14—C15—H15 | 120.0 |
O1A—Zn1—N1i | 89.86 (5) | C17—C16—C21 | 117.25 (17) |
O2Ai—Zn1—N1 | 92.05 (5) | C17—C16—C8 | 122.22 (16) |
O2A—Zn1—N1 | 87.95 (5) | C21—C16—C8 | 120.52 (16) |
O1Ai—Zn1—N1 | 89.86 (5) | C18—C17—C16 | 121.54 (17) |
O1A—Zn1—N1 | 90.14 (5) | C18—C17—H17 | 119.2 |
N1i—Zn1—N1 | 180.00 (7) | C16—C17—H17 | 119.2 |
C19—S1—C22 | 106.11 (11) | C17—C18—C19 | 120.28 (17) |
C3—N1—C2 | 116.04 (16) | C17—C18—H18 | 119.9 |
C3—N1—Zn1 | 118.94 (12) | C19—C18—H18 | 119.9 |
C2—N1—Zn1 | 124.46 (13) | C18—C19—C20 | 118.99 (17) |
C6—N2—C10 | 117.34 (16) | C18—C19—S1 | 125.74 (15) |
C14—N3—C13 | 114.7 (2) | C20—C19—S1 | 115.27 (15) |
C2—C1—C5 | 120.03 (18) | C21—C20—C19 | 119.99 (18) |
C2—C1—H1 | 120.0 | C21—C20—H20 | 120.0 |
C5—C1—H1 | 120.0 | C19—C20—H20 | 120.0 |
N1—C2—C1 | 123.42 (18) | C20—C21—C16 | 121.93 (17) |
N1—C2—H2 | 118.3 | C20—C21—H21 | 119.0 |
C1—C2—H2 | 118.3 | C16—C21—H21 | 119.0 |
N1—C3—C4 | 124.40 (17) | S1—C22—H22A | 109.5 |
N1—C3—H3 | 117.8 | S1—C22—H22B | 109.5 |
C4—C3—H3 | 117.8 | H22A—C22—H22B | 109.5 |
C3—C4—C5 | 119.50 (17) | S1—C22—H22C | 109.5 |
C3—C4—H4 | 120.2 | H22A—C22—H22C | 109.5 |
C5—C4—H4 | 120.2 | H22B—C22—H22C | 109.5 |
C4—C5—C1 | 116.57 (16) | C2A—O1A—Zn1 | 126.67 (12) |
C4—C5—C6 | 121.86 (16) | C4A—O2A—Zn1 | 127.10 (12) |
C1—C5—C6 | 121.55 (16) | C2A—C1A—H1AA | 109.5 |
N2—C6—C7 | 123.14 (17) | C2A—C1A—H1AB | 109.5 |
N2—C6—C5 | 114.80 (16) | H1AA—C1A—H1AB | 109.5 |
C7—C6—C5 | 122.04 (16) | C2A—C1A—H1AC | 109.5 |
C6—C7—C8 | 119.83 (16) | H1AA—C1A—H1AC | 109.5 |
C6—C7—H7 | 120.1 | H1AB—C1A—H1AC | 109.5 |
C8—C7—H7 | 120.1 | O1A—C2A—C3A | 125.43 (17) |
C9—C8—C7 | 116.45 (16) | O1A—C2A—C1A | 115.52 (19) |
C9—C8—C16 | 120.70 (16) | C3A—C2A—C1A | 119.04 (19) |
C7—C8—C16 | 122.85 (16) | C2A—C3A—C4A | 126.04 (19) |
C10—C9—C8 | 120.52 (17) | C2A—C3A—H3A | 117.0 |
C10—C9—H9 | 119.7 | C4A—C3A—H3A | 117.0 |
C8—C9—H9 | 119.7 | O2A—C4A—C3A | 125.94 (19) |
N2—C10—C9 | 122.70 (17) | O2A—C4A—C5A | 115.83 (19) |
N2—C10—C11 | 115.07 (16) | C3A—C4A—C5A | 118.24 (19) |
C9—C10—C11 | 122.22 (16) | C4A—C5A—H5AA | 109.5 |
C15—C11—C12 | 115.62 (19) | C4A—C5A—H5AB | 109.5 |
C15—C11—C10 | 121.49 (17) | H5AA—C5A—H5AB | 109.5 |
C12—C11—C10 | 122.89 (18) | C4A—C5A—H5AC | 109.5 |
C11—C12—C13 | 120.3 (2) | H5AA—C5A—H5AC | 109.5 |
C11—C12—H12 | 119.9 | H5AB—C5A—H5AC | 109.5 |
C13—C12—H12 | 119.9 | | |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) topTable 1. C—H···π contacts in (I) (Å, °). Cg1 is the centroid of the Zn1/O1A/C2A/C3A/C4A/O2A chelate ring
and Cg2 is the centroid of the N1/C1–C5 pyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1i | 0.93 | 2.66 | 3.187 (2) | 116 |
C3—H3···Cg1 | 0.93 | 2.43 | 3.001 (2) | 120 |
C21—H21···Cg2ii | 0.93 | 2.87 | 3.560 (2) | 132 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x, −y+1, −z. |
(II) {µ-4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine-
κ2N1:
N1''}bis[bis(acetylacetonato-
κ2O,
O')zinc(II)]
top
Crystal data top
[Zn2(C5H7O2)4(C22H17N3S)] | F(000) = 1832 |
Mr = 882.61 | Dx = 1.344 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 27845 reflections |
a = 14.1522 (3) Å | θ = 3.9–29.0° |
b = 13.4408 (3) Å | µ = 1.20 mm−1 |
c = 23.3887 (5) Å | T = 295 K |
β = 101.342 (2)° | Polyhedra, colourless |
V = 4362.05 (16) Å3 | 0.32 × 0.16 × 0.14 mm |
Z = 4 | |
Data collection top
Oxford Diffraction Gemini CCD S Ultra diffractometer | 9862 independent reflections |
Radiation source: fine-focus sealed tube | 6308 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scans, thick slices | θmax = 29.0°, θmin = 3.9° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −17→18 |
Tmin = 0.80, Tmax = 0.85 | k = −15→18 |
27845 measured reflections | l = −30→31 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3 |
9862 reflections | (Δ/σ)max < 0.001 |
505 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
[Zn2(C5H7O2)4(C22H17N3S)] | V = 4362.05 (16) Å3 |
Mr = 882.61 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.1522 (3) Å | µ = 1.20 mm−1 |
b = 13.4408 (3) Å | T = 295 K |
c = 23.3887 (5) Å | 0.32 × 0.16 × 0.14 mm |
β = 101.342 (2)° | |
Data collection top
Oxford Diffraction Gemini CCD S Ultra diffractometer | 9862 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 6308 reflections with I > 2σ(I) |
Tmin = 0.80, Tmax = 0.85 | Rint = 0.028 |
27845 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.41 e Å−3 |
9862 reflections | Δρmin = −0.35 e Å−3 |
505 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.218436 (19) | −0.023500 (19) | 0.349827 (10) | 0.04179 (8) | |
Zn2 | 0.249447 (19) | 0.788509 (17) | 0.095196 (11) | 0.04252 (8) | |
S1 | 0.26203 (8) | −0.04367 (6) | −0.22174 (3) | 0.0864 (3) | |
N1 | 0.23827 (13) | 0.03543 (12) | 0.27084 (7) | 0.0402 (4) | |
N2 | 0.26390 (13) | 0.27281 (12) | 0.11112 (7) | 0.0384 (4) | |
N3 | 0.26336 (12) | 0.63883 (12) | 0.08122 (7) | 0.0377 (4) | |
C1 | 0.2783 (2) | 0.17360 (18) | 0.21648 (9) | 0.0622 (7) | |
H1 | 0.3006 | 0.2388 | 0.2170 | 0.075* | |
C2 | 0.2695 (2) | 0.12781 (17) | 0.26771 (9) | 0.0654 (8) | |
H2 | 0.2863 | 0.1638 | 0.3022 | 0.079* | |
C3 | 0.2163 (2) | −0.01285 (16) | 0.22092 (10) | 0.0577 (7) | |
H3 | 0.1953 | −0.0783 | 0.2215 | 0.069* | |
C4 | 0.2229 (2) | 0.02835 (16) | 0.16801 (10) | 0.0609 (7) | |
H4 | 0.2055 | −0.0090 | 0.1341 | 0.073* | |
C5 | 0.25462 (16) | 0.12378 (14) | 0.16501 (9) | 0.0376 (5) | |
C6 | 0.25986 (15) | 0.17335 (15) | 0.10865 (8) | 0.0357 (5) | |
C7 | 0.25918 (16) | 0.12118 (15) | 0.05764 (8) | 0.0403 (5) | |
H7 | 0.2567 | 0.0520 | 0.0579 | 0.048* | |
C8 | 0.26220 (14) | 0.17133 (14) | 0.00593 (8) | 0.0347 (5) | |
C9 | 0.26433 (16) | 0.27450 (14) | 0.00884 (9) | 0.0387 (5) | |
H9 | 0.2649 | 0.3117 | −0.0246 | 0.046* | |
C10 | 0.26559 (15) | 0.32220 (14) | 0.06159 (8) | 0.0347 (5) | |
C11 | 0.26723 (15) | 0.43249 (14) | 0.06757 (8) | 0.0356 (5) | |
C12 | 0.25005 (16) | 0.49616 (14) | 0.01986 (9) | 0.0394 (5) | |
H12 | 0.2400 | 0.4705 | −0.0178 | 0.047* | |
C13 | 0.24805 (15) | 0.59650 (15) | 0.02846 (9) | 0.0404 (5) | |
H13 | 0.2354 | 0.6377 | −0.0041 | 0.049* | |
C14 | 0.28264 (18) | 0.57757 (15) | 0.12719 (9) | 0.0492 (6) | |
H14 | 0.2954 | 0.6052 | 0.1644 | 0.059* | |
C15 | 0.28448 (19) | 0.47635 (16) | 0.12209 (9) | 0.0495 (6) | |
H15 | 0.2974 | 0.4369 | 0.1554 | 0.059* | |
C16 | 0.26189 (15) | 0.11671 (14) | −0.04945 (8) | 0.0355 (5) | |
C17 | 0.24822 (17) | 0.01453 (15) | −0.05372 (9) | 0.0433 (5) | |
H17 | 0.2403 | −0.0210 | −0.0208 | 0.052* | |
C18 | 0.24604 (17) | −0.03592 (16) | −0.10542 (9) | 0.0475 (6) | |
H18 | 0.2360 | −0.1043 | −0.1069 | 0.057* | |
C19 | 0.25856 (18) | 0.01415 (16) | −0.15492 (9) | 0.0463 (6) | |
C20 | 0.27351 (19) | 0.11550 (17) | −0.15099 (10) | 0.0544 (6) | |
H20 | 0.2826 | 0.1505 | −0.1838 | 0.065* | |
C21 | 0.27534 (18) | 0.16609 (17) | −0.09943 (9) | 0.0498 (6) | |
H21 | 0.2858 | 0.2344 | −0.0981 | 0.060* | |
C22 | 0.2009 (3) | −0.1586 (2) | −0.21953 (13) | 0.0987 (12) | |
H22A | 0.2369 | −0.2000 | −0.1895 | 0.148* | |
H22B | 0.1946 | −0.1915 | −0.2565 | 0.148* | |
H22C | 0.1380 | −0.1464 | −0.2113 | 0.148* | |
O1A | 0.29796 (13) | −0.13868 (11) | 0.38313 (7) | 0.0583 (4) | |
O2A | 0.32724 (11) | 0.07003 (11) | 0.39319 (6) | 0.0442 (4) | |
C1A | 0.4306 (3) | −0.2400 (2) | 0.42020 (16) | 0.1062 (13) | |
H1AA | 0.4051 | −0.2677 | 0.4519 | 0.159* | |
H1AB | 0.4993 | −0.2341 | 0.4315 | 0.159* | |
H1AC | 0.4148 | −0.2828 | 0.3868 | 0.159* | |
C2A | 0.3871 (2) | −0.13828 (19) | 0.40509 (11) | 0.0607 (7) | |
C3A | 0.4441 (2) | −0.0551 (2) | 0.41636 (12) | 0.0673 (7) | |
H3A | 0.5097 | −0.0655 | 0.4294 | 0.081* | |
C4A | 0.41288 (18) | 0.04379 (18) | 0.41012 (10) | 0.0496 (6) | |
C5A | 0.4852 (2) | 0.1264 (2) | 0.42386 (16) | 0.0896 (10) | |
H5AA | 0.5053 | 0.1469 | 0.3888 | 0.134* | |
H5AB | 0.5402 | 0.1034 | 0.4516 | 0.134* | |
H5AC | 0.4565 | 0.1817 | 0.4400 | 0.134* | |
O1B | 0.13151 (12) | 0.05352 (13) | 0.38961 (7) | 0.0612 (4) | |
O2B | 0.10714 (13) | −0.11416 (14) | 0.31358 (7) | 0.0686 (5) | |
C1B | 0.0021 (3) | 0.0937 (3) | 0.4345 (2) | 0.1332 (16) | |
H1BA | 0.0508 | 0.1150 | 0.4668 | 0.200* | |
H1BB | −0.0463 | 0.0563 | 0.4487 | 0.200* | |
H1BC | −0.0270 | 0.1508 | 0.4135 | 0.200* | |
C2B | 0.0472 (2) | 0.0294 (3) | 0.39461 (14) | 0.0772 (9) | |
C3B | −0.0035 (2) | −0.0486 (3) | 0.36671 (17) | 0.0913 (10) | |
H3B | −0.0644 | −0.0592 | 0.3749 | 0.110* | |
C4B | 0.0249 (2) | −0.1140 (2) | 0.32762 (13) | 0.0753 (9) | |
C5B | −0.0453 (3) | −0.1923 (3) | 0.29922 (16) | 0.1174 (14) | |
H5BA | −0.0819 | −0.1669 | 0.2632 | 0.176* | |
H5BB | −0.0882 | −0.2093 | 0.3248 | 0.176* | |
H5BC | −0.0105 | −0.2505 | 0.2915 | 0.176* | |
O1C | 0.33071 (13) | 0.78156 (11) | 0.17868 (7) | 0.0557 (4) | |
O2C | 0.34574 (12) | 0.87955 (12) | 0.07399 (8) | 0.0602 (5) | |
C1C | 0.4520 (3) | 0.8109 (3) | 0.26122 (14) | 0.1178 (14) | |
H1CA | 0.4077 | 0.8336 | 0.2847 | 0.177* | |
H1CB | 0.5109 | 0.8479 | 0.2710 | 0.177* | |
H1CC | 0.4651 | 0.7415 | 0.2685 | 0.177* | |
C2C | 0.4079 (2) | 0.8261 (2) | 0.19713 (11) | 0.0637 (7) | |
C3C | 0.4542 (2) | 0.8875 (2) | 0.16381 (15) | 0.0792 (9) | |
H3C | 0.5121 | 0.9159 | 0.1824 | 0.095* | |
C4C | 0.4228 (2) | 0.9106 (2) | 0.10598 (15) | 0.0695 (8) | |
C5C | 0.4834 (2) | 0.9787 (3) | 0.07552 (19) | 0.1181 (15) | |
H5CA | 0.5158 | 0.9398 | 0.0508 | 0.177* | |
H5CB | 0.5302 | 1.0127 | 0.1042 | 0.177* | |
H5CC | 0.4423 | 1.0266 | 0.0523 | 0.177* | |
O1D | 0.16383 (14) | 0.81287 (13) | 0.01464 (7) | 0.0643 (5) | |
O2D | 0.13678 (13) | 0.81541 (13) | 0.13117 (7) | 0.0612 (5) | |
C1D | 0.0275 (2) | 0.8421 (3) | −0.05845 (13) | 0.1007 (11) | |
H1DA | 0.0682 | 0.8756 | −0.0806 | 0.151* | |
H1DB | −0.0323 | 0.8775 | −0.0619 | 0.151* | |
H1DC | 0.0150 | 0.7756 | −0.0730 | 0.151* | |
C2D | 0.0774 (2) | 0.83809 (19) | 0.00505 (12) | 0.0621 (7) | |
C3D | 0.0246 (2) | 0.8601 (3) | 0.04699 (15) | 0.0855 (9) | |
H3D | −0.0368 | 0.8861 | 0.0343 | 0.103* | |
C4D | 0.0549 (2) | 0.8469 (3) | 0.10617 (14) | 0.0808 (9) | |
C5D | −0.0148 (3) | 0.8663 (5) | 0.14618 (18) | 0.178 (3) | |
H5DA | −0.0336 | 0.8042 | 0.1609 | 0.267* | |
H5DB | −0.0708 | 0.8997 | 0.1249 | 0.267* | |
H5DC | 0.0157 | 0.9073 | 0.1781 | 0.267* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.04805 (16) | 0.04775 (16) | 0.03023 (13) | −0.00284 (12) | 0.00929 (11) | 0.00155 (11) |
Zn2 | 0.05416 (17) | 0.02841 (13) | 0.04535 (15) | −0.00145 (12) | 0.01067 (12) | 0.00171 (11) |
S1 | 0.1568 (8) | 0.0639 (5) | 0.0494 (4) | −0.0240 (5) | 0.0473 (5) | −0.0213 (3) |
N1 | 0.0592 (12) | 0.0317 (10) | 0.0301 (9) | −0.0006 (9) | 0.0098 (8) | 0.0002 (8) |
N2 | 0.0548 (11) | 0.0292 (9) | 0.0330 (9) | −0.0001 (8) | 0.0130 (8) | 0.0009 (7) |
N3 | 0.0507 (11) | 0.0297 (9) | 0.0343 (9) | 0.0014 (8) | 0.0126 (8) | 0.0011 (8) |
C1 | 0.111 (2) | 0.0370 (12) | 0.0348 (13) | −0.0201 (14) | 0.0054 (13) | 0.0020 (10) |
C2 | 0.124 (2) | 0.0419 (14) | 0.0273 (12) | −0.0168 (15) | 0.0075 (14) | −0.0045 (10) |
C3 | 0.108 (2) | 0.0307 (12) | 0.0384 (12) | −0.0150 (13) | 0.0236 (13) | −0.0036 (10) |
C4 | 0.121 (2) | 0.0328 (12) | 0.0343 (12) | −0.0124 (14) | 0.0277 (14) | −0.0076 (10) |
C5 | 0.0529 (13) | 0.0287 (11) | 0.0335 (11) | 0.0050 (10) | 0.0145 (10) | 0.0017 (9) |
C6 | 0.0464 (12) | 0.0290 (10) | 0.0334 (11) | 0.0026 (10) | 0.0121 (9) | 0.0026 (9) |
C7 | 0.0605 (14) | 0.0268 (11) | 0.0358 (11) | 0.0019 (10) | 0.0146 (10) | 0.0005 (9) |
C8 | 0.0429 (12) | 0.0309 (11) | 0.0316 (10) | 0.0006 (9) | 0.0100 (9) | −0.0003 (9) |
C9 | 0.0549 (14) | 0.0317 (12) | 0.0316 (11) | 0.0005 (10) | 0.0139 (10) | 0.0030 (9) |
C10 | 0.0443 (12) | 0.0295 (11) | 0.0317 (11) | 0.0002 (9) | 0.0110 (9) | 0.0012 (9) |
C11 | 0.0473 (12) | 0.0297 (11) | 0.0322 (11) | −0.0005 (10) | 0.0133 (9) | 0.0018 (9) |
C12 | 0.0591 (14) | 0.0316 (11) | 0.0280 (10) | 0.0012 (10) | 0.0098 (10) | −0.0006 (8) |
C13 | 0.0533 (14) | 0.0365 (12) | 0.0320 (11) | 0.0013 (10) | 0.0095 (10) | 0.0061 (9) |
C14 | 0.0880 (18) | 0.0310 (12) | 0.0300 (11) | −0.0034 (12) | 0.0146 (11) | −0.0018 (10) |
C15 | 0.0857 (18) | 0.0324 (12) | 0.0313 (11) | 0.0009 (12) | 0.0140 (11) | 0.0049 (10) |
C16 | 0.0462 (12) | 0.0319 (11) | 0.0302 (10) | 0.0008 (9) | 0.0114 (9) | 0.0005 (8) |
C17 | 0.0671 (16) | 0.0307 (11) | 0.0344 (11) | −0.0009 (11) | 0.0160 (11) | 0.0030 (9) |
C18 | 0.0687 (16) | 0.0324 (12) | 0.0445 (12) | −0.0020 (11) | 0.0188 (12) | −0.0067 (10) |
C19 | 0.0644 (15) | 0.0427 (13) | 0.0350 (12) | −0.0003 (12) | 0.0178 (11) | −0.0049 (10) |
C20 | 0.0902 (19) | 0.0416 (13) | 0.0371 (12) | −0.0052 (13) | 0.0263 (12) | 0.0015 (10) |
C21 | 0.0827 (18) | 0.0316 (12) | 0.0385 (12) | −0.0055 (12) | 0.0203 (12) | 0.0004 (10) |
C22 | 0.155 (3) | 0.074 (2) | 0.071 (2) | −0.033 (2) | 0.033 (2) | −0.0329 (17) |
O1A | 0.0686 (12) | 0.0476 (10) | 0.0546 (10) | −0.0011 (9) | 0.0021 (9) | 0.0064 (8) |
O2A | 0.0454 (9) | 0.0482 (9) | 0.0375 (8) | −0.0003 (8) | 0.0044 (7) | −0.0012 (7) |
C1A | 0.121 (3) | 0.0625 (19) | 0.116 (3) | 0.030 (2) | −0.023 (2) | 0.000 (2) |
C2A | 0.0713 (19) | 0.0572 (16) | 0.0502 (15) | 0.0129 (15) | 0.0034 (13) | 0.0033 (12) |
C3A | 0.0494 (16) | 0.0669 (18) | 0.0803 (19) | 0.0096 (14) | 0.0000 (14) | 0.0039 (15) |
C4A | 0.0460 (15) | 0.0612 (16) | 0.0408 (12) | −0.0044 (12) | 0.0070 (11) | −0.0001 (11) |
C5A | 0.0578 (18) | 0.083 (2) | 0.121 (3) | −0.0132 (16) | 0.0003 (17) | 0.009 (2) |
O1B | 0.0530 (11) | 0.0768 (12) | 0.0559 (10) | 0.0093 (9) | 0.0160 (8) | −0.0014 (9) |
O2B | 0.0654 (12) | 0.0812 (13) | 0.0585 (11) | −0.0264 (10) | 0.0101 (9) | −0.0053 (9) |
C1B | 0.096 (3) | 0.154 (4) | 0.168 (4) | 0.044 (3) | 0.069 (3) | −0.013 (3) |
C2B | 0.0530 (18) | 0.100 (2) | 0.082 (2) | 0.0240 (18) | 0.0224 (16) | 0.0166 (19) |
C3B | 0.0545 (19) | 0.123 (3) | 0.100 (3) | −0.007 (2) | 0.0243 (18) | 0.004 (2) |
C4B | 0.0608 (19) | 0.094 (2) | 0.0652 (19) | −0.0268 (18) | −0.0027 (15) | 0.0240 (17) |
C5B | 0.088 (2) | 0.143 (3) | 0.112 (3) | −0.061 (2) | −0.003 (2) | 0.007 (2) |
O1C | 0.0653 (11) | 0.0541 (10) | 0.0454 (9) | −0.0117 (9) | 0.0051 (8) | 0.0002 (8) |
O2C | 0.0584 (11) | 0.0524 (10) | 0.0694 (11) | −0.0072 (9) | 0.0112 (9) | 0.0201 (9) |
C1C | 0.093 (3) | 0.185 (4) | 0.066 (2) | −0.024 (3) | −0.0092 (18) | 0.002 (2) |
C2C | 0.0586 (17) | 0.0739 (18) | 0.0560 (16) | 0.0018 (15) | 0.0053 (13) | −0.0048 (14) |
C3C | 0.0532 (17) | 0.087 (2) | 0.092 (2) | −0.0222 (16) | 0.0011 (16) | 0.0018 (18) |
C4C | 0.0488 (17) | 0.0579 (17) | 0.103 (2) | −0.0007 (14) | 0.0177 (16) | 0.0238 (17) |
C5C | 0.066 (2) | 0.125 (3) | 0.165 (4) | −0.021 (2) | 0.025 (2) | 0.069 (3) |
O1D | 0.0656 (12) | 0.0698 (12) | 0.0556 (11) | 0.0053 (10) | 0.0075 (9) | 0.0172 (9) |
O2D | 0.0557 (11) | 0.0717 (12) | 0.0562 (10) | 0.0030 (9) | 0.0112 (9) | −0.0194 (9) |
C1D | 0.084 (2) | 0.131 (3) | 0.076 (2) | −0.007 (2) | −0.0116 (17) | 0.028 (2) |
C2D | 0.0652 (19) | 0.0494 (15) | 0.0649 (17) | −0.0096 (14) | −0.0036 (15) | 0.0109 (13) |
C3D | 0.0575 (18) | 0.107 (3) | 0.086 (2) | 0.0180 (18) | −0.0005 (17) | 0.0000 (19) |
C4D | 0.062 (2) | 0.105 (2) | 0.074 (2) | 0.0068 (18) | 0.0116 (17) | −0.0230 (18) |
C5D | 0.080 (3) | 0.362 (8) | 0.096 (3) | 0.056 (4) | 0.027 (2) | −0.039 (4) |
Geometric parameters (Å, º) top
Zn1—O1B | 1.9752 (17) | C22—H22B | 0.9600 |
Zn1—O1A | 1.9812 (16) | C22—H22C | 0.9600 |
Zn1—O2B | 2.0394 (17) | O1A—C2A | 1.265 (3) |
Zn1—N1 | 2.0793 (16) | O2A—C4A | 1.250 (3) |
Zn1—O2A | 2.0894 (15) | C1A—C2A | 1.513 (4) |
Zn2—O2C | 1.9663 (16) | C1A—H1AA | 0.9600 |
Zn2—O2D | 1.9770 (17) | C1A—H1AB | 0.9600 |
Zn2—N3 | 2.0538 (16) | C1A—H1AC | 0.9600 |
Zn2—O1D | 2.0560 (17) | C2A—C3A | 1.373 (4) |
Zn2—O1C | 2.0641 (16) | C3A—C4A | 1.399 (3) |
S1—C19 | 1.755 (2) | C3A—H3A | 0.9300 |
S1—C22 | 1.777 (3) | C4A—C5A | 1.502 (3) |
N1—C3 | 1.318 (3) | C5A—H5AA | 0.9600 |
N1—C2 | 1.325 (3) | C5A—H5AB | 0.9600 |
N2—C6 | 1.339 (3) | C5A—H5AC | 0.9600 |
N2—C10 | 1.340 (2) | O1B—C2B | 1.264 (3) |
N3—C13 | 1.337 (2) | O2B—C4B | 1.270 (3) |
N3—C14 | 1.339 (3) | C1B—C2B | 1.503 (4) |
C1—C5 | 1.361 (3) | C1B—H1BA | 0.9600 |
C1—C2 | 1.375 (3) | C1B—H1BB | 0.9600 |
C1—H1 | 0.9300 | C1B—H1BC | 0.9600 |
C2—H2 | 0.9300 | C2B—C3B | 1.363 (5) |
C3—C4 | 1.375 (3) | C3B—C4B | 1.383 (4) |
C3—H3 | 0.9300 | C3B—H3B | 0.9300 |
C4—C5 | 1.365 (3) | C4B—C5B | 1.509 (4) |
C4—H4 | 0.9300 | C5B—H5BA | 0.9600 |
C5—C6 | 1.492 (3) | C5B—H5BB | 0.9600 |
C6—C7 | 1.382 (3) | C5B—H5BC | 0.9600 |
C7—C8 | 1.393 (3) | O1C—C2C | 1.246 (3) |
C7—H7 | 0.9300 | O2C—C4C | 1.266 (3) |
C8—C9 | 1.388 (3) | C1C—C2C | 1.520 (4) |
C8—C16 | 1.488 (3) | C1C—H1CA | 0.9600 |
C9—C10 | 1.387 (3) | C1C—H1CB | 0.9600 |
C9—H9 | 0.9300 | C1C—H1CC | 0.9600 |
C10—C11 | 1.489 (3) | C2C—C3C | 1.385 (4) |
C11—C15 | 1.382 (3) | C3C—C4C | 1.374 (4) |
C11—C12 | 1.389 (3) | C3C—H3C | 0.9300 |
C12—C13 | 1.365 (3) | C4C—C5C | 1.523 (4) |
C12—H12 | 0.9300 | C5C—H5CA | 0.9600 |
C13—H13 | 0.9300 | C5C—H5CB | 0.9600 |
C14—C15 | 1.366 (3) | C5C—H5CC | 0.9600 |
C14—H14 | 0.9300 | O1D—C2D | 1.247 (3) |
C15—H15 | 0.9300 | O2D—C4D | 1.264 (3) |
C16—C17 | 1.388 (3) | C1D—C2D | 1.515 (4) |
C16—C21 | 1.389 (3) | C1D—H1DA | 0.9600 |
C17—C18 | 1.381 (3) | C1D—H1DB | 0.9600 |
C17—H17 | 0.9300 | C1D—H1DC | 0.9600 |
C18—C19 | 1.380 (3) | C2D—C3D | 1.377 (4) |
C18—H18 | 0.9300 | C3D—C4D | 1.377 (4) |
C19—C20 | 1.379 (3) | C3D—H3D | 0.9300 |
C20—C21 | 1.380 (3) | C4D—C5D | 1.509 (4) |
C20—H20 | 0.9300 | C5D—H5DA | 0.9600 |
C21—H21 | 0.9300 | C5D—H5DB | 0.9600 |
C22—H22A | 0.9600 | C5D—H5DC | 0.9600 |
| | | |
O1B—Zn1—O1A | 125.64 (7) | H22A—C22—H22C | 109.5 |
O1B—Zn1—O2B | 90.42 (8) | H22B—C22—H22C | 109.5 |
O1A—Zn1—O2B | 91.67 (7) | C2A—O1A—Zn1 | 126.89 (16) |
O1B—Zn1—N1 | 115.11 (7) | C4A—O2A—Zn1 | 124.07 (15) |
O1A—Zn1—N1 | 118.78 (7) | C2A—C1A—H1AA | 109.5 |
O2B—Zn1—N1 | 94.96 (7) | C2A—C1A—H1AB | 109.5 |
O1B—Zn1—O2A | 85.63 (7) | H1AA—C1A—H1AB | 109.5 |
O1A—Zn1—O2A | 88.39 (6) | C2A—C1A—H1AC | 109.5 |
O2B—Zn1—O2A | 175.17 (7) | H1AA—C1A—H1AC | 109.5 |
N1—Zn1—O2A | 89.24 (6) | H1AB—C1A—H1AC | 109.5 |
O2C—Zn2—O2D | 130.58 (7) | O1A—C2A—C3A | 125.6 (2) |
O2C—Zn2—N3 | 118.46 (7) | O1A—C2A—C1A | 114.7 (3) |
O2D—Zn2—N3 | 110.95 (7) | C3A—C2A—C1A | 119.6 (3) |
O2C—Zn2—O1D | 88.99 (7) | C2A—C3A—C4A | 126.3 (2) |
O2D—Zn2—O1D | 88.94 (7) | C2A—C3A—H3A | 116.9 |
N3—Zn2—O1D | 93.89 (7) | C4A—C3A—H3A | 116.9 |
O2C—Zn2—O1C | 88.96 (7) | O2A—C4A—C3A | 124.6 (2) |
O2D—Zn2—O1C | 87.23 (7) | O2A—C4A—C5A | 115.9 (2) |
N3—Zn2—O1C | 93.05 (6) | C3A—C4A—C5A | 119.5 (2) |
O1D—Zn2—O1C | 172.91 (7) | C4A—C5A—H5AA | 109.5 |
C19—S1—C22 | 105.07 (12) | C4A—C5A—H5AB | 109.5 |
C3—N1—C2 | 115.83 (18) | H5AA—C5A—H5AB | 109.5 |
C3—N1—Zn1 | 123.36 (14) | C4A—C5A—H5AC | 109.5 |
C2—N1—Zn1 | 120.71 (14) | H5AA—C5A—H5AC | 109.5 |
C6—N2—C10 | 117.73 (16) | H5AB—C5A—H5AC | 109.5 |
C13—N3—C14 | 116.73 (17) | C2B—O1B—Zn1 | 126.6 (2) |
C13—N3—Zn2 | 124.09 (13) | C4B—O2B—Zn1 | 124.3 (2) |
C14—N3—Zn2 | 119.03 (13) | C2B—C1B—H1BA | 109.5 |
C5—C1—C2 | 120.1 (2) | C2B—C1B—H1BB | 109.5 |
C5—C1—H1 | 119.9 | H1BA—C1B—H1BB | 109.5 |
C2—C1—H1 | 119.9 | C2B—C1B—H1BC | 109.5 |
N1—C2—C1 | 123.8 (2) | H1BA—C1B—H1BC | 109.5 |
N1—C2—H2 | 118.1 | H1BB—C1B—H1BC | 109.5 |
C1—C2—H2 | 118.1 | O1B—C2B—C3B | 124.8 (3) |
N1—C3—C4 | 123.6 (2) | O1B—C2B—C1B | 115.7 (3) |
N1—C3—H3 | 118.2 | C3B—C2B—C1B | 119.4 (3) |
C4—C3—H3 | 118.2 | C2B—C3B—C4B | 127.6 (3) |
C5—C4—C3 | 120.4 (2) | C2B—C3B—H3B | 116.2 |
C5—C4—H4 | 119.8 | C4B—C3B—H3B | 116.2 |
C3—C4—H4 | 119.8 | O2B—C4B—C3B | 124.9 (3) |
C1—C5—C4 | 116.31 (19) | O2B—C4B—C5B | 116.2 (3) |
C1—C5—C6 | 121.03 (18) | C3B—C4B—C5B | 118.8 (3) |
C4—C5—C6 | 122.61 (18) | C4B—C5B—H5BA | 109.5 |
N2—C6—C7 | 122.46 (17) | C4B—C5B—H5BB | 109.5 |
N2—C6—C5 | 114.64 (16) | H5BA—C5B—H5BB | 109.5 |
C7—C6—C5 | 122.89 (17) | C4B—C5B—H5BC | 109.5 |
C6—C7—C8 | 120.52 (18) | H5BA—C5B—H5BC | 109.5 |
C6—C7—H7 | 119.7 | H5BB—C5B—H5BC | 109.5 |
C8—C7—H7 | 119.7 | C2C—O1C—Zn2 | 126.40 (16) |
C9—C8—C7 | 116.43 (17) | C4C—O2C—Zn2 | 127.99 (17) |
C9—C8—C16 | 122.11 (17) | C2C—C1C—H1CA | 109.5 |
C7—C8—C16 | 121.46 (17) | C2C—C1C—H1CB | 109.5 |
C10—C9—C8 | 120.09 (18) | H1CA—C1C—H1CB | 109.5 |
C10—C9—H9 | 120.0 | C2C—C1C—H1CC | 109.5 |
C8—C9—H9 | 120.0 | H1CA—C1C—H1CC | 109.5 |
N2—C10—C9 | 122.74 (17) | H1CB—C1C—H1CC | 109.5 |
N2—C10—C11 | 114.50 (16) | O1C—C2C—C3C | 124.8 (3) |
C9—C10—C11 | 122.75 (17) | O1C—C2C—C1C | 116.0 (3) |
C15—C11—C12 | 116.71 (18) | C3C—C2C—C1C | 119.2 (3) |
C15—C11—C10 | 120.54 (17) | C4C—C3C—C2C | 126.3 (3) |
C12—C11—C10 | 122.74 (17) | C4C—C3C—H3C | 116.9 |
C13—C12—C11 | 119.71 (18) | C2C—C3C—H3C | 116.9 |
C13—C12—H12 | 120.1 | O2C—C4C—C3C | 125.5 (2) |
C11—C12—H12 | 120.1 | O2C—C4C—C5C | 114.9 (3) |
N3—C13—C12 | 123.53 (18) | C3C—C4C—C5C | 119.6 (3) |
N3—C13—H13 | 118.2 | C4C—C5C—H5CA | 109.5 |
C12—C13—H13 | 118.2 | C4C—C5C—H5CB | 109.5 |
N3—C14—C15 | 123.13 (19) | H5CA—C5C—H5CB | 109.5 |
N3—C14—H14 | 118.4 | C4C—C5C—H5CC | 109.5 |
C15—C14—H14 | 118.4 | H5CA—C5C—H5CC | 109.5 |
C14—C15—C11 | 120.15 (19) | H5CB—C5C—H5CC | 109.5 |
C14—C15—H15 | 119.9 | C2D—O1D—Zn2 | 126.08 (18) |
C11—C15—H15 | 119.9 | C4D—O2D—Zn2 | 127.40 (19) |
C17—C16—C21 | 116.91 (18) | C2D—C1D—H1DA | 109.5 |
C17—C16—C8 | 121.82 (17) | C2D—C1D—H1DB | 109.5 |
C21—C16—C8 | 121.27 (18) | H1DA—C1D—H1DB | 109.5 |
C18—C17—C16 | 121.83 (19) | C2D—C1D—H1DC | 109.5 |
C18—C17—H17 | 119.1 | H1DA—C1D—H1DC | 109.5 |
C16—C17—H17 | 119.1 | H1DB—C1D—H1DC | 109.5 |
C19—C18—C17 | 120.69 (19) | O1D—C2D—C3D | 125.5 (3) |
C19—C18—H18 | 119.7 | O1D—C2D—C1D | 115.9 (3) |
C17—C18—H18 | 119.7 | C3D—C2D—C1D | 118.5 (3) |
C20—C19—C18 | 117.98 (19) | C2D—C3D—C4D | 125.7 (3) |
C20—C19—S1 | 117.78 (17) | C2D—C3D—H3D | 117.2 |
C18—C19—S1 | 124.18 (16) | C4D—C3D—H3D | 117.2 |
C19—C20—C21 | 121.4 (2) | O2D—C4D—C3D | 125.7 (3) |
C19—C20—H20 | 119.3 | O2D—C4D—C5D | 115.0 (3) |
C21—C20—H20 | 119.3 | C3D—C4D—C5D | 119.3 (3) |
C20—C21—C16 | 121.2 (2) | C4D—C5D—H5DA | 109.5 |
C20—C21—H21 | 119.4 | C4D—C5D—H5DB | 109.5 |
C16—C21—H21 | 119.4 | H5DA—C5D—H5DB | 109.5 |
S1—C22—H22A | 109.5 | C4D—C5D—H5DC | 109.5 |
S1—C22—H22B | 109.5 | H5DA—C5D—H5DC | 109.5 |
H22A—C22—H22B | 109.5 | H5DB—C5D—H5DC | 109.5 |
S1—C22—H22C | 109.5 | | |
Hydrogen-bond geometry (Å, º) topTable 3. C—H···π contacts in (II) (Å, °). Cg4 is the centroid of the Zn2/O1D/C2D/C3D/C4D/O2D chelate ring and
Cg8 is the centroid of the C16–C21 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg4i | 0.93 | 2.85 | 3.712 (3) | 155 |
C1B—H1BC···Cg4ii | 0.96 | 2.78 | 3.563 (4) | 140 |
C5D—H5DB···Cg8iii | 0.96 | 2.67 | 3.549 (5) | 152 |
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Zn(C5H7O2)2(C22H17N3S)2] | [Zn2(C5H7O2)4(C22H17N3S)] |
Mr | 974.47 | 882.61 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 26.6479 (7), 10.7706 (3), 16.4983 (5) | 14.1522 (3), 13.4408 (3), 23.3887 (5) |
β (°) | 99.187 (3) | 101.342 (2) |
V (Å3) | 4674.5 (2) | 4362.05 (16) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.67 | 1.20 |
Crystal size (mm) | 0.26 × 0.20 × 0.12 | 0.32 × 0.16 × 0.14 |
|
Data collection |
Diffractometer | Oxford Diffraction Gemini CCD S Ultra diffractometer | Oxford Diffraction Gemini CCD S Ultra diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.83, 0.92 | 0.80, 0.85 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9886, 5288, 3620 | 27845, 9862, 6308 |
Rint | 0.017 | 0.028 |
(sin θ/λ)max (Å−1) | 0.680 | 0.683 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.00 | 0.034, 0.087, 0.98 |
No. of reflections | 5288 | 9862 |
No. of parameters | 307 | 505 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.40 | 0.41, −0.35 |
Hydrogen-bond geometry (Å, º) for (I) topTable 1. C—H···π contacts in (I) (Å, °). Cg1 is the centroid of the Zn1/O1A/C2A/C3A/C4A/O2A chelate ring
and Cg2 is the centroid of the N1/C1–C5 pyridine ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1i | 0.93 | 2.66 | 3.187 (2) | 116 |
C3—H3···Cg1 | 0.93 | 2.43 | 3.001 (2) | 120 |
C21—H21···Cg2ii | 0.93 | 2.87 | 3.560 (2) | 132 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x, −y+1, −z. |
Table 2. π–π contacts in (I) (Å, °)
Cg4 is the centroid of the N3/C11-C15 pyridine ring. topGroup 1/Group 2 | ccd (Å) | da (°) | ipd (Å) | sa (°) |
Cg4···Cg4iii | 3.945 (2) | 0 | 3.7822 (14) | 16.48 |
Symmetry code: (iii) -x, -y+1, -z.
Notes: ccd is the center-to-center distance (distance between ring centroids);
da is the dihedral angle between rings; ipd is the interplanar distance
(distance from one plane to the neighbouring centroid), sa is the slippage
angle (angle subtended by the intercentroid vector to the plane normal).
For details, see Janiak (2000). |
Hydrogen-bond geometry (Å, º) for (II) topTable 3. C—H···π contacts in (II) (Å, °). Cg4 is the centroid of the Zn2/O1D/C2D/C3D/C4D/O2D chelate ring and
Cg8 is the centroid of the C16–C21 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cg4i | 0.93 | 2.85 | 3.712 (3) | 155 |
C1B—H1BC···Cg4ii | 0.96 | 2.78 | 3.563 (4) | 140 |
C5D—H5DB···Cg8iii | 0.96 | 2.67 | 3.549 (5) | 152 |
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x, −y+1, −z. |
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The study of the coordination chemistry of 2,2':6',2''-terpyridine and its derivatives has been directed more commonly to their behaviour as chelating ligands, i.e. in systems in which they present a convergent disposition of their pyridine N-donor atoms to link to metal centres (Constable, 2007; Eryazici et al., 2008). In contrast, 4'-aryl-substituted terpyridine-based ligands with divergent coordinating geometry, able to bridge at least two metal centers, have been scarce and structural reports on their complexes are relatively recent. The pioneering work of Cave & Raston (2002) was based on the 4'-(4-octyloxyphenyl)-4,2':6',4''-terpyridine ligand (L2), which in its reaction with ZnCl2 produced the helical coordination polymer [ZnCl2(L2)]n, in which the ligand bridges two ZnII centres via only its terminal pyridine N atoms. The remaining reports using this type of functionalized 4,2':6',4''-terpyridine are very recent, from 2008 onward (Li et al., 2008; Constable, Zhang, Coronado et al., 2010; Constable, Zhang, Housecroft et al., 2010; Constable et al., 2011; Li et al. 2011). A common feature in all of these compounds is the bridging behaviour of the terpyridine-based derivatives, which gives rise to polymeric structures of from one to three dimensions, with the sole exception of a discrete molecular metallohexacycle obtained from the reaction of ZnCl2 and 4'-ethynylphenyl-4,2':6',4''-terpyridine (Constable et al., 2011).
We report herein two ZnII complexes containing a ligand of this type, namely 4'-[4-(methylsulfanyl)phenyl]-4,2':6',4''-terpyridine (L1), along with the acetylacetonate (acac) anion. Both complexes have unusual discrete molecular character, viz. [Zn(acac)2(L1)2], (I), is mononuclear and [Zn2(acac)4(µ-L1)], (II), is dinuclear. To our knowledge, (I) is the first reported complex with monodentate coordination for a functionalized 4'-aryl-substituted 4,2':6',4''-terpyridine ligand. This is in contrast to the three known complexes involving the L1 ligand, which are polymers, one (one-dimensional) obtained by reacting L1 with Zn(NO3)2 (Constable, Zhang, Coronado et al., 2010) and the other two (one- and two-dimensional) with Cd(NO3)2 (Constable, Zhang, Housecroft et al., 2010).
Compound (I) (Fig. 1) consists of two centrosymmetrically related monodentate L1 ligands bound to atom Zn1, which sits on an inversion centre, and two (also centrosymmetrically related) chelating acac groups which bind laterally via carbonyl O-atom donors to provide a nearly regular N2O4 octahedral environment [Zn1—O2A = 2.0448 (13) Å, Zn1—O1A = 2.0667 (12) Å and Zn1—N1 = 2.2607 (14) Å, cis angles are in the range 90±2.05 (5)°].
Sharing with (I) its novel discrete character, but differing from it in being a binuclear structure, compound (II) consists of a bis-monodentate L1 ligand bridging two ZnII (Zn1 and Zn2) atoms from two different Zn(acac)2 fragments (Fig. 2). Each ZnII centre has an NO4 coordination sphere; four sites are provided by two different acac groups [Zn—O = 1.9663 (16)–2.0894 (15) Å] coordinated in the usual chelating form through their carbonyl O-atom donors, with the planar rings forming dihedral angles of 52.00 (9) and 52.60 (10)° for Zn1 and Zn2, respectively. This contrasts markedly with the rigorous coplanarity of the acac ligands in (I), due to the center of symmetry. The fifth site of the coordination polyhedron in (II) is occupied by a pyridine N atom from the L1 ligand [Zn1—N = 2.0793 (16) Å and Zn2—N = 2.0538 (16) Å]. The geometry around each ZnII atom is trigonal bipyramidal, with O2A—Zn1—O2B and O1C—Zn2—O1D angles of 175.17 (7) and 172.91 (7)°, respectively, and apical–equatorial angles in the range 90±4.96 (7) and 90±3.89 (7)°.
In both structures, the L1 ligand deviates from planarity, involving rotation of neighboring six-membered rings. In (I), the N2/C6–C10 and N3/C11–C16 pyridine rings are almost coplanar [dihedral angle = 1.92 (6)°], while the N1/C1–C5 pyridine ring and the methylsulfanyl-substituted benzene ring (C16–C21) deviate significantly from this disposition [dihedral angle = 54.95 (9)°]. Compound (II), instead, presents all three lateral rings, viz. pyridine N1/C1–C5, pyridine N2/C6–C10 and benzene C16–C21 (Fig. 2), rotated with respect to the central N3/C11–C15 pyridine ring by dihedral angles of 18.20 (12), 12.91 (11) and 7.37 (11)°, respectively.
Nonbonding interactions in (I) and (II) (C—H···π and π–π) are very weak and could probably be assigned the character of London forces and/or dipole-induced dipole interactions. In spite of their weakness, however, they play an esential role in crystal stability to be discussed below.
In (I), two intramolecular C—H···π contacts (Table 1, first and second entries, and Fig. 3a) serve to limit the free rotation of the N1/C1–C5 pyridine ring around the Zn1—N1 bond. The N1/C1–C5 pyridine ring and its symmetry equivalent partner at (-x+1/2, -y+1/2, -z) are rigorously parallel by symmetry. The remaining C—H···π (Table 1, third entry and Fig. 3b) and π–π (Table 2 and Fig. 3c) contacts complete the intermolecular interaction scheme. The final result is the formation of planar arrays of Zn(L1)2 groups parallel to (102) (Fig. 4a) formed by parallel molecules extending along b, with the acac anions roughly perpendicular to the principal plane of the array. These planes have the peculiarity of not presenting any direct `in-plane' interaction, but rather of being connected only through indirect `interplanar' contacts mediated by molecules in neighbouring planes, in a staggered pattern as shown in Fig. 4b.
In contrast to (I), in (II) there are no intramolecular interactions, the most significant intermolecular interactions being three weak C—H···π contacts (Table 3 and Fig. 5). The overall arrangement is again a pattern of planar arrays (formed by the Zn2L1 groups) parallel to (100) (Fig. 6). As in (I), there are no direct `in-plane' interactions present, cohesion being achieved through indirect zigzag contacts between molecules in neighbouring planes. What appear to be voids in Fig. 6 are in fact visual artifacts – the locus of unrepresented H atoms – as can be seen in a space-filling drawing. PLATON (Spek, 2009) was used to confirm the absence of voids.
Compound (II) is similar to a recently published dinuclear [Zn2(acac)4(µ-L3)], (III), analogue {L3 is 4'-[4-(methylsulfantl)phenyl)-3,2':6',3''-terpyridine; Granifo et al., 2011}, with a similar dinuclear configuration despite an important difference in that the the pyridine N-donor atoms have a convergent disposition in L3. The point to be highlighted, however, is the significant influence that sulfur-mediated nonbonded interactions have in (III), while their influence appears almost nil in the structures of (I) and (II) reported here.