Commercial histamine dihydrochloride (98%+, Alfa Aesar) and
4(5)-hydroxymethylimidazole (97%, Aldrich) were used. The synthesis of
tri-tert-butoxysilanethiol was as described by Piękoś & Wojnowski
(1962) and the synthesis of zinc acetyloacetonate was as described by
Hassanein & Hewaidy (1970).
For the preparation of (III), triethylamine (2 mmol, 0.28 ml) was added to a
CoII chloride hexahydrate (0.5 mmol, 0.12 g) solution in 50 ml of water.
Histamine dihydrochloride (2 mmol, 0.37 g) and neat
tri-tert-butoxysilanethiol (1 mmol, 1.37 ml) were added to the
resulting suspension. The reaction flask was closed with a rubber septum and
the suspension was shaken vigorously for 20 min. A blue hydrophobic
precipitate was collected, washed with water and dried in air. The dry solid
was dissolved in methanol, the solution was filtered and the filtrate was left
at 273–278 K. After a weekend, dark-blue crystals were collected [m.p. slow
decomposition 403–423 K, black product melts at 456–458 K; yield 78% (crude
product)].
Compound (IV) was synthesized in the same manner as (III). ZnII chloride
hexahydrate (0.5 mmol, 0.12 g) was used instead of CoII chloride
hexahydrate, and the resulting white, hydrophobic precipitate was
recrystallized from methanol–acetonitrile mixture (80% v/v
methanol) [m.p. 471–475 K with decomposition; yield 99% (crude product)].
For the preparation of (V), zinc acetyloacetonate (1 mmol, 0.27 g) and
tri-tert-butoxysilanethiol (6 mmol, 0.9 ml) were suspended in 5 ml of
methanol and warmed till dissolution. 4(5)-Hydroxyimidazole (1 mmol, 0.098 g)
in 1 ml of methanol was added to the reaction mixture. Crystallization
occurred immediately. Crystals were collected and recrystallized from a
toluene/methanol mixture (50% v/v) (yield 87% of crude
product).
The tBu groups attached to atom O6 are disordered over two
orientations. In (III), the disordered atoms were set as isotropic. The site
occupancies of the disordered groups are 0.641 (9) and 0.359 (9) in (III),
0.612 (17) and 0.388 (17) in (IV), and 0.65 (3) and 0.35 (3) in (V). H atoms were
positioned geometrically and refined using a riding model, with C—H =
0.95–0.98 Å, N—H = 0.88–0.92 Å, O—H = 0.84 Å and Uiso(H)
= 1.2Ueq(C,O,N), 1.3Ueq(C,N) [all methylene C and NH2 in
(IV)] or 1.5Ueq(C) (all methyl C).
There were missing reflections reported by PLATON in (III) and (IV). An
inspection of the structure factors has revealed that the missing reflections
are located either below Θmin or above Θ = 19°. The calculated values of
intensity for the missing reflections above Θ = 19° [13 for (III) and 19 for
(IV)] indicate that their intensity is low or very low. Since the overall
completeness of both measurements is above 99%, we assume that the missing
reflections do not have a significant influence on the refinement results.
The most discrepant low-angle reflections (outliers) removed from the
refinements were 100 for (III); 111 for (IV); and 111, 200, 110 and 112 for
(V).
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006). Program(s) used to solve structure: SHELXS86 (Sheldrick, 2008) for (III); SHELXS97 (Sheldrick, 2008) for (IV), (V). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(III) [2-(1H-imidazol-4-yl-
κN
3)ethylamine-
κ2N]bis(tri-
tert-butoxysilanethiolato-
κS)cobalt(II)
top
Crystal data top
[Co(C12H27O3SSi)2(C5H9N3)] | Z = 2 |
Mr = 729.05 | F(000) = 786 |
Triclinic, P1 | Dx = 1.217 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2498 (4) Å | Cell parameters from 12335 reflections |
b = 14.3000 (9) Å | θ = 2.3–32.5° |
c = 16.0164 (11) Å | µ = 0.64 mm−1 |
α = 95.190 (5)° | T = 120 K |
β = 96.805 (4)° | Prism, blue |
γ = 107.336 (4)° | 0.16 × 0.10 × 0.06 mm |
V = 1990.3 (2) Å3 | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7381 independent reflections |
Graphite monochromator | 6248 reflections with I > 2σ(I) |
Detector resolution: 8.1883 pixels mm-1 | Rint = 0.026 |
ω scans, 0.75 deg width | θmax = 25.5°, θmin = 2.4° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by Clark & Reid [(1995).
Acta Cryst. A51, 887-897] | h = −11→11 |
Tmin = 0.842, Tmax = 0.93 | k = −16→17 |
13851 measured reflections | l = −19→16 |
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) = 0.093 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.061P)2 + 0.0814P] where P = (Fo2 + 2Fc2)/3 |
7381 reflections | (Δ/σ)max = 0.001 |
407 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
[Co(C12H27O3SSi)2(C5H9N3)] | γ = 107.336 (4)° |
Mr = 729.05 | V = 1990.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2498 (4) Å | Mo Kα radiation |
b = 14.3000 (9) Å | µ = 0.64 mm−1 |
c = 16.0164 (11) Å | T = 120 K |
α = 95.190 (5)° | 0.16 × 0.10 × 0.06 mm |
β = 96.805 (4)° | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7381 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by Clark & Reid [(1995).
Acta Cryst. A51, 887-897] | 6248 reflections with I > 2σ(I) |
Tmin = 0.842, Tmax = 0.93 | Rint = 0.026 |
13851 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.64 e Å−3 |
7381 reflections | Δρmin = −0.33 e Å−3 |
407 parameters | |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F2, conventional R-factors R are based
on F, with F set to zero for negative F2. The threshold expression of
F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.3788 (2) | 0.15877 (14) | 0.11437 (12) | 0.0265 (4) | |
C2 | 0.4409 (2) | 0.25794 (16) | 0.08301 (13) | 0.0314 (5) | |
H2A | 0.5461 | 0.2672 | 0.0724 | 0.047* | |
H2B | 0.4401 | 0.3109 | 0.1261 | 0.047* | |
H2C | 0.3765 | 0.2597 | 0.0303 | 0.047* | |
C3 | 0.4768 (2) | 0.15259 (15) | 0.19555 (13) | 0.0326 (5) | |
H3A | 0.4355 | 0.0876 | 0.2138 | 0.049* | |
H3B | 0.4759 | 0.2042 | 0.24 | 0.049* | |
H3C | 0.5822 | 0.162 | 0.1852 | 0.049* | |
C4 | 0.3713 (3) | 0.07452 (18) | 0.04676 (15) | 0.0457 (6) | |
H4A | 0.3308 | 0.0112 | 0.068 | 0.068* | |
H4B | 0.4743 | 0.0814 | 0.0334 | 0.068* | |
H4C | 0.3039 | 0.0768 | −0.0046 | 0.068* | |
C5 | −0.0738 (2) | 0.07958 (13) | 0.24616 (11) | 0.0219 (4) | |
C6 | −0.1115 (2) | 0.13698 (14) | 0.32097 (12) | 0.0292 (4) | |
H6A | −0.0203 | 0.1918 | 0.3466 | 0.044* | |
H6B | −0.1442 | 0.0929 | 0.3633 | 0.044* | |
H6C | −0.1942 | 0.1631 | 0.3012 | 0.044* | |
C7 | 0.0538 (2) | 0.03738 (15) | 0.27501 (14) | 0.0323 (5) | |
H7A | 0.0785 | 0.0026 | 0.2258 | 0.048* | |
H7B | 0.02 | −0.0089 | 0.3155 | 0.048* | |
H7C | 0.1449 | 0.0913 | 0.3023 | 0.048* | |
C8 | −0.2145 (2) | −0.00252 (14) | 0.20242 (13) | 0.0309 (4) | |
H8A | −0.2922 | 0.026 | 0.1792 | 0.046* | |
H8B | −0.2557 | −0.0463 | 0.2435 | 0.046* | |
H8C | −0.1868 | −0.0404 | 0.1563 | 0.046* | |
C9 | 0.0014 (2) | 0.26009 (14) | 0.01681 (11) | 0.0238 (4) | |
C10 | 0.0164 (2) | 0.16796 (15) | −0.03108 (12) | 0.0308 (5) | |
H10A | 0.1233 | 0.1791 | −0.0391 | 0.046* | |
H10B | −0.0489 | 0.1527 | −0.0865 | 0.046* | |
H10C | −0.0156 | 0.1124 | 0.0014 | 0.046* | |
C11 | 0.0587 (3) | 0.34908 (16) | −0.02986 (13) | 0.0377 (5) | |
H11A | 0.0498 | 0.4081 | 0.0026 | 0.057* | |
H11B | −0.0032 | 0.3373 | −0.0861 | 0.057* | |
H11C | 0.1662 | 0.359 | −0.036 | 0.057* | |
C12 | −0.1652 (2) | 0.24452 (17) | 0.02788 (13) | 0.0339 (5) | |
H12A | −0.1746 | 0.3054 | 0.0568 | 0.051* | |
H12B | −0.1985 | 0.1906 | 0.0619 | 0.051* | |
H12C | −0.2296 | 0.2276 | −0.0279 | 0.051* | |
C13 | 0.4944 (2) | 0.63086 (14) | 0.18349 (11) | 0.0245 (4) | |
C14 | 0.3985 (3) | 0.57563 (17) | 0.09988 (13) | 0.0365 (5) | |
H14A | 0.3376 | 0.5094 | 0.1087 | 0.055* | |
H14B | 0.4663 | 0.5702 | 0.0583 | 0.055* | |
H14C | 0.33 | 0.6118 | 0.0788 | 0.055* | |
C15 | 0.5884 (2) | 0.57052 (16) | 0.22226 (13) | 0.0323 (5) | |
H15A | 0.6488 | 0.6066 | 0.2763 | 0.048* | |
H15B | 0.6574 | 0.559 | 0.1834 | 0.048* | |
H15C | 0.5197 | 0.507 | 0.2321 | 0.048* | |
C16 | 0.5967 (3) | 0.73176 (15) | 0.17099 (13) | 0.0350 (5) | |
H16A | 0.5336 | 0.7695 | 0.1463 | 0.053* | |
H16B | 0.6686 | 0.7237 | 0.1327 | 0.053* | |
H16C | 0.6541 | 0.7672 | 0.2259 | 0.053* | |
C17 | 0.6714 (2) | 0.78619 (14) | 0.45211 (12) | 0.0268 (4) | |
C18 | 0.7561 (2) | 0.71228 (17) | 0.47151 (14) | 0.0369 (5) | |
H18A | 0.6824 | 0.6494 | 0.479 | 0.055* | |
H18B | 0.83 | 0.7383 | 0.5237 | 0.055* | |
H18C | 0.8104 | 0.7016 | 0.4244 | 0.055* | |
C19 | 0.7845 (3) | 0.88428 (16) | 0.44070 (14) | 0.0432 (6) | |
H19A | 0.8384 | 0.8743 | 0.3932 | 0.065* | |
H19B | 0.8589 | 0.9102 | 0.4927 | 0.065* | |
H19C | 0.7292 | 0.9315 | 0.4289 | 0.065* | |
C20 | 0.5800 (2) | 0.80003 (17) | 0.52218 (12) | 0.0337 (5) | |
H20A | 0.5258 | 0.8474 | 0.5087 | 0.051* | |
H20B | 0.6496 | 0.8252 | 0.576 | 0.051* | |
H20C | 0.5055 | 0.7365 | 0.5272 | 0.051* | |
C21 | 0.2262 (2) | 0.79912 (14) | 0.33877 (14) | 0.0330 (5) | |
C22 | 0.0731 (3) | 0.76010 (17) | 0.28161 (16) | 0.0557 (8) | |
H22A | 0.0831 | 0.7208 | 0.2305 | 0.084* | |
H22B | 0.0394 | 0.8156 | 0.2655 | 0.084* | |
H22C | −0.0026 | 0.7186 | 0.3118 | 0.084* | |
C23 | 0.1935 (5) | 0.8467 (3) | 0.4253 (2) | 0.0251 (9)* | 0.641 (9) |
H23A | 0.113 | 0.7977 | 0.447 | 0.038* | 0.641 (9) |
H23B | 0.16 | 0.9041 | 0.4152 | 0.038* | 0.641 (9) |
H23C | 0.2873 | 0.8676 | 0.4669 | 0.038* | 0.641 (9) |
C24 | 0.3594 (5) | 0.8744 (3) | 0.3101 (3) | 0.0362 (12)* | 0.641 (9) |
H24A | 0.4471 | 0.8959 | 0.3559 | 0.054* | 0.641 (9) |
H24B | 0.3284 | 0.9316 | 0.296 | 0.054* | 0.641 (9) |
H24C | 0.3883 | 0.8442 | 0.2599 | 0.054* | 0.641 (9) |
C23A | 0.2342 (10) | 0.8645 (6) | 0.4088 (5) | 0.039 (2)* | 0.359 (9) |
H23D | 0.1781 | 0.8289 | 0.4505 | 0.059* | 0.359 (9) |
H23E | 0.1884 | 0.9148 | 0.3918 | 0.059* | 0.359 (9) |
H23F | 0.3416 | 0.8964 | 0.4339 | 0.059* | 0.359 (9) |
C24A | 0.3136 (9) | 0.8484 (6) | 0.2677 (6) | 0.043 (2)* | 0.359 (9) |
H24D | 0.2825 | 0.906 | 0.2552 | 0.064* | 0.359 (9) |
H24E | 0.2887 | 0.8005 | 0.2162 | 0.064* | 0.359 (9) |
H24F | 0.4243 | 0.8693 | 0.2872 | 0.064* | 0.359 (9) |
C25 | −0.0407 (2) | 0.39194 (14) | 0.45256 (12) | 0.0268 (4) | |
H25 | 0.0356 | 0.3934 | 0.4984 | 0.032* | |
C26 | −0.2614 (2) | 0.38520 (15) | 0.38122 (13) | 0.0326 (5) | |
H26 | −0.3658 | 0.3818 | 0.3675 | 0.039* | |
C27 | −0.1579 (2) | 0.39160 (13) | 0.32665 (12) | 0.0238 (4) | |
C28 | −0.1789 (2) | 0.39131 (14) | 0.23306 (12) | 0.0271 (4) | |
H28A | −0.2852 | 0.3902 | 0.2136 | 0.035* | |
H28B | −0.1658 | 0.33 | 0.2059 | 0.035* | |
C29 | −0.0685 (2) | 0.47959 (14) | 0.20329 (13) | 0.0264 (4) | |
H29A | −0.105 | 0.4835 | 0.1435 | 0.034* | |
H29B | −0.066 | 0.5411 | 0.2379 | 0.034* | |
N1 | −0.01775 (17) | 0.39683 (10) | 0.37253 (9) | 0.0211 (3) | |
N2 | −0.18577 (19) | 0.38466 (13) | 0.45961 (11) | 0.0332 (4) | |
H2 | −0.2259 | 0.3803 | 0.5068 | 0.04* | |
N3 | 0.08812 (17) | 0.47106 (11) | 0.21059 (9) | 0.0213 (3) | |
H3D | 0.1542 | 0.5317 | 0.2047 | 0.026* | |
H3E | 0.0903 | 0.4273 | 0.1653 | 0.026* | |
O1 | 0.22245 (14) | 0.14213 (9) | 0.12977 (8) | 0.0222 (3) | |
O2 | −0.03000 (14) | 0.14633 (9) | 0.18415 (8) | 0.0220 (3) | |
O3 | 0.09578 (14) | 0.28665 (9) | 0.09992 (7) | 0.0200 (3) | |
O4 | 0.38474 (14) | 0.64547 (9) | 0.23786 (7) | 0.0202 (3) | |
O5 | 0.57292 (15) | 0.75172 (9) | 0.37099 (8) | 0.0255 (3) | |
O6 | 0.26689 (16) | 0.71306 (10) | 0.36144 (9) | 0.0311 (3) | |
Si1 | 0.13711 (5) | 0.21651 (3) | 0.16951 (3) | 0.01754 (12) | |
S1 | 0.27562 (5) | 0.30659 (3) | 0.27643 (3) | 0.02047 (11) | |
S2 | 0.37744 (5) | 0.54534 (3) | 0.40429 (3) | 0.01957 (11) | |
Si2 | 0.40510 (6) | 0.66934 (3) | 0.34178 (3) | 0.01830 (12) | |
Co1 | 0.17535 (3) | 0.426332 (16) | 0.320022 (14) | 0.01759 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0191 (9) | 0.0297 (10) | 0.0308 (10) | 0.0106 (8) | 0.0040 (8) | −0.0062 (8) |
C2 | 0.0212 (10) | 0.0430 (12) | 0.0301 (11) | 0.0097 (9) | 0.0062 (8) | 0.0027 (9) |
C3 | 0.0262 (10) | 0.0325 (11) | 0.0411 (12) | 0.0154 (9) | 0.0004 (9) | 0.0007 (9) |
C4 | 0.0324 (12) | 0.0532 (15) | 0.0498 (14) | 0.0203 (11) | 0.0047 (10) | −0.0232 (11) |
C5 | 0.0234 (9) | 0.0183 (9) | 0.0232 (9) | 0.0042 (8) | 0.0039 (7) | 0.0055 (7) |
C6 | 0.0368 (12) | 0.0245 (10) | 0.0256 (10) | 0.0063 (9) | 0.0093 (9) | 0.0044 (8) |
C7 | 0.0315 (11) | 0.0288 (11) | 0.0392 (12) | 0.0118 (9) | 0.0029 (9) | 0.0123 (9) |
C8 | 0.0309 (11) | 0.0220 (10) | 0.0347 (11) | 0.0017 (9) | 0.0035 (9) | 0.0019 (8) |
C9 | 0.0250 (10) | 0.0285 (10) | 0.0163 (9) | 0.0070 (8) | 0.0009 (7) | 0.0025 (7) |
C10 | 0.0305 (11) | 0.0332 (11) | 0.0253 (10) | 0.0096 (9) | −0.0024 (8) | −0.0041 (8) |
C11 | 0.0503 (14) | 0.0360 (12) | 0.0210 (10) | 0.0060 (11) | 0.0009 (9) | 0.0051 (9) |
C12 | 0.0262 (11) | 0.0510 (13) | 0.0264 (10) | 0.0169 (10) | 0.0007 (8) | 0.0029 (9) |
C13 | 0.0258 (10) | 0.0256 (10) | 0.0211 (9) | 0.0048 (8) | 0.0102 (8) | 0.0009 (7) |
C14 | 0.0386 (12) | 0.0415 (13) | 0.0245 (10) | 0.0060 (10) | 0.0090 (9) | −0.0050 (9) |
C15 | 0.0309 (11) | 0.0381 (12) | 0.0334 (11) | 0.0156 (10) | 0.0153 (9) | 0.0030 (9) |
C16 | 0.0401 (12) | 0.0307 (11) | 0.0312 (11) | 0.0014 (10) | 0.0182 (9) | 0.0043 (9) |
C17 | 0.0259 (10) | 0.0253 (10) | 0.0230 (10) | −0.0003 (8) | 0.0024 (8) | 0.0017 (8) |
C18 | 0.0285 (11) | 0.0399 (12) | 0.0387 (12) | 0.0093 (10) | 0.0001 (9) | −0.0018 (9) |
C19 | 0.0430 (13) | 0.0342 (12) | 0.0351 (12) | −0.0104 (10) | −0.0016 (10) | 0.0019 (9) |
C20 | 0.0330 (11) | 0.0431 (13) | 0.0221 (10) | 0.0105 (10) | 0.0002 (9) | −0.0011 (9) |
C21 | 0.0353 (12) | 0.0205 (10) | 0.0516 (13) | 0.0170 (9) | 0.0146 (10) | 0.0085 (9) |
C22 | 0.088 (2) | 0.0343 (13) | 0.0420 (14) | 0.0301 (14) | −0.0215 (14) | −0.0029 (10) |
C25 | 0.0312 (11) | 0.0222 (10) | 0.0261 (10) | 0.0052 (8) | 0.0112 (8) | −0.0007 (8) |
C26 | 0.0216 (10) | 0.0316 (11) | 0.0414 (12) | 0.0039 (9) | 0.0107 (9) | −0.0041 (9) |
C27 | 0.0205 (9) | 0.0160 (9) | 0.0335 (10) | 0.0029 (7) | 0.0076 (8) | 0.0008 (7) |
C28 | 0.0199 (9) | 0.0258 (10) | 0.0337 (11) | 0.0047 (8) | 0.0030 (8) | 0.0040 (8) |
C29 | 0.0213 (10) | 0.0247 (10) | 0.0341 (11) | 0.0079 (8) | 0.0036 (8) | 0.0070 (8) |
N1 | 0.0246 (8) | 0.0155 (7) | 0.0239 (8) | 0.0056 (6) | 0.0090 (6) | 0.0011 (6) |
N2 | 0.0296 (9) | 0.0336 (10) | 0.0320 (9) | 0.0004 (8) | 0.0190 (8) | −0.0039 (7) |
N3 | 0.0195 (8) | 0.0199 (8) | 0.0252 (8) | 0.0059 (6) | 0.0056 (6) | 0.0039 (6) |
O1 | 0.0176 (6) | 0.0237 (7) | 0.0246 (7) | 0.0070 (5) | 0.0035 (5) | −0.0031 (5) |
O2 | 0.0192 (6) | 0.0237 (7) | 0.0238 (6) | 0.0068 (5) | 0.0036 (5) | 0.0068 (5) |
O3 | 0.0217 (6) | 0.0216 (6) | 0.0161 (6) | 0.0063 (5) | 0.0019 (5) | 0.0022 (5) |
O4 | 0.0197 (6) | 0.0221 (6) | 0.0195 (6) | 0.0068 (5) | 0.0052 (5) | 0.0032 (5) |
O5 | 0.0286 (7) | 0.0229 (7) | 0.0191 (6) | −0.0010 (6) | 0.0044 (5) | 0.0023 (5) |
O6 | 0.0360 (8) | 0.0247 (7) | 0.0430 (8) | 0.0171 (6) | 0.0210 (7) | 0.0117 (6) |
Si1 | 0.0172 (2) | 0.0182 (2) | 0.0177 (2) | 0.0066 (2) | 0.00305 (19) | 0.00090 (18) |
S1 | 0.0211 (2) | 0.0213 (2) | 0.0194 (2) | 0.00957 (18) | 0.00054 (17) | −0.00205 (17) |
S2 | 0.0218 (2) | 0.0182 (2) | 0.0187 (2) | 0.00543 (18) | 0.00431 (17) | 0.00317 (17) |
Si2 | 0.0204 (3) | 0.0164 (2) | 0.0189 (2) | 0.0057 (2) | 0.00666 (19) | 0.00200 (18) |
Co1 | 0.01831 (14) | 0.01689 (14) | 0.01882 (14) | 0.00631 (10) | 0.00581 (10) | 0.00205 (9) |
Geometric parameters (Å, º) top
C1—O1 | 1.449 (2) | C18—H18C | 0.98 |
C1—C2 | 1.518 (3) | C19—H19A | 0.98 |
C1—C3 | 1.519 (3) | C19—H19B | 0.98 |
C1—C4 | 1.525 (3) | C19—H19C | 0.98 |
C2—H2A | 0.98 | C20—H20A | 0.98 |
C2—H2B | 0.98 | C20—H20B | 0.98 |
C2—H2C | 0.98 | C20—H20C | 0.98 |
C3—H3A | 0.98 | C21—C23A | 1.373 (8) |
C3—H3B | 0.98 | C21—O6 | 1.453 (2) |
C3—H3C | 0.98 | C21—C22 | 1.512 (3) |
C4—H4A | 0.98 | C21—C24 | 1.523 (4) |
C4—H4B | 0.98 | C21—C23 | 1.589 (4) |
C4—H4C | 0.98 | C21—C24A | 1.572 (7) |
C5—O2 | 1.449 (2) | C22—H22A | 0.98 |
C5—C8 | 1.512 (3) | C22—H22B | 0.98 |
C5—C7 | 1.522 (3) | C22—H22C | 0.98 |
C5—C6 | 1.524 (3) | C23—H23A | 0.98 |
C6—H6A | 0.98 | C23—H23B | 0.98 |
C6—H6B | 0.98 | C23—H23C | 0.98 |
C6—H6C | 0.98 | C24—H24A | 0.98 |
C7—H7A | 0.98 | C24—H24B | 0.98 |
C7—H7B | 0.98 | C24—H24C | 0.98 |
C7—H7C | 0.98 | C23A—H23D | 0.98 |
C8—H8A | 0.98 | C23A—H23E | 0.98 |
C8—H8B | 0.98 | C23A—H23F | 0.98 |
C8—H8C | 0.98 | C24A—H24D | 0.98 |
C9—O3 | 1.454 (2) | C24A—H24E | 0.98 |
C9—C10 | 1.515 (3) | C24A—H24F | 0.98 |
C9—C12 | 1.524 (3) | C25—N1 | 1.328 (2) |
C9—C11 | 1.524 (3) | C25—N2 | 1.334 (3) |
C10—H10A | 0.98 | C25—H25 | 0.95 |
C10—H10B | 0.98 | C26—C27 | 1.360 (3) |
C10—H10C | 0.98 | C26—N2 | 1.365 (3) |
C11—H11A | 0.98 | C26—H26 | 0.95 |
C11—H11B | 0.98 | C27—N1 | 1.390 (2) |
C11—H11C | 0.98 | C27—C28 | 1.488 (3) |
C12—H12A | 0.98 | C28—C29 | 1.523 (3) |
C12—H12B | 0.98 | C28—H28A | 0.99 |
C12—H12C | 0.98 | C28—H28B | 0.99 |
C13—O4 | 1.461 (2) | C29—N3 | 1.481 (2) |
C13—C15 | 1.517 (3) | C29—H29A | 0.99 |
C13—C16 | 1.517 (3) | C29—H29B | 0.99 |
C13—C14 | 1.521 (3) | N1—Co1 | 2.0116 (15) |
C14—H14A | 0.98 | N2—H2 | 0.88 |
C14—H14B | 0.98 | N3—Co1 | 2.0754 (15) |
C14—H14C | 0.98 | N3—H3D | 0.92 |
C15—H15A | 0.98 | N3—H3E | 0.92 |
C15—H15B | 0.98 | O1—Si1 | 1.6298 (13) |
C15—H15C | 0.98 | O2—Si1 | 1.6295 (13) |
C16—H16A | 0.98 | O3—Si1 | 1.6506 (12) |
C16—H16B | 0.98 | O4—Si2 | 1.6453 (12) |
C16—H16C | 0.98 | O5—Si2 | 1.6293 (13) |
C17—O5 | 1.448 (2) | O6—Si2 | 1.6310 (14) |
C17—C20 | 1.516 (3) | Si1—S1 | 2.0810 (7) |
C17—C19 | 1.521 (3) | S1—Co1 | 2.2724 (5) |
C17—C18 | 1.524 (3) | S2—Si2 | 2.0794 (6) |
C18—H18A | 0.98 | S2—Co1 | 2.3028 (5) |
C18—H18B | 0.98 | | |
| | | |
O1—C1—C2 | 110.90 (15) | C17—C19—H19A | 109.5 |
O1—C1—C3 | 109.00 (16) | C17—C19—H19B | 109.5 |
C2—C1—C3 | 111.12 (16) | H19A—C19—H19B | 109.5 |
O1—C1—C4 | 105.32 (15) | C17—C19—H19C | 109.5 |
C2—C1—C4 | 110.62 (18) | H19A—C19—H19C | 109.5 |
C3—C1—C4 | 109.70 (17) | H19B—C19—H19C | 109.5 |
C1—C2—H2A | 109.5 | C17—C20—H20A | 109.5 |
C1—C2—H2B | 109.5 | C17—C20—H20B | 109.5 |
H2A—C2—H2B | 109.5 | H20A—C20—H20B | 109.5 |
C1—C2—H2C | 109.5 | C17—C20—H20C | 109.5 |
H2A—C2—H2C | 109.5 | H20A—C20—H20C | 109.5 |
H2B—C2—H2C | 109.5 | H20B—C20—H20C | 109.5 |
C1—C3—H3A | 109.5 | C23A—C21—O6 | 112.2 (4) |
C1—C3—H3B | 109.5 | C23A—C21—C22 | 116.1 (4) |
H3A—C3—H3B | 109.5 | O6—C21—C22 | 106.32 (17) |
C1—C3—H3C | 109.5 | C23A—C21—C24 | 90.4 (4) |
H3A—C3—H3C | 109.5 | O6—C21—C24 | 111.66 (19) |
H3B—C3—H3C | 109.5 | C22—C21—C24 | 119.8 (3) |
C1—C4—H4A | 109.5 | O6—C21—C23 | 103.83 (19) |
C1—C4—H4B | 109.5 | C22—C21—C23 | 105.8 (2) |
H4A—C4—H4B | 109.5 | C24—C21—C23 | 108.2 (2) |
C1—C4—H4C | 109.5 | C23A—C21—C24A | 113.8 (5) |
H4A—C4—H4C | 109.5 | O6—C21—C24A | 113.0 (3) |
H4B—C4—H4C | 109.5 | C22—C21—C24A | 94.0 (4) |
O2—C5—C8 | 106.03 (14) | C23—C21—C24A | 130.9 (3) |
O2—C5—C7 | 111.20 (15) | C21—C22—H22A | 109.5 |
C8—C5—C7 | 110.13 (16) | C21—C22—H22B | 109.5 |
O2—C5—C6 | 107.83 (14) | H22A—C22—H22B | 109.5 |
C8—C5—C6 | 110.78 (16) | C21—C22—H22C | 109.5 |
C7—C5—C6 | 110.74 (16) | H22A—C22—H22C | 109.5 |
C5—C6—H6A | 109.5 | H22B—C22—H22C | 109.5 |
C5—C6—H6B | 109.5 | C21—C23—H23A | 109.5 |
H6A—C6—H6B | 109.5 | C21—C23—H23B | 109.5 |
C5—C6—H6C | 109.5 | C21—C23—H23C | 109.5 |
H6A—C6—H6C | 109.5 | C21—C24—H24A | 109.5 |
H6B—C6—H6C | 109.5 | C21—C24—H24B | 109.5 |
C5—C7—H7A | 109.5 | C21—C24—H24C | 109.5 |
C5—C7—H7B | 109.5 | C21—C23A—H23D | 109.5 |
H7A—C7—H7B | 109.5 | C21—C23A—H23E | 109.5 |
C5—C7—H7C | 109.5 | H23D—C23A—H23E | 109.5 |
H7A—C7—H7C | 109.5 | C21—C23A—H23F | 109.5 |
H7B—C7—H7C | 109.5 | H23D—C23A—H23F | 109.5 |
C5—C8—H8A | 109.5 | H23E—C23A—H23F | 109.5 |
C5—C8—H8B | 109.5 | C21—C24A—H24D | 109.5 |
H8A—C8—H8B | 109.5 | C21—C24A—H24E | 109.5 |
C5—C8—H8C | 109.5 | H24D—C24A—H24E | 109.5 |
H8A—C8—H8C | 109.5 | C21—C24A—H24F | 109.5 |
H8B—C8—H8C | 109.5 | H24D—C24A—H24F | 109.5 |
O3—C9—C10 | 112.16 (15) | H24E—C24A—H24F | 109.5 |
O3—C9—C12 | 108.85 (15) | N1—C25—N2 | 110.52 (18) |
C10—C9—C12 | 110.00 (17) | N1—C25—H25 | 124.7 |
O3—C9—C11 | 105.01 (15) | N2—C25—H25 | 124.7 |
C10—C9—C11 | 110.67 (16) | C27—C26—N2 | 106.45 (18) |
C12—C9—C11 | 110.04 (17) | C27—C26—H26 | 126.8 |
C9—C10—H10A | 109.5 | N2—C26—H26 | 126.8 |
C9—C10—H10B | 109.5 | C26—C27—N1 | 108.50 (17) |
H10A—C10—H10B | 109.5 | C26—C27—C28 | 129.68 (18) |
C9—C10—H10C | 109.5 | N1—C27—C28 | 121.81 (16) |
H10A—C10—H10C | 109.5 | C27—C28—C29 | 114.13 (16) |
H10B—C10—H10C | 109.5 | C27—C28—H28A | 108.7 |
C9—C11—H11A | 109.5 | C29—C28—H28A | 108.7 |
C9—C11—H11B | 109.5 | C27—C28—H28B | 108.7 |
H11A—C11—H11B | 109.5 | C29—C28—H28B | 108.7 |
C9—C11—H11C | 109.5 | H28A—C28—H28B | 107.6 |
H11A—C11—H11C | 109.5 | N3—C29—C28 | 111.08 (15) |
H11B—C11—H11C | 109.5 | N3—C29—H29A | 109.4 |
C9—C12—H12A | 109.5 | C28—C29—H29A | 109.4 |
C9—C12—H12B | 109.5 | N3—C29—H29B | 109.4 |
H12A—C12—H12B | 109.5 | C28—C29—H29B | 109.4 |
C9—C12—H12C | 109.5 | H29A—C29—H29B | 108 |
H12A—C12—H12C | 109.5 | C25—N1—C27 | 106.07 (16) |
H12B—C12—H12C | 109.5 | C25—N1—Co1 | 131.45 (14) |
O4—C13—C15 | 111.03 (14) | C27—N1—Co1 | 121.89 (12) |
O4—C13—C16 | 108.08 (15) | C25—N2—C26 | 108.44 (16) |
C15—C13—C16 | 110.94 (17) | C25—N2—H2 | 125.8 |
O4—C13—C14 | 105.59 (15) | C26—N2—H2 | 125.8 |
C15—C13—C14 | 110.32 (17) | C29—N3—Co1 | 118.59 (11) |
C16—C13—C14 | 110.74 (16) | C29—N3—H3D | 107.7 |
C13—C14—H14A | 109.5 | Co1—N3—H3D | 107.7 |
C13—C14—H14B | 109.5 | C29—N3—H3E | 107.7 |
H14A—C14—H14B | 109.5 | Co1—N3—H3E | 107.7 |
C13—C14—H14C | 109.5 | H3D—N3—H3E | 107.1 |
H14A—C14—H14C | 109.5 | C1—O1—Si1 | 131.67 (11) |
H14B—C14—H14C | 109.5 | C5—O2—Si1 | 131.36 (11) |
C13—C15—H15A | 109.5 | C9—O3—Si1 | 130.58 (11) |
C13—C15—H15B | 109.5 | C13—O4—Si2 | 129.95 (11) |
H15A—C15—H15B | 109.5 | C17—O5—Si2 | 132.89 (11) |
C13—C15—H15C | 109.5 | C21—O6—Si2 | 133.08 (12) |
H15A—C15—H15C | 109.5 | O1—Si1—O2 | 105.95 (7) |
H15B—C15—H15C | 109.5 | O1—Si1—O3 | 111.60 (7) |
C13—C16—H16A | 109.5 | O2—Si1—O3 | 103.88 (6) |
C13—C16—H16B | 109.5 | O1—Si1—S1 | 110.19 (5) |
H16A—C16—H16B | 109.5 | O2—Si1—S1 | 116.05 (5) |
C13—C16—H16C | 109.5 | O3—Si1—S1 | 109.06 (5) |
H16A—C16—H16C | 109.5 | Si1—S1—Co1 | 110.43 (2) |
H16B—C16—H16C | 109.5 | Si2—S2—Co1 | 103.84 (2) |
O5—C17—C20 | 111.17 (16) | O5—Si2—O6 | 111.83 (7) |
O5—C17—C19 | 105.13 (15) | O5—Si2—O4 | 106.04 (6) |
C20—C17—C19 | 110.77 (18) | O6—Si2—O4 | 105.85 (7) |
O5—C17—C18 | 109.16 (16) | O5—Si2—S2 | 112.73 (5) |
C20—C17—C18 | 110.44 (17) | O6—Si2—S2 | 106.07 (5) |
C19—C17—C18 | 110.05 (18) | O4—Si2—S2 | 114.20 (5) |
C17—C18—H18A | 109.5 | N1—Co1—N3 | 96.46 (6) |
C17—C18—H18B | 109.5 | N1—Co1—S1 | 122.45 (4) |
H18A—C18—H18B | 109.5 | N3—Co1—S1 | 106.17 (4) |
C17—C18—H18C | 109.5 | N1—Co1—S2 | 112.32 (4) |
H18A—C18—H18C | 109.5 | N3—Co1—S2 | 115.05 (4) |
H18B—C18—H18C | 109.5 | S1—Co1—S2 | 104.567 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2i | 0.88 | 2.49 | 3.2365 (16) | 143 |
N2—H2···O6i | 0.88 | 2.60 | 3.367 (2) | 146 |
N3—H3D···O4 | 0.92 | 2.23 | 3.0626 (19) | 150 |
N3—H3E···O3 | 0.92 | 2.2 | 3.0654 (19) | 157 |
Symmetry code: (i) −x, −y+1, −z+1. |
(IV) [2-(1H-imidazol-4-yl-
κN
3)ethylamine-
κ2N]bis(tri-
tert-butoxysilanethiolato-
κS)zinc(II)
top
Crystal data top
[Zn(C12H27O3SSi)2(C5H9N3)] | Z = 2 |
Mr = 735.49 | F(000) = 792 |
Triclinic, P1 | Dx = 1.227 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2535 (3) Å | Cell parameters from 14894 reflections |
b = 14.3163 (5) Å | θ = 2.1–32.3° |
c = 15.9899 (6) Å | µ = 0.82 mm−1 |
α = 95.086 (3)° | T = 120 K |
β = 96.805 (3)° | Prism, colourless |
γ = 107.337 (3)° | 0.21 × 0.15 × 0.09 mm |
V = 1990.55 (12) Å3 | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7386 independent reflections |
Graphite monochromator | 6730 reflections with I > 2σ(I) |
Detector resolution: 8.1883 pixels mm-1 | Rint = 0.021 |
ω scans, 0.75 deg width | θmax = 25.5°, θmin = 2.4° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897]. | h = −10→11 |
Tmin = 0.79, Tmax = 0.857 | k = −17→17 |
13696 measured reflections | l = −19→15 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0541P)2 + 0.3294P] where P = (Fo2 + 2Fc2)/3 |
7386 reflections | (Δ/σ)max = 0.001 |
427 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
[Zn(C12H27O3SSi)2(C5H9N3)] | γ = 107.337 (3)° |
Mr = 735.49 | V = 1990.55 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2535 (3) Å | Mo Kα radiation |
b = 14.3163 (5) Å | µ = 0.82 mm−1 |
c = 15.9899 (6) Å | T = 120 K |
α = 95.086 (3)° | 0.21 × 0.15 × 0.09 mm |
β = 96.805 (3)° | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7386 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897]. | 6730 reflections with I > 2σ(I) |
Tmin = 0.79, Tmax = 0.857 | Rint = 0.021 |
13696 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.74 e Å−3 |
7386 reflections | Δρmin = −0.32 e Å−3 |
427 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.37862 (18) | 0.15906 (13) | 0.11451 (11) | 0.0262 (4) | |
C2 | 0.4761 (2) | 0.15242 (14) | 0.19562 (12) | 0.0324 (4) | |
H2A | 0.4779 | 0.2051 | 0.2397 | 0.049* | |
H2B | 0.5807 | 0.1597 | 0.1848 | 0.049* | |
H2C | 0.4327 | 0.0882 | 0.2148 | 0.049* | |
C3 | 0.44174 (19) | 0.25839 (14) | 0.08313 (12) | 0.0319 (4) | |
H3A | 0.3773 | 0.2607 | 0.0306 | 0.048* | |
H3B | 0.5466 | 0.2671 | 0.0722 | 0.048* | |
H3C | 0.4419 | 0.3113 | 0.1264 | 0.048* | |
C4 | 0.3701 (2) | 0.07517 (17) | 0.04610 (14) | 0.0461 (5) | |
H4A | 0.3276 | 0.0117 | 0.0667 | 0.069* | |
H4B | 0.4731 | 0.0812 | 0.0331 | 0.069* | |
H4C | 0.304 | 0.0788 | −0.0054 | 0.069* | |
C5 | 0.00302 (19) | 0.26218 (12) | 0.01727 (10) | 0.0233 (3) | |
C6 | 0.0175 (2) | 0.16974 (13) | −0.03073 (11) | 0.0303 (4) | |
H6A | 0.1245 | 0.1805 | −0.0384 | 0.045* | |
H6B | −0.0472 | 0.155 | −0.0864 | 0.045* | |
H6C | −0.0154 | 0.1142 | 0.0017 | 0.045* | |
C7 | 0.0615 (2) | 0.35093 (14) | −0.02938 (11) | 0.0369 (4) | |
H7A | 0.0545 | 0.4102 | 0.0034 | 0.055* | |
H7B | −0.0008 | 0.3399 | −0.0855 | 0.055* | |
H7C | 0.1685 | 0.3598 | −0.0361 | 0.055* | |
C8 | −0.1633 (2) | 0.24701 (16) | 0.02817 (12) | 0.0343 (4) | |
H8A | −0.1967 | 0.1936 | 0.0627 | 0.051* | |
H8B | −0.2276 | 0.2296 | −0.0277 | 0.051* | |
H8C | −0.1727 | 0.308 | 0.0565 | 0.051* | |
C9 | −0.07397 (18) | 0.08058 (11) | 0.24590 (10) | 0.0216 (3) | |
C10 | −0.2151 (2) | −0.00135 (13) | 0.20138 (12) | 0.0312 (4) | |
H10A | −0.293 | 0.0273 | 0.1789 | 0.047* | |
H10B | −0.2559 | −0.046 | 0.242 | 0.047* | |
H10C | −0.1873 | −0.0382 | 0.1546 | 0.047* | |
C11 | 0.0530 (2) | 0.03816 (14) | 0.27478 (13) | 0.0332 (4) | |
H11A | 0.0786 | 0.0042 | 0.2254 | 0.05* | |
H11B | 0.0185 | −0.0088 | 0.3148 | 0.05* | |
H11C | 0.1438 | 0.0917 | 0.3027 | 0.05* | |
C12 | −0.1123 (2) | 0.13729 (12) | 0.32074 (11) | 0.0291 (4) | |
H12A | −0.022 | 0.1928 | 0.346 | 0.044* | |
H12B | −0.1434 | 0.0933 | 0.3634 | 0.044* | |
H12C | −0.1964 | 0.1623 | 0.301 | 0.044* | |
C13 | 0.49693 (19) | 0.63110 (12) | 0.18555 (10) | 0.0239 (3) | |
C14 | 0.4033 (2) | 0.57499 (15) | 0.10159 (11) | 0.0363 (4) | |
H14A | 0.3424 | 0.5089 | 0.1107 | 0.055* | |
H14B | 0.4723 | 0.5693 | 0.0608 | 0.055* | |
H14C | 0.3348 | 0.6106 | 0.0792 | 0.055* | |
C15 | 0.5912 (2) | 0.57143 (14) | 0.22552 (12) | 0.0326 (4) | |
H15A | 0.6503 | 0.6078 | 0.2798 | 0.049* | |
H15B | 0.6613 | 0.5602 | 0.1873 | 0.049* | |
H15C | 0.5227 | 0.5078 | 0.2353 | 0.049* | |
C16 | 0.5993 (2) | 0.73228 (13) | 0.17283 (12) | 0.0356 (4) | |
H16A | 0.5363 | 0.7692 | 0.1466 | 0.053* | |
H16B | 0.6731 | 0.7244 | 0.1358 | 0.053* | |
H16C | 0.6544 | 0.7685 | 0.228 | 0.053* | |
C17 | 0.66838 (19) | 0.79047 (12) | 0.45315 (10) | 0.0265 (4) | |
C18 | 0.7554 (2) | 0.71781 (15) | 0.47269 (13) | 0.0373 (4) | |
H18A | 0.6829 | 0.6546 | 0.4804 | 0.056* | |
H18B | 0.8292 | 0.7443 | 0.5248 | 0.056* | |
H18C | 0.8099 | 0.7078 | 0.4255 | 0.056* | |
C19 | 0.7801 (3) | 0.88895 (15) | 0.44128 (13) | 0.0445 (5) | |
H19A | 0.8347 | 0.8793 | 0.394 | 0.067* | |
H19B | 0.8539 | 0.9156 | 0.4934 | 0.067* | |
H19C | 0.7235 | 0.9353 | 0.4288 | 0.067* | |
C20 | 0.5768 (2) | 0.80362 (15) | 0.52365 (11) | 0.0333 (4) | |
H20A | 0.5244 | 0.8521 | 0.5111 | 0.05* | |
H20B | 0.6461 | 0.8269 | 0.5777 | 0.05* | |
H20C | 0.5009 | 0.7403 | 0.5276 | 0.05* | |
C21 | 0.2219 (2) | 0.79809 (13) | 0.33632 (13) | 0.0342 (4) | |
C22 | 0.0666 (3) | 0.75888 (16) | 0.28195 (15) | 0.0565 (7) | |
H22A | 0.0741 | 0.7207 | 0.2296 | 0.085* | |
H22B | 0.0305 | 0.8142 | 0.2677 | 0.085* | |
H22C | −0.0059 | 0.7163 | 0.3132 | 0.085* | |
C23 | 0.3540 (9) | 0.8728 (4) | 0.3074 (6) | 0.0454 (17) | 0.612 (17) |
H23A | 0.442 | 0.894 | 0.353 | 0.068* | 0.612 (17) |
H23B | 0.3231 | 0.9301 | 0.2935 | 0.068* | 0.612 (17) |
H23C | 0.3822 | 0.8427 | 0.2569 | 0.068* | 0.612 (17) |
C24 | 0.1935 (11) | 0.8492 (9) | 0.4232 (7) | 0.0343 (14) | 0.612 (17) |
H24A | 0.1159 | 0.8012 | 0.4477 | 0.051* | 0.612 (17) |
H24B | 0.1578 | 0.9054 | 0.4119 | 0.051* | 0.612 (17) |
H24C | 0.2895 | 0.8722 | 0.4633 | 0.051* | 0.612 (17) |
C23A | 0.3059 (11) | 0.8431 (9) | 0.2585 (12) | 0.053 (3) | 0.388 (17) |
H23D | 0.4172 | 0.8648 | 0.2758 | 0.079* | 0.388 (17) |
H23E | 0.2732 | 0.8994 | 0.2437 | 0.079* | 0.388 (17) |
H23F | 0.2779 | 0.7922 | 0.209 | 0.079* | 0.388 (17) |
C24A | 0.233 (2) | 0.8623 (14) | 0.4069 (11) | 0.056 (4) | 0.388 (17) |
H24D | 0.1766 | 0.8265 | 0.4486 | 0.084* | 0.388 (17) |
H24E | 0.1883 | 0.9137 | 0.3911 | 0.084* | 0.388 (17) |
H24F | 0.3405 | 0.8928 | 0.4316 | 0.084* | 0.388 (17) |
C25 | −0.0325 (2) | 0.39171 (12) | 0.45325 (11) | 0.0266 (4) | |
H25 | 0.0452 | 0.3946 | 0.4988 | 0.032* | |
C26 | −0.2556 (2) | 0.38211 (13) | 0.38281 (12) | 0.0333 (4) | |
H26 | −0.3605 | 0.3777 | 0.3696 | 0.04* | |
C27 | −0.15301 (18) | 0.38960 (11) | 0.32763 (11) | 0.0239 (3) | |
C28 | −0.17608 (18) | 0.38940 (12) | 0.23392 (11) | 0.0268 (4) | |
H28A | −0.2832 | 0.3868 | 0.2149 | 0.035* | |
H28B | −0.1611 | 0.3289 | 0.2064 | 0.035* | |
C29 | −0.06848 (18) | 0.47907 (12) | 0.20409 (11) | 0.0259 (4) | |
H29A | −0.1066 | 0.4833 | 0.1445 | 0.034* | |
H29B | −0.0673 | 0.5398 | 0.2394 | 0.034* | |
N1 | −0.01195 (15) | 0.39653 (9) | 0.37287 (8) | 0.0203 (3) | |
N2 | −0.17823 (17) | 0.38222 (11) | 0.46097 (10) | 0.0339 (4) | |
H2 | −0.2176 | 0.3769 | 0.5085 | 0.041* | |
N3 | 0.08939 (15) | 0.47270 (10) | 0.21009 (8) | 0.0205 (3) | |
H3D | 0.1532 | 0.5337 | 0.2035 | 0.027* | |
H3E | 0.0916 | 0.4293 | 0.1646 | 0.027* | |
O1 | 0.22235 (12) | 0.14306 (8) | 0.12960 (7) | 0.0221 (2) | |
O2 | 0.09709 (12) | 0.28836 (8) | 0.10056 (7) | 0.0195 (2) | |
O3 | −0.02970 (12) | 0.14760 (8) | 0.18413 (7) | 0.0213 (2) | |
O4 | 0.38640 (12) | 0.64553 (8) | 0.23892 (7) | 0.0195 (2) | |
O5 | 0.57009 (13) | 0.75507 (8) | 0.37208 (7) | 0.0256 (3) | |
O6 | 0.26328 (14) | 0.71277 (9) | 0.35991 (8) | 0.0316 (3) | |
Si1 | 0.13785 (5) | 0.21774 (3) | 0.17001 (3) | 0.01689 (10) | |
Si2 | 0.40432 (5) | 0.67100 (3) | 0.34264 (3) | 0.01777 (10) | |
S1 | 0.27735 (4) | 0.30608 (3) | 0.27709 (2) | 0.01976 (9) | |
S2 | 0.37927 (4) | 0.54869 (3) | 0.40704 (2) | 0.01889 (9) | |
Zn1 | 0.183032 (19) | 0.429801 (12) | 0.319338 (10) | 0.01723 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0193 (8) | 0.0309 (9) | 0.0294 (9) | 0.0124 (7) | 0.0037 (7) | −0.0066 (7) |
C2 | 0.0269 (9) | 0.0333 (9) | 0.0397 (10) | 0.0168 (8) | 0.0001 (8) | −0.0006 (8) |
C3 | 0.0200 (8) | 0.0454 (11) | 0.0318 (9) | 0.0109 (8) | 0.0075 (7) | 0.0049 (8) |
C4 | 0.0347 (11) | 0.0530 (13) | 0.0500 (12) | 0.0218 (10) | 0.0043 (9) | −0.0228 (10) |
C5 | 0.0249 (8) | 0.0278 (8) | 0.0165 (7) | 0.0080 (7) | 0.0009 (6) | 0.0033 (6) |
C6 | 0.0301 (9) | 0.0327 (9) | 0.0251 (9) | 0.0096 (7) | −0.0015 (7) | −0.0037 (7) |
C7 | 0.0506 (12) | 0.0337 (10) | 0.0217 (9) | 0.0062 (9) | 0.0021 (8) | 0.0068 (8) |
C8 | 0.0258 (9) | 0.0512 (11) | 0.0281 (9) | 0.0168 (8) | 0.0004 (7) | 0.0051 (8) |
C9 | 0.0221 (8) | 0.0177 (7) | 0.0250 (8) | 0.0046 (6) | 0.0043 (6) | 0.0072 (6) |
C10 | 0.0299 (9) | 0.0231 (8) | 0.0349 (10) | 0.0018 (7) | 0.0017 (8) | 0.0014 (7) |
C11 | 0.0319 (10) | 0.0292 (9) | 0.0417 (11) | 0.0120 (8) | 0.0038 (8) | 0.0154 (8) |
C12 | 0.0388 (10) | 0.0221 (8) | 0.0255 (9) | 0.0057 (7) | 0.0101 (7) | 0.0052 (7) |
C13 | 0.0254 (8) | 0.0258 (8) | 0.0199 (8) | 0.0048 (7) | 0.0108 (6) | 0.0017 (6) |
C14 | 0.0378 (10) | 0.0410 (11) | 0.0243 (9) | 0.0046 (8) | 0.0087 (8) | −0.0054 (8) |
C15 | 0.0287 (9) | 0.0395 (10) | 0.0367 (10) | 0.0174 (8) | 0.0153 (8) | 0.0048 (8) |
C16 | 0.0423 (11) | 0.0301 (9) | 0.0310 (10) | 0.0006 (8) | 0.0198 (8) | 0.0049 (8) |
C17 | 0.0267 (8) | 0.0251 (8) | 0.0216 (8) | −0.0003 (7) | 0.0026 (7) | 0.0011 (7) |
C18 | 0.0273 (9) | 0.0400 (11) | 0.0403 (11) | 0.0080 (8) | −0.0005 (8) | −0.0016 (9) |
C19 | 0.0483 (12) | 0.0331 (10) | 0.0332 (10) | −0.0124 (9) | 0.0000 (9) | 0.0020 (8) |
C20 | 0.0328 (10) | 0.0427 (11) | 0.0223 (8) | 0.0111 (8) | 0.0014 (7) | −0.0004 (8) |
C21 | 0.0367 (10) | 0.0212 (8) | 0.0541 (12) | 0.0181 (8) | 0.0163 (9) | 0.0099 (8) |
C22 | 0.0881 (19) | 0.0347 (11) | 0.0428 (12) | 0.0279 (12) | −0.0223 (12) | −0.0023 (10) |
C23 | 0.060 (3) | 0.035 (2) | 0.061 (4) | 0.029 (2) | 0.031 (3) | 0.029 (3) |
C24 | 0.037 (3) | 0.034 (2) | 0.036 (3) | 0.020 (2) | 0.004 (2) | −0.0056 (19) |
C23A | 0.042 (4) | 0.047 (4) | 0.086 (9) | 0.024 (3) | 0.021 (5) | 0.045 (5) |
C24A | 0.073 (10) | 0.044 (7) | 0.054 (9) | 0.045 (7) | −0.028 (6) | −0.018 (5) |
C25 | 0.0305 (9) | 0.0207 (8) | 0.0280 (9) | 0.0046 (7) | 0.0124 (7) | 0.0007 (7) |
C26 | 0.0224 (9) | 0.0313 (9) | 0.0433 (11) | 0.0031 (7) | 0.0135 (8) | −0.0036 (8) |
C27 | 0.0202 (8) | 0.0158 (7) | 0.0345 (9) | 0.0030 (6) | 0.0077 (7) | 0.0013 (7) |
C28 | 0.0187 (8) | 0.0252 (8) | 0.0347 (9) | 0.0043 (7) | 0.0032 (7) | 0.0049 (7) |
C29 | 0.0206 (8) | 0.0246 (8) | 0.0346 (9) | 0.0087 (7) | 0.0039 (7) | 0.0098 (7) |
N1 | 0.0223 (7) | 0.0149 (6) | 0.0243 (7) | 0.0048 (5) | 0.0097 (5) | 0.0019 (5) |
N2 | 0.0314 (8) | 0.0336 (8) | 0.0328 (8) | 0.0004 (7) | 0.0207 (7) | −0.0038 (7) |
N3 | 0.0197 (7) | 0.0189 (6) | 0.0234 (7) | 0.0057 (5) | 0.0043 (5) | 0.0049 (5) |
O1 | 0.0182 (5) | 0.0224 (5) | 0.0252 (6) | 0.0076 (4) | 0.0032 (4) | −0.0033 (5) |
O2 | 0.0210 (5) | 0.0212 (5) | 0.0168 (5) | 0.0072 (4) | 0.0025 (4) | 0.0028 (4) |
O3 | 0.0192 (5) | 0.0222 (6) | 0.0236 (6) | 0.0061 (4) | 0.0041 (4) | 0.0082 (5) |
O4 | 0.0202 (5) | 0.0200 (5) | 0.0190 (5) | 0.0060 (4) | 0.0057 (4) | 0.0040 (4) |
O5 | 0.0297 (6) | 0.0216 (6) | 0.0193 (6) | −0.0019 (5) | 0.0047 (5) | 0.0027 (5) |
O6 | 0.0359 (7) | 0.0229 (6) | 0.0481 (8) | 0.0179 (5) | 0.0245 (6) | 0.0141 (5) |
Si1 | 0.0165 (2) | 0.0173 (2) | 0.0179 (2) | 0.00677 (16) | 0.00326 (16) | 0.00172 (16) |
Si2 | 0.0204 (2) | 0.0152 (2) | 0.0190 (2) | 0.00560 (17) | 0.00774 (16) | 0.00249 (16) |
S1 | 0.0209 (2) | 0.02000 (19) | 0.01943 (19) | 0.00990 (15) | 0.00085 (15) | −0.00110 (15) |
S2 | 0.02169 (19) | 0.01690 (18) | 0.01846 (19) | 0.00549 (15) | 0.00487 (15) | 0.00369 (14) |
Zn1 | 0.01840 (11) | 0.01617 (10) | 0.01894 (11) | 0.00653 (7) | 0.00625 (7) | 0.00335 (7) |
Geometric parameters (Å, º) top
C1—O1 | 1.4480 (19) | C18—H18C | 0.98 |
C1—C2 | 1.517 (2) | C19—H19A | 0.98 |
C1—C3 | 1.522 (3) | C19—H19B | 0.98 |
C1—C4 | 1.528 (2) | C19—H19C | 0.98 |
C2—H2A | 0.98 | C20—H20A | 0.98 |
C2—H2B | 0.98 | C20—H20B | 0.98 |
C2—H2C | 0.98 | C20—H20C | 0.98 |
C3—H3A | 0.98 | C21—C24A | 1.365 (18) |
C3—H3B | 0.98 | C21—O6 | 1.451 (2) |
C3—H3C | 0.98 | C21—C22 | 1.508 (3) |
C4—H4A | 0.98 | C21—C23 | 1.515 (5) |
C4—H4B | 0.98 | C21—C24 | 1.598 (10) |
C4—H4C | 0.98 | C21—C23A | 1.625 (11) |
C5—O2 | 1.4541 (18) | C22—H22A | 0.98 |
C5—C6 | 1.519 (2) | C22—H22B | 0.98 |
C5—C8 | 1.522 (2) | C22—H22C | 0.98 |
C5—C7 | 1.522 (2) | C23—H23A | 0.98 |
C6—H6A | 0.98 | C23—H23B | 0.98 |
C6—H6B | 0.98 | C23—H23C | 0.98 |
C6—H6C | 0.98 | C24—H24A | 0.98 |
C7—H7A | 0.98 | C24—H24B | 0.98 |
C7—H7B | 0.98 | C24—H24C | 0.98 |
C7—H7C | 0.98 | C23A—H23D | 0.98 |
C8—H8A | 0.98 | C23A—H23E | 0.98 |
C8—H8B | 0.98 | C23A—H23F | 0.98 |
C8—H8C | 0.98 | C24A—H24D | 0.98 |
C9—O3 | 1.4469 (18) | C24A—H24E | 0.98 |
C9—C10 | 1.519 (2) | C24A—H24F | 0.98 |
C9—C11 | 1.520 (2) | C25—N1 | 1.326 (2) |
C9—C12 | 1.522 (2) | C25—N2 | 1.336 (2) |
C10—H10A | 0.98 | C25—H25 | 0.95 |
C10—H10B | 0.98 | C26—C27 | 1.359 (2) |
C10—H10C | 0.98 | C26—N2 | 1.364 (3) |
C11—H11A | 0.98 | C26—H26 | 0.95 |
C11—H11B | 0.98 | C27—N1 | 1.387 (2) |
C11—H11C | 0.98 | C27—C28 | 1.488 (2) |
C12—H12A | 0.98 | C28—C29 | 1.525 (2) |
C12—H12B | 0.98 | C28—H28A | 0.99 |
C12—H12C | 0.98 | C28—H28B | 0.99 |
C13—O4 | 1.4555 (18) | C29—N3 | 1.483 (2) |
C13—C15 | 1.519 (2) | C29—H29A | 0.99 |
C13—C16 | 1.522 (2) | C29—H29B | 0.99 |
C13—C14 | 1.522 (2) | N1—Zn1 | 2.0350 (13) |
C14—H14A | 0.98 | N2—H2 | 0.88 |
C14—H14B | 0.98 | N3—Zn1 | 2.0804 (13) |
C14—H14C | 0.98 | N3—H3D | 0.92 |
C15—H15A | 0.98 | N3—H3E | 0.92 |
C15—H15B | 0.98 | O1—Si1 | 1.6333 (11) |
C15—H15C | 0.98 | O2—Si1 | 1.6507 (11) |
C16—H16A | 0.98 | O3—Si1 | 1.6305 (11) |
C16—H16B | 0.98 | O4—Si2 | 1.6441 (11) |
C16—H16C | 0.98 | O5—Si2 | 1.6282 (12) |
C17—O5 | 1.447 (2) | O6—Si2 | 1.6304 (12) |
C17—C20 | 1.519 (2) | Si1—S1 | 2.0776 (6) |
C17—C19 | 1.522 (2) | Si2—S2 | 2.0771 (6) |
C17—C18 | 1.525 (3) | S1—Zn1 | 2.2813 (4) |
C18—H18A | 0.98 | S2—Zn1 | 2.3005 (4) |
C18—H18B | 0.98 | | |
| | | |
O1—C1—C2 | 109.26 (14) | C17—C19—H19A | 109.5 |
O1—C1—C3 | 110.79 (13) | C17—C19—H19B | 109.5 |
C2—C1—C3 | 111.04 (14) | H19A—C19—H19B | 109.5 |
O1—C1—C4 | 105.16 (14) | C17—C19—H19C | 109.5 |
C2—C1—C4 | 110.12 (15) | H19A—C19—H19C | 109.5 |
C3—C1—C4 | 110.30 (16) | H19B—C19—H19C | 109.5 |
C1—C2—H2A | 109.5 | C17—C20—H20A | 109.5 |
C1—C2—H2B | 109.5 | C17—C20—H20B | 109.5 |
H2A—C2—H2B | 109.5 | H20A—C20—H20B | 109.5 |
C1—C2—H2C | 109.5 | C17—C20—H20C | 109.5 |
H2A—C2—H2C | 109.5 | H20A—C20—H20C | 109.5 |
H2B—C2—H2C | 109.5 | H20B—C20—H20C | 109.5 |
C1—C3—H3A | 109.5 | C24A—C21—O6 | 110.5 (8) |
C1—C3—H3B | 109.5 | C24A—C21—C22 | 115.9 (8) |
H3A—C3—H3B | 109.5 | O6—C21—C22 | 106.55 (15) |
C1—C3—H3C | 109.5 | C24A—C21—C23 | 90.3 (8) |
H3A—C3—H3C | 109.5 | O6—C21—C23 | 111.6 (2) |
H3B—C3—H3C | 109.5 | C22—C21—C23 | 121.3 (4) |
C1—C4—H4A | 109.5 | O6—C21—C24 | 104.3 (5) |
C1—C4—H4B | 109.5 | C22—C21—C24 | 105.3 (4) |
H4A—C4—H4B | 109.5 | C23—C21—C24 | 106.3 (5) |
C1—C4—H4C | 109.5 | C24A—C21—C23A | 117.4 (7) |
H4A—C4—H4C | 109.5 | O6—C21—C23A | 112.0 (3) |
H4B—C4—H4C | 109.5 | C22—C21—C23A | 93.2 (6) |
O2—C5—C6 | 112.16 (13) | C24—C21—C23A | 132.2 (6) |
O2—C5—C8 | 108.87 (13) | C21—C22—H22A | 109.5 |
C6—C5—C8 | 109.92 (14) | C21—C22—H22B | 109.5 |
O2—C5—C7 | 104.91 (13) | H22A—C22—H22B | 109.5 |
C6—C5—C7 | 110.59 (14) | C21—C22—H22C | 109.5 |
C8—C5—C7 | 110.27 (15) | H22A—C22—H22C | 109.5 |
C5—C6—H6A | 109.5 | H22B—C22—H22C | 109.5 |
C5—C6—H6B | 109.5 | C21—C23—H23A | 109.5 |
H6A—C6—H6B | 109.5 | C21—C23—H23B | 109.5 |
C5—C6—H6C | 109.5 | C21—C23—H23C | 109.5 |
H6A—C6—H6C | 109.5 | C21—C24—H24A | 109.5 |
H6B—C6—H6C | 109.5 | C21—C24—H24B | 109.5 |
C5—C7—H7A | 109.5 | C21—C24—H24C | 109.5 |
C5—C7—H7B | 109.5 | C21—C23A—H23D | 109.5 |
H7A—C7—H7B | 109.5 | C21—C23A—H23E | 109.5 |
C5—C7—H7C | 109.5 | H23D—C23A—H23E | 109.5 |
H7A—C7—H7C | 109.5 | C21—C23A—H23F | 109.5 |
H7B—C7—H7C | 109.5 | H23D—C23A—H23F | 109.5 |
C5—C8—H8A | 109.5 | H23E—C23A—H23F | 109.5 |
C5—C8—H8B | 109.5 | C21—C24A—H24D | 109.5 |
H8A—C8—H8B | 109.5 | C21—C24A—H24E | 109.5 |
C5—C8—H8C | 109.5 | H24D—C24A—H24E | 109.5 |
H8A—C8—H8C | 109.5 | C21—C24A—H24F | 109.5 |
H8B—C8—H8C | 109.5 | H24D—C24A—H24F | 109.5 |
O3—C9—C10 | 105.88 (13) | H24E—C24A—H24F | 109.5 |
O3—C9—C11 | 111.24 (13) | N1—C25—N2 | 110.26 (16) |
C10—C9—C11 | 110.17 (14) | N1—C25—H25 | 124.9 |
O3—C9—C12 | 107.89 (12) | N2—C25—H25 | 124.9 |
C10—C9—C12 | 110.72 (14) | C27—C26—N2 | 106.40 (16) |
C11—C9—C12 | 110.82 (15) | C27—C26—H26 | 126.8 |
C9—C10—H10A | 109.5 | N2—C26—H26 | 126.8 |
C9—C10—H10B | 109.5 | C26—C27—N1 | 108.50 (16) |
H10A—C10—H10B | 109.5 | C26—C27—C28 | 129.54 (16) |
C9—C10—H10C | 109.5 | N1—C27—C28 | 121.95 (14) |
H10A—C10—H10C | 109.5 | C27—C28—C29 | 113.81 (14) |
H10B—C10—H10C | 109.5 | C27—C28—H28A | 108.8 |
C9—C11—H11A | 109.5 | C29—C28—H28A | 108.8 |
C9—C11—H11B | 109.5 | C27—C28—H28B | 108.8 |
H11A—C11—H11B | 109.5 | C29—C28—H28B | 108.8 |
C9—C11—H11C | 109.5 | H28A—C28—H28B | 107.7 |
H11A—C11—H11C | 109.5 | N3—C29—C28 | 111.16 (13) |
H11B—C11—H11C | 109.5 | N3—C29—H29A | 109.4 |
C9—C12—H12A | 109.5 | C28—C29—H29A | 109.4 |
C9—C12—H12B | 109.5 | N3—C29—H29B | 109.4 |
H12A—C12—H12B | 109.5 | C28—C29—H29B | 109.4 |
C9—C12—H12C | 109.5 | H29A—C29—H29B | 108 |
H12A—C12—H12C | 109.5 | C25—N1—C27 | 106.35 (14) |
H12B—C12—H12C | 109.5 | C25—N1—Zn1 | 130.86 (12) |
O4—C13—C15 | 111.07 (13) | C27—N1—Zn1 | 122.09 (11) |
O4—C13—C16 | 108.04 (13) | C25—N2—C26 | 108.48 (14) |
C15—C13—C16 | 110.90 (15) | C25—N2—H2 | 125.8 |
O4—C13—C14 | 105.89 (13) | C26—N2—H2 | 125.8 |
C15—C13—C14 | 110.01 (15) | C29—N3—Zn1 | 118.82 (10) |
C16—C13—C14 | 110.81 (15) | C29—N3—H3D | 107.6 |
C13—C14—H14A | 109.5 | Zn1—N3—H3D | 107.6 |
C13—C14—H14B | 109.5 | C29—N3—H3E | 107.6 |
H14A—C14—H14B | 109.5 | Zn1—N3—H3E | 107.6 |
C13—C14—H14C | 109.5 | H3D—N3—H3E | 107 |
H14A—C14—H14C | 109.5 | C1—O1—Si1 | 131.67 (10) |
H14B—C14—H14C | 109.5 | C5—O2—Si1 | 130.44 (10) |
C13—C15—H15A | 109.5 | C9—O3—Si1 | 131.24 (10) |
C13—C15—H15B | 109.5 | C13—O4—Si2 | 130.32 (10) |
H15A—C15—H15B | 109.5 | C17—O5—Si2 | 133.16 (10) |
C13—C15—H15C | 109.5 | C21—O6—Si2 | 132.98 (11) |
H15A—C15—H15C | 109.5 | O3—Si1—O1 | 105.69 (6) |
H15B—C15—H15C | 109.5 | O3—Si1—O2 | 103.76 (6) |
C13—C16—H16A | 109.5 | O1—Si1—O2 | 111.48 (6) |
C13—C16—H16B | 109.5 | O3—Si1—S1 | 116.42 (5) |
H16A—C16—H16B | 109.5 | O1—Si1—S1 | 109.95 (4) |
C13—C16—H16C | 109.5 | O2—Si1—S1 | 109.40 (4) |
H16A—C16—H16C | 109.5 | O5—Si2—O6 | 111.88 (7) |
H16B—C16—H16C | 109.5 | O5—Si2—O4 | 106.16 (6) |
O5—C17—C20 | 111.33 (14) | O6—Si2—O4 | 105.71 (6) |
O5—C17—C19 | 105.23 (14) | O5—Si2—S2 | 112.71 (5) |
C20—C17—C19 | 110.80 (16) | O6—Si2—S2 | 106.20 (5) |
O5—C17—C18 | 109.01 (14) | O4—Si2—S2 | 114.06 (4) |
C20—C17—C18 | 110.48 (15) | Si1—S1—Zn1 | 110.33 (2) |
C19—C17—C18 | 109.86 (16) | Si2—S2—Zn1 | 102.24 (2) |
C17—C18—H18A | 109.5 | N1—Zn1—N3 | 95.74 (5) |
C17—C18—H18B | 109.5 | N1—Zn1—S1 | 119.20 (4) |
H18A—C18—H18B | 109.5 | N3—Zn1—S1 | 107.25 (4) |
C17—C18—H18C | 109.5 | N1—Zn1—S2 | 110.88 (4) |
H18A—C18—H18C | 109.5 | N3—Zn1—S2 | 116.88 (4) |
H18B—C18—H18C | 109.5 | S1—Zn1—S2 | 107.053 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2i | 0.88 | 2.52 | 3.2481 (14) | 140 |
N2—H2···O6i | 0.88 | 2.57 | 3.355 (2) | 148 |
N3—H3D···O4 | 0.92 | 2.24 | 3.0550 (17) | 147 |
N3—H3E···O2 | 0.92 | 2.20 | 3.0592 (17) | 156 |
Symmetry code: (i) −x, −y+1, −z+1. |
(V) [2-(1H-imidazol-4-yl-
κN
3)methanol]bis(tri-
tert-
butoxysilanethiolato-
κ2O,
S)zinc(II)
top
Crystal data top
[Zn(C12H27O3SSi)2(C4H6N2O)] | F(000) = 1552 |
Mr = 722.45 | Dx = 1.225 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 24929 reflections |
a = 16.2546 (5) Å | θ = 2.2–32.4° |
b = 9.2094 (2) Å | µ = 0.83 mm−1 |
c = 26.1831 (7) Å | T = 120 K |
β = 91.874 (2)° | Prism, colourless |
V = 3917.39 (18) Å3 | 0.39 × 0.2 × 0.04 mm |
Z = 4 | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7283 independent reflections |
Graphite monochromator | 6253 reflections with I > 2σ(I) |
Detector resolution: 8.1883 pixels mm-1 | Rint = 0.043 |
ω scans, 0.65 deg width | θmax = 25.5°, θmin = 2.3° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897] | h = −19→14 |
Tmin = 0.685, Tmax = 0.855 | k = −10→11 |
25278 measured reflections | l = −31→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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0666P)2 + 2.7099P] where P = (Fo2 + 2Fc2)/3 |
7283 reflections | (Δ/σ)max = 0.001 |
429 parameters | Δρmax = 0.99 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
[Zn(C12H27O3SSi)2(C4H6N2O)] | V = 3917.39 (18) Å3 |
Mr = 722.45 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.2546 (5) Å | µ = 0.83 mm−1 |
b = 9.2094 (2) Å | T = 120 K |
c = 26.1831 (7) Å | 0.39 × 0.2 × 0.04 mm |
β = 91.874 (2)° | |
Data collection top
Oxford Diffraction KM-4 CCD diffractometer | 7283 independent reflections |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897] | 6253 reflections with I > 2σ(I) |
Tmin = 0.685, Tmax = 0.855 | Rint = 0.043 |
25278 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.99 e Å−3 |
7283 reflections | Δρmin = −0.41 e Å−3 |
429 parameters | |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F2, conventional R-factors R are based
on F, with F set to zero for negative F2. The threshold expression of
F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F2 are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.23346 (15) | 0.3039 (3) | 0.16915 (9) | 0.0238 (5) | |
C2 | 0.14046 (16) | 0.2951 (3) | 0.16199 (12) | 0.0377 (7) | |
H2A | 0.1259 | 0.2103 | 0.141 | 0.057* | |
H2B | 0.12 | 0.3834 | 0.1449 | 0.057* | |
H2C | 0.1155 | 0.286 | 0.1954 | 0.057* | |
C3 | 0.27371 (17) | 0.3146 (3) | 0.11735 (10) | 0.0289 (6) | |
H3A | 0.3337 | 0.3184 | 0.1225 | 0.043* | |
H3B | 0.2546 | 0.4028 | 0.0997 | 0.043* | |
H3C | 0.2587 | 0.2294 | 0.0966 | 0.043* | |
C4 | 0.2586 (2) | 0.4303 (3) | 0.20298 (11) | 0.0365 (7) | |
H4A | 0.2331 | 0.4203 | 0.2362 | 0.055* | |
H4B | 0.2405 | 0.5213 | 0.1868 | 0.055* | |
H4C | 0.3187 | 0.4312 | 0.2079 | 0.055* | |
C5 | 0.31387 (15) | −0.1437 (3) | 0.09502 (9) | 0.0247 (5) | |
C6 | 0.23949 (17) | −0.2289 (3) | 0.07445 (11) | 0.0360 (6) | |
H6A | 0.2134 | −0.2789 | 0.1027 | 0.054* | |
H6B | 0.2573 | −0.3004 | 0.0494 | 0.054* | |
H6C | 0.1999 | −0.162 | 0.058 | 0.054* | |
C7 | 0.3549 (2) | −0.0601 (4) | 0.05273 (11) | 0.0408 (7) | |
H7A | 0.3151 | 0.0071 | 0.0367 | 0.061* | |
H7B | 0.3743 | −0.1283 | 0.027 | 0.061* | |
H7C | 0.4017 | −0.0051 | 0.0672 | 0.061* | |
C8 | 0.37455 (16) | −0.2458 (3) | 0.12210 (11) | 0.0308 (6) | |
H8A | 0.4223 | −0.1903 | 0.135 | 0.046* | |
H8B | 0.3926 | −0.3198 | 0.098 | 0.046* | |
H8C | 0.3478 | −0.2929 | 0.1507 | 0.046* | |
C9 | 0.48478 (14) | 0.1475 (3) | 0.19331 (10) | 0.0232 (5) | |
C10 | 0.4992 (2) | 0.2909 (4) | 0.16792 (14) | 0.0540 (10) | |
H10A | 0.5037 | 0.2763 | 0.131 | 0.081* | |
H10B | 0.5504 | 0.3339 | 0.1819 | 0.081* | |
H10C | 0.4531 | 0.3563 | 0.1743 | 0.081* | |
C11 | 0.4724 (2) | 0.1677 (5) | 0.24981 (12) | 0.0578 (11) | |
H11A | 0.4232 | 0.2269 | 0.2548 | 0.087* | |
H11B | 0.5206 | 0.2165 | 0.2654 | 0.087* | |
H11C | 0.4654 | 0.0726 | 0.2659 | 0.087* | |
C12 | 0.5552 (2) | 0.0463 (4) | 0.1851 (2) | 0.0666 (12) | |
H12A | 0.5444 | −0.047 | 0.2015 | 0.1* | |
H12B | 0.6059 | 0.0884 | 0.2001 | 0.1* | |
H12C | 0.5616 | 0.0314 | 0.1484 | 0.1* | |
C13 | 0.17112 (16) | −0.1797 (3) | 0.38238 (9) | 0.0237 (5) | |
C14 | 0.07796 (17) | −0.1894 (3) | 0.37548 (12) | 0.0371 (7) | |
H14A | 0.0523 | −0.1125 | 0.3954 | 0.056* | |
H14B | 0.0592 | −0.2843 | 0.3874 | 0.056* | |
H14C | 0.0624 | −0.1776 | 0.3392 | 0.056* | |
C15 | 0.2130 (2) | −0.2910 (3) | 0.34966 (12) | 0.0385 (7) | |
H15A | 0.1959 | −0.2767 | 0.3138 | 0.058* | |
H15B | 0.1974 | −0.3888 | 0.3605 | 0.058* | |
H15C | 0.2729 | −0.2797 | 0.3535 | 0.058* | |
C16 | 0.19733 (19) | −0.1970 (3) | 0.43842 (10) | 0.0344 (6) | |
H16A | 0.257 | −0.1841 | 0.4423 | 0.052* | |
H16B | 0.1824 | −0.2942 | 0.4501 | 0.052* | |
H16C | 0.1694 | −0.1238 | 0.4588 | 0.052* | |
C17 | 0.35957 (15) | 0.1461 (3) | 0.44011 (10) | 0.0267 (6) | |
C18 | 0.38183 (18) | 0.3051 (3) | 0.43204 (12) | 0.0394 (7) | |
H18A | 0.3644 | 0.3348 | 0.3974 | 0.059* | |
H18B | 0.4415 | 0.3175 | 0.4365 | 0.059* | |
H18C | 0.3539 | 0.3653 | 0.457 | 0.059* | |
C19 | 0.39767 (17) | 0.0502 (4) | 0.40023 (13) | 0.0401 (7) | |
H19A | 0.3795 | −0.0503 | 0.4049 | 0.06* | |
H19B | 0.4578 | 0.0549 | 0.404 | 0.06* | |
H19C | 0.3803 | 0.0839 | 0.366 | 0.06* | |
C20 | 0.38595 (18) | 0.0986 (4) | 0.49390 (12) | 0.0451 (8) | |
H20A | 0.3585 | 0.1594 | 0.5189 | 0.068* | |
H20B | 0.4457 | 0.109 | 0.4985 | 0.068* | |
H20C | 0.3706 | −0.0032 | 0.4989 | 0.068* | |
C21 | 0.08733 (16) | 0.2399 (3) | 0.45826 (10) | 0.0276 (6) | |
C22 | 0.1249 (9) | 0.2071 (16) | 0.5090 (5) | 0.039 (3) | 0.65 (3) |
H22A | 0.1102 | 0.1082 | 0.519 | 0.058* | 0.65 (3) |
H22B | 0.1047 | 0.2762 | 0.5341 | 0.058* | 0.65 (3) |
H22C | 0.1849 | 0.2152 | 0.5076 | 0.058* | 0.65 (3) |
C23 | 0.1017 (9) | 0.3944 (8) | 0.4405 (4) | 0.046 (2) | 0.65 (3) |
H23A | 0.1605 | 0.4092 | 0.4353 | 0.069* | 0.65 (3) |
H23B | 0.083 | 0.4625 | 0.4664 | 0.069* | 0.65 (3) |
H23C | 0.0708 | 0.4113 | 0.4083 | 0.069* | 0.65 (3) |
C24 | −0.0087 (7) | 0.2140 (14) | 0.4594 (5) | 0.035 (2) | 0.65 (3) |
H24A | −0.0332 | 0.2299 | 0.4251 | 0.052* | 0.65 (3) |
H24B | −0.0329 | 0.2819 | 0.4835 | 0.052* | 0.65 (3) |
H24C | −0.0195 | 0.1141 | 0.4702 | 0.052* | 0.65 (3) |
C22A | 0.117 (2) | 0.156 (3) | 0.5082 (10) | 0.043 (5) | 0.35 (3) |
H22D | 0.0976 | 0.056 | 0.5068 | 0.064* | 0.35 (3) |
H22E | 0.0957 | 0.2048 | 0.5383 | 0.064* | 0.35 (3) |
H22F | 0.1778 | 0.1568 | 0.5106 | 0.064* | 0.35 (3) |
C23A | 0.1363 (14) | 0.3883 (16) | 0.4589 (11) | 0.051 (5) | 0.35 (3) |
H23D | 0.1944 | 0.3698 | 0.4677 | 0.076* | 0.35 (3) |
H23E | 0.1133 | 0.4536 | 0.4843 | 0.076* | 0.35 (3) |
H23F | 0.1317 | 0.4335 | 0.425 | 0.076* | 0.35 (3) |
C24A | 0.0038 (14) | 0.260 (3) | 0.4559 (9) | 0.042 (5) | 0.35 (3) |
H24D | −0.0107 | 0.3273 | 0.428 | 0.063* | 0.35 (3) |
H24E | −0.0141 | 0.3007 | 0.4883 | 0.063* | 0.35 (3) |
H24F | −0.0236 | 0.1667 | 0.4496 | 0.063* | 0.35 (3) |
C25 | 0.03948 (14) | 0.0966 (3) | 0.28075 (9) | 0.0219 (5) | |
H25 | 0.0489 | 0.1558 | 0.3101 | 0.026* | |
C26 | −0.02386 (15) | −0.0196 (3) | 0.21849 (10) | 0.0242 (5) | |
H26 | −0.0658 | −0.0569 | 0.196 | 0.029* | |
C27 | 0.05823 (14) | −0.0441 (3) | 0.21601 (9) | 0.0201 (5) | |
C28 | 0.10370 (14) | −0.1292 (3) | 0.17747 (9) | 0.0226 (5) | |
H28A | 0.0638 | −0.1661 | 0.1512 | 0.029* | |
H28B | 0.1423 | −0.0635 | 0.1602 | 0.029* | |
N1 | 0.09808 (12) | 0.0310 (2) | 0.25592 (7) | 0.0194 (4) | |
N2 | −0.03456 (12) | 0.0697 (2) | 0.25973 (8) | 0.0239 (5) | |
H2 | −0.0818 | 0.1031 | 0.2703 | 0.029* | |
O1 | 0.25909 (10) | 0.17131 (17) | 0.19624 (6) | 0.0197 (3) | |
O2 | 0.28119 (10) | −0.03839 (18) | 0.13005 (6) | 0.0206 (4) | |
O3 | 0.41294 (10) | 0.08376 (18) | 0.16767 (6) | 0.0216 (4) | |
O4 | 0.19715 (10) | −0.03761 (17) | 0.36335 (6) | 0.0213 (4) | |
O5 | 0.27078 (10) | 0.13174 (19) | 0.43794 (6) | 0.0219 (4) | |
O6 | 0.11396 (10) | 0.14540 (19) | 0.41829 (6) | 0.0242 (4) | |
O7 | 0.14903 (10) | −0.24901 (18) | 0.19865 (7) | 0.0242 (4) | |
H7 | 0.1954 | −0.2202 | 0.2096 | 0.029* | |
Si1 | 0.32091 (4) | 0.03626 (7) | 0.18176 (2) | 0.01611 (14) | |
Si2 | 0.20247 (4) | 0.12294 (7) | 0.39136 (2) | 0.01828 (15) | |
S1 | 0.31089 (3) | −0.09740 (6) | 0.24631 (2) | 0.01777 (13) | |
S2 | 0.22374 (4) | 0.26116 (6) | 0.33014 (2) | 0.02213 (15) | |
Zn1 | 0.218216 (16) | 0.06420 (3) | 0.277116 (10) | 0.02073 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0302 (13) | 0.0195 (12) | 0.0217 (12) | 0.0051 (10) | 0.0024 (10) | 0.0067 (10) |
C2 | 0.0298 (14) | 0.0428 (17) | 0.0406 (16) | 0.0090 (12) | 0.0041 (12) | 0.0212 (14) |
C3 | 0.0355 (14) | 0.0279 (14) | 0.0234 (13) | 0.0050 (11) | 0.0043 (11) | 0.0086 (11) |
C4 | 0.0607 (19) | 0.0231 (14) | 0.0260 (14) | 0.0051 (13) | 0.0053 (13) | 0.0044 (11) |
C5 | 0.0296 (13) | 0.0264 (13) | 0.0185 (12) | −0.0014 (10) | 0.0076 (10) | −0.0050 (10) |
C6 | 0.0363 (15) | 0.0451 (17) | 0.0266 (14) | −0.0032 (13) | 0.0000 (11) | −0.0148 (13) |
C7 | 0.0514 (18) | 0.0476 (18) | 0.0244 (14) | −0.0036 (14) | 0.0171 (13) | 0.0003 (13) |
C8 | 0.0320 (14) | 0.0288 (14) | 0.0317 (14) | 0.0037 (11) | 0.0031 (11) | −0.0108 (12) |
C9 | 0.0198 (11) | 0.0235 (12) | 0.0261 (13) | −0.0057 (9) | 0.0004 (10) | 0.0019 (10) |
C10 | 0.054 (2) | 0.0476 (19) | 0.058 (2) | −0.0290 (16) | −0.0263 (17) | 0.0217 (17) |
C11 | 0.0433 (18) | 0.100 (3) | 0.0301 (16) | −0.0392 (19) | −0.0011 (14) | −0.0116 (18) |
C12 | 0.0311 (17) | 0.053 (2) | 0.114 (4) | 0.0096 (15) | −0.017 (2) | −0.030 (2) |
C13 | 0.0342 (13) | 0.0164 (12) | 0.0207 (12) | −0.0049 (10) | 0.0025 (10) | 0.0038 (10) |
C14 | 0.0354 (15) | 0.0287 (15) | 0.0469 (18) | −0.0103 (12) | −0.0015 (13) | 0.0077 (13) |
C15 | 0.0612 (19) | 0.0202 (13) | 0.0351 (16) | −0.0031 (13) | 0.0160 (14) | 0.0018 (12) |
C16 | 0.0510 (17) | 0.0275 (14) | 0.0244 (14) | −0.0057 (12) | −0.0014 (12) | 0.0068 (11) |
C17 | 0.0204 (12) | 0.0384 (15) | 0.0214 (12) | −0.0001 (10) | 0.0016 (10) | −0.0072 (11) |
C18 | 0.0353 (15) | 0.0450 (18) | 0.0380 (16) | −0.0132 (13) | 0.0027 (12) | −0.0104 (14) |
C19 | 0.0266 (14) | 0.0499 (19) | 0.0442 (17) | 0.0008 (12) | 0.0086 (12) | −0.0182 (15) |
C20 | 0.0277 (15) | 0.072 (2) | 0.0355 (17) | 0.0053 (15) | −0.0052 (12) | 0.0035 (16) |
C21 | 0.0315 (14) | 0.0307 (14) | 0.0213 (12) | 0.0022 (11) | 0.0099 (10) | −0.0030 (11) |
C22 | 0.036 (3) | 0.058 (7) | 0.021 (3) | 0.014 (5) | −0.002 (2) | −0.010 (5) |
C23 | 0.050 (6) | 0.032 (3) | 0.058 (5) | 0.000 (3) | 0.029 (4) | −0.009 (3) |
C24 | 0.016 (3) | 0.056 (6) | 0.032 (3) | 0.003 (3) | 0.010 (2) | 0.015 (4) |
C22A | 0.063 (11) | 0.050 (12) | 0.016 (6) | 0.017 (9) | 0.013 (6) | −0.009 (8) |
C23A | 0.048 (9) | 0.022 (5) | 0.083 (13) | −0.002 (6) | 0.025 (8) | −0.019 (7) |
C24A | 0.040 (8) | 0.065 (13) | 0.023 (6) | −0.014 (8) | 0.015 (5) | −0.007 (7) |
C25 | 0.0230 (12) | 0.0205 (12) | 0.0225 (12) | 0.0017 (9) | 0.0050 (10) | 0.0001 (10) |
C26 | 0.0224 (12) | 0.0214 (12) | 0.0287 (13) | −0.0008 (10) | −0.0010 (10) | −0.0013 (10) |
C27 | 0.0212 (11) | 0.0189 (11) | 0.0201 (12) | −0.0018 (9) | 0.0003 (9) | 0.0034 (9) |
C28 | 0.0207 (11) | 0.0270 (13) | 0.0200 (12) | −0.0024 (10) | 0.0002 (9) | −0.0019 (10) |
N1 | 0.0192 (10) | 0.0205 (10) | 0.0184 (10) | 0.0006 (8) | 0.0027 (8) | −0.0003 (8) |
N2 | 0.0182 (10) | 0.0228 (11) | 0.0310 (12) | 0.0025 (8) | 0.0046 (8) | 0.0001 (9) |
O1 | 0.0257 (8) | 0.0184 (8) | 0.0151 (8) | 0.0032 (7) | 0.0027 (6) | 0.0039 (7) |
O2 | 0.0227 (8) | 0.0234 (9) | 0.0159 (8) | −0.0008 (7) | 0.0008 (6) | −0.0020 (7) |
O3 | 0.0217 (8) | 0.0236 (9) | 0.0198 (8) | −0.0054 (7) | 0.0035 (7) | −0.0015 (7) |
O4 | 0.0302 (9) | 0.0168 (8) | 0.0170 (8) | −0.0040 (7) | 0.0027 (7) | 0.0019 (7) |
O5 | 0.0210 (8) | 0.0286 (9) | 0.0160 (8) | −0.0004 (7) | 0.0020 (6) | −0.0018 (7) |
O6 | 0.0244 (9) | 0.0299 (9) | 0.0186 (8) | −0.0004 (7) | 0.0043 (7) | −0.0031 (7) |
O7 | 0.0193 (8) | 0.0206 (9) | 0.0329 (10) | −0.0024 (7) | 0.0038 (7) | −0.0041 (7) |
Si1 | 0.0175 (3) | 0.0168 (3) | 0.0141 (3) | −0.0008 (2) | 0.0017 (2) | 0.0003 (2) |
Si2 | 0.0229 (3) | 0.0184 (3) | 0.0137 (3) | −0.0013 (2) | 0.0024 (2) | −0.0005 (2) |
S1 | 0.0188 (3) | 0.0174 (3) | 0.0172 (3) | 0.0016 (2) | 0.0025 (2) | 0.0029 (2) |
S2 | 0.0337 (3) | 0.0170 (3) | 0.0159 (3) | −0.0026 (2) | 0.0036 (2) | −0.0002 (2) |
Zn1 | 0.01924 (16) | 0.02318 (17) | 0.01979 (16) | 0.00064 (10) | 0.00101 (11) | −0.00635 (11) |
Geometric parameters (Å, º) top
C1—O1 | 1.466 (3) | C18—H18C | 0.98 |
C1—C4 | 1.511 (4) | C19—H19A | 0.98 |
C1—C2 | 1.519 (4) | C19—H19B | 0.98 |
C1—C3 | 1.528 (3) | C19—H19C | 0.98 |
C2—H2A | 0.98 | C20—H20A | 0.98 |
C2—H2B | 0.98 | C20—H20B | 0.98 |
C2—H2C | 0.98 | C20—H20C | 0.98 |
C3—H3A | 0.98 | C21—C24A | 1.37 (2) |
C3—H3B | 0.98 | C21—O6 | 1.439 (3) |
C3—H3C | 0.98 | C21—C22 | 1.476 (14) |
C4—H4A | 0.98 | C21—C23 | 1.517 (8) |
C4—H4B | 0.98 | C21—C24 | 1.580 (11) |
C4—H4C | 0.98 | C21—C23A | 1.582 (15) |
C5—O2 | 1.448 (3) | C21—C22A | 1.58 (3) |
C5—C7 | 1.521 (4) | C22—H22A | 0.98 |
C5—C8 | 1.521 (4) | C22—H22B | 0.98 |
C5—C6 | 1.524 (4) | C22—H22C | 0.98 |
C6—H6A | 0.98 | C23—H23A | 0.98 |
C6—H6B | 0.98 | C23—H23B | 0.98 |
C6—H6C | 0.98 | C23—H23C | 0.98 |
C7—H7A | 0.98 | C24—H24A | 0.98 |
C7—H7B | 0.98 | C24—H24B | 0.98 |
C7—H7C | 0.98 | C24—H24C | 0.98 |
C8—H8A | 0.98 | C22A—H22D | 0.98 |
C8—H8B | 0.98 | C22A—H22E | 0.98 |
C8—H8C | 0.98 | C22A—H22F | 0.98 |
C9—O3 | 1.452 (3) | C23A—H23D | 0.98 |
C9—C12 | 1.497 (4) | C23A—H23E | 0.98 |
C9—C10 | 1.501 (4) | C23A—H23F | 0.98 |
C9—C11 | 1.511 (4) | C24A—H24D | 0.98 |
C10—H10A | 0.98 | C24A—H24E | 0.98 |
C10—H10B | 0.98 | C24A—H24F | 0.98 |
C10—H10C | 0.98 | C25—N1 | 1.317 (3) |
C11—H11A | 0.98 | C25—N2 | 1.330 (3) |
C11—H11B | 0.98 | C25—H25 | 0.95 |
C11—H11C | 0.98 | C26—C27 | 1.357 (3) |
C12—H12A | 0.98 | C26—N2 | 1.373 (3) |
C12—H12B | 0.98 | C26—H26 | 0.95 |
C12—H12C | 0.98 | C27—N1 | 1.395 (3) |
C13—O4 | 1.467 (3) | C27—C28 | 1.492 (3) |
C13—C15 | 1.512 (4) | C28—O7 | 1.429 (3) |
C13—C14 | 1.522 (4) | C28—H28A | 0.99 |
C13—C16 | 1.523 (3) | C28—H28B | 0.99 |
C14—H14A | 0.98 | N1—Zn1 | 2.0357 (19) |
C14—H14B | 0.98 | N2—H2 | 0.88 |
C14—H14C | 0.98 | O1—Si1 | 1.6507 (17) |
C15—H15A | 0.98 | O1—Zn1 | 2.4477 (15) |
C15—H15B | 0.98 | O2—Si1 | 1.6326 (17) |
C15—H15C | 0.98 | O3—Si1 | 1.6129 (16) |
C16—H16A | 0.98 | O4—Si2 | 1.6514 (17) |
C16—H16B | 0.98 | O4—Zn1 | 2.4789 (16) |
C16—H16C | 0.98 | O5—Si2 | 1.6242 (17) |
C17—O5 | 1.449 (3) | O6—Si2 | 1.6358 (17) |
C17—C19 | 1.515 (4) | O7—H7 | 0.84 |
C17—C20 | 1.523 (4) | Si1—S1 | 2.1016 (8) |
C17—C18 | 1.525 (4) | Si2—S2 | 2.0846 (9) |
C18—H18A | 0.98 | S1—Zn1 | 2.2835 (6) |
C18—H18B | 0.98 | S2—Zn1 | 2.2841 (6) |
| | | |
O1—C1—C4 | 106.90 (19) | C17—C19—H19C | 109.5 |
O1—C1—C2 | 106.32 (19) | H19A—C19—H19C | 109.5 |
C4—C1—C2 | 111.3 (2) | H19B—C19—H19C | 109.5 |
O1—C1—C3 | 111.09 (19) | C17—C20—H20A | 109.5 |
C4—C1—C3 | 110.8 (2) | C17—C20—H20B | 109.5 |
C2—C1—C3 | 110.3 (2) | H20A—C20—H20B | 109.5 |
C1—C2—H2A | 109.5 | C17—C20—H20C | 109.5 |
C1—C2—H2B | 109.5 | H20A—C20—H20C | 109.5 |
H2A—C2—H2B | 109.5 | H20B—C20—H20C | 109.5 |
C1—C2—H2C | 109.5 | C24A—C21—O6 | 111.7 (10) |
H2A—C2—H2C | 109.5 | C24A—C21—C22 | 116.7 (11) |
H2B—C2—H2C | 109.5 | O6—C21—C22 | 113.9 (6) |
C1—C3—H3A | 109.5 | C24A—C21—C23 | 91.2 (9) |
C1—C3—H3B | 109.5 | O6—C21—C23 | 106.9 (3) |
H3A—C3—H3B | 109.5 | C22—C21—C23 | 113.9 (5) |
C1—C3—H3C | 109.5 | O6—C21—C24 | 104.0 (5) |
H3A—C3—H3C | 109.5 | C22—C21—C24 | 109.5 (7) |
H3B—C3—H3C | 109.5 | C23—C21—C24 | 108.0 (5) |
C1—C4—H4A | 109.5 | C24A—C21—C23A | 112.4 (10) |
C1—C4—H4B | 109.5 | O6—C21—C23A | 111.5 (6) |
H4A—C4—H4B | 109.5 | C22—C21—C23A | 88.5 (10) |
C1—C4—H4C | 109.5 | C24—C21—C23A | 128.9 (7) |
H4A—C4—H4C | 109.5 | C24A—C21—C22A | 112.5 (14) |
H4B—C4—H4C | 109.5 | O6—C21—C22A | 102.4 (9) |
O2—C5—C7 | 107.5 (2) | C23—C21—C22A | 131.5 (9) |
O2—C5—C8 | 111.4 (2) | C24—C21—C22A | 101.0 (12) |
C7—C5—C8 | 111.1 (2) | C23A—C21—C22A | 105.6 (11) |
O2—C5—C6 | 105.39 (19) | C21—C22—H22A | 109.5 |
C7—C5—C6 | 111.4 (2) | C21—C22—H22B | 109.5 |
C8—C5—C6 | 110.0 (2) | C21—C22—H22C | 109.5 |
C5—C6—H6A | 109.5 | C21—C23—H23A | 109.5 |
C5—C6—H6B | 109.5 | C21—C23—H23B | 109.5 |
H6A—C6—H6B | 109.5 | C21—C23—H23C | 109.5 |
C5—C6—H6C | 109.5 | C21—C24—H24A | 109.5 |
H6A—C6—H6C | 109.5 | C21—C24—H24B | 109.5 |
H6B—C6—H6C | 109.5 | C21—C24—H24C | 109.5 |
C5—C7—H7A | 109.5 | C21—C22A—H22D | 109.5 |
C5—C7—H7B | 109.5 | C21—C22A—H22E | 109.5 |
H7A—C7—H7B | 109.5 | H22D—C22A—H22E | 109.5 |
C5—C7—H7C | 109.5 | C21—C22A—H22F | 109.5 |
H7A—C7—H7C | 109.5 | H22D—C22A—H22F | 109.5 |
H7B—C7—H7C | 109.5 | H22E—C22A—H22F | 109.5 |
C5—C8—H8A | 109.5 | C21—C23A—H23D | 109.5 |
C5—C8—H8B | 109.5 | C21—C23A—H23E | 109.5 |
H8A—C8—H8B | 109.5 | H23D—C23A—H23E | 109.5 |
C5—C8—H8C | 109.5 | C21—C23A—H23F | 109.5 |
H8A—C8—H8C | 109.5 | H23D—C23A—H23F | 109.5 |
H8B—C8—H8C | 109.5 | H23E—C23A—H23F | 109.5 |
O3—C9—C12 | 106.8 (2) | C21—C24A—H24D | 109.5 |
O3—C9—C10 | 106.6 (2) | C21—C24A—H24E | 109.5 |
C12—C9—C10 | 110.6 (3) | H24D—C24A—H24E | 109.5 |
O3—C9—C11 | 111.8 (2) | C21—C24A—H24F | 109.5 |
C12—C9—C11 | 110.1 (3) | H24D—C24A—H24F | 109.5 |
C10—C9—C11 | 110.7 (3) | H24E—C24A—H24F | 109.5 |
C9—C10—H10A | 109.5 | N1—C25—N2 | 111.7 (2) |
C9—C10—H10B | 109.5 | N1—C25—H25 | 124.2 |
H10A—C10—H10B | 109.5 | N2—C25—H25 | 124.2 |
C9—C10—H10C | 109.5 | C27—C26—N2 | 106.7 (2) |
H10A—C10—H10C | 109.5 | C27—C26—H26 | 126.6 |
H10B—C10—H10C | 109.5 | N2—C26—H26 | 126.6 |
C9—C11—H11A | 109.5 | C26—C27—N1 | 108.4 (2) |
C9—C11—H11B | 109.5 | C26—C27—C28 | 129.0 (2) |
H11A—C11—H11B | 109.5 | N1—C27—C28 | 122.6 (2) |
C9—C11—H11C | 109.5 | O7—C28—C27 | 113.79 (19) |
H11A—C11—H11C | 109.5 | O7—C28—H28A | 108.8 |
H11B—C11—H11C | 109.5 | C27—C28—H28A | 108.8 |
C9—C12—H12A | 109.5 | O7—C28—H28B | 108.8 |
C9—C12—H12B | 109.5 | C27—C28—H28B | 108.8 |
H12A—C12—H12B | 109.5 | H28A—C28—H28B | 107.7 |
C9—C12—H12C | 109.5 | C25—N1—C27 | 105.8 (2) |
H12A—C12—H12C | 109.5 | C25—N1—Zn1 | 119.94 (17) |
H12B—C12—H12C | 109.5 | C27—N1—Zn1 | 134.16 (16) |
O4—C13—C15 | 105.78 (19) | C25—N2—C26 | 107.5 (2) |
O4—C13—C14 | 108.0 (2) | C25—N2—H2 | 126.3 |
C15—C13—C14 | 111.0 (2) | C26—N2—H2 | 126.3 |
O4—C13—C16 | 110.2 (2) | C1—O1—Si1 | 133.01 (14) |
C15—C13—C16 | 111.0 (2) | C1—O1—Zn1 | 132.33 (13) |
C14—C13—C16 | 110.7 (2) | Si1—O1—Zn1 | 94.56 (7) |
C13—C14—H14A | 109.5 | C5—O2—Si1 | 131.63 (15) |
C13—C14—H14B | 109.5 | C9—O3—Si1 | 137.89 (15) |
H14A—C14—H14B | 109.5 | C13—O4—Si2 | 131.22 (15) |
C13—C14—H14C | 109.5 | C13—O4—Zn1 | 134.15 (14) |
H14A—C14—H14C | 109.5 | Si2—O4—Zn1 | 93.38 (7) |
H14B—C14—H14C | 109.5 | C17—O5—Si2 | 133.62 (15) |
C13—C15—H15A | 109.5 | C21—O6—Si2 | 132.83 (16) |
C13—C15—H15B | 109.5 | C28—O7—H7 | 109.5 |
H15A—C15—H15B | 109.5 | O3—Si1—O2 | 105.61 (9) |
C13—C15—H15C | 109.5 | O3—Si1—O1 | 115.10 (9) |
H15A—C15—H15C | 109.5 | O2—Si1—O1 | 106.30 (9) |
H15B—C15—H15C | 109.5 | O3—Si1—S1 | 116.08 (7) |
C13—C16—H16A | 109.5 | O2—Si1—S1 | 112.42 (7) |
C13—C16—H16B | 109.5 | O1—Si1—S1 | 101.12 (6) |
H16A—C16—H16B | 109.5 | O5—Si2—O6 | 105.03 (9) |
C13—C16—H16C | 109.5 | O5—Si2—O4 | 113.75 (9) |
H16A—C16—H16C | 109.5 | O6—Si2—O4 | 105.70 (9) |
H16B—C16—H16C | 109.5 | O5—Si2—S2 | 114.86 (7) |
O5—C17—C19 | 110.4 (2) | O6—Si2—S2 | 115.12 (7) |
O5—C17—C20 | 105.1 (2) | O4—Si2—S2 | 102.29 (6) |
C19—C17—C20 | 111.1 (3) | Si1—S1—Zn1 | 88.38 (3) |
O5—C17—C18 | 108.8 (2) | Si2—S2—Zn1 | 88.75 (3) |
C19—C17—C18 | 111.1 (2) | N1—Zn1—S1 | 116.34 (6) |
C20—C17—C18 | 110.1 (2) | N1—Zn1—S2 | 107.66 (6) |
C17—C18—H18A | 109.5 | S1—Zn1—S2 | 135.97 (2) |
C17—C18—H18B | 109.5 | N1—Zn1—O1 | 96.30 (7) |
H18A—C18—H18B | 109.5 | S1—Zn1—O1 | 75.89 (4) |
C17—C18—H18C | 109.5 | S2—Zn1—O1 | 101.51 (4) |
H18A—C18—H18C | 109.5 | N1—Zn1—O4 | 91.81 (7) |
H18B—C18—H18C | 109.5 | S1—Zn1—O4 | 100.81 (4) |
C17—C19—H19A | 109.5 | S2—Zn1—O4 | 75.56 (4) |
C17—C19—H19B | 109.5 | O1—Zn1—O4 | 171.88 (5) |
H19A—C19—H19B | 109.5 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O7i | 0.88 | 1.94 | 2.751 (3) | 152 |
O7—H7···S1 | 0.84 | 2.37 | 3.1959 (17) | 168 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Experimental details
| (III) | (IV) | (V) |
Crystal data |
Chemical formula | [Co(C12H27O3SSi)2(C5H9N3)] | [Zn(C12H27O3SSi)2(C5H9N3)] | [Zn(C12H27O3SSi)2(C4H6N2O)] |
Mr | 729.05 | 735.49 | 722.45 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 9.2498 (4), 14.3000 (9), 16.0164 (11) | 9.2535 (3), 14.3163 (5), 15.9899 (6) | 16.2546 (5), 9.2094 (2), 26.1831 (7) |
α, β, γ (°) | 95.190 (5), 96.805 (4), 107.336 (4) | 95.086 (3), 96.805 (3), 107.337 (3) | 90, 91.874 (2), 90 |
V (Å3) | 1990.3 (2) | 1990.55 (12) | 3917.39 (18) |
Z | 2 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.64 | 0.82 | 0.83 |
Crystal size (mm) | 0.16 × 0.10 × 0.06 | 0.21 × 0.15 × 0.09 | 0.39 × 0.2 × 0.04 |
|
Data collection |
Diffractometer | Oxford Diffraction KM-4 CCD diffractometer | Oxford Diffraction KM-4 CCD diffractometer | Oxford Diffraction KM-4 CCD diffractometer |
Absorption correction | Analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by Clark & Reid [(1995).
Acta Cryst. A51, 887-897] | Analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897]. | Analytical (CrysAlis RED; Oxford Diffraction, 2006)
analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by
Clark & Reid [(1995). Acta Cryst. A51, 887-897] |
Tmin, Tmax | 0.842, 0.93 | 0.79, 0.857 | 0.685, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13851, 7381, 6248 | 13696, 7386, 6730 | 25278, 7283, 6253 |
Rint | 0.026 | 0.021 | 0.043 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.093, 1.10 | 0.031, 0.082, 1.11 | 0.041, 0.112, 1.09 |
No. of reflections | 7381 | 7386 | 7283 |
No. of parameters | 407 | 427 | 429 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.33 | 0.74, −0.32 | 0.99, −0.41 |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2i | 0.88 | 2.49 | 3.2365 (16) | 142.7 |
N2—H2···O6i | 0.88 | 2.60 | 3.367 (2) | 145.8 |
N3—H3D···O4 | 0.92 | 2.23 | 3.0626 (19) | 149.7 |
N3—H3E···O3 | 0.92 | 2.2 | 3.0654 (19) | 156.5 |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···S2i | 0.88 | 2.52 | 3.2481 (14) | 140.1 |
N2—H2···O6i | 0.88 | 2.57 | 3.355 (2) | 148.4 |
N3—H3D···O4 | 0.92 | 2.24 | 3.0550 (17) | 146.9 |
N3—H3E···O2 | 0.92 | 2.20 | 3.0592 (17) | 155.7 |
Symmetry code: (i) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O7i | 0.88 | 1.94 | 2.751 (3) | 152.3 |
O7—H7···S1 | 0.84 | 2.37 | 3.1959 (17) | 168.3 |
Symmetry code: (i) −x, y+1/2, −z+1/2. |
Comparative geometrical parameters (Å, °) for (III), (IV)
and (V) topBonds | (III)a | (IV)b | (V)b |
M1—S1 | 2.2724 (5) | 2.2813 (4) | 2.2835 (6) |
M1—S2 | 2.3028 (5) | 2.3005 (4) | 2.2841 (6) |
M1—N1 | 2.0116 (15) | 2.0350 (13) | 2.0357 (19) |
M1—N3 | 2.0754 (15) | 2.0804 (13) | – |
M1—O1 | – | – | 2.4477 (15) |
M1—O4 | – | – | 2.4789 (16) |
Angles | | | |
N1—M1—N3 | 96.46 (6) | 95.74 (5) | – |
N1—M1—S1 | 122.45 (4) | 119.20 (4) | 116.34 (6) |
N1—M1—S2 | 112.32 (4) | 110.88 (4) | 107.66 (6) |
N3—M1—S1 | 106.17 (5) | 107.25 (4) | – |
N3—M1—S2 | 115.05 (4) | 116.88 (4) | – |
S1—M1—S2 | 104.567 (18) | 107.053 (15) | 135.97 (2) |
N1—M1—O1 | – | – | 96.30 (7) |
N1—M1—O4 | – | – | 91.81 (7) |
O1—M1—S1 | – | – | 75.89 (4) |
O1—M1—S2 | – | – | 101.51 (4) |
O4—M1—S1 | – | – | 100.81 (4) |
O4—M1—S2 | – | – | 75.56 (4) |
O1—M1—O4 | – | – | 171.88 (5) |
Notes: (a) M1=Co1;
(b) M1=Zn1. |
Structural and spectroscopic studies on heteroleptic, transition metal tri-tert-butoxysilanethiolates have been undertaken to provide a source of reference data for cysteine-ligated metal centers in proteins (Becker, Zalewska et al., 2001; Becker et al., 2002; Dołęga et al., 2004, 2007, 2008; Kropidłowska et al., 2007). Unfortunately, 113Cd NMR and UV–vis solution studies revealed low stability of these complexes; in solution N-containing ligands are discarded and homoleptic metal thiolates restored (Becker, Zalewska et al., 2001; Dołęga et al., 2007; Dołęga & Walewski, 2007). We have not noticed any correlation between ligand–metal bond lengths in solids and the stability of the obtained complexes in solution. Even complexes with short metal–nitrogen bonds in the solid state, such as imidazole derivatives, tend to dissociate (Dołęga et al., 2007). Since our aim is to obtain solution UV–vis and NMR spectroscopic parameters correlated with well defined metal coordination, we decided to use N-containing ligands with additional chelating OH and NH2 groups in order to stabilize the resulting species in solution (Barszcz, 2005). Histamine, (I), and 4(5)-hydroxymethylimidazole, (II), have been applied as potentially chelating ligands. The crystal structures of one CoII and two ZnII complexes have been determined.
The molecular structure of [2-(1H-imidazol-4-yl-κN3)ethylamine- κ2N]bis(tri-tert-butoxysilanethiolato-κS)cobalt(II), (III), is presented in Fig. 1. The zinc analogue, (IV), is isomorphic; geometrical parameters are compared in Table 4. As in some previously described complexes (eg. Wojtczak et al., 1990; Garnuszek et al., 2002), histamine acts as a bidentate ligand, forming a six-membered ring including the metal ion, the latter displaying a distorted tetrahedral geometry in (III0 and (IV). Complexation of the amine N atom with the metal ion is stabilized by hydrogen bonds with O atoms from the tri-tert-butoxysilanethiolate ligands. These additional intramolecular interactions influence the regularity of the crystal packing of molecular tri-tert-butoxysilanethiolates; bulky, alkoxy substituents of tri-tert-butoxysilanethiol often exhibit static disorder in crystals (Kloskowska et al., 2006). Sometimes it is not possible to find an appropriate model for the disordered groups – such results then remain unpublished. If intramolecular hydrogen bonds are formed between ligands and adjacent tert-butoxy groups, the possibility of rotation and disorder is significantly diminished (Becker, Dołęga et al., 2001, Dołęga et al., 2006, 2008). In (III) and (IV), the methyl groups at C21 exhibit disorder and so were refined over two positions. The refinement of (IV) was stable without additional constraints; in (III), atom pairs based on C23 and C24 were refined with isotropic displacement parameters.
Compounds (III) and (IV) are the first structurally characterized complexes of histamine with ZnII and CoII. The geometrical parameters of ZnII-bonded histamine are comparable to those of other N1,N3-chelating histidine ligands in complexes with zinc(II) (Harding & Cole, 1963; Dalosto et al., 2001). The bond lengths found in (III) are in the range typical for neutral, tetrahedral CoII complexes with imidazole-based and tri-tert-butoxysilanethiolate ligands (Becker, Zalewska et al., 2001; Dołęga et al., 2008). The Co—N bond lengths in a known complex of CoIII with histamine are certainly shorter than those in (III), but the chelating angles are close to those in (III) (Wojtczak et al., 1990). Our results confirm the structural similarity of tetrahedral ZnII and CoII complexes with the same ligands (Horrocks et al., 1982; Dołęga et al., 2008).
Centrosymmetrically related molecules of (III) and (IV) form hydrogen-bonded dimers (Table 1), which are shown in Fig. 2. The planes of the imidazole rings are parallel, but there are no stacking interactions because of the inter-ring distance.
2-Hydroxymethylimidazole does not act as a bidentate chelating ligand in [2-(1H-imidazol-4-yl-κN3)methanol]bis(tri-tert-butoxysilanethiolato-κ2O,S)zinc(II), (V), but rather is bonded to zinc only via an N atom of the imidazole ring (Fig. 3). Ignoring the assymetric conformation of the imidazole ring, (V) would exhibit an approximate twofold symmetry. The position of ligating atoms in (V) may be approximated to a distorted trigonal bipyramid, which is a coordination geometry often observed in mixed-ligand zinc tri-tert-butoxysilanethiolates (Becker et al., 1996; Dołęga et al., 2004). Atoms O1 and O4 occupy the apical positions of the bipyramid and the O1—Zn1—O4 angle is close to 180°. The deviations from the least-squares equatorial plane are -0.0152 (3) for Zn1, 0.0055 (5) for S1, 0.0052 (5) for S2 and 0.0045 (18) Å for N1, with O1 and O4 distances of -2.3833 (16) and 2.3894 (16) Å, respectively. The methyl groups bound to C21 exhibit disorder, and it was necessary to refine them over two positions.
Complex (V) possesses a typically large (> 120°) S—Zn—S angle, as is always found in five-coordinated zinc–tri-tert-butoxysilanethiolates with ZnNO2S2 kernels (Becker et al., 1996; Dołęga et al., 2004, 2005). This angle becomes much smaller when the Zn coordination geometry approaches tetrahedral in complexes with ZnN2S2 or ZnNOS2 coordination cores; indeed, it is this angle that shows the most pronounced difference among the greometric parameters of the title compounds (Becker, Dołęga et al., 2001; Dołęga et al., 2004, 2008; this work, Table 4).
We do not think that an additional, weak intramolecular O—H···S interaction between 2-hydroxymethylimidazole and tri-tert-butoxysilanethiolate observed here (Table 3) would enhance stability of (V) in solution. It is evident that the side chain must be extended to achieve chelation in the studied systems. The molecules in (V) pack in one-dimensional zigzag chains linked by N—H···O hydrogen bonds that are approximately parallel to the b axis (Fig. 4).