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For the first time, cocrystallization of two isomorphous silanethiolate complexes has been carried out. (Acetonitrile)bis(tri-tert-butoxysilanethiolato-κ2O,S)cobalt(II) and (acetonitrile)bis(tri-tert-butoxysilanethiolato-κ2O,S)zinc(II) gave orthorhombic monocrystals of their solid solution with a Co:Zn ratio refined to 0.81 (5):0.19 (5), viz. [Co(C12H27O3SSi)2(C2H3N)]0.81[Zn(C12H27O3SSi)2(C2H3N)]0.19. The product retained the structural characteristics of the substrates, viz. distorted trigonal–bipyramidal arrangement of ligands around the MII atom and crystallographically imposed C2 symmetry with the M—NCMe fragment lying on a twofold rotation axis.
Supporting information
CCDC reference: 621382
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.007 Å
- Disorder in main residue
- R factor = 0.051
- wR factor = 0.118
- Data-to-parameter ratio = 17.1
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSMU01_ALERT_1_C The ratio of given/expected absorption coefficient lies
outside the range 0.99 <> 1.01
Calculated value of mu = 0.726
Value of mu given = 0.713
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms .. ?
PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 25.04
From the CIF: _reflns_number_total 3183
Count of symmetry unique reflns 1713
Completeness (_total/calc) 185.81%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1470
Fraction of Friedel pairs measured 0.858
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: CrysAlis CCD (Oxford Diffraction, 2005).; cell refinement: CrysAlis RED (Oxford Diffraction, 2005).; data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(Acetonitrile)bis(tri-
tert-butoxysilanethiolato-
κ2O,
S)cobalt(II)–
(acetonitrile)bis(tri-
tert-butoxysilanethiolato-
κ2O,
S)zinc(II) [0.81 (5)/0.19 (5)]
top
Crystal data top
[Co(C12H27O3SSi)2(C2H3N)]0.81
[Zn(C12H27O3SSi)2(C2H3N)]0.19 | F(000) = 2843 |
Mr = 659.76 | Dx = 1.206 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 3136 reflections |
a = 17.832 (3) Å | θ = 2.5–30° |
b = 45.098 (4) Å | µ = 0.71 mm−1 |
c = 9.0363 (7) Å | T = 120 K |
V = 7266.9 (15) Å3 | Prism, violet |
Z = 8 | 0.2 × 0.19 × 0.14 mm |
Data collection top
Four-axis κ geometry diffractometer | 2972 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.08 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
Detector resolution: 8.1883 pixels mm-1 | h = −19→21 |
0.75° ω scans | k = −33→53 |
9144 measured reflections | l = −10→10 |
3183 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0545P)2 + 37.5182P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3183 reflections | Δρmax = 0.63 e Å−3 |
186 parameters | Δρmin = −0.54 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 1470 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.10 (2) |
Special details top
Experimental. Thermal measurements were performed using PerkinElmer Differential Scanning
Calorimeter DSC 7 for encapsulated (aluminium pans) samples of ca
5–10?mg at a heating rate of 20?K/min under nitrogen flow. The calibration of
the temperature and heat flow scales at the same heating rate was performed
with In and Zn. |
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) |
Co1 | 0 | 0.5 | 0.52020 (8) | 0.0170 (3) | 0.81 (5) |
Zn1 | 0 | 0.5 | 0.52020 (8) | 0.0170 (3) | 0.19 (4) |
Si1 | 0.10869 (7) | 0.54516 (2) | 0.42262 (14) | 0.0167 (3) | |
S1 | 0.11205 (6) | 0.49930 (2) | 0.39705 (12) | 0.0198 (3) | |
O1 | 0.03148 (16) | 0.54921 (5) | 0.5237 (3) | 0.0196 (6) | |
O2 | 0.18170 (16) | 0.55995 (6) | 0.5000 (4) | 0.0206 (7) | |
O3 | 0.09464 (16) | 0.56456 (6) | 0.2735 (4) | 0.0241 (7) | |
N1 | 0 | 0.5 | 0.7507 (6) | 0.0217 (11) | |
C1 | 0 | 0.5 | 0.8768 (8) | 0.0220 (13) | |
C2 | 0 | 0.5 | 1.0374 (8) | 0.0354 (16) | |
H2A | −0.0486 | 0.4928 | 1.0736 | 0.042* | 0.5 |
H2B | 0.04 | 0.487 | 1.0736 | 0.042* | 0.5 |
H2C | 0.0086 | 0.5202 | 1.0736 | 0.042* | 0.5 |
C10 | −0.0117 (2) | 0.57598 (9) | 0.5602 (5) | 0.0231 (10) | |
C11 | 0.0422 (3) | 0.60055 (10) | 0.6075 (5) | 0.0235 (10) | |
H11A | 0.0772 | 0.6048 | 0.5265 | 0.035* | |
H11B | 0.0704 | 0.5941 | 0.6949 | 0.035* | |
H11C | 0.0137 | 0.6185 | 0.6314 | 0.035* | |
C12 | −0.0577 (3) | 0.58468 (10) | 0.4255 (6) | 0.0339 (12) | |
H12A | −0.0905 | 0.5682 | 0.3975 | 0.051* | |
H12B | −0.024 | 0.5893 | 0.3431 | 0.051* | |
H12C | −0.0882 | 0.6021 | 0.4491 | 0.051* | |
C13 | −0.0629 (3) | 0.56786 (10) | 0.6875 (6) | 0.0346 (12) | |
H13A | −0.0326 | 0.5616 | 0.7724 | 0.052* | |
H13B | −0.096 | 0.5516 | 0.6574 | 0.052* | |
H13C | −0.0931 | 0.5851 | 0.7152 | 0.052* | |
C20 | 0.2353 (2) | 0.55023 (10) | 0.6091 (5) | 0.0233 (10) | |
C21 | 0.2636 (3) | 0.57890 (11) | 0.6810 (7) | 0.0398 (13) | |
H21A | 0.2209 | 0.59 | 0.721 | 0.06* | |
H21B | 0.2894 | 0.591 | 0.6067 | 0.06* | |
H21C | 0.2984 | 0.574 | 0.7613 | 0.06* | |
C22 | 0.1978 (3) | 0.53085 (11) | 0.7262 (5) | 0.0291 (11) | |
H22A | 0.179 | 0.5127 | 0.6799 | 0.044* | |
H22B | 0.156 | 0.5417 | 0.771 | 0.044* | |
H22C | 0.2345 | 0.5257 | 0.8028 | 0.044* | |
C23 | 0.2982 (3) | 0.53370 (11) | 0.5331 (6) | 0.0338 (11) | |
H23A | 0.3204 | 0.5464 | 0.4566 | 0.051* | |
H23B | 0.2783 | 0.5156 | 0.4874 | 0.051* | |
H23C | 0.3366 | 0.5284 | 0.606 | 0.051* | |
C30 | 0.1462 (3) | 0.57794 (9) | 0.1695 (5) | 0.0255 (10) | |
C31 | 0.0992 (3) | 0.58496 (12) | 0.0333 (6) | 0.0376 (12) | |
H31A | 0.0574 | 0.5979 | 0.0613 | 0.056* | |
H31B | 0.0795 | 0.5665 | −0.0087 | 0.056* | |
H31C | 0.1304 | 0.595 | −0.0405 | 0.056* | |
C32 | 0.1781 (4) | 0.60645 (10) | 0.2362 (6) | 0.0416 (14) | |
H32A | 0.2098 | 0.6015 | 0.3213 | 0.062* | |
H32B | 0.1369 | 0.6193 | 0.2684 | 0.062* | |
H32C | 0.2082 | 0.6168 | 0.1615 | 0.062* | |
C33 | 0.2086 (3) | 0.55639 (11) | 0.1317 (6) | 0.0344 (12) | |
H33A | 0.1869 | 0.5381 | 0.0918 | 0.052* | |
H33B | 0.2374 | 0.5518 | 0.2212 | 0.052* | |
H33C | 0.2418 | 0.5653 | 0.0577 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0161 (4) | 0.0184 (4) | 0.0167 (5) | −0.0013 (3) | 0 | 0 |
Zn1 | 0.0161 (4) | 0.0184 (4) | 0.0167 (5) | −0.0013 (3) | 0 | 0 |
Si1 | 0.0170 (5) | 0.0166 (5) | 0.0166 (6) | −0.0001 (4) | −0.0018 (5) | 0.0014 (4) |
S1 | 0.0198 (5) | 0.0166 (5) | 0.0230 (6) | −0.0008 (4) | 0.0027 (5) | −0.0032 (4) |
O1 | 0.0258 (15) | 0.0114 (12) | 0.0217 (16) | 0.0041 (11) | −0.0012 (15) | −0.0027 (13) |
O2 | 0.0200 (15) | 0.0186 (14) | 0.0233 (16) | −0.0009 (11) | −0.0039 (14) | 0.0026 (12) |
O3 | 0.0232 (16) | 0.0266 (15) | 0.0226 (16) | −0.0010 (13) | 0.0004 (15) | 0.0077 (14) |
N1 | 0.029 (3) | 0.017 (2) | 0.019 (3) | 0.001 (2) | 0 | 0 |
C1 | 0.021 (3) | 0.021 (3) | 0.023 (4) | 0.001 (3) | 0 | 0 |
C2 | 0.030 (4) | 0.059 (4) | 0.017 (4) | 0.003 (4) | 0 | 0 |
C10 | 0.020 (2) | 0.0149 (19) | 0.034 (3) | 0.0027 (17) | −0.002 (2) | −0.0060 (17) |
C11 | 0.026 (2) | 0.021 (2) | 0.023 (2) | −0.0003 (19) | −0.001 (2) | −0.0038 (17) |
C12 | 0.033 (3) | 0.028 (2) | 0.041 (3) | 0.012 (2) | −0.014 (3) | −0.006 (2) |
C13 | 0.033 (3) | 0.025 (2) | 0.046 (3) | 0.007 (2) | 0.013 (3) | 0.001 (2) |
C20 | 0.017 (2) | 0.027 (2) | 0.025 (3) | 0.0059 (18) | −0.0059 (19) | 0.0013 (18) |
C21 | 0.040 (3) | 0.033 (3) | 0.047 (3) | −0.005 (2) | −0.015 (3) | −0.008 (2) |
C22 | 0.029 (3) | 0.038 (2) | 0.020 (2) | 0.002 (2) | −0.004 (2) | 0.0011 (19) |
C23 | 0.028 (3) | 0.041 (3) | 0.033 (3) | 0.009 (2) | 0.001 (2) | 0.005 (2) |
C30 | 0.028 (2) | 0.026 (2) | 0.022 (2) | −0.0036 (18) | 0.002 (2) | 0.0045 (19) |
C31 | 0.044 (3) | 0.046 (3) | 0.024 (3) | 0.006 (2) | −0.005 (3) | 0.011 (2) |
C32 | 0.069 (4) | 0.027 (2) | 0.029 (3) | −0.016 (3) | 0.002 (3) | 0.004 (2) |
C33 | 0.036 (3) | 0.043 (3) | 0.024 (3) | 0.006 (2) | 0.004 (2) | 0.003 (2) |
Geometric parameters (Å, º) top
Co1—N1 | 2.083 (5) | C13—H13B | 0.98 |
Co1—S1i | 2.2873 (12) | C13—H13C | 0.98 |
Co1—S1 | 2.2873 (12) | C20—C23 | 1.512 (6) |
Co1—O1i | 2.289 (3) | C20—C22 | 1.526 (7) |
Co1—O1 | 2.289 (3) | C20—C21 | 1.532 (6) |
Si1—O2 | 1.621 (3) | C21—H21A | 0.98 |
Si1—O3 | 1.626 (3) | C21—H21B | 0.98 |
Si1—O1 | 1.662 (3) | C21—H21C | 0.98 |
Si1—S1 | 2.0821 (14) | C22—H22A | 0.98 |
O1—C10 | 1.469 (5) | C22—H22B | 0.98 |
O2—C20 | 1.441 (5) | C22—H22C | 0.98 |
O3—C30 | 1.446 (5) | C23—H23A | 0.98 |
N1—C1 | 1.139 (9) | C23—H23B | 0.98 |
C1—C2 | 1.452 (10) | C23—H23C | 0.98 |
C2—H2A | 0.98 | C30—C33 | 1.516 (7) |
C2—H2B | 0.9801 | C30—C31 | 1.522 (7) |
C2—H2C | 0.9799 | C30—C32 | 1.530 (6) |
C10—C13 | 1.514 (7) | C31—H31A | 0.98 |
C10—C12 | 1.519 (7) | C31—H31B | 0.98 |
C10—C11 | 1.528 (6) | C31—H31C | 0.98 |
C11—H11A | 0.98 | C32—H32A | 0.98 |
C11—H11B | 0.98 | C32—H32B | 0.98 |
C11—H11C | 0.98 | C32—H32C | 0.98 |
C12—H12A | 0.98 | C33—H33A | 0.98 |
C12—H12B | 0.98 | C33—H33B | 0.98 |
C12—H12C | 0.98 | C33—H33C | 0.98 |
C13—H13A | 0.98 | | |
| | | |
N1—Co1—S1i | 119.11 (3) | C10—C13—H13C | 109.5 |
N1—Co1—S1 | 119.11 (3) | H13A—C13—H13C | 109.5 |
S1i—Co1—S1 | 121.77 (6) | H13B—C13—H13C | 109.5 |
N1—Co1—O1i | 89.20 (8) | O2—C20—C23 | 109.3 (4) |
S1i—Co1—O1i | 78.81 (8) | O2—C20—C22 | 111.0 (4) |
S1—Co1—O1i | 101.98 (8) | C23—C20—C22 | 110.9 (4) |
N1—Co1—O1 | 89.20 (8) | O2—C20—C21 | 104.6 (4) |
S1i—Co1—O1 | 101.98 (8) | C23—C20—C21 | 111.4 (4) |
S1—Co1—O1 | 78.81 (8) | C22—C20—C21 | 109.5 (4) |
O1i—Co1—O1 | 178.40 (16) | C20—C21—H21A | 109.5 |
O2—Si1—O3 | 105.05 (16) | C20—C21—H21B | 109.5 |
O2—Si1—O1 | 112.52 (16) | H21A—C21—H21B | 109.5 |
O3—Si1—O1 | 105.60 (16) | C20—C21—H21C | 109.5 |
O2—Si1—S1 | 115.68 (12) | H21A—C21—H21C | 109.5 |
O3—Si1—S1 | 116.55 (13) | H21B—C21—H21C | 109.5 |
O1—Si1—S1 | 101.18 (11) | C20—C22—H22A | 109.5 |
Si1—S1—Co1 | 84.67 (5) | C20—C22—H22B | 109.5 |
C10—O1—Si1 | 130.3 (3) | H22A—C22—H22B | 109.5 |
C10—O1—Co1 | 132.2 (2) | C20—C22—H22C | 109.5 |
Si1—O1—Co1 | 95.11 (12) | H22A—C22—H22C | 109.5 |
C20—O2—Si1 | 134.6 (3) | H22B—C22—H22C | 109.5 |
C30—O3—Si1 | 131.7 (3) | C20—C23—H23A | 109.5 |
C1—N1—Co1 | 180.000 (4) | C20—C23—H23B | 109.5 |
N1—C1—C2 | 180.000 (9) | H23A—C23—H23B | 109.5 |
C1—C2—H2A | 109.5 | C20—C23—H23C | 109.5 |
C1—C2—H2B | 109.5 | H23A—C23—H23C | 109.5 |
H2A—C2—H2B | 109.5 | H23B—C23—H23C | 109.5 |
C1—C2—H2C | 109.5 | O3—C30—C33 | 110.2 (4) |
H2A—C2—H2C | 109.5 | O3—C30—C31 | 105.2 (4) |
H2B—C2—H2C | 109.5 | C33—C30—C31 | 110.8 (4) |
O1—C10—C13 | 106.7 (3) | O3—C30—C32 | 109.4 (4) |
O1—C10—C12 | 108.4 (3) | C33—C30—C32 | 110.7 (4) |
C13—C10—C12 | 110.2 (4) | C31—C30—C32 | 110.4 (4) |
O1—C10—C11 | 109.2 (3) | C30—C31—H31A | 109.5 |
C13—C10—C11 | 110.0 (4) | C30—C31—H31B | 109.5 |
C12—C10—C11 | 112.1 (4) | H31A—C31—H31B | 109.5 |
C10—C11—H11A | 109.5 | C30—C31—H31C | 109.5 |
C10—C11—H11B | 109.5 | H31A—C31—H31C | 109.5 |
H11A—C11—H11B | 109.5 | H31B—C31—H31C | 109.5 |
C10—C11—H11C | 109.5 | C30—C32—H32A | 109.5 |
H11A—C11—H11C | 109.5 | C30—C32—H32B | 109.5 |
H11B—C11—H11C | 109.5 | H32A—C32—H32B | 109.5 |
C10—C12—H12A | 109.5 | C30—C32—H32C | 109.5 |
C10—C12—H12B | 109.5 | H32A—C32—H32C | 109.5 |
H12A—C12—H12B | 109.5 | H32B—C32—H32C | 109.5 |
C10—C12—H12C | 109.5 | C30—C33—H33A | 109.5 |
H12A—C12—H12C | 109.5 | C30—C33—H33B | 109.5 |
H12B—C12—H12C | 109.5 | H33A—C33—H33B | 109.5 |
C10—C13—H13A | 109.5 | C30—C33—H33C | 109.5 |
C10—C13—H13B | 109.5 | H33A—C33—H33C | 109.5 |
H13A—C13—H13B | 109.5 | H33B—C33—H33C | 109.5 |
Symmetry code: (i) −x, −y+1, z. |
Comparison of selected bond lengths (Å) and angles (°) for
[M{SSi(OBut)3}2(NCMe)] where M = Co (1), M = Zn (2) and M = Co/Zn (3).
Standard deviations in parentheses. top | (1)a | (2)b | (3)c |
M-S | 2.2680 (7) | 2.2491 (1) | 2.2873 (12) |
M-N | 2.065 (4) | 2.087 (4) | 2.083 (5) |
M-O | 2.283 (2) | 2.378 (2) | 2.289 (3) |
Si-S | 2.0666 (8) | 2.0680 (11) | 2.0821 (14) |
S-M-S | 119.14 (4) | 125.81 (5) | 121.77 (6) |
Notes: (a) Becker et al. (1995);
(b) Becker et al. (1996);
(c) this work. |
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