Solid solution of [M{SSi(OBut)3}2(NCMe)], where M = Zn and Co

Kropidłowska, A.; Chojnacki, J.; Gołaszewska, J.; Becker, B.

doi:10.1107/S1600536806032673

Solid solution of [M{SSi(OBu^t)₃}₂(NCMe)], where M = Zn and Co

A. Kropidłowska, J. Chojnacki, J. Gołaszewska and B. Becker

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 M^II atom and crystallographically imposed C₂ symmetry with the M—NCMe fragment lying on a twofold rotation axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806032673/kj2024sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806032673/kj20243sup2.hkl Contains datablock 3

CCDC reference: 621382

checkCIF report

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

Computing details top

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
M_r = 659.76	D_x = 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	R_int = 0.08
Graphite monochromator	θ_max = 25.0°, θ_min = 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(F_o²) + (0.0545P)² + 37.5182P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
3183 reflections	Δρ_max = 0.63 e Å⁻³
186 parameters	Δρ_min = −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	U_iso*/U_eq	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(OBu^t)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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