Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300713X/wn6146sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680300713X/wn6146Isup2.hkl |
CCDC reference: 214554
To [C5H5Fe(CO)2]2SnCl2 (54 g, 1 mmol) and potassium N,N-diisobutyldithiocarbamate (2.1 mmol) were added 20 ml of mixed solvent (C6H6–THF 1:1). The mixture was stirred for ca 6 h under an argon atmosphere at room temperature, and the reaction was followed by thin-layer chromatography. The resulting KCl was filtered off, the remainder washed with a small amount of benzene and the filtrate was concentrated under reduced pressure at 318 K, until the volume was about 5 ml. An equivalent volume of petroleum ether was added. The solid product was collected in a Büchner funnel, washed with diethyl ether and petroleum ether, then recrystallized from benzene and dried under vacuum.
All H atoms were positioned geometrically and refined isotropically, using a riding model. The C—H distances range from 0.96 to 0.98 Å.
Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[SnFe2(C5H5)2(C9H18NS2)2(CO)4] | F(000) = 1800 |
Mr = 881.34 | Dx = 1.482 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 21.800 (4) Å | θ = 2.0–17.5° |
b = 11.587 (2) Å | µ = 1.60 mm−1 |
c = 16.886 (3) Å | T = 293 K |
β = 112.17 (3)° | Block, black |
V = 3950.0 (15) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 4 |
Bruker P4 diffractometer | 2132 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.063 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −25→24 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = 0→13 |
Tmin = 0.69, Tmax = 0.72 | l = 0→20 |
6972 measured reflections | 3 standard reflections every 97 reflections |
3488 independent reflections | intensity decay: none |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.07P)2 + 1.66P] where P = (Fo2 + 2Fc2)/3 |
3488 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −0.96 e Å−3 |
[SnFe2(C5H5)2(C9H18NS2)2(CO)4] | V = 3950.0 (15) Å3 |
Mr = 881.34 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.800 (4) Å | µ = 1.60 mm−1 |
b = 11.587 (2) Å | T = 293 K |
c = 16.886 (3) Å | 0.3 × 0.2 × 0.2 mm |
β = 112.17 (3)° |
Bruker P4 diffractometer | 2132 reflections with I > 2σ(I) |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | Rint = 0.063 |
Tmin = 0.69, Tmax = 0.72 | 3 standard reflections every 97 reflections |
6972 measured reflections | intensity decay: none |
3488 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.78 e Å−3 |
3488 reflections | Δρmin = −0.96 e Å−3 |
208 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 1.08704 (6) | 0.90777 (10) | 0.38100 (7) | 0.0750 (4) | |
Sn1 | 1.0000 | 0.81279 (5) | 0.2500 | 0.0539 (2) | |
O1 | 0.9917 (3) | 1.0797 (6) | 0.3832 (5) | 0.114 (2) | |
O2 | 1.1365 (3) | 1.0538 (6) | 0.2773 (5) | 0.114 (2) | |
S1 | 0.94815 (11) | 0.63240 (17) | 0.28891 (14) | 0.0788 (6) | |
S2 | 0.90183 (11) | 0.83421 (17) | 0.35645 (15) | 0.0815 (6) | |
N1 | 0.8743 (3) | 0.6162 (5) | 0.3812 (4) | 0.0780 (18) | |
C1 | 0.9042 (4) | 0.6900 (6) | 0.3467 (5) | 0.075 (2) | |
C2 | 0.8688 (4) | 0.4901 (7) | 0.3653 (5) | 0.080 (2) | |
H2A | 0.8795 | 0.4507 | 0.4196 | 0.097* | |
H2B | 0.9015 | 0.4674 | 0.3421 | 0.097* | |
C3 | 0.8018 (5) | 0.4504 (7) | 0.3052 (6) | 0.093 (2) | |
H3 | 0.7700 | 0.4677 | 0.3318 | 0.111* | |
C4 | 0.7775 (5) | 0.5069 (8) | 0.2190 (6) | 0.111 (3) | |
H4A | 0.7668 | 0.5861 | 0.2244 | 0.166* | |
H4B | 0.7387 | 0.4674 | 0.1815 | 0.166* | |
H4C | 0.8114 | 0.5032 | 0.1957 | 0.166* | |
C5 | 0.8032 (5) | 0.3190 (7) | 0.2946 (6) | 0.110 (3) | |
H5A | 0.8409 | 0.2981 | 0.2814 | 0.165* | |
H5B | 0.7634 | 0.2947 | 0.2489 | 0.165* | |
H5C | 0.8062 | 0.2820 | 0.3468 | 0.165* | |
C6 | 0.8400 (5) | 0.6578 (8) | 0.4359 (6) | 0.093 (3) | |
H6A | 0.8191 | 0.7309 | 0.4131 | 0.111* | |
H6B | 0.8050 | 0.6035 | 0.4314 | 0.111* | |
C7 | 0.8805 (6) | 0.6742 (10) | 0.5272 (6) | 0.118 (3) | |
H7 | 0.9012 | 0.7473 | 0.5218 | 0.142* | |
C8 | 0.9436 (7) | 0.6057 (11) | 0.5692 (7) | 0.147 (5) | |
H8A | 0.9345 | 0.5382 | 0.5959 | 0.221* | |
H8B | 0.9759 | 0.6525 | 0.6116 | 0.221* | |
H8C | 0.9606 | 0.5828 | 0.5267 | 0.221* | |
C9 | 0.8445 (7) | 0.7171 (12) | 0.5780 (7) | 0.144 (4) | |
H9A | 0.8057 | 0.6707 | 0.5675 | 0.216* | |
H9B | 0.8316 | 0.7958 | 0.5626 | 0.216* | |
H9C | 0.8724 | 0.7133 | 0.6376 | 0.216* | |
C10 | 1.0295 (5) | 1.0095 (8) | 0.3828 (6) | 0.090 (2) | |
C11 | 1.1164 (5) | 0.9924 (8) | 0.3169 (6) | 0.093 (3) | |
C12 | 1.1104 (5) | 0.7408 (10) | 0.4330 (6) | 0.102 (3) | |
H12 | 1.0890 | 0.6698 | 0.4041 | 0.122* | |
C13 | 1.0873 (5) | 0.8087 (9) | 0.4826 (6) | 0.103 (3) | |
H13 | 1.0495 | 0.7925 | 0.4988 | 0.124* | |
C14 | 1.1347 (6) | 0.9011 (9) | 0.5142 (6) | 0.108 (3) | |
H14 | 1.1339 | 0.9614 | 0.5544 | 0.130* | |
C15 | 1.1801 (5) | 0.8911 (10) | 0.4773 (6) | 0.109 (3) | |
H15 | 1.2175 | 0.9434 | 0.4867 | 0.131* | |
C16 | 1.1660 (5) | 0.7910 (10) | 0.4250 (6) | 0.105 (3) | |
H16 | 1.1917 | 0.7606 | 0.3930 | 0.126* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0740 (7) | 0.0808 (7) | 0.0635 (7) | 0.0008 (6) | 0.0182 (5) | −0.0096 (5) |
Sn1 | 0.0591 (4) | 0.0496 (4) | 0.0551 (4) | 0.000 | 0.0240 (3) | 0.000 |
O1 | 0.108 (5) | 0.089 (4) | 0.133 (5) | 0.011 (4) | 0.031 (4) | −0.037 (4) |
O2 | 0.111 (5) | 0.109 (5) | 0.125 (5) | −0.028 (4) | 0.046 (4) | 0.003 (4) |
S1 | 0.0949 (15) | 0.0627 (11) | 0.1008 (15) | −0.0050 (11) | 0.0621 (13) | 0.0000 (10) |
S2 | 0.0973 (15) | 0.0621 (12) | 0.0999 (15) | 0.0016 (10) | 0.0539 (13) | 0.0053 (10) |
N1 | 0.096 (5) | 0.071 (4) | 0.087 (4) | −0.007 (4) | 0.056 (4) | 0.003 (3) |
C1 | 0.092 (5) | 0.064 (4) | 0.085 (5) | −0.004 (4) | 0.052 (4) | 0.002 (4) |
C2 | 0.097 (6) | 0.072 (5) | 0.086 (5) | −0.011 (5) | 0.050 (5) | 0.002 (4) |
C3 | 0.106 (7) | 0.079 (5) | 0.095 (6) | −0.014 (5) | 0.040 (5) | 0.003 (5) |
C4 | 0.120 (8) | 0.092 (6) | 0.105 (7) | −0.006 (6) | 0.026 (6) | 0.012 (5) |
C5 | 0.126 (8) | 0.079 (6) | 0.105 (7) | −0.016 (6) | 0.021 (6) | 0.002 (5) |
C6 | 0.112 (7) | 0.095 (6) | 0.093 (6) | −0.003 (5) | 0.064 (6) | −0.003 (5) |
C7 | 0.139 (9) | 0.129 (9) | 0.099 (7) | 0.005 (8) | 0.059 (7) | −0.010 (7) |
C8 | 0.166 (12) | 0.141 (10) | 0.119 (9) | 0.025 (10) | 0.034 (9) | −0.006 (8) |
C9 | 0.174 (12) | 0.171 (11) | 0.106 (8) | 0.002 (10) | 0.074 (8) | −0.030 (8) |
C10 | 0.092 (6) | 0.080 (6) | 0.087 (6) | 0.004 (5) | 0.022 (5) | −0.023 (4) |
C11 | 0.087 (6) | 0.092 (6) | 0.093 (6) | −0.025 (5) | 0.025 (5) | −0.005 (5) |
C12 | 0.098 (7) | 0.107 (7) | 0.077 (6) | 0.015 (6) | 0.005 (5) | 0.016 (5) |
C13 | 0.101 (7) | 0.122 (8) | 0.069 (5) | 0.008 (7) | 0.011 (5) | 0.015 (6) |
C14 | 0.101 (7) | 0.128 (9) | 0.072 (6) | 0.007 (7) | 0.006 (6) | −0.001 (6) |
C15 | 0.089 (7) | 0.127 (9) | 0.085 (7) | 0.006 (6) | 0.003 (6) | 0.000 (6) |
C16 | 0.087 (7) | 0.120 (8) | 0.086 (6) | 0.019 (6) | 0.007 (5) | 0.005 (6) |
Fe1—C10 | 1.729 (10) | C4—H4C | 0.9600 |
Fe1—C11 | 1.751 (10) | C5—H5A | 0.9600 |
Fe1—C13 | 2.063 (9) | C5—H5B | 0.9600 |
Fe1—C15 | 2.075 (9) | C5—H5C | 0.9600 |
Fe1—C16 | 2.093 (10) | C6—C7 | 1.471 (13) |
Fe1—C14 | 2.093 (9) | C6—H6A | 0.9700 |
Fe1—C12 | 2.106 (10) | C6—H6B | 0.9700 |
Fe1—Sn1 | 2.5568 (14) | C7—C9 | 1.453 (13) |
Sn1—Fe1i | 2.5568 (14) | C7—C8 | 1.513 (15) |
Sn1—S1 | 2.577 (2) | C7—H7 | 0.9800 |
Sn1—S1i | 2.577 (2) | C8—H8A | 0.9600 |
O1—C10 | 1.161 (10) | C8—H8B | 0.9600 |
O2—C11 | 1.170 (10) | C8—H8C | 0.9600 |
S1—C1 | 1.738 (7) | C9—H9A | 0.9600 |
S2—C1 | 1.682 (7) | C9—H9B | 0.9600 |
N1—C1 | 1.335 (9) | C9—H9C | 0.9600 |
N1—C6 | 1.471 (9) | C12—C13 | 1.376 (13) |
N1—C2 | 1.482 (10) | C12—C16 | 1.396 (14) |
C2—C3 | 1.502 (12) | C12—H12 | 0.9800 |
C2—H2A | 0.9700 | C13—C14 | 1.444 (13) |
C2—H2B | 0.9700 | C13—H13 | 0.9800 |
C3—C4 | 1.499 (11) | C14—C15 | 1.357 (14) |
C3—C5 | 1.535 (11) | C14—H14 | 0.9800 |
C3—H3 | 0.9800 | C15—C16 | 1.419 (14) |
C4—H4A | 0.9600 | C15—H15 | 0.9800 |
C4—H4B | 0.9600 | C16—H16 | 0.9800 |
C10—Fe1—C11 | 93.7 (5) | H5A—C5—H5B | 109.5 |
C10—Fe1—C13 | 98.0 (4) | C3—C5—H5C | 109.5 |
C11—Fe1—C13 | 159.9 (4) | H5A—C5—H5C | 109.5 |
C10—Fe1—C15 | 123.4 (4) | H5B—C5—H5C | 109.5 |
C11—Fe1—C15 | 93.4 (4) | C7—C6—N1 | 117.0 (8) |
C13—Fe1—C15 | 66.5 (4) | C7—C6—H6A | 108.0 |
C10—Fe1—C16 | 159.9 (4) | N1—C6—H6A | 108.0 |
C11—Fe1—C16 | 97.9 (5) | C7—C6—H6B | 108.0 |
C13—Fe1—C16 | 66.5 (4) | N1—C6—H6B | 108.0 |
C15—Fe1—C16 | 39.8 (4) | H6A—C6—H6B | 107.3 |
C10—Fe1—C14 | 94.4 (4) | C9—C7—C6 | 114.7 (10) |
C11—Fe1—C14 | 122.4 (4) | C9—C7—C8 | 120.1 (10) |
C13—Fe1—C14 | 40.6 (4) | C6—C7—C8 | 120.2 (9) |
C15—Fe1—C14 | 38.0 (4) | C9—C7—H7 | 97.4 |
C16—Fe1—C14 | 65.5 (4) | C6—C7—H7 | 97.4 |
C10—Fe1—C12 | 133.0 (5) | C8—C7—H7 | 97.4 |
C11—Fe1—C12 | 133.2 (5) | C7—C8—H8A | 109.5 |
C13—Fe1—C12 | 38.5 (4) | C7—C8—H8B | 109.5 |
C15—Fe1—C12 | 65.0 (4) | H8A—C8—H8B | 109.5 |
C16—Fe1—C12 | 38.8 (4) | C7—C8—H8C | 109.5 |
C14—Fe1—C12 | 64.8 (4) | H8A—C8—H8C | 109.5 |
C10—Fe1—Sn1 | 90.1 (3) | H8B—C8—H8C | 109.5 |
C11—Fe1—Sn1 | 91.8 (3) | C7—C9—H9A | 109.5 |
C13—Fe1—Sn1 | 104.4 (3) | C7—C9—H9B | 109.5 |
C15—Fe1—Sn1 | 145.6 (3) | H9A—C9—H9B | 109.5 |
C16—Fe1—Sn1 | 105.7 (3) | C7—C9—H9C | 109.5 |
C14—Fe1—Sn1 | 145.0 (3) | H9A—C9—H9C | 109.5 |
C12—Fe1—Sn1 | 87.1 (3) | H9B—C9—H9C | 109.5 |
Fe1—Sn1—Fe1i | 129.01 (6) | O1—C10—Fe1 | 178.3 (9) |
Fe1—Sn1—S1 | 112.48 (6) | O2—C11—Fe1 | 176.3 (8) |
Fe1i—Sn1—S1 | 108.43 (6) | C13—C12—C16 | 110.6 (10) |
Fe1—Sn1—S1i | 108.43 (6) | C13—C12—Fe1 | 69.0 (6) |
Fe1i—Sn1—S1i | 112.48 (6) | C16—C12—Fe1 | 70.0 (6) |
S1—Sn1—S1i | 71.57 (9) | C13—C12—H12 | 124.7 |
C1—S1—Sn1 | 102.7 (3) | C16—C12—H12 | 124.7 |
C1—N1—C6 | 120.8 (6) | Fe1—C12—H12 | 124.7 |
C1—N1—C2 | 124.9 (6) | C12—C13—C14 | 105.8 (10) |
C6—N1—C2 | 114.3 (6) | C12—C13—Fe1 | 72.4 (6) |
N1—C1—S2 | 123.8 (6) | C14—C13—Fe1 | 70.8 (6) |
N1—C1—S1 | 117.5 (5) | C12—C13—H13 | 126.9 |
S2—C1—S1 | 118.7 (4) | C14—C13—H13 | 126.9 |
N1—C2—C3 | 114.5 (7) | Fe1—C13—H13 | 126.9 |
N1—C2—H2A | 108.6 | C15—C14—C13 | 108.2 (10) |
C3—C2—H2A | 108.6 | C15—C14—Fe1 | 70.3 (6) |
N1—C2—H2B | 108.6 | C13—C14—Fe1 | 68.6 (5) |
C3—C2—H2B | 108.6 | C15—C14—H14 | 125.9 |
H2A—C2—H2B | 107.6 | C13—C14—H14 | 125.9 |
C4—C3—C2 | 114.8 (7) | Fe1—C14—H14 | 125.9 |
C4—C3—C5 | 109.5 (8) | C14—C15—C16 | 109.3 (11) |
C2—C3—C5 | 109.1 (8) | C14—C15—Fe1 | 71.7 (6) |
C4—C3—H3 | 107.7 | C16—C15—Fe1 | 70.8 (5) |
C2—C3—H3 | 107.7 | C14—C15—H15 | 125.3 |
C5—C3—H3 | 107.7 | C16—C15—H15 | 125.3 |
C3—C4—H4A | 109.5 | Fe1—C15—H15 | 125.3 |
C3—C4—H4B | 109.5 | C12—C16—C15 | 105.8 (10) |
H4A—C4—H4B | 109.5 | C12—C16—Fe1 | 71.1 (6) |
C3—C4—H4C | 109.5 | C15—C16—Fe1 | 69.4 (6) |
H4A—C4—H4C | 109.5 | C12—C16—H16 | 127.0 |
H4B—C4—H4C | 109.5 | C15—C16—H16 | 127.0 |
C3—C5—H5A | 109.5 | Fe1—C16—H16 | 127.0 |
C3—C5—H5B | 109.5 |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···S1 | 0.97 | 2.49 | 3.009 (8) | 114 |
C6—H6A···S2 | 0.97 | 2.63 | 3.026 (9) | 105 |
C8—H8C···N1 | 0.96 | 2.50 | 2.960 (13) | 109 |
Experimental details
Crystal data | |
Chemical formula | [SnFe2(C5H5)2(C9H18NS2)2(CO)4] |
Mr | 881.34 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 21.800 (4), 11.587 (2), 16.886 (3) |
β (°) | 112.17 (3) |
V (Å3) | 3950.0 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.69, 0.72 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6972, 3488, 2132 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.153, 1.05 |
No. of reflections | 3488 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.96 |
Computer programs: XSCANS (Bruker, 2000), XSCANS, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···S1 | 0.97 | 2.49 | 3.009 (8) | 114 |
C6—H6A···S2 | 0.97 | 2.63 | 3.026 (9) | 105 |
C8—H8C···N1 | 0.96 | 2.50 | 2.960 (13) | 109 |
Because of its varied uses and strong coordinating ability, the dithiocarbamate ligand has attracted the attention of many investigators. Examples of its use are as a chelating agent in the treatment of metal poisoning (Tandon et al., 1996) and as a lubricant additive (Tanaka et al., 1996). The dithiocarbamate group can coordinate in either monodentate or bidentate mode (Johnson et al., 1969), the latter being much more common. In the present study, we have synthesized a new organotin–iron complex by the reaction of potassium N,N-diisobutyldithiocarbamate with dichlorobis[dicarbonyl(η5-cyclopentadienyl)iron]tin and report its crystal structure here.
In the title complex, [CpFe(CO)2]2Sn[S2CN(C4H9-i)2]2, (I), the Sn atom is situated on a twofold rotation axis. The coordination number of the Sn atom is four and that of the Fe atoms is eight. The Sn atom adopts a distorted tetrahedral configuration, the range of angles around Sn being 71.57 (9)–129.01 (6)°. The Sn—S distance is 2.577 (2) Å and the Sn—Fe distance is 2.5568 (14) Å. The C1—S1 and C1═S2 distances (Fig. 1) are 1.738 (7) and 1.682 (7) Å, respectively, indicating localization of the single and double bonds. A search of the Cambridge Structural Database (Allen, 2002) for the N,N-diisobutyldithiocarbamate ligand coordinated to any metal yielded only five hits. Of these, only one involved monodentate coordination, viz. bis(diisobutyldithiocarbamato)bis(dimethylphenylphosphine)platinum(II) (Lin et al., 1978). In the crystal structure, there are three non-conventional hydrogen bonds. Details are reported in Table 1.