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The title compound, [{CpFe(CO)2}2Sn{S2CN(C4H9-i)2}2] or [SnFe2(C5H5)2(C9H18NS2)2(CO)4], is obtained from the reaction of [C5H5Fe(CO)2]2SnCl2 and potassium N,N-diiso­butyl­di­thio­carbamate in a mixed solvent (C6H6–THF 1:1). The crystal structure shows that the Sn atom is situated on a twofold rotation axis. An Fe—Sn—Fe cluster is present in the complex, the Sn and Fe atoms having coordination numbers 4 and 8, respectively. There are non-conventional intramolec­ular C—H...S and C—H...N hydrogen bonds in the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300713X/wn6146sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680300713X/wn6146Isup2.hkl
Contains datablock I

CCDC reference: 214554

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.015 Å
  • R factor = 0.054
  • wR factor = 0.153
  • Data-to-parameter ratio = 16.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

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 C1S2 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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Ellipsoids are drawn at the 50% probability level. Atoms labelled with the suffix A are symmetry-related to those with no suffix.
[Figure 2] Fig. 2. The crystal packing, viewed down the b axis.
Bis[dicarbonyl(η5-cyclopentadienyl)ferrio](N,N- diisobutyldithiocarbamato)tin(II) top
Crystal data top
[SnFe2(C5H5)2(C9H18NS2)2(CO)4]F(000) = 1800
Mr = 881.34Dx = 1.482 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 21.800 (4) Åθ = 2.0–17.5°
b = 11.587 (2) ŵ = 1.60 mm1
c = 16.886 (3) ÅT = 293 K
β = 112.17 (3)°Block, black
V = 3950.0 (15) Å30.3 × 0.2 × 0.2 mm
Z = 4
Data collection top
Bruker P4
diffractometer
2132 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.063
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ω scansh = 2524
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
k = 013
Tmin = 0.69, Tmax = 0.72l = 020
6972 measured reflections3 standard reflections every 97 reflections
3488 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-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 parametersΔρmax = 0.78 e Å3
0 restraintsΔρmin = 0.96 e Å3
Crystal data top
[SnFe2(C5H5)2(C9H18NS2)2(CO)4]V = 3950.0 (15) Å3
Mr = 881.34Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.800 (4) ŵ = 1.60 mm1
b = 11.587 (2) ÅT = 293 K
c = 16.886 (3) Å0.3 × 0.2 × 0.2 mm
β = 112.17 (3)°
Data collection top
Bruker P4
diffractometer
2132 reflections with I > 2σ(I)
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
Rint = 0.063
Tmin = 0.69, Tmax = 0.723 standard reflections every 97 reflections
6972 measured reflections intensity decay: none
3488 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.05Δρmax = 0.78 e Å3
3488 reflectionsΔρmin = 0.96 e Å3
208 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
xyzUiso*/Ueq
Fe11.08704 (6)0.90777 (10)0.38100 (7)0.0750 (4)
Sn11.00000.81279 (5)0.25000.0539 (2)
O10.9917 (3)1.0797 (6)0.3832 (5)0.114 (2)
O21.1365 (3)1.0538 (6)0.2773 (5)0.114 (2)
S10.94815 (11)0.63240 (17)0.28891 (14)0.0788 (6)
S20.90183 (11)0.83421 (17)0.35645 (15)0.0815 (6)
N10.8743 (3)0.6162 (5)0.3812 (4)0.0780 (18)
C10.9042 (4)0.6900 (6)0.3467 (5)0.075 (2)
C20.8688 (4)0.4901 (7)0.3653 (5)0.080 (2)
H2A0.87950.45070.41960.097*
H2B0.90150.46740.34210.097*
C30.8018 (5)0.4504 (7)0.3052 (6)0.093 (2)
H30.77000.46770.33180.111*
C40.7775 (5)0.5069 (8)0.2190 (6)0.111 (3)
H4A0.76680.58610.22440.166*
H4B0.73870.46740.18150.166*
H4C0.81140.50320.19570.166*
C50.8032 (5)0.3190 (7)0.2946 (6)0.110 (3)
H5A0.84090.29810.28140.165*
H5B0.76340.29470.24890.165*
H5C0.80620.28200.34680.165*
C60.8400 (5)0.6578 (8)0.4359 (6)0.093 (3)
H6A0.81910.73090.41310.111*
H6B0.80500.60350.43140.111*
C70.8805 (6)0.6742 (10)0.5272 (6)0.118 (3)
H70.90120.74730.52180.142*
C80.9436 (7)0.6057 (11)0.5692 (7)0.147 (5)
H8A0.93450.53820.59590.221*
H8B0.97590.65250.61160.221*
H8C0.96060.58280.52670.221*
C90.8445 (7)0.7171 (12)0.5780 (7)0.144 (4)
H9A0.80570.67070.56750.216*
H9B0.83160.79580.56260.216*
H9C0.87240.71330.63760.216*
C101.0295 (5)1.0095 (8)0.3828 (6)0.090 (2)
C111.1164 (5)0.9924 (8)0.3169 (6)0.093 (3)
C121.1104 (5)0.7408 (10)0.4330 (6)0.102 (3)
H121.08900.66980.40410.122*
C131.0873 (5)0.8087 (9)0.4826 (6)0.103 (3)
H131.04950.79250.49880.124*
C141.1347 (6)0.9011 (9)0.5142 (6)0.108 (3)
H141.13390.96140.55440.130*
C151.1801 (5)0.8911 (10)0.4773 (6)0.109 (3)
H151.21750.94340.48670.131*
C161.1660 (5)0.7910 (10)0.4250 (6)0.105 (3)
H161.19170.76060.39300.126*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0740 (7)0.0808 (7)0.0635 (7)0.0008 (6)0.0182 (5)0.0096 (5)
Sn10.0591 (4)0.0496 (4)0.0551 (4)0.0000.0240 (3)0.000
O10.108 (5)0.089 (4)0.133 (5)0.011 (4)0.031 (4)0.037 (4)
O20.111 (5)0.109 (5)0.125 (5)0.028 (4)0.046 (4)0.003 (4)
S10.0949 (15)0.0627 (11)0.1008 (15)0.0050 (11)0.0621 (13)0.0000 (10)
S20.0973 (15)0.0621 (12)0.0999 (15)0.0016 (10)0.0539 (13)0.0053 (10)
N10.096 (5)0.071 (4)0.087 (4)0.007 (4)0.056 (4)0.003 (3)
C10.092 (5)0.064 (4)0.085 (5)0.004 (4)0.052 (4)0.002 (4)
C20.097 (6)0.072 (5)0.086 (5)0.011 (5)0.050 (5)0.002 (4)
C30.106 (7)0.079 (5)0.095 (6)0.014 (5)0.040 (5)0.003 (5)
C40.120 (8)0.092 (6)0.105 (7)0.006 (6)0.026 (6)0.012 (5)
C50.126 (8)0.079 (6)0.105 (7)0.016 (6)0.021 (6)0.002 (5)
C60.112 (7)0.095 (6)0.093 (6)0.003 (5)0.064 (6)0.003 (5)
C70.139 (9)0.129 (9)0.099 (7)0.005 (8)0.059 (7)0.010 (7)
C80.166 (12)0.141 (10)0.119 (9)0.025 (10)0.034 (9)0.006 (8)
C90.174 (12)0.171 (11)0.106 (8)0.002 (10)0.074 (8)0.030 (8)
C100.092 (6)0.080 (6)0.087 (6)0.004 (5)0.022 (5)0.023 (4)
C110.087 (6)0.092 (6)0.093 (6)0.025 (5)0.025 (5)0.005 (5)
C120.098 (7)0.107 (7)0.077 (6)0.015 (6)0.005 (5)0.016 (5)
C130.101 (7)0.122 (8)0.069 (5)0.008 (7)0.011 (5)0.015 (6)
C140.101 (7)0.128 (9)0.072 (6)0.007 (7)0.006 (6)0.001 (6)
C150.089 (7)0.127 (9)0.085 (7)0.006 (6)0.003 (6)0.000 (6)
C160.087 (7)0.120 (8)0.086 (6)0.019 (6)0.007 (5)0.005 (6)
Geometric parameters (Å, º) top
Fe1—C101.729 (10)C4—H4C0.9600
Fe1—C111.751 (10)C5—H5A0.9600
Fe1—C132.063 (9)C5—H5B0.9600
Fe1—C152.075 (9)C5—H5C0.9600
Fe1—C162.093 (10)C6—C71.471 (13)
Fe1—C142.093 (9)C6—H6A0.9700
Fe1—C122.106 (10)C6—H6B0.9700
Fe1—Sn12.5568 (14)C7—C91.453 (13)
Sn1—Fe1i2.5568 (14)C7—C81.513 (15)
Sn1—S12.577 (2)C7—H70.9800
Sn1—S1i2.577 (2)C8—H8A0.9600
O1—C101.161 (10)C8—H8B0.9600
O2—C111.170 (10)C8—H8C0.9600
S1—C11.738 (7)C9—H9A0.9600
S2—C11.682 (7)C9—H9B0.9600
N1—C11.335 (9)C9—H9C0.9600
N1—C61.471 (9)C12—C131.376 (13)
N1—C21.482 (10)C12—C161.396 (14)
C2—C31.502 (12)C12—H120.9800
C2—H2A0.9700C13—C141.444 (13)
C2—H2B0.9700C13—H130.9800
C3—C41.499 (11)C14—C151.357 (14)
C3—C51.535 (11)C14—H140.9800
C3—H30.9800C15—C161.419 (14)
C4—H4A0.9600C15—H150.9800
C4—H4B0.9600C16—H160.9800
C10—Fe1—C1193.7 (5)H5A—C5—H5B109.5
C10—Fe1—C1398.0 (4)C3—C5—H5C109.5
C11—Fe1—C13159.9 (4)H5A—C5—H5C109.5
C10—Fe1—C15123.4 (4)H5B—C5—H5C109.5
C11—Fe1—C1593.4 (4)C7—C6—N1117.0 (8)
C13—Fe1—C1566.5 (4)C7—C6—H6A108.0
C10—Fe1—C16159.9 (4)N1—C6—H6A108.0
C11—Fe1—C1697.9 (5)C7—C6—H6B108.0
C13—Fe1—C1666.5 (4)N1—C6—H6B108.0
C15—Fe1—C1639.8 (4)H6A—C6—H6B107.3
C10—Fe1—C1494.4 (4)C9—C7—C6114.7 (10)
C11—Fe1—C14122.4 (4)C9—C7—C8120.1 (10)
C13—Fe1—C1440.6 (4)C6—C7—C8120.2 (9)
C15—Fe1—C1438.0 (4)C9—C7—H797.4
C16—Fe1—C1465.5 (4)C6—C7—H797.4
C10—Fe1—C12133.0 (5)C8—C7—H797.4
C11—Fe1—C12133.2 (5)C7—C8—H8A109.5
C13—Fe1—C1238.5 (4)C7—C8—H8B109.5
C15—Fe1—C1265.0 (4)H8A—C8—H8B109.5
C16—Fe1—C1238.8 (4)C7—C8—H8C109.5
C14—Fe1—C1264.8 (4)H8A—C8—H8C109.5
C10—Fe1—Sn190.1 (3)H8B—C8—H8C109.5
C11—Fe1—Sn191.8 (3)C7—C9—H9A109.5
C13—Fe1—Sn1104.4 (3)C7—C9—H9B109.5
C15—Fe1—Sn1145.6 (3)H9A—C9—H9B109.5
C16—Fe1—Sn1105.7 (3)C7—C9—H9C109.5
C14—Fe1—Sn1145.0 (3)H9A—C9—H9C109.5
C12—Fe1—Sn187.1 (3)H9B—C9—H9C109.5
Fe1—Sn1—Fe1i129.01 (6)O1—C10—Fe1178.3 (9)
Fe1—Sn1—S1112.48 (6)O2—C11—Fe1176.3 (8)
Fe1i—Sn1—S1108.43 (6)C13—C12—C16110.6 (10)
Fe1—Sn1—S1i108.43 (6)C13—C12—Fe169.0 (6)
Fe1i—Sn1—S1i112.48 (6)C16—C12—Fe170.0 (6)
S1—Sn1—S1i71.57 (9)C13—C12—H12124.7
C1—S1—Sn1102.7 (3)C16—C12—H12124.7
C1—N1—C6120.8 (6)Fe1—C12—H12124.7
C1—N1—C2124.9 (6)C12—C13—C14105.8 (10)
C6—N1—C2114.3 (6)C12—C13—Fe172.4 (6)
N1—C1—S2123.8 (6)C14—C13—Fe170.8 (6)
N1—C1—S1117.5 (5)C12—C13—H13126.9
S2—C1—S1118.7 (4)C14—C13—H13126.9
N1—C2—C3114.5 (7)Fe1—C13—H13126.9
N1—C2—H2A108.6C15—C14—C13108.2 (10)
C3—C2—H2A108.6C15—C14—Fe170.3 (6)
N1—C2—H2B108.6C13—C14—Fe168.6 (5)
C3—C2—H2B108.6C15—C14—H14125.9
H2A—C2—H2B107.6C13—C14—H14125.9
C4—C3—C2114.8 (7)Fe1—C14—H14125.9
C4—C3—C5109.5 (8)C14—C15—C16109.3 (11)
C2—C3—C5109.1 (8)C14—C15—Fe171.7 (6)
C4—C3—H3107.7C16—C15—Fe170.8 (5)
C2—C3—H3107.7C14—C15—H15125.3
C5—C3—H3107.7C16—C15—H15125.3
C3—C4—H4A109.5Fe1—C15—H15125.3
C3—C4—H4B109.5C12—C16—C15105.8 (10)
H4A—C4—H4B109.5C12—C16—Fe171.1 (6)
C3—C4—H4C109.5C15—C16—Fe169.4 (6)
H4A—C4—H4C109.5C12—C16—H16127.0
H4B—C4—H4C109.5C15—C16—H16127.0
C3—C5—H5A109.5Fe1—C16—H16127.0
C3—C5—H5B109.5
Symmetry code: (i) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···S10.972.493.009 (8)114
C6—H6A···S20.972.633.026 (9)105
C8—H8C···N10.962.502.960 (13)109

Experimental details

Crystal data
Chemical formula[SnFe2(C5H5)2(C9H18NS2)2(CO)4]
Mr881.34
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)21.800 (4), 11.587 (2), 16.886 (3)
β (°) 112.17 (3)
V3)3950.0 (15)
Z4
Radiation typeMo Kα
µ (mm1)1.60
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.69, 0.72
No. of measured, independent and
observed [I > 2σ(I)] reflections
6972, 3488, 2132
Rint0.063
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.153, 1.05
No. of reflections3488
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.78, 0.96

Computer programs: XSCANS (Bruker, 2000), XSCANS, SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2B···S10.972.493.009 (8)114
C6—H6A···S20.972.633.026 (9)105
C8—H8C···N10.962.502.960 (13)109
 

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