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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): m130.
Published online 2010 January 9. doi:  10.1107/S1600536809055810
PMCID: PMC2979832

Dichlorido[(Z)-4-(2,6-diisopropyl­anilino)pent-3-en-2-one]dimethyl­tin(IV)

Abstract

In the crystal structure of the title compound, [Sn(CH3)2Cl2(C17H25NO)], the Sn atom adopts a trigonal-bipyramidal geometry with the O and one Cl atom in axial positions. A weak intra­molecular N—H(...)O hydrogen bond occurs. The crystal structure displays weak inter­molecular C—H(...)Cl inter­actions.

Related literature

For dichloridodiorganotin(IV) complexes, see: Cunningham et al. (2004 [triangle]); Curnow et al. (2006 [triangle]); Ianelli et al. (1993 [triangle]); Mahadevan et al. (1982 [triangle]); Ng (1996 [triangle]); Papadaki et al. (2008 [triangle]); Tian et al. (2006 [triangle]); Valle et al. (1982 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m130-scheme1.jpg

Experimental

Crystal data

  • [Sn(CH3)2Cl2(C17H25NO)]
  • M r = 479.04
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m130-efi1.jpg
  • a = 8.504 (4) Å
  • b = 10.212 (4) Å
  • c = 14.507 (6) Å
  • α = 71.070 (7)°
  • β = 83.300 (8)°
  • γ = 76.984 (7)°
  • V = 1159.8 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.34 mm−1
  • T = 297 K
  • 0.36 × 0.35 × 0.33 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.626, T max = 0.645
  • 8415 measured reflections
  • 4044 independent reflections
  • 3433 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.104
  • S = 1.06
  • 4044 reflections
  • 229 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.57 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2009 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809055810/nc2173sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055810/nc2173Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National University Research Council (CNCSIS) of Romania (research project TD-340/2007).

supplementary crystallographic information

Comment

In our attempts to prepare compounds of type Me2R'2Sn, where R' = ketinimate ligand, starting from RLi and Me2SnCl2, accidental hydrolysis of the lithium derivative lead to the formation of the title complex. A rational preparation of the complex was acomplished later starting from R'H and Me2SnCl2.

In the structure of the title compound the geometry around the tin can be described as distorted trigonal bipyramidal, with the Cl(2) and O(1) atoms occupying the axial positions (Fig. 1). The equatorial plane is formed by the two methyl carbon atoms C(18) and C(19) and the Cl(1) atom.

A weak intramolecular hydrogen bond exist between the hydrogen atom bonded to nitrogen and the oxygen atom (Table 2). There are additional weak C–H···Cl interactions (Table 2).

Experimental

A solution of Me2SnCl2 in Et2O (0.84 g, 3.82 mmol) was added to a stirred solution of (Z)-4-[(2,6-diisopropylphenyl)amino]pent-3-en-2-one (1 g, 3.85 mmol) in 50 ml Et2O resulting in a clear red-brown solution. The reaction mixture was stirred for 24 h and than the solvent was removed under reduced presure to give the title compound as a white-yellow powder. Crystals were obtained by slow diffusion of hexane into a dichloromethane solution of the title compound. Yield: 0.6 g (33%). mp = 124–125 °C.

1H NMR (CDCl3, 300 MHz): δ 1.15 [d, 6HA, –CH(CH3)2, 3J(H,H) = 6.8 Hz], 1.19 [s, 6H, SnCH3, 2J(117Sn,H) = 75.3, 2J(119Sn,H) = 78.7 Hz], 1.20 [d, 6HB, –CH(CH3)2, 3J(H,H) = 6.9 Hz], 1.67 [s, 3H, CH3C(N)], 2.11 [s, 3H, CH3C(O)], 2.92 [sept, 2H, –CH(CH3)2, 3J(H,H) = 6.9 Hz], 5.22 [s, 1H, –CH-], 7.18 [d, 2H, H8,10, 3J(H,H) = 7.7 Hz], 7.32 [t, 1H, H9, 3J(H,H) = 7.7 Hz], 11.83 [s, 1H, –NH-].

13C NMR (CDCl3, 75.5 MHz): δ 10.73 [s, SnCH3, 1J(117Sn,C) = 587.1, 1J(119Sn,C) = 614.4 Hz], 19.49 [s, CH3C(N)], 22.57 [s, –CH(CH3)2, (B)], 24.45 [s, –CH(CH3)2, (A)], 28.01 [s, -CH(CH3)2], 28.43 [s, CH3C(O)], 96.31 [s, -CH–], 123.68 [s, C8,10], 128.81 [s, C9], 132.27 [s, C6], 145.53 [s, C7,11], 166.74 [s, CH3C(N)], 193.59 [s, CH3C(O)].

119Sn NMR (CDCl3, 111.9 MHz): δ -1.33.

Refinement

The C-H H atoms were placed in calculated positions (methyl H atoms allowed to rotate but not to tip) with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms). The N-H H atom was located in a difference map and its position was refined with istotropic displacement parameters with a restrained N–H distance of 0.86 Å.

Figures

Fig. 1.
Crystal structure of the title compound with labelling and displacement ellipsoids drawn at 30% probability level. Hydrogen atoms, except that bonded to nitrogen, were omitted for clarity. Intramolecular hydrogen bonding is shown as a dashed line.

Crystal data

[Sn(CH3)2Cl2(C17H25NO)]Z = 2
Mr = 479.04F(000) = 488
Triclinic, P1Dx = 1.372 Mg m3
Hall symbol: -P 1Melting point = 397–398 K
a = 8.504 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.212 (4) ÅCell parameters from 2254 reflections
c = 14.507 (6) Åθ = 2.2–20.4°
α = 71.070 (7)°µ = 1.34 mm1
β = 83.300 (8)°T = 297 K
γ = 76.984 (7)°Block, colourless
V = 1159.8 (9) Å30.36 × 0.35 × 0.33 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer4044 independent reflections
Radiation source: fine-focus sealed tube3433 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 25°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −10→10
Tmin = 0.626, Tmax = 0.645k = −12→12
8415 measured reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.045P)2 + 0.2662P] where P = (Fo2 + 2Fc2)/3
4044 reflections(Δ/σ)max = 0.001
229 parametersΔρmax = 0.57 e Å3
1 restraintΔρmin = −0.41 e Å3

Special details

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)

xyzUiso*/Ueq
C10.6984 (5)0.9135 (5)0.5930 (3)0.0605 (11)
C20.6594 (5)1.0064 (4)0.6472 (3)0.0541 (10)
H20.69081.09310.62090.065*
C30.5787 (5)0.9812 (4)0.7360 (3)0.0494 (10)
C40.7852 (8)0.9572 (6)0.4950 (4)0.101 (2)
H4A0.87390.88250.48990.152*
H4B0.82521.04080.48790.152*
H4C0.71190.97620.44460.152*
C50.5455 (7)1.0906 (5)0.7874 (4)0.0781 (15)
H5A0.43091.12090.79590.117*
H5B0.5921.170.74940.117*
H5C0.59221.05110.85010.117*
C60.4417 (5)0.8299 (4)0.8734 (3)0.0486 (10)
C70.5269 (5)0.7605 (4)0.9578 (3)0.0527 (10)
C80.4401 (6)0.7330 (5)1.0457 (3)0.0603 (11)
H80.4940.6851.1030.072*
C90.2759 (6)0.7751 (5)1.0501 (3)0.0641 (12)
H90.21950.75691.11030.077*
C100.1943 (5)0.8433 (5)0.9674 (3)0.0648 (12)
H100.08260.8720.97160.078*
C110.2755 (5)0.8706 (5)0.8765 (3)0.0565 (11)
C120.7095 (5)0.7131 (5)0.9532 (4)0.0650 (12)
H120.75070.7740.89230.078*
C130.7902 (7)0.7273 (8)1.0355 (5)0.109 (2)
H13A0.76110.66151.09580.163*
H13B0.75560.82181.03920.163*
H13C0.90530.70781.02390.163*
C140.7528 (8)0.5650 (7)0.9482 (6)0.120 (2)
H14A0.72340.50131.00950.18*
H14B0.8670.54080.93480.18*
H14C0.69570.5580.89720.18*
C150.1811 (6)0.9386 (6)0.7843 (4)0.0727 (14)
H150.25490.9790.73090.087*
C160.1201 (8)0.8259 (8)0.7587 (4)0.112 (2)
H16A0.20960.7520.75320.169*
H16B0.0680.86750.69770.169*
H16C0.04440.78740.8090.169*
C170.0427 (8)1.0556 (8)0.7938 (5)0.132 (3)
H17A−0.03471.01720.8430.198*
H17B−0.00811.10.73260.198*
H17C0.08251.12420.81190.198*
C180.6696 (7)0.6652 (5)0.4531 (3)0.0799 (15)
H18A0.59090.74960.45150.12*
H18B0.62020.60010.43720.12*
H18C0.75680.68860.40650.12*
C190.9525 (7)0.5569 (7)0.6771 (4)0.1025 (19)
H19A0.99780.45920.70770.154*
H19B0.91380.60230.72620.154*
H19C1.03390.60220.63560.154*
Cl10.5420 (2)0.51095 (17)0.70215 (11)0.1040 (5)
Cl20.8568 (2)0.33755 (15)0.57138 (13)0.1102 (6)
H10.547 (5)0.801 (3)0.752 (3)0.055 (13)*
N10.5289 (4)0.8616 (4)0.7806 (3)0.0513 (8)
O10.6627 (4)0.7925 (3)0.6232 (2)0.0761 (10)
Sn10.75936 (4)0.57249 (3)0.59303 (2)0.06287 (15)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.064 (3)0.058 (3)0.056 (3)−0.011 (2)0.010 (2)−0.019 (2)
C20.060 (3)0.047 (2)0.056 (3)−0.018 (2)0.003 (2)−0.014 (2)
C30.048 (2)0.046 (2)0.057 (3)−0.0075 (19)−0.0061 (19)−0.019 (2)
C40.131 (5)0.096 (4)0.077 (4)−0.048 (4)0.042 (3)−0.027 (3)
C50.111 (4)0.056 (3)0.078 (3)−0.024 (3)0.013 (3)−0.036 (3)
C60.052 (2)0.046 (2)0.053 (2)−0.0107 (19)0.004 (2)−0.024 (2)
C70.056 (3)0.050 (2)0.057 (3)−0.011 (2)−0.002 (2)−0.023 (2)
C80.072 (3)0.059 (3)0.050 (3)−0.015 (2)−0.001 (2)−0.016 (2)
C90.073 (3)0.069 (3)0.052 (3)−0.019 (3)0.017 (2)−0.024 (2)
C100.052 (3)0.074 (3)0.067 (3)−0.014 (2)0.004 (2)−0.023 (3)
C110.060 (3)0.059 (3)0.054 (3)−0.014 (2)0.002 (2)−0.022 (2)
C120.055 (3)0.065 (3)0.074 (3)−0.008 (2)−0.004 (2)−0.022 (2)
C130.069 (4)0.152 (6)0.125 (5)−0.024 (4)−0.020 (4)−0.062 (5)
C140.087 (4)0.093 (5)0.188 (7)0.020 (4)−0.030 (4)−0.070 (5)
C150.055 (3)0.094 (4)0.064 (3)−0.012 (3)−0.008 (2)−0.019 (3)
C160.117 (5)0.156 (7)0.081 (4)−0.052 (5)−0.023 (4)−0.035 (4)
C170.103 (5)0.141 (7)0.118 (6)0.040 (5)−0.030 (4)−0.028 (5)
C180.100 (4)0.074 (3)0.058 (3)0.002 (3)−0.021 (3)−0.017 (3)
C190.097 (4)0.121 (5)0.101 (5)−0.013 (4)−0.029 (4)−0.048 (4)
Cl10.1360 (13)0.1014 (11)0.0782 (9)−0.0581 (10)0.0188 (9)−0.0174 (8)
Cl20.1549 (15)0.0523 (8)0.1206 (13)−0.0019 (9)−0.0277 (11)−0.0282 (8)
N10.058 (2)0.046 (2)0.055 (2)−0.0101 (17)0.0052 (17)−0.0250 (18)
O10.106 (3)0.061 (2)0.068 (2)−0.0291 (19)0.0276 (19)−0.0314 (17)
Sn10.0865 (3)0.0497 (2)0.0515 (2)−0.01062 (16)−0.00813 (16)−0.01462 (15)

Geometric parameters (Å, °)

C1—O11.264 (5)C13—H13A0.96
C1—C21.382 (6)C13—H13B0.96
C1—C41.502 (6)C13—H13C0.96
C2—C31.362 (5)C14—H14A0.96
C2—H20.93C14—H14B0.96
C3—N11.322 (5)C14—H14C0.96
C3—C51.494 (6)C15—C171.506 (8)
C4—H4A0.96C15—C161.524 (8)
C4—H4B0.96C15—H150.98
C4—H4C0.96C16—H16A0.96
C5—H5A0.96C16—H16B0.96
C5—H5B0.96C16—H16C0.96
C5—H5C0.96C17—H17A0.96
C6—C111.381 (6)C17—H17B0.96
C6—C71.392 (6)C17—H17C0.96
C6—N11.435 (5)C18—Sn12.095 (5)
C7—C81.376 (6)C18—H18A0.96
C7—C121.519 (6)C18—H18B0.96
C8—C91.366 (6)C18—H18C0.96
C8—H80.93C19—Sn12.105 (5)
C9—C101.356 (6)C19—H19A0.96
C9—H90.93C19—H19B0.96
C10—C111.389 (6)C19—H19C0.96
C10—H100.93Cl1—Sn12.3478 (16)
C11—C151.520 (6)Cl2—Sn12.4644 (17)
C12—C141.497 (7)N1—H10.833 (18)
C12—C131.505 (7)O1—Sn12.375 (3)
C12—H120.98
O1—C1—C2121.9 (4)C12—C14—H14A109.5
O1—C1—C4118.8 (4)C12—C14—H14B109.5
C2—C1—C4119.3 (4)H14A—C14—H14B109.5
C3—C2—C1125.3 (4)C12—C14—H14C109.5
C3—C2—H2117.3H14A—C14—H14C109.5
C1—C2—H2117.3H14B—C14—H14C109.5
N1—C3—C2122.7 (4)C17—C15—C11112.4 (5)
N1—C3—C5117.4 (4)C17—C15—C16110.5 (5)
C2—C3—C5119.9 (4)C11—C15—C16109.5 (4)
C1—C4—H4A109.5C17—C15—H15108.1
C1—C4—H4B109.5C11—C15—H15108.1
H4A—C4—H4B109.5C16—C15—H15108.1
C1—C4—H4C109.5C15—C16—H16A109.5
H4A—C4—H4C109.5C15—C16—H16B109.5
H4B—C4—H4C109.5H16A—C16—H16B109.5
C3—C5—H5A109.5C15—C16—H16C109.5
C3—C5—H5B109.5H16A—C16—H16C109.5
H5A—C5—H5B109.5H16B—C16—H16C109.5
C3—C5—H5C109.5C15—C17—H17A109.5
H5A—C5—H5C109.5C15—C17—H17B109.5
H5B—C5—H5C109.5H17A—C17—H17B109.5
C11—C6—C7121.8 (4)C15—C17—H17C109.5
C11—C6—N1118.9 (4)H17A—C17—H17C109.5
C7—C6—N1119.2 (4)H17B—C17—H17C109.5
C8—C7—C6117.9 (4)Sn1—C18—H18A109.5
C8—C7—C12120.8 (4)Sn1—C18—H18B109.5
C6—C7—C12121.3 (4)H18A—C18—H18B109.5
C9—C8—C7121.0 (4)Sn1—C18—H18C109.5
C9—C8—H8119.5H18A—C18—H18C109.5
C7—C8—H8119.5H18B—C18—H18C109.5
C10—C9—C8120.6 (4)Sn1—C19—H19A109.5
C10—C9—H9119.7Sn1—C19—H19B109.5
C8—C9—H9119.7H19A—C19—H19B109.5
C9—C10—C11120.8 (4)Sn1—C19—H19C109.5
C9—C10—H10119.6H19A—C19—H19C109.5
C11—C10—H10119.6H19B—C19—H19C109.5
C6—C11—C10117.9 (4)C3—N1—C6125.1 (3)
C6—C11—C15122.0 (4)C3—N1—H1117 (3)
C10—C11—C15120.1 (4)C6—N1—H1117 (3)
C14—C12—C13111.3 (5)C1—O1—Sn1136.4 (3)
C14—C12—C7109.7 (4)C18—Sn1—C19142.9 (3)
C13—C12—C7113.5 (4)C18—Sn1—Cl1107.61 (16)
C14—C12—H12107.3C19—Sn1—Cl1107.20 (18)
C13—C12—H12107.3C18—Sn1—O188.67 (17)
C7—C12—H12107.3C19—Sn1—O184.0 (2)
C12—C13—H13A109.5Cl1—Sn1—O181.74 (9)
C12—C13—H13B109.5C18—Sn1—Cl294.04 (15)
H13A—C13—H13B109.5C19—Sn1—Cl294.78 (18)
C12—C13—H13C109.5Cl1—Sn1—Cl295.82 (6)
H13A—C13—H13C109.5O1—Sn1—Cl2176.81 (8)
H13B—C13—H13C109.5
O1—C1—C2—C3−1.0 (7)C8—C7—C12—C1487.0 (6)
C4—C1—C2—C3178.8 (5)C6—C7—C12—C14−91.4 (5)
C1—C2—C3—N10.4 (7)C8—C7—C12—C13−38.2 (6)
C1—C2—C3—C5179.4 (4)C6—C7—C12—C13143.3 (5)
C11—C6—C7—C80.0 (6)C6—C11—C15—C17−140.8 (5)
N1—C6—C7—C8179.3 (4)C10—C11—C15—C1741.3 (7)
C11—C6—C7—C12178.5 (4)C6—C11—C15—C1696.0 (5)
N1—C6—C7—C12−2.2 (6)C10—C11—C15—C16−81.8 (6)
C6—C7—C8—C9−1.3 (6)C2—C3—N1—C6−179.2 (4)
C12—C7—C8—C9−179.8 (4)C5—C3—N1—C61.7 (6)
C7—C8—C9—C101.0 (7)C11—C6—N1—C386.6 (5)
C8—C9—C10—C110.6 (7)C7—C6—N1—C3−92.8 (5)
C7—C6—C11—C101.6 (6)C2—C1—O1—Sn1−156.7 (3)
N1—C6—C11—C10−177.7 (4)C4—C1—O1—Sn123.6 (7)
C7—C6—C11—C15−176.3 (4)C1—O1—Sn1—C18−68.9 (5)
N1—C6—C11—C154.4 (6)C1—O1—Sn1—C1974.7 (5)
C9—C10—C11—C6−1.8 (7)C1—O1—Sn1—Cl1−176.9 (5)
C9—C10—C11—C15176.1 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O10.83 (3)2.03 (4)2.662 (5)133 (4)
C8i—H8i···Cl10.932.913.695 (4)143
C17ii—H17Bii···Cl20.962.893.783 (6)155
C19iii—H19Ciii···Cl20.962.943.700 (6)137

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1, y−1, z; (iii) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2173).

References

  • Brandenburg, K. (2009). DIAMOND Crystal Impact GbR, Bonn, Germany.
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