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Acta Cryst. (2007). E63, m1242    [ doi:10.1107/S1600536807013840 ]

Bis(2-fluorobenzyl)(N-salicylidenevalinato-[kappa]3N,O,O')tin(IV)

R. Ding, J. Zhu, D. Zhang, A. Ling and H. Yin

Abstract top

In the title compound, [Sn(C7H6F)2(C12H13NO3)], the Schiff base acts as a tridentate ligand, chelating the Sn atom. The Sn atom is five-coordinate in a distorted trigonal-bipyramidal geometry, with the O atoms occupying the axial positions, and the N and C atoms occupying the equatorial positions. In addition, in the crystal, one of the F atoms is disordered over two positions.

Related literature top

Corresponding organotin(IV) complexes with Schiff bases have similar structures (Yin & Wang, 2004; Yin, Wang & Xue, 2004; Beltrán et al., 2003).

Experimental top

A sample of salicylidene-valine (1.0 mmol) and sodium methylate (1.0 mmol) was stirred in 20 ml dichloromethane at room temperature for 30 min. To this solution was added di(o-fluorobenzyl)tin dichloride (1.0 mmol). The mixture was stirred at 40°C under nitrogen for 18 h. Evaporation of the filtrate left a yellow solid, which was recrystallized from dichloromethane-hexane (1:3) to give yellow crystals (yield 67%).

Refinement top

One of the F atoms is disordered over two positions with site occupation factors of 0.841 (5) and 0.159 (5) A l l the H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.98 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C). The methyl groups were allowed to rotate but not to tip.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
(N-Salicylidene-valinoto-N,O,O') di(o-fluorobenzyl)tin(IV) top
Crystal data top
[Sn(C12H13NO3)(C7H6F)2]Z = 2
Mr = 556.16F(000) = 560
Triclinic, P1Dx = 1.582 Mg m−3
a = 10.0184 (16) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.5814 (17) ÅCell parameters from 4740 reflections
c = 11.9367 (19) Åθ = 2.2–28.0°
α = 84.915 (2)°µ = 1.14 mm−1
β = 81.776 (2)°T = 273 K
γ = 68.880 (2)°Block, yellow
V = 1167.3 (3) Å30.45 × 0.41 × 0.37 mm
Data collection top
CCD area detector
diffractometer		4073 independent reflections
Radiation source: fine-focus sealed tube3698 reflections with I > 2σ(I)
graphiteRint = 0.012
φ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −11→11
Tmin = 0.628, Tmax = 0.678k = −12→9
6178 measured reflectionsl = −14→14
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0222P)2 + 0.4867P]
where P = (Fo2 + 2Fc2)/3
4073 reflections(Δ/σ)max = 0.002
310 parametersΔρmax = 0.57 e Å−3
1 restraintΔρmin = −0.45 e Å−3
Crystal data top
[Sn(C12H13NO3)(C7H6F)2]γ = 68.880 (2)°
Mr = 556.16V = 1167.3 (3) Å3
Triclinic, P1Z = 2
a = 10.0184 (16) ÅMo Kα radiation
b = 10.5814 (17) ŵ = 1.14 mm−1
c = 11.9367 (19) ÅT = 273 K
α = 84.915 (2)°0.45 × 0.41 × 0.37 mm
β = 81.776 (2)°
Data collection top
CCD area detector
diffractometer		4073 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		3698 reflections with I > 2σ(I)
Tmin = 0.628, Tmax = 0.678Rint = 0.012
6178 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.055Δρmax = 0.57 e Å−3
S = 1.12Δρmin = −0.45 e Å−3
4073 reflectionsAbsolute structure: ?
310 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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*/UeqOcc. (<1)
Sn10.418762 (18)0.060765 (17)0.674028 (14)0.02904 (7)
F20.1869 (2)−0.1933 (2)0.59952 (17)0.0770 (6)
N10.2350 (2)0.2516 (2)0.67652 (16)0.0302 (5)
O10.37365 (18)0.10634 (17)0.50130 (14)0.0338 (4)
O20.2373 (2)0.2416 (2)0.37691 (15)0.0508 (5)
O30.3804 (2)0.08235 (18)0.85103 (14)0.0387 (4)
C10.2652 (3)0.2114 (3)0.4735 (2)0.0339 (6)
C20.1685 (3)0.2969 (3)0.5702 (2)0.0333 (6)
H20.16050.39140.55270.040*
C30.0169 (3)0.2891 (3)0.5788 (2)0.0407 (7)
H3−0.01530.31500.50370.049*
C40.0189 (4)0.1456 (3)0.6064 (3)0.0586 (9)
H4A0.08840.08530.55310.088*
H4B−0.07480.14270.60200.088*
H4C0.04450.11810.68160.088*
C5−0.0929 (3)0.3876 (4)0.6605 (3)0.0579 (9)
H5A−0.09280.47750.64100.087*
H5B−0.06850.36240.73620.087*
H5C−0.18680.38520.65610.087*
C60.2016 (3)0.3394 (3)0.7549 (2)0.0349 (6)
H60.14410.42720.73530.042*
C70.2411 (3)0.3190 (3)0.8666 (2)0.0340 (6)
C80.3252 (3)0.1914 (3)0.9116 (2)0.0332 (6)
C90.3474 (3)0.1824 (3)1.0263 (2)0.0428 (7)
H90.40060.09941.05850.051*
C100.2916 (3)0.2947 (4)1.0910 (2)0.0490 (8)
H100.30710.28611.16680.059*
C110.2126 (3)0.4208 (4)1.0462 (2)0.0522 (8)
H110.17710.49631.09080.063*
C120.1881 (3)0.4322 (3)0.9360 (2)0.0459 (7)
H120.13530.51650.90560.055*
C130.6098 (3)0.1116 (3)0.6583 (2)0.0357 (6)
H13A0.68370.04020.69490.043*
H13B0.64540.11710.57870.043*
C140.5823 (3)0.2432 (3)0.7102 (2)0.0334 (6)
F10.4747 (2)0.3601 (2)0.55215 (16)0.0564 (7)0.841 (5)
C150.51278 (9)0.3657 (3)0.65269 (17)0.0393 (6)
C190.6182 (3)0.2515 (3)0.81989 (18)0.0407 (6)
H190.66460.17260.86080.049*0.841 (5)
H19'0.48810.36370.58080.049*0.159 (5)
F1'0.6811 (13)0.1350 (11)0.8679 (9)0.058 (4)0.159 (5)
C160.4813 (3)0.4895 (3)0.7010 (3)0.0505 (8)
H160.43660.56990.66130.061*
C170.5164 (4)0.4930 (3)0.8075 (3)0.0544 (8)
H170.49350.57580.84040.065*
C180.5848 (3)0.3749 (3)0.8654 (3)0.0505 (8)
H180.60910.37860.93710.061*
C200.3965 (3)−0.1340 (3)0.6949 (2)0.0365 (6)
H20A0.4025−0.16560.61990.044*
H20B0.4795−0.19560.72910.044*
C210.2645 (3)−0.1481 (2)0.7631 (2)0.0336 (6)
C220.1638 (3)−0.1774 (3)0.7132 (3)0.0477 (7)
C230.0419 (4)−0.1934 (4)0.7721 (4)0.0668 (10)
H23−0.0240−0.21200.73480.080*
C240.0204 (4)−0.1812 (4)0.8874 (4)0.0733 (11)
H24−0.0615−0.19040.92910.088*
C250.1196 (4)−0.1552 (4)0.9413 (3)0.0646 (10)
H250.1056−0.14861.01960.078*
C260.2396 (3)−0.1389 (3)0.8795 (2)0.0470 (7)
H260.3058−0.12120.91710.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03388 (10)0.02846 (10)0.02714 (10)−0.01294 (7)−0.00491 (7)−0.00292 (7)
F20.1004 (16)0.0969 (16)0.0589 (12)−0.0578 (14)−0.0287 (11)−0.0034 (11)
N10.0316 (11)0.0329 (12)0.0252 (10)−0.0091 (9)−0.0043 (9)−0.0053 (9)
O10.0366 (10)0.0330 (10)0.0274 (9)−0.0059 (8)−0.0040 (7)−0.0061 (7)
O20.0570 (13)0.0585 (13)0.0241 (10)−0.0036 (10)−0.0077 (9)−0.0027 (9)
O30.0546 (12)0.0358 (10)0.0259 (9)−0.0156 (9)−0.0061 (8)−0.0022 (8)
C10.0361 (14)0.0371 (15)0.0271 (13)−0.0108 (12)−0.0027 (11)−0.0048 (11)
C20.0373 (14)0.0328 (14)0.0261 (12)−0.0065 (11)−0.0071 (11)−0.0023 (11)
C30.0355 (15)0.0496 (17)0.0335 (14)−0.0089 (13)−0.0093 (12)−0.0016 (13)
C40.0514 (19)0.060 (2)0.072 (2)−0.0259 (17)−0.0119 (17)−0.0046 (18)
C50.0377 (16)0.068 (2)0.058 (2)−0.0084 (15)0.0013 (14)−0.0103 (17)
C60.0327 (14)0.0349 (15)0.0345 (14)−0.0082 (11)−0.0031 (11)−0.0056 (12)
C70.0322 (13)0.0422 (16)0.0296 (13)−0.0145 (12)−0.0005 (11)−0.0101 (12)
C80.0326 (13)0.0447 (16)0.0267 (13)−0.0203 (12)0.0022 (11)−0.0044 (12)
C90.0449 (16)0.0571 (19)0.0278 (13)−0.0196 (14)−0.0027 (12)−0.0046 (13)
C100.0444 (17)0.082 (2)0.0264 (14)−0.0270 (17)−0.0008 (12)−0.0142 (15)
C110.0481 (18)0.067 (2)0.0416 (17)−0.0157 (16)−0.0012 (14)−0.0287 (16)
C120.0441 (16)0.0494 (18)0.0427 (16)−0.0119 (14)−0.0030 (13)−0.0169 (14)
C130.0330 (14)0.0378 (15)0.0391 (14)−0.0146 (12)−0.0035 (11)−0.0076 (12)
C140.0306 (13)0.0395 (15)0.0349 (14)−0.0193 (12)0.0034 (11)−0.0085 (12)
F10.0777 (16)0.0574 (14)0.0390 (12)−0.0278 (12)−0.0162 (10)0.0053 (10)
C150.0422 (15)0.0432 (16)0.0365 (15)−0.0204 (13)−0.0011 (12)−0.0049 (12)
C190.0436 (16)0.0441 (17)0.0405 (15)−0.0220 (13)−0.0062 (13)−0.0035 (13)
F1'0.073 (8)0.045 (7)0.057 (7)−0.014 (6)−0.035 (6)0.003 (5)
C160.0584 (19)0.0364 (17)0.0565 (19)−0.0200 (14)0.0024 (15)−0.0012 (14)
C170.066 (2)0.0431 (18)0.059 (2)−0.0264 (16)0.0089 (16)−0.0225 (16)
C180.062 (2)0.061 (2)0.0407 (16)−0.0347 (17)−0.0018 (14)−0.0158 (15)
C200.0418 (15)0.0300 (14)0.0385 (15)−0.0142 (12)−0.0006 (12)−0.0050 (12)
C210.0360 (14)0.0255 (13)0.0405 (15)−0.0125 (11)−0.0036 (12)−0.0008 (11)
C220.0507 (18)0.0448 (18)0.0521 (18)−0.0200 (14)−0.0124 (15)−0.0003 (14)
C230.049 (2)0.062 (2)0.100 (3)−0.0296 (17)−0.020 (2)0.005 (2)
C240.050 (2)0.069 (2)0.098 (3)−0.0284 (19)0.019 (2)−0.001 (2)
C250.072 (2)0.070 (2)0.056 (2)−0.037 (2)0.0195 (18)−0.0093 (18)
C260.0517 (18)0.0477 (18)0.0452 (17)−0.0240 (15)0.0008 (14)−0.0026 (14)
Geometric parameters (Å, °) top
Sn1—O32.1104 (17)C11—H110.9300
Sn1—C202.140 (3)C12—H120.9300
Sn1—C132.147 (3)C13—C141.493 (4)
Sn1—O12.1496 (17)C13—H13A0.9700
Sn1—N12.187 (2)C13—H13B0.9700
F2—C221.359 (3)C14—C151.402 (3)
N1—C61.300 (3)C14—C191.424 (3)
N1—C21.480 (3)F1—C151.323 (3)
O1—C11.301 (3)F1—H19'0.3947
O2—C11.213 (3)F1'—C191.290 (3)
O3—C81.316 (3)F1'—H190.378
C1—C21.524 (3)C15—C161.390 (4)
C2—C31.539 (4)C15—H19'0.9300
C2—H20.9800C19—C181.368 (4)
C3—C51.514 (4)C19—H190.9300
C3—C41.519 (4)C16—C171.373 (4)
C3—H30.9800C16—H160.9300
C4—H4A0.9600C17—C181.369 (5)
C4—H4B0.9600C17—H170.9300
C4—H4C0.9600C18—H180.9300
C5—H5A0.9600C20—C211.499 (4)
C5—H5B0.9600C20—H20A0.9700
C5—H5C0.9600C20—H20B0.9700
C6—C71.421 (4)C21—C221.378 (4)
C6—H60.9300C21—C261.382 (4)
C7—C121.412 (4)C22—C231.378 (5)
C7—C81.415 (4)C23—C241.372 (5)
C8—C91.408 (3)C23—H230.9300
C9—C101.372 (4)C24—C251.374 (5)
C9—H90.9300C24—H240.9300
C10—C111.388 (4)C25—C261.375 (4)
C10—H100.9300C25—H250.9300
C11—C121.359 (4)C26—H260.9300
O3—Sn1—C2090.67 (9)C10—C11—H11120.5
O3—Sn1—C1393.05 (9)C11—C12—C7121.5 (3)
C20—Sn1—C13129.53 (10)C11—C12—H12119.2
O3—Sn1—O1156.21 (7)C7—C12—H12119.2
C20—Sn1—O198.42 (9)C14—C13—Sn1111.90 (17)
C13—Sn1—O197.87 (9)C14—C13—H13A109.2
O3—Sn1—N182.27 (7)Sn1—C13—H13A109.2
C20—Sn1—N1123.25 (9)C14—C13—H13B109.2
C13—Sn1—N1107.11 (9)Sn1—C13—H13B109.2
O1—Sn1—N174.34 (7)H13A—C13—H13B107.9
C6—N1—C2117.7 (2)C15—C14—C19117.1 (2)
C6—N1—Sn1123.80 (17)C15—C14—C13120.0 (2)
C2—N1—Sn1116.80 (15)C19—C14—C13122.9 (2)
C1—O1—Sn1121.60 (15)C15—F1—H19'5.1
C8—O3—Sn1130.98 (16)F1—C15—C16120.8 (2)
O2—C1—O1123.6 (2)F1—C15—C14118.1 (2)
O2—C1—C2119.8 (2)F1'—C19—C14113.6 (2)
O1—C1—C2116.6 (2)F1'—C19—C18126.0 (5)
N1—C2—C1109.6 (2)C16—C15—C14121.1 (2)
N1—C2—C3112.7 (2)F1—C15—H19'2.1
C1—C2—C3109.5 (2)F1'—C19—H196.2
N1—C2—H2108.3C16—C15—H19'119.7
C1—C2—H2108.3C14—C15—H19'119.2
C3—C2—H2108.3C18—C19—C14120.4 (3)
C5—C3—C4111.0 (3)C18—C19—H19119.8
C5—C3—C2113.3 (2)C14—C19—H19119.8
C4—C3—C2111.9 (2)C17—C16—C15120.0 (3)
C5—C3—H3106.7C17—C16—H16120.0
C4—C3—H3106.7C15—C16—H16120.0
C2—C3—H3106.7C18—C17—C16120.2 (3)
C3—C4—H4A109.5C18—C17—H17119.9
C3—C4—H4B109.5C16—C17—H17119.9
H4A—C4—H4B109.5C19—C18—C17121.3 (3)
C3—C4—H4C109.5C19—C18—H18119.4
H4A—C4—H4C109.5C17—C18—H18119.4
H4B—C4—H4C109.5C21—C20—Sn1119.40 (17)
C3—C5—H5A109.5C21—C20—H20A107.5
C3—C5—H5B109.5Sn1—C20—H20A107.5
H5A—C5—H5B109.5C21—C20—H20B107.5
C3—C5—H5C109.5Sn1—C20—H20B107.5
H5A—C5—H5C109.5H20A—C20—H20B107.0
H5B—C5—H5C109.5C22—C21—C26116.0 (3)
N1—C6—C7128.7 (2)C22—C21—C20121.5 (3)
N1—C6—H6115.7C26—C21—C20122.4 (2)
C7—C6—H6115.7F2—C22—C23118.0 (3)
C12—C7—C8119.4 (2)F2—C22—C21118.2 (3)
C12—C7—C6117.3 (2)C23—C22—C21123.8 (3)
C8—C7—C6123.3 (2)C24—C23—C22118.0 (3)
O3—C8—C9119.7 (2)C24—C23—H23121.0
O3—C8—C7122.6 (2)C22—C23—H23121.0
C9—C8—C7117.7 (2)C23—C24—C25120.2 (3)
C10—C9—C8120.8 (3)C23—C24—H24119.9
C10—C9—H9119.6C25—C24—H24119.9
C8—C9—H9119.6C24—C25—C26120.0 (3)
C9—C10—C11121.6 (3)C24—C25—H25120.0
C9—C10—H10119.2C26—C25—H25120.0
C11—C10—H10119.2C25—C26—C21121.8 (3)
C12—C11—C10119.0 (3)C25—C26—H26119.1
C12—C11—H11120.5C21—C26—H26119.1
Table 1
Selected geometric parameters (Å, °) top
Sn1—O32.1104 (17)Sn1—O12.1496 (17)
Sn1—C202.140 (3)Sn1—N12.187 (2)
Sn1—C132.147 (3)
O3—Sn1—C2090.67 (9)C13—Sn1—O197.87 (9)
O3—Sn1—C1393.05 (9)O3—Sn1—N182.27 (7)
C20—Sn1—C13129.53 (10)C20—Sn1—N1123.25 (9)
O3—Sn1—O1156.21 (7)C13—Sn1—N1107.11 (9)
C20—Sn1—O198.42 (9)O1—Sn1—N174.34 (7)
Acknowledgements top

The authors thank the Shandong Province Science Foundation for financial support.

references
References top

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