supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m232    [ doi:10.1107/S1600536809002426 ]

[N-(3-Methoxy-2-oxidobenzylidene-[kappa]O2)alaninato-[kappa]2N,O]diphenyltin(IV)

H.-J. Yang and Y.-Q. Dang

Abstract top

The Sn atom of the title compound, [Sn(C6H5)2(C11H11NO4)], adopts a distorted SnNC2O2 trigonal-bipyramidal geometry with the O atoms in the axial positions. The metal atom forms five- and six-membered chelate rings with the O,N,O'-tridentate ligand.

Comment top

The diorganotin complexes with Schiff bases derived from α-amino acids continue to receive attention because of their biological activities and their quadratic nonlinear optical properties (e.g. Rivera et al., 2006). The structures of two diorganotin complexes based on the Schiff base ligand [N-(2-hydroxyphenylmethylene)alanine, [N-(2-oxidophenylmethylene)alaninato]diphenyltin(IV) (Beltran et al., 2003) and dicyclohexyl[N-(3,5-dibromo-2-oxidophenylmethylene)alaninato]tin(IV) (Tian et al., 2007) have been reported. As a continuation of these studies, the structure of the title compound, (I), is now described.

The coordination geometry of the Sn atom in (I) is that of a distorted trigonal bipyramid with two phenyl groups and the imino N1 atom occupying the equatorial positions and the axial positions being occupied by a unidentate carboxylate O1 atom and phenoxide O3 atom (Fig. 1). The Sn atom is 0.061 (3) Å out of the NC2 trigonal plane in the direction of the O3 atom. The bond length of Sn1—O1 [2.1360 (16) Å] is longer than that of Sn1—O3 [2.0752 (14) Å]. The bond angle O1—Sn1—O3 is 158.35 (6)°, which is slightly larger than that observed in [N-(2-oxidophenylmethylene)alaninato]diphenyltin(IV) [156.90 (9)°] (Beltran et al., 2003) and dicyclohexyl[N-(3,5-dibromo-2-oxidophenylmethylene)alaninato]tin(IV) [154.9 (1)°] (Tian et al., 2007). The monodentate mode of coordination of carboxylate is reflected in the disparate C23—O1 and C23—O2 bond lengths of 1.290 (3) and 1.213 (3) Å, respectively.

Related literature top

For background, see: Rivera et al. (2006). For related structures, see: Beltran et al. (2003); Tian et al. (2007).

Experimental top

The title compound was prepared by the reaction of diphenyltin dichloride (0.69 g, 2 mmol) with potassium N-(3-methoxy-2-hydroxyphenylmethylene)alaninate (0.29 g, 2 mmol) in the presence of Et3N (0.20 g, 2 mmol) in methanol (30 ml). The reaction mixture was refluxed for 2 h and filtered. The yellow solid obtained by removal of solvent under reduced pressure was recrystallized from methanol and yellow blocks of (I) were obtained from dichloromethane–hexane (1:1 v/v) by slow evaporation at room temperature (yield 76%, m.p. 535–536 K).

Refinement top

The H atoms were placed at calculated positions (C—H = 0.93–0.98Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I) with displacement ellipsoids drawn at the 30% probability level. The H atoms have been omitted for clarity.
[N-(3-Methoxy-2-oxidobenzylidene-κO2)alaninato- κ2N,O]diphenyltin(IV) top
Crystal data top
[Sn(C6H5)2(C11H11NO4)]F(000) = 992
Mr = 494.10Dx = 1.572 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6772 reflections
a = 13.3881 (10) Åθ = 2.4–27.7°
b = 9.0304 (6) ŵ = 1.25 mm−1
c = 17.3398 (12) ÅT = 295 K
β = 95.077 (1)°Block, yellow
V = 2088.2 (3) Å30.16 × 0.12 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX area-detector
diffractometer		4326 independent reflections
Radiation source: fine-focus sealed tube3475 reflections with I > 2σ(I)
graphiteRint = 0.022
φ and ω scansθmax = 26.5°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −16→16
Tmin = 0.825, Tmax = 0.885k = −11→11
16481 measured reflectionsl = −21→20
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.029P)2 + 0.7005P]
where P = (Fo2 + 2Fc2)/3
4326 reflections(Δ/σ)max = 0.002
262 parametersΔρmax = 0.44 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
[Sn(C6H5)2(C11H11NO4)]V = 2088.2 (3) Å3
Mr = 494.10Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.3881 (10) ŵ = 1.25 mm−1
b = 9.0304 (6) ÅT = 295 K
c = 17.3398 (12) Å0.16 × 0.12 × 0.10 mm
β = 95.077 (1)°
Data collection top
Bruker SMART APEX area-detector
diffractometer		4326 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		3475 reflections with I > 2σ(I)
Tmin = 0.825, Tmax = 0.885Rint = 0.022
16481 measured reflectionsθmax = 26.5°
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.063Δρmax = 0.44 e Å−3
S = 1.04Δρmin = −0.26 e Å−3
4326 reflectionsAbsolute structure: ?
262 parametersFlack parameter: ?
0 restraintsRogers 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*/Ueq
Sn10.292357 (11)0.503657 (15)0.348838 (8)0.03542 (6)
N10.32598 (13)0.28485 (19)0.30979 (10)0.0385 (4)
O10.41792 (13)0.53434 (17)0.28262 (10)0.0467 (4)
O20.52345 (14)0.4293 (2)0.20800 (11)0.0638 (5)
O30.18288 (11)0.39202 (16)0.40344 (9)0.0450 (4)
O40.07445 (14)0.3448 (2)0.51854 (10)0.0609 (5)
C10.36449 (17)0.6022 (2)0.44906 (13)0.0415 (5)
C20.4416 (2)0.7013 (3)0.44224 (16)0.0575 (7)
H20.46640.71510.39430.069*
C30.4825 (2)0.7803 (4)0.50548 (18)0.0727 (9)
H30.53400.84760.50010.087*
C40.4471 (2)0.7590 (4)0.57586 (18)0.0782 (10)
H40.47360.81310.61850.094*
C50.3736 (3)0.6596 (5)0.58371 (17)0.0905 (11)
H50.35150.64320.63230.109*
C60.3305 (2)0.5816 (4)0.52079 (15)0.0706 (8)
H60.27870.51540.52690.085*
C70.18958 (16)0.6179 (2)0.27068 (12)0.0403 (5)
C80.2149 (2)0.7542 (3)0.24244 (18)0.0664 (8)
H80.27650.79650.25880.080*
C90.1487 (3)0.8287 (4)0.1896 (2)0.0847 (10)
H90.16640.92060.17080.102*
C100.0582 (2)0.7683 (4)0.16505 (18)0.0717 (9)
H100.01440.81840.12950.086*
C110.0321 (2)0.6336 (4)0.19299 (16)0.0660 (8)
H11−0.02970.59200.17660.079*
C120.0976 (2)0.5588 (3)0.24582 (16)0.0554 (6)
H120.07910.46740.26470.066*
C130.18852 (16)0.2585 (2)0.43474 (13)0.0383 (5)
C140.24719 (17)0.1438 (3)0.40775 (13)0.0426 (5)
C150.2462 (2)0.0026 (3)0.44269 (19)0.0591 (7)
H150.2848−0.07350.42470.071*
C160.1894 (2)−0.0228 (3)0.50210 (19)0.0670 (8)
H160.1900−0.11590.52510.080*
C170.1301 (2)0.0894 (3)0.52905 (15)0.0575 (7)
H170.09060.07020.56940.069*
C180.12930 (18)0.2276 (3)0.49671 (13)0.0461 (5)
C190.0072 (2)0.3215 (4)0.57615 (18)0.0810 (10)
H19A−0.02590.41290.58620.121*
H19B0.04380.28720.62280.121*
H19C−0.04170.24870.55840.121*
C200.30727 (16)0.1628 (2)0.34391 (13)0.0434 (5)
H200.33580.07760.32520.052*
C210.38800 (17)0.2828 (3)0.24357 (13)0.0441 (5)
H210.43260.19670.24760.053*
C220.3194 (2)0.2741 (4)0.16856 (15)0.0698 (8)
H22A0.28070.18460.16810.105*
H22B0.35920.27450.12520.105*
H22C0.27510.35790.16520.105*
C230.45012 (17)0.4244 (3)0.24431 (13)0.0422 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03617 (10)0.03374 (10)0.03691 (10)0.00146 (6)0.00633 (6)−0.00038 (6)
N10.0354 (10)0.0370 (10)0.0442 (10)−0.0001 (8)0.0092 (8)−0.0041 (8)
O10.0492 (10)0.0413 (9)0.0520 (10)−0.0067 (7)0.0170 (8)−0.0066 (7)
O20.0622 (12)0.0598 (11)0.0751 (13)−0.0118 (10)0.0371 (10)−0.0114 (10)
O30.0425 (9)0.0395 (9)0.0553 (10)0.0031 (7)0.0178 (7)0.0053 (7)
O40.0676 (12)0.0582 (11)0.0616 (11)−0.0035 (9)0.0319 (9)−0.0034 (9)
C10.0420 (12)0.0427 (12)0.0393 (12)0.0061 (10)0.0013 (10)−0.0014 (10)
C20.0552 (16)0.0639 (17)0.0529 (15)−0.0079 (13)0.0025 (12)−0.0048 (13)
C30.0643 (19)0.076 (2)0.075 (2)−0.0132 (16)−0.0058 (16)−0.0190 (16)
C40.065 (2)0.100 (3)0.066 (2)0.0131 (18)−0.0173 (16)−0.0356 (18)
C50.081 (2)0.148 (3)0.0427 (17)−0.009 (2)0.0074 (15)−0.0224 (19)
C60.0678 (19)0.099 (2)0.0462 (16)−0.0162 (18)0.0093 (14)−0.0058 (16)
C70.0389 (12)0.0427 (12)0.0398 (12)0.0056 (10)0.0064 (10)−0.0013 (10)
C80.0541 (16)0.0578 (17)0.085 (2)−0.0018 (13)−0.0081 (14)0.0189 (15)
C90.078 (2)0.069 (2)0.105 (3)0.0064 (17)−0.0068 (19)0.0410 (18)
C100.0600 (19)0.084 (2)0.069 (2)0.0265 (17)−0.0059 (15)0.0106 (17)
C110.0445 (15)0.084 (2)0.0676 (18)0.0065 (14)−0.0082 (13)−0.0043 (16)
C120.0507 (15)0.0580 (15)0.0571 (16)−0.0025 (13)0.0030 (12)0.0009 (13)
C130.0336 (11)0.0410 (12)0.0399 (12)−0.0044 (9)0.0006 (9)0.0014 (9)
C140.0359 (12)0.0401 (12)0.0520 (14)−0.0024 (10)0.0040 (10)0.0032 (10)
C150.0550 (16)0.0432 (15)0.080 (2)0.0048 (11)0.0086 (15)0.0113 (13)
C160.072 (2)0.0533 (17)0.076 (2)−0.0052 (14)0.0070 (17)0.0236 (14)
C170.0606 (16)0.0632 (17)0.0498 (15)−0.0092 (14)0.0106 (13)0.0099 (13)
C180.0444 (13)0.0507 (14)0.0434 (13)−0.0088 (11)0.0041 (10)−0.0001 (11)
C190.084 (2)0.085 (2)0.081 (2)−0.0113 (18)0.0471 (18)−0.0079 (18)
C200.0364 (12)0.0348 (12)0.0594 (15)0.0014 (9)0.0062 (11)−0.0048 (10)
C210.0411 (12)0.0447 (13)0.0476 (13)0.0002 (10)0.0110 (10)−0.0062 (10)
C220.0623 (18)0.098 (2)0.0494 (16)−0.0171 (16)0.0049 (13)−0.0207 (15)
C230.0406 (12)0.0460 (13)0.0406 (12)−0.0002 (10)0.0065 (10)−0.0008 (10)
Geometric parameters (Å, °) top
Sn1—C12.109 (2)C9—C101.363 (4)
Sn1—C72.113 (2)C9—H90.9300
Sn1—O12.1360 (16)C10—C111.366 (4)
Sn1—O32.0752 (14)C10—H100.9300
Sn1—N12.1493 (17)C11—C121.387 (4)
N1—C201.286 (3)C11—H110.9300
N1—C211.475 (3)C12—H120.9300
O1—C231.290 (3)C13—C141.405 (3)
O2—C231.213 (3)C13—C181.418 (3)
O3—C131.321 (2)C14—C151.412 (3)
O4—C181.361 (3)C14—C201.435 (3)
O4—C191.418 (3)C15—C161.353 (4)
C1—C61.374 (3)C15—H150.9300
C1—C21.379 (3)C16—C171.394 (4)
C2—C31.380 (4)C16—H160.9300
C2—H20.9300C17—C181.368 (3)
C3—C41.361 (4)C17—H170.9300
C3—H30.9300C19—H19A0.9600
C4—C51.348 (5)C19—H19B0.9600
C4—H40.9300C19—H19C0.9600
C5—C61.381 (4)C20—H200.9300
C5—H50.9300C21—C231.525 (3)
C6—H60.9300C21—C221.527 (3)
C7—C121.376 (3)C21—H210.9800
C7—C81.378 (3)C22—H22A0.9600
C8—C91.391 (4)C22—H22B0.9600
C8—H80.9300C22—H22C0.9600
O3—Sn1—C196.86 (8)C10—C11—H11120.0
O3—Sn1—C794.80 (7)C12—C11—H11120.0
C1—Sn1—C7123.18 (9)C7—C12—C11121.0 (3)
O3—Sn1—O1158.35 (6)C7—C12—H12119.5
C1—Sn1—O193.64 (8)C11—C12—H12119.5
C7—Sn1—O195.20 (8)O3—C13—C14123.3 (2)
O3—Sn1—N182.71 (6)O3—C13—C18118.4 (2)
C1—Sn1—N1123.66 (8)C14—C13—C18118.3 (2)
C7—Sn1—N1112.92 (8)C13—C14—C15119.7 (2)
O1—Sn1—N175.71 (6)C13—C14—C20122.5 (2)
C20—N1—C21119.56 (19)C15—C14—C20117.8 (2)
C20—N1—Sn1126.04 (15)C16—C15—C14120.5 (3)
C21—N1—Sn1113.85 (14)C16—C15—H15119.8
C23—O1—Sn1119.47 (15)C14—C15—H15119.8
C13—O3—Sn1127.85 (13)C15—C16—C17120.5 (2)
C18—O4—C19118.2 (2)C15—C16—H16119.8
C6—C1—C2118.4 (2)C17—C16—H16119.8
C6—C1—Sn1121.65 (19)C18—C17—C16120.7 (3)
C2—C1—Sn1119.66 (17)C18—C17—H17119.7
C1—C2—C3121.0 (3)C16—C17—H17119.7
C1—C2—H2119.5O4—C18—C17125.5 (2)
C3—C2—H2119.5O4—C18—C13114.1 (2)
C4—C3—C2119.6 (3)C17—C18—C13120.4 (2)
C4—C3—H3120.2O4—C19—H19A109.5
C2—C3—H3120.2O4—C19—H19B109.5
C5—C4—C3120.0 (3)H19A—C19—H19B109.5
C5—C4—H4120.0O4—C19—H19C109.5
C3—C4—H4120.0H19A—C19—H19C109.5
C4—C5—C6121.1 (3)H19B—C19—H19C109.5
C4—C5—H5119.4N1—C20—C14127.0 (2)
C6—C5—H5119.4N1—C20—H20116.5
C1—C6—C5119.9 (3)C14—C20—H20116.5
C1—C6—H6120.1N1—C21—C23109.11 (18)
C5—C6—H6120.1N1—C21—C22109.03 (19)
C12—C7—C8118.5 (2)C23—C21—C22109.7 (2)
C12—C7—Sn1121.71 (18)N1—C21—H21109.7
C8—C7—Sn1119.80 (18)C23—C21—H21109.7
C7—C8—C9120.2 (3)C22—C21—H21109.7
C7—C8—H8119.9C21—C22—H22A109.5
C9—C8—H8119.9C21—C22—H22B109.5
C10—C9—C8120.6 (3)H22A—C22—H22B109.5
C10—C9—H9119.7C21—C22—H22C109.5
C8—C9—H9119.7H22A—C22—H22C109.5
C9—C10—C11119.6 (3)H22B—C22—H22C109.5
C9—C10—H10120.2O2—C23—O1124.2 (2)
C11—C10—H10120.2O2—C23—C21119.5 (2)
C10—C11—C12120.1 (3)O1—C23—C21116.3 (2)
O3—Sn1—N1—C20−25.19 (18)C12—C7—C8—C9−0.5 (4)
C1—Sn1—N1—C2068.2 (2)Sn1—C7—C8—C9178.5 (2)
C7—Sn1—N1—C20−117.34 (19)C7—C8—C9—C100.0 (5)
O1—Sn1—N1—C20153.0 (2)C8—C9—C10—C110.4 (5)
O3—Sn1—N1—C21163.36 (15)C9—C10—C11—C12−0.2 (5)
C1—Sn1—N1—C21−103.22 (16)C8—C7—C12—C110.6 (4)
C7—Sn1—N1—C2171.22 (16)Sn1—C7—C12—C11−178.3 (2)
O1—Sn1—N1—C21−18.44 (14)C10—C11—C12—C7−0.3 (4)
O3—Sn1—O1—C2311.9 (3)Sn1—O3—C13—C14−30.4 (3)
C1—Sn1—O1—C23130.87 (18)Sn1—O3—C13—C18152.16 (16)
C7—Sn1—O1—C23−105.33 (18)O3—C13—C14—C15−177.7 (2)
N1—Sn1—O1—C237.03 (16)C18—C13—C14—C15−0.3 (3)
C1—Sn1—O3—C13−87.66 (18)O3—C13—C14—C200.7 (3)
C7—Sn1—O3—C13148.07 (18)C18—C13—C14—C20178.1 (2)
O1—Sn1—O3—C1330.8 (3)C13—C14—C15—C16−0.2 (4)
N1—Sn1—O3—C1335.53 (18)C20—C14—C15—C16−178.7 (3)
O3—Sn1—C1—C6−1.4 (2)C14—C15—C16—C170.8 (5)
C7—Sn1—C1—C698.9 (2)C15—C16—C17—C18−0.9 (5)
O1—Sn1—C1—C6−162.4 (2)C19—O4—C18—C17−4.3 (4)
N1—Sn1—C1—C6−87.2 (2)C19—O4—C18—C13175.4 (2)
O3—Sn1—C1—C2−174.98 (19)C16—C17—C18—O4−179.9 (3)
C7—Sn1—C1—C2−74.7 (2)C16—C17—C18—C130.4 (4)
O1—Sn1—C1—C224.0 (2)O3—C13—C18—O4−2.0 (3)
N1—Sn1—C1—C299.2 (2)C14—C13—C18—O4−179.5 (2)
C6—C1—C2—C3−1.3 (4)O3—C13—C18—C17177.7 (2)
Sn1—C1—C2—C3172.5 (2)C14—C13—C18—C170.2 (3)
C1—C2—C3—C40.7 (5)C21—N1—C20—C14−178.7 (2)
C2—C3—C4—C51.1 (5)Sn1—N1—C20—C1410.3 (3)
C3—C4—C5—C6−2.3 (6)C13—C14—C20—N19.1 (4)
C2—C1—C6—C50.1 (5)C15—C14—C20—N1−172.4 (2)
Sn1—C1—C6—C5−173.6 (3)C20—N1—C21—C23−146.0 (2)
C4—C5—C6—C11.7 (6)Sn1—N1—C21—C2326.0 (2)
O3—Sn1—C7—C12−29.5 (2)C20—N1—C21—C2294.2 (3)
C1—Sn1—C7—C12−130.88 (19)Sn1—N1—C21—C22−93.8 (2)
O1—Sn1—C7—C12131.3 (2)Sn1—O1—C23—O2−176.5 (2)
N1—Sn1—C7—C1254.6 (2)Sn1—O1—C23—C215.7 (3)
O3—Sn1—C7—C8151.6 (2)N1—C21—C23—O2161.4 (2)
C1—Sn1—C7—C850.2 (2)C22—C21—C23—O2−79.3 (3)
O1—Sn1—C7—C8−47.6 (2)N1—C21—C23—O1−20.8 (3)
N1—Sn1—C7—C8−124.3 (2)C22—C21—C23—O198.6 (2)
Table 1
Selected geometric parameters (Å) top
Sn1—C12.109 (2)Sn1—O32.0752 (14)
Sn1—C72.113 (2)Sn1—N12.1493 (17)
Sn1—O12.1360 (16)
Acknowledgements top

The authors thank the Science Foundation of Binzhou University for supporting this work (grant No. BZXYQNLG200820).

references
References top

Beltran, H. I., Zamudio-Rivera, L. S., Mancilla, T., Santillan, R. & Farfan, N. (2003). Chem. Eur. J. 9, 2291–2306.

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Rivera, J. M., Reyes, H., Cortes, A., Santillan, R., Lacroix, P. G., Lepetit, C., Nakatani, K. & Farfan, N. (2006). Chem. Mater. 18, 1174–1183.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tian, L., Sun, Y., Zheng, X., Liu, X., You, Y., Liu, X. & Qian, B. (2007). Chin. J. Chem. 25, 312–318.