(2,2′-Bipyridine-κ2 N,N′){[(3-meth­oxy-2-oxidobenzyl­idene-κO 2)hydrazono]methano­lato-κ2 N 2,O}dimethyl­tin(IV)

Shaukat Shuja; Saqib Ali; M Nawaz Tahir; Nasir Khalid; Islam Ullah Khan

doi:10.1107/S1600536808006090

. 2008 Mar 7;64(Pt 4):m531–m532. doi: 10.1107/S1600536808006090

(2,2′-Bipyridine-κ² N,N′){[(3-methoxy-2-oxidobenzylidene-κO ²)hydrazono]methanolato-κ² N ²,O}dimethyltin(IV)

Shaukat Shuja ^a, Saqib Ali ^a, M Nawaz Tahir ^b, Nasir Khalid ^c, Islam Ullah Khan ^d,^*

PMCID: PMC2961040 PMID: 21201994

Abstract

In the crystal structure of the title compound, [Sn(CH₃)₂(C₉H₈N₂O₃)(C₁₀H₈N₂)], the Sn atom exhibits a pentagonal bipyramidal coordination geometry defined by two C, three N and two O atoms. The bond distances for Sn—C, Sn—N and Sn—O are in the ranges 2.097 (3)–2.098 (3), 2.298 (2)–2.623 (2) and 2.157 (2)–2.266 (2) Å, respectively. The molecular structure of the monomeric compound is stabilized by three intramolecular C—H⋯O hydrogen bonds, all involving bipyridine C—H groups.

Related literature

For related literature, see: Chen et al. (2006 ▶); Diouf et al. (2004 ▶); Shuja et al. (2007a ▶,b ▶, 2007c ▶). For bond-length data, see: Allen (2002 ▶).

Experimental

Crystal data

[Sn(CH₃)₂(C₉H₈N₂O₃)(C₁₀H₈N₂)]
M _r = 497.12
Monoclinic,
a = 12.3834 (3) Å
b = 9.9094 (2) Å
c = 17.1730 (4) Å
β = 103.302 (1)°
V = 2050.80 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 296 (2) K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.749, T _max = 0.820
24401 measured reflections
5524 independent reflections
4407 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.066
S = 1.04
5524 reflections
280 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); 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 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006090/im2056sup1.cif

e-64-0m531-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006090/im2056Isup2.hkl

e-64-0m531-Isup2.hkl^{(265KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Sn1—C9	2.097 (3)
Sn1—C10	2.098 (3)
Sn1—O1	2.1572 (14)
Sn1—O2	2.2658 (15)
Sn1—N1	2.2980 (18)
Sn1—N3	2.5825 (18)
Sn1—N4	2.6231 (19)

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C9—Sn1—C10	169.76 (11)
C9—Sn1—O1	93.97 (9)
C10—Sn1—O1	90.20 (9)
C9—Sn1—O2	94.23 (9)
C10—Sn1—O2	87.60 (11)
O1—Sn1—O2	145.23 (6)
C9—Sn1—N1	94.39 (9)
C10—Sn1—N1	95.65 (10)
O1—Sn1—N1	77.12 (6)
O2—Sn1—N1	68.60 (6)
C9—Sn1—N3	80.37 (9)
C10—Sn1—N3	90.33 (9)
O1—Sn1—N3	138.83 (6)
O2—Sn1—N3	75.90 (6)
N1—Sn1—N3	143.65 (6)
O1—Sn1—N4	76.91 (6)
O2—Sn1—N4	136.43 (6)
N1—Sn1—N4	153.65 (6)
N3—Sn1—N4	62.68 (6)
N4—Sn1—C9	91.77 (9)
N4—Sn1—C10	80.06 (10)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2	0.93	2.40	2.993 (3)	121
C21—H21⋯O1	0.93	2.36	2.968 (3)	123
C21—H21⋯O3	0.93	2.50	3.390 (3)	161

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Acknowledgments

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, for funding the purchase of the diffractometer and for financial support to SS for PhD under the Indigenous Scholarship Scheme (PIN Code: 042–111889).

supplementary crystallographic information

Comment

Diorganotin(IV) complexes of Schiff base ligands derived from 3-methoxysalicylaldehyde and hydrazine derivatives are limited in number (Chen et al., 2006, Diouf et al., 2004). In continuation of our efforts to synthesize various Schiff base ligands of substituted salicylaldehydes with hydrazines or amino acids as well as the corresponding organotin derivatives (Shuja et al., 2007a, 2007b, 2007c), we herein report the structure of the title compound (I).

In the monomeric structure of the title compound (I), the coordination around Sn consists of two O-atoms and one N-atom of the Schiff base ligand [N-Formyl-N'-(3-methoxy-2-oxidobenzylidene)hydrazine], two N-atoms of 2,2'-bipyridine and two C-atoms of methyl groups. The shortest bond of Sn is realised with the methyl C-atoms showing nearly equal values (2.097 (3) and 2.098 (3) Å) corresponding very well with the bond lengths observed in [(3-Methoxy-2-oxidobenzaldehyde benzoylhydrazonato)dimethyltin(IV)] (Chen et al., 2006). The Sn1—O1 bond distance of 2.157 (1) Å is greater than the values reported for [diphenyl(methoxy-N-salicylideneacetylhydrazonato)tin(IV)] (2.068 (2) Å, Diouf et al., 2004 and 2.131 (3) Å, Chen et al., 2006). The same is true for the bonds Sn1—O2 (2.266 (2) Å) and Sn1—N1 (2.298 (2) Å) also being longer compared to those previously reported (Diouf et al., 2004, Chen et al., 2006). These observations are most probably due to the additional coordination of bipyridine to tin. A CCDC search (Allen, 2002) showed that the title compund is indeed the first structurally characterized tin organyl with a bipyridine ligand attached to tin. The bond distances of N-atoms of bipyridine measure to 2.583 (2) Å (Sn1—N3) and 2.623 (2) Å (Sn1—N4), respectively. The bond distances in the hydrazine ligand are comparable with those reported for {[N-Formyl-N'-(2-oxidobenzylidene)hydrazine-κ³O,N,O']diphenyl tin(IV)} (Shuja et al., 2007b). The bond angles around Sn1 are in the range between 68.60 (6)° and 169.8 (1)°. The dihedral angle between (O1/C1/C2/C3/C4 /C5/C6/C7) and (N1/N2/C8/O2) is 36.0 (1)° while the angle between the rings (N3/C12/C13/C14/C15/C16) and (N4/C17/C18/C19/C20/C21) is 17.0 (1)°. The molecular structure of the title compound as well as the observed conformation are stabilized by three intramolecular H-bonds of C—H···O type (Fig. 1) all involving bipyridine C–H functions (Table 2). The closest intermolecular contact of molecules is at a distance of 3.208 (3) Å between O1···C15ⁱ [symmetry code: i = x, -y + 1/2, z + 1/2]. A postive electron peak corresponding to 1.12 Å^-3 remains at a distance of 0.93 Å near Sn1.

Experimental

N-(2-hydroxy-3-methoxy-benzylidene)formylhydrazine (0.58 g, 3 mmol) and Et₃N (0.86 ml, 6 mmol) were added to anhydrous toluene (100 ml) in a round bottom flask equipped with a reflux condenser. Dimethyltin(IV) dichloride (0.66 g, 3 mmol) dissolved in anhydrous toluene (20 ml) and 2,2'-bipyridine (0.47 g, 3 mmol) were then added. The reaction mixture was stirred at room temperature for 5 hr and allowed to stand overnight. The Et₃NHCl salt formed during the reaction was filtered off and the resulting clear yellow solution was evaporated with a rotary evaporator under reduced pressure. Recrystallization from chloroform yielded crystals suitable for X-ray diffraction.