Dimethyl­bis­(pyrazine-2-carboxyl­ato-κ2N1,O)tin(IV)

Vafaee, M.; Najafi, E.; Amini, M.M.; Ng, S.W.

doi:10.1107/S160053681204295X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1384

doi:10.1107/S160053681204295X

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Dimethylbis(pyrazine-2-carboxylato-κ²N¹,O)tin(IV)

Marzieh Vafaee,^a Ezzatollah Najafi,^a Mostafa M. Amini ^a ^* and Seik Weng Ng ^b

^aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: m-pouramini@cc.sbu.ac.ir

(Received 4 October 2012; accepted 15 October 2012; online 20 October 2012)

In the title compound, [Sn(CH₃)₂(C₅H₃N₂O₂)₂], the Sn^IV atom is twice N,O-chelated by two pyrazine-2-carboxylate ligands. The distorted six-coordination is completed by two tin-bound methyl C atoms. The C₂N₂O₂ donor set defines a skewed trapezoidal–bipyramidal geometry. Intermolecular π–π interactions between the pyrazine rings [centroid–centroid distance = 3.8112 (13) Å] are observed.

Related literature

For background to organotin compounds, see: Dakternieks et al. (2003 ); Tiekink (1991 ); Yin et al. (2005 ).

Experimental

Crystal data

[Sn(CH₃)₂(C₅H₃N₂O₂)₂]
M_r = 394.95
Monoclinic, P 2₁ /c
a = 9.2887 (6) Å
b = 12.3253 (7) Å
c = 12.6596 (7) Å
β = 103.738 (1)°
V = 1407.88 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.84 mm⁻¹
T = 295 K
0.40 × 0.40 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.527, T_max = 0.710
8657 measured reflections
3193 independent reflections
2892 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.051
S = 1.06
3193 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—C1	2.097 (2)
Sn1—C2	2.095 (2)
Sn1—O1	2.1506 (16)
Sn1—O3	2.1238 (15)
Sn1—N1	2.6646 (18)
Sn1—N3	2.5107 (18)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681204295X/hy2594sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681204295X/hy2594Isup2.hkl

checkCIF report

Comment top

The reaction of appropriate amount of dimethyltin dichloride and pyrazine-2-carboxylic acid in dry methanol provided the title compound in good yield. The six-coordinated geometry around the Sn^IV atom is better described as skew-trapezoidal bipyramidal (Fig. 1, Table 1). Intermolecular π–π interactions between the pyrazine rings [centroid–centroid distance = 3.8112 (13) Å] stabilize the structure.

Related literature top

For background to organotin compounds, see: Dakternieks et al. (2003); Tiekink (1991); Yin et al. (2005).

Experimental top

Dimethyltin dichloride (0.22 g, 1 mmol) was treated with sodium methoxide (0.1 g, 2 mmol) in methanol (10 ml) to produce dimethyltin dimethoxide and sodium chloride. The sodium chloride precipitate was removed by filtration and then pyrazine-2-carboxylic acid (0.248 g, 2 mmol) in methanol (20 ml) was added to the filtrate. The solution was refluxed for 3 h. Evaporation of the solvent yielded a white solid, which was purified by recrystallization from methanol (yield: 70%. m.p.: 118–120°C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Dimethylbis(pyrazine-2-carboxylato-κ²N¹,O)tin(IV) top

Crystal data top

[Sn(CH₃)₂(C₅H₃N₂O₂)₂]	F(000) = 776
M_r = 394.95	D_x = 1.863 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5890 reflections
a = 9.2887 (6) Å	θ = 2.3–28.3°
b = 12.3253 (7) Å	µ = 1.84 mm⁻¹
c = 12.6596 (7) Å	T = 295 K
β = 103.738 (1)°	Prism, colorless
V = 1407.88 (14) Å³	0.40 × 0.40 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3193 independent reflections
Radiation source: fine-focus sealed tube	2892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.527, T_max = 0.710	k = −16→13
8657 measured reflections	l = −15→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0201P)² + 0.7349P] where P = (F_o² + 2F_c²)/3
3193 reflections	(Δ/σ)_max = 0.001
192 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Sn(CH₃)₂(C₅H₃N₂O₂)₂]	V = 1407.88 (14) Å³
M_r = 394.95	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2887 (6) Å	µ = 1.84 mm⁻¹
b = 12.3253 (7) Å	T = 295 K
c = 12.6596 (7) Å	0.40 × 0.40 × 0.20 mm
β = 103.738 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3193 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2892 reflections with I > 2σ(I)
T_min = 0.527, T_max = 0.710	R_int = 0.022
8657 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.051	H-atom parameters constrained
S = 1.06	Δρ_max = 0.35 e Å⁻³
3193 reflections	Δρ_min = −0.47 e Å⁻³
192 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.826212 (14)	0.699389 (11)	0.602141 (11)	0.02943 (6)
O1	0.87907 (17)	0.71196 (14)	0.44616 (13)	0.0415 (4)
O2	0.99121 (19)	0.78275 (16)	0.32619 (13)	0.0493 (4)
O3	0.62830 (16)	0.65997 (14)	0.48535 (12)	0.0374 (3)
O4	0.39196 (17)	0.61066 (15)	0.43503 (13)	0.0469 (4)
N1	1.09601 (19)	0.77904 (14)	0.61292 (14)	0.0320 (4)
N2	1.3488 (2)	0.87890 (18)	0.57415 (17)	0.0478 (5)
N3	0.62453 (19)	0.65022 (15)	0.69497 (14)	0.0340 (4)
N4	0.3759 (2)	0.57674 (16)	0.76062 (16)	0.0421 (4)
C1	0.7815 (3)	0.86219 (19)	0.6305 (2)	0.0466 (6)
H1A	0.8346	0.9084	0.5918	0.070*
H1B	0.8123	0.8772	0.7070	0.070*
H1C	0.6770	0.8755	0.6057	0.070*
C2	0.9233 (3)	0.54697 (19)	0.6433 (2)	0.0444 (5)
H2A	1.0075	0.5391	0.6123	0.067*
H2B	0.8523	0.4912	0.6155	0.067*
H2C	0.9546	0.5408	0.7210	0.067*
C3	0.9857 (2)	0.76167 (19)	0.41998 (17)	0.0346 (4)
C4	1.1116 (2)	0.79754 (16)	0.51203 (17)	0.0302 (4)
C5	1.2359 (3)	0.8484 (2)	0.49323 (19)	0.0405 (5)
H5	1.2409	0.8618	0.4219	0.049*
C6	1.3319 (3)	0.86057 (19)	0.67419 (19)	0.0417 (5)
H6	1.4074	0.8812	0.7331	0.050*
C7	1.2068 (3)	0.81211 (17)	0.69396 (18)	0.0361 (5)
H7	1.1996	0.8023	0.7654	0.043*
C12	0.6207 (3)	0.6469 (2)	0.79961 (18)	0.0445 (6)
H12	0.7030	0.6696	0.8523	0.053*
C13	0.4970 (3)	0.6103 (2)	0.83094 (19)	0.0449 (6)
H13	0.4986	0.6092	0.9047	0.054*
C14	0.3798 (2)	0.58104 (18)	0.65644 (18)	0.0367 (5)
H14	0.2974	0.5577	0.6042	0.044*
C15	0.5024 (2)	0.61905 (16)	0.62266 (16)	0.0295 (4)
C16	0.5045 (2)	0.62962 (16)	0.50495 (17)	0.0321 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.02845 (8)	0.03258 (9)	0.02919 (9)	0.00030 (5)	0.01068 (6)	0.00025 (5)
O1	0.0333 (8)	0.0637 (11)	0.0291 (8)	−0.0101 (7)	0.0106 (6)	−0.0007 (7)
O2	0.0415 (9)	0.0830 (13)	0.0266 (8)	−0.0074 (8)	0.0144 (7)	0.0015 (8)
O3	0.0337 (8)	0.0518 (9)	0.0280 (7)	−0.0071 (7)	0.0097 (6)	0.0015 (7)
O4	0.0346 (8)	0.0667 (11)	0.0359 (8)	−0.0095 (8)	0.0012 (7)	−0.0012 (8)
N1	0.0310 (9)	0.0379 (9)	0.0296 (9)	0.0011 (7)	0.0123 (7)	0.0020 (7)
N2	0.0421 (11)	0.0589 (13)	0.0449 (11)	−0.0164 (9)	0.0151 (9)	−0.0052 (10)
N3	0.0278 (8)	0.0442 (10)	0.0309 (9)	−0.0032 (7)	0.0088 (7)	−0.0047 (8)
N4	0.0380 (10)	0.0471 (11)	0.0464 (11)	−0.0019 (8)	0.0203 (9)	0.0023 (9)
C1	0.0429 (13)	0.0383 (12)	0.0571 (15)	0.0043 (10)	0.0089 (11)	−0.0073 (11)
C2	0.0437 (13)	0.0380 (12)	0.0511 (14)	0.0060 (10)	0.0104 (11)	0.0047 (10)
C3	0.0303 (10)	0.0456 (12)	0.0303 (10)	0.0039 (9)	0.0119 (8)	−0.0010 (9)
C4	0.0287 (10)	0.0363 (10)	0.0289 (10)	0.0026 (8)	0.0134 (8)	−0.0002 (8)
C5	0.0397 (12)	0.0510 (13)	0.0353 (11)	−0.0075 (10)	0.0175 (9)	0.0000 (10)
C6	0.0394 (12)	0.0449 (13)	0.0404 (12)	−0.0090 (10)	0.0082 (10)	−0.0043 (10)
C7	0.0402 (12)	0.0396 (11)	0.0296 (11)	0.0002 (9)	0.0106 (9)	−0.0006 (8)
C12	0.0348 (11)	0.0687 (16)	0.0308 (11)	−0.0037 (11)	0.0093 (9)	−0.0065 (11)
C13	0.0424 (12)	0.0627 (15)	0.0338 (11)	0.0054 (11)	0.0171 (10)	0.0010 (11)
C14	0.0301 (10)	0.0415 (12)	0.0399 (12)	−0.0040 (9)	0.0109 (9)	−0.0025 (9)
C15	0.0276 (9)	0.0286 (10)	0.0333 (10)	0.0016 (7)	0.0091 (8)	−0.0016 (8)
C16	0.0305 (10)	0.0330 (10)	0.0328 (10)	−0.0004 (8)	0.0079 (8)	−0.0006 (8)

Geometric parameters (Å, º) top

Sn1—C1	2.097 (2)	C1—H1A	0.9600
Sn1—C2	2.095 (2)	C1—H1B	0.9600
Sn1—O1	2.1506 (16)	C1—H1C	0.9600
Sn1—O3	2.1238 (15)	C2—H2A	0.9600
Sn1—N1	2.6646 (18)	C2—H2B	0.9600
Sn1—N3	2.5107 (18)	C2—H2C	0.9600
O1—C3	1.274 (3)	C3—C4	1.508 (3)
O2—C3	1.228 (3)	C4—C5	1.383 (3)
O3—C16	1.288 (3)	C5—H5	0.9300
O4—C16	1.221 (2)	C6—C7	1.382 (3)
N1—C7	1.332 (3)	C6—H6	0.9300
N1—C4	1.339 (3)	C7—H7	0.9300
N2—C6	1.332 (3)	C12—C13	1.378 (3)
N2—C5	1.334 (3)	C12—H12	0.9300
N3—C12	1.334 (3)	C13—H13	0.9300
N3—C15	1.334 (3)	C14—C15	1.389 (3)
N4—C13	1.324 (3)	C14—H14	0.9300
N4—C14	1.329 (3)	C15—C16	1.501 (3)

C2—Sn1—C1	154.98 (10)	Sn1—C2—H2C	109.5
C2—Sn1—O3	102.62 (8)	H2A—C2—H2C	109.5
C1—Sn1—O3	99.44 (8)	H2B—C2—H2C	109.5
C2—Sn1—O1	96.58 (8)	O2—C3—O1	124.5 (2)
C1—Sn1—O1	100.72 (9)	O2—C3—C4	118.9 (2)
O3—Sn1—O1	74.09 (6)	O1—C3—C4	116.63 (18)
C2—Sn1—N3	89.54 (8)	N1—C4—C5	121.7 (2)
C1—Sn1—N3	87.17 (9)	N1—C4—C3	116.59 (18)
O3—Sn1—N3	69.63 (6)	C5—C4—C3	121.71 (19)
O1—Sn1—N3	143.67 (6)	N2—C5—C4	122.1 (2)
C2—Sn1—N1	88.49 (8)	N2—C5—H5	118.9
C1—Sn1—N1	82.01 (8)	C4—C5—H5	118.9
O3—Sn1—N1	140.17 (5)	N2—C6—C7	122.7 (2)
O1—Sn1—N1	66.64 (6)	N2—C6—H6	118.7
N3—Sn1—N1	149.56 (5)	C7—C6—H6	118.7
C3—O1—Sn1	129.40 (14)	N1—C7—C6	121.4 (2)
C16—O3—Sn1	126.66 (13)	N1—C7—H7	119.3
C7—N1—C4	116.35 (18)	C6—C7—H7	119.3
C7—N1—Sn1	134.17 (14)	N3—C12—C13	121.1 (2)
C4—N1—Sn1	109.12 (13)	N3—C12—H12	119.5
C6—N2—C5	115.7 (2)	C13—C12—H12	119.5
C12—N3—C15	116.99 (19)	N4—C13—C12	122.8 (2)
C12—N3—Sn1	132.12 (15)	N4—C13—H13	118.6
C15—N3—Sn1	110.85 (13)	C12—C13—H13	118.6
C13—N4—C14	115.86 (19)	N4—C14—C15	122.4 (2)
Sn1—C1—H1A	109.5	N4—C14—H14	118.8
Sn1—C1—H1B	109.5	C15—C14—H14	118.8
H1A—C1—H1B	109.5	N3—C15—C14	120.76 (19)
Sn1—C1—H1C	109.5	N3—C15—C16	116.52 (18)
H1A—C1—H1C	109.5	C14—C15—C16	122.70 (18)
H1B—C1—H1C	109.5	O4—C16—O3	124.5 (2)
Sn1—C2—H2A	109.5	O4—C16—C15	119.47 (19)
Sn1—C2—H2B	109.5	O3—C16—C15	116.07 (17)
H2A—C2—H2B	109.5

C2—Sn1—O1—C3	−98.1 (2)	C7—N1—C4—C5	−0.1 (3)
C1—Sn1—O1—C3	63.8 (2)	Sn1—N1—C4—C5	173.91 (17)
O3—Sn1—O1—C3	160.6 (2)	C7—N1—C4—C3	−179.20 (18)
N3—Sn1—O1—C3	163.69 (17)	Sn1—N1—C4—C3	−5.2 (2)
N1—Sn1—O1—C3	−12.59 (18)	O2—C3—C4—N1	175.7 (2)
C2—Sn1—O3—C16	83.58 (19)	O1—C3—C4—N1	−3.5 (3)
C1—Sn1—O3—C16	−84.53 (19)	O2—C3—C4—C5	−3.4 (3)
O1—Sn1—O3—C16	176.92 (19)	O1—C3—C4—C5	177.4 (2)
N3—Sn1—O3—C16	−1.15 (17)	C6—N2—C5—C4	−2.2 (4)
N1—Sn1—O3—C16	−173.35 (15)	N1—C4—C5—N2	2.0 (4)
C2—Sn1—N1—C7	−81.4 (2)	C3—C4—C5—N2	−178.9 (2)
C1—Sn1—N1—C7	75.4 (2)	C5—N2—C6—C7	0.7 (4)
O3—Sn1—N1—C7	170.55 (17)	C4—N1—C7—C6	−1.4 (3)
O1—Sn1—N1—C7	−179.2 (2)	Sn1—N1—C7—C6	−173.53 (16)
N3—Sn1—N1—C7	5.1 (3)	N2—C6—C7—N1	1.2 (4)
C2—Sn1—N1—C4	106.05 (15)	C15—N3—C12—C13	1.5 (4)
C1—Sn1—N1—C4	−97.16 (15)	Sn1—N3—C12—C13	−175.99 (18)
O3—Sn1—N1—C4	−1.98 (18)	C14—N4—C13—C12	−0.5 (4)
O1—Sn1—N1—C4	8.22 (13)	N3—C12—C13—N4	0.0 (4)
N3—Sn1—N1—C4	−167.44 (13)	C13—N4—C14—C15	−0.5 (3)
C2—Sn1—N3—C12	77.7 (2)	C12—N3—C15—C14	−2.4 (3)
C1—Sn1—N3—C12	−77.5 (2)	Sn1—N3—C15—C14	175.58 (16)
O3—Sn1—N3—C12	−178.7 (2)	C12—N3—C15—C16	176.3 (2)
O1—Sn1—N3—C12	178.2 (2)	Sn1—N3—C15—C16	−5.6 (2)
N1—Sn1—N3—C12	−8.5 (3)	N4—C14—C15—N3	2.0 (3)
C2—Sn1—N3—C15	−99.93 (15)	N4—C14—C15—C16	−176.7 (2)
C1—Sn1—N3—C15	104.88 (15)	Sn1—O3—C16—O4	177.83 (17)
O3—Sn1—N3—C15	3.72 (13)	Sn1—O3—C16—C15	−1.4 (3)
O1—Sn1—N3—C15	0.6 (2)	N3—C15—C16—O4	−174.2 (2)
N1—Sn1—N3—C15	173.84 (12)	C14—C15—C16—O4	4.6 (3)
Sn1—O1—C3—O2	−164.70 (18)	N3—C15—C16—O3	5.1 (3)
Sn1—O1—C3—C4	14.5 (3)	C14—C15—C16—O3	−176.11 (19)

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₂(C₅H₃N₂O₂)₂]
M_r	394.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.2887 (6), 12.3253 (7), 12.6596 (7)
β (°)	103.738 (1)
V (Å³)	1407.88 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.84
Crystal size (mm)	0.40 × 0.40 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.527, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	8657, 3193, 2892
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.051, 1.06
No. of reflections	3193
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.47

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Sn1—C1	2.097 (2)	Sn1—O3	2.1238 (15)
Sn1—C2	2.095 (2)	Sn1—N1	2.6646 (18)
Sn1—O1	2.1506 (16)	Sn1—N3	2.5107 (18)

Acknowledgements

We thank Shahid Beheshti University for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dakternieks, D., Duthie, A., Smyth, D. R., Stapleton, C. P. D. & Tiekink, E. R. T. (2003). Organometallics, 22, 4599–4603. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiekink, E. R. T. (1991). Appl. Organomet. Chem. 5, 1–23. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yin, H.-D., Wang, Q.-B. & Xue, C.-C. (2005). J. Organomet. Chem. 690, 3111–3117. Web of Science CSD CrossRef CAS Google Scholar