3-Meth­oxy­carbonyl-1-methyl­pyrazinium tetra­chlorido(pyrazine-2-carboxyl­ato-κ2N1,O)stannate(IV)

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

doi:10.1107/S1600536811001929

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m238

doi:10.1107/S1600536811001929

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3-Methoxycarbonyl-1-methylpyrazinium tetrachlorido(pyrazine-2-carboxylato-κ²N¹,O)stannate(IV)

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: seikweng@um.edu.my

(Received 8 January 2011; accepted 12 January 2011; online 22 January 2011)

In the reaction of pyrazine-2-carboxylic acid and stannic chloride in methanol, one equivalent of the carboxylic acid is methylated at the 4-amino site and is also esterified, yielding the title salt, (C₇H₉N₂O₂)[SnCl₄(C₅H₃N₂O₂)]. The Sn^IV atom in the anion is N,O-chelated by a pyrazine-2-carboxylate in a cis-SnNOCl₄ octahedral geometry.

Related literature

For related organotin structures, see: Ma et al. (2004 ).

Experimental

Crystal data

(C₇H₉N₂O₂)[SnCl₄(C₅H₃N₂O₂)]
M_r = 536.75
Monoclinic, P 2₁ /n
a = 7.0655 (2) Å
b = 26.7603 (7) Å
c = 9.5220 (2) Å
β = 94.554 (2)°
V = 1794.69 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010 ) T_min = 0.579, T_max = 0.685
8726 measured reflections
3964 independent reflections
3582 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.059
S = 1.02
3964 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: CrysAlis PRO (Agilent Technologies, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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/S1600536811001929/si2325sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001929/si2325Isup2.hkl

checkCIF report

Comment top

The direct synthesis of a potentially chelating amino-carboxylic acid with stannic tetrachloride has not been reported. Pyrazine-2-carboxylic acid yields a number of derivatives with organotin compounds; these are either synthesized by condensing the amino-carboxylic acids with an organotin oxide/hydroxide or by reacting the amino-carboxylic acids with an organotin chloride in the presence of a proton abstractor. With the latter route, the product may be an organostannate in which the pyridine-2-carboxylate chelates to the chlorine-bonded tin atom (Ma et al., 2004). In the reaction of pyrazine-2-carboxylic acid and stannic chloride in methanol, one equivalent of the carboxylic acid is methylated at the 4-amino site and is also esterified to yield the salt, [C₇H₉N₂O₂]⁺ [SnCl₄(C₅H₃N₂O₂)]^- (Scheme I, Fig. 1). The tin atom in the anion is N,O-chelated by a pyrazine-2-carboxylate in a cis-SnNOCl₄ octahedral geometry.

Related literature top

For related organotin structures, see: Ma et al. (2004).

Experimental top

Stannic chloride pentahydrate 0.35 g, 1 mmol) and pyrazine-2-carboxylic acid (0.13 g, 1 mmol) were loaded into a convection tube; the tube was filled with dry methanol and kept at 333 K. Colorless crystals were collected from the side arm after several days.

Computing details top

Data collection: CrysAlis PRO (Agilent Technologies, 2010); cell refinement: CrysAlis PRO (Agilent Technologies, 2010); data reduction: CrysAlis PRO (Agilent Technologies, 2010); 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. Thermal ellipsoid plot (Barbour, 2001) of [C₇H₉N₂O₂]⁺ [SnCl₄(C₅H₃N₂O₂)]^- at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

3-Methoxycarbonyl-1-methylpyrazinium tetrachlorido(pyrazine-2-carboxylato-κ²N¹,O)stannate(IV) top

Crystal data top

(C₇H₉N₂O₂)[SnCl₄(C₅H₃N₂O₂)]	F(000) = 1048
M_r = 536.75	D_x = 1.987 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5671 reflections
a = 7.0655 (2) Å	θ = 2.3–29.2°
b = 26.7603 (7) Å	µ = 2.05 mm⁻¹
c = 9.5220 (2) Å	T = 100 K
β = 94.554 (2)°	Prism, colorless
V = 1794.69 (8) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3964 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3582 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scans	h = −7→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)	k = −19→33
T_min = 0.579, T_max = 0.685	l = −12→11
8726 measured reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0273P)² + 1.1852P] where P = (F_o² + 2F_c²)/3
3964 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

(C₇H₉N₂O₂)[SnCl₄(C₅H₃N₂O₂)]	V = 1794.69 (8) Å³
M_r = 536.75	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0655 (2) Å	µ = 2.05 mm⁻¹
b = 26.7603 (7) Å	T = 100 K
c = 9.5220 (2) Å	0.30 × 0.25 × 0.20 mm
β = 94.554 (2)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3964 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)	3582 reflections with I > 2σ(I)
T_min = 0.579, T_max = 0.685	R_int = 0.024
8726 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.02	Δρ_max = 0.58 e Å⁻³
3964 reflections	Δρ_min = −0.71 e Å⁻³
228 parameters

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

	x	y	z	U_iso*/U_eq
Sn1	0.60924 (2)	0.655455 (6)	0.329618 (16)	0.01294 (6)
Cl1	0.37306 (8)	0.67760 (2)	0.14686 (6)	0.01817 (13)
Cl2	0.86908 (9)	0.70312 (3)	0.26342 (7)	0.02392 (15)
Cl3	0.50421 (8)	0.72003 (2)	0.48125 (6)	0.01835 (13)
Cl4	0.70745 (9)	0.58382 (2)	0.20077 (6)	0.02003 (14)
O1	0.7650 (2)	0.62593 (7)	0.50542 (17)	0.0159 (4)
O2	0.7745 (3)	0.56931 (7)	0.67716 (18)	0.0218 (4)
O3	1.1503 (3)	0.55738 (7)	1.01670 (19)	0.0237 (4)
O4	1.4080 (3)	0.57009 (8)	0.89617 (19)	0.0265 (4)
N1	0.4045 (3)	0.60323 (8)	0.4241 (2)	0.0137 (4)
N2	0.2115 (3)	0.52822 (8)	0.5541 (2)	0.0189 (5)
N3	0.8601 (3)	0.67062 (8)	0.8236 (2)	0.0157 (4)
N4	1.2150 (3)	0.64576 (8)	0.7473 (2)	0.0194 (5)
C1	0.6920 (3)	0.59043 (9)	0.5772 (2)	0.0151 (5)
C2	0.4893 (3)	0.57708 (9)	0.5319 (2)	0.0135 (5)
C3	0.3911 (4)	0.53973 (9)	0.5957 (2)	0.0167 (5)
H3	0.4537	0.5217	0.6717	0.020*
C4	0.1292 (3)	0.55520 (10)	0.4485 (3)	0.0187 (5)
H4	0.0009	0.5483	0.4172	0.022*
C5	0.2236 (3)	0.59312 (10)	0.3823 (3)	0.0170 (5)
H5	0.1597	0.6117	0.3079	0.020*
C6	1.2439 (4)	0.51458 (11)	1.0871 (3)	0.0283 (6)
H6A	1.1620	0.5007	1.1558	0.042*
H6B	1.3646	0.5253	1.1357	0.042*
H6C	1.2680	0.4890	1.0172	0.042*
C7	1.2504 (4)	0.58058 (10)	0.9240 (3)	0.0190 (5)
C8	1.1371 (3)	0.62241 (10)	0.8531 (2)	0.0161 (5)
C9	0.9594 (3)	0.63438 (10)	0.8935 (3)	0.0171 (5)
H9	0.9082	0.6173	0.9693	0.021*
C10	0.9332 (4)	0.69445 (10)	0.7175 (3)	0.0178 (5)
H10	0.8632	0.7200	0.6675	0.021*
C11	1.1126 (4)	0.68141 (10)	0.6813 (3)	0.0201 (5)
H11	1.1643	0.6987	0.6060	0.024*
C12	0.6682 (3)	0.68313 (11)	0.8634 (3)	0.0225 (6)
H12A	0.6061	0.7056	0.7928	0.034*
H12B	0.6777	0.6996	0.9556	0.034*
H12C	0.5933	0.6525	0.8684	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01198 (9)	0.01295 (10)	0.01393 (9)	−0.00115 (6)	0.00119 (6)	0.00060 (6)
Cl1	0.0190 (3)	0.0184 (3)	0.0166 (3)	0.0002 (2)	−0.0016 (2)	0.0015 (2)
Cl2	0.0176 (3)	0.0224 (4)	0.0324 (3)	−0.0056 (3)	0.0063 (3)	0.0047 (3)
Cl3	0.0208 (3)	0.0170 (3)	0.0172 (3)	0.0022 (2)	0.0015 (2)	−0.0020 (2)
Cl4	0.0217 (3)	0.0188 (3)	0.0199 (3)	0.0023 (2)	0.0029 (2)	−0.0030 (2)
O1	0.0132 (8)	0.0157 (9)	0.0180 (8)	−0.0006 (7)	−0.0036 (7)	0.0014 (7)
O2	0.0225 (9)	0.0220 (11)	0.0200 (9)	−0.0004 (8)	−0.0048 (7)	0.0033 (8)
O3	0.0239 (10)	0.0209 (11)	0.0259 (10)	0.0029 (8)	−0.0005 (8)	0.0048 (8)
O4	0.0220 (10)	0.0319 (12)	0.0253 (10)	0.0089 (8)	0.0009 (8)	−0.0018 (8)
N1	0.0120 (9)	0.0124 (11)	0.0169 (10)	−0.0008 (8)	0.0017 (8)	−0.0009 (8)
N2	0.0182 (10)	0.0157 (12)	0.0230 (11)	−0.0018 (9)	0.0030 (9)	0.0006 (9)
N3	0.0156 (10)	0.0153 (11)	0.0159 (10)	−0.0013 (8)	−0.0009 (8)	−0.0031 (8)
N4	0.0159 (10)	0.0218 (13)	0.0204 (11)	−0.0029 (9)	0.0006 (9)	−0.0014 (9)
C1	0.0188 (12)	0.0119 (13)	0.0143 (11)	0.0015 (10)	−0.0010 (10)	−0.0027 (9)
C2	0.0158 (11)	0.0114 (12)	0.0135 (11)	0.0025 (9)	0.0022 (9)	−0.0007 (9)
C3	0.0223 (12)	0.0133 (13)	0.0147 (11)	0.0003 (10)	0.0025 (10)	−0.0008 (10)
C4	0.0133 (11)	0.0186 (14)	0.0243 (13)	−0.0015 (10)	0.0021 (10)	−0.0018 (11)
C5	0.0154 (11)	0.0171 (14)	0.0183 (12)	0.0007 (10)	0.0002 (10)	0.0006 (10)
C6	0.0344 (16)	0.0207 (16)	0.0282 (14)	0.0040 (12)	−0.0068 (12)	0.0027 (12)
C7	0.0194 (13)	0.0199 (14)	0.0172 (12)	−0.0016 (11)	−0.0025 (10)	−0.0052 (10)
C8	0.0164 (12)	0.0149 (13)	0.0165 (12)	−0.0015 (10)	−0.0012 (10)	−0.0036 (9)
C9	0.0182 (12)	0.0158 (13)	0.0168 (12)	−0.0006 (10)	−0.0010 (10)	−0.0013 (10)
C10	0.0198 (12)	0.0145 (13)	0.0187 (12)	−0.0020 (10)	−0.0019 (10)	−0.0008 (10)
C11	0.0214 (13)	0.0198 (15)	0.0191 (12)	−0.0054 (11)	0.0018 (10)	−0.0004 (11)
C12	0.0147 (12)	0.0246 (16)	0.0284 (14)	0.0036 (11)	0.0037 (11)	−0.0007 (12)

Geometric parameters (Å, º) top

Sn1—O1	2.0843 (17)	N4—C8	1.340 (3)
Sn1—N1	2.2499 (19)	C1—C2	1.506 (3)
Sn1—Cl2	2.3619 (6)	C2—C3	1.384 (3)
Sn1—Cl1	2.3881 (6)	C3—H3	0.9500
Sn1—Cl3	2.4065 (6)	C4—C5	1.392 (4)
Sn1—Cl4	2.4076 (6)	C4—H4	0.9500
O1—C1	1.301 (3)	C5—H5	0.9500
O2—C1	1.215 (3)	C6—H6A	0.9800
O3—C7	1.328 (3)	C6—H6B	0.9800
O3—C6	1.459 (3)	C6—H6C	0.9800
O4—C7	1.199 (3)	C7—C8	1.504 (4)
N1—C5	1.336 (3)	C8—C9	1.380 (3)
N1—C2	1.343 (3)	C9—H9	0.9500
N2—C4	1.333 (3)	C10—C11	1.384 (4)
N2—C3	1.335 (3)	C10—H10	0.9500
N3—C10	1.333 (3)	C11—H11	0.9500
N3—C9	1.342 (3)	C12—H12A	0.9800
N3—C12	1.475 (3)	C12—H12B	0.9800
N4—C11	1.326 (3)	C12—H12C	0.9800

O1—Sn1—N1	76.03 (7)	N2—C4—C5	122.7 (2)
O1—Sn1—Cl2	92.70 (5)	N2—C4—H4	118.6
N1—Sn1—Cl2	168.60 (5)	C5—C4—H4	118.6
O1—Sn1—Cl1	166.67 (5)	N1—C5—C4	119.6 (2)
N1—Sn1—Cl1	90.65 (5)	N1—C5—H5	120.2
Cl2—Sn1—Cl1	100.63 (2)	C4—C5—H5	120.2
O1—Sn1—Cl3	87.62 (5)	O3—C6—H6A	109.5
N1—Sn1—Cl3	88.13 (5)	O3—C6—H6B	109.5
Cl2—Sn1—Cl3	93.19 (2)	H6A—C6—H6B	109.5
Cl1—Sn1—Cl3	91.61 (2)	O3—C6—H6C	109.5
O1—Sn1—Cl4	87.27 (5)	H6A—C6—H6C	109.5
N1—Sn1—Cl4	85.97 (5)	H6B—C6—H6C	109.5
Cl2—Sn1—Cl4	91.86 (2)	O4—C7—O3	126.2 (3)
Cl1—Sn1—Cl4	92.25 (2)	O4—C7—C8	123.1 (2)
Cl3—Sn1—Cl4	172.98 (2)	O3—C7—C8	110.7 (2)
C1—O1—Sn1	119.54 (15)	N4—C8—C9	122.6 (2)
C7—O3—C6	115.3 (2)	N4—C8—C7	116.6 (2)
C5—N1—C2	118.7 (2)	C9—C8—C7	120.8 (2)
C5—N1—Sn1	129.58 (17)	N3—C9—C8	118.7 (2)
C2—N1—Sn1	111.54 (15)	N3—C9—H9	120.6
C4—N2—C3	116.5 (2)	C8—C9—H9	120.6
C10—N3—C9	120.2 (2)	N3—C10—C11	119.1 (2)
C10—N3—C12	120.4 (2)	N3—C10—H10	120.5
C9—N3—C12	119.4 (2)	C11—C10—H10	120.5
C11—N4—C8	116.8 (2)	N4—C11—C10	122.6 (2)
O2—C1—O1	124.5 (2)	N4—C11—H11	118.7
O2—C1—C2	120.0 (2)	C10—C11—H11	118.7
O1—C1—C2	115.5 (2)	N3—C12—H12A	109.5
N1—C2—C3	120.2 (2)	N3—C12—H12B	109.5
N1—C2—C1	116.9 (2)	H12A—C12—H12B	109.5
C3—C2—C1	122.9 (2)	N3—C12—H12C	109.5
N2—C3—C2	122.3 (2)	H12A—C12—H12C	109.5
N2—C3—H3	118.9	H12B—C12—H12C	109.5
C2—C3—H3	118.9

N1—Sn1—O1—C1	6.32 (17)	O1—C1—C2—C3	179.1 (2)
Cl2—Sn1—O1—C1	−171.93 (17)	C4—N2—C3—C2	−1.1 (4)
Cl1—Sn1—O1—C1	8.0 (3)	N1—C2—C3—N2	0.0 (4)
Cl3—Sn1—O1—C1	94.98 (17)	C1—C2—C3—N2	−179.8 (2)
Cl4—Sn1—O1—C1	−80.20 (17)	C3—N2—C4—C5	0.8 (4)
O1—Sn1—N1—C5	178.9 (2)	C2—N1—C5—C4	−1.6 (4)
Cl2—Sn1—N1—C5	−172.28 (19)	Sn1—N1—C5—C4	173.07 (17)
Cl1—Sn1—N1—C5	−0.7 (2)	N2—C4—C5—N1	0.5 (4)
Cl3—Sn1—N1—C5	90.9 (2)	C6—O3—C7—O4	−1.4 (4)
Cl4—Sn1—N1—C5	−92.9 (2)	C6—O3—C7—C8	177.4 (2)
O1—Sn1—N1—C2	−6.18 (15)	C11—N4—C8—C9	−0.2 (4)
Cl2—Sn1—N1—C2	2.7 (4)	C11—N4—C8—C7	177.6 (2)
Cl1—Sn1—N1—C2	174.22 (15)	O4—C7—C8—N4	5.1 (4)
Cl3—Sn1—N1—C2	−94.20 (15)	O3—C7—C8—N4	−173.7 (2)
Cl4—Sn1—N1—C2	82.01 (15)	O4—C7—C8—C9	−177.1 (2)
Sn1—O1—C1—O2	176.53 (19)	O3—C7—C8—C9	4.1 (3)
Sn1—O1—C1—C2	−5.3 (3)	C10—N3—C9—C8	−0.1 (4)
C5—N1—C2—C3	1.4 (3)	C12—N3—C9—C8	178.7 (2)
Sn1—N1—C2—C3	−174.21 (18)	N4—C8—C9—N3	0.4 (4)
C5—N1—C2—C1	−178.8 (2)	C7—C8—C9—N3	−177.3 (2)
Sn1—N1—C2—C1	5.6 (3)	C9—N3—C10—C11	−0.3 (4)
O2—C1—C2—N1	177.5 (2)	C12—N3—C10—C11	−179.1 (2)
O1—C1—C2—N1	−0.7 (3)	C8—N4—C11—C10	−0.2 (4)
O2—C1—C2—C3	−2.7 (4)	N3—C10—C11—N4	0.5 (4)

Experimental details

Crystal data
Chemical formula	(C₇H₉N₂O₂)[SnCl₄(C₅H₃N₂O₂)]
M_r	536.75
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.0655 (2), 26.7603 (7), 9.5220 (2)
β (°)	94.554 (2)
V (Å³)	1794.69 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.05
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent Technologies, 2010)
T_min, T_max	0.579, 0.685
No. of measured, independent and observed [I > 2σ(I)] reflections	8726, 3964, 3582
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.059, 1.02
No. of reflections	3964
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.71

Computer programs: CrysAlis PRO (Agilent Technologies, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Shahid Beheshti University and the University of Malaya for supporting this study.

References

Agilent Technologies (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
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