Triethyl­ammonium tetra­chlorido(pyrazine-2-carboxyl­ato-κ2N1,O)stannate(IV)

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

doi:10.1107/S1600536811016473

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m711

doi:10.1107/S1600536811016473

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Triethylammonium 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 26 April 2011; accepted 2 May 2011; online 7 May 2011)

The Sn^IV atom in the title ammonium stannate, (Et₃NH)[Sn(C₅H₃N₂O₂)Cl₄], is chelated by an pyrazine-2-carboxylate ligand and exists in a cis-SnCl₄NO octahedral geometry. The cation and the anion are linked by an N—H⋯N hydrogen bond.

Related literature

For triethylammonium tetrachlorido(pyridine-2-carboxylato)stannate(IV), see: Najafi et al. (2011 ).

Experimental

Crystal data

(C₆H₁₆N)[Sn(C₅H₃N₂O₂)Cl₄]
M_r = 485.78
Triclinic, $[P \overline 1]$
a = 7.4497 (2) Å
b = 9.9752 (3) Å
c = 12.3728 (4) Å
α = 86.491 (2)°
β = 80.125 (3)°
γ = 83.817 (2)°
V = 899.70 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 100 K
0.35 × 0.30 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.538, T_max = 0.632
15321 measured reflections
4094 independent reflections
3800 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.052
S = 1.02
4094 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯N2	0.91 (3)	2.10 (3)	2.999 (2)	167 (2)

Data collection: CrysAlis PRO (Agilent, 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/S1600536811016473/qk2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016473/qk2007Isup2.hkl

checkCIF report

Comment top

We have recently reported the crystal structure of triethylammonium tetrachlorido(pyridine-2-carboxylato)stannate, which was synthesized by the reaction of triethylammonium pyridine-2-carboxylate and stannic chloride. The Sn^IV atom in the anion is N,O-chelated by the pyridine-2-carboxylate in a cis-SnCl₄NO octahedral geometry (Najafi et al., 2011). In our previous studies, we have reacted aromatic carboxylic acid with stannic chloride, with/without a proton-abstraction agent. In the present study, replacing pyrdine-2-carboxylic acid by pyrazine-2-carboxylic acid affords a similar salt, (Et₃NH)⁺ [SnCl₄(C₅H₃N₂O₂)]^- (Scheme I, Fig. 1). The tin atom in the stannate is chelated by the pyrazine-2-carboxylate group in a cis-SnCl₄NO octahedral geometry. The cation forms an N–H···N hydrogen bond with the anion. Of the four Sn–Cl bonds, the ones that are trans to the Sn–O/Sn–N bonds are somewhat shorter than the other two. No Cl···Cl interactions are present.

Related literature top

For triethylammonium tetrachlorido(pyridine-2-carboxylato)stannate, see: Najafi et al. (2011).

Experimental top

The reaction was carried out under a nitrogen atmosphere. Pyrazine-2-carboxylic acid (1.0 mmol, 0.12 g) and the triethylamine (1.0 mmol, 0.10 g) were dissolved in dry methanol (20 ml). Stannic chloride (1.0 mmol, 0.35 g) was added to the mixture and stirred for 12 h. Suitable crystals were obtained by slow evaporation of the solvent.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 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 (Et₃NH)⁺ [SnCl₄(C₅H₃N₂O₂)]^- at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The hydrogen bond is denoted by a dashed bond.

Triethylammonium tetrachlorido(pyrazine-2-carboxylato-κ²N¹,O)stannate(IV) top

Crystal data top

(C₆H₁₆N)[Sn(C₅H₃N₂O₂)Cl₄]	Z = 2
M_r = 485.78	F(000) = 480
Triclinic, P1	D_x = 1.793 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4497 (2) Å	Cell parameters from 10335 reflections
b = 9.9752 (3) Å	θ = 2.6–29.2°
c = 12.3728 (4) Å	µ = 2.02 mm⁻¹
α = 86.491 (2)°	T = 100 K
β = 80.125 (3)°	Irregular block, colorless
γ = 83.817 (2)°	0.35 × 0.30 × 0.25 mm
V = 899.70 (5) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4094 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3800 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −12→12
T_min = 0.538, T_max = 0.632	l = −15→16
15321 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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0257P)² + 0.2896P] where P = (F_o² + 2F_c²)/3
4094 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

(C₆H₁₆N)[Sn(C₅H₃N₂O₂)Cl₄]	γ = 83.817 (2)°
M_r = 485.78	V = 899.70 (5) Å³
Triclinic, P1	Z = 2
a = 7.4497 (2) Å	Mo Kα radiation
b = 9.9752 (3) Å	µ = 2.02 mm⁻¹
c = 12.3728 (4) Å	T = 100 K
α = 86.491 (2)°	0.35 × 0.30 × 0.25 mm
β = 80.125 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	4094 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	3800 reflections with I > 2σ(I)
T_min = 0.538, T_max = 0.632	R_int = 0.030
15321 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.35 e Å⁻³
4094 reflections	Δρ_min = −0.65 e Å⁻³
194 parameters

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

	x	y	z	U_iso*/U_eq
Sn1	0.310753 (18)	0.248889 (13)	0.740250 (10)	0.01198 (5)
Cl1	0.46068 (7)	0.34171 (5)	0.86858 (4)	0.01988 (11)
Cl2	0.00680 (7)	0.26586 (5)	0.83792 (4)	0.01703 (11)
Cl3	0.39067 (7)	0.02423 (5)	0.80641 (4)	0.01605 (11)
Cl4	0.26028 (7)	0.46373 (5)	0.64356 (4)	0.02064 (11)
O1	0.22917 (19)	0.16094 (14)	0.60971 (11)	0.0149 (3)
O2	0.3047 (2)	0.10363 (15)	0.43513 (11)	0.0194 (3)
N1	0.5661 (2)	0.22659 (16)	0.61249 (13)	0.0128 (3)
N2	0.8334 (2)	0.21721 (17)	0.42643 (14)	0.0171 (4)
N3	1.0881 (2)	0.24246 (17)	0.21208 (14)	0.0142 (3)
C1	0.3419 (3)	0.14663 (19)	0.51771 (16)	0.0134 (4)
C2	0.5317 (3)	0.18609 (19)	0.51747 (16)	0.0128 (4)
C3	0.6667 (3)	0.18070 (19)	0.42525 (16)	0.0155 (4)
H3A	0.6397	0.1501	0.3592	0.019*
C4	0.8662 (3)	0.2544 (2)	0.52239 (17)	0.0179 (4)
H4A	0.9846	0.2789	0.5264	0.021*
C5	0.7345 (3)	0.2587 (2)	0.61660 (17)	0.0168 (4)
H5A	0.7638	0.2844	0.6837	0.020*
C6	0.9980 (3)	0.3321 (2)	0.13009 (16)	0.0161 (4)
H6A	1.0734	0.3221	0.0564	0.019*
H6B	0.9943	0.4272	0.1495	0.019*
C7	0.8062 (3)	0.3011 (2)	0.12490 (18)	0.0201 (5)
H7A	0.7565	0.3610	0.0691	0.030*
H7B	0.7288	0.3151	0.1966	0.030*
H7C	0.8084	0.2070	0.1057	0.030*
C8	1.2722 (3)	0.2874 (2)	0.22036 (17)	0.0173 (4)
H8A	1.3358	0.3118	0.1459	0.021*
H8B	1.3477	0.2116	0.2511	0.021*
C9	1.2544 (3)	0.4075 (2)	0.29232 (19)	0.0220 (5)
H9A	1.3763	0.4344	0.2947	0.033*
H9B	1.1952	0.3827	0.3668	0.033*
H9C	1.1801	0.4829	0.2620	0.033*
C10	1.1019 (3)	0.0937 (2)	0.19176 (16)	0.0168 (4)
H10A	1.1673	0.0429	0.2470	0.020*
H10B	0.9769	0.0646	0.2021	0.020*
C11	1.2003 (3)	0.0582 (2)	0.07822 (17)	0.0189 (4)
H11A	1.2039	−0.0392	0.0701	0.028*
H11B	1.3255	0.0840	0.0681	0.028*
H11C	1.1352	0.1067	0.0230	0.028*
H1	1.015 (3)	0.249 (2)	0.279 (2)	0.027 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01291 (8)	0.01297 (8)	0.00947 (8)	0.00012 (5)	−0.00092 (5)	−0.00091 (5)
Cl1	0.0232 (3)	0.0225 (3)	0.0154 (2)	−0.0057 (2)	−0.0037 (2)	−0.0045 (2)
Cl2	0.0141 (2)	0.0218 (3)	0.0137 (2)	0.00087 (19)	0.00009 (19)	−0.00038 (19)
Cl3	0.0189 (3)	0.0141 (2)	0.0142 (2)	0.00126 (19)	−0.00218 (19)	0.00034 (18)
Cl4	0.0249 (3)	0.0158 (2)	0.0181 (2)	0.0031 (2)	0.0002 (2)	0.00323 (19)
O1	0.0143 (7)	0.0201 (7)	0.0107 (7)	−0.0020 (6)	−0.0023 (6)	−0.0023 (6)
O2	0.0241 (8)	0.0229 (8)	0.0123 (7)	−0.0054 (6)	−0.0030 (6)	−0.0027 (6)
N1	0.0154 (9)	0.0120 (8)	0.0104 (8)	0.0013 (7)	−0.0017 (7)	−0.0008 (6)
N2	0.0182 (9)	0.0166 (9)	0.0150 (9)	0.0021 (7)	−0.0011 (7)	0.0008 (7)
N3	0.0151 (9)	0.0164 (9)	0.0103 (8)	−0.0020 (7)	0.0002 (7)	−0.0004 (7)
C1	0.0183 (10)	0.0092 (9)	0.0121 (9)	0.0000 (8)	−0.0028 (8)	0.0015 (7)
C2	0.0167 (10)	0.0088 (9)	0.0116 (9)	0.0016 (7)	−0.0011 (8)	0.0006 (7)
C3	0.0201 (11)	0.0130 (10)	0.0126 (10)	0.0001 (8)	−0.0023 (8)	0.0004 (8)
C4	0.0133 (10)	0.0222 (11)	0.0180 (10)	−0.0011 (8)	−0.0038 (8)	0.0028 (8)
C5	0.0157 (10)	0.0189 (10)	0.0161 (10)	−0.0010 (8)	−0.0040 (8)	−0.0005 (8)
C6	0.0195 (11)	0.0144 (10)	0.0139 (10)	0.0010 (8)	−0.0035 (8)	0.0002 (8)
C7	0.0199 (11)	0.0211 (11)	0.0190 (10)	0.0015 (9)	−0.0046 (9)	−0.0012 (9)
C8	0.0140 (10)	0.0213 (11)	0.0164 (10)	−0.0028 (8)	−0.0017 (8)	0.0005 (8)
C9	0.0199 (11)	0.0191 (11)	0.0283 (12)	−0.0030 (9)	−0.0062 (10)	−0.0019 (9)
C10	0.0207 (11)	0.0135 (10)	0.0158 (10)	−0.0022 (8)	−0.0022 (9)	0.0009 (8)
C11	0.0215 (11)	0.0176 (11)	0.0169 (10)	0.0008 (9)	−0.0018 (9)	−0.0031 (8)

Geometric parameters (Å, º) top

Sn1—O1	2.0911 (13)	C4—H4A	0.9500
Sn1—N1	2.2558 (16)	C5—H5A	0.9500
Sn1—Cl2	2.3707 (5)	C6—C7	1.507 (3)
Sn1—Cl1	2.3742 (5)	C6—H6A	0.9900
Sn1—Cl3	2.3879 (5)	C6—H6B	0.9900
Sn1—Cl4	2.4150 (5)	C7—H7A	0.9800
O1—C1	1.299 (2)	C7—H7B	0.9800
O2—C1	1.217 (2)	C7—H7C	0.9800
N1—C5	1.337 (3)	C8—C9	1.517 (3)
N1—C2	1.340 (2)	C8—H8A	0.9900
N2—C3	1.334 (3)	C8—H8B	0.9900
N2—C4	1.334 (3)	C9—H9A	0.9800
N3—C6	1.508 (3)	C9—H9B	0.9800
N3—C8	1.509 (3)	C9—H9C	0.9800
N3—C10	1.510 (3)	C10—C11	1.513 (3)
N3—H1	0.91 (3)	C10—H10A	0.9900
C1—C2	1.508 (3)	C10—H10B	0.9900
C2—C3	1.385 (3)	C11—H11A	0.9800
C3—H3A	0.9500	C11—H11B	0.9800
C4—C5	1.389 (3)	C11—H11C	0.9800

O1—Sn1—N1	75.62 (6)	N1—C5—H5A	120.1
O1—Sn1—Cl2	91.17 (4)	C4—C5—H5A	120.1
N1—Sn1—Cl2	166.13 (4)	C7—C6—N3	113.48 (17)
O1—Sn1—Cl1	168.99 (4)	C7—C6—H6A	108.9
N1—Sn1—Cl1	93.47 (4)	N3—C6—H6A	108.9
Cl2—Sn1—Cl1	99.813 (18)	C7—C6—H6B	108.9
O1—Sn1—Cl3	86.56 (4)	N3—C6—H6B	108.9
N1—Sn1—Cl3	88.14 (4)	H6A—C6—H6B	107.7
Cl2—Sn1—Cl3	95.397 (18)	C6—C7—H7A	109.5
Cl1—Sn1—Cl3	91.748 (18)	C6—C7—H7B	109.5
O1—Sn1—Cl4	87.08 (4)	H7A—C7—H7B	109.5
N1—Sn1—Cl4	82.96 (4)	C6—C7—H7C	109.5
Cl2—Sn1—Cl4	92.285 (18)	H7A—C7—H7C	109.5
Cl1—Sn1—Cl4	93.058 (19)	H7B—C7—H7C	109.5
Cl3—Sn1—Cl4	170.120 (17)	N3—C8—C9	111.95 (17)
C1—O1—Sn1	119.66 (12)	N3—C8—H8A	109.2
C5—N1—C2	118.45 (17)	C9—C8—H8A	109.2
C5—N1—Sn1	129.40 (13)	N3—C8—H8B	109.2
C2—N1—Sn1	111.85 (13)	C9—C8—H8B	109.2
C3—N2—C4	116.56 (18)	H8A—C8—H8B	107.9
C6—N3—C8	110.51 (15)	C8—C9—H9A	109.5
C6—N3—C10	114.20 (15)	C8—C9—H9B	109.5
C8—N3—C10	111.59 (16)	H9A—C9—H9B	109.5
C6—N3—H1	108.5 (15)	C8—C9—H9C	109.5
C8—N3—H1	108.8 (15)	H9A—C9—H9C	109.5
C10—N3—H1	102.8 (15)	H9B—C9—H9C	109.5
O2—C1—O1	124.81 (19)	N3—C10—C11	113.47 (16)
O2—C1—C2	119.63 (17)	N3—C10—H10A	108.9
O1—C1—C2	115.56 (16)	C11—C10—H10A	108.9
N1—C2—C3	120.55 (18)	N3—C10—H10B	108.9
N1—C2—C1	116.58 (17)	C11—C10—H10B	108.9
C3—C2—C1	122.87 (17)	H10A—C10—H10B	107.7
N2—C3—C2	121.97 (18)	C10—C11—H11A	109.5
N2—C3—H3A	119.0	C10—C11—H11B	109.5
C2—C3—H3A	119.0	H11A—C11—H11B	109.5
N2—C4—C5	122.67 (19)	C10—C11—H11C	109.5
N2—C4—H4A	118.7	H11A—C11—H11C	109.5
C5—C4—H4A	118.7	H11B—C11—H11C	109.5
N1—C5—C4	119.72 (18)

N1—Sn1—O1—C1	−6.70 (13)	C5—N1—C2—C1	178.09 (16)
Cl2—Sn1—O1—C1	169.01 (13)	Sn1—N1—C2—C1	−7.6 (2)
Cl1—Sn1—O1—C1	−14.2 (3)	O2—C1—C2—N1	−176.95 (18)
Cl3—Sn1—O1—C1	−95.65 (13)	O1—C1—C2—N1	2.4 (3)
Cl4—Sn1—O1—C1	76.78 (13)	O2—C1—C2—C3	2.6 (3)
O1—Sn1—N1—C5	−178.97 (18)	O1—C1—C2—C3	−178.07 (18)
Cl2—Sn1—N1—C5	162.83 (14)	C4—N2—C3—C2	2.5 (3)
Cl1—Sn1—N1—C5	−0.41 (17)	N1—C2—C3—N2	−1.1 (3)
Cl3—Sn1—N1—C5	−92.05 (17)	C1—C2—C3—N2	179.39 (18)
Cl4—Sn1—N1—C5	92.25 (17)	C3—N2—C4—C5	−1.5 (3)
O1—Sn1—N1—C2	7.47 (12)	C2—N1—C5—C4	2.4 (3)
Cl2—Sn1—N1—C2	−10.7 (3)	Sn1—N1—C5—C4	−170.79 (14)
Cl1—Sn1—N1—C2	−173.97 (12)	N2—C4—C5—N1	−1.0 (3)
Cl3—Sn1—N1—C2	94.39 (13)	C8—N3—C6—C7	−174.78 (16)
Cl4—Sn1—N1—C2	−81.31 (12)	C10—N3—C6—C7	58.4 (2)
Sn1—O1—C1—O2	−175.82 (15)	C6—N3—C8—C9	79.8 (2)
Sn1—O1—C1—C2	4.8 (2)	C10—N3—C8—C9	−151.96 (17)
C5—N1—C2—C3	−1.4 (3)	C6—N3—C10—C11	56.1 (2)
Sn1—N1—C2—C3	172.92 (15)	C8—N3—C10—C11	−70.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N2	0.91 (3)	2.10 (3)	2.999 (2)	167 (2)

Experimental details

Crystal data
Chemical formula	(C₆H₁₆N)[Sn(C₅H₃N₂O₂)Cl₄]
M_r	485.78
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.4497 (2), 9.9752 (3), 12.3728 (4)
α, β, γ (°)	86.491 (2), 80.125 (3), 83.817 (2)
V (Å³)	899.70 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.02
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.538, 0.632
No. of measured, independent and observed [I > 2σ(I)] reflections	15321, 4094, 3800
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.052, 1.02
No. of reflections	4094
No. of parameters	194
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.65

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N2	0.91 (3)	2.10 (3)	2.999 (2)	167 (2)

Acknowledgements

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

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