4-(Dimethyl­amino)­pyridinium tetra­chlorido(pyridine-2-carboxyl­ato-κ² N,O)stannate(IV)

Abstract

The reaction of 4-(dimethyl­amino)­pyridine, picolinic acid and stannic chloride yields the title salt, (C₇H₁₁N₂)[SnCl₄(C₆H₄NO₂)], in which the Sn^IV atom is N,O-chelated by the picolinate ion in a cis-SnNOCl₄ octa­hedral geometry. The cation is linked to the anion by an N—H⋯O hydrogen bond.

Related literature  

For 4-(dimethyl­amino)­pyridinium tetra­chlorido(quinoline-2-carboxyl­ato)stannate, see: Najafi et al. (2011 ▶).

Experimental  

Crystal data  

• (C₇H₁₁N₂)[SnCl₄(C₆H₄NO₂)]

• M _r = 505.77

• Triclinic,

• a = 7.6658 (2) Å

• b = 9.8948 (4) Å

• c = 13.5722 (6) Å

• α = 69.485 (4)°

• β = 83.159 (3)°

• γ = 67.900 (3)°

• V = 893.25 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 2.04 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, 2012 ▶) T _min = 0.580, T _max = 0.686

• 12966 measured reflections

• 4109 independent reflections

• 3744 reflections with I > 2σ(I)

• R _int = 0.029

Refinement  

• R[F ² > 2σ(F ²)] = 0.020

• wR(F ²) = 0.049

• S = 1.02

• 4109 reflections

• 214 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.61 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); 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 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.87 (1)	1.93 (1)	2.802 (2)	176 (2)

supplementary crystallographic information

Comment

A previous study reported 4-(dimethylamino)pyridinium tetrachlorido(quinoline-2-carboxylato)stannate, which was synthesized by the reaction of 4-(dimethylamino)pyridine, quinoline-2-carboxylic acid and stannic chloride in methanol (Najafi et al., 2011). The reaction with picolinic acid in place of quinoline-2-carboxylic acid yielded the analogous salt, (C₇H₁₁N₂)[SnCl₄(C₆H₄NO₂)] (Scheme I). The Sn^IV atom is N,O-chelated by the picolinate ion in a cis-SnNOCl₄ octahedral geometry (Fig. 1). The cation is linked to the anion by an N–H···O hydrogen bond (Table 1).

Experimental

Stannic chloride pentahydrate (0.35 g, 1 mmol), picolinic acid (0.12 g, 1 mmol) and 4-(dimethylamino)pyridine (0.12 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.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 0.98 Å, U_iso(H) 1.2 to 1.5U_eq(C)] and were included in the refinement in the riding model approximation.

The pyridinium H-atom was located in a difference Fourier map, and was refined isotropically with a distance restraint of N–H 0.88±0.01 Å.

Figures

Fig. 1.

Anisotropic displacement ellipsoid plot (Barbour, 2001) of (C7H11N2)[SnCl4(C6H4NO2)] at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

(C7H11N2)[SnCl4(C6H4NO2)]	Z = 2
Mr = 505.77	F(000) = 496
Triclinic, P1	Dx = 1.880 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6658 (2) Å	Cell parameters from 8614 reflections
b = 9.8948 (4) Å	θ = 2.4–27.5°
c = 13.5722 (6) Å	µ = 2.04 mm−1
α = 69.485 (4)°	T = 100 K
β = 83.159 (3)°	Prism, colorless
γ = 67.900 (3)°	0.30 × 0.25 × 0.20 mm
V = 893.25 (6) Å3

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	4109 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3744 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.4°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −12→12
Tmin = 0.580, Tmax = 0.686	l = −17→17
12966 measured reflections

Refinement

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) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0217P)2 + 0.1127P] where P = (Fo2 + 2Fc2)/3
4109 reflections	(Δ/σ)max = 0.002
214 parameters	Δρmax = 0.61 e Å−3
1 restraint	Δρmin = −0.41 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.471694 (16)	0.931155 (14)	0.787934 (10)	0.01225 (5)
Cl1	0.41910 (7)	1.16043 (5)	0.82535 (4)	0.01887 (11)
Cl2	0.63070 (7)	0.97801 (6)	0.62519 (4)	0.01884 (11)
Cl3	0.76267 (6)	0.79583 (6)	0.88640 (4)	0.01957 (11)
Cl4	0.16639 (6)	1.04910 (5)	0.70014 (4)	0.01687 (10)
O1	0.48413 (18)	0.72139 (15)	0.77597 (11)	0.0164 (3)
O2	0.3917 (2)	0.51987 (16)	0.84279 (12)	0.0231 (3)
N1	0.3269 (2)	0.83176 (18)	0.93069 (12)	0.0137 (3)
N2	0.6230 (2)	0.5870 (2)	0.61853 (14)	0.0184 (4)
H2	0.574 (3)	0.630 (3)	0.6665 (15)	0.038 (7)*
N3	0.8688 (2)	0.35910 (18)	0.40725 (13)	0.0153 (3)
C1	0.3977 (3)	0.6389 (2)	0.84580 (16)	0.0159 (4)
C2	0.3057 (3)	0.7014 (2)	0.93305 (15)	0.0155 (4)
C3	0.2055 (3)	0.6298 (2)	1.01141 (17)	0.0217 (5)
H3	0.1910	0.5382	1.0122	0.026*
C4	0.1268 (3)	0.6952 (3)	1.08887 (17)	0.0270 (5)
H4	0.0545	0.6500	1.1428	0.032*
C5	0.1535 (3)	0.8254 (3)	1.08742 (16)	0.0235 (5)
H5	0.1024	0.8694	1.1412	0.028*
C6	0.2552 (3)	0.8922 (2)	1.00731 (15)	0.0178 (4)
H6	0.2744	0.9819	1.0066	0.021*
C7	0.6389 (3)	0.4385 (2)	0.64189 (16)	0.0176 (4)
H7	0.5927	0.3883	0.7070	0.021*
C8	0.7198 (2)	0.3592 (2)	0.57414 (15)	0.0153 (4)
H8	0.7304	0.2546	0.5922	0.018*
C9	0.7888 (2)	0.4335 (2)	0.47584 (15)	0.0137 (4)
C10	0.7676 (3)	0.5896 (2)	0.45468 (16)	0.0159 (4)
H10	0.8102	0.6444	0.3900	0.019*
C11	0.6865 (3)	0.6614 (2)	0.52659 (17)	0.0183 (4)
H11	0.6745	0.7657	0.5117	0.022*
C12	0.8845 (3)	0.1993 (2)	0.42939 (17)	0.0213 (5)
H12A	0.9601	0.1329	0.4937	0.032*
H12B	0.9454	0.1647	0.3704	0.032*
H12C	0.7585	0.1933	0.4390	0.032*
C13	0.9392 (3)	0.4362 (2)	0.30663 (16)	0.0201 (4)
H13A	1.0157	0.4893	0.3186	0.030*
H13B	0.8327	0.5118	0.2599	0.030*
H13C	1.0164	0.3592	0.2741	0.030*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Sn1	0.01423 (8)	0.01017 (8)	0.01266 (8)	−0.00471 (5)	0.00094 (5)	−0.00403 (5)
Cl1	0.0237 (2)	0.0125 (2)	0.0218 (3)	−0.00547 (19)	−0.00284 (19)	−0.0074 (2)
Cl2	0.0212 (2)	0.0168 (2)	0.0171 (3)	−0.00816 (19)	0.00602 (18)	−0.00436 (19)
Cl3	0.0165 (2)	0.0175 (2)	0.0221 (3)	−0.00282 (19)	−0.00390 (18)	−0.0058 (2)
Cl4	0.0166 (2)	0.0169 (2)	0.0167 (2)	−0.00586 (19)	−0.00196 (17)	−0.00459 (19)
O1	0.0222 (7)	0.0122 (7)	0.0173 (7)	−0.0088 (6)	0.0041 (5)	−0.0062 (6)
O2	0.0294 (8)	0.0166 (8)	0.0270 (9)	−0.0130 (6)	0.0004 (6)	−0.0063 (6)
N1	0.0137 (8)	0.0129 (8)	0.0121 (8)	−0.0034 (6)	−0.0013 (6)	−0.0025 (7)
N2	0.0170 (8)	0.0200 (9)	0.0193 (9)	−0.0035 (7)	−0.0013 (7)	−0.0105 (8)
N3	0.0178 (8)	0.0118 (8)	0.0167 (9)	−0.0054 (7)	0.0020 (6)	−0.0054 (7)
C1	0.0149 (9)	0.0134 (10)	0.0178 (10)	−0.0052 (8)	−0.0041 (7)	−0.0019 (8)
C2	0.0136 (9)	0.0131 (10)	0.0156 (10)	−0.0032 (8)	−0.0040 (7)	−0.0001 (8)
C3	0.0189 (10)	0.0203 (11)	0.0214 (11)	−0.0093 (8)	−0.0026 (8)	0.0020 (9)
C4	0.0186 (10)	0.0331 (13)	0.0181 (12)	−0.0088 (9)	0.0027 (8)	0.0032 (10)
C5	0.0190 (10)	0.0286 (12)	0.0143 (11)	−0.0009 (9)	−0.0011 (8)	−0.0050 (9)
C6	0.0168 (10)	0.0197 (11)	0.0133 (10)	−0.0028 (8)	−0.0017 (7)	−0.0047 (8)
C7	0.0144 (9)	0.0201 (11)	0.0168 (10)	−0.0071 (8)	−0.0009 (7)	−0.0031 (8)
C8	0.0138 (9)	0.0125 (10)	0.0177 (10)	−0.0052 (8)	−0.0010 (7)	−0.0018 (8)
C9	0.0105 (9)	0.0130 (10)	0.0165 (10)	−0.0035 (7)	−0.0027 (7)	−0.0036 (8)
C10	0.0174 (9)	0.0120 (10)	0.0179 (10)	−0.0060 (8)	−0.0029 (7)	−0.0027 (8)
C11	0.0177 (10)	0.0120 (10)	0.0244 (11)	−0.0036 (8)	−0.0062 (8)	−0.0048 (8)
C12	0.0227 (10)	0.0138 (10)	0.0289 (12)	−0.0058 (8)	0.0011 (9)	−0.0099 (9)
C13	0.0208 (10)	0.0208 (11)	0.0170 (11)	−0.0067 (9)	0.0030 (8)	−0.0059 (9)

Geometric parameters (Å, º)

Sn1—O1	2.1041 (13)	C4—C5	1.372 (3)
Sn1—N1	2.2194 (16)	C4—H4	0.9500
Sn1—Cl1	2.3743 (5)	C5—C6	1.381 (3)
Sn1—Cl2	2.3761 (5)	C5—H5	0.9500
Sn1—Cl3	2.4006 (5)	C6—H6	0.9500
Sn1—Cl4	2.4277 (5)	C7—C8	1.359 (3)
O1—C1	1.311 (2)	C7—H7	0.9500
O2—C1	1.210 (2)	C8—C9	1.427 (3)
N1—C6	1.339 (2)	C8—H8	0.9500
N1—C2	1.348 (3)	C9—C10	1.416 (3)
N2—C11	1.348 (3)	C10—C11	1.361 (3)
N2—C7	1.350 (3)	C10—H10	0.9500
N2—H2	0.874 (10)	C11—H11	0.9500
N3—C9	1.338 (2)	C12—H12A	0.9800
N3—C12	1.462 (3)	C12—H12B	0.9800
N3—C13	1.464 (2)	C12—H12C	0.9800
C1—C2	1.506 (3)	C13—H13A	0.9800
C2—C3	1.382 (3)	C13—H13B	0.9800
C3—C4	1.386 (3)	C13—H13C	0.9800
C3—H3	0.9500
O1—Sn1—N1	75.84 (6)	C5—C4—H4	120.1
O1—Sn1—Cl1	169.89 (4)	C3—C4—H4	120.1
N1—Sn1—Cl1	94.27 (4)	C4—C5—C6	119.6 (2)
O1—Sn1—Cl2	88.75 (4)	C4—C5—H5	120.2
N1—Sn1—Cl2	164.57 (4)	C6—C5—H5	120.2
Cl1—Sn1—Cl2	101.090 (18)	N1—C6—C5	120.7 (2)
O1—Sn1—Cl3	89.31 (4)	N1—C6—H6	119.6
N1—Sn1—Cl3	88.57 (4)	C5—C6—H6	119.6
Cl1—Sn1—Cl3	92.581 (18)	N2—C7—C8	121.32 (19)
Cl2—Sn1—Cl3	92.190 (18)	N2—C7—H7	119.3
O1—Sn1—Cl4	87.20 (4)	C8—C7—H7	119.3
N1—Sn1—Cl4	86.38 (4)	C7—C8—C9	119.91 (19)
Cl1—Sn1—Cl4	90.124 (17)	C7—C8—H8	120.0
Cl2—Sn1—Cl4	92.055 (17)	C9—C8—H8	120.0
Cl3—Sn1—Cl4	174.439 (17)	N3—C9—C10	121.88 (18)
C1—O1—Sn1	119.22 (12)	N3—C9—C8	121.49 (18)
C6—N1—C2	120.02 (17)	C10—C9—C8	116.63 (18)
C6—N1—Sn1	126.65 (14)	C11—C10—C9	120.29 (19)
C2—N1—Sn1	113.24 (12)	C11—C10—H10	119.9
C11—N2—C7	120.66 (18)	C9—C10—H10	119.9
C11—N2—H2	122.3 (18)	N2—C11—C10	121.18 (19)
C7—N2—H2	117.0 (18)	N2—C11—H11	119.4
C9—N3—C12	120.98 (17)	C10—C11—H11	119.4
C9—N3—C13	121.09 (17)	N3—C12—H12A	109.5
C12—N3—C13	117.91 (16)	N3—C12—H12B	109.5
O2—C1—O1	123.64 (18)	H12A—C12—H12B	109.5
O2—C1—C2	121.19 (18)	N3—C12—H12C	109.5
O1—C1—C2	115.16 (17)	H12A—C12—H12C	109.5
N1—C2—C3	121.61 (19)	H12B—C12—H12C	109.5
N1—C2—C1	116.16 (17)	N3—C13—H13A	109.5
C3—C2—C1	122.22 (19)	N3—C13—H13B	109.5
C2—C3—C4	118.2 (2)	H13A—C13—H13B	109.5
C2—C3—H3	120.9	N3—C13—H13C	109.5
C4—C3—H3	120.9	H13A—C13—H13C	109.5
C5—C4—C3	119.8 (2)	H13B—C13—H13C	109.5
N1—Sn1—O1—C1	4.83 (13)	O1—C1—C2—N1	−1.6 (2)
Cl1—Sn1—O1—C1	−7.3 (3)	O2—C1—C2—C3	−2.2 (3)
Cl2—Sn1—O1—C1	−174.26 (13)	O1—C1—C2—C3	178.52 (17)
Cl3—Sn1—O1—C1	93.53 (13)	N1—C2—C3—C4	−0.3 (3)
Cl4—Sn1—O1—C1	−82.14 (13)	C1—C2—C3—C4	179.61 (17)
O1—Sn1—N1—C6	178.01 (16)	C2—C3—C4—C5	−1.5 (3)
Cl1—Sn1—N1—C6	−4.12 (15)	C3—C4—C5—C6	1.5 (3)
Cl2—Sn1—N1—C6	−178.59 (11)	C2—N1—C6—C5	−2.2 (3)
Cl3—Sn1—N1—C6	88.36 (15)	Sn1—N1—C6—C5	174.16 (13)
Cl4—Sn1—N1—C6	−93.97 (15)	C4—C5—C6—N1	0.4 (3)
O1—Sn1—N1—C2	−5.40 (12)	C11—N2—C7—C8	0.3 (3)
Cl1—Sn1—N1—C2	172.47 (12)	N2—C7—C8—C9	−0.4 (3)
Cl2—Sn1—N1—C2	−2.0 (2)	C12—N3—C9—C10	−178.27 (17)
Cl3—Sn1—N1—C2	−95.05 (12)	C13—N3—C9—C10	0.2 (3)
Cl4—Sn1—N1—C2	82.62 (12)	C12—N3—C9—C8	1.5 (3)
Sn1—O1—C1—O2	177.24 (15)	C13—N3—C9—C8	−179.96 (16)
Sn1—O1—C1—C2	−3.5 (2)	C7—C8—C9—N3	−179.87 (17)
C6—N1—C2—C3	2.2 (3)	C7—C8—C9—C10	−0.1 (3)
Sn1—N1—C2—C3	−174.69 (14)	N3—C9—C10—C11	−179.60 (17)
C6—N1—C2—C1	−177.72 (16)	C8—C9—C10—C11	0.6 (3)
Sn1—N1—C2—C1	5.44 (19)	C7—N2—C11—C10	0.3 (3)
O2—C1—C2—N1	177.67 (17)	C9—C10—C11—N2	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.87 (1)	1.93 (1)	2.802 (2)	176 (2)