4-Cyano-1-methyl­pyridinium perchlor­ate

Nguyen, V.D.; McCormick, C.A.; Koplitz, L.V.; Mague, J.T.

doi:10.1107/S1600536814012860

organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Pages o756-o757

https://doi.org/10.1107/S1600536814012860

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4-Cyano-1-methylpyridinium perchlorate

Vu D. Nguyen,^a Cameron A. McCormick,^b Lynn V. Koplitz ^a and Joel T. Mague ^c ^*

^aDepartment of Chemistry, Loyola University, New Orleans, LA 70118, USA, ^bDepartment of Physics, Loyola University, New Orleans, LA 70118, USA, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: joelt@tulane.edu

(Received 30 May 2014; accepted 3 June 2014; online 7 June 2014)

The title salt, C₇H₇N₂⁺·ClO₄⁻, crystallizes with alternating cations and anions in wavy sheets, which are formed by a number of C—H⋯O and C—H⋯N hydrogen bonds, lying approximately parallel to (001).

CCDC reference: 1006394

Related literature

For the crystal structures of other 4-cyano-1-methylpyridinium salts, see: McCormick et al. (2013 ); Kammer et al. (2012a ,b ); Hardacre et al. (2008 , 2010 ); Glavcheva et al. (2004 ); Bockman & Kochi (1989 , 1992 ). For the structure of 3-cyano-1-methylpyridinium perchlorate, see: McCormick et al. (2014 ) and for the structure of 4-cyanoanilinium perchlorate, see: Dai (2008 ). For a discussion of anion–π interactions, see: Frontera et al. (2011 ).

Experimental

Crystal data

C₇H₇N₂⁺·ClO₄⁻
M_r = 218.60
Orthorhombic, P b c a
a = 10.232 (2) Å
b = 10.872 (3) Å
c = 16.769 (4) Å
V = 1865.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 100 K
0.23 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.86, T_max = 0.95
30647 measured reflections
2475 independent reflections
2235 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.07
2475 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O4ⁱ	0.98	2.37	3.245 (2)	149
C1—H1C⋯O2ⁱⁱ	0.98	2.61	3.2540 (19)	123
C2—H2⋯O1ⁱⁱ	0.95	2.46	3.4001 (18)	173
C2—H2⋯O2ⁱⁱ	0.95	2.63	3.2549 (18)	123
C3—H3⋯N2ⁱⁱⁱ	0.95	2.67	3.3098 (18)	125
C3—H3⋯O3^iv	0.95	2.46	3.300 (2)	148
C6—H6⋯O4ⁱ	0.95	2.50	3.351 (2)	149
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x, -y+2, -z+1; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008)').

Supporting information

CCDC reference: 1006394

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536814012860/su2740sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012860/su2740Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012860/su2740Isup3.cml

checkCIF report

Comment top

The title compound, Fig. 1, crystallizes with alternating cations and anions in wavy sheets, which are formed by a number of C—H···O and C—H···N hydrogen bonds, which are approximately parallel to (001) [see Table 1 and Fig. 2].

As with 3-cyano-1-methylpyridinium perchlorate (McCormick et al., 2014), the perchlorate ions are located near the pyridinium nitrogen atoms as the result of electrostatic attraction but the remainder of the two structures differ considerably due to the different position of the cyano group and the effect this has on the weak interionic interactions.

Related literature top

For the crystal structures of other 4-cyano-1-methylpyridinium salts, see: McCormick et al. (2013); Kammer et al. (2012a,b); Hardacre et al. (2008, 2010); Glavcheva et al. (2004); Bockman & Kochi (1989, 1992). For the structure of 3-cyano-1-methylpyridinium perchlorate, see: McCormick et al. (2014) and for the structure of 4-cyanoanilinium perchlorate, see: Dai (2008). For [please specify subject], see: Frontera et al. (2011).

Experimental top

4-Cyanopyridine (10.55 g) was dissolved in benzene (40 ml). Iodomethane (9.5 ml) was added to this solution slowly with stirring and the solution was refluxed for 75 minutes. Yellow solid 4-cyano-1-methylpyridinium iodide (m.p. 189–193° C) was collected by vacuum filtration. This solid (0.98 g) was then dissolved in a solution of silver perchlorate previously prepared by reacting Ag₂O (0.47 g) with 0.5 M aqueous HClO₄(8.0 ml). After stirring, precipitated AgI was removed by vacuum filtration and the filtrate containing 4-cyano-1-methylpyridinium perchlorate (m.p.114–119° C) was slowly evaporated to dryness to form crystals of the title compound.

Structure description top

For the crystal structures of other 4-cyano-1-methylpyridinium salts, see: McCormick et al. (2013); Kammer et al. (2012a,b); Hardacre et al. (2008, 2010); Glavcheva et al. (2004); Bockman & Kochi (1989, 1992). For the structure of 3-cyano-1-methylpyridinium perchlorate, see: McCormick et al. (2014) and for the structure of 4-cyanoanilinium perchlorate, see: Dai (2008). For [please specify subject], see: Frontera et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008)').

Figures top

	Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the crystal packing along the b axis, with the C—H···O and C—H···N hydrogen bonds as red and blue dashed lines, respectively (see Table 1 for details).

4-Cyano-1-methylpyridinium perchlorate top

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	F(000) = 896
M_r = 218.60	D_x = 1.557 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9543 reflections
a = 10.232 (2) Å	θ = 3.0–29.1°
b = 10.872 (3) Å	µ = 0.40 mm⁻¹
c = 16.769 (4) Å	T = 100 K
V = 1865.3 (7) Å³	Block, colourless
Z = 8	0.23 × 0.16 × 0.12 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2475 independent reflections
Radiation source: fine-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
φ and ω scans	θ_max = 29.1°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −13→14
T_min = 0.86, T_max = 0.95	k = −14→14
30647 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0474P)² + 1.204P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2475 reflections	Δρ_max = 0.38 e Å⁻³
129 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (7)

Crystal data top

C₇H₇N₂⁺·ClO₄⁻	V = 1865.3 (7) Å³
M_r = 218.60	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.232 (2) Å	µ = 0.40 mm⁻¹
b = 10.872 (3) Å	T = 100 K
c = 16.769 (4) Å	0.23 × 0.16 × 0.12 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2475 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	2235 reflections with I > 2σ(I)
T_min = 0.86, T_max = 0.95	R_int = 0.054
30647 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.07	Δρ_max = 0.38 e Å⁻³
2475 reflections	Δρ_min = −0.39 e Å⁻³
129 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. H-atoms were placed in calculated positions (C—H = 0.95 - 0.98 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached carbon atoms.

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

	x	y	z	U_iso*/U_eq
N1	0.07438 (11)	0.87020 (10)	0.65230 (6)	0.0173 (2)
N2	−0.23590 (12)	0.56153 (11)	0.49548 (7)	0.0259 (3)
C1	0.15878 (14)	0.95747 (13)	0.69622 (9)	0.0238 (3)
H1A	0.2307	0.9125	0.7215	0.036*
H1B	0.1071	0.9994	0.7372	0.036*
H1C	0.1944	1.0183	0.6590	0.036*
C2	−0.04511 (13)	0.90672 (12)	0.62884 (8)	0.0201 (3)
H2	−0.0730	0.9884	0.6394	0.024*
C3	−0.12714 (13)	0.82710 (12)	0.58970 (8)	0.0198 (3)
H3	−0.2115	0.8530	0.5731	0.024*
C4	−0.08458 (13)	0.70782 (12)	0.57475 (7)	0.0175 (3)
C5	0.03964 (13)	0.67124 (12)	0.59898 (8)	0.0204 (3)
H5	0.0700	0.5902	0.5887	0.024*
C6	0.11766 (14)	0.75535 (13)	0.63820 (8)	0.0200 (3)
H6	0.2026	0.7320	0.6554	0.024*
C7	−0.16859 (13)	0.62451 (12)	0.53131 (8)	0.0201 (3)
Cl1	0.01260 (3)	0.73669 (3)	0.35515 (2)	0.01939 (12)
O1	0.12396 (10)	0.79937 (10)	0.32127 (6)	0.0253 (2)
O2	−0.05193 (12)	0.81513 (10)	0.41181 (6)	0.0285 (3)
O3	0.05528 (12)	0.62622 (10)	0.39448 (9)	0.0386 (3)
O4	−0.07787 (11)	0.70787 (15)	0.29216 (7)	0.0432 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0169 (5)	0.0170 (5)	0.0180 (5)	−0.0015 (4)	0.0016 (4)	0.0016 (4)
N2	0.0280 (6)	0.0231 (6)	0.0265 (6)	−0.0034 (5)	−0.0028 (5)	0.0021 (5)
C1	0.0233 (6)	0.0201 (6)	0.0278 (7)	−0.0042 (5)	−0.0028 (5)	−0.0017 (5)
C2	0.0206 (6)	0.0157 (6)	0.0241 (6)	0.0022 (5)	0.0010 (5)	0.0026 (5)
C3	0.0177 (6)	0.0184 (6)	0.0232 (6)	0.0023 (5)	−0.0001 (5)	0.0039 (5)
C4	0.0187 (6)	0.0182 (6)	0.0155 (5)	−0.0011 (5)	0.0017 (4)	0.0020 (4)
C5	0.0200 (6)	0.0183 (6)	0.0229 (6)	0.0040 (5)	0.0013 (5)	−0.0013 (5)
C6	0.0160 (6)	0.0210 (6)	0.0229 (6)	0.0030 (5)	0.0007 (5)	0.0007 (5)
C7	0.0208 (6)	0.0184 (6)	0.0211 (6)	0.0010 (5)	0.0005 (5)	0.0041 (5)
Cl1	0.01679 (17)	0.01989 (18)	0.02150 (19)	0.00045 (11)	0.00104 (11)	−0.00297 (11)
O1	0.0221 (5)	0.0261 (5)	0.0277 (5)	−0.0036 (4)	0.0033 (4)	0.0018 (4)
O2	0.0401 (6)	0.0236 (5)	0.0217 (5)	0.0050 (4)	0.0099 (4)	−0.0012 (4)
O3	0.0292 (6)	0.0213 (5)	0.0654 (9)	0.0055 (4)	0.0110 (6)	0.0133 (5)
O4	0.0193 (5)	0.0806 (10)	0.0297 (6)	−0.0081 (6)	−0.0003 (5)	−0.0213 (6)

Geometric parameters (Å, º) top

N1—C2	1.3443 (18)	C3—H3	0.9500
N1—C6	1.3458 (17)	C4—C5	1.3924 (19)
N1—C1	1.4793 (17)	C4—C7	1.4456 (18)
N2—C7	1.1420 (18)	C5—C6	1.3806 (19)
C1—H1A	0.9800	C5—H5	0.9500
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	Cl1—O2	1.4373 (10)
C2—C3	1.3728 (19)	Cl1—O3	1.4382 (12)
C2—H2	0.9500	Cl1—O4	1.4389 (12)
C3—C4	1.3907 (18)	Cl1—O1	1.4441 (10)

C2—N1—C6	121.46 (12)	C3—C4—C7	119.27 (12)
C2—N1—C1	119.16 (11)	C5—C4—C7	120.72 (12)
C6—N1—C1	119.36 (11)	C6—C5—C4	118.54 (12)
N1—C1—H1A	109.5	C6—C5—H5	120.7
N1—C1—H1B	109.5	C4—C5—H5	120.7
H1A—C1—H1B	109.5	N1—C6—C5	120.52 (12)
N1—C1—H1C	109.5	N1—C6—H6	119.7
H1A—C1—H1C	109.5	C5—C6—H6	119.7
H1B—C1—H1C	109.5	N2—C7—C4	177.94 (14)
N1—C2—C3	120.65 (12)	O2—Cl1—O3	109.38 (7)
N1—C2—H2	119.7	O2—Cl1—O4	108.60 (7)
C3—C2—H2	119.7	O3—Cl1—O4	110.50 (9)
C2—C3—C4	118.86 (12)	O2—Cl1—O1	110.03 (7)
C2—C3—H3	120.6	O3—Cl1—O1	109.56 (7)
C4—C3—H3	120.6	O4—Cl1—O1	108.76 (7)
C3—C4—C5	119.97 (12)

C6—N1—C2—C3	0.2 (2)	C3—C4—C5—C6	0.48 (19)
C1—N1—C2—C3	−178.38 (12)	C7—C4—C5—C6	178.09 (12)
N1—C2—C3—C4	0.0 (2)	C2—N1—C6—C5	−0.1 (2)
C2—C3—C4—C5	−0.4 (2)	C1—N1—C6—C5	178.49 (12)
C2—C3—C4—C7	−178.02 (12)	C4—C5—C6—N1	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.98	2.37	3.245 (2)	149
C1—H1C···O2ⁱⁱ	0.98	2.61	3.2540 (19)	123
C2—H2···O1ⁱⁱ	0.95	2.46	3.4001 (18)	173
C2—H2···O2ⁱⁱ	0.95	2.63	3.2549 (18)	123
C3—H3···N2ⁱⁱⁱ	0.95	2.67	3.3098 (18)	125
C3—H3···O3^iv	0.95	2.46	3.300 (2)	148
C6—H6···O4ⁱ	0.95	2.50	3.351 (2)	149

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x−1/2, y+1/2, z; (iv) x−1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O4ⁱ	0.98	2.37	3.245 (2)	149
C1—H1C···O2ⁱⁱ	0.98	2.61	3.2540 (19)	123
C2—H2···O1ⁱⁱ	0.95	2.46	3.4001 (18)	173
C2—H2···O2ⁱⁱ	0.95	2.63	3.2549 (18)	123
C3—H3···N2ⁱⁱⁱ	0.95	2.67	3.3098 (18)	125
C3—H3···O3^iv	0.95	2.46	3.300 (2)	148
C6—H6···O4ⁱ	0.95	2.50	3.351 (2)	149

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x−1/2, y+1/2, z; (iv) x−1/2, −y+3/2, −z+1.

Acknowledgements

We thank the Chemistry Department of Tulane University for support of the X-ray laboratory and the Louisiana Board of Regents through the Louisiana Educational Quality Support Fund [grant LEQSF (2003–2003)-ENH–TR-67] for the purchase of the APEX diffractometer.

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