Pyridinium nitrate at 290 K

Batsanov, A.S.

doi:10.1107/S1600536804030168

organic compounds

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Volume 60| Part 12| December 2004| Pages o2424-o2425

https://doi.org/10.1107/S1600536804030168

Pyridinium nitrate at 290 K

Andrei S. Batsanov ^a ^*

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk

(Received 15 November 2004; accepted 19 November 2004; online 27 November 2004)

A previous structural study [Serewicz et al. (1965 ). J. Phys. Chem. 69, 1915–1921] of pyridinium nitrate, C₅H₆N⁺·NO₃⁻, has been repeated at 290 K.

Comment

The crystal structure of pyridinium nitrate, (I), as determined by Serewicz et al. (1965), implied the existence of a strong hydrogen bond between the pyridinium and nitrate ions, but the precision of the data (measured at room temperature by the Weissenberg method) was insufficient to locate H atoms directly. We have redetermined this structure at two temperatures in the course of screening for materials suitable for neutron-diffraction and charge-density studies of hydrogen bonds. The 290 K structure (Fig. 1 and Table 1) is reported here. The results reported by Serewicz et al. (1965) are essentially confirmed, though the unit cell is slightly larger than reported previously (without s.u. values): a = 3.905, b = 12.286, c = 13.470 Å, β = 90.5° and V = 646 Å³.

For the low-temperature results and the general discussion, see Batsanov (2004 ).

Figure 1
The molecular structure of (I

) at 290 K. Displacement ellipsoids are drawn at the 50% probability level. The dashed and dotted lines indicate strong and weak hydrogen bonds, respectively.

Experimental

The crystals of (I) were grown by slow evaporation, at room temperature, of an aqueous solution of equimolar amounts of pyridine and nitric acid.

Crystal data

C₅H₆N⁺·NO₃⁻
M_r = 142.12
Monoclinic, P2₁/c
a = 3.9015 (6) Å
b = 12.324 (2) Å
c = 13.503 (2) Å
β = 90.57 (1)°
V = 649.2 (2) Å³
Z = 4
D_x = 1.454 Mg m⁻³
Mo Kα radiation
Cell parameters from 1107 reflections
θ = 2.2–22.4°
μ = 0.12 mm⁻¹
T = 290 (2) K
Plate, colourless
0.42 × 0.37 × 0.03 mm

Data collection

Bruker APEX CCD area-detector diffractometer
ω scans
Absorption correction: none
5258 measured reflections
1154 independent reflections
735 reflections with I > 2σ(I)
R_int = 0.073
θ_max = 25.0°
h = −4 → 4
k = −14 → 14
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.157
S = 1.04
1154 reflections
95 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.086P)² + 0.0078P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.003
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

N1—C2	1.328 (4)
N1—C6	1.338 (4)
C2—C3	1.352 (4)
C3—C4	1.343 (4)
C4—C5	1.337 (4)
C5—C6	1.337 (4)
O1—N2	1.251 (2)
O2—N2	1.217 (3)
O3—N2	1.225 (3)

C2—N1—C6	121.0 (2)
N1—C2—C3	119.8 (2)
C4—C3—C2	119.1 (2)
C5—C4—C3	120.6 (2)
C6—C5—C4	120.0 (2)
C5—C6—N1	119.5 (2)
O2—N2—O3	122.1 (2)
O2—N2—O1	119.5 (2)
O3—N2—O1	118.4 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.94 (4)	1.86 (4)	2.787 (3)	171 (3)
N1—H1⋯O3	0.94 (4)	2.45 (4)	3.149 (3)	131 (3)
C2—H2⋯O3	0.93	2.78	3.307 (4)	117
C2—H2⋯O2ⁱ	0.93	2.56	3.177 (3)	124
C3—H3⋯O2ⁱⁱ	0.93	2.67	3.324 (3)	128
C4—H4⋯O3ⁱⁱⁱ	0.93	2.70	3.330 (3)	126
C5—H5⋯O3ⁱⁱⁱ	0.93	2.77	3.365 (4)	123
C6—H6⋯O1^iv	0.93	2.38	3.196 (3)	146
C6—H6⋯O2^iv	0.93	2.68	3.456 (3)	141
Symmetry codes: (i) $[-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (ii) $[1-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ ; (iii) $[1+x,{\script{1\over 2}}-y,z-{\script{1\over 2}}]$ ; (iv) -x,1-y,1-z.

All H atoms were located in a difference Fourier map. Atom H1 was refined in isotropic approximation [N—H = 0.94 (4) Å], other H atoms were treated as riding in idealized positions, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804030168/lh6318sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804030168/lh6318Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

pyridinium nitrate top

Crystal data top

C₅H₆N⁺·NO₃⁻	F(000) = 296
M_r = 142.12	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1107 reflections
a = 3.9015 (6) Å	θ = 2.2–22.4°
b = 12.324 (2) Å	µ = 0.12 mm⁻¹
c = 13.503 (2) Å	T = 290 K
β = 90.57 (1)°	Plate, colourless
V = 649.2 (2) Å³	0.42 × 0.37 × 0.03 mm
Z = 4

Data collection top

ProteumM APEX CCD area-detector diffractometer	735 reflections with I > 2σ(I)
Radiation source: 60 W microfocus Bede Microsource with glass polycapillary optics	R_int = 0.073
Graphite monochromator	θ_max = 25.0°, θ_min = 2.2°
Detector resolution: 8 pixels mm^-1	h = −4→4
ω scans	k = −14→14
5258 measured reflections	l = −16→16
1154 independent 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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F²) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.086P)² + 0.0078P] where P = (F_o² + 2F_c²)/3
1154 reflections	(Δ/σ)_max = 0.003
95 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Special details top

Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 4 sets of ω scans, each set at different φ and/or 2θ angles and each scan (15 s exposure) covering 0.3° in ω. Crystal to detector distance 4.95 cm. Crystal decay was monitored by repeating the first 50 frames at the end of the data collection and comparing the intensities of 31 duplicate reflections.

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. H(1) atom (N-bonded) was refined in isotropic approximation (All H-atom parameters refined), other H atoms treated as riding (H-atom parameters constrained).

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

	x	y	z	U_iso*/U_eq
N1	0.3970 (5)	0.31105 (19)	0.5473 (2)	0.0746 (7)
H1	0.260 (9)	0.365 (3)	0.577 (3)	0.123 (11)*
C2	0.4746 (7)	0.2227 (3)	0.59912 (17)	0.0723 (8)
H2	0.4203	0.2188	0.6659	0.087*
C3	0.6325 (7)	0.1385 (2)	0.5545 (2)	0.0721 (8)
H3	0.6882	0.0763	0.5902	0.086*
C4	0.7081 (6)	0.1458 (2)	0.4579 (2)	0.0696 (7)
H4	0.8141	0.0879	0.4264	0.084*
C5	0.6317 (7)	0.2356 (2)	0.40669 (18)	0.0739 (8)
H5	0.6891	0.2405	0.3402	0.089*
C6	0.4739 (7)	0.3184 (2)	0.4512 (2)	0.0713 (8)
H6	0.4175	0.3805	0.4156	0.086*
O1	0.0061 (6)	0.48422 (14)	0.61596 (12)	0.0860 (7)
O2	−0.1119 (6)	0.5580 (2)	0.75437 (14)	0.1064 (8)
O3	0.1348 (6)	0.4033 (2)	0.75035 (14)	0.1090 (8)
N2	0.0100 (6)	0.48242 (17)	0.70861 (15)	0.0665 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0566 (13)	0.0572 (13)	0.110 (2)	−0.0043 (10)	0.0108 (12)	−0.0313 (14)
C2	0.0796 (18)	0.089 (2)	0.0482 (14)	−0.0210 (15)	0.0028 (12)	−0.0044 (13)
C3	0.0750 (18)	0.0580 (16)	0.0828 (19)	0.0013 (13)	−0.0170 (14)	0.0139 (13)
C4	0.0602 (16)	0.0644 (17)	0.0842 (18)	0.0078 (12)	0.0030 (13)	−0.0192 (13)
C5	0.0761 (18)	0.095 (2)	0.0507 (14)	−0.0087 (15)	0.0043 (12)	−0.0001 (13)
C6	0.0641 (16)	0.0586 (16)	0.091 (2)	−0.0029 (12)	−0.0099 (14)	0.0235 (13)
O1	0.1372 (18)	0.0713 (12)	0.0496 (10)	0.0160 (11)	0.0042 (9)	−0.0017 (7)
O2	0.129 (2)	0.1131 (16)	0.0774 (13)	0.0207 (14)	0.0102 (12)	−0.0367 (11)
O3	0.130 (2)	0.1229 (18)	0.0742 (13)	0.0350 (14)	0.0169 (12)	0.0369 (12)
N2	0.0795 (15)	0.0677 (14)	0.0524 (12)	−0.0064 (11)	0.0099 (10)	−0.0057 (10)

Geometric parameters (Å, º) top

N1—C2	1.328 (4)	C4—H4	0.9300
N1—C6	1.338 (4)	C5—C6	1.337 (4)
N1—H1	0.94 (4)	C5—H5	0.9300
C2—C3	1.352 (4)	C6—H6	0.9300
C2—H2	0.9300	O1—N2	1.251 (2)
C3—C4	1.343 (4)	O2—N2	1.217 (3)
C3—H3	0.9300	O3—N2	1.225 (3)
C4—C5	1.337 (4)

C2—N1—C6	121.0 (2)	C3—C4—H4	119.7
C2—N1—H1	119 (2)	C6—C5—C4	120.0 (2)
C6—N1—H1	120 (2)	C6—C5—H5	120.0
N1—C2—C3	119.8 (2)	C4—C5—H5	120.0
N1—C2—H2	120.1	C5—C6—N1	119.5 (2)
C3—C2—H2	120.1	C5—C6—H6	120.3
C4—C3—C2	119.1 (2)	N1—C6—H6	120.2
C4—C3—H3	120.4	O2—N2—O3	122.1 (2)
C2—C3—H3	120.5	O2—N2—O1	119.5 (2)
C5—C4—C3	120.6 (2)	O3—N2—O1	118.4 (2)
C5—C4—H4	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.94 (4)	1.86 (4)	2.787 (3)	171 (3)
N1—H1···O3	0.94 (4)	2.45 (4)	3.149 (3)	131 (3)
C2—H2···O3	0.93	2.78	3.307 (4)	117
C2—H2···O2ⁱ	0.93	2.56	3.177 (3)	124
C3—H3···O2ⁱⁱ	0.93	2.67	3.324 (3)	128
C4—H4···O3ⁱⁱⁱ	0.93	2.70	3.330 (3)	126
C5—H5···O3ⁱⁱⁱ	0.93	2.77	3.365 (4)	123
C6—H6···O1^iv	0.93	2.38	3.196 (3)	146
C6—H6···O2^iv	0.93	2.68	3.456 (3)	141

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

Acknowledgements

The author thanks Dr I. F. Perepichka for providing single crystals of (I).

References

Batsanov, A. S. (2004). Acta Cryst. E60, o2426–o2428. CSD CrossRef IUCr Journals Google Scholar
Bruker (2001). SMART (Version 5.625) & SHELXTL (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2002). SAINT. Version 6.28A. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Serewicz, A. J., Robertson, B. K. & Meyers, E. A. (1965). J. Phys. Chem. 69, 1915–1921. CrossRef CAS Web of Science Google Scholar

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