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The structure of the title compound, C6H7N2O3+·Cl, (I), comprises the hydro­chloride salt of an essentially flat mol­ecule with a single N—H...Cl association. Two additional C—H...Cl close contacts are also observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020729/cf6034sup1.cif
Contains datablocks I, default

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020729/cf6034Isup2.hkl
Contains datablock I

CCDC reference: 155900

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.043
  • wR factor = 0.121
  • Data-to-parameter ratio = 16.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

The basified form of 4-methoxy-3-nitropyridine, i.e. the title compound 4-methoxy-3-nitropyridinium chloride, (I), is a useful intermediate in which the methoxy group of can be readily replaced by nucleophiles. The molecule is also commercially available as the 4-ethoxy derivative but the methoxy version is less expensive. Both derivatives are prepared via the 4-chloro analogue, which is then treated with the appropriate alcohol. The 4-chloro compound has increased reactivity to nucleophiles but it is very lipophilic and corrosive to the skin, so it is much easier to handle as a 4-alkoxy compound.

Experimental top

The title compound, (I), was prepared by Spa Contract Synthesis. Crystals of (I) were grown from a methanol solution.

Refinement top

All H atoms were included in the refinement at calculated positions as riding models, with C—H set to 0.95 (Ar—H) and 0.98 Å (CH3), except for the pyridinium H atom, which was located on difference syntheses and for which both positional and displacement parameters were refined.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-numbering scheme for (I), showing 50% probability ellipsoids.
4-Methoxy-3-nitropyridinium chloride top
Crystal data top
C6H7N2O3+·ClF(000) = 392
Mr = 190.59Dx = 1.576 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.6185 (4) ÅCell parameters from 4004 reflections
b = 7.1517 (4) Åθ = 2.9–27.5°
c = 11.3701 (5) ŵ = 0.44 mm1
β = 111.523 (3)°T = 150 K
V = 803.24 (6) Å3Block, colourless
Z = 40.15 × 0.15 × 0.10 mm
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
1835 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode1219 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.3°
ϕ and ω scansh = 1313
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 89
Tmin = 0.937, Tmax = 0.957l = 1314
5993 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.0664P)2]
where P = (Fo2 + 2Fc2)/3
1835 reflections(Δ/σ)max < 0.001
114 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C6H7N2O3+·ClV = 803.24 (6) Å3
Mr = 190.59Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.6185 (4) ŵ = 0.44 mm1
b = 7.1517 (4) ÅT = 150 K
c = 11.3701 (5) Å0.15 × 0.15 × 0.10 mm
β = 111.523 (3)°
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
1835 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1219 reflections with I > 2σ(I)
Tmin = 0.937, Tmax = 0.957Rint = 0.042
5993 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.25 e Å3
1835 reflectionsΔρmin = 0.26 e Å3
114 parameters
Special details top

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.14928 (5)0.48448 (7)0.68197 (5)0.0504 (2)
N10.29721 (17)0.4262 (3)0.95746 (18)0.0483 (5)
H10.245 (2)0.426 (4)0.870 (3)0.078 (8)*
C20.3021 (2)0.2817 (3)1.03233 (19)0.0455 (5)
H20.25850.16760.99750.057*
C30.37018 (18)0.2979 (3)1.15977 (17)0.0387 (5)
N310.36643 (19)0.1332 (2)1.23515 (17)0.0500 (5)
O310.29498 (18)0.0033 (2)1.18145 (18)0.0687 (5)
O320.4352 (2)0.1318 (2)1.34665 (16)0.0872 (6)
C40.43571 (18)0.4643 (3)1.21323 (18)0.0377 (5)
O410.49836 (15)0.47804 (18)1.33625 (13)0.0460 (4)
C420.5523 (2)0.6580 (3)1.3888 (2)0.0584 (6)
H4210.47880.75011.36610.073*
H4220.59390.64821.48110.073*
H4230.62050.69771.35490.073*
C50.42871 (19)0.6114 (3)1.12890 (18)0.0426 (5)
H50.47270.72681.15970.053*
C60.35892 (19)0.5873 (3)1.00372 (19)0.0462 (5)
H60.35370.68770.94740.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0667 (4)0.0442 (4)0.0359 (3)0.0050 (2)0.0138 (3)0.0012 (2)
N10.0532 (10)0.0567 (12)0.0342 (10)0.0028 (9)0.0150 (9)0.0030 (9)
C20.0552 (12)0.0428 (12)0.0408 (12)0.0066 (10)0.0203 (10)0.0073 (9)
C30.0499 (11)0.0323 (10)0.0374 (11)0.0019 (8)0.0199 (9)0.0027 (8)
N310.0715 (12)0.0371 (10)0.0475 (12)0.0018 (9)0.0289 (10)0.0029 (8)
O310.0751 (11)0.0511 (11)0.0778 (13)0.0212 (8)0.0255 (10)0.0042 (8)
O320.1658 (19)0.0456 (11)0.0422 (10)0.0023 (11)0.0285 (11)0.0065 (8)
C40.0420 (10)0.0394 (11)0.0328 (11)0.0050 (8)0.0149 (9)0.0020 (8)
O410.0550 (8)0.0447 (9)0.0331 (8)0.0060 (6)0.0101 (7)0.0010 (6)
C420.0693 (14)0.0559 (14)0.0452 (13)0.0136 (12)0.0152 (11)0.0104 (11)
C50.0498 (11)0.0343 (11)0.0448 (12)0.0022 (9)0.0187 (10)0.0014 (9)
C60.0543 (12)0.0438 (12)0.0440 (12)0.0107 (10)0.0223 (10)0.0109 (10)
Geometric parameters (Å, º) top
N1—C21.328 (3)C4—O411.314 (2)
N1—C61.335 (3)C4—C51.407 (3)
N1—H10.94 (3)O41—C421.446 (2)
C2—C31.366 (3)C42—H4210.98
C2—H20.95C42—H4220.98
C3—C41.400 (3)C42—H4230.98
C3—N311.466 (2)C5—C61.353 (3)
N31—O321.209 (2)C5—H50.95
N31—O311.213 (2)C6—H60.95
C2—N1—C6121.42 (19)C3—C4—C5116.50 (18)
C2—N1—H1123.0 (16)C4—O41—C42118.42 (16)
C6—N1—H1115.4 (16)O41—C42—H421109.5
N1—C2—C3119.7 (2)O41—C42—H422109.5
N1—C2—H2120.2H421—C42—H422109.5
C3—C2—H2120.2O41—C42—H423109.5
C2—C3—C4121.19 (17)H421—C42—H423109.5
C2—C3—N31115.77 (18)H422—C42—H423109.5
C4—C3—N31123.02 (17)C6—C5—C4119.58 (18)
O32—N31—O31123.16 (18)C6—C5—H5120.2
O32—N31—C3118.99 (18)C4—C5—H5120.2
O31—N31—C3117.85 (18)N1—C6—C5121.63 (19)
O41—C4—C3120.20 (17)N1—C6—H6119.2
O41—C4—C5123.30 (17)C5—C6—H6119.2
C6—N1—C2—C30.8 (3)C2—C3—C4—C50.7 (3)
N1—C2—C3—C40.3 (3)N31—C3—C4—C5178.98 (16)
N1—C2—C3—N31178.12 (16)C3—C4—O41—C42173.49 (18)
C2—C3—N31—O32172.9 (2)C5—C4—O41—C425.8 (3)
C4—C3—N31—O328.7 (3)O41—C4—C5—C6178.18 (18)
C2—C3—N31—O316.2 (3)C3—C4—C5—C61.2 (3)
C4—C3—N31—O31172.20 (18)C2—N1—C6—C50.3 (3)
C2—C3—C4—O41178.69 (17)C4—C5—C6—N10.7 (3)
N31—C3—C4—O410.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.94 (3)2.05 (3)2.974 (2)167 (2)
C5—H5···Cl1i0.952.743.629 (2)157
C6—H6···Cl1ii0.952.583.521 (2)173
Symmetry codes: (i) x+1/2, y3/2, z+1/2; (ii) x+1/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC6H7N2O3+·Cl
Mr190.59
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)10.6185 (4), 7.1517 (4), 11.3701 (5)
β (°) 111.523 (3)
V3)803.24 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.44
Crystal size (mm)0.15 × 0.15 × 0.10
Data collection
DiffractometerEnraf Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.937, 0.957
No. of measured, independent and
observed [I > 2σ(I)] reflections
5993, 1835, 1219
Rint0.042
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.121, 1.00
No. of reflections1835
No. of parameters114
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.26

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.94 (3)2.05 (3)2.974 (2)167 (2)
C5—H5···Cl1i0.952.743.629 (2)157
C6—H6···Cl1ii0.952.583.521 (2)173
Symmetry codes: (i) x+1/2, y3/2, z+1/2; (ii) x+1/2, y1/2, z+3/2.
 

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