Download citation
Download citation
link to html
In the isomeric title compounds, viz. 2-, 3- and 4-(chloro­methyl)pyridinium chloride, C6H7ClN+·Cl, the secondary interactions have been established as follows. Classical N—H...Cl hydrogen bonds are observed in the 2- and 3-isomers, whereas the 4-isomer forms inversion-symmetric N—H(...Cl...)2H—N dimers involving three-centre hydrogen bonds. Short Cl...Cl contacts are formed in both the 2-isomer (C—Cl...Cl, approximately linear at the central Cl) and the 4-isomer (C—Cl...Cl—C, angles at Cl of ca 75°). Additionally, each compound displays contacts of the form C—H...Cl, mainly to the Cl anion. The net effect is to create either a layer structure (3-isomer) or a three-dimensional packing with easily identifiable layer substructures (2- and 4-isomers).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017018/bm1509sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017018/bm1509Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017018/bm1509IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017018/bm1509IIIsup4.hkl
Contains datablock III

CCDC references: 199433; 199434; 199435

Comment top

We are interested in secondary bonding interactions (generally hydrogen bonds and halogen-halogen contacts) in halides of simple halogenated nitrogen bases, such as anilines (Gray & Jones, 2002, and references therein) and pyridines (Freytag & Jones, 2001, and references therein). Here, we present the structures of the series of isomers 2-, 3- and 4-chloromethylpyridinium chloride (chloro-2-, -3- and -4-picolinium chloride), (I), (II) and (III), respectively. \sch

All three structures crystallize without imposed symmetry. For reasons discussed below, each is shown as a hydrogen-bonded dimer in Figs. 1–3. The numbering is standard; C7 is the methylene C atom and Cl2 the anionic Cl-.

The structures of the cations of (I), (II) and (III) are unexceptional. Common features, consistent with previous observations (Freytag & Jones, 2001), include the wider ring angles at the N atom (ca 122–123°), slightly narrow ring angles at the CH2Cl substituent (ca 119°) and C—N bond lengths of ca 1.32–1.35 Å. For the 2- and 3-isomers, the substituent is rotated by ca 70° out of the ring plane, but for the 4-isomer, it is approximately coplanar with the ring. This may explain the wide C3—C4—C7 angle (for detailed values see Tables 1, 3 and 5).

As in the other series of compounds, the main interest centres on the packing features. In the 2-isomer, (I), the classical N—H···Cl- hydrogen bond combines with the shortest H···Cl interaction, C6—H6···Cl2, to form a centrosymmetric dimer (Fig. 1). The central R44(10) ring is easily recognisable in the extended packing diagram (Fig. 4), which involves three additional H···Cl interactions (Table 2) and a Cl1···Cl2i contact of 3.5505 (7) Å [symmetry code: (i) 2 - x, 1 - y, 1 - z; C—Cl···Cl 157.26 (4)°]. Although the packing is three-dimensional, vertical layers perpendicular to the b axis at y 1/4, 3/4, etc., are easily recognisable and can be seen edge-on in Fig. 4a. Perhaps ironically, these layers involve all the secondary contacts except the classical hydrogen bond. The perpendicular view onto such a layer is given in Fig. 4 b.

In the 3-isomer, (II), a centrosymmetric dimeric unit can be constructed that involves the classical N—H···Cl- hydrogen bond, the very short H2···Cl2 interaction and the H7B···Cl2 interaction (Fig. 2). The dimers are linked by H6···Cl2 interactions to form layers perpendicular to the bc plane at x 0, 1/2, 1, etc. (Fig. 5). The other H···Cl contacts (Table 4) are all much longer (>= 2.93 Å). There are no significant Cl···Cl contacts; the shortest is Cl1···Cl1ii 3.9210 (10) Å [symmetry code: (ii) 1/2 - x, 1/2 + y, 3/2 - z].

In the 4-isomer, (III), centrosymmetric dimers (Fig. 3) are built up via a three-centre N—H(···Cl)2 hydrogen bond. Within this dimer, the short and highly angled H2···Cl2 and H6···Cl2 contacts are probably imposed by the three-centre hydrogen bond, rather than being of intrinsic significance. Further secondary interactions build up a three-dimensional packing, but the layer shown in Fig. 6 shows most of the salient features. The four-membered rings of Fig. 3 are capped above and below by another three-centre interaction, H7B···Cl2, to form distorted octahedra. The H7A···Cl2 hydrogen bond and, finally, the Cl1···Cl1iii contact [3.6051 (6) Å, C—Cl···Cl 74.54 (3)°; symmetry code: (iii) 1 - x,-y,-z], link the octahedra to form a thick layer with the hydrophilic region at x 0. The next such layer at x 1 provides the three-dimensional extension. The other two H···Cl contacts, involving atoms H3 and H6 (Table 6), are long and have narrow angles, but both lie within the layer of Fig. 6 (from which, however, they have been omitted for clarity) and may make a small contribution to the stability of the packing.

It is notable that the crystallographically determined density increases significantly in the order 2-isomer < 3-isomer < 4-isomer, as was also observed for the series of chloropyridines (Freytag & Jones, 2001; Freytag et al., 1999). One might then postulate an increased efficiency of packing in the same sequence, but it is not easy to identify the factors concerned at the molecular level, beyond commenting that the isomer with the highest density also has the largest number of hydrogen bonds.

Experimental top

The title compounds were purchased from Avocada Research Chemicals Ltd. and dried carefully under vacuum. Single crystals were obtained by liquid-liquid diffusion at 253 K, for (I) from ethanol-diethyl ether (Ratio?), and for (II) and (III) from dimethylformamide-diethyl ether (Ratio?). Crystals of (I) are hygroscopic and those of (II) extremely so; they had to be transferred rapidly from the mother liquor to the mounting oil, thence to the glass fibre and finally to the cold gas stream. The crystals of (II), being thin needles, of necessity then lay at the side of the fibre in a moderately large oil drop. The long exposure times precluded the measurement of sufficient equivalents to perform an adequate absorption correction.

Refinement top

The acidic H atoms (at N) were refined freely. The remaining H atoms were refined with a riding model, with C—H distances of 0.95 Å for aromatic C—H and 0.99 Å for CH2, and with Uiso(H) = 1.2Ueq(C). The crystal of (I) gave diffraction patterns suggestive of twinning; although a unit cell was found without difficulty, an appreciable number of significant reflections remained unindexed. The original data collection involved 12218 reflections, 2138 unique. The refinement gave satisfactory R values (Rint 0.031 and R1 0.039; however, wR2 was rather high at 0.118) but unsatisfactory residual electron density (1.05 e Å-3). Inspection with the program GEMINI (Bruker, 2002) clearly showed two twin domains related by a rotation of 180° about [001]. The data were integrated with SAINT32A (Bruker, 2002), which allows the use of two orientation matrices for the two twin domains. The program TWINABS 1.02 (Bruker, 2002) was used for scaling and merging. Because SAINT treats equivalent reflections independently, ca 30% of the data were integrated as non-overlapped, although equivalents of them were overlapped by a reflection of the second domain. These reflections could not be merged, which led to an artificially high apparent number of data. Therefore, these data were omitted. The fractional contribution of the second domain refined to 0.1854 (12).

Computing details top

For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the dimeric unit of the 2-isomer in the crystal. Only the asymmetric unit is numbered. Ellipsoids represent 50% probability levels and H atom radii are arbitrary. Classical hydrogen bonds are shown as thick dashed lines and C—H···Cl hydrogen bonds as thin dashed lines.
[Figure 2] Fig. 2. A view of the dimeric unit of the 3-isomer in the crystal. Only the asymmetric unit is numbered. Ellipsoids represent 50% probability levels and H atom radii are arbitrary. Classical hydrogen bonds are shown as thick dashed lines and C—H···Cl hydrogen bonds as thin dashed lines.
[Figure 3] Fig. 3. A view of the dimeric unit of the 4-isomer in the crystal. Only the asymmetric unit is numbered. Ellipsoids represent 50% probability levels and H atom radii are arbitrary. Classical (but three-centre) hydrogen bonds are shown as thick dashed lines.
[Figure 4] Fig. 4. The crystal packing of the 2-isomer. (a) The view direction is approximately perpendicular to the ab plane. Atom radii are arbitrary and only H atoms participating in the hydrogen bonding are included. Hydrogen bonds and Cl···Cl interactions (see text) are shown as dashed lines. Molecules shown with thin bonds are farther away from the viewer. (b) Perpendicular view onto the layer at y 1/4 (classical hydrogen bonds are not involved in these layers; see text).
[Figure 5] Fig. 5. The crystal packing of the 3-isomer. The view direction is approximately perpendicular to the bc plane. Atom radii are arbitrary and only H atoms participating in the hydrogen bonding are included. Hydrogen bonds and Cl···Cl interactions (see text) are shown as dashed lines. The layer shown is at x 1/2.
[Figure 6] Fig. 6. The crystal packing of the 4-isomer, showing a thick layer, centred at x 0, of the three-dimensional structure. The view direction is perpendicular to the ab plane. Atom radii are arbitrary and only H atoms participating in the hydrogen bonding are included. Three-centre N—H(···Cl)2 hydrogen bonds and Cl···Cl interactions are shown as thick dashed lines and other hydrogen bonds as thin dashed lines.
(I) 2-chloromethylpyridinium chloride top
Crystal data top
C6H7ClN+·ClF(000) = 336
Mr = 164.03Dx = 1.479 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.9273 (14) ÅCell parameters from 7727 reflections
b = 12.721 (2) Åθ = 2.6–30.5°
c = 7.4773 (14) ŵ = 0.79 mm1
β = 102.382 (6)°T = 133 K
V = 736.5 (2) Å3Lath, colourless
Z = 40.45 × 0.15 × 0.09 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
2150 independent reflections
Radiation source: normal-focus sealed tube1864 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 8.192 pixels mm-1θmax = 30.0°, θmin = 2.6°
ω and ϕ scansh = 1110
Absorption correction: multi-scan
(TWINABS; Bruker, 2002)
k = 017
Tmin = 0.795, Tmax = 0.928l = 010
15781 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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0474P)2 + 0.0509P]
where P = (Fo2 + 2Fc2)/3
2150 reflections(Δ/σ)max = 0.001
87 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C6H7ClN+·ClV = 736.5 (2) Å3
Mr = 164.03Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9273 (14) ŵ = 0.79 mm1
b = 12.721 (2) ÅT = 133 K
c = 7.4773 (14) Å0.45 × 0.15 × 0.09 mm
β = 102.382 (6)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
2150 independent reflections
Absorption correction: multi-scan
(TWINABS; Bruker, 2002)
1864 reflections with I > 2σ(I)
Tmin = 0.795, Tmax = 0.928Rint = 0.030
15781 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.51 e Å3
2150 reflectionsΔρmin = 0.22 e Å3
87 parameters
Special details top

Experimental. 2-chloromethylpyridinium chloride

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl11.13705 (4)0.38768 (2)0.65418 (4)0.02290 (9)
Cl20.74048 (4)0.56737 (2)0.76914 (4)0.02132 (9)
N10.73592 (14)0.34524 (9)0.65134 (14)0.0203 (2)
H00.751 (2)0.4136 (16)0.676 (3)0.032 (4)*
C20.86485 (15)0.27775 (10)0.71730 (15)0.0182 (2)
C30.83591 (15)0.17123 (10)0.69203 (16)0.0208 (2)
H30.92500.12230.73860.025*
C40.67506 (17)0.13633 (10)0.59774 (18)0.0246 (3)
H40.65300.06320.58120.029*
C50.54737 (16)0.20847 (11)0.52814 (19)0.0255 (3)
H50.43800.18550.46100.031*
C60.58063 (15)0.31375 (11)0.55736 (17)0.0241 (3)
H60.49380.36420.51110.029*
C71.03361 (17)0.32280 (11)0.81455 (17)0.0260 (3)
H7A1.10900.26590.87710.031*
H7B1.01420.37360.90840.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02133 (14)0.02466 (16)0.02290 (15)0.00464 (10)0.00515 (11)0.00051 (11)
Cl20.02065 (14)0.02001 (15)0.02203 (15)0.00069 (10)0.00176 (11)0.00155 (10)
N10.0234 (5)0.0195 (5)0.0178 (5)0.0014 (4)0.0041 (4)0.0002 (4)
C20.0177 (5)0.0243 (6)0.0127 (5)0.0009 (5)0.0033 (4)0.0009 (4)
C30.0202 (5)0.0227 (6)0.0198 (6)0.0035 (5)0.0050 (4)0.0018 (4)
C40.0281 (6)0.0224 (6)0.0238 (6)0.0055 (5)0.0070 (5)0.0037 (5)
C50.0187 (5)0.0354 (7)0.0212 (6)0.0059 (5)0.0017 (5)0.0010 (5)
C60.0186 (5)0.0321 (7)0.0211 (6)0.0046 (5)0.0028 (4)0.0047 (5)
C70.0239 (6)0.0363 (7)0.0160 (6)0.0108 (5)0.0000 (4)0.0037 (5)
Geometric parameters (Å, º) top
Cl1—C71.7925 (13)N1—H00.89 (2)
N1—C61.3411 (16)C3—H30.9500
N1—C21.3449 (16)C4—H40.9500
C2—C31.3805 (17)C5—H50.9500
C2—C71.4932 (16)C6—H60.9500
C3—C41.3909 (18)C7—H7A0.9900
C4—C51.3826 (19)C7—H7B0.9900
C5—C61.373 (2)
C6—N1—C2122.78 (11)C4—C3—H3120.3
N1—C2—C3119.04 (11)C5—C4—H4120.1
N1—C2—C7117.69 (11)C3—C4—H4120.1
C3—C2—C7123.27 (11)C6—C5—H5120.4
C2—C3—C4119.34 (11)C4—C5—H5120.4
C5—C4—C3119.77 (12)N1—C6—H6120.1
C6—C5—C4119.16 (11)C5—C6—H6120.1
N1—C6—C5119.87 (11)C2—C7—H7A109.7
C2—C7—Cl1109.97 (8)Cl1—C7—H7A109.7
C6—N1—H0117.9 (12)C2—C7—H7B109.7
C2—N1—H0119.2 (12)Cl1—C7—H7B109.7
C2—C3—H3120.3H7A—C7—H7B108.2
C6—N1—C2—C31.75 (17)C3—C4—C5—C61.54 (19)
C6—N1—C2—C7178.08 (11)C2—N1—C6—C51.23 (18)
N1—C2—C3—C40.59 (17)C4—C5—C6—N10.45 (19)
C7—C2—C3—C4179.22 (11)N1—C2—C7—Cl170.54 (13)
C2—C3—C4—C51.02 (18)C3—C2—C7—Cl1109.28 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H0···Cl20.89 (2)2.08 (2)2.9578 (12)166 (2)
C3—H3···Cl2i0.952.753.5621 (13)143
C6—H6···Cl2ii0.952.633.4730 (13)148
C7—H7B···Cl2iii0.992.853.5296 (14)126
C7—H7A···Cl1iv0.992.823.6603 (15)143
Symmetry codes: (i) x+2, y1/2, z+3/2; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z+2; (iv) x, y+1/2, z+1/2.
(II) 3-chloromethylpyridinium chloride top
Crystal data top
C6H7ClN+·ClF(000) = 672
Mr = 164.03Dx = 1.518 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 23.037 (4) ÅCell parameters from 3132 reflections
b = 4.3310 (8) Åθ = 2.8–30.4°
c = 14.855 (3) ŵ = 0.81 mm1
β = 104.441 (12)°T = 133 K
V = 1435.3 (5) Å3Needle, colourless
Z = 80.50 × 0.06 × 0.03 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1582 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.179
Graphite monochromatorθmax = 30.0°, θmin = 1.8°
Detector resolution: 8.192 pixels mm-1h = 3231
ω and ϕ scansk = 66
8435 measured reflectionsl = 2020
2098 independent 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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0468P)2]
where P = (Fo2 + 2Fc2)/3
2098 reflections(Δ/σ)max = 0.002
86 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
C6H7ClN+·ClV = 1435.3 (5) Å3
Mr = 164.03Z = 8
Monoclinic, C2/cMo Kα radiation
a = 23.037 (4) ŵ = 0.81 mm1
b = 4.3310 (8) ÅT = 133 K
c = 14.855 (3) Å0.50 × 0.06 × 0.03 mm
β = 104.441 (12)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
1582 reflections with I > 2σ(I)
8435 measured reflectionsRint = 0.179
2098 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.54 e Å3
2098 reflectionsΔρmin = 0.57 e Å3
86 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.23991 (3)0.21847 (14)0.63712 (3)0.02789 (17)
Cl20.05793 (3)0.40869 (12)0.33846 (3)0.02246 (16)
N10.05678 (9)0.0692 (4)0.40334 (12)0.0211 (4)
H10.0261 (14)0.166 (7)0.3818 (19)0.031 (8)*
C20.08531 (11)0.1126 (5)0.49168 (14)0.0215 (4)
H20.06820.24110.53010.026*
C30.13930 (10)0.0273 (5)0.52752 (12)0.0189 (4)
C40.16232 (10)0.2140 (5)0.46944 (13)0.0215 (4)
H40.19970.31480.49250.026*
C50.13112 (11)0.2546 (5)0.37808 (14)0.0231 (5)
H50.14680.38340.33810.028*
C60.07780 (11)0.1089 (5)0.34585 (13)0.0221 (4)
H60.05580.13390.28310.027*
C70.17049 (11)0.0168 (6)0.62706 (13)0.0239 (5)
H7A0.17850.18660.65800.029*
H7B0.14460.13640.65840.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0258 (3)0.0329 (3)0.0224 (2)0.0011 (2)0.0011 (2)0.0024 (2)
Cl20.0253 (3)0.0253 (3)0.0176 (2)0.0062 (2)0.00681 (18)0.00161 (18)
N10.0201 (10)0.0224 (9)0.0200 (7)0.0036 (8)0.0034 (7)0.0013 (7)
C20.0246 (12)0.0205 (10)0.0214 (9)0.0009 (9)0.0096 (8)0.0008 (8)
C30.0210 (11)0.0217 (10)0.0144 (7)0.0009 (8)0.0052 (7)0.0017 (7)
C40.0214 (11)0.0249 (11)0.0186 (8)0.0028 (9)0.0054 (8)0.0017 (8)
C50.0248 (12)0.0275 (12)0.0181 (8)0.0019 (9)0.0072 (8)0.0037 (8)
C60.0248 (12)0.0252 (11)0.0155 (8)0.0007 (9)0.0037 (8)0.0009 (8)
C70.0249 (12)0.0306 (11)0.0161 (8)0.0006 (10)0.0048 (8)0.0007 (8)
Geometric parameters (Å, º) top
Cl1—C71.795 (2)N1—H10.81 (3)
N1—C21.326 (3)C2—H20.9500
N1—C61.328 (3)C4—H40.9500
C2—C31.366 (3)C5—H50.9500
C3—C41.381 (3)C6—H60.9500
C3—C71.486 (3)C7—H7A0.9900
C4—C51.379 (3)C7—H7B0.9900
C5—C61.358 (3)
C2—N1—C6123.2 (2)C3—C2—H2120.0
N1—C2—C3120.06 (19)C5—C4—H4119.9
C2—C3—C4118.05 (19)C3—C4—H4119.9
C2—C3—C7119.86 (19)C6—C5—H5120.3
C4—C3—C7122.1 (2)C4—C5—H5120.3
C5—C4—C3120.1 (2)N1—C6—H6120.5
C6—C5—C4119.43 (19)C5—C6—H6120.5
N1—C6—C5119.1 (2)C3—C7—H7A109.6
C3—C7—Cl1110.18 (14)Cl1—C7—H7A109.6
C2—N1—H1119 (2)C3—C7—H7B109.6
C6—N1—H1117.7 (19)Cl1—C7—H7B109.6
N1—C2—H2120.0H7A—C7—H7B108.1
C6—N1—C2—C30.5 (3)C3—C4—C5—C60.2 (3)
N1—C2—C3—C40.5 (3)C2—N1—C6—C50.1 (3)
N1—C2—C3—C7178.7 (2)C4—C5—C6—N10.2 (3)
C2—C3—C4—C50.2 (3)C2—C3—C7—Cl1115.5 (2)
C7—C3—C4—C5178.4 (2)C4—C3—C7—Cl166.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl20.81 (3)2.16 (3)2.967 (2)174 (3)
C2—H2···Cl2i0.952.533.443 (2)161
C7—H7B···Cl2i0.992.813.720 (3)153
C6—H6···Cl2ii0.952.693.383 (2)130
C4—H4···Cl1iii0.952.933.636 (2)132
C5—H5···Cl1iv0.952.933.640 (2)133
C7—H7A···Cl1iii0.992.993.797 (3)139
C7—H7A···Cl2v0.992.953.323 (2)103
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z+1/2; (iii) x, y1, z; (iv) x+1/2, y1/2, z+1; (v) x, y, z+1.
(III) 4-chloromethylpyridinium chloride top
Crystal data top
C6H7ClN+·ClZ = 2
Mr = 164.03F(000) = 168
Triclinic, P1Dx = 1.569 Mg m3
a = 6.9531 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.4755 (6) ÅCell parameters from 4785 reflections
c = 7.4978 (4) Åθ = 2.9–30.5°
α = 71.119 (3)°µ = 0.84 mm1
β = 75.731 (3)°T = 133 K
γ = 72.694 (3)°Tablet, colourless
V = 347.16 (4) Å30.3 × 0.2 × 0.1 mm
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
2024 independent reflections
Radiation source: normal-focus sealed tube1856 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
Detector resolution: 8.192 pixels mm-1θmax = 30.0°, θmin = 2.9°
ω and ϕ scansh = 99
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
k = 1010
Tmin = 0.797, Tmax = 0.928l = 1010
6548 measured reflections
Refinement top
Refinement on F2Primary atom site location: Patterson
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0407P)2 + 0.0639P]
where P = (Fo2 + 2Fc2)/3
2024 reflections(Δ/σ)max = 0.001
86 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C6H7ClN+·Clγ = 72.694 (3)°
Mr = 164.03V = 347.16 (4) Å3
Triclinic, P1Z = 2
a = 6.9531 (4) ÅMo Kα radiation
b = 7.4755 (6) ŵ = 0.84 mm1
c = 7.4978 (4) ÅT = 133 K
α = 71.119 (3)°0.3 × 0.2 × 0.1 mm
β = 75.731 (3)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
2024 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1856 reflections with I > 2σ(I)
Tmin = 0.797, Tmax = 0.928Rint = 0.015
6548 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.48 e Å3
2024 reflectionsΔρmin = 0.25 e Å3
86 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.

Non-bonded distances etc.:

3.6051 (0.0006) Cl1 - Cl1_$7

74.54 (0.03) C7 - Cl1 - Cl1_$7

Operator $7: 1 - x,-y,-z

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.33807 (4)0.06919 (4)0.22620 (4)0.02315 (9)
Cl20.16744 (4)0.67292 (4)0.90416 (3)0.01863 (8)
N10.16318 (14)0.36330 (15)0.70640 (13)0.01928 (19)
H10.108 (3)0.413 (3)0.811 (3)0.048 (5)*
C20.14217 (17)0.18762 (17)0.71882 (15)0.0203 (2)
H20.08370.11200.83670.024*
C30.20571 (16)0.11577 (16)0.55986 (14)0.0182 (2)
H30.19190.00950.56830.022*
C40.29005 (15)0.22861 (15)0.38753 (14)0.01510 (19)
C50.31261 (16)0.41082 (16)0.38110 (15)0.0177 (2)
H50.37200.48930.26570.021*
C60.24790 (17)0.47519 (17)0.54370 (15)0.0194 (2)
H60.26300.59830.54100.023*
C70.35539 (17)0.17116 (16)0.20384 (14)0.0181 (2)
H7A0.49850.18080.15230.022*
H7B0.26960.26490.11010.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02739 (15)0.02024 (15)0.02529 (14)0.00887 (11)0.00080 (10)0.01170 (11)
Cl20.02168 (14)0.01816 (14)0.01735 (13)0.00826 (10)0.00121 (9)0.00660 (9)
N10.0192 (4)0.0218 (5)0.0167 (4)0.0002 (4)0.0035 (3)0.0089 (3)
C20.0204 (5)0.0216 (5)0.0159 (4)0.0038 (4)0.0002 (4)0.0044 (4)
C30.0206 (5)0.0163 (5)0.0178 (4)0.0056 (4)0.0011 (4)0.0051 (4)
C40.0141 (4)0.0155 (5)0.0159 (4)0.0023 (4)0.0028 (3)0.0054 (3)
C50.0199 (5)0.0158 (5)0.0177 (4)0.0058 (4)0.0023 (4)0.0044 (4)
C60.0211 (5)0.0173 (5)0.0213 (5)0.0031 (4)0.0052 (4)0.0073 (4)
C70.0243 (5)0.0159 (5)0.0156 (4)0.0063 (4)0.0014 (4)0.0062 (4)
Geometric parameters (Å, º) top
N1—C21.3353 (15)N1—H10.921 (19)
N1—C61.3466 (14)C2—H20.9500
C2—C31.3849 (15)C3—H30.9500
C3—C41.3929 (14)C5—H50.9500
C4—C51.4011 (14)C6—H60.9500
C4—C71.4987 (14)C7—H7A0.9900
C5—C61.3787 (15)C7—H7B0.9900
C7—Cl11.7874 (11)
C2—N1—C6122.40 (9)C3—C2—H2120.0
N1—C2—C3119.98 (10)C2—C3—H3120.3
C2—C3—C4119.48 (10)C4—C3—H3120.3
C3—C4—C5118.81 (9)C6—C5—H5120.3
C3—C4—C7124.51 (9)C4—C5—H5120.3
C5—C4—C7116.66 (9)N1—C6—H6120.1
C6—C5—C4119.41 (9)C5—C6—H6120.1
N1—C6—C5119.89 (10)C4—C7—H7A108.7
C4—C7—Cl1114.14 (7)Cl1—C7—H7A108.7
C2—N1—H1118.1 (12)C4—C7—H7B108.7
C6—N1—H1119.3 (12)Cl1—C7—H7B108.7
N1—C2—H2120.0H7A—C7—H7B107.6
C6—N1—C2—C31.03 (16)C7—C4—C5—C6177.50 (10)
N1—C2—C3—C40.42 (17)C2—N1—C6—C51.37 (16)
C2—C3—C4—C51.46 (16)C4—C5—C6—N10.27 (16)
C2—C3—C4—C7177.04 (10)C3—C4—C7—Cl15.40 (14)
C3—C4—C5—C61.12 (15)C5—C4—C7—Cl1176.07 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl2i0.921 (19)2.545 (19)3.2301 (10)131.6 (15)
N1—H1···Cl20.921 (19)2.440 (19)3.1369 (10)132.5 (15)
C2—H2···Cl2i0.952.843.3592 (11)115
C6—H6···Cl20.952.843.3393 (11)114
C7—H7B···Cl2ii0.992.903.7286 (11)142
C7—H7B···Cl2iii0.992.963.6809 (12)131
C7—H7A···Cl2iv0.992.743.6589 (11)155
C6—H6···Cl1v0.952.903.5983 (12)132
C3—H3···Cl2vi0.952.863.5141 (11)127
Symmetry codes: (i) x, y+1, z+2; (ii) x, y, z1; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1; (v) x, y+1, z; (vi) x, y1, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC6H7ClN+·ClC6H7ClN+·ClC6H7ClN+·Cl
Mr164.03164.03164.03
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/cTriclinic, P1
Temperature (K)133133133
a, b, c (Å)7.9273 (14), 12.721 (2), 7.4773 (14)23.037 (4), 4.3310 (8), 14.855 (3)6.9531 (4), 7.4755 (6), 7.4978 (4)
α, β, γ (°)90, 102.382 (6), 9090, 104.441 (12), 9071.119 (3), 75.731 (3), 72.694 (3)
V3)736.5 (2)1435.3 (5)347.16 (4)
Z482
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.790.810.84
Crystal size (mm)0.45 × 0.15 × 0.090.50 × 0.06 × 0.030.3 × 0.2 × 0.1
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Bruker SMART 1000 CCD area-detector
diffractometer
Bruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(TWINABS; Bruker, 2002)
Multi-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.795, 0.9280.797, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
15781, 2150, 1864 8435, 2098, 1582 6548, 2024, 1856
Rint0.0300.1790.015
(sin θ/λ)max1)0.7040.7040.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.071, 1.04 0.047, 0.123, 1.01 0.024, 0.070, 1.12
No. of reflections215020982024
No. of parameters878686
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.51, 0.220.54, 0.570.48, 0.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
N1—C61.3411 (16)N1—C21.3449 (16)
C6—N1—C2122.78 (11)N1—C2—C3119.04 (11)
C3—C2—C7—Cl1109.28 (12)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H0···Cl20.89 (2)2.08 (2)2.9578 (12)166 (2)
C3—H3···Cl2i0.952.753.5621 (13)143
C6—H6···Cl2ii0.952.633.4730 (13)148
C7—H7B···Cl2iii0.992.853.5296 (14)126
C7—H7A···Cl1iv0.992.823.6603 (15)143
Symmetry codes: (i) x+2, y1/2, z+3/2; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z+2; (iv) x, y+1/2, z+1/2.
Selected geometric parameters (Å, º) for (II) top
N1—C21.326 (3)N1—C61.328 (3)
C2—N1—C6123.2 (2)C2—C3—C4118.05 (19)
C4—C3—C7—Cl166.3 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl20.81 (3)2.16 (3)2.967 (2)174 (3)
C2—H2···Cl2i0.952.533.443 (2)161
C7—H7B···Cl2i0.992.813.720 (3)153
C6—H6···Cl2ii0.952.693.383 (2)130
C4—H4···Cl1iii0.952.933.636 (2)132
C5—H5···Cl1iv0.952.933.640 (2)133
C7—H7A···Cl1iii0.992.993.797 (3)139
C7—H7A···Cl2v0.992.953.323 (2)103
Symmetry codes: (i) x, y+1, z+1; (ii) x, y1, z+1/2; (iii) x, y1, z; (iv) x+1/2, y1/2, z+1; (v) x, y, z+1.
Selected geometric parameters (Å, º) for (III) top
N1—C21.3353 (15)N1—C61.3466 (14)
C2—N1—C6122.40 (9)C3—C4—C7124.51 (9)
C3—C4—C5118.81 (9)
C3—C4—C7—Cl15.40 (14)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl2i0.921 (19)2.545 (19)3.2301 (10)131.6 (15)
N1—H1···Cl20.921 (19)2.440 (19)3.1369 (10)132.5 (15)
C2—H2···Cl2i0.952.843.3592 (11)115
C6—H6···Cl20.952.843.3393 (11)114
C7—H7B···Cl2ii0.992.903.7286 (11)142
C7—H7B···Cl2iii0.992.963.6809 (12)131
C7—H7A···Cl2iv0.992.743.6589 (11)155
C6—H6···Cl1v0.952.903.5983 (12)132
C3—H3···Cl2vi0.952.863.5141 (11)127
Symmetry codes: (i) x, y+1, z+2; (ii) x, y, z1; (iii) x, y+1, z+1; (iv) x+1, y+1, z+1; (v) x, y+1, z; (vi) x, y1, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds