N-Chloromethyl-4-(dimethylamino)-N,N-dimethylanilinium chloride

Batsanov, A.S.; Collings, J.C.; Marder, T.B.

doi:10.1107/S1600536804033860

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 2| February 2005| Pages o201-o202

https://doi.org/10.1107/S1600536804033860

N-Chloromethyl-4-(dimethylamino)-N,N-dimethylanilinium chloride

Andrei S. Batsanov,^a ^* Jonathan C. Collings ^a and Todd B. Marder ^a

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

(Received 14 December 2004; accepted 20 December 2004; online 8 January 2005)

In the cation of the title compound C₁₁H₁₈ClN₂⁺·Cl⁻, the quaternary N atom has a distorted tetrahedral geometry, and the other N a nearly planar-trigonal (owing to conjugation with the benzene ring) bonding geometry.

Comment

The title compound, (I), was obtained as an accidental by-product while co-crystallizing N,N,N′,N′-tetramethyl-1,4-phenylenediamine (TMPD) and octafluoronaphthalene (OFN) from CH₂Cl₂ (Collings et al., 2004 ). The asymmetric unit comprises one chloride anion and one Me₂(ClCH₂)N⁺–C₆H₄–NMe₂ cation. This cation has been structurally studied earlier as its tetraphenylborate salt dichloromethane solvate (II) by Winter (2001 ), and the non-chlorinated analogue trimethyl{4-(dimethylamino)phenyl}ammonium cation as its ozonide salt (III) by Assenmacher & Jansen (1995 ). Unfortunately, the precision of both structure determinations was limited (R = 0.09), in (III) owing to disorder of the ozonide anion and to chemical instability (the compound explodes at 303 K), and in (II) probably because of some unrecognized disorder, as indicated by the discrepant N⁺—CH₃ bond lengths of 1.50 (1) and 1.62 (1) Å.

The atom N2 has nearly planar geometry, the sum of the bond angles being 358.1°. The C10/N2/C11 plane forms an angle of 11.9 (1)° with the benzene ring plane, so that the pπ orbitals of N2 and C4 are nearly coplanar. This and the N2—C4 bond distance of 1.371 (2) Å are indicative of strong π-conjugation. The quaternary atom N1 has a distorted tetrahedral environment. The chloride anion is surrounded by eight H atoms of four different cations at Cl⋯H distances of 2.46 (2) to 2.60 (2) Å (calculated for the idealized C—H bond lengths of 1.08 Å).

Figure 1
The cation and anion in the structure of (I

). Atomic displacement ellipsoids are drawn at the 50% probability level.

Experimental

Slow evaporation at room temperature of a dichloromethane solution of equimolar amounts of TMPD and OFN yielded mainly co-crystals of TMPD and OFN (1:1) and a few smaller crystals of different habit, which were identified by the present study as (I).

Crystal data

C₁₁H₁₈ClN₂⁺·Cl⁻
M_r = 249.17
Monoclinic, P2₁/c
a = 15.121 (3) Å
b = 7.234 (1) Å
c = 12.773 (2) Å
β = 114.95 (1)°
V = 1266.8 (4) Å³
Z = 4
D_x = 1.306 Mg m⁻³
Mo Kα radiation
Cell parameters from 977 reflections
θ = 10.2–26.9°
μ = 0.48 mm⁻¹
T = 120 (2) K
Parallelepiped, colourless
0.22 × 0.15 × 0.10 mm

Data collection

Bruker SMART 6000 CCD area-detector diffractometer
ω scans
Absorption correction: by integration (XPREP in SHELXTL; Bruker, 2001b )T_min = 0.923, T_max = 0.962
17336 measured reflections
3689 independent reflections
2994 reflections with I > 2σ(I)
R_int = 0.047
θ_max = 30.0°
h = −21 → 21
k = −10 → 10
l = −17 → 17

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.115
S = 1.05
3689 reflections
138 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0621P)² + 0.4607P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Methyl groups bonded to N2 were refined as rigid bodies rotating around the N2—C bonds, and other H atoms were treated as riding on the corresponding C atoms in idealized positions. The C—H distances were fixed at 0.98 Å for methyl, 0.99 Å for methylene, 0.95 Å for benzene H atoms, with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the rest.

Data collection: SMART (Bruker, 2001a ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001a); program(s) used to solve structure: SHELXTL (Bruker, 2001b); 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/S1600536804033860/bt6570sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804033860/bt6570Isup2.hkl

Computing details top

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

N-Chloromethyl-4-(dimethylamino)-N,N-dimethylanilinium chloride top

Crystal data top

C₁₁H₁₈ClN₂⁺·Cl⁻	F(000) = 528
M_r = 249.17	D_x = 1.306 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 977 reflections
a = 15.121 (3) Å	θ = 10.2–26.9°
b = 7.234 (1) Å	µ = 0.48 mm⁻¹
c = 12.773 (2) Å	T = 120 K
β = 114.95 (1)°	Parallelepiped, colourless
V = 1266.8 (4) Å³	0.22 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker SMART 6000 CCD area-detector diffractometer	3689 independent reflections
Radiation source: fine-focus sealed tube	2994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 5.6 pixels mm^-1	θ_max = 30.0°, θ_min = 1.5°
ω scans	h = −21→21
Absorption correction: integration (XPREP;SHELXTL), R(int) = 0.053 before correction	k = −10→10
T_min = 0.923, T_max = 0.962	l = −17→17
17336 measured 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0621P)² + 0.4607P] where P = (F_o² + 2F_c²)/3
3689 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.51 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 (30 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.83 cm.

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.13260 (3)	0.94831 (6)	0.50991 (4)	0.03711 (13)
N1	0.14834 (9)	0.61049 (18)	0.42545 (11)	0.0191 (2)
N2	0.56069 (10)	0.6864 (2)	0.65487 (13)	0.0270 (3)
C1	0.25717 (10)	0.6300 (2)	0.48375 (13)	0.0196 (3)
C2	0.30675 (11)	0.5631 (2)	0.59580 (13)	0.0212 (3)
H2	0.2715	0.5060	0.6335	0.025*
C3	0.40730 (11)	0.5796 (2)	0.65257 (14)	0.0233 (3)
H3	0.4403	0.5332	0.7289	0.028*
C4	0.46152 (11)	0.6645 (2)	0.59844 (14)	0.0216 (3)
C5	0.40898 (11)	0.7286 (2)	0.48480 (14)	0.0237 (3)
H5	0.4433	0.7837	0.4454	0.028*
C6	0.30805 (11)	0.7133 (2)	0.42875 (14)	0.0233 (3)
H6	0.2741	0.7602	0.3527	0.028*
C7	0.10071 (11)	0.7136 (2)	0.49168 (14)	0.0232 (3)
H72	0.1205	0.6556	0.5685	0.028*
H73	0.0290	0.7026	0.4497	0.028*
C8	0.11909 (11)	0.4104 (2)	0.42498 (14)	0.0226 (3)
H81	0.0478	0.4009	0.3904	0.034*
H82	0.1455	0.3639	0.5044	0.034*
H83	0.1450	0.3368	0.3798	0.034*
C9	0.10507 (12)	0.6747 (3)	0.30206 (14)	0.0285 (4)
H91	0.0338	0.6671	0.2703	0.043*
H92	0.1287	0.5960	0.2568	0.043*
H93	0.1245	0.8030	0.2987	0.043*
C10	0.61542 (12)	0.5952 (3)	0.76493 (16)	0.0328 (4)
H101	0.6052	0.4614	0.7555	0.049*
H102	0.5930	0.6403	0.8219	0.049*
H103	0.6850	0.6226	0.7915	0.049*
C11	0.61399 (12)	0.7603 (3)	0.59259 (16)	0.0292 (4)
H111	0.6829	0.7744	0.6457	0.044*
H112	0.5869	0.8810	0.5599	0.044*
H113	0.6081	0.6754	0.5302	0.044*
Cl2	0.13930 (3)	0.37737 (6)	0.70918 (3)	0.02326 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0342 (2)	0.0226 (2)	0.0516 (3)	0.00034 (16)	0.0153 (2)	−0.00322 (18)
N1	0.0148 (5)	0.0219 (6)	0.0193 (6)	−0.0002 (5)	0.0059 (4)	0.0022 (5)
N2	0.0160 (6)	0.0309 (7)	0.0293 (7)	−0.0019 (5)	0.0046 (5)	−0.0022 (6)
C1	0.0136 (6)	0.0208 (7)	0.0223 (7)	0.0000 (5)	0.0055 (5)	0.0012 (5)
C2	0.0191 (7)	0.0227 (7)	0.0216 (7)	0.0000 (5)	0.0083 (6)	0.0011 (5)
C3	0.0187 (7)	0.0251 (8)	0.0220 (7)	0.0013 (6)	0.0048 (6)	0.0008 (6)
C4	0.0162 (6)	0.0192 (7)	0.0272 (7)	−0.0006 (5)	0.0070 (6)	−0.0023 (6)
C5	0.0174 (7)	0.0227 (7)	0.0306 (8)	−0.0004 (5)	0.0097 (6)	0.0046 (6)
C6	0.0187 (7)	0.0241 (7)	0.0248 (7)	0.0005 (6)	0.0071 (6)	0.0065 (6)
C7	0.0191 (7)	0.0220 (7)	0.0279 (8)	0.0005 (6)	0.0093 (6)	−0.0028 (6)
C8	0.0213 (7)	0.0213 (7)	0.0232 (7)	−0.0037 (5)	0.0076 (6)	−0.0041 (5)
C9	0.0180 (7)	0.0426 (10)	0.0208 (7)	0.0005 (7)	0.0043 (6)	0.0102 (7)
C10	0.0199 (8)	0.0352 (10)	0.0332 (9)	0.0005 (7)	0.0013 (7)	0.0002 (7)
C11	0.0167 (7)	0.0258 (8)	0.0415 (10)	−0.0033 (6)	0.0090 (7)	−0.0016 (7)
Cl2	0.01681 (17)	0.0308 (2)	0.02126 (18)	0.00192 (13)	0.00712 (13)	0.00527 (14)

Geometric parameters (Å, º) top

Cl1—C7	1.7532 (17)	C5—H5	0.9500
N1—C1	1.4995 (19)	C6—H6	0.9500
N1—C9	1.5027 (19)	C7—H72	0.9900
N1—C8	1.513 (2)	C7—H73	0.9900
N1—C7	1.518 (2)	C8—H81	0.9800
N2—C4	1.372 (2)	C8—H82	0.9800
N2—C11	1.452 (2)	C8—H83	0.9800
N2—C10	1.454 (2)	C9—H91	0.9800
C1—C6	1.380 (2)	C9—H92	0.9800
C1—C2	1.392 (2)	C9—H93	0.9800
C2—C3	1.386 (2)	C10—H101	0.9800
C2—H2	0.9500	C10—H102	0.9800
C3—C4	1.416 (2)	C10—H103	0.9800
C3—H3	0.9500	C11—H111	0.9800
C4—C5	1.407 (2)	C11—H112	0.9800
C5—C6	1.390 (2)	C11—H113	0.9800

C1—N1—C9	113.14 (12)	Cl1—C7—H72	109.1
C1—N1—C8	110.47 (12)	N1—C7—H73	109.1
C9—N1—C8	107.13 (12)	Cl1—C7—H73	109.1
C1—N1—C7	110.87 (12)	H72—C7—H73	107.9
C9—N1—C7	109.47 (12)	N1—C8—H81	109.5
C8—N1—C7	105.42 (11)	N1—C8—H82	109.5
C4—N2—C11	119.40 (14)	H81—C8—H82	109.5
C4—N2—C10	120.39 (14)	N1—C8—H83	109.5
C11—N2—C10	118.40 (14)	H81—C8—H83	109.5
C6—C1—C2	120.06 (14)	H82—C8—H83	109.5
C6—C1—N1	121.26 (13)	N1—C9—H91	109.5
C2—C1—N1	118.68 (13)	N1—C9—H92	109.5
C3—C2—C1	120.26 (14)	H91—C9—H92	109.5
C3—C2—H2	119.9	N1—C9—H93	109.5
C1—C2—H2	119.9	H91—C9—H93	109.5
C2—C3—C4	121.00 (14)	H92—C9—H93	109.5
C2—C3—H3	119.5	N2—C10—H101	109.5
C4—C3—H3	119.5	N2—C10—H102	109.5
N2—C4—C5	121.36 (14)	H101—C10—H102	109.5
N2—C4—C3	121.55 (14)	N2—C10—H103	109.5
C5—C4—C3	117.08 (14)	H101—C10—H103	109.5
C6—C5—C4	121.64 (14)	H102—C10—H103	109.5
C6—C5—H5	119.2	N2—C11—H111	109.5
C4—C5—H5	119.2	N2—C11—H112	109.5
C1—C6—C5	119.95 (14)	H111—C11—H112	109.5
C1—C6—H6	120.0	N2—C11—H113	109.5
C5—C6—H6	120.0	H111—C11—H113	109.5
N1—C7—Cl1	112.42 (11)	H112—C11—H113	109.5
N1—C7—H72	109.1

Cl1—C7—N1—C1	56.59 (14)	C5—C4—N2—C11	−6.2 (2)
C7—N1—C1—C2	61.05 (18)	C3—C4—N2—C10	10.5 (2)
C6—C1—N1—C9	4.9 (2)

References

Assenmacher, W. & Jansen, M. (1995). Z. Kristallogr. 210, 704–706. CrossRef CAS Web of Science Google Scholar
Bruker (2001a). SMART (Version 5.625) and SAINT (Version 6.02A). Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Bruker (2001b). SHELXTL. Versions 5.10 & 6.12. Bruker AXS, Madison, Wisconsin, USA. Google Scholar
Collings, J. C., Batsanov, A. S. & Marder, T. B. (2004). Unpublished results. Google Scholar
Winter, R. (2001). PhD Thesis, Institut für Anorganische Chemie, University of Stuttgart, Germany. Cited from CCDC-175408, refcode XILVET. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 2| February 2005| Pages o201-o202

https://doi.org/10.1107/S1600536804033860

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-Chloro­methyl-4-(di­methylamino)-N,N-di­methylanilinium chloride

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

N-Chloromethyl-4-(dimethylamino)-N,N-dimethylanilinium chloride