N-[3-(2,6-Dimethylanilino)-1-methylbut-2-enylidene]-2,6-dimethylanilinium chloride

Jiménez-Pérez, V.M.; Bernès, S.; Munõz, B.M.; Kharisov, B.I.; Vela, A.V.

doi:10.1107/S1600536809020571

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages o1671-o1672

doi:10.1107/S1600536809020571

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N-[3-(2,6-Dimethylanilino)-1-methylbut-2-enylidene]-2,6-dimethylanilinium chloride †

Víctor M. Jiménez-Pérez,^a ^* Sylvain Bernès,^a Blanca M. Munõz,^b Boris I. Kharisov ^a and Andrea V. Vela ^a

^aFacultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, Av. Pedro de Alba s/n, 66451 San Nicolás de los Garza, N. L., Mexico, and ^bCINVESTAV-Monterrey, Vía del conocimiento 201, PIIT. Autopista al Aeropuerto Km. 9.5, Apodaca, N. L. Mexico
^*Correspondence e-mail: vjimenez@fcq.uanl.mx

(Received 18 March 2009; accepted 29 May 2009; online 24 June 2009)

The title salt, C₂₁H₂₇N₂⁺·Cl⁻ resulted from the condensation between 2,6-dimethylaniline and acetylacetone in acidified ethanol. The bulky cation is stabilized in a β-iminoenamine tautomeric form, and presents a W-shaped conformation. The benzene rings are arranged almost parallel, with a dihedral angle of 6.58 (4)° between the mean planes. Both N—H groups in the cation form strong hydrogen bonds with two symmetry-related chloride anions. The resulting supramolecular structure is a one dimensional polymer running along [001], alternating cations and anions. The π–π interaction observed in the molecule, characterized by a centroid–centroid separation of 4.298 (4) Å, is thus extended to the chains, with separations of 5.222 (4) Å between benzene rings of neighbouring cations in the crystal.

Related literature

For the synthesis, properties, and uses of β-diketimines and β-diketiminates, see: Dorman (1966 ); Park (2007 ); Bourget-Merle et al. (2002 ); Nagendran & Roesky (2008 ); Holland & Tolman (2000 ); Stender et al. (2001 ); Carey et al., 2003 . For W-shaped cations related to the title compound, see: Brownstein et al. (1983 ); Kuhn et al. (2000 ); Lesikar & Richards (2006 ).

Experimental

Crystal data

C₂₁H₂₇N₂⁺·Cl⁻
M_r = 342.90
Tetragonal, I 4₁ /a
a = 28.639 (5) Å
c = 10.150 (3) Å
V = 8325 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 298 K
0.50 × 0.36 × 0.22 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan XSCANS (Siemens, 1996 ) T_min = 0.854, T_max = 0.959
7193 measured reflections
3671 independent reflections
1541 reflections with I > 2σ(I)
R_int = 0.049
3 standard reflections every 97 reflections intensity decay: 1.5%

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.171
S = 1.12
3671 reflections
229 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯Cl1	1.01 (3)	2.12 (3)	3.115 (3)	170 (3)
N7—H7⋯Cl1ⁱ	1.00 (3)	2.12 (3)	3.110 (4)	170 (3)
Symmetry code: (i) x, y, z-1.

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020571/fl2243sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020571/fl2243Isup2.hkl

checkCIF report

Comment top

Many synthetic routes are currently available to synthesize symmetric and unsymmetric β-diketimines, including the co-condensation reaction of a ketone and a primary amine (Dorman, 1966; Park, 2007). These ligands proved to be very versatile and diverse, considering the possible variation of both coordination modes and of groups bonded to the N atoms and to the α- and β- C atoms. Indeed, β-diketiminates are the most used ligands in coordination chemistry for the stabilization of low coordinate and low oxidation states of main group or transition elements (Bourget-Merle et al., 2002; Nagendran & Roesky, 2008). β-Diketiminates complexes have been used as catalysts and even as structural models of protein active sites (Holland & Tolman, 2000).

Neutral β-diketimines invariably show a U-shaped conformation, favoured over other possible conformers by the formation of an intramolecular hydrogen bond involving the amine and imine N atoms (Dorman, 1966; Stender et al., 2001; Carey et al., 2003). However, if the β-diketimine is protonated, the backbone molecule adopts a new W-conformation, since the protonated N atom is able to form a strong intra-ionic N—H···Cl bond. Such behaviour has been observed in three salts closely related to the title compound where phenyl (Brownstein et al., 1983), methyl (Kuhn et al., 2000), and mesityl (Lesikar & Richards, 2006) have replaced the 2,6-dimethylphenyl. The supramolecular one-dimensional structure generated by this hydrogen bond is expected to be a strong stabilizing factor, as anions and cations alternate in a chain structure, which has a theoretical Madelung constant of 1.38.

In the title salt, the cation adopts the W-shaped conformation, and thus presents a non-crystallographic twofold axis passing through the central atom C9 (Fig. 1). Both N atoms are protonated, indicating that the β-iminoenamine tautomeric form is stabilized in the solid state. A parallel arrangement is observed for benzene rings, which are separated by 4.298 (4) Å. A similar arrangement was found with the mesityl-including cation, although the benzene separations are larger, probably because of the hindering character of mesityl (centroid-to-centroid distances: 4.348, 4.823, or 4.881 Å, depending of the nature of the counterion; Lesikar & Richards, 2006). Unexpectedly, the phenyl-containing salt has little intramolecular π–π interaction, with non-parallel phenyl rings separated by 5.480 Å (Brownstein et al., 1983). In the title cation, benzene rings are close to be parallel, the dihedral angle between mean planes being 6.58 (4)°.

Regarding the crystal structure, both amine and imine NH functionalities, N7 and N11, are involved in strong N—H···Cl hydrogen bonds with symmetry-related Cl^- ions. The network of hydrogen bonds forms a one-dimensional supramolecular structure along the short cell axis c (Fig. 2). Cations and anions alternate in a chain, with all benzene rings oriented in the same direction. This arrangement allows to extend the π–π interactions to the whole polymeric structure, with a separation of 5.222 (4) Å between benzene rings of neighbouring cations. No significant contacts are observed between chains in the crystal.

Related literature top

For the synthesis, properties, and uses of β-diketimines and β-diketiminates, see: Dorman (1966); Park (2007); Bourget-Merle et al. (2002); Nagendran & Roesky (2008); Holland & Tolman (2000); Stender et al. (2001); Carey et al., 2003. For W-shaped cations related to the title compound, see: Brownstein et al. (1983); Kuhn et al. (2000); Lesikar & Richards (2006).

Experimental top

The title salt was prepared by mixing acetylacetone (25.03 g, 0.25 mol) and 2,6-dimethylaniline (60.5 g, 0.5 mol) in 12 N hydrochloric acid (20.8 ml, 0.25 mol HCl). The mixture was heated to 393 K for 4 h., allowing the water to distil. The reaction was then further heated to 413 K overnight. The resulting solid was recrystallized from hot ethanol, yielding 87.6 g of the title salt (94%). NMR data are in agreement with the X-ray structure (see archived CIF).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The title compound (asymmetric unit) with displacement ellipsoids at the 25% probability level. The dashed bond corresponds to the N—H···Cl hydrogen bond.
	Fig. 2. A part of the crystal structure of the title compound, with hydrogen bonds displayed as dashed lines. Two neighbouring chains are shown, with Cl^- ions represented as green spheres, and omitting all C-bonded H atoms.

N-[3-(2,6-Dimethylanilino)-1-methylbut-2-enylidene]-2,6-dimethylanilinium chloride top

Crystal data top

C₂₁H₂₇N₂⁺·Cl⁻	D_x = 1.094 Mg m⁻³
M_r = 342.90	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 77 reflections
Hall symbol: -I 4ad	θ = 4.6–12.3°
a = 28.639 (5) Å	µ = 0.19 mm⁻¹
c = 10.150 (3) Å	T = 298 K
V = 8325 (3) Å³	Prism, colorless
Z = 16	0.50 × 0.36 × 0.22 mm
F(000) = 2944

Data collection top

Bruker P4 diffractometer	1541 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.049
Graphite monochromator	θ_max = 25.1°, θ_min = 2.0°
ω scans	h = −34→13
Absorption correction: ψ scan XSCANS (Siemens, 1996)	k = −34→1
T_min = 0.854, T_max = 0.959	l = −12→12
7193 measured reflections	3 standard reflections every 97 reflections
3671 independent reflections	intensity decay: 1.5%

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.06P)²] where P = (F_o² + 2F_c²)/3
3671 reflections	(Δ/σ)_max < 0.001
229 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³
0 constraints

Crystal data top

C₂₁H₂₇N₂⁺·Cl⁻	Z = 16
M_r = 342.90	Mo Kα radiation
Tetragonal, I4₁/a	µ = 0.19 mm⁻¹
a = 28.639 (5) Å	T = 298 K
c = 10.150 (3) Å	0.50 × 0.36 × 0.22 mm
V = 8325 (3) Å³

Data collection top

Bruker P4 diffractometer	1541 reflections with I > 2σ(I)
Absorption correction: ψ scan XSCANS (Siemens, 1996)	R_int = 0.049
T_min = 0.854, T_max = 0.959	3 standard reflections every 97 reflections
7193 measured reflections	intensity decay: 1.5%
3671 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.43 e Å⁻³
3671 reflections	Δρ_min = −0.32 e Å⁻³
229 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.89962 (3)	0.22980 (3)	0.87464 (9)	0.0839 (4)
C1	0.84317 (12)	0.14527 (11)	0.1392 (5)	0.0623 (9)
C2	0.79611 (13)	0.15570 (13)	0.1335 (6)	0.0824 (11)
C3	0.76486 (14)	0.11910 (17)	0.1272 (7)	0.1044 (14)
H3A	0.7330	0.1251	0.1223	0.125*
C4	0.78047 (16)	0.07434 (16)	0.1282 (8)	0.1031 (13)
H4A	0.7591	0.0499	0.1251	0.124*
C5	0.82605 (17)	0.06477 (14)	0.1334 (7)	0.1001 (13)
H5A	0.8360	0.0339	0.1322	0.120*
C6	0.85857 (13)	0.10015 (13)	0.1404 (6)	0.0800 (12)
N7	0.87572 (10)	0.18264 (10)	0.1423 (4)	0.0623 (8)
H7	0.8870 (13)	0.1961 (13)	0.057 (3)	0.075*
C8	0.89275 (12)	0.20174 (12)	0.2519 (3)	0.0528 (9)
C9	0.87894 (9)	0.18619 (10)	0.3745 (3)	0.0565 (8)
H9A	0.8571	0.1622	0.3753	0.068*
C10	0.89372 (12)	0.20212 (12)	0.4965 (3)	0.0527 (9)
N11	0.87729 (10)	0.18288 (10)	0.6051 (3)	0.0592 (8)
H11	0.8875 (13)	0.1952 (12)	0.693 (3)	0.071*
C12	0.84451 (12)	0.14556 (11)	0.6106 (5)	0.0589 (9)
C13	0.79765 (13)	0.15614 (12)	0.6194 (7)	0.0801 (10)
C14	0.76658 (13)	0.11931 (15)	0.6254 (7)	0.1053 (13)
H14A	0.7347	0.1253	0.6284	0.126*
C15	0.78209 (15)	0.07445 (14)	0.6271 (7)	0.0982 (12)
H15A	0.7607	0.0501	0.6335	0.118*
C16	0.82809 (16)	0.06482 (12)	0.6197 (6)	0.0886 (11)
H16A	0.8380	0.0339	0.6192	0.106*
C17	0.86083 (12)	0.10022 (12)	0.6127 (6)	0.0725 (10)
C18	0.78029 (14)	0.20557 (14)	0.1303 (8)	0.144 (2)
H18A	0.7929	0.2219	0.2049	0.217*
H18B	0.7468	0.2067	0.1336	0.217*
H18C	0.7910	0.2201	0.0506	0.217*
C19	0.90988 (14)	0.08956 (14)	0.1468 (7)	0.130 (2)
H19A	0.9144	0.0564	0.1496	0.195*
H19B	0.9230	0.1035	0.2245	0.195*
H19C	0.9251	0.1021	0.0702	0.195*
C20	0.92742 (11)	0.23930 (11)	0.2268 (3)	0.0681 (10)
H20A	0.9303	0.2443	0.1336	0.102*
H20B	0.9572	0.2303	0.2622	0.102*
H20C	0.9172	0.2676	0.2683	0.102*
C21	0.92784 (11)	0.23993 (11)	0.5203 (3)	0.0685 (10)
H21A	0.9306	0.2454	0.6134	0.103*
H21B	0.9174	0.2680	0.4777	0.103*
H21C	0.9577	0.2310	0.4854	0.103*
C22	0.78164 (14)	0.20619 (14)	0.6190 (8)	0.1295 (17)
H22A	0.7974	0.2230	0.6876	0.194*
H22B	0.7486	0.2073	0.6338	0.194*
H22C	0.7887	0.2201	0.5354	0.194*
C23	0.91199 (13)	0.08983 (13)	0.6062 (7)	0.1174 (17)
H23A	0.9168	0.0567	0.6127	0.176*
H23B	0.9277	0.1052	0.6778	0.176*
H23C	0.9244	0.1009	0.5241	0.176*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1080 (7)	0.1037 (7)	0.0400 (4)	−0.0103 (5)	−0.0002 (6)	0.0004 (6)
C1	0.077 (2)	0.063 (2)	0.047 (2)	−0.0056 (19)	−0.003 (2)	−0.007 (2)
C2	0.084 (3)	0.076 (2)	0.087 (3)	−0.002 (2)	−0.023 (4)	−0.011 (4)
C3	0.081 (3)	0.119 (3)	0.113 (3)	−0.013 (3)	−0.034 (5)	0.002 (7)
C4	0.106 (3)	0.098 (3)	0.105 (3)	−0.028 (3)	0.000 (6)	0.001 (6)
C5	0.121 (3)	0.075 (3)	0.105 (3)	−0.007 (3)	0.000 (5)	−0.023 (4)
C6	0.089 (3)	0.068 (2)	0.083 (3)	−0.009 (2)	−0.006 (3)	−0.003 (3)
N7	0.0791 (19)	0.0624 (17)	0.045 (2)	−0.0064 (15)	−0.0018 (18)	−0.0033 (18)
C8	0.062 (2)	0.054 (2)	0.0422 (19)	0.0017 (18)	−0.0027 (17)	−0.0015 (17)
C9	0.0653 (18)	0.0616 (18)	0.0426 (15)	−0.0103 (14)	−0.0007 (19)	−0.0040 (19)
C10	0.060 (2)	0.052 (2)	0.045 (2)	−0.0028 (17)	−0.0009 (17)	−0.0006 (17)
N11	0.0787 (18)	0.0613 (17)	0.038 (2)	−0.0112 (14)	−0.0008 (17)	0.0027 (16)
C12	0.073 (2)	0.064 (2)	0.040 (2)	−0.0079 (19)	0.006 (2)	0.004 (2)
C13	0.085 (3)	0.072 (2)	0.082 (3)	−0.009 (2)	0.011 (4)	−0.001 (4)
C14	0.078 (3)	0.106 (3)	0.132 (4)	−0.013 (3)	0.007 (5)	0.015 (7)
C15	0.105 (3)	0.082 (3)	0.107 (3)	−0.021 (2)	0.025 (5)	0.011 (5)
C16	0.118 (3)	0.068 (2)	0.079 (3)	−0.007 (2)	0.009 (5)	−0.005 (4)
C17	0.084 (2)	0.066 (2)	0.067 (3)	−0.007 (2)	−0.006 (3)	0.011 (3)
C18	0.108 (3)	0.104 (3)	0.221 (6)	0.025 (3)	−0.046 (7)	−0.006 (7)
C19	0.103 (3)	0.092 (3)	0.194 (6)	0.016 (2)	−0.004 (5)	−0.012 (5)
C20	0.087 (2)	0.070 (2)	0.0476 (18)	−0.017 (2)	0.010 (2)	0.0013 (17)
C21	0.083 (2)	0.072 (2)	0.0499 (19)	−0.013 (2)	−0.006 (2)	0.0015 (18)
C22	0.103 (3)	0.095 (3)	0.190 (5)	0.017 (2)	0.028 (7)	−0.001 (6)
C23	0.096 (3)	0.092 (3)	0.164 (5)	0.013 (2)	−0.022 (4)	0.006 (4)

Geometric parameters (Å, º) top

C1—C6	1.366 (4)	C14—C15	1.360 (5)
C1—C2	1.382 (5)	C14—H14A	0.9300
C1—N7	1.419 (4)	C15—C16	1.348 (5)
C2—C3	1.380 (5)	C15—H15A	0.9300
C2—C18	1.499 (5)	C16—C17	1.383 (4)
C3—C4	1.358 (5)	C16—H16A	0.9300
C3—H3A	0.9300	C17—C23	1.497 (4)
C4—C5	1.335 (5)	C18—H18A	0.9600
C4—H4A	0.9300	C18—H18B	0.9600
C5—C6	1.378 (5)	C18—H18C	0.9600
C5—H5A	0.9300	C19—H19A	0.9600
C6—C19	1.502 (5)	C19—H19B	0.9600
N7—C8	1.332 (4)	C19—H19C	0.9600
N7—H7	1.00 (3)	C20—H20A	0.9600
C8—C9	1.379 (4)	C20—H20B	0.9600
C8—C20	1.486 (4)	C20—H20C	0.9600
C9—C10	1.386 (4)	C21—H21A	0.9600
C9—H9A	0.9300	C21—H21B	0.9600
C10—N11	1.319 (4)	C21—H21C	0.9600
C10—C21	1.479 (4)	C22—H22A	0.9600
N11—C12	1.424 (4)	C22—H22B	0.9600
N11—H11	1.01 (3)	C22—H22C	0.9600
C12—C13	1.379 (4)	C23—H23A	0.9600
C12—C17	1.380 (4)	C23—H23B	0.9600
C13—C14	1.381 (5)	C23—H23C	0.9600
C13—C22	1.505 (5)

C6—C1—C2	121.3 (3)	C14—C15—H15A	119.6
C6—C1—N7	120.1 (3)	C15—C16—C17	121.0 (4)
C2—C1—N7	118.6 (3)	C15—C16—H16A	119.5
C3—C2—C1	118.1 (3)	C17—C16—H16A	119.5
C3—C2—C18	121.8 (4)	C12—C17—C16	117.4 (3)
C1—C2—C18	120.1 (3)	C12—C17—C23	121.2 (3)
C4—C3—C2	120.2 (4)	C16—C17—C23	121.4 (3)
C4—C3—H3A	119.9	C2—C18—H18A	109.5
C2—C3—H3A	119.9	C2—C18—H18B	109.5
C5—C4—C3	121.1 (4)	H18A—C18—H18B	109.5
C5—C4—H4A	119.5	C2—C18—H18C	109.5
C3—C4—H4A	119.5	H18A—C18—H18C	109.5
C4—C5—C6	120.8 (4)	H18B—C18—H18C	109.5
C4—C5—H5A	119.6	C6—C19—H19A	109.5
C6—C5—H5A	119.6	C6—C19—H19B	109.5
C1—C6—C5	118.5 (4)	H19A—C19—H19B	109.5
C1—C6—C19	120.5 (3)	C6—C19—H19C	109.5
C5—C6—C19	121.0 (4)	H19A—C19—H19C	109.5
C8—N7—C1	124.6 (4)	H19B—C19—H19C	109.5
C8—N7—H7	117 (2)	C8—C20—H20A	109.5
C1—N7—H7	119 (2)	C8—C20—H20B	109.5
N7—C8—C9	121.0 (3)	H20A—C20—H20B	109.5
N7—C8—C20	113.5 (3)	C8—C20—H20C	109.5
C9—C8—C20	125.5 (3)	H20A—C20—H20C	109.5
C8—C9—C10	127.7 (3)	H20B—C20—H20C	109.5
C8—C9—H9A	116.1	C10—C21—H21A	109.5
C10—C9—H9A	116.1	C10—C21—H21B	109.5
N11—C10—C9	120.0 (3)	H21A—C21—H21B	109.5
N11—C10—C21	113.9 (3)	C10—C21—H21C	109.5
C9—C10—C21	126.1 (3)	H21A—C21—H21C	109.5
C10—N11—C12	125.6 (4)	H21B—C21—H21C	109.5
C10—N11—H11	120 (2)	C13—C22—H22A	109.5
C12—N11—H11	115 (2)	C13—C22—H22B	109.5
C13—C12—C17	122.4 (3)	H22A—C22—H22B	109.5
C13—C12—N11	118.6 (3)	C13—C22—H22C	109.5
C17—C12—N11	118.9 (3)	H22A—C22—H22C	109.5
C12—C13—C14	117.5 (3)	H22B—C22—H22C	109.5
C12—C13—C22	120.4 (3)	C17—C23—H23A	109.5
C14—C13—C22	122.1 (4)	C17—C23—H23B	109.5
C15—C14—C13	120.8 (4)	H23A—C23—H23B	109.5
C15—C14—H14A	119.6	C17—C23—H23C	109.5
C13—C14—H14A	119.6	H23A—C23—H23C	109.5
C16—C15—C14	120.8 (4)	H23B—C23—H23C	109.5
C16—C15—H15A	119.6

C6—C1—C2—C3	−0.9 (11)	C8—C9—C10—N11	−179.2 (3)
N7—C1—C2—C3	178.4 (6)	C8—C9—C10—C21	0.3 (5)
C6—C1—C2—C18	−179.1 (6)	C9—C10—N11—C12	0.3 (5)
N7—C1—C2—C18	0.2 (11)	C21—C10—N11—C12	−179.3 (3)
C1—C2—C3—C4	0.7 (12)	C10—N11—C12—C13	−92.5 (6)
C18—C2—C3—C4	178.9 (8)	C10—N11—C12—C17	90.3 (6)
C2—C3—C4—C5	−0.9 (14)	C17—C12—C13—C14	−2.5 (11)
C3—C4—C5—C6	1.2 (15)	N11—C12—C13—C14	−179.6 (6)
C2—C1—C6—C5	1.2 (10)	C17—C12—C13—C22	178.9 (6)
N7—C1—C6—C5	−178.1 (6)	N11—C12—C13—C22	1.8 (10)
C2—C1—C6—C19	−179.9 (6)	C12—C13—C14—C15	2.2 (12)
N7—C1—C6—C19	0.8 (10)	C22—C13—C14—C15	−179.3 (8)
C4—C5—C6—C1	−1.4 (12)	C13—C14—C15—C16	−1.6 (14)
C4—C5—C6—C19	179.8 (8)	C14—C15—C16—C17	1.2 (14)
C6—C1—N7—C8	−88.2 (6)	C13—C12—C17—C16	2.1 (10)
C2—C1—N7—C8	92.5 (6)	N11—C12—C17—C16	179.2 (6)
C1—N7—C8—C9	−0.8 (5)	C13—C12—C17—C23	−178.5 (6)
C1—N7—C8—C20	178.1 (3)	N11—C12—C17—C23	−1.4 (9)
N7—C8—C9—C10	179.4 (3)	C15—C16—C17—C12	−1.4 (11)
C20—C8—C9—C10	0.6 (5)	C15—C16—C17—C23	179.2 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···Cl1	1.01 (3)	2.12 (3)	3.115 (3)	170 (3)
N7—H7···Cl1ⁱ	1.00 (3)	2.12 (3)	3.110 (4)	170 (3)

Symmetry code: (i) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₇N₂⁺·Cl⁻
M_r	342.90
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	298
a, c (Å)	28.639 (5), 10.150 (3)
V (Å³)	8325 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.50 × 0.36 × 0.22

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	ψ scan XSCANS (Siemens, 1996)
T_min, T_max	0.854, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	7193, 3671, 1541
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.171, 1.12
No. of reflections	3671
No. of parameters	229
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.32

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···Cl1	1.01 (3)	2.12 (3)	3.115 (3)	170 (3)
N7—H7···Cl1ⁱ	1.00 (3)	2.12 (3)	3.110 (4)	170 (3)

Symmetry code: (i) x, y, z−1.

Footnotes

†This paper is dedicated to Professor Dr Dr mult. h.c. Herbert W. Roesky.

Acknowledgements

This work was supported by PROMEP (Programa de Mejoramiento del Profesorado), grant No. 103.5/08/3125.

References

Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev. 102, 3031–3066. Web of Science CrossRef PubMed CAS Google Scholar
Brownstein, S., Gabe, E. J. & Prasad, L. (1983). Can. J. Chem. 61, 1410–1413. CrossRef CAS Web of Science Google Scholar
Carey, D. T., Cope-Eatough, E. K., Vilaplana-Mafé, E., Mair, F. S., Pritchard, R. G., Warren, J. E. & Woods, R. J. (2003). Dalton Trans. pp. 1083–1093. Web of Science CSD CrossRef Google Scholar
Dorman, L. C. (1966). Tetrahedron Lett. 7, 459–464. CrossRef Google Scholar
Holland, P. L. & Tolman, W. B. (2000). J. Am. Chem. Soc. 122, 6331–6332. Web of Science CSD CrossRef CAS Google Scholar
Kuhn, N., Fahl, J., Fuchs, S. & Henkel, G. (2000). Z. Naturforsch. Teil B, 55, 345–346. CAS Google Scholar
Lesikar, L. A. & Richards, A. F. (2006). J. Organomet. Chem. 691, 4250–4256. Web of Science CSD CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nagendran, S. & Roesky, W. H. (2008). Organometallics, 27, 457–492. Web of Science CrossRef CAS Google Scholar
Park, K.-H. (2007). US Patent Appl. US 2007 191 638. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Stender, M., Wright, R. J., Eichler, B. E., Prust, J., Olmstead, M. M., Roesky, H. W. & Power, P. P. (2001). Dalton Trans. pp. 3465–3469. CrossRef Google Scholar

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Volume 65| Part 7| July 2009| Pages o1671-o1672

doi:10.1107/S1600536809020571

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

N-[3-(2,6-Di­methylanilino)-1-methylbut-2-enyl­idene]-2,6-di­methylanilinium chloride†

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

N-[3-(2,6-Dimethylanilino)-1-methylbut-2-enylidene]-2,6-dimethylanilinium chloride †