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

The title salt, C(21)H(27)N(2) (+)·Cl(-) resulted from the condensation between 2,6-dimethyl-aniline and acetyl-acetone in acidified ethanol. The bulky cation is stabilized in a β-imino-enamine 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 supra-molecular structure is a one dimensional polymer running along [001], alternating cations and anions. The π-π inter-action observed in the mol-ecule, 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 = 342.90

Tetragonal,

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[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.171

S = 1.12

3671 reflections

229 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.32 e Å−3

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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H27N2+·Cl−	Dx = 1.094 Mg m−3
Mr = 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

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

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(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3
3671 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.31 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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)

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) .