1,3-Bis[4-(dimethyl-amino)benz-yl]-4,5,6,7-tetra-hydro-1H-1,3-diazepan-2-ium chloride.

The title N-heterocyclic carbene derivative, C(23)H(33)N(4) (+)·Cl(-), has been synthesized and characterized by elemental analysis, (1)H and (13)C NMR, IR spectroscopy and a single-crystal X-ray diffraction study. Ions of the title compound are linked by three C-H⋯Cl inter-actions. The seven-membered 1,3-diazepane ring has a form inter-mediate between twist-chair and twist-boat.

Related literature

For the synthesis, see: Özdemir et al. (2005 ▶); Yaşar et al. (2008 ▶). For general background, see: Hermann (2002 ▶); Littke & Fu (2002 ▶); Evans & Boeyens (1989 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For related compounds, see: Arslan et al. (2007a ▶,b ▶,c ▶). For general background to the use of N-heterocyclic carbenes as phosphine mimics and in catalysis, see: Arduengo & Krafczyk (1998 ▶); Dullius et al. (1998 ▶); Glorius (2007 ▶); Hermann & Köcher (1997 ▶); Nolan (2006 ▶); Regitz (1996 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

n class="Chemical">C23H33N4 +·n class="Chemical">Cl−

M = 400.98

Orthorhombin class="Chemical">c,

a = 22.663 (5) Å

b = 10.081 (2) Å

n class="Chemical">c = 9.6368 (19) Å

V = 2201.7 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 153 (2) K

0.46 × 0.12 × 0.07 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.918, T max = 0.987

14704 measured reflen class="Chemical">ctionpan>s

1947 independent reflen class="Chemical">ctions

1481 reflen class="Chemical">ctionpan>s with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.160

S = 1.10

1947 reflen class="Chemical">ctionpan>s

130 parameters

H-atom parameters n class="Chemical">conpan>strained

Δρmax = 0.28 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041603/hg2445sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041603/hg2445Isup2.hkl

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

C23H33N4+·Cl−	F(000) = 864
Mr = 400.98	Dx = 1.210 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 5004 reflections
a = 22.663 (5) Å	θ = 3.1–26.4°
b = 10.081 (2) Å	µ = 0.19 mm−1
c = 9.6368 (19) Å	T = 153 K
V = 2201.7 (8) Å3	Rod, colorless
Z = 4	0.46 × 0.12 × 0.07 mm

Rigaku Mercury CCD diffractometer	1947 independent reflections
Radiation source: Sealed Tube	1481 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.053
Detector resolution: 14.6306 pixels mm-1	θmax = 25.1°, θmin = 3.1°
ω scans	h = −27→23
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −12→11
Tmin = 0.918, Tmax = 0.987	l = −11→11
14704 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0629P)2 + 3.1587P] where P = (Fo2 + 2Fc2)/3
1947 reflections	(Δ/σ)max < 0.001
130 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.5000	0.27328 (9)	0.2500	0.0326 (3)
N1	0.53058 (10)	0.3281 (2)	0.8530 (2)	0.0263 (5)
N2	0.81399 (11)	0.3446 (3)	0.8340 (3)	0.0465 (8)
C1	0.5000	0.3809 (4)	0.7500	0.0234 (8)
H1	0.5000	0.4761	0.7500	0.028*
C2	0.54103 (13)	0.1885 (3)	0.8905 (3)	0.0320 (7)
H2A	0.5391	0.1810	0.9897	0.038*
H2B	0.5805	0.1656	0.8631	0.038*
C3	0.49952 (13)	0.0887 (3)	0.8287 (3)	0.0299 (7)
H3A	0.4602	0.1074	0.8599	0.036*
H3B	0.5100	0.0019	0.8616	0.036*
C4	0.56701 (12)	0.4207 (3)	0.9380 (3)	0.0286 (6)
H4A	0.5588	0.4062	1.0345	0.034*
H4B	0.5564	0.5104	0.9160	0.034*
C5	0.63188 (12)	0.4015 (3)	0.9123 (3)	0.0280 (6)
C6	0.65910 (13)	0.4560 (3)	0.7968 (3)	0.0361 (7)
H6	0.6359	0.5068	0.7327	0.043*
C7	0.71893 (14)	0.4394 (3)	0.7709 (4)	0.0410 (8)
H7	0.7364	0.4791	0.6902	0.049*
C8	0.75396 (13)	0.3648 (3)	0.8622 (3)	0.0359 (7)
C9	0.72698 (13)	0.3100 (3)	0.9785 (3)	0.0359 (7)
H9	0.7500	0.2585	1.0425	0.043*
C10	0.66696 (13)	0.3289 (3)	1.0031 (3)	0.0316 (7)
H10	0.6494	0.2909	1.0846	0.038*
C11	0.84333 (15)	0.4411 (4)	0.7441 (5)	0.0577 (11)
H11A	0.8243	0.4424	0.6552	0.087*
H11B	0.8840	0.4166	0.7328	0.087*
H11C	0.8410	0.5276	0.7854	0.087*
C12	0.85025 (15)	0.2829 (4)	0.9408 (4)	0.0569 (11)
H12A	0.8501	0.3374	1.0225	0.085*
H12B	0.8900	0.2737	0.9074	0.085*
H12C	0.8346	0.1970	0.9628	0.085*

	U11	U22	U33	U12	U13	U23
Cl1	0.0410 (6)	0.0223 (5)	0.0347 (5)	0.000	0.0031 (4)	0.000
N1	0.0280 (12)	0.0207 (11)	0.0302 (12)	−0.0008 (9)	0.0021 (10)	−0.0010 (10)
N2	0.0300 (14)	0.0458 (17)	0.064 (2)	−0.0016 (12)	0.0035 (13)	−0.0117 (15)
C1	0.0210 (17)	0.0196 (18)	0.030 (2)	0.000	0.0053 (16)	0.000
C2	0.0399 (16)	0.0206 (14)	0.0356 (16)	0.0035 (12)	−0.0043 (13)	0.0019 (12)
C3	0.0376 (15)	0.0191 (13)	0.0331 (16)	0.0013 (12)	0.0030 (13)	0.0035 (11)
C4	0.0303 (14)	0.0239 (14)	0.0315 (15)	0.0006 (11)	0.0013 (12)	−0.0053 (12)
C5	0.0300 (15)	0.0251 (14)	0.0290 (15)	−0.0003 (11)	0.0000 (11)	−0.0032 (12)
C6	0.0331 (16)	0.0372 (17)	0.0379 (17)	0.0004 (13)	0.0013 (13)	0.0056 (14)
C7	0.0386 (17)	0.0415 (18)	0.0430 (19)	−0.0055 (14)	0.0073 (14)	0.0058 (15)
C8	0.0299 (15)	0.0327 (16)	0.0450 (17)	−0.0011 (12)	0.0007 (14)	−0.0093 (14)
C9	0.0353 (16)	0.0350 (17)	0.0373 (17)	0.0069 (13)	−0.0062 (13)	−0.0036 (14)
C10	0.0348 (16)	0.0299 (15)	0.0300 (15)	−0.0002 (12)	0.0000 (12)	−0.0013 (13)
C11	0.0358 (18)	0.045 (2)	0.092 (3)	−0.0136 (15)	0.0185 (19)	−0.014 (2)
C12	0.0326 (17)	0.067 (3)	0.071 (3)	0.0097 (17)	−0.0076 (18)	−0.024 (2)

N1—C1	1.322 (3)	C5—C6	1.386 (4)
N1—C2	1.472 (3)	C5—C10	1.391 (4)
N1—C4	1.491 (3)	C6—C7	1.389 (4)
N2—C8	1.402 (4)	C6—H6	0.9600
N2—C12	1.456 (5)	C7—C8	1.404 (5)
N2—C11	1.462 (5)	C7—H7	0.9600
C1—N1i	1.322 (3)	C8—C9	1.391 (4)
C1—H1	0.9600	C9—C10	1.394 (4)
C2—C3	1.501 (4)	C9—H9	0.9600
C2—H2A	0.9600	C10—H10	0.9600
C2—H2B	0.9600	C11—H11A	0.9599
C3—C3i	1.517 (6)	C11—H11B	0.9599
C3—H3A	0.9600	C11—H11C	0.9599
C3—H3B	0.9600	C12—H12A	0.9599
C4—C5	1.503 (4)	C12—H12B	0.9599
C4—H4A	0.9600	C12—H12C	0.9599
C4—H4B	0.9600
C1—N1—C2	130.8 (3)	C10—C5—C4	121.5 (3)
C1—N1—C4	116.8 (2)	C5—C6—C7	122.1 (3)
C2—N1—C4	112.0 (2)	C5—C6—H6	119.0
C8—N2—C12	118.2 (3)	C7—C6—H6	119.0
C8—N2—C11	117.3 (3)	C6—C7—C8	120.3 (3)
C12—N2—C11	116.5 (3)	C6—C7—H7	119.9
N1i—C1—N1	132.6 (4)	C8—C7—H7	119.9
N1i—C1—H1	113.7	C9—C8—N2	121.7 (3)
N1—C1—H1	113.7	C9—C8—C7	118.0 (3)
N1—C2—C3	116.3 (2)	N2—C8—C7	120.3 (3)
N1—C2—H2A	108.2	C8—C9—C10	120.8 (3)
C3—C2—H2A	108.2	C8—C9—H9	119.6
N1—C2—H2B	108.2	C10—C9—H9	119.6
C3—C2—H2B	108.2	C5—C10—C9	121.5 (3)
H2A—C2—H2B	107.4	C5—C10—H10	119.2
C2—C3—C3i	112.8 (2)	C9—C10—H10	119.2
C2—C3—H3A	109.0	N2—C11—H11A	109.5
C3i—C3—H3A	109.0	N2—C11—H11B	109.5
C2—C3—H3B	109.0	H11A—C11—H11B	109.5
C3i—C3—H3B	109.0	N2—C11—H11C	109.5
H3A—C3—H3B	107.8	H11A—C11—H11C	109.5
N1—C4—C5	111.8 (2)	H11B—C11—H11C	109.5
N1—C4—H4A	109.3	N2—C12—H12A	109.5
C5—C4—H4A	109.3	N2—C12—H12B	109.5
N1—C4—H4B	109.3	H12A—C12—H12B	109.5
C5—C4—H4B	109.3	N2—C12—H12C	109.5
H4A—C4—H4B	107.9	H12A—C12—H12C	109.5
C6—C5—C10	117.4 (3)	H12B—C12—H12C	109.5
C6—C5—C4	121.1 (3)
C2—N1—C1—N1i	−0.7 (2)	C12—N2—C8—C9	−10.0 (4)
C4—N1—C1—N1i	171.0 (2)	C11—N2—C8—C9	−157.9 (3)
C1—N1—C2—C3	−18.0 (4)	C12—N2—C8—C7	171.5 (3)
C4—N1—C2—C3	170.0 (2)	C11—N2—C8—C7	23.6 (5)
N1—C2—C3—C3i	59.9 (4)	C6—C7—C8—C9	−0.5 (5)
C1—N1—C4—C5	−109.3 (2)	C6—C7—C8—N2	178.0 (3)
C2—N1—C4—C5	63.9 (3)	N2—C8—C9—C10	−178.6 (3)
N1—C4—C5—C6	80.0 (3)	C7—C8—C9—C10	−0.1 (5)
N1—C4—C5—C10	−100.1 (3)	C6—C5—C10—C9	−0.8 (4)
C10—C5—C6—C7	0.2 (5)	C4—C5—C10—C9	179.3 (3)
C4—C5—C6—C7	−179.9 (3)	C8—C9—C10—C5	0.7 (5)
C5—C6—C7—C8	0.4 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl1ii	0.96	2.53	3.486 (4)	180
C2—H2A···Cl1iii	0.96	2.82	3.688 (3)	151
C4—H4A···Cl1iii	0.96	2.81	3.682 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl1i	0.96	2.53	3.486 (4)	180
C2—H2A⋯Cl1ii	0.96	2.82	3.688 (3)	151
C4—H4A⋯Cl1ii	0.96	2.81	3.682 (3)	152

Symmetry codes: (i) ; (ii) .