Intermolecular interactions and ­molecular geometry in molecular complexes of N,N-di­methyl­aniline: the 1:1 complex with 1,2,4,5-tetra­cyano­benzene

The partner mol­ecules of N,N-di­methyl­aniline-1,2,4,5-tetra­cyano­benzene (1/1), C₈H₁₁N·C₁₀H₂N₄, are stacked alternately in infinite columns. The N atom of the N,N-di­methyl­aniline mol­ecule has a partially tetrahedral character and the distance between neighbouring mol­ecules in the stack is relatively short on the side where the lone-pair electrons of this atom are located. Molecular-packing analysis of this and three other complexes of N,N-di­methyl­aniline shows that there is a close relationship between the strength of the intermolecular interaction on this side and the tetrahedral character of the N atom.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998).

(DMA-TCNB)

Crystal data

C8H11N·C10H2N4	Z = 2
Mr = 299.33	F(000) = 312
Triclinic, P1	Dx = 1.331 Mg m^−3 Dm = not mesured Mg m^−3 Dm measured by not measured
a = 7.325 (3) Å	Mo Kα radiation, λ = 0.71069 Å
b = 7.982 (4) Å	Cell parameters from 25 reflections
c = 13.452 (6) Å	θ = 6.5–13.1°
α = 74.44 (4)°	µ = 0.08 mm^−1
β = 87.05 (3)°	T = 100 K
γ = 80.30 (3)°	Plate, brown
V = 746.8 (6) Å^3	0.45 × 0.35 × 0.15 mm

Data collection

Enraf-Nonius CAD4 diffractometer	2501 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 28.0°, θmin = 1.6°
ω–2θ scans	h = 0→9
Absorption correction: gaussian Platon (Spek, 1998)	k = −10→10
Tmin = 0.973, Tmax = 0.988	l = −17→17
3648 measured reflections	3 standard reflections every 60 min
3603 independent reflections	intensity decay: 12%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.150	Calculated w = 1/[σ^2(Fo^2) + (0.0806P)^2 + 0.2695P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
3603 reflections	Δρmax = 0.33 e Å^−3
211 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.4545 (2)	0.2873 (2)	0.28746 (12)	0.0178 (3)
C2	0.5234 (2)	0.3766 (2)	0.19209 (12)	0.0194 (3)
H2	0.5195	0.5005	0.1761	0.023*
C3	0.5966 (2)	0.2858 (2)	0.12149 (13)	0.0242 (4)
H3	0.6413	0.3487	0.0571	0.029*
C4	0.6065 (2)	0.1056 (3)	0.14221 (15)	0.0267 (4)
H4	0.6552	0.0445	0.0925	0.032*
C5	0.5440 (2)	0.0163 (2)	0.23684 (15)	0.0265 (4)
H5	0.5526	−0.1081	0.2528	0.032*
C6	0.4688 (2)	0.1038 (2)	0.30913 (14)	0.0225 (4)
H6	0.4268	0.0391	0.3738	0.027*
N1	0.3672 (2)	0.37941 (19)	0.35501 (11)	0.0221 (3)
C7	0.4002 (3)	0.5574 (2)	0.34391 (16)	0.0293 (4)
H71	0.3288	0.6057	0.3964	0.041*
H72	0.3616	0.6308	0.2751	0.041*
H73	0.5324	0.5562	0.3527	0.041*
C8	0.3250 (3)	0.2832 (3)	0.45917 (14)	0.0307 (4)
H81	0.2578	0.1883	0.4565	0.043*
H82	0.2481	0.3636	0.4940	0.043*
H83	0.4404	0.2329	0.4974	0.043*
C11	−0.0416 (2)	0.2050 (2)	0.30765 (12)	0.0160 (3)
C12	−0.0001 (2)	0.3693 (2)	0.25121 (12)	0.0164 (3)
C13	0.0828 (2)	0.3884 (2)	0.15502 (12)	0.0172 (3)
H13	0.1122	0.4995	0.1171	0.021*
C14	0.1226 (2)	0.2436 (2)	0.11426 (12)	0.0161 (3)
C15	0.0794 (2)	0.0804 (2)	0.17050 (12)	0.0160 (3)
C16	−0.0017 (2)	0.0604 (2)	0.26718 (12)	0.0167 (3)
H16	−0.0297	−0.0510	0.3054	0.020*
C17	−0.1242 (2)	0.1861 (2)	0.40830 (13)	0.0187 (3)
C18	−0.0433 (2)	0.5188 (2)	0.29338 (13)	0.0199 (3)
C19	0.2067 (2)	0.2641 (2)	0.01405 (13)	0.0184 (3)
C20	0.1214 (2)	−0.0682 (2)	0.12705 (12)	0.0190 (3)
N11	−0.1864 (2)	0.1714 (2)	0.48905 (11)	0.0257 (3)
N12	−0.0801 (2)	0.63783 (19)	0.32639 (12)	0.0247 (3)
N13	0.2700 (2)	0.2827 (2)	−0.06665 (11)	0.0252 (3)
N14	0.1545 (2)	−0.18553 (19)	0.09263 (12)	0.0259 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0142 (7)	0.0209 (8)	0.0182 (8)	−0.0039 (6)	−0.0020 (6)	−0.0038 (6)
C2	0.0178 (8)	0.0182 (7)	0.0206 (8)	−0.0036 (6)	0.0000 (6)	−0.0021 (6)
C3	0.0183 (8)	0.0349 (10)	0.0189 (8)	−0.0061 (7)	0.0024 (6)	−0.0056 (7)
C4	0.0200 (8)	0.0333 (10)	0.0308 (10)	−0.0009 (7)	0.0003 (7)	−0.0174 (8)
C5	0.0219 (8)	0.0181 (8)	0.0400 (11)	−0.0020 (6)	−0.0046 (7)	−0.0085 (7)
C6	0.0200 (8)	0.0198 (8)	0.0246 (8)	−0.0051 (6)	−0.0019 (6)	0.0010 (6)
N1	0.0219 (7)	0.0255 (7)	0.0196 (7)	−0.0048 (6)	0.0032 (5)	−0.0072 (6)
C7	0.0291 (9)	0.0283 (9)	0.0356 (10)	−0.0046 (7)	−0.0006 (8)	−0.0169 (8)
C8	0.0271 (9)	0.0465 (11)	0.0183 (8)	−0.0077 (8)	0.0043 (7)	−0.0078 (8)
C11	0.0151 (7)	0.0172 (7)	0.0157 (7)	−0.0039 (6)	0.0013 (6)	−0.0037 (6)
C12	0.0147 (7)	0.0162 (7)	0.0181 (7)	−0.0031 (6)	−0.0001 (6)	−0.0039 (6)
C13	0.0166 (7)	0.0151 (7)	0.0190 (8)	−0.0046 (6)	−0.0013 (6)	−0.0012 (6)
C14	0.0154 (7)	0.0172 (7)	0.0154 (7)	−0.0039 (6)	−0.0001 (6)	−0.0028 (6)
C15	0.0164 (7)	0.0146 (7)	0.0176 (7)	−0.0032 (6)	−0.0009 (6)	−0.0045 (6)
C16	0.0167 (7)	0.0138 (7)	0.0189 (8)	−0.0036 (6)	0.0008 (6)	−0.0028 (6)
C17	0.0179 (7)	0.0157 (7)	0.0224 (8)	−0.0030 (6)	0.0011 (6)	−0.0051 (6)
C18	0.0201 (8)	0.0183 (8)	0.0202 (8)	−0.0055 (6)	0.0026 (6)	−0.0023 (6)
C19	0.0202 (8)	0.0153 (7)	0.0202 (8)	−0.0051 (6)	−0.0008 (6)	−0.0038 (6)
C20	0.0224 (8)	0.0162 (7)	0.0175 (7)	−0.0061 (6)	0.0017 (6)	−0.0016 (6)
N11	0.0271 (8)	0.0268 (8)	0.0230 (8)	−0.0055 (6)	0.0051 (6)	−0.0064 (6)
N12	0.0292 (8)	0.0185 (7)	0.0266 (8)	−0.0046 (6)	0.0059 (6)	−0.0070 (6)
N13	0.0315 (8)	0.0239 (7)	0.0205 (7)	−0.0091 (6)	0.0035 (6)	−0.0043 (6)
N14	0.0342 (8)	0.0196 (7)	0.0255 (8)	−0.0083 (6)	0.0061 (6)	−0.0071 (6)

Geometric parameters (Å, º)

C1—N1	1.384 (2)	C12—C13	1.382 (2)
C1—C6	1.401 (2)	C12—C18	1.437 (2)
C1—C2	1.404 (2)	C13—C14	1.390 (2)
C2—C3	1.379 (2)	C14—C15	1.398 (2)
C3—C4	1.380 (3)	C14—C19	1.433 (2)
C4—C5	1.379 (3)	C15—C16	1.382 (2)
C5—C6	1.384 (3)	C15—C20	1.440 (2)
N1—C7	1.448 (2)	C17—N11	1.140 (2)
N1—C8	1.451 (2)	C18—N12	1.140 (2)
C11—C16	1.386 (2)	C19—N13	1.140 (2)
C11—C12	1.401 (2)	C20—N14	1.138 (2)
C11—C17	1.435 (2)
N1—C1—C6	121.48 (15)	C13—C12—C18	119.63 (14)
N1—C1—C2	120.69 (15)	C11—C12—C18	119.99 (15)
C6—C1—C2	117.75 (16)	C12—C13—C14	119.33 (15)
C3—C2—C1	120.50 (16)	C13—C14—C15	120.08 (15)
C4—C3—C2	121.51 (17)	C13—C14—C19	119.31 (14)
C3—C4—C5	118.33 (17)	C15—C14—C19	120.61 (14)
C4—C5—C6	121.52 (17)	C16—C15—C14	120.71 (15)
C5—C6—C1	120.34 (16)	C16—C15—C20	119.95 (14)
C1—N1—C7	118.76 (15)	C14—C15—C20	119.34 (15)
C1—N1—C8	119.20 (15)	C15—C16—C11	119.15 (15)
C7—N1—C8	115.22 (15)	N11—C17—C11	178.58 (18)
C16—C11—C12	120.35 (15)	N12—C18—C12	179.04 (18)
C16—C11—C17	119.82 (14)	N13—C19—C14	178.44 (18)
C12—C11—C17	119.82 (14)	N14—C20—C15	179.91 (18)
C13—C12—C11	120.38 (15)