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The determination of the crystal structure of the title compound, C12H11N3, was carried out in order to explain its observed optical and electrical properties. Parallel and overlapping supramolecular packing was found in the crystal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001957/na6047sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001957/na6047Isup2.hkl
Contains datablock I

CCDC reference: 159846

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.039
  • wR factor = 0.106
  • Data-to-parameter ratio = 8.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(1) - C(3) = 1.43 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(2) - C(3) = 1.43 Ang. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.51 From the CIF: _reflns_number_total 1239 Count of symmetry unique reflns 1265 Completeness (_total/calc) 97.94% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

Organic compounds with a donor–π-acceptor structure have been drawing attention because of their being potent second-order non-linear optical materials which offer potential applications in optical signal processing, such as amplification, frequency conversion and modulation (Williams, 1984). Also, as one of the polynitrile π acceptors, the title compound, (I), has found application in electronic switching devices (Wang et al., 1995; Li et al., 2000). Parallel molecular arrangements in its vacuum-deposited film have been observed by scanning tunnel microscopy. The cystal structure determination of (I) has been understaken in order to understand the relationship between its optical and electrical properties, and its structure.

The molecular structure with the atom labelling scheme of (I) is shown in Fig. 1. Mean values of six aromatic C—C bonds and two CN bond lengths are 1.395 (3) and 1.143 (3) Å,respectively. The mean C—CN bond length is 1.427 (10) Å. This bond length is intermediate between the expected value of 1.419 Å for sp–sp2 C—C bond lengths and the value of 1.466 (10) Å for sp–sp3 C—C bond lengths (Allen et al., 1987), indicating strong intramolecular charge transfer (Janczak et al., 1995; Stoechett, 1962). The mutual arrangement of the title compound is illustrated in Fig. 2. The structure is composed of linear stacks of parrallel and overlapping molecules forming a supramolecular columnar aggregation. The mean distance between two successive packed benzene rings is 3.582 (2) Å. This value is a little larger than the van der Waals distance of 3.4 (4) Å for aromatic C atoms (Pauling, 1960). The non-H atoms of the molecule are almost coplanar; two least-squares planes defined by N1/N2/C1—C5 and N3/C4—C12 give r.m.s deviations of 0.0079 (1) and 0.0173 (2) Å, respectively. The dihedral angle between the two planes is 6.65 (5)°. This lay the basis for the supramolecular array of the molecules in the crystal observed.

Experimental top

The title compound was prepared according to the literature method of Wang et al. (1995). Crystals suitable for X-ray analysis were grown by slow evaporation of a 1:1 (v/v) CH2Cl2/C2H5OH solution at room temperature.

Structure description top

Organic compounds with a donor–π-acceptor structure have been drawing attention because of their being potent second-order non-linear optical materials which offer potential applications in optical signal processing, such as amplification, frequency conversion and modulation (Williams, 1984). Also, as one of the polynitrile π acceptors, the title compound, (I), has found application in electronic switching devices (Wang et al., 1995; Li et al., 2000). Parallel molecular arrangements in its vacuum-deposited film have been observed by scanning tunnel microscopy. The cystal structure determination of (I) has been understaken in order to understand the relationship between its optical and electrical properties, and its structure.

The molecular structure with the atom labelling scheme of (I) is shown in Fig. 1. Mean values of six aromatic C—C bonds and two CN bond lengths are 1.395 (3) and 1.143 (3) Å,respectively. The mean C—CN bond length is 1.427 (10) Å. This bond length is intermediate between the expected value of 1.419 Å for sp–sp2 C—C bond lengths and the value of 1.466 (10) Å for sp–sp3 C—C bond lengths (Allen et al., 1987), indicating strong intramolecular charge transfer (Janczak et al., 1995; Stoechett, 1962). The mutual arrangement of the title compound is illustrated in Fig. 2. The structure is composed of linear stacks of parrallel and overlapping molecules forming a supramolecular columnar aggregation. The mean distance between two successive packed benzene rings is 3.582 (2) Å. This value is a little larger than the van der Waals distance of 3.4 (4) Å for aromatic C atoms (Pauling, 1960). The non-H atoms of the molecule are almost coplanar; two least-squares planes defined by N1/N2/C1—C5 and N3/C4—C12 give r.m.s deviations of 0.0079 (1) and 0.0173 (2) Å, respectively. The dihedral angle between the two planes is 6.65 (5)°. This lay the basis for the supramolecular array of the molecules in the crystal observed.

Computing details top

Data collection: COLLECT (Nonius B. V., 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) & maXus (Mackay et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the molecules of (I) in the crystal.
2-[4-(Dimethylamino)phenyl]ethylene-1,1-dinitrile top
Crystal data top
C12H11N3F(000) = 208
Mr = 197.24Dx = 1.242 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 3.9972 (4) ÅCell parameters from 8650 reflections
b = 14.0618 (17) Åθ = 4.3–27.5°
c = 9.5477 (11) ŵ = 0.08 mm1
β = 100.600 (7)°T = 293 K
V = 527.50 (10) Å3Block, orange
Z = 20.50 × 0.33 × 0.25 mm
Data collection top
Nonius KappaCCD
diffractometer
1067 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Graphite monochromatorθmax = 27.5°, θmin = 4.3°
Detector resolution: 0.76 pixels mm-1h = 55
CCD scansk = 1818
8650 measured reflectionsl = 1212
1239 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0599P)2 + 0.0411P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1239 reflectionsΔρmax = 0.12 e Å3
139 parametersΔρmin = 0.12 e Å3
1 restraintExtinction correction: SHELXL, Fc*3DkFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.18 (5)
Crystal data top
C12H11N3V = 527.50 (10) Å3
Mr = 197.24Z = 2
Monoclinic, P21Mo Kα radiation
a = 3.9972 (4) ŵ = 0.08 mm1
b = 14.0618 (17) ÅT = 293 K
c = 9.5477 (11) Å0.50 × 0.33 × 0.25 mm
β = 100.600 (7)°
Data collection top
Nonius KappaCCD
diffractometer
1067 reflections with I > 2σ(I)
8650 measured reflectionsRint = 0.040
1239 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0391 restraint
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.12 e Å3
1239 reflectionsΔρmin = 0.12 e Å3
139 parameters
Special details top

Experimental. ? #Insert any special details here.

Geometry. Mean-plane data from final SHELXL refinement run:

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.5318 (0.0010) x + 1.0068 (0.0108) y - 5.8950 (0.0041) z 1.2323 (0.0106)

* 0.0078 (0.0014) N1 * 0.0075 (0.0012) N2 * -0.0057(0.0021) C1 * -0.0159 (0.0017) C3 * 0.0017(0.0015) C4 * 0.0058 (0.0011) C5

Rms deviation of fitted atoms 0.0079

3.5683 (0.0007) x + 2.4932 (0.0091) y - 5.4558 (0.0036) z 2.6112 (0.0082)

Angle to previous plane (with approximate e.s.d.) 6.69(0.05)

* -0.0063 (0.0018) N3 * -0.0195 (0.0014) C4 * -0.0006 (0.0016) C5 * -0.0066 (0.0016) C6 * -0.0014 (0.0019) C7 * -0.0293 (0.0017) C9 * 0.0110 (0.0017) C10 * 0.0116 (0.0016) C11 * 0.0338 (0.0018) C12

Rms deviation of fitted atoms 0.0173

3.5632 (0.0006) x + 1.6037 (0.0068) y - 5.6816 (0.0028) z 1.8197 (0.0066)

Angle to previous plane (with approximate e.s.d.) 3.88(0.04)

* 0.1371 (0.0019) N1 * -0.0426 (0.0018) N2 * 0.672 (0.0021) C1 * -0.0276 (0.0017) C2 * -0.0137 (0.0017) C3 - 0.0365 (0.0015) C4 - 0.0181 (0.0016) C5

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.2312 (8)1.14461 (18)0.1238 (3)0.0861 (8)
N20.3504 (6)1.00734 (18)0.2481 (2)0.0715 (6)
N31.0065 (6)0.74834 (14)0.5228 (2)0.0541 (5)
C10.1540 (7)1.07409 (19)0.0677 (3)0.0585 (6)
C20.1712 (6)0.9990 (2)0.1409 (2)0.0555 (6)
C30.0522 (6)0.98748 (18)0.0064 (2)0.0501 (5)
C40.1575 (6)0.89822 (16)0.0384 (2)0.0509 (6)
H10.06980.85000.02440.061*
C50.3772 (5)0.86581 (16)0.1637 (2)0.0468 (5)
C60.5169 (6)0.92172 (16)0.2819 (2)0.0516 (6)
H20.46720.98640.28050.062*
C70.7234 (6)0.88429 (16)0.3989 (2)0.0531 (6)
H30.81010.92370.47520.064*
C80.8072 (6)0.78659 (17)0.4056 (2)0.0465 (5)
C90.6698 (6)0.72954 (17)0.2876 (2)0.0526 (6)
H40.72150.66500.28840.063*
C100.4616 (6)0.76806 (16)0.1721 (2)0.0528 (6)
H50.37210.72860.09620.063*
C111.1555 (7)0.8063 (2)0.6437 (3)0.0666 (7)
H61.25700.86190.61070.100*
H71.32670.77040.70520.100*
H80.98150.82510.69520.100*
C121.0824 (8)0.64759 (18)0.5319 (3)0.0653 (7)
H90.87430.61220.52380.098*
H101.22540.63390.62190.098*
H111.19770.62980.45610.098*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.1135 (18)0.0610 (13)0.0735 (13)0.0019 (12)0.0106 (12)0.0039 (11)
N20.0840 (12)0.0614 (11)0.0591 (10)0.0070 (10)0.0079 (9)0.0034 (9)
N30.0599 (9)0.0510 (10)0.0479 (9)0.0065 (7)0.0031 (7)0.0007 (7)
C10.0678 (12)0.0528 (13)0.0503 (11)0.0006 (9)0.0035 (9)0.0041 (9)
C20.0625 (11)0.0503 (11)0.0512 (11)0.0003 (9)0.0092 (8)0.0006 (9)
C30.0516 (9)0.0534 (11)0.0431 (9)0.0024 (8)0.0068 (7)0.0000 (8)
C40.0532 (10)0.0517 (10)0.0457 (11)0.0034 (8)0.0085 (8)0.0014 (8)
C50.0500 (9)0.0453 (10)0.0443 (10)0.0033 (8)0.0095 (8)0.0017 (8)
C60.0632 (12)0.0388 (10)0.0493 (11)0.0007 (8)0.0052 (9)0.0006 (8)
C70.0647 (12)0.0434 (10)0.0464 (11)0.0041 (8)0.0023 (8)0.0065 (8)
C80.0488 (9)0.0470 (9)0.0435 (10)0.0010 (7)0.0113 (7)0.0015 (7)
C90.0604 (11)0.0407 (10)0.0551 (11)0.0000 (8)0.0077 (8)0.0040 (8)
C100.0613 (11)0.0468 (11)0.0477 (10)0.0047 (8)0.0052 (8)0.0073 (8)
C110.0699 (13)0.0690 (16)0.0529 (12)0.0029 (10)0.0067 (10)0.0019 (9)
C120.0726 (13)0.0547 (13)0.0638 (13)0.0145 (10)0.0056 (11)0.0061 (10)
Geometric parameters (Å, º) top
N1—C11.142 (4)C4—C51.423 (3)
N2—C21.143 (3)C5—C61.404 (3)
N3—C81.359 (3)C5—C101.414 (3)
N3—C121.448 (3)C6—C71.366 (3)
N3—C111.449 (3)C7—C81.413 (3)
C1—C31.429 (4)C8—C91.410 (3)
C2—C31.432 (3)C9—C101.366 (3)
C3—C41.367 (3)
C8—N3—C12121.4 (2)C6—C5—C4126.1 (2)
C8—N3—C11121.7 (2)C10—C5—C4117.6 (2)
C12—N3—C11116.9 (2)C7—C6—C5122.2 (2)
N1—C1—C3178.2 (3)C6—C7—C8120.9 (2)
N2—C2—C3179.4 (3)N3—C8—C9121.0 (2)
C4—C3—C1125.8 (2)N3—C8—C7121.4 (2)
C4—C3—C2119.3 (2)C9—C8—C7117.6 (2)
C1—C3—C2114.9 (2)C10—C9—C8120.6 (2)
C3—C4—C5131.6 (2)C9—C10—C5122.3 (2)
C6—C5—C10116.3 (2)

Experimental details

Crystal data
Chemical formulaC12H11N3
Mr197.24
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)3.9972 (4), 14.0618 (17), 9.5477 (11)
β (°) 100.600 (7)
V3)527.50 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.50 × 0.33 × 0.25
Data collection
DiffractometerNonius KappaCCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8650, 1239, 1067
Rint0.040
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.106, 1.06
No. of reflections1239
No. of parameters139
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.12, 0.12

Computer programs: COLLECT (Nonius B. V., 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) & maXus (Mackay et al., 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998).

 

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