Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001957/na6047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001957/na6047Isup2.hkl |
CCDC reference: 159846
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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
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.
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 C≡N 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.
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).
Fig. 1. A view of (I) with the atomic numbering scheme. | |
Fig. 2. Packing diagram of the molecules of (I) in the crystal. |
C12H11N3 | F(000) = 208 |
Mr = 197.24 | Dx = 1.242 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9972 (4) Å | Cell parameters from 8650 reflections |
b = 14.0618 (17) Å | θ = 4.3–27.5° |
c = 9.5477 (11) Å | µ = 0.08 mm−1 |
β = 100.600 (7)° | T = 293 K |
V = 527.50 (10) Å3 | Block, orange |
Z = 2 | 0.50 × 0.33 × 0.25 mm |
Nonius KappaCCD diffractometer | 1067 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.040 |
Graphite monochromator | θmax = 27.5°, θmin = 4.3° |
Detector resolution: 0.76 pixels mm-1 | h = −5→5 |
CCD scans | k = −18→18 |
8650 measured reflections | l = −12→12 |
1239 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H 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 reflections | Δρmax = 0.12 e Å−3 |
139 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*3DkFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.18 (5) |
C12H11N3 | V = 527.50 (10) Å3 |
Mr = 197.24 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 3.9972 (4) Å | µ = 0.08 mm−1 |
b = 14.0618 (17) Å | T = 293 K |
c = 9.5477 (11) Å | 0.50 × 0.33 × 0.25 mm |
β = 100.600 (7)° |
Nonius KappaCCD diffractometer | 1067 reflections with I > 2σ(I) |
8650 measured reflections | Rint = 0.040 |
1239 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.12 e Å−3 |
1239 reflections | Δρmin = −0.12 e Å−3 |
139 parameters |
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 |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2312 (8) | 1.14461 (18) | 0.1238 (3) | 0.0861 (8) | |
N2 | −0.3504 (6) | 1.00734 (18) | −0.2481 (2) | 0.0715 (6) | |
N3 | 1.0065 (6) | 0.74834 (14) | 0.5228 (2) | 0.0541 (5) | |
C1 | 0.1540 (7) | 1.07409 (19) | 0.0677 (3) | 0.0585 (6) | |
C2 | −0.1712 (6) | 0.9990 (2) | −0.1409 (2) | 0.0555 (6) | |
C3 | 0.0522 (6) | 0.98748 (18) | −0.0064 (2) | 0.0501 (5) | |
C4 | 0.1575 (6) | 0.89822 (16) | 0.0384 (2) | 0.0509 (6) | |
H1 | 0.0698 | 0.8500 | −0.0244 | 0.061* | |
C5 | 0.3772 (5) | 0.86581 (16) | 0.1637 (2) | 0.0468 (5) | |
C6 | 0.5169 (6) | 0.92172 (16) | 0.2819 (2) | 0.0516 (6) | |
H2 | 0.4672 | 0.9864 | 0.2805 | 0.062* | |
C7 | 0.7234 (6) | 0.88429 (16) | 0.3989 (2) | 0.0531 (6) | |
H3 | 0.8101 | 0.9237 | 0.4752 | 0.064* | |
C8 | 0.8072 (6) | 0.78659 (17) | 0.4056 (2) | 0.0465 (5) | |
C9 | 0.6698 (6) | 0.72954 (17) | 0.2876 (2) | 0.0526 (6) | |
H4 | 0.7215 | 0.6650 | 0.2884 | 0.063* | |
C10 | 0.4616 (6) | 0.76806 (16) | 0.1721 (2) | 0.0528 (6) | |
H5 | 0.3721 | 0.7286 | 0.0962 | 0.063* | |
C11 | 1.1555 (7) | 0.8063 (2) | 0.6437 (3) | 0.0666 (7) | |
H6 | 1.2570 | 0.8619 | 0.6107 | 0.100* | |
H7 | 1.3267 | 0.7704 | 0.7052 | 0.100* | |
H8 | 0.9815 | 0.8251 | 0.6952 | 0.100* | |
C12 | 1.0824 (8) | 0.64759 (18) | 0.5319 (3) | 0.0653 (7) | |
H9 | 0.8743 | 0.6122 | 0.5238 | 0.098* | |
H10 | 1.2254 | 0.6339 | 0.6219 | 0.098* | |
H11 | 1.1977 | 0.6298 | 0.4561 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.1135 (18) | 0.0610 (13) | 0.0735 (13) | −0.0019 (12) | −0.0106 (12) | −0.0039 (11) |
N2 | 0.0840 (12) | 0.0614 (11) | 0.0591 (10) | 0.0070 (10) | −0.0079 (9) | 0.0034 (9) |
N3 | 0.0599 (9) | 0.0510 (10) | 0.0479 (9) | 0.0065 (7) | 0.0031 (7) | 0.0007 (7) |
C1 | 0.0678 (12) | 0.0528 (13) | 0.0503 (11) | 0.0006 (9) | 0.0035 (9) | 0.0041 (9) |
C2 | 0.0625 (11) | 0.0503 (11) | 0.0512 (11) | 0.0003 (9) | 0.0092 (8) | 0.0006 (9) |
C3 | 0.0516 (9) | 0.0534 (11) | 0.0431 (9) | −0.0024 (8) | 0.0068 (7) | 0.0000 (8) |
C4 | 0.0532 (10) | 0.0517 (10) | 0.0457 (11) | −0.0034 (8) | 0.0085 (8) | −0.0014 (8) |
C5 | 0.0500 (9) | 0.0453 (10) | 0.0443 (10) | −0.0033 (8) | 0.0095 (8) | −0.0017 (8) |
C6 | 0.0632 (12) | 0.0388 (10) | 0.0493 (11) | 0.0007 (8) | 0.0052 (9) | −0.0006 (8) |
C7 | 0.0647 (12) | 0.0434 (10) | 0.0464 (11) | −0.0041 (8) | 0.0023 (8) | −0.0065 (8) |
C8 | 0.0488 (9) | 0.0470 (9) | 0.0435 (10) | −0.0010 (7) | 0.0113 (7) | 0.0015 (7) |
C9 | 0.0604 (11) | 0.0407 (10) | 0.0551 (11) | 0.0000 (8) | 0.0077 (8) | −0.0040 (8) |
C10 | 0.0613 (11) | 0.0468 (11) | 0.0477 (10) | −0.0047 (8) | 0.0052 (8) | −0.0073 (8) |
C11 | 0.0699 (13) | 0.0690 (16) | 0.0529 (12) | 0.0029 (10) | −0.0067 (10) | −0.0019 (9) |
C12 | 0.0726 (13) | 0.0547 (13) | 0.0638 (13) | 0.0145 (10) | 0.0056 (11) | 0.0061 (10) |
N1—C1 | 1.142 (4) | C4—C5 | 1.423 (3) |
N2—C2 | 1.143 (3) | C5—C6 | 1.404 (3) |
N3—C8 | 1.359 (3) | C5—C10 | 1.414 (3) |
N3—C12 | 1.448 (3) | C6—C7 | 1.366 (3) |
N3—C11 | 1.449 (3) | C7—C8 | 1.413 (3) |
C1—C3 | 1.429 (4) | C8—C9 | 1.410 (3) |
C2—C3 | 1.432 (3) | C9—C10 | 1.366 (3) |
C3—C4 | 1.367 (3) | ||
C8—N3—C12 | 121.4 (2) | C6—C5—C4 | 126.1 (2) |
C8—N3—C11 | 121.7 (2) | C10—C5—C4 | 117.6 (2) |
C12—N3—C11 | 116.9 (2) | C7—C6—C5 | 122.2 (2) |
N1—C1—C3 | 178.2 (3) | C6—C7—C8 | 120.9 (2) |
N2—C2—C3 | 179.4 (3) | N3—C8—C9 | 121.0 (2) |
C4—C3—C1 | 125.8 (2) | N3—C8—C7 | 121.4 (2) |
C4—C3—C2 | 119.3 (2) | C9—C8—C7 | 117.6 (2) |
C1—C3—C2 | 114.9 (2) | C10—C9—C8 | 120.6 (2) |
C3—C4—C5 | 131.6 (2) | C9—C10—C5 | 122.3 (2) |
C6—C5—C10 | 116.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C12H11N3 |
Mr | 197.24 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 3.9972 (4), 14.0618 (17), 9.5477 (11) |
β (°) | 100.600 (7) |
V (Å3) | 527.50 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.33 × 0.25 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8650, 1239, 1067 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.106, 1.06 |
No. of reflections | 1239 |
No. of parameters | 139 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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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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 C≡N 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.