2,6-Bis­[1-(phenyl­imino)­ethyl]­pyridine

Mentes, A.; Fawcett, J.; Kemmitt, R.D.W.

doi:10.1107/S1600536801005943

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2,6-Bis[1-(phenylimino)ethyl]pyridine

A. Mentes, J. Fawcett and R. D. W. Kemmitt

The structure of the title compound, C₂₁H₁₉N₃ (BIP1), has been determined. The molecule lies on a crystallographic mirror plane. The terminal phenyl groups are rotated 60.2 (2)° from the plane of the ethylidenepyridine system.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005943/na6065sup1.cif Contains datablocks I, NA6065
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005943/na6065Isup2.hkl Contains datablock I

CCDC reference: 165655

checkCIF report

Key indicators

Single-crystal X-ray study
T = 290 K
Mean (C-C) = 0.005 Å
R factor = 0.049
wR factor = 0.151
Data-to-parameter ratio = 8.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_030  Alert C Refined Extinction parameter within range ....       2.84 Sigma

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C6   -C7      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(4), Rep     1.39000 ....    Missing s.u.
                     C6   -C11     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C7   -C8      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(4), Rep     1.39000 ....    Missing s.u.
                     C8   -C9      1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(4), Rep     1.39000 ....    Missing s.u.
                     C9   -C10     1.555   1.555

PLAT_741  Alert C Bond    Calc    1.390(3), Rep     1.39000 ....    Missing s.u.
                     C10  -C11     1.555   1.555

PLAT_742  Alert C Angle   Calc  119.99(19), Rep      120.00 ....    Missing s.u.
                     C7   -C6   -C11     1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc    120.0(2), Rep      120.00 ....    Missing s.u.
                     C8   -C7   -C6      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc    120.0(2), Rep      120.00 ....    Missing s.u.
                     C7   -C8   -C9      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc    120.0(2), Rep      120.00 ....    Missing s.u.
                     C10  -C9   -C8      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc    120.0(3), Rep      120.00 ....    Missing s.u.
                     C11  -C10  -C9      1.555   1.555   1.555

PLAT_742  Alert C Angle   Calc    120.0(2), Rep      120.00 ....    Missing s.u.
                     C10  -C11  -C6      1.555   1.555   1.555

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.97
         From the CIF: _reflns_number_total                849
         Count of symmetry unique reflns          851
         Completeness (_total/calc)             99.76%
         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

 13 Alert Level C = Please check

Comment top

The title compound, (I) or BIP1, was previously described (Blake et al., 1989). Platinum complexes of the type fac-[PtXMe₃(BIP1)] (X = Cl, Br, I) have been recently reported (Orrell et al., 1998), the crystal structure of the iodine derivative, fac-[PtIMe₃(BIP1)], was determined to confirm the proposed stereochemistry.

Pentacoordinate complexes of iron, {[(ArN═C(Me)]₂C₅H₃N}FeCl₂ (Ar= alkyl substituted aryl ring), have been used for the isospecific polymerization of propylene (Small & Brookhart, 1999). [Please check that the above formula has the correct format as the original parentheses were confusing]

Our interest in tetracarbonyl complexes of molybdenum and tungsten with chelating nitrogen-donor ligands (Mentes, 1999; Mentes et al., 1999) lead us to investigate in situ reactions of 2,6-diacetylpyridine with aniline in the presence of [Mo(CO)₄(pip)₂] (pip is ?), from which reaction crystals of BIP1 were obtained.

The molecular structure of BIP1 is shown in Fig. 1 and selected bond distances and angles are given in Table 1. Atoms C1 and N1 lie on a crystallographic mirror plane which is orthogonal to the ring. The terminal phenyl groups are rotated by 60.2 (2)° from the plane of the ethylidenepyridine system. The bond length of the symmetric imine group (C4—N2) of 1.266 (4) Å is similar to that in fac-[PtIMe₃(BIP1)], 1.277 (8) (coordinated to Pt) and 1.291 (9) Å (uncoordinated), and also in [FeCl₂[(BIP2)] (BIP2 is ?) 1.273 (3) and 1.284 (3) Å. The C═N bond lengths in [Mo(CO)₄{C₅H₄NC(CH₃)═ NCH₃}] and [Mo(CO)₄{C₅H₄NC(C₆H₅)═NCH₃}] are 1.289 (5) and 1.283 (4) Å, respectively.

Experimental top

The Schiff base compound (BIP1) was isolated by refluxing 2,6-diacetylpyridine (0.489 g, 3 mmol) and excess of aniline (5 ml, 55 mmol) in propan-2-ol (10 ml) for 2 h. cis-[Mo(CO)₄(pip)₂] (1.134 g, 3 mmol) was added to the reaction. The reaction mixture was cooled to room temperature and the solvent removed by rotary evaporation. The intermediate (BIP1) was isolated and recrystallized as pale-yellow crystals from an acetone–methanol (50:50) mixture.

Computing details top

Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure of BIP1 showing the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level. H atoms are shown as spheres of arbitrary radii. Primed atoms are generated by the symmetry operation -x, y, z.

2,6-Bis[1-(phenylimino)ethyl]pyridine top

Crystal data top

C₂₁H₁₉N₃	D_x = 1.199 Mg m⁻³
M_r = 313.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmc2₁	Cell parameters from 33 reflections
a = 33.805 (5) Å	θ = 5.3–12.4°
b = 7.1247 (9) Å	µ = 0.07 mm⁻¹
c = 7.2074 (10) Å	T = 290 K
V = 1735.9 (4) Å³	Block, yellow
Z = 4	0.46 × 0.39 × 0.31 mm
F(000) = 664

Data collection top

Bruker P4 diffractometer	R_int = 0.043
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.9°
Graphite monochromator	h = −1→40
ω scans	k = 0→8
1096 measured reflections	l = −8→1
849 independent reflections	3 standard reflections every 100 reflections
663 reflections with I > 2σ(I)	intensity decay: <1%

Refinement top

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0779P)² + 0.947P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
849 reflections	Δρ_max = 0.18 e Å⁻³
101 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0054 (19)

Crystal data top

C₂₁H₁₉N₃	V = 1735.9 (4) Å³
M_r = 313.39	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 33.805 (5) Å	µ = 0.07 mm⁻¹
b = 7.1247 (9) Å	T = 290 K
c = 7.2074 (10) Å	0.46 × 0.39 × 0.31 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.043
1096 measured reflections	3 standard reflections every 100 reflections
849 independent reflections	intensity decay: <1%
663 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.18 e Å⁻³
849 reflections	Δρ_min = −0.19 e Å⁻³
101 parameters

Special details top

Experimental. The compound was also characterized by NMR (250 MHz, CDCl₃), δ: 2.32 (6H, s, CH₃—C), 6.73–8.35 (13H, m, arom.) p.p.m., IR (NaCl plates in Nujol): 1640 ν(C=N) cm^-1, Mass spectrum (FAB)m [MH]⁺ 314, and microanalysis Found: C, 80.0; H,6.1; N, 13.3%. calc.: C, 80.5; H, 6.1; N, 13.4 C₂₁H₁₉N₃

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 based on F.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.5000	0.2468 (5)	0.3061 (6)	0.0388 (11)
N2	0.39677 (8)	0.2700 (5)	0.3834 (5)	0.0508 (10)
C1	0.5000	0.3046 (9)	0.6858 (10)	0.0553 (15)
H1B	0.5000	0.3259	0.8131	0.066*
C2	0.46513 (10)	0.2886 (6)	0.5903 (7)	0.0503 (10)
H2B	0.4411	0.2959	0.6525	0.060*
C3	0.46603 (10)	0.2616 (5)	0.4008 (6)	0.0402 (10)
C4	0.42839 (9)	0.2462 (5)	0.2923 (6)	0.0401 (9)
C5	0.43096 (10)	0.2059 (7)	0.0878 (7)	0.0580 (12)
H5A	0.4048	0.1993	0.0365	0.087*
H5B	0.4442	0.0883	0.0688	0.087*
H5C	0.4455	0.3043	0.0276	0.087*
C6	0.35871 (5)	0.2606 (4)	0.2992 (4)	0.0458 (10)
C7	0.33256 (6)	0.1237 (3)	0.3611 (4)	0.0534 (11)
H7A	0.3407	0.0365	0.4493	0.064*
C8	0.29426 (6)	0.1171 (3)	0.2913 (5)	0.0587 (11)
H8A	0.2768	0.0255	0.3327	0.070*
C9	0.28210 (5)	0.2474 (4)	0.1596 (5)	0.0584 (13)
H9A	0.2565	0.2430	0.1129	0.070*
C10	0.30825 (7)	0.3843 (4)	0.0977 (5)	0.0617 (12)
H10A	0.3001	0.4715	0.0096	0.074*
C11	0.34655 (6)	0.3909 (3)	0.1675 (4)	0.0573 (12)
H11A	0.3640	0.4826	0.1261	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.033 (2)	0.044 (2)	0.040 (3)	0.000	0.000	−0.004 (2)
N2	0.0307 (17)	0.077 (2)	0.045 (2)	0.0018 (14)	0.0002 (16)	0.002 (2)
C1	0.045 (3)	0.077 (4)	0.044 (3)	0.000	0.000	−0.006 (4)
C2	0.036 (2)	0.069 (3)	0.046 (2)	0.0012 (18)	0.007 (2)	−0.001 (3)
C3	0.032 (2)	0.041 (2)	0.048 (3)	0.0010 (14)	0.0004 (16)	−0.0019 (19)
C4	0.0324 (19)	0.043 (2)	0.045 (2)	−0.0036 (14)	0.0004 (18)	0.0007 (19)
C5	0.0362 (19)	0.084 (3)	0.054 (3)	0.0027 (19)	−0.001 (2)	−0.023 (3)
C6	0.0293 (16)	0.068 (3)	0.040 (2)	0.0031 (16)	0.0042 (17)	−0.003 (2)
C7	0.0399 (18)	0.071 (3)	0.050 (2)	0.0045 (18)	0.003 (2)	0.007 (2)
C8	0.0405 (19)	0.072 (3)	0.063 (3)	−0.0063 (19)	0.004 (2)	0.000 (3)
C9	0.0363 (19)	0.083 (3)	0.056 (3)	0.0059 (19)	−0.0018 (19)	−0.013 (3)
C10	0.0396 (19)	0.085 (3)	0.061 (3)	0.0098 (19)	0.000 (2)	0.013 (3)
C11	0.0403 (19)	0.074 (3)	0.057 (3)	0.0000 (19)	0.004 (2)	0.018 (3)

Geometric parameters (Å, º) top

N1—C3	1.340 (4)	C4—C5	1.504 (7)
N1—C3ⁱ	1.340 (4)	C6—C7	1.3900
N2—C4	1.266 (4)	C6—C11	1.3900
N2—C6	1.424 (3)	C7—C8	1.3900
C1—C2	1.370 (5)	C8—C9	1.3900
C1—C2ⁱ	1.370 (5)	C9—C10	1.3900
C2—C3	1.379 (7)	C10—C11	1.3900
C3—C4	1.497 (5)

C3—N1—C3ⁱ	117.9 (4)	C3—C4—C5	118.5 (3)
C4—N2—C6	122.4 (3)	C7—C6—C11	120.0
C2—C1—C2ⁱ	118.7 (6)	C7—C6—N2	118.1 (2)
C1—C2—C3	119.4 (4)	C11—C6—N2	121.8 (2)
N1—C3—C2	122.3 (4)	C8—C7—C6	120.0
N1—C3—C4	117.2 (3)	C7—C8—C9	120.0
C2—C3—C4	120.5 (3)	C10—C9—C8	120.0
N2—C4—C3	115.9 (3)	C11—C10—C9	120.0
N2—C4—C5	125.6 (4)	C10—C11—C6	120.0

Symmetry code: (i) −x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉N₃
M_r	313.39
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	290
a, b, c (Å)	33.805 (5), 7.1247 (9), 7.2074 (10)
V (Å³)	1735.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.46 × 0.39 × 0.31

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1096, 849, 663
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.151, 1.07
No. of reflections	849
No. of parameters	101
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected bond lengths (Å) top

N1—C3	1.340 (4)	C3—C4	1.497 (5)
N2—C4	1.266 (4)	C4—C5	1.504 (7)
N2—C6	1.424 (3)

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