N-Phenyl-2-(phenyl­imino­meth­yl)pyrrole-1-carboxamide

Imhof, W.

doi:10.1107/S1600536807048416

N-Phenyl-2-(phenyliminomethyl)pyrrole-1-carboxamide

The title compound, C₁₈H₁₅N₃O, was prepared from phenyl(1H-pyrrol-2-ylmethylene)amine and phenyl isocyanate in the presence of catalytic amounts of [Pd(PPh₃)₄]. The conformation of the molecular structure is determined by an intramolecular hydrogen bond between the amide NH function and the imine N atom. The molecule is essentially planar. Only the peripheral phenyl substitutents are bent out of the plane.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048416/lh2518sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048416/lh2518Isup2.hkl Contains datablock I

CCDC reference: 667314

checkCIF report

Key indicators

Single-crystal X-ray study
T = 183 K
Mean (C-C) = 0.003 Å
R factor = 0.041
wR factor = 0.082
Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N2     -   C5      ..       7.20 su

Author Response: In the case N2 - C5 this might be caused by the fact that N2 is engaged in an intramolecular hydrogen bond and is therefore limited in it's thermal motions. In addition, the number of observed reflections is quite low with respect to the refined parameters caused by the very small crystal size.


Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.743

Author Response: Crystals of sufficient quality were very small, so the reflections were very weak, see also observed/unique reflections ratio. This led to the quite low goodness of fit parameter.

PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         43 Perc.

Author Response: Crystals of sufficient quality were very small, so the reflections were very weak.

PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1     -   C2      ..       5.12 su


   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Derivatives of the title compound have only been described once as intermediates in the synthesis of 1H-pyrrolo[1,2-c]imidazoles which were synthesized because of their molluscicidal activity (Mishriky et al., 1998). To the best of our knowledge none of these derivatives have been structurally characterized.

The title compound is produced by the formal insertion of an isocyanate into the N—H bond of the pyrrol ring. The conformation of the amide and the imine substituent relative to each other is determined by an intramolecular N3—H3N···N2 hydrogen bond between the amide NH function and the imine nitrogen atom. The other bond lengths and angles are of expected values.

Related literature top

For related literature, see: Mishriky et al. (1998).

Experimental top

230 mg (1.35 mmol) Phenyl-(1H-pyrrol-2-ylmethylene)-amine and 240 mg (2.025 mmol) phenylisocyanate were refluxed in 20 ml of THF together with 65 mg (0.056 mmol) [Pd(PPh₃)₄] and 4 mg glacial acetic acid for 2 hrs. Evaporation of the solvent yielded an orange oil. Column chromatography on silica yielded 90 mg (23%) of the title compound using a mixture of pentane and ethyl acetate (5:1) as the eluent. With a ratio of 2:1 a compound which corresponding to it's mass spectrum is composed of one equivalent of imine and two equivalents of isocyanate was obtained (40 mg, 7%). Colorless crystals of the title compound were produced from a solution in a pentane/ethyl acetate mixture (10:1) at -20 °.

MS (EI) [m/z (%)]: 289 (M⁺, 4), 197 (C₁₂H₉N₂O⁺, 40), 169 (C₁₁H₉N₂⁺, 100), 119 (PhNCO⁺, 76), 91 (C₇H₇⁺, 41), 77 (C₆H₅⁺, 28), 64 (C₅H₄⁺, 16), 51 (C₄H₃⁺, 15), 39 (C₃H₃⁺, 10; ¹H-NMR (CDCl₃, 293 K) [p.p.m.]: 6.44–6.48 (m, 2 H, CH_pyrrole), 7.01–7.05 (m, 1H, CH_pyrrole), 7.18–7.77 (m, 8H, CH_ar), 8.21–8.23 (m, 2H, CH_ar), 8.38 (s, 1H, CH_imine), 14.74 (s, 1H, CH_amide); ¹³C-NMR (CDCl₃, 293 K) [p.p.m.]: 110.7, 120.7, 120.9, 124.1, 126.6, 128.1, 129.0, 129.6, 130.3, 131.4, 138.4, 148.2, 148.8, 151.3.

Structure description top

For related literature, see: Mishriky et al. (1998).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and XP (Siemens, 1990).

Figures top

Fig. 1. The molecular structure of the title compoud showing the labelling scheme. Displacement ellipsoids are presented at the 40% probalitiy level. The dashed line indicates a hydrogen bond.

N-Phenyl-2-(phenyliminomethyl)pyrrole-1-carboxamide top

Crystal data top

C₁₈H₁₅N₃O	F(000) = 1216
M_r = 289.33	D_x = 1.341 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 11352 reflections
a = 18.292 (2) Å	θ = 3.0–27.5°
b = 19.966 (2) Å	µ = 0.09 mm⁻¹
c = 7.8479 (4) Å	T = 183 K
V = 2866.1 (4) Å³	Cuboid, colorless
Z = 8	0.15 × 0.1 × 0.1 mm

Data collection top

Nonius KappaCCD diffractometer	1391 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.082
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
φ and ω scans	h = −23→23
11352 measured reflections	k = −25→25
3270 independent reflections	l = −8→10

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.74	w = 1/[σ²(F_o²) + (0.0346P)² + 0.003P] where P = (F_o² + 2F_c²)/3
3270 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₈H₁₅N₃O	V = 2866.1 (4) Å³
M_r = 289.33	Z = 8
Orthorhombic, Pccn	Mo Kα radiation
a = 18.292 (2) Å	µ = 0.09 mm⁻¹
b = 19.966 (2) Å	T = 183 K
c = 7.8479 (4) Å	0.15 × 0.1 × 0.1 mm

Data collection top

Nonius KappaCCD diffractometer	1391 reflections with I > 2σ(I)
11352 measured reflections	R_int = 0.082
3270 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.74	Δρ_max = 0.14 e Å⁻³
3270 reflections	Δρ_min = −0.20 e Å⁻³
199 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.06301 (7)	0.63509 (6)	0.91292 (14)	0.0458 (3)
N1	0.07867 (7)	0.52183 (7)	0.88728 (15)	0.0363 (4)
C1	0.14376 (10)	0.52718 (10)	0.9744 (2)	0.0416 (5)
H1	0.1614	0.5668	1.0271	0.062*
C2	0.17911 (10)	0.46711 (9)	0.9736 (2)	0.0449 (5)
H2	0.2250	0.4575	1.0246	0.067*
C3	0.13464 (10)	0.42195 (9)	0.8828 (2)	0.0439 (5)
H3	0.1454	0.3761	0.8625	0.066*
C4	0.07299 (10)	0.45515 (9)	0.8283 (2)	0.0376 (4)
C5	0.01475 (10)	0.42109 (9)	0.73953 (18)	0.0385 (4)
H5	0.0220	0.3749	0.7156	0.058*
N2	−0.04575 (8)	0.44677 (7)	0.68969 (16)	0.0374 (4)
N3	−0.01941 (7)	0.57710 (7)	0.75188 (16)	0.0379 (4)
H3N	−0.0357	0.5364	0.7318	0.057*
C6	−0.09948 (9)	0.40501 (9)	0.61349 (19)	0.0356 (4)
C7	−0.14260 (10)	0.43399 (9)	0.4869 (2)	0.0407 (5)
H7	−0.1360	0.4797	0.4575	0.061*
C8	−0.19501 (10)	0.39616 (9)	0.4044 (2)	0.0416 (5)
H8	−0.2235	0.4157	0.3162	0.062*
C9	−0.20604 (10)	0.33021 (9)	0.4496 (2)	0.0447 (5)
H9	−0.2422	0.3044	0.3927	0.067*
C10	−0.16424 (10)	0.30146 (9)	0.5786 (2)	0.0466 (5)
H10	−0.1719	0.2560	0.6100	0.070*
C11	−0.11140 (10)	0.33934 (9)	0.6612 (2)	0.0415 (5)
H11	−0.0834	0.3201	0.7506	0.062*
C12	0.03966 (10)	0.58330 (9)	0.8518 (2)	0.0380 (4)
C13	−0.05737 (10)	0.63125 (8)	0.67646 (19)	0.0365 (4)
C14	−0.13024 (10)	0.62156 (9)	0.6346 (2)	0.0440 (5)
H14	−0.1543	0.5814	0.6670	0.066*
C15	−0.16813 (11)	0.67072 (9)	0.5450 (2)	0.0501 (5)
H15	−0.2180	0.6640	0.5160	0.075*
C16	−0.13333 (12)	0.72922 (9)	0.4984 (2)	0.0507 (5)
H16	−0.1590	0.7626	0.4361	0.076*
C17	−0.06071 (11)	0.73919 (9)	0.5428 (2)	0.0465 (5)
H17	−0.0369	0.7797	0.5116	0.070*
C18	−0.02248 (11)	0.69054 (8)	0.63223 (19)	0.0410 (5)
H18	0.0271	0.6977	0.6630	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0529 (9)	0.0375 (8)	0.0470 (7)	−0.0021 (6)	−0.0039 (6)	−0.0077 (6)
N1	0.0378 (9)	0.0349 (9)	0.0362 (7)	−0.0004 (7)	0.0002 (7)	−0.0013 (7)
C1	0.0363 (12)	0.0492 (13)	0.0393 (10)	−0.0057 (10)	−0.0025 (8)	−0.0016 (8)
C2	0.0409 (12)	0.0450 (12)	0.0489 (11)	0.0015 (10)	−0.0008 (9)	0.0034 (9)
C3	0.0466 (12)	0.0370 (11)	0.0480 (11)	0.0026 (10)	0.0026 (9)	−0.0003 (9)
C4	0.0405 (12)	0.0360 (11)	0.0362 (9)	−0.0023 (10)	0.0037 (9)	0.0006 (8)
C5	0.0470 (12)	0.0343 (10)	0.0342 (9)	−0.0039 (10)	0.0070 (8)	−0.0009 (8)
N2	0.0385 (10)	0.0370 (9)	0.0369 (8)	−0.0013 (8)	0.0025 (7)	0.0001 (6)
N3	0.0394 (9)	0.0315 (8)	0.0428 (8)	−0.0016 (8)	−0.0021 (7)	−0.0018 (7)
C6	0.0389 (11)	0.0332 (11)	0.0346 (9)	−0.0028 (9)	0.0037 (8)	−0.0026 (8)
C7	0.0444 (12)	0.0361 (11)	0.0415 (10)	−0.0021 (9)	0.0068 (9)	0.0028 (8)
C8	0.0400 (12)	0.0472 (13)	0.0377 (9)	−0.0008 (9)	0.0022 (9)	0.0018 (9)
C9	0.0445 (13)	0.0473 (13)	0.0423 (10)	−0.0082 (10)	0.0017 (9)	−0.0043 (9)
C10	0.0550 (14)	0.0397 (11)	0.0450 (10)	−0.0087 (10)	0.0007 (9)	0.0019 (9)
C11	0.0461 (13)	0.0391 (12)	0.0394 (9)	−0.0039 (10)	0.0013 (9)	−0.0001 (8)
C12	0.0412 (12)	0.0369 (11)	0.0358 (10)	−0.0005 (10)	0.0053 (8)	−0.0004 (9)
C13	0.0447 (13)	0.0302 (11)	0.0345 (9)	0.0038 (9)	0.0046 (9)	−0.0020 (8)
C14	0.0431 (12)	0.0393 (12)	0.0497 (11)	−0.0012 (10)	0.0004 (9)	0.0020 (9)
C15	0.0503 (14)	0.0427 (13)	0.0573 (12)	0.0033 (10)	−0.0048 (10)	0.0028 (9)
C16	0.0669 (16)	0.0387 (12)	0.0465 (11)	0.0071 (10)	−0.0047 (10)	0.0030 (9)
C17	0.0648 (15)	0.0333 (11)	0.0415 (10)	−0.0014 (10)	0.0027 (9)	0.0005 (8)
C18	0.0496 (13)	0.0389 (12)	0.0344 (9)	−0.0027 (10)	0.0031 (8)	−0.0045 (8)

Geometric parameters (Å, º) top

O1—C12	1.2172 (19)	C7—H7	0.9500
N1—C1	1.377 (2)	C8—C9	1.379 (2)
N1—C4	1.413 (2)	C8—H8	0.9500
N1—C12	1.447 (2)	C9—C10	1.393 (2)
C1—C2	1.363 (2)	C9—H9	0.9500
C1—H1	0.9500	C10—C11	1.388 (2)
C2—C3	1.408 (2)	C10—H10	0.9500
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.376 (2)	C13—C14	1.386 (2)
C3—H3	0.9500	C13—C18	1.389 (2)
C4—C5	1.443 (2)	C14—C15	1.392 (2)
C5—N2	1.281 (2)	C14—H14	0.9500
C5—H5	0.9500	C15—C16	1.380 (2)
N2—C6	1.421 (2)	C15—H15	0.9500
N3—C12	1.341 (2)	C16—C17	1.388 (2)
N3—C13	1.415 (2)	C16—H16	0.9500
N3—H3N	0.8800	C17—C18	1.388 (2)
C6—C11	1.381 (2)	C17—H17	0.9500
C6—C7	1.394 (2)	C18—H18	0.9500
C7—C8	1.382 (2)

C1—N1—C4	107.41 (14)	C8—C9—C10	120.03 (17)
C1—N1—C12	117.15 (14)	C8—C9—H9	120.0
C4—N1—C12	134.41 (14)	C10—C9—H9	120.0
C2—C1—N1	109.87 (16)	C11—C10—C9	119.82 (17)
C2—C1—H1	125.1	C11—C10—H10	120.1
N1—C1—H1	125.1	C9—C10—H10	120.1
C1—C2—C3	106.96 (17)	C6—C11—C10	120.05 (17)
C1—C2—H2	126.5	C6—C11—H11	120.0
C3—C2—H2	126.5	C10—C11—H11	120.0
C4—C3—C2	108.79 (17)	O1—C12—N3	126.29 (17)
C4—C3—H3	125.6	O1—C12—N1	118.13 (16)
C2—C3—H3	125.6	N3—C12—N1	115.58 (16)
C3—C4—N1	106.96 (15)	C14—C13—C18	120.09 (17)
C3—C4—C5	121.87 (17)	C14—C13—N3	117.68 (15)
N1—C4—C5	131.01 (16)	C18—C13—N3	122.03 (16)
N2—C5—C4	126.63 (17)	C13—C14—C15	120.00 (18)
N2—C5—H5	116.7	C13—C14—H14	120.0
C4—C5—H5	116.7	C15—C14—H14	120.0
C5—N2—C6	119.43 (15)	C16—C15—C14	120.08 (19)
C12—N3—C13	124.72 (15)	C16—C15—H15	120.0
C12—N3—H3N	117.6	C14—C15—H15	120.0
C13—N3—H3N	117.6	C15—C16—C17	119.77 (18)
C11—C6—C7	119.87 (16)	C15—C16—H16	120.1
C11—C6—N2	123.53 (15)	C17—C16—H16	120.1
C7—C6—N2	116.59 (15)	C18—C17—C16	120.60 (18)
C8—C7—C6	119.98 (16)	C18—C17—H17	119.7
C8—C7—H7	120.0	C16—C17—H17	119.7
C6—C7—H7	120.0	C17—C18—C13	119.44 (18)
C9—C8—C7	120.20 (17)	C17—C18—H18	120.3
C9—C8—H8	119.9	C13—C18—H18	120.3
C7—C8—H8	119.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N2	0.88	1.83	2.691 (2)	166

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅N₃O
M_r	289.33
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	183
a, b, c (Å)	18.292 (2), 19.966 (2), 7.8479 (4)
V (Å³)	2866.1 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.15 × 0.1 × 0.1

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11352, 3270, 1391
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.082, 0.74
No. of reflections	3270
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997) and XP (Siemens, 1990).