2-[(1-Methyl-1H-pyrrol-2-yl)methyl­idene]propane­dinitrile

Asiri, A.M.; Faidallah, H.M.; Al-Thabaiti, S.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S160053681201197X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1170

doi:10.1107/S160053681201197X

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2-[(1-Methyl-1H-pyrrol-2-yl)methylidene]propanedinitrile

Abdullah M. Asiri,^a,^b ‡ Hassan M. Faidallah,^a Shaeel A. Al-Thabaiti,^a Seik Weng Ng ^c,^a and Edward R. T. Tiekink ^c ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah, Saudi Arabia, ^bThe Center of Excellence for Advanced Materials Research, King Abdulaziz University, Jeddah, PO Box 80203, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 18 March 2012; accepted 20 March 2012; online 24 March 2012)

In the title compound, C₉H₇N₃, the N-bound methyl group and vinyl H atom are syn. The 12 non-H atoms comprising the molecule are essentially coplanar (r.m.s. deviation = 0.071 Å). Supramolecular tapes feature in the crystal packing, orientated perpendicular to [10-1], and are formed by C—H⋯N interactions involving each cyano N atom. The tapes are connected into layers via π–π interactions occurring between translationally related pyrrole rings [ring centroid–centroid distance = 3.8754 (10) Å]; the layers stack along the b axis.

Related literature

For the anti-cancer effects of related compounds, see: Rostom et al. (2011 ). For structural studies of di-carbonitrile compounds, see: Asiri et al. (2011 ); Al-Youbi et al. (2012 ).

Experimental

Crystal data

C₉H₇N₃
M_r = 157.18
Triclinic, $[P \overline 1]$
a = 3.8754 (2) Å
b = 8.7795 (5) Å
c = 12.1773 (7) Å
α = 97.517 (5)°
β = 90.962 (5)°
γ = 98.689 (5)°
V = 405.76 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.980, T_max = 0.996
5871 measured reflections
1866 independent reflections
1463 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.124
S = 1.01
1866 reflections
137 parameters
All H-atom parameters refined
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N3ⁱ	0.976 (19)	2.612 (19)	3.579 (2)	170.8 (16)
C6—H6⋯N2ⁱⁱ	0.969 (17)	2.515 (17)	3.469 (2)	167.8 (14)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201197X/bt5851sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201197X/bt5851Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201197X/bt5851Isup3.cml

checkCIF report

Comment top

Arylidenes are considered as key intermediates for the synthesis of a variety of heterocycles of biological importance, such as pyridine, pyridazine and quinoline derivatives. Previous studies have shown that the derived compounds exhibit a variety of biological activities, including anti-cancer effects (Rostom et al., 2011). In continuation of structural studies of di-carbonitrile compounds (Asiri et al., 2011; Al-Youbi et al., 2012), the title compound, (I), was investigated.

In (I), Fig. 1, the N-bound methyl group and vinyl-H atom are syn. The 12 non-hydrogen atoms are co-planar having a r.m.s. deviation = 0.071 Å, with the maximum deviations being 0.118 (2) Å for the C1 atom and -0.084 (2) Å for the N2 atom.

In the crystal packing, each cyano-N atom participates in a C—H···N interaction, Table 1, with a centrosymmetrically related molecule to form a supramolecular tape. The tape is orientated along [101] and comprises alternating 10-membered {···HC₃N}₂ and 16-membered {···HC₆N}₂ synthons, Fig. 2. The tapes are connected into layers via π—π interactions occurring between translationally related pyrrazole rings [ring centroid..centroid distance = 3.8754 (10) Å for symmetry operation 1 + x, y, z]. The layers stack along the b axis, Fig. 3.

Related literature top

For the anti-cancer effects of related compounds, see: Rostom et al. (2011). For structural studies of di-carbonitrile compounds, see: Asiri et al. (2011); Al-Youbi et al. (2012).

Experimental top

A mixture of 1-methylpyrrole-2-carboxaldehyde (1.1 g, 0.01 mmol) and malononitrile (1.1 g, 0.01 mmol) in absolute ethanol (50 ml) was refluxed for 2 h. The reaction mixture was allowed to cool, and the formed precipitate was filtered, washed with water, dried and recrystallized from ethanol. Yield: 72%. M.pt: 427–229 K.

Structure description top

For the anti-cancer effects of related compounds, see: Rostom et al. (2011). For structural studies of di-carbonitrile compounds, see: Asiri et al. (2011); Al-Youbi et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 2. A view of the supramolecular tape in (I) with C—H···N interactions shown as blue dashed lines.
	Fig. 3. A view in projection down the c axis of the unit-cell contents of (I) showing the stacking of layers along the b axis. The C—H···N and π—π interactions are shown as blue and purple dashed lines, respectively.

2-[(1-Methyl-1H-pyrrol-2-yl)methylidene]propanedinitrile top

Crystal data top

C₉H₇N₃	Z = 2
M_r = 157.18	F(000) = 164
Triclinic, P1	D_x = 1.286 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8754 (2) Å	Cell parameters from 1724 reflections
b = 8.7795 (5) Å	θ = 2.4–27.5°
c = 12.1773 (7) Å	µ = 0.08 mm⁻¹
α = 97.517 (5)°	T = 100 K
β = 90.962 (5)°	Prism, light-brown
γ = 98.689 (5)°	0.25 × 0.15 × 0.05 mm
V = 405.76 (4) Å³

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1866 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1463 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.039
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.6°, θ_min = 2.4°
ω scan	h = −5→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→11
T_min = 0.980, T_max = 0.996	l = −15→15
5871 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	All H-atom parameters refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0531P)² + 0.1622P] where P = (F_o² + 2F_c²)/3
1866 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₇N₃	γ = 98.689 (5)°
M_r = 157.18	V = 405.76 (4) Å³
Triclinic, P1	Z = 2
a = 3.8754 (2) Å	Mo Kα radiation
b = 8.7795 (5) Å	µ = 0.08 mm⁻¹
c = 12.1773 (7) Å	T = 100 K
α = 97.517 (5)°	0.25 × 0.15 × 0.05 mm
β = 90.962 (5)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1866 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1463 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.996	R_int = 0.039
5871 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.124	All H-atom parameters refined
S = 1.01	Δρ_max = 0.24 e Å⁻³
1866 reflections	Δρ_min = −0.29 e Å⁻³
137 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.3583 (3)	0.18886 (15)	0.26433 (10)	0.0202 (3)
N2	0.2317 (4)	0.71488 (16)	0.02337 (11)	0.0267 (3)
N3	0.8617 (4)	0.78536 (16)	0.32981 (11)	0.0267 (3)
C1	0.1644 (5)	0.0922 (2)	0.16953 (14)	0.0250 (4)
C2	0.4697 (4)	0.13538 (19)	0.35574 (13)	0.0234 (4)
C3	0.6539 (4)	0.25848 (19)	0.42647 (13)	0.0246 (4)
C4	0.6548 (4)	0.39208 (19)	0.37650 (12)	0.0220 (4)
C5	0.4681 (4)	0.34899 (17)	0.27400 (12)	0.0188 (3)
C6	0.3763 (4)	0.43469 (17)	0.19062 (12)	0.0185 (3)
C7	0.4655 (4)	0.59152 (18)	0.18566 (12)	0.0190 (3)
C8	0.3370 (4)	0.65898 (17)	0.09541 (12)	0.0202 (3)
C9	0.6828 (4)	0.69787 (17)	0.26673 (12)	0.0196 (3)
H11	0.106 (5)	−0.015 (3)	0.1842 (17)	0.041 (6)*
H12	0.308 (5)	0.090 (2)	0.1053 (17)	0.038 (5)*
H13	−0.050 (5)	0.132 (2)	0.1524 (16)	0.033 (5)*
H2	0.412 (5)	0.027 (2)	0.3608 (15)	0.025 (4)*
H3	0.763 (5)	0.250 (2)	0.4978 (16)	0.031 (5)*
H4	0.769 (5)	0.500 (2)	0.4051 (14)	0.024 (4)*
H6	0.220 (4)	0.378 (2)	0.1311 (14)	0.020 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0225 (7)	0.0198 (7)	0.0189 (6)	0.0031 (5)	0.0018 (5)	0.0047 (5)
N2	0.0320 (8)	0.0269 (7)	0.0215 (7)	0.0040 (6)	−0.0007 (6)	0.0056 (6)
N3	0.0310 (8)	0.0241 (7)	0.0245 (7)	0.0008 (6)	−0.0021 (6)	0.0062 (6)
C1	0.0282 (9)	0.0221 (8)	0.0235 (8)	0.0002 (7)	−0.0013 (7)	0.0037 (6)
C2	0.0255 (8)	0.0227 (8)	0.0244 (8)	0.0054 (6)	0.0050 (6)	0.0097 (6)
C3	0.0254 (8)	0.0301 (9)	0.0201 (8)	0.0054 (7)	0.0008 (6)	0.0089 (6)
C4	0.0209 (8)	0.0249 (8)	0.0204 (8)	0.0024 (6)	0.0018 (6)	0.0046 (6)
C5	0.0188 (7)	0.0196 (7)	0.0182 (7)	0.0022 (6)	0.0029 (6)	0.0045 (6)
C6	0.0179 (7)	0.0213 (8)	0.0163 (7)	0.0034 (6)	0.0018 (6)	0.0023 (6)
C7	0.0195 (7)	0.0221 (8)	0.0162 (7)	0.0042 (6)	0.0023 (6)	0.0041 (6)
C8	0.0214 (8)	0.0201 (7)	0.0191 (8)	0.0028 (6)	0.0022 (6)	0.0023 (6)
C9	0.0208 (7)	0.0201 (7)	0.0198 (8)	0.0041 (6)	0.0037 (6)	0.0079 (6)

Geometric parameters (Å, º) top

N1—C2	1.352 (2)	C3—C4	1.390 (2)
N1—C5	1.3949 (19)	C3—H3	0.977 (19)
N1—C1	1.463 (2)	C4—C5	1.410 (2)
N2—C8	1.157 (2)	C4—H4	1.002 (19)
N3—C9	1.152 (2)	C5—C6	1.412 (2)
C1—H11	0.97 (2)	C6—C7	1.378 (2)
C1—H12	0.97 (2)	C6—H6	0.969 (17)
C1—H13	0.98 (2)	C7—C8	1.431 (2)
C2—C3	1.386 (2)	C7—C9	1.431 (2)
C2—H2	0.952 (19)

C2—N1—C5	108.97 (13)	C3—C4—C5	107.69 (14)
C2—N1—C1	124.98 (13)	C3—C4—H4	127.8 (10)
C5—N1—C1	126.02 (13)	C5—C4—H4	124.5 (10)
N1—C1—H11	110.6 (12)	N1—C5—C4	106.64 (13)
N1—C1—H12	109.7 (11)	N1—C5—C6	120.42 (13)
H11—C1—H12	106.9 (17)	C4—C5—C6	132.91 (14)
N1—C1—H13	111.0 (11)	C7—C6—C5	128.23 (14)
H11—C1—H13	109.4 (17)	C7—C6—H6	115.2 (10)
H12—C1—H13	109.2 (16)	C5—C6—H6	116.5 (10)
N1—C2—C3	109.17 (14)	C6—C7—C8	120.18 (13)
N1—C2—H2	118.3 (11)	C6—C7—C9	124.54 (13)
C3—C2—H2	132.5 (11)	C8—C7—C9	115.29 (13)
C2—C3—C4	107.53 (14)	N2—C8—C7	179.15 (16)
C2—C3—H3	125.1 (11)	N3—C9—C7	178.23 (16)
C4—C3—H3	127.3 (11)

C5—N1—C2—C3	−0.11 (17)	C1—N1—C5—C6	3.9 (2)
C1—N1—C2—C3	177.99 (14)	C3—C4—C5—N1	−0.10 (17)
N1—C2—C3—C4	0.05 (18)	C3—C4—C5—C6	177.75 (16)
C2—C3—C4—C5	0.04 (18)	N1—C5—C6—C7	−178.89 (14)
C2—N1—C5—C4	0.13 (17)	C4—C5—C6—C7	3.5 (3)
C1—N1—C5—C4	−177.94 (14)	C5—C6—C7—C8	−177.93 (14)
C2—N1—C5—C6	−178.05 (13)	C5—C6—C7—C9	1.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N3ⁱ	0.976 (19)	2.612 (19)	3.579 (2)	170.8 (16)
C6—H6···N2ⁱⁱ	0.969 (17)	2.515 (17)	3.469 (2)	167.8 (14)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₉H₇N₃
M_r	157.18
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	3.8754 (2), 8.7795 (5), 12.1773 (7)
α, β, γ (°)	97.517 (5), 90.962 (5), 98.689 (5)
V (Å³)	405.76 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.15 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.980, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	5871, 1866, 1463
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.01
No. of reflections	1866
No. of parameters	137
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N3ⁱ	0.976 (19)	2.612 (19)	3.579 (2)	170.8 (16)
C6—H6···N2ⁱⁱ	0.969 (17)	2.515 (17)	3.469 (2)	167.8 (14)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x, −y+1, −z.

Footnotes

‡Additional correspondence author, e-mail: aasiri2@kau.edu.sa.

Acknowledgements

The authors are thankful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

References

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