organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

5,5′-(1-Phenyl­ethane-1,1-di­yl)bis­­(1H-pyrrole-2-carboxaldehyde)

aVignan's Foundation for Science Technology and Research, Division of Chemistry, Department of Sciences and Humanities, Vadlamudi, Andhra, Pradesh-522213, India
*Correspondence e-mail: ravikottalanka@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 11 November 2019; accepted 9 December 2019; online 17 December 2019)

In the title compound, C18H16N2O2, the dihedral angle between the pyrrole rings is 79.47 (9)°, with the N—H groups approximately orthogonal (H—N⋯N—H pseudo torsion angle = −106°). In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into [11[\overline{1}]] chains. A C—H⋯O inter­action is also observed.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Dipyrro­methane-di­aldehydes are inter­mediates for the preparation of various macrocyclic (Love et al., 2003[Love, J. B., Blake, A. J., Wilson, C., Reid, S. D., Novak, A. & Hitchcock, P. B. (2003). Chem. Commun. pp. 1682-1684.]) and acyclic di­imino­dipyrro­methane Schiff bases (e.g.: Deliomeroglu et al., 2016[Deliomeroglu, M. K., Lynch, V. M. & Sessler, J. L. (2016). Chem. Sci. 7, 3843-3850.]). As a part of our studies in this area, we now report the crystal structure of the title compound.

The dihedral angles between the N1-pyrrole ring (A), N2-pyrrole ring (B) and the C13–C18 phenyl ring (C) are A/B = 79.47 (9), A/C = 87.21 (8) and B/C = 70.40 (8)°. The N1—C6—C7—O1 [−2.7 (2)°] and N2—C11—C12—O2 [2.8 (2)°] torsion angles indicate that the aldehyde groups are almost coplanar with their adjacent pyrrole ring systems (Fig. 1[link]).

[Figure 1]
Figure 1
The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

In the crystal, N—H⋯O hydrogen bonds (Table 1[link]) link the mol­ecules into [11[\overline{1}]] chains (Fig. 2[link]). A weak C—H⋯O hydrogen bond consolidates the chains. The Hirshfeld surface and two-dimensional fingerprint plots were generated with CrystalExplorer17.5 (Turner et al., 2017[Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. http://hirshfeldsurface.net]) (see supplementary materials). The percentage contributions from the different inter­atomic contacts to the Hirshfeld surfaces are as follows: H⋯H (47.9%), C⋯H/H⋯C (27.5%), O⋯H/H⋯O (21.5%), N⋯H/H⋯N (1.5%) and C⋯O/O⋯C (1.5%).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 2.08 2.9321 (16) 171
N2—H2⋯O2ii 0.86 2.03 2.8838 (15) 173
C1—H1B⋯O1i 0.96 2.58 3.3419 (18) 137
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x+2, -y+1, -z+1.
[Figure 2]
Figure 2
Illustration of the different hydrogen bonds (N—H⋯O and C—H⋯O) in the title compound viewed along [001]. Hydrogen bonds are drawn as dashed lines.

Synthesis and crystallization

The title compound, C18H16N2O2 was prepared by the reported method (Fig. 3[link]); Muwal et al. 2018[Muwal, P. K., Nayal, A., Jaiswal, M. K. & Pandey, P. S. (2018). Tetrahedron Lett. 59, 29-32.]) and colourless cubes were recrystallized from a toluene–hexane solvent mixture at −4°C.

[Figure 3]
Figure 3
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C18H16N2O2
Mr 292.33
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 293
a, b, c (Å) 7.0679 (2), 9.6856 (4), 12.1510 (5)
α, β, γ (°) 101.560 (3), 93.302 (3), 111.270 (4)
V3) 751.66 (5)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.18 × 0.15 × 0.13
 
Data collection
Diffractometer XtaLAB Pro: Kappa dual offset/far
Absorption correction Multi-scan (CrysAlis PRO; Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.])
Tmin, Tmax 0.901, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 13274, 4208, 3307
Rint 0.022
(sin θ/λ)max−1) 0.726
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.142, 1.03
No. of reflections 4208
No. of parameters 200
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.32, −0.19
Computer programs: CrysAlis PRO (Rigaku OD, 2015[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]), SHELXT2014/5 (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2018/3 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]), , ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Structural data


Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).

5,5'-(1-Phenylethane-1,1-diyl)bis(1H-pyrrole-2-carboxaldehyde) top
Crystal data top
C18H16N2O2Z = 2
Mr = 292.33F(000) = 308
Triclinic, P1Dx = 1.292 Mg m3
a = 7.0679 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.6856 (4) ÅCell parameters from 5094 reflections
c = 12.1510 (5) Åθ = 3.7–29.9°
α = 101.560 (3)°µ = 0.09 mm1
β = 93.302 (3)°T = 293 K
γ = 111.270 (4)°Cube, colourless
V = 751.66 (5) Å30.18 × 0.15 × 0.13 mm
Data collection top
XtaLAB Pro: Kappa dual offset/far
diffractometer
Rint = 0.022
Radiation source: fine-focus sealed X-ray tubeθmax = 31.1°, θmin = 3.1°
ω scansh = 910
Absorption correction: multi-scan
(CrysAlisPro; Rigaku OD, 2015)
k = 1313
Tmin = 0.901, Tmax = 1.000l = 1717
13274 measured reflectionsStandard reflections: see text; every none reflections
4208 independent reflections intensity decay: none
3307 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.142 w = 1/[σ2(Fo2) + (0.0767P)2 + 0.1364P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
4208 reflectionsΔρmax = 0.32 e Å3
200 parametersΔρmin = 0.19 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.69498 (16)0.13760 (11)0.87005 (8)0.0348 (2)
H10.5922790.1312800.9062600.042*
N20.94852 (16)0.52913 (11)0.69220 (8)0.0350 (2)
H20.8976930.4702140.6257660.042*
O21.18939 (19)0.67425 (13)0.53044 (9)0.0593 (3)
O10.63340 (19)0.10500 (15)0.98826 (12)0.0649 (3)
C80.87280 (19)0.50458 (13)0.78942 (10)0.0349 (3)
C130.53349 (18)0.30398 (14)0.68621 (10)0.0346 (3)
C60.8011 (2)0.04229 (15)0.86453 (11)0.0399 (3)
C30.77809 (19)0.24329 (14)0.80925 (10)0.0347 (3)
C20.69195 (19)0.36169 (13)0.79432 (10)0.0338 (2)
C111.1197 (2)0.66317 (14)0.71604 (11)0.0398 (3)
C140.4611 (2)0.40434 (16)0.64815 (12)0.0445 (3)
H140.5122120.5064790.6868360.053*
C180.4538 (2)0.15255 (16)0.62642 (12)0.0452 (3)
H180.5007150.0836600.6501400.054*
C70.7592 (2)0.07648 (17)0.92390 (13)0.0471 (3)
H70.8354580.1374030.9120500.057*
C121.2317 (2)0.72554 (15)0.63178 (13)0.0464 (3)
H121.3485090.8142250.6573580.056*
C90.9961 (2)0.62497 (16)0.87798 (11)0.0470 (3)
H90.9786350.6377120.9541180.056*
C50.9541 (2)0.09002 (19)0.79891 (13)0.0505 (3)
H51.0491160.0462640.7807290.061*
C10.5846 (3)0.40046 (18)0.89673 (12)0.0478 (3)
H1A0.6773900.4292000.9657530.072*
H1B0.4651290.3127600.8980670.072*
H1C0.5446890.4834800.8899150.072*
C101.1508 (2)0.72322 (16)0.83195 (12)0.0500 (3)
H101.2559850.8129890.8719590.060*
C40.9407 (2)0.21604 (18)0.76469 (13)0.0495 (3)
H41.0256610.2715840.7200180.059*
C150.3139 (2)0.3539 (2)0.55333 (14)0.0543 (4)
H150.2671420.4224080.5287600.065*
C170.3053 (2)0.10196 (19)0.53181 (15)0.0574 (4)
H170.2525170.0002560.4932420.069*
C160.2361 (2)0.2028 (2)0.49507 (15)0.0587 (4)
H160.1373920.1692680.4313070.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0370 (5)0.0360 (5)0.0340 (5)0.0132 (4)0.0090 (4)0.0142 (4)
N20.0403 (5)0.0302 (5)0.0283 (5)0.0065 (4)0.0053 (4)0.0066 (4)
O20.0674 (7)0.0533 (6)0.0445 (6)0.0066 (5)0.0180 (5)0.0121 (5)
O10.0602 (7)0.0681 (7)0.0862 (9)0.0277 (6)0.0297 (6)0.0500 (7)
C80.0428 (6)0.0322 (5)0.0298 (5)0.0134 (5)0.0067 (4)0.0090 (4)
C130.0334 (5)0.0372 (6)0.0361 (6)0.0122 (5)0.0132 (4)0.0154 (5)
C60.0428 (6)0.0395 (6)0.0410 (6)0.0172 (5)0.0057 (5)0.0147 (5)
C30.0404 (6)0.0355 (6)0.0300 (5)0.0135 (5)0.0095 (4)0.0126 (4)
C20.0419 (6)0.0336 (5)0.0304 (5)0.0157 (5)0.0130 (4)0.0129 (4)
C110.0420 (6)0.0316 (6)0.0398 (6)0.0069 (5)0.0042 (5)0.0090 (5)
C140.0451 (7)0.0405 (7)0.0518 (8)0.0176 (6)0.0084 (6)0.0168 (6)
C180.0481 (7)0.0379 (6)0.0485 (7)0.0141 (6)0.0066 (6)0.0124 (5)
C70.0457 (7)0.0445 (7)0.0589 (8)0.0201 (6)0.0090 (6)0.0237 (6)
C120.0457 (7)0.0344 (6)0.0493 (8)0.0031 (5)0.0105 (6)0.0106 (5)
C90.0616 (8)0.0420 (7)0.0301 (6)0.0133 (6)0.0037 (6)0.0057 (5)
C50.0530 (8)0.0583 (9)0.0560 (8)0.0320 (7)0.0202 (6)0.0246 (7)
C10.0636 (9)0.0518 (8)0.0415 (7)0.0306 (7)0.0270 (6)0.0191 (6)
C100.0560 (8)0.0386 (7)0.0404 (7)0.0050 (6)0.0015 (6)0.0036 (5)
C40.0522 (8)0.0569 (8)0.0554 (8)0.0276 (7)0.0270 (6)0.0303 (7)
C150.0474 (8)0.0620 (9)0.0625 (9)0.0251 (7)0.0064 (7)0.0270 (8)
C170.0521 (8)0.0481 (8)0.0589 (9)0.0100 (7)0.0009 (7)0.0036 (7)
C160.0433 (8)0.0718 (11)0.0548 (9)0.0165 (7)0.0016 (6)0.0143 (8)
Geometric parameters (Å, º) top
N1—C31.3622 (14)C14—C151.384 (2)
N1—C61.3793 (16)C14—H140.9300
N1—H10.8600C18—C171.388 (2)
N2—C81.3533 (15)C18—H180.9300
N2—C111.3795 (16)C7—H70.9300
N2—H20.8600C12—H120.9300
O2—C121.2071 (18)C9—C101.394 (2)
O1—C71.2113 (18)C9—H90.9300
C8—C91.3888 (18)C5—C41.398 (2)
C8—C21.5202 (16)C5—H50.9300
C13—C181.3867 (19)C1—H1A0.9600
C13—C141.3907 (18)C1—H1B0.9600
C13—C21.5410 (17)C1—H1C0.9600
C6—C51.3798 (19)C10—H100.9300
C6—C71.4288 (18)C4—H40.9300
C3—C41.3850 (18)C15—C161.380 (3)
C3—C21.5152 (17)C15—H150.9300
C2—C11.5470 (16)C17—C161.374 (3)
C11—C101.3833 (19)C17—H170.9300
C11—C121.4261 (18)C16—H160.9300
C3—N1—C6109.44 (10)O1—C7—C6125.90 (14)
C3—N1—H1125.3O1—C7—H7117.0
C6—N1—H1125.3C6—C7—H7117.0
C8—N2—C11109.55 (10)O2—C12—C11126.24 (13)
C8—N2—H2125.2O2—C12—H12116.9
C11—N2—H2125.2C11—C12—H12116.9
N2—C8—C9107.91 (11)C8—C9—C10107.53 (12)
N2—C8—C2123.11 (10)C8—C9—H9126.2
C9—C8—C2128.86 (11)C10—C9—H9126.2
C18—C13—C14118.02 (12)C6—C5—C4107.65 (12)
C18—C13—C2122.18 (11)C6—C5—H5126.2
C14—C13—C2119.76 (11)C4—C5—H5126.2
N1—C6—C5107.49 (11)C2—C1—H1A109.5
N1—C6—C7123.62 (12)C2—C1—H1B109.5
C5—C6—C7128.80 (13)H1A—C1—H1B109.5
N1—C3—C4107.70 (11)C2—C1—H1C109.5
N1—C3—C2122.84 (10)H1A—C1—H1C109.5
C4—C3—C2129.42 (11)H1B—C1—H1C109.5
C3—C2—C8106.88 (10)C11—C10—C9107.68 (12)
C3—C2—C13111.23 (10)C11—C10—H10126.2
C8—C2—C13111.41 (9)C9—C10—H10126.2
C3—C2—C1110.70 (9)C3—C4—C5107.72 (12)
C8—C2—C1108.65 (10)C3—C4—H4126.1
C13—C2—C1107.96 (11)C5—C4—H4126.1
N2—C11—C10107.32 (11)C16—C15—C14120.39 (15)
N2—C11—C12123.89 (12)C16—C15—H15119.8
C10—C11—C12128.73 (13)C14—C15—H15119.8
C15—C14—C13120.75 (14)C16—C17—C18120.05 (15)
C15—C14—H14119.6C16—C17—H17120.0
C13—C14—H14119.6C18—C17—H17120.0
C13—C18—C17121.17 (14)C17—C16—C15119.60 (15)
C13—C18—H18119.4C17—C16—H16120.2
C17—C18—H18119.4C15—C16—H16120.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.082.9321 (16)171
N2—H2···O2ii0.862.032.8838 (15)173
C1—H1B···O1i0.962.583.3419 (18)137
Symmetry codes: (i) x+1, y, z+2; (ii) x+2, y+1, z+1.
 

Acknowledgements

This work was supported by the VFSTR Deemed to be University, Vadlamudi, Andhra Pradesh, India, under the scheme of seed grant for research faculties. SKL and EP thanks to VFSTR for providing facilities and fellowships.

Funding information

Funding for this research was provided by: Vignan's Foundation for Science, Technology and Research (grant No. VFSTRU/Reg/A4/14/2017-18/278 to Dr. Ravi K Kottalanka).

References

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