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

Loke, S.K.; Pagadala, E.; Kottalanka, R.K.

doi:10.1107/S2414314619016602

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 12| December 2019| x191660

https://doi.org/10.1107/S2414314619016602

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

Shiva Krishna Loke,^a Eswar Pagadala ^a and Ravi K. Kottalanka ^a ^*

^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.

Keywords: crystal structure; pyrrole; hydrogen bonding; Hirshfeld surface analysis.

CCDC reference: 1912418

Structure description

Dipyrromethane-dialdehydes are intermediates for the preparation of various macrocyclic (Love et al., 2003 ) and acyclic diiminodipyrromethane Schiff bases (e.g.: Deliomeroglu et al., 2016 ). 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).

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 the molecules into [11 $[\overline{1}]$ ] chains (Fig. 2). 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 ) (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	D⋯A	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
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); Muwal et al. 2018 ) and colourless cubes were recrystallized from a toluene–hexane solvent mixture at −4°C.

Figure 3
Reaction scheme.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂O₂
M_r	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)
V (Å³)	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 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.901, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13274, 4208, 3307
R_int	0.022
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (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 ), SHELXL2018/3 (Sheldrick, 2015b ), , ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1912418

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016602/hb4326sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2414314619016602/hb4326Isup3.cdx

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619016602/hb4326Isup4.hkl

Hirshfeld surface and fingerprint plots. DOI: https://doi.org/10.1107/S2414314619016602/hb4326sup5.docx

checkCIF report

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

C₁₈H₁₆N₂O₂	Z = 2
M_r = 292.33	F(000) = 308
Triclinic, P1	D_x = 1.292 Mg m⁻³
a = 7.0679 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6856 (4) Å	Cell parameters from 5094 reflections
c = 12.1510 (5) Å	θ = 3.7–29.9°
α = 101.560 (3)°	µ = 0.09 mm⁻¹
β = 93.302 (3)°	T = 293 K
γ = 111.270 (4)°	Cube, colourless
V = 751.66 (5) Å³	0.18 × 0.15 × 0.13 mm

Data collection top

XtaLAB Pro: Kappa dual offset/far diffractometer	R_int = 0.022
Radiation source: fine-focus sealed X-ray tube	θ_max = 31.1°, θ_min = 3.1°
ω scans	h = −9→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015)	k = −13→13
T_min = 0.901, T_max = 1.000	l = −17→17
13274 measured reflections	Standard reflections: see text; every none reflections
4208 independent reflections	intensity decay: none
3307 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0767P)² + 0.1364P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4208 reflections	Δρ_max = 0.32 e Å⁻³
200 parameters	Δρ_min = −0.19 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.69498 (16)	0.13760 (11)	0.87005 (8)	0.0348 (2)
H1	0.592279	0.131280	0.906260	0.042*
N2	0.94852 (16)	0.52913 (11)	0.69220 (8)	0.0350 (2)
H2	0.897693	0.470214	0.625766	0.042*
O2	1.18939 (19)	0.67425 (13)	0.53044 (9)	0.0593 (3)
O1	0.63340 (19)	−0.10500 (15)	0.98826 (12)	0.0649 (3)
C8	0.87280 (19)	0.50458 (13)	0.78942 (10)	0.0349 (3)
C13	0.53349 (18)	0.30398 (14)	0.68621 (10)	0.0346 (3)
C6	0.8011 (2)	0.04229 (15)	0.86453 (11)	0.0399 (3)
C3	0.77809 (19)	0.24329 (14)	0.80925 (10)	0.0347 (3)
C2	0.69195 (19)	0.36169 (13)	0.79432 (10)	0.0338 (2)
C11	1.1197 (2)	0.66317 (14)	0.71604 (11)	0.0398 (3)
C14	0.4611 (2)	0.40434 (16)	0.64815 (12)	0.0445 (3)
H14	0.512212	0.506479	0.686836	0.053*
C18	0.4538 (2)	0.15255 (16)	0.62642 (12)	0.0452 (3)
H18	0.500715	0.083660	0.650140	0.054*
C7	0.7592 (2)	−0.07648 (17)	0.92390 (13)	0.0471 (3)
H7	0.835458	−0.137403	0.912050	0.057*
C12	1.2317 (2)	0.72554 (15)	0.63178 (13)	0.0464 (3)
H12	1.348509	0.814225	0.657358	0.056*
C9	0.9961 (2)	0.62497 (16)	0.87798 (11)	0.0470 (3)
H9	0.978635	0.637712	0.954118	0.056*
C5	0.9541 (2)	0.09002 (19)	0.79891 (13)	0.0505 (3)
H5	1.049116	0.046264	0.780729	0.061*
C1	0.5846 (3)	0.40046 (18)	0.89673 (12)	0.0478 (3)
H1A	0.677390	0.429200	0.965753	0.072*
H1B	0.465129	0.312760	0.898067	0.072*
H1C	0.544689	0.483480	0.889915	0.072*
C10	1.1508 (2)	0.72322 (16)	0.83195 (12)	0.0500 (3)
H10	1.255985	0.812989	0.871959	0.060*
C4	0.9407 (2)	0.21604 (18)	0.76469 (13)	0.0495 (3)
H4	1.025661	0.271584	0.720018	0.059*
C15	0.3139 (2)	0.3539 (2)	0.55333 (14)	0.0543 (4)
H15	0.267142	0.422408	0.528760	0.065*
C17	0.3053 (2)	0.10196 (19)	0.53181 (15)	0.0574 (4)
H17	0.252517	−0.000256	0.493242	0.069*
C16	0.2361 (2)	0.2028 (2)	0.49507 (15)	0.0587 (4)
H16	0.137392	0.169268	0.431307	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0370 (5)	0.0360 (5)	0.0340 (5)	0.0132 (4)	0.0090 (4)	0.0142 (4)
N2	0.0403 (5)	0.0302 (5)	0.0283 (5)	0.0065 (4)	0.0053 (4)	0.0066 (4)
O2	0.0674 (7)	0.0533 (6)	0.0445 (6)	0.0066 (5)	0.0180 (5)	0.0121 (5)
O1	0.0602 (7)	0.0681 (7)	0.0862 (9)	0.0277 (6)	0.0297 (6)	0.0500 (7)
C8	0.0428 (6)	0.0322 (5)	0.0298 (5)	0.0134 (5)	0.0067 (4)	0.0090 (4)
C13	0.0334 (5)	0.0372 (6)	0.0361 (6)	0.0122 (5)	0.0132 (4)	0.0154 (5)
C6	0.0428 (6)	0.0395 (6)	0.0410 (6)	0.0172 (5)	0.0057 (5)	0.0147 (5)
C3	0.0404 (6)	0.0355 (6)	0.0300 (5)	0.0135 (5)	0.0095 (4)	0.0126 (4)
C2	0.0419 (6)	0.0336 (5)	0.0304 (5)	0.0157 (5)	0.0130 (4)	0.0129 (4)
C11	0.0420 (6)	0.0316 (6)	0.0398 (6)	0.0069 (5)	0.0042 (5)	0.0090 (5)
C14	0.0451 (7)	0.0405 (7)	0.0518 (8)	0.0176 (6)	0.0084 (6)	0.0168 (6)
C18	0.0481 (7)	0.0379 (6)	0.0485 (7)	0.0141 (6)	0.0066 (6)	0.0124 (5)
C7	0.0457 (7)	0.0445 (7)	0.0589 (8)	0.0201 (6)	0.0090 (6)	0.0237 (6)
C12	0.0457 (7)	0.0344 (6)	0.0493 (8)	0.0031 (5)	0.0105 (6)	0.0106 (5)
C9	0.0616 (8)	0.0420 (7)	0.0301 (6)	0.0133 (6)	0.0037 (6)	0.0057 (5)
C5	0.0530 (8)	0.0583 (9)	0.0560 (8)	0.0320 (7)	0.0202 (6)	0.0246 (7)
C1	0.0636 (9)	0.0518 (8)	0.0415 (7)	0.0306 (7)	0.0270 (6)	0.0191 (6)
C10	0.0560 (8)	0.0386 (7)	0.0404 (7)	0.0050 (6)	−0.0015 (6)	0.0036 (5)
C4	0.0522 (8)	0.0569 (8)	0.0554 (8)	0.0276 (7)	0.0270 (6)	0.0303 (7)
C15	0.0474 (8)	0.0620 (9)	0.0625 (9)	0.0251 (7)	0.0064 (7)	0.0270 (8)
C17	0.0521 (8)	0.0481 (8)	0.0589 (9)	0.0100 (7)	0.0009 (7)	0.0036 (7)
C16	0.0433 (8)	0.0718 (11)	0.0548 (9)	0.0165 (7)	−0.0016 (6)	0.0143 (8)

Geometric parameters (Å, º) top

N1—C3	1.3622 (14)	C14—C15	1.384 (2)
N1—C6	1.3793 (16)	C14—H14	0.9300
N1—H1	0.8600	C18—C17	1.388 (2)
N2—C8	1.3533 (15)	C18—H18	0.9300
N2—C11	1.3795 (16)	C7—H7	0.9300
N2—H2	0.8600	C12—H12	0.9300
O2—C12	1.2071 (18)	C9—C10	1.394 (2)
O1—C7	1.2113 (18)	C9—H9	0.9300
C8—C9	1.3888 (18)	C5—C4	1.398 (2)
C8—C2	1.5202 (16)	C5—H5	0.9300
C13—C18	1.3867 (19)	C1—H1A	0.9600
C13—C14	1.3907 (18)	C1—H1B	0.9600
C13—C2	1.5410 (17)	C1—H1C	0.9600
C6—C5	1.3798 (19)	C10—H10	0.9300
C6—C7	1.4288 (18)	C4—H4	0.9300
C3—C4	1.3850 (18)	C15—C16	1.380 (3)
C3—C2	1.5152 (17)	C15—H15	0.9300
C2—C1	1.5470 (16)	C17—C16	1.374 (3)
C11—C10	1.3833 (19)	C17—H17	0.9300
C11—C12	1.4261 (18)	C16—H16	0.9300

C3—N1—C6	109.44 (10)	O1—C7—C6	125.90 (14)
C3—N1—H1	125.3	O1—C7—H7	117.0
C6—N1—H1	125.3	C6—C7—H7	117.0
C8—N2—C11	109.55 (10)	O2—C12—C11	126.24 (13)
C8—N2—H2	125.2	O2—C12—H12	116.9
C11—N2—H2	125.2	C11—C12—H12	116.9
N2—C8—C9	107.91 (11)	C8—C9—C10	107.53 (12)
N2—C8—C2	123.11 (10)	C8—C9—H9	126.2
C9—C8—C2	128.86 (11)	C10—C9—H9	126.2
C18—C13—C14	118.02 (12)	C6—C5—C4	107.65 (12)
C18—C13—C2	122.18 (11)	C6—C5—H5	126.2
C14—C13—C2	119.76 (11)	C4—C5—H5	126.2
N1—C6—C5	107.49 (11)	C2—C1—H1A	109.5
N1—C6—C7	123.62 (12)	C2—C1—H1B	109.5
C5—C6—C7	128.80 (13)	H1A—C1—H1B	109.5
N1—C3—C4	107.70 (11)	C2—C1—H1C	109.5
N1—C3—C2	122.84 (10)	H1A—C1—H1C	109.5
C4—C3—C2	129.42 (11)	H1B—C1—H1C	109.5
C3—C2—C8	106.88 (10)	C11—C10—C9	107.68 (12)
C3—C2—C13	111.23 (10)	C11—C10—H10	126.2
C8—C2—C13	111.41 (9)	C9—C10—H10	126.2
C3—C2—C1	110.70 (9)	C3—C4—C5	107.72 (12)
C8—C2—C1	108.65 (10)	C3—C4—H4	126.1
C13—C2—C1	107.96 (11)	C5—C4—H4	126.1
N2—C11—C10	107.32 (11)	C16—C15—C14	120.39 (15)
N2—C11—C12	123.89 (12)	C16—C15—H15	119.8
C10—C11—C12	128.73 (13)	C14—C15—H15	119.8
C15—C14—C13	120.75 (14)	C16—C17—C18	120.05 (15)
C15—C14—H14	119.6	C16—C17—H17	120.0
C13—C14—H14	119.6	C18—C17—H17	120.0
C13—C18—C17	121.17 (14)	C17—C16—C15	119.60 (15)
C13—C18—H18	119.4	C17—C16—H16	120.2
C17—C18—H18	119.4	C15—C16—H16	120.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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.

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).

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