4-[Bis(2-chloro­eth­yl)amino]­benzaldehyde

Seethalakshmi, P.; Palanivel, C.

doi:10.1107/S2414314616020435

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x162043

https://doi.org/10.1107/S2414314616020435

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access

4-[Bis(2-chloroethyl)amino]benzaldehyde

P. Seethalakshmi ^a and C. Palanivel ^b ^*

^aResearch Scholar, Bharathiyar university, Coimbatore 641 046, India, and ^bPG & Research Department of Chemistry, Government Arts College, Chidambaram, India
^*Correspondence e-mail: palanivelchem@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 25 October 2016; accepted 23 December 2016; online 13 January 2017)

In the title compound, C₁₁H₁₃Cl₂NO, the chloroethyl amino groups are twisted with respect to the amino group, with N—C—C—Cl torsion angles of −177.4 (4) and 179.2 (3)°. The carbonyl group lies in the plane of the benzene ring to which it is attached; torsion angles C_ar—C_ar—C=O are 0.1 (8) and −178.2 (5)°. In the crystal, C—H⋯Cl and C—H⋯O hydrogen bonds link the molecules, forming sheets parallel to (20-1). The sheets are linked by C—H⋯π interactions, forming a three-dimensional framework.

Keywords: crystal structure; aniline; benzaldehyde; C—H⋯O and C—H⋯Cl hydrogen bonding; C—H⋯π interactions; framework.

CCDC reference: 1524296

Structure description

An heterocyclic skeleton containing an N atom is the basis of many essential pharmaceuticals and of many physiologically active natural products. Molecules containing heterocyclic substructures continue to be attractive targets for synthesis since they often exhibit diverse and important biological properties. For example, pyridine is used in the pharmaceutical industry as a raw material for various drugs, vitamins and fungicides, and as a solvent (Shinkai et al., 2000 ; Jansen et al., 2001 ; Amr et al., 2006 ) while 2-amino-3-cyanopyridines have been identified as IKK-inhibitors (Murata et al., 2003 ).

In the title compound (Fig. 1), torsion angle N1—C8—C9—Cl1 = −177.4 (4)°, indicates a (−)antiperiplanar conformation and torsion angle N1—C10—C11—Cl2 = 179.2 (3)°, indicates a (+)antiperiplanar conformation of the chloroethyl amino groups. Atom N1 deviates by −0.029 (3) Å from the benzene ring plane, while the carbonyl group (considering the plane C3/C7/O1) is inclined to the benzene ring by 1.7 (7)°.

Figure 1
The molecular structure of the title compound, showing the atom labelling and 30% probability displacement ellipsoids.

In the crystal, C—H⋯Cl and C—H⋯O hydrogen bonds link the molecules, forming sheets parallel to (20 $[\overline{1}]$ ) (Fig. 2 and Table 1). The sheets are linked by C—H⋯π interactions, forming a three-dimensional framework (Fig. 3 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cl1ⁱ	0.93	2.81	3.715 (5)	164
C8—H8A⋯O1ⁱⁱ	0.97	2.51	3.367 (6)	147
C8—H8B⋯Cgⁱⁱⁱ	0.97	2.73	3.482 (5)	134
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z+1]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z-1]$ ; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
A view normal to plane (20 $[\overline{1}]$ ) of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 1

). For clarity, H atoms not involved in hydrogen bonding have been omitted.

Figure 3
A view, almost along the a axis, of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 1

). For clarity, H atoms not involved in the various intermolecular interactions have been omitted.

Synthesis and crystallization

A flask containing dimethyl formaldehyde (1 equiv) was placed in an ice bath and (1.1 equiv) of phosphorus oxychloride was added dropwise over 30 min with constant stirring at 273 K. Then N,N-bis(2-chloroethyl)aniline and 10 ml of dimethylformamide were added dropwise. After completion of the addition, the solution was stirred at 273 K for 15 min, then the reaction mixture was allowed to warm up to room temperature over a period of 3 h. After completion of the reaction, the mixture was poured into crushed ice, and a yellowish brown precipitate of the title compound formed. It was recrystallized from ethanol solution yielding violet block-like crystals.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₃Cl₂NO
M_r	246.12
Crystal system, space group	Monoclinic, Cc
Temperature (K)	296
a, b, c (Å)	14.7725 (5), 9.3588 (3), 9.8079 (3)
β (°)	116.3080 (14)
V (Å³)	1215.52 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.51
Crystal size (mm)	0.35 × 0.22 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.842, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	4392, 2044, 1926
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.103, 1.02
No. of reflections	2044
No. of parameters	136
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.29
Absolute structure	Flack x determined using 848 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )
Absolute structure parameter	0.08 (2)
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 and SHELXTL (Sheldrick 2008 ), Mercury (Macrae et al., 2008 ), SHELXL2014 (Sheldrick, 2015 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1524296

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616020435/su4089sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616020435/su4089Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616020435/su4089Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(I) top

Crystal data top

C₁₁H₁₃Cl₂NO	F(000) = 512
M_r = 246.12	D_x = 1.345 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 14.7725 (5) Å	Cell parameters from 2835 reflections
b = 9.3588 (3) Å	θ = 2.7–26.2°
c = 9.8079 (3) Å	µ = 0.51 mm⁻¹
β = 116.3080 (14)°	T = 296 K
V = 1215.52 (7) Å³	Block, violet
Z = 4	0.35 × 0.22 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1926 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.013
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θ_max = 25.0°, θ_min = 2.7°
T_min = 0.842, T_max = 0.951	h = −17→17
4392 measured reflections	k = −11→11
2044 independent reflections	l = −11→11

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.0553P)² + 0.7925P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2044 reflections	Δρ_max = 0.25 e Å⁻³
136 parameters	Δρ_min = −0.29 e Å⁻³
2 restraints	Absolute structure: Flack x determined using 848 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (2)

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
C1	0.6673 (3)	0.3236 (4)	0.2692 (4)	0.0449 (8)
H1	0.6576	0.2252	0.2634	0.054*
C2	0.7354 (3)	0.3839 (5)	0.4026 (4)	0.0514 (9)
H2	0.7704	0.3253	0.4863	0.062*
C3	0.7538 (3)	0.5297 (5)	0.4168 (4)	0.0499 (9)
C4	0.7002 (3)	0.6147 (4)	0.2902 (4)	0.0473 (9)
H4	0.7113	0.7128	0.2968	0.057*
C5	0.6309 (3)	0.5565 (4)	0.1552 (4)	0.0432 (8)
H5	0.5961	0.6159	0.0721	0.052*
C6	0.6119 (3)	0.4089 (4)	0.1410 (4)	0.0379 (7)
C7	0.8248 (4)	0.5912 (6)	0.5606 (5)	0.0729 (13)
H7	0.8581	0.5279	0.6404	0.087*
C8	0.4888 (3)	0.4367 (4)	−0.1290 (4)	0.0476 (8)
H8A	0.4717	0.3777	−0.2184	0.057*
H8B	0.5330	0.5127	−0.1306	0.057*
C9	0.3941 (4)	0.5004 (6)	−0.1334 (5)	0.0649 (11)
H9A	0.4110	0.5636	−0.0472	0.078*
H9B	0.3507	0.4252	−0.1279	0.078*
C10	0.5119 (3)	0.2010 (4)	−0.0036 (5)	0.0549 (9)
H10A	0.4420	0.1908	−0.0782	0.066*
H10B	0.5175	0.1689	0.0939	0.066*
C11	0.5779 (4)	0.1099 (5)	−0.0490 (6)	0.0673 (12)
H11A	0.6480	0.1203	0.0248	0.081*
H11B	0.5716	0.1403	−0.1474	0.081*
Cl1	0.33067 (14)	0.5973 (2)	−0.30549 (17)	0.1116 (7)
Cl2	0.54009 (14)	−0.07305 (13)	−0.0583 (2)	0.1026 (6)
N1	0.5415 (2)	0.3503 (3)	0.0072 (3)	0.0485 (8)
O1	0.8448 (3)	0.7153 (5)	0.5867 (4)	0.1042 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0492 (19)	0.0381 (18)	0.0434 (18)	0.0023 (15)	0.0169 (15)	0.0023 (15)
C2	0.046 (2)	0.064 (3)	0.0378 (19)	0.0090 (17)	0.0129 (17)	0.0093 (16)
C3	0.0434 (19)	0.064 (2)	0.0401 (18)	−0.0042 (18)	0.0163 (15)	−0.0097 (18)
C4	0.054 (2)	0.044 (2)	0.049 (2)	−0.0157 (16)	0.0269 (18)	−0.0147 (17)
C5	0.050 (2)	0.0394 (19)	0.0380 (18)	−0.0018 (15)	0.0178 (17)	0.0007 (15)
C6	0.0400 (16)	0.0358 (17)	0.0372 (16)	−0.0025 (14)	0.0164 (14)	−0.0039 (13)
C7	0.061 (3)	0.096 (4)	0.049 (3)	−0.013 (3)	0.014 (2)	−0.020 (2)
C8	0.051 (2)	0.049 (2)	0.0374 (17)	−0.0015 (16)	0.0155 (16)	−0.0061 (15)
C9	0.057 (2)	0.079 (3)	0.057 (2)	0.011 (2)	0.0236 (19)	0.007 (2)
C10	0.048 (2)	0.048 (2)	0.059 (2)	−0.0081 (17)	0.0150 (17)	−0.0059 (18)
C11	0.065 (3)	0.053 (2)	0.078 (3)	−0.0001 (19)	0.027 (2)	−0.011 (2)
Cl1	0.1303 (13)	0.1108 (12)	0.0692 (8)	0.0702 (10)	0.0221 (8)	0.0210 (8)
Cl2	0.1109 (11)	0.0428 (6)	0.1303 (13)	0.0013 (6)	0.0317 (9)	−0.0175 (7)
N1	0.0513 (17)	0.0396 (16)	0.0401 (16)	−0.0029 (13)	0.0071 (14)	−0.0009 (13)
O1	0.108 (3)	0.109 (4)	0.072 (2)	−0.041 (3)	0.018 (2)	−0.040 (2)

Geometric parameters (Å, º) top

C1—C2	1.370 (5)	C8—N1	1.457 (5)
C1—C6	1.405 (5)	C8—C9	1.504 (6)
C1—H1	0.9300	C8—H8A	0.9700
C2—C3	1.385 (6)	C8—H8B	0.9700
C2—H2	0.9300	C9—Cl1	1.774 (5)
C3—C4	1.389 (6)	C9—H9A	0.9700
C3—C7	1.453 (6)	C9—H9B	0.9700
C4—C5	1.377 (5)	C10—N1	1.454 (5)
C4—H4	0.9300	C10—C11	1.503 (6)
C5—C6	1.405 (5)	C10—H10A	0.9700
C5—H5	0.9300	C10—H10B	0.9700
C6—N1	1.377 (4)	C11—Cl2	1.791 (5)
C7—O1	1.197 (7)	C11—H11A	0.9700
C7—H7	0.9300	C11—H11B	0.9700

C2—C1—C6	120.7 (3)	N1—C8—H8B	109.4
C2—C1—H1	119.6	C9—C8—H8B	109.4
C6—C1—H1	119.6	H8A—C8—H8B	108.0
C1—C2—C3	122.0 (3)	C8—C9—Cl1	108.9 (3)
C1—C2—H2	119.0	C8—C9—H9A	109.9
C3—C2—H2	119.0	Cl1—C9—H9A	109.9
C2—C3—C4	117.8 (3)	C8—C9—H9B	109.9
C2—C3—C7	120.8 (4)	Cl1—C9—H9B	109.9
C4—C3—C7	121.4 (4)	H9A—C9—H9B	108.3
C5—C4—C3	121.3 (4)	N1—C10—C11	110.7 (3)
C5—C4—H4	119.4	N1—C10—H10A	109.5
C3—C4—H4	119.4	C11—C10—H10A	109.5
C4—C5—C6	120.9 (3)	N1—C10—H10B	109.5
C4—C5—H5	119.5	C11—C10—H10B	109.5
C6—C5—H5	119.5	H10A—C10—H10B	108.1
N1—C6—C5	121.3 (3)	C10—C11—Cl2	109.2 (3)
N1—C6—C1	121.4 (3)	C10—C11—H11A	109.8
C5—C6—C1	117.3 (3)	Cl2—C11—H11A	109.8
O1—C7—C3	126.6 (5)	C10—C11—H11B	109.8
O1—C7—H7	116.7	Cl2—C11—H11B	109.8
C3—C7—H7	116.7	H11A—C11—H11B	108.3
N1—C8—C9	111.0 (3)	C6—N1—C10	121.9 (3)
N1—C8—H8A	109.4	C6—N1—C8	121.6 (3)
C9—C8—H8A	109.4	C10—N1—C8	116.5 (3)

C6—C1—C2—C3	−0.9 (6)	C4—C3—C7—O1	0.1 (8)
C1—C2—C3—C4	0.2 (6)	N1—C8—C9—Cl1	−177.4 (3)
C1—C2—C3—C7	178.6 (4)	N1—C10—C11—Cl2	179.2 (3)
C2—C3—C4—C5	0.2 (6)	C5—C6—N1—C10	−172.2 (3)
C7—C3—C4—C5	−178.2 (4)	C1—C6—N1—C10	7.4 (5)
C3—C4—C5—C6	0.1 (6)	C5—C6—N1—C8	4.7 (5)
C4—C5—C6—N1	178.8 (3)	C1—C6—N1—C8	−175.8 (3)
C4—C5—C6—C1	−0.8 (5)	C11—C10—N1—C6	−90.4 (4)
C2—C1—C6—N1	−178.4 (3)	C11—C10—N1—C8	92.6 (4)
C2—C1—C6—C5	1.2 (5)	C9—C8—N1—C6	−88.8 (5)
C2—C3—C7—O1	−178.2 (5)	C9—C8—N1—C10	88.2 (4)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cl1ⁱ	0.93	2.81	3.715 (5)	164
C8—H8A···O1ⁱⁱ	0.97	2.51	3.367 (6)	147
C8—H8B···Cgⁱⁱⁱ	0.97	2.73	3.482 (5)	134

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

Acknowledgements

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

References

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ISSN: 2414-3146

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

4-[Bis(2-chloro­eth­yl)amino]­benzaldehyde

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

4-[Bis(2-chloroethyl)amino]benzaldehyde