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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

N,N′-Bis[(E)-(2-chloro-8-methyl­quinolin-3-yl)methyl­­idene]ethane-1,2-di­amine

aChemistry Group, BITS, Pilani - K. K. Birla Goa Campus, Goa 403 726, India, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: edward.tiekink@gmail.com

(Received 4 November 2010; accepted 5 November 2010; online 10 November 2010)

The complete mol­ecule of the title compound, C24H20Cl2N4, is generated by a crystallographic inversion centre. A kink in the mol­ecule is evident [C—N—C—C torsion angle = −147.0 (3)°] owing to the twist in the central ethyl­ene bridge. Further, there is a small twist between the imine [N=C = 1.267 (3) Å] and quinoline residues [N—C—C—C = −12.4 (4)°]. In the crystal, a combination of ππ [pyridine–benzene centroid–centroid distance = 3.5670 (14) Å] and C—H⋯N contacts leads to supra­molecular chains propagating in [010].

Related literature

For background to the photophysical properties of Schiff base complexes derivativatized with quinoline residues, see: Liu et al. (2010[Liu, Z.-C., Wang, B.-D., Yang, Z.-Y., Li, T.-R. & Li, Y. (2010). Inorg. Chem. Commun. 13, 606-608.]).

[Scheme 1]

Experimental

Crystal data
  • C24H20Cl2N4

  • Mr = 435.34

  • Monoclinic, P 21 /c

  • a = 18.363 (2) Å

  • b = 3.9494 (5) Å

  • c = 14.1726 (19) Å

  • β = 99.056 (2)°

  • V = 1015.0 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.34 mm−1

  • T = 100 K

  • 0.30 × 0.15 × 0.05 mm

Data collection
  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.756, Tmax = 0.862

  • 8859 measured reflections

  • 2324 independent reflections

  • 1863 reflections with I > 2σ(I)

  • Rint = 0.055

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.140

  • S = 1.05

  • 2324 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 0.72 e Å−3

  • Δρmin = −0.46 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1a⋯N1i 0.99 2.59 3.299 (3) 128
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Interest in the title compound arises as a result of the recent report of the photophysical properties of Schiff base complexes derivativatized with quinoline residues (Liu et al., 2010). The title molecule, Fig. 1, is disposed about a centre of inversion so that the pendent quinoline groups are co-planar. Owing to the twist in the central ethylene bridge, there is a kink in the molecule as manifested in the value of the C2—N1—C1—C1i torsion angle of -147.0 (3) °; i: 1 - x, 1 - y, 1 - z. There is a smaller twist between the imine [N1C2 = 1.267 (3) Å] and quinoline residues as seen in the N1—C2—C3—C5 torsion angle of -12.4 (4) °.

The crystal packing is dominated by weak ππ and C—H···N contacts that lead to the formation of a supramolecular chain along the b axis, Fig. 2. The ππ contacts occur between translationally related quinoline rings [ring centroid(N2,C3–C6,C11)···ring centroid(C6–C11)ii = 3.5670 (14) Å with an angle of inclination = 0.41 (11) ° for ii: x, -1 + y, z] and the C—H···N contacts occur between the methylene-H and imine-N1 atoms, Table 1. Chains pack as shown in Fig. 3.

Related literature top

For background to the photophysical properties of Schiff base complexes derivativatized with quinoline residues, see: Liu et al. (2010).

Experimental top

A mixture of 2-chloro-3-formyl-8-methylquinoline (0.2 g, 1 mM) and ethylenediamine (0.03 ml, 0.5 mM) was stirred in dichloromethane for 3 h at room temperature. The solvent from the reaction mixture was removed under reduced pressure. The resulting solid was dried and purified by column chromatography using a 1:1 mixture of ethyl acetate and hexane. Recrystallization was by slow evaporation of a dichloromethane solution which yielded yellow prisms of (I). Yield: 65%. M.pt. 475–477 K.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2–1.5Uequiv(C).

Structure description top

Interest in the title compound arises as a result of the recent report of the photophysical properties of Schiff base complexes derivativatized with quinoline residues (Liu et al., 2010). The title molecule, Fig. 1, is disposed about a centre of inversion so that the pendent quinoline groups are co-planar. Owing to the twist in the central ethylene bridge, there is a kink in the molecule as manifested in the value of the C2—N1—C1—C1i torsion angle of -147.0 (3) °; i: 1 - x, 1 - y, 1 - z. There is a smaller twist between the imine [N1C2 = 1.267 (3) Å] and quinoline residues as seen in the N1—C2—C3—C5 torsion angle of -12.4 (4) °.

The crystal packing is dominated by weak ππ and C—H···N contacts that lead to the formation of a supramolecular chain along the b axis, Fig. 2. The ππ contacts occur between translationally related quinoline rings [ring centroid(N2,C3–C6,C11)···ring centroid(C6–C11)ii = 3.5670 (14) Å with an angle of inclination = 0.41 (11) ° for ii: x, -1 + y, z] and the C—H···N contacts occur between the methylene-H and imine-N1 atoms, Table 1. Chains pack as shown in Fig. 3.

For background to the photophysical properties of Schiff base complexes derivativatized with quinoline residues, see: Liu et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure showing displacement ellipsoids at the 50% probability level. Symmetry operation i: 1 - x, 1 - y, 1 - z.
[Figure 2] Fig. 2. A view of the supramolecular chain along the b axis mediated by ππ and C—H···N contacts are shown as purple and orange dashed lines, respectively.
[Figure 3] Fig. 3. Stacking of chains in the crystal structure. The ππ and C—H···N contacts are shown as purple and orange dashed lines, respectively.
N,N'-Bis[(E)-(2-chloro-8-methylquinolin-3- yl)methylidene]ethane-1,2-diamine top
Crystal data top
C24H20Cl2N4F(000) = 452
Mr = 435.34Dx = 1.424 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1737 reflections
a = 18.363 (2) Åθ = 2.9–28.1°
b = 3.9494 (5) ŵ = 0.34 mm1
c = 14.1726 (19) ÅT = 100 K
β = 99.056 (2)°Prism, yellow
V = 1015.0 (2) Å30.30 × 0.15 × 0.05 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer
2324 independent reflections
Radiation source: fine-focus sealed tube1863 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2321
Tmin = 0.756, Tmax = 0.862k = 55
8859 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.073P)2 + 0.7018P]
where P = (Fo2 + 2Fc2)/3
2324 reflections(Δ/σ)max = 0.001
137 parametersΔρmax = 0.72 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C24H20Cl2N4V = 1015.0 (2) Å3
Mr = 435.34Z = 2
Monoclinic, P21/cMo Kα radiation
a = 18.363 (2) ŵ = 0.34 mm1
b = 3.9494 (5) ÅT = 100 K
c = 14.1726 (19) Å0.30 × 0.15 × 0.05 mm
β = 99.056 (2)°
Data collection top
Bruker SMART APEX
diffractometer
2324 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1863 reflections with I > 2σ(I)
Tmin = 0.756, Tmax = 0.862Rint = 0.055
8859 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.140H-atom parameters constrained
S = 1.05Δρmax = 0.72 e Å3
2324 reflectionsΔρmin = 0.46 e Å3
137 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
xyzUiso*/Ueq
Cl10.66489 (3)0.91685 (16)0.86511 (4)0.0207 (2)
N10.57606 (11)0.7565 (5)0.56683 (14)0.0198 (4)
N20.77325 (10)1.1953 (5)0.79768 (12)0.0146 (4)
C10.50497 (13)0.5852 (7)0.54853 (16)0.0193 (5)
H1A0.46490.75160.55050.023*
H1B0.50220.41370.59880.023*
C20.60887 (13)0.7696 (6)0.65240 (16)0.0182 (5)
H20.58780.66180.70160.022*
C30.67969 (12)0.9510 (6)0.67619 (16)0.0163 (5)
C40.71175 (12)1.0337 (6)0.77157 (15)0.0156 (5)
C50.71871 (12)1.0545 (6)0.60569 (15)0.0159 (5)
H50.69991.00760.54070.019*
C60.78589 (12)1.2285 (6)0.62878 (14)0.0144 (5)
C70.82776 (13)1.3369 (6)0.55873 (15)0.0161 (5)
H70.81081.29340.49300.019*
C80.89247 (13)1.5042 (6)0.58613 (15)0.0176 (5)
H80.92091.57410.53910.021*
C90.91795 (12)1.5753 (6)0.68373 (15)0.0163 (5)
H90.96301.69500.70080.020*
C100.87912 (12)1.4754 (6)0.75412 (15)0.0142 (5)
C110.81194 (12)1.2958 (6)0.72724 (15)0.0141 (5)
C120.90516 (13)1.5567 (6)0.85775 (15)0.0181 (5)
H12A0.95081.68910.86370.027*
H12B0.91441.34570.89410.027*
H12C0.86721.68800.88290.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0217 (3)0.0290 (4)0.0120 (3)0.0042 (2)0.0040 (2)0.0005 (2)
N10.0181 (10)0.0211 (11)0.0184 (10)0.0028 (8)0.0021 (7)0.0020 (8)
N20.0164 (10)0.0186 (10)0.0089 (8)0.0010 (8)0.0022 (7)0.0005 (7)
C10.0185 (12)0.0208 (12)0.0176 (12)0.0030 (10)0.0003 (9)0.0001 (9)
C20.0184 (11)0.0191 (12)0.0168 (11)0.0001 (9)0.0019 (8)0.0006 (9)
C30.0178 (11)0.0160 (12)0.0144 (10)0.0022 (9)0.0001 (8)0.0012 (9)
C40.0187 (12)0.0171 (12)0.0114 (10)0.0016 (9)0.0031 (8)0.0019 (8)
C50.0201 (12)0.0172 (11)0.0095 (9)0.0020 (9)0.0009 (8)0.0008 (8)
C60.0182 (11)0.0150 (11)0.0093 (10)0.0039 (9)0.0005 (8)0.0002 (8)
C70.0200 (12)0.0209 (12)0.0071 (9)0.0046 (9)0.0009 (8)0.0011 (8)
C80.0203 (12)0.0221 (12)0.0109 (10)0.0038 (9)0.0041 (8)0.0018 (8)
C90.0172 (11)0.0171 (12)0.0141 (10)0.0004 (9)0.0006 (8)0.0000 (9)
C100.0190 (11)0.0145 (11)0.0086 (9)0.0031 (9)0.0009 (8)0.0006 (8)
C110.0159 (11)0.0163 (11)0.0097 (10)0.0029 (9)0.0012 (8)0.0007 (8)
C120.0194 (11)0.0252 (13)0.0088 (10)0.0030 (10)0.0005 (8)0.0018 (9)
Geometric parameters (Å, º) top
Cl1—C41.752 (2)C6—C71.414 (3)
N1—C21.267 (3)C6—C111.427 (3)
N1—C11.457 (3)C7—C81.362 (3)
N2—C41.299 (3)C7—H70.9500
N2—C111.372 (3)C8—C91.417 (3)
C1—C1i1.517 (4)C8—H80.9500
C1—H1A0.9900C9—C101.372 (3)
C1—H1B0.9900C9—H90.9500
C2—C31.477 (3)C10—C111.422 (3)
C2—H20.9500C10—C121.506 (3)
C3—C51.380 (3)C12—H12A0.9800
C3—C41.425 (3)C12—H12B0.9800
C5—C61.405 (3)C12—H12C0.9800
C5—H50.9500
C2—N1—C1117.8 (2)C7—C6—C11119.6 (2)
C4—N2—C11117.47 (18)C8—C7—C6119.5 (2)
N1—C1—C1i110.1 (2)C8—C7—H7120.2
N1—C1—H1A109.6C6—C7—H7120.2
C1i—C1—H1A109.6C7—C8—C9120.9 (2)
N1—C1—H1B109.6C7—C8—H8119.5
C1i—C1—H1B109.6C9—C8—H8119.5
H1A—C1—H1B108.1C10—C9—C8121.6 (2)
N1—C2—C3120.5 (2)C10—C9—H9119.2
N1—C2—H2119.8C8—C9—H9119.2
C3—C2—H2119.8C9—C10—C11118.47 (19)
C5—C3—C4115.8 (2)C9—C10—C12121.8 (2)
C5—C3—C2121.2 (2)C11—C10—C12119.77 (19)
C4—C3—C2123.1 (2)N2—C11—C10118.43 (19)
N2—C4—C3126.4 (2)N2—C11—C6121.7 (2)
N2—C4—Cl1114.97 (16)C10—C11—C6119.9 (2)
C3—C4—Cl1118.60 (18)C10—C12—H12A109.5
C3—C5—C6120.9 (2)C10—C12—H12B109.5
C3—C5—H5119.6H12A—C12—H12B109.5
C6—C5—H5119.6C10—C12—H12C109.5
C5—C6—C7122.61 (19)H12A—C12—H12C109.5
C5—C6—C11117.8 (2)H12B—C12—H12C109.5
C2—N1—C1—C1i147.0 (3)C11—C6—C7—C80.1 (3)
C1—N1—C2—C3177.6 (2)C6—C7—C8—C90.9 (3)
N1—C2—C3—C512.4 (4)C7—C8—C9—C100.8 (4)
N1—C2—C3—C4167.0 (2)C8—C9—C10—C110.1 (3)
C11—N2—C4—C30.4 (4)C8—C9—C10—C12178.7 (2)
C11—N2—C4—Cl1179.41 (16)C4—N2—C11—C10179.5 (2)
C5—C3—C4—N20.1 (4)C4—N2—C11—C60.4 (3)
C2—C3—C4—N2179.3 (2)C9—C10—C11—N2179.8 (2)
C5—C3—C4—Cl1179.03 (17)C12—C10—C11—N21.3 (3)
C2—C3—C4—Cl10.3 (3)C9—C10—C11—C61.0 (3)
C4—C3—C5—C60.3 (3)C12—C10—C11—C6177.9 (2)
C2—C3—C5—C6179.7 (2)C5—C6—C11—N20.1 (3)
C3—C5—C6—C7179.6 (2)C7—C6—C11—N2180.0 (2)
C3—C5—C6—C110.4 (3)C5—C6—C11—C10179.1 (2)
C5—C6—C7—C8180.0 (2)C7—C6—C11—C100.9 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1a···N1ii0.992.593.299 (3)128
Symmetry code: (ii) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC24H20Cl2N4
Mr435.34
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)18.363 (2), 3.9494 (5), 14.1726 (19)
β (°) 99.056 (2)
V3)1015.0 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.34
Crystal size (mm)0.30 × 0.15 × 0.05
Data collection
DiffractometerBruker SMART APEX
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.756, 0.862
No. of measured, independent and
observed [I > 2σ(I)] reflections
8859, 2324, 1863
Rint0.055
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.140, 1.05
No. of reflections2324
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.72, 0.46

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1a···N1i0.992.593.299 (3)128
Symmetry code: (i) x+1, y+2, z+1.
 

Footnotes

Additional correspondence author, e-mail: juliebhavana@gmail.com.

Acknowledgements

PB acknowledges the Department of Science and Technology (DST), India, for a research grant (SR/FTP/CS-57/2007). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

References

First citationBrandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationLiu, Z.-C., Wang, B.-D., Yang, Z.-Y., Li, T.-R. & Li, Y. (2010). Inorg. Chem. Commun. 13, 606–608.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds