PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o382.
Published online 2010 January 16. doi:  10.1107/S160053681000125X
PMCID: PMC2979698

4-Chloro-N-[4-(diethyl­amino)benzyl­idene]aniline

Abstract

The asymmetric unit of the title compound, C17H19ClN2, contains two independent mol­ecules which differ by a 180° flip in the orientation of the 4-chloro­aniline unit with respect to the diethyl­amino­benzyl­idene unit [N=C—C—C = 10.0 (3) and −170.6 (2)°]. The dihedral angles between the two aromatic rings are 64.0 (1) and 66.5 (1)° in the two independent mol­ecules.

Related literature

For general background to Schiff base compounds in coordin­ation chemistry, see: Yu et al. (2007 [triangle]). For a related structure, see: You et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o382-scheme1.jpg

Experimental

Crystal data

  • C17H19ClN2
  • M r = 286.79
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o382-efi1.jpg
  • a = 20.153 (2) Å
  • b = 8.7434 (7) Å
  • c = 20.1446 (19) Å
  • β = 118.444 (2)°
  • V = 3121.0 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 293 K
  • 0.25 × 0.22 × 0.18 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.942, T max = 0.958
  • 22416 measured reflections
  • 5494 independent reflections
  • 4266 reflections with I > 2σ(I)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.127
  • S = 1.07
  • 5494 reflections
  • 361 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681000125X/ci2995sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681000125X/ci2995Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Schiff base compounds have been used as fine chemicals and medical substrates. They are important ligands in coordination chemistry due to their ease of preparation and can both electronically and sterically modified (Yu et al., 2007). In this paper, the crystal structure of the title compound is reported.

The asymmetric unit of the title compound consists of two independent molecules, as illustrated in Fig. 1. The two molecules differ by a 180° flip in the orientation of the 4-chloroaniline unit with respect to the diethylaminobenzylidene moiety. The N4—C28—C25—C24 and N2—C11—C8—C9 torsion angles are 10.0 (3)° and -170.6 (2)°, respectively. In the two independent molecules, the dihedral angles between the two aromatic rings are 64.0 (1)° and 66.5 (1) °, respectively. Bond lengths and angles are comparable to those observed for 4-chloro-N-[4-(dimethylamino)benzylidene]aniline (You et al., 2004).

Experimental

A mixture of 4-(diethylamino)benzaldehyde (0.01 mol) and 4-chloroaniline (0.01 mol) in ethanol (10 ml) was refluxed for 2 h. After cooling, filtration and drying, the title compound was obtained. The title compound (10 mg) was dissolved in ethanol (15 ml) and the solution was kept at room temperature for 5 d. Natural evaporation gave light-yellow single crystals of the title compound, suitable for X-ray analysis.

Refinement

H atoms were initially located in a difference map and then refined in a riding model, with C–H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(methyl C).

Figures

Fig. 1.
The two independent molecules of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C17H19ClN2F(000) = 1216
Mr = 286.79Dx = 1.221 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1362 reflections
a = 20.153 (2) Åθ = 2.4–21.4°
b = 8.7434 (7) ŵ = 0.24 mm1
c = 20.1446 (19) ÅT = 293 K
β = 118.444 (2)°Block, light yellow
V = 3121.0 (5) Å30.25 × 0.22 × 0.18 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer5494 independent reflections
Radiation source: fine-focus sealed tube4266 reflections with I > 2σ(I)
graphiteRint = 0.034
ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −23→23
Tmin = 0.942, Tmax = 0.958k = −10→10
22416 measured reflectionsl = −23→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0646P)2 + 0.3803P] where P = (Fo2 + 2Fc2)/3
5494 reflections(Δ/σ)max = 0.001
361 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.34 e Å3

Special details

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)

xyzUiso*/Ueq
Cl20.85148 (4)−0.53996 (7)0.76082 (4)0.0984 (2)
Cl10.64613 (4)1.53729 (7)0.41511 (4)0.1002 (2)
N20.59641 (9)1.07076 (17)0.18309 (8)0.0637 (4)
N30.90381 (8)0.57265 (16)0.41592 (8)0.0619 (4)
C70.58844 (9)0.83306 (19)0.07682 (9)0.0562 (4)
H7A0.57310.92990.05600.067*
C50.60395 (9)0.56348 (18)0.05880 (9)0.0530 (4)
C230.91666 (10)0.30238 (19)0.44633 (10)0.0581 (4)
H23A0.93210.28370.41030.070*
C60.58355 (9)0.71363 (19)0.03069 (9)0.0567 (4)
H6A0.56640.7319−0.02040.068*
N40.90566 (9)−0.05533 (17)0.58706 (9)0.0659 (4)
C240.91207 (10)0.18314 (19)0.48779 (9)0.0583 (4)
H24A0.92520.08550.47980.070*
C220.89856 (9)0.45309 (18)0.45679 (9)0.0522 (4)
C280.88144 (10)0.0793 (2)0.58554 (9)0.0593 (4)
H28A0.85770.09920.61450.071*
N10.59608 (9)0.44244 (16)0.01260 (9)0.0627 (4)
C110.62332 (9)0.9374 (2)0.20476 (10)0.0568 (4)
H11A0.64950.91860.25640.068*
C250.88817 (9)0.20400 (19)0.54188 (9)0.0559 (4)
C270.87455 (10)0.47377 (19)0.51171 (10)0.0585 (4)
H27A0.86190.57120.52050.070*
C80.61580 (9)0.81317 (19)0.15426 (9)0.0539 (4)
C100.63215 (10)0.5445 (2)0.13724 (10)0.0612 (4)
H10A0.64740.44800.15850.073*
C120.61080 (10)1.18249 (19)0.23937 (9)0.0564 (4)
C260.86968 (10)0.3532 (2)0.55194 (10)0.0609 (4)
H26A0.85340.37080.58740.073*
C290.89088 (10)−0.16858 (19)0.62846 (9)0.0571 (4)
C90.63739 (10)0.6647 (2)0.18232 (10)0.0609 (4)
H9A0.65600.64760.23370.073*
C150.63294 (11)1.4018 (2)0.34658 (11)0.0645 (5)
C340.95037 (10)−0.25322 (19)0.68199 (11)0.0628 (5)
H34A0.9991−0.23390.69030.075*
C320.86616 (10)−0.3967 (2)0.70916 (10)0.0625 (4)
C170.68257 (10)1.2175 (2)0.29554 (11)0.0669 (5)
H17A0.72381.16630.29720.080*
C160.69412 (11)1.3272 (2)0.34924 (12)0.0704 (5)
H16A0.74271.35040.38670.084*
C140.56102 (11)1.3704 (2)0.29018 (12)0.0730 (5)
H14A0.51991.42200.28850.088*
C330.93858 (10)−0.3652 (2)0.72303 (11)0.0660 (5)
H33A0.9792−0.41940.75980.079*
C20.61471 (11)0.2868 (2)0.04203 (12)0.0709 (5)
H2B0.58670.21560.00120.085*
H2C0.59820.27250.07960.085*
C130.55034 (10)1.2624 (2)0.23647 (11)0.0674 (5)
H13A0.50191.24300.19770.081*
C300.81858 (10)−0.2037 (2)0.61520 (11)0.0696 (5)
H30A0.7778−0.14960.57870.084*
C40.57312 (12)0.4657 (2)−0.06713 (11)0.0720 (5)
H4B0.53170.5382−0.08780.086*
H4C0.55460.3696−0.09360.086*
C190.88835 (11)0.72995 (19)0.42921 (12)0.0699 (5)
H19A0.91640.79890.41410.084*
H19B0.90680.74380.48290.084*
C210.92008 (12)0.5464 (2)0.35369 (12)0.0730 (5)
H21A0.96270.47720.37050.088*
H21B0.93470.64270.34050.088*
C310.80608 (11)−0.3174 (2)0.65510 (12)0.0714 (5)
H31A0.7572−0.34020.64550.086*
C200.85481 (14)0.4803 (3)0.28411 (12)0.0883 (7)
H20A0.86930.46690.24550.132*
H20B0.81260.54880.26640.132*
H20C0.84100.38320.29620.132*
C30.63511 (14)0.5236 (3)−0.08195 (13)0.0882 (7)
H3A0.61600.5365−0.13530.132*
H3B0.67580.4512−0.06300.132*
H3C0.65310.6201−0.05700.132*
C180.80592 (12)0.7741 (2)0.38778 (15)0.0933 (7)
H18A0.80030.87820.39950.140*
H18B0.77760.70810.40310.140*
H18C0.78740.76420.33440.140*
C10.69744 (13)0.2482 (3)0.07706 (15)0.0991 (8)
H1A0.70530.14490.09540.149*
H1B0.72570.31670.11820.149*
H1C0.71410.25840.03980.149*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl20.1067 (5)0.0772 (4)0.1268 (5)−0.0034 (3)0.0682 (4)0.0204 (3)
Cl10.1127 (5)0.0755 (4)0.1135 (5)−0.0022 (3)0.0549 (4)−0.0307 (3)
N20.0695 (9)0.0627 (9)0.0590 (9)0.0001 (7)0.0307 (8)0.0018 (7)
N30.0668 (9)0.0526 (8)0.0632 (9)−0.0015 (6)0.0283 (8)−0.0032 (7)
C70.0584 (10)0.0542 (9)0.0571 (10)0.0021 (7)0.0285 (8)0.0076 (7)
C50.0499 (9)0.0542 (9)0.0561 (9)−0.0034 (7)0.0263 (8)0.0027 (7)
C230.0627 (10)0.0593 (10)0.0541 (9)0.0065 (8)0.0292 (8)−0.0027 (8)
C60.0590 (10)0.0612 (10)0.0489 (9)−0.0001 (7)0.0250 (8)0.0058 (8)
N40.0775 (10)0.0637 (9)0.0628 (9)0.0058 (7)0.0386 (8)−0.0002 (7)
C240.0643 (10)0.0539 (9)0.0556 (10)0.0077 (7)0.0279 (8)−0.0038 (7)
C220.0468 (8)0.0536 (9)0.0462 (9)−0.0011 (7)0.0140 (7)−0.0058 (7)
C280.0617 (10)0.0649 (11)0.0503 (9)0.0030 (8)0.0258 (8)−0.0044 (8)
N10.0700 (9)0.0542 (8)0.0627 (9)−0.0029 (6)0.0306 (8)−0.0007 (7)
C110.0531 (9)0.0658 (11)0.0538 (10)−0.0010 (8)0.0275 (8)0.0034 (8)
C250.0561 (9)0.0593 (10)0.0469 (9)0.0017 (7)0.0202 (8)−0.0042 (7)
C270.0618 (10)0.0533 (9)0.0547 (10)0.0029 (7)0.0231 (8)−0.0117 (8)
C80.0506 (9)0.0603 (10)0.0535 (9)−0.0019 (7)0.0269 (8)0.0015 (7)
C100.0674 (11)0.0572 (10)0.0583 (10)0.0029 (8)0.0295 (9)0.0111 (8)
C120.0627 (10)0.0536 (9)0.0563 (10)−0.0012 (7)0.0311 (8)0.0073 (7)
C260.0655 (10)0.0649 (11)0.0511 (9)0.0028 (8)0.0268 (8)−0.0111 (8)
C290.0644 (10)0.0549 (9)0.0543 (9)0.0026 (8)0.0302 (8)−0.0080 (7)
C90.0656 (10)0.0670 (11)0.0509 (9)0.0011 (8)0.0285 (8)0.0089 (8)
C150.0738 (12)0.0501 (9)0.0743 (12)−0.0026 (8)0.0390 (10)−0.0017 (8)
C340.0560 (10)0.0571 (10)0.0753 (12)0.0021 (8)0.0313 (9)−0.0027 (9)
C320.0703 (11)0.0512 (9)0.0708 (11)−0.0025 (8)0.0376 (10)−0.0052 (8)
C170.0571 (10)0.0704 (11)0.0779 (12)0.0002 (8)0.0358 (10)−0.0042 (10)
C160.0578 (10)0.0689 (12)0.0783 (13)−0.0053 (8)0.0275 (10)−0.0101 (10)
C140.0632 (11)0.0575 (11)0.0990 (15)0.0086 (8)0.0391 (11)0.0011 (10)
C330.0603 (10)0.0568 (10)0.0727 (12)0.0047 (8)0.0250 (9)0.0030 (9)
C20.0719 (12)0.0535 (10)0.0827 (13)−0.0025 (8)0.0332 (10)0.0006 (9)
C130.0558 (10)0.0578 (10)0.0772 (12)0.0040 (8)0.0225 (9)0.0035 (9)
C300.0580 (11)0.0717 (12)0.0693 (12)0.0081 (9)0.0223 (9)0.0018 (9)
C40.0848 (13)0.0649 (11)0.0613 (11)−0.0090 (9)0.0307 (10)−0.0107 (9)
C190.0666 (11)0.0515 (10)0.0813 (13)−0.0012 (8)0.0267 (10)−0.0028 (9)
C210.0829 (13)0.0669 (12)0.0791 (13)−0.0034 (9)0.0465 (11)0.0061 (10)
C310.0574 (10)0.0690 (12)0.0881 (14)−0.0030 (9)0.0349 (10)−0.0062 (10)
C200.1086 (18)0.0907 (15)0.0606 (12)0.0092 (12)0.0362 (12)0.0058 (11)
C30.1165 (19)0.0832 (14)0.0860 (16)0.0070 (13)0.0652 (15)−0.0008 (12)
C180.0720 (13)0.0778 (14)0.1146 (18)0.0135 (10)0.0319 (13)0.0052 (13)
C10.0780 (15)0.0875 (16)0.1166 (19)0.0177 (12)0.0342 (14)0.0075 (14)

Geometric parameters (Å, °)

Cl2—C321.7415 (19)C15—C161.373 (3)
Cl1—C151.7407 (19)C15—C141.378 (3)
N2—C111.273 (2)C34—C331.373 (2)
N2—C121.418 (2)C34—H34A0.93
N3—C221.366 (2)C32—C311.370 (3)
N3—C211.457 (2)C32—C331.377 (2)
N3—C191.463 (2)C17—C161.380 (3)
C7—C61.370 (2)C17—H17A0.93
C7—C81.396 (2)C16—H16A0.93
C7—H7A0.93C14—C131.373 (3)
C5—N11.368 (2)C14—H14A0.93
C5—C61.411 (2)C33—H33A0.93
C5—C101.411 (2)C2—C11.507 (3)
C23—C241.366 (2)C2—H2B0.97
C23—C221.410 (2)C2—H2C0.97
C23—H23A0.93C13—H13A0.93
C6—H6A0.93C30—C311.375 (3)
N4—C281.269 (2)C30—H30A0.93
N4—C291.415 (2)C4—C31.504 (3)
C24—C251.397 (2)C4—H4B0.97
C24—H24A0.93C4—H4C0.97
C22—C271.414 (2)C19—C181.511 (3)
C28—C251.447 (2)C19—H19A0.97
C28—H28A0.93C19—H19B0.97
N1—C41.459 (2)C21—C201.507 (3)
N1—C21.460 (2)C21—H21A0.97
C11—C81.446 (2)C21—H21B0.97
C11—H11A0.93C31—H31A0.93
C25—C261.398 (2)C20—H20A0.96
C27—C261.361 (2)C20—H20B0.96
C27—H27A0.93C20—H20C0.96
C8—C91.400 (2)C3—H3A0.96
C10—C91.360 (2)C3—H3B0.96
C10—H10A0.93C3—H3C0.96
C12—C171.381 (3)C18—H18A0.96
C12—C131.381 (2)C18—H18B0.96
C26—H26A0.93C18—H18C0.96
C29—C341.384 (2)C1—H1A0.96
C29—C301.385 (3)C1—H1B0.96
C9—H9A0.93C1—H1C0.96
C11—N2—C12117.75 (15)C12—C17—H17A119.5
C22—N3—C21120.79 (14)C15—C16—C17119.11 (18)
C22—N3—C19121.66 (16)C15—C16—H16A120.4
C21—N3—C19117.42 (16)C17—C16—H16A120.4
C6—C7—C8121.71 (15)C13—C14—C15119.69 (17)
C6—C7—H7A119.1C13—C14—H14A120.2
C8—C7—H7A119.1C15—C14—H14A120.2
N1—C5—C6121.97 (15)C34—C33—C32119.40 (17)
N1—C5—C10121.69 (15)C34—C33—H33A120.3
C6—C5—C10116.33 (15)C32—C33—H33A120.3
C24—C23—C22121.62 (16)N1—C2—C1114.34 (17)
C24—C23—H23A119.2N1—C2—H2B108.7
C22—C23—H23A119.2C1—C2—H2B108.7
C7—C6—C5121.59 (15)N1—C2—H2C108.7
C7—C6—H6A119.2C1—C2—H2C108.7
C5—C6—H6A119.2H2B—C2—H2C107.6
C28—N4—C29118.48 (15)C14—C13—C12120.69 (17)
C23—C24—C25121.73 (15)C14—C13—H13A119.7
C23—C24—H24A119.1C12—C13—H13A119.7
C25—C24—H24A119.1C31—C30—C29121.10 (17)
N3—C22—C23121.71 (16)C31—C30—H30A119.4
N3—C22—C27121.83 (15)C29—C30—H30A119.5
C23—C22—C27116.47 (16)N1—C4—C3114.07 (18)
N4—C28—C25124.55 (17)N1—C4—H4B108.7
N4—C28—H28A117.7C3—C4—H4B108.7
C25—C28—H28A117.7N1—C4—H4C108.7
C5—N1—C4120.95 (14)C3—C4—H4C108.7
C5—N1—C2121.38 (15)H4B—C4—H4C107.6
C4—N1—C2117.57 (15)N3—C19—C18114.41 (16)
N2—C11—C8124.21 (16)N3—C19—H19A108.7
N2—C11—H11A117.9C18—C19—H19A108.7
C8—C11—H11A117.9N3—C19—H19B108.7
C24—C25—C26116.71 (16)C18—C19—H19B108.7
C24—C25—C28122.85 (15)H19A—C19—H19B107.6
C26—C25—C28120.43 (16)N3—C21—C20113.96 (18)
C26—C27—C22121.02 (15)N3—C21—H21A108.8
C26—C27—H27A119.5C20—C21—H21A108.8
C22—C27—H27A119.5N3—C21—H21B108.8
C7—C8—C9116.62 (16)C20—C21—H21B108.8
C7—C8—C11123.10 (15)H21A—C21—H21B107.7
C9—C8—C11120.27 (15)C32—C31—C30119.47 (18)
C9—C10—C5121.25 (16)C32—C31—H31A120.3
C9—C10—H10A119.4C30—C31—H31A120.3
C5—C10—H10A119.4C21—C20—H20A109.5
C17—C12—C13118.74 (17)C21—C20—H20B109.5
C17—C12—N2122.91 (16)H20A—C20—H20B109.5
C13—C12—N2118.32 (16)C21—C20—H20C109.5
C27—C26—C25122.45 (17)H20A—C20—H20C109.5
C27—C26—H26A118.8H20B—C20—H20C109.5
C25—C26—H26A118.8C4—C3—H3A109.5
C34—C29—C30118.21 (17)C4—C3—H3B109.5
C34—C29—N4119.08 (16)H3A—C3—H3B109.5
C30—C29—N4122.63 (16)C4—C3—H3C109.5
C10—C9—C8122.46 (16)H3A—C3—H3C109.5
C10—C9—H9A118.8H3B—C3—H3C109.5
C8—C9—H9A118.8C19—C18—H18A109.5
C16—C15—C14120.64 (18)C19—C18—H18B109.5
C16—C15—Cl1119.81 (15)H18A—C18—H18B109.5
C14—C15—Cl1119.54 (15)C19—C18—H18C109.5
C33—C34—C29121.09 (17)H18A—C18—H18C109.5
C33—C34—H34A119.5H18B—C18—H18C109.5
C29—C34—H34A119.5C2—C1—H1A109.5
C31—C32—C33120.69 (18)C2—C1—H1B109.5
C31—C32—Cl2120.11 (15)H1A—C1—H1B109.5
C33—C32—Cl2119.20 (14)C2—C1—H1C109.5
C16—C17—C12121.07 (17)H1A—C1—H1C109.5
C16—C17—H17A119.5H1B—C1—H1C109.5

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2995).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • You, X.-L., Lu, C.-R., Zhang, Y. & Zhang, D.-C. (2004). Acta Cryst. C60, o693–o695. [PubMed]
  • Yu, Y. Y., Zhao, G. L. & Wen, Y. H. (2007). Chin. J. Struct. Chem.26, 1359–1362.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography