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

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Ethyl (Z)-2-chloro-2-[2-(4-meth­­oxy­phenyl)hydrazin-1-yl­­idene]acetate

aChemistry Department and the, Center of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, bCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and dDepartment of Chemistry, Government College University, 38000, Faisalabad, Pakistan
*Correspondence e-mail: aasiri2@kau.edu.sa, hafizshafique@hotmail.com

(Received 18 October 2012; accepted 25 October 2012; online 3 November 2012)

The mol­ecule of the title compound, C11H13ClN2O3, is planar (r.m.s. deviation = 0.0587 Å for non-H atoms) and adopts a Z conformation about the C=N double bond. In the crystal, mol­ecules are linked via an N—H⋯O hydrogen bond, forming zigzag chains propagating along [010]. These chains are consolidated by C—H⋯O hydrogen bonds.

Related literature

For closely related structures, see: Asiri et al. (2011a[Asiri, A. M., Al-Youbi, A. O., Zayed, M. E. M. & Ng, S. W. (2011a). Acta Cryst. E67, o1961.],b[Asiri, A. M., Al-Youbi, A. O., Zayed, M. E. M. & Ng, S. W. (2011b). Acta Cryst. E67, o1964.]). For graph-set notation, see: Bernstein et al. (1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]).

[Scheme 1]

Experimental

Crystal data
  • C11H13ClN2O3

  • Mr = 256.68

  • Monoclinic, P 21

  • a = 4.7480 (2) Å

  • b = 9.9256 (4) Å

  • c = 13.3084 (4) Å

  • β = 91.468 (3)°

  • V = 626.98 (4) Å3

  • Z = 2

  • Cu Kα radiation

  • μ = 2.71 mm−1

  • T = 296 K

  • 0.23 × 0.11 × 0.06 mm

Data collection
  • Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]) Tmin = 0.860, Tmax = 1.000

  • 3153 measured reflections

  • 1824 independent reflections

  • 1685 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.109

  • S = 1.07

  • 1824 reflections

  • 159 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.20 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 466 Friedel pairs

  • Flack parameter: 0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1N⋯O2i 0.97 (4) 2.11 (4) 3.053 (3) 164 (3)
C6—H6⋯O2i 0.93 2.59 3.368 (3) 141
Symmetry code: (i) [-x+2, y-{\script{1\over 2}}, -z+1].

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]).

Supporting information


Comment top

The present structure analysis is a continuation of our interest in related compounds already reported by our group, that is, 1-Chloro-1-[(4-methoxyphenyl)hydrazinylidene]propan-2-one (Asiri et al., 2011a) and 1-Chloro-1-[(4-methylphenyl)hydrazinylidene]propan-2-one (Asiri et al., 2011b).

In the title compound, Fig. 1, the methoxy aromatic ring (C1—C6) is oriented at a dihedral angle of 3.05 (2) ° with respect to the mean plane of the ester moiety (N1/N2/C7-Cl1; planar to within 0.0 \%A). The molecule adopts a Z conformation around the C7N2 double bond.

In the crystal, N-H···O and C-H···O hydrogen bonds connect the molecules to form zigzag chains along the b axis, enclosing six membered R12(6) ring motifs (Bernstein et al., 1995) - see Table 1 and Fig. 2.

Related literature top

For closely related structures, see: Asiri et al. (2011a,b). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The molecule was synthesised according to the literature procedure (Asiri et al., 2011a) and recrystallized from ethanol giving yellow needle-like crystals.

Refinement top

The NH H atom was located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(N). The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.93, 0.96 and 0.97 Å for CH(aromatic), CH3, and CH2 H atoms, respectively, with Uiso(H) = k × Ueq(parent C-atom), where k = 1.5 for CH3 H atoms and = 1.2 for other H atoms.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial view along the a axis of the crystal packing of the title compound. The N-H···O and C-H···O hydrogen bonds are shown as dashed lines - see Table 1 for details.
Ethyl (Z)-2-chloro-2-[2-(4-methoxyphenyl)hydrazin-1-ylidene]acetate top
Crystal data top
C11H13ClN2O3F(000) = 268
Mr = 256.68Dx = 1.360 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ybCell parameters from 2064 reflections
a = 4.7480 (2) Åθ = 4.5–75.6°
b = 9.9256 (4) ŵ = 2.71 mm1
c = 13.3084 (4) ÅT = 296 K
β = 91.468 (3)°Needle, yellow
V = 626.98 (4) Å30.23 × 0.11 × 0.06 mm
Z = 2
Data collection top
Agilent SuperNova (Dual, Cu at zero, Atlas) CCD
diffractometer
1824 independent reflections
Radiation source: SuperNova (Cu) X-ray Source1685 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.018
ω scansθmax = 75.8°, θmin = 5.6°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
h = 55
Tmin = 0.860, Tmax = 1.000k = 129
3153 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.0575P)2 + 0.0434P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1824 reflectionsΔρmax = 0.16 e Å3
159 parametersΔρmin = 0.20 e Å3
1 restraintAbsolute structure: Flack (1983), 466 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (2)
Crystal data top
C11H13ClN2O3V = 626.98 (4) Å3
Mr = 256.68Z = 2
Monoclinic, P21Cu Kα radiation
a = 4.7480 (2) ŵ = 2.71 mm1
b = 9.9256 (4) ÅT = 296 K
c = 13.3084 (4) Å0.23 × 0.11 × 0.06 mm
β = 91.468 (3)°
Data collection top
Agilent SuperNova (Dual, Cu at zero, Atlas) CCD
diffractometer
1824 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
1685 reflections with I > 2σ(I)
Tmin = 0.860, Tmax = 1.000Rint = 0.018
3153 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109Δρmax = 0.16 e Å3
S = 1.07Δρmin = 0.20 e Å3
1824 reflectionsAbsolute structure: Flack (1983), 466 Friedel pairs
159 parametersAbsolute structure parameter: 0.01 (2)
1 restraint
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.

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 > 2sigma(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
Cl11.03853 (17)0.46169 (11)0.45757 (5)0.0873 (3)
O10.1393 (5)0.2136 (3)0.96956 (16)0.0895 (7)
O21.4090 (4)0.6817 (2)0.52714 (16)0.0785 (6)
O31.2764 (5)0.6800 (2)0.68691 (15)0.0735 (6)
N10.7239 (5)0.3882 (3)0.63734 (15)0.0607 (5)
N20.9085 (4)0.4860 (2)0.64964 (14)0.0566 (5)
C10.5738 (5)0.3420 (3)0.72120 (18)0.0542 (5)
C20.6135 (6)0.4022 (3)0.81488 (19)0.0616 (6)
H20.74050.47280.82350.074*
C30.4620 (6)0.3557 (3)0.89470 (19)0.0675 (7)
H30.48690.39600.95740.081*
C40.2750 (6)0.2509 (3)0.8836 (2)0.0656 (7)
C50.2349 (6)0.1908 (3)0.7907 (2)0.0666 (7)
H50.10830.11990.78240.080*
C60.3865 (6)0.2378 (3)0.7097 (2)0.0637 (7)
H60.36040.19790.64690.076*
C71.0590 (6)0.5288 (3)0.57810 (18)0.0584 (6)
C81.2652 (6)0.6375 (3)0.59250 (18)0.0605 (6)
C91.4822 (8)0.7834 (4)0.7110 (2)0.0894 (10)
H9A1.66810.75330.69230.107*
H9B1.43760.86470.67340.107*
C101.4804 (13)0.8107 (5)0.8152 (3)0.1310 (18)
H10A1.29760.84300.83290.197*
H10B1.61950.87800.83150.197*
H10C1.52280.72970.85200.197*
C110.0364 (8)0.1011 (4)0.9655 (3)0.0903 (11)
H11A0.18460.11570.91620.135*
H11B0.11660.08691.03010.135*
H11C0.07090.02330.94730.135*
H1N0.712 (7)0.330 (5)0.579 (3)0.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1022 (6)0.1004 (6)0.0602 (4)0.0065 (5)0.0182 (3)0.0155 (4)
O10.0895 (14)0.112 (2)0.0679 (12)0.0237 (15)0.0142 (10)0.0084 (13)
O20.0887 (14)0.0810 (15)0.0666 (11)0.0067 (12)0.0164 (9)0.0181 (10)
O30.0847 (13)0.0763 (13)0.0597 (10)0.0197 (11)0.0073 (9)0.0004 (9)
N10.0667 (12)0.0627 (13)0.0528 (11)0.0039 (11)0.0032 (9)0.0050 (9)
N20.0595 (11)0.0586 (14)0.0518 (9)0.0038 (10)0.0020 (8)0.0034 (9)
C10.0548 (13)0.0542 (13)0.0537 (12)0.0056 (11)0.0003 (9)0.0011 (10)
C20.0642 (14)0.0615 (15)0.0591 (14)0.0054 (13)0.0007 (10)0.0026 (11)
C30.0701 (16)0.0773 (19)0.0551 (13)0.0018 (15)0.0021 (11)0.0052 (13)
C40.0605 (14)0.0745 (18)0.0619 (15)0.0016 (14)0.0031 (11)0.0094 (13)
C50.0634 (15)0.0655 (17)0.0708 (15)0.0077 (14)0.0009 (11)0.0018 (13)
C60.0685 (16)0.0640 (16)0.0583 (14)0.0046 (14)0.0035 (11)0.0065 (12)
C70.0618 (14)0.0601 (15)0.0533 (12)0.0101 (12)0.0053 (10)0.0017 (10)
C80.0687 (15)0.0577 (15)0.0554 (12)0.0069 (13)0.0042 (10)0.0079 (11)
C90.106 (3)0.083 (2)0.0788 (19)0.026 (2)0.0017 (17)0.0007 (17)
C100.191 (5)0.103 (3)0.098 (3)0.042 (4)0.014 (3)0.020 (3)
C110.081 (2)0.088 (3)0.103 (2)0.006 (2)0.0184 (18)0.020 (2)
Geometric parameters (Å, º) top
Cl1—C71.737 (3)C3—H30.9300
O1—C41.378 (3)C4—C51.381 (4)
O1—C111.394 (5)C5—C61.393 (4)
O2—C81.202 (3)C5—H50.9300
O3—C81.325 (3)C6—H60.9300
O3—C91.447 (4)C7—C81.466 (4)
N1—N21.315 (3)C9—C101.414 (5)
N1—C11.416 (3)C9—H9A0.9700
N1—H1N0.97 (4)C9—H9B0.9700
N2—C71.277 (3)C10—H10A0.9600
C1—C61.370 (4)C10—H10B0.9600
C1—C21.391 (3)C10—H10C0.9600
C2—C31.378 (4)C11—H11A0.9600
C2—H20.9300C11—H11B0.9600
C3—C41.373 (4)C11—H11C0.9600
C4—O1—C11118.3 (3)N2—C7—C8122.1 (2)
C8—O3—C9116.5 (2)N2—C7—Cl1122.8 (2)
N2—N1—C1119.3 (2)C8—C7—Cl1115.10 (19)
N2—N1—H1N124 (2)O2—C8—O3124.1 (3)
C1—N1—H1N115 (2)O2—C8—C7124.3 (3)
C7—N2—N1122.4 (2)O3—C8—C7111.6 (2)
C6—C1—C2119.8 (2)C10—C9—O3109.4 (3)
C6—C1—N1119.7 (2)C10—C9—H9A109.8
C2—C1—N1120.5 (3)O3—C9—H9A109.8
C3—C2—C1119.1 (3)C10—C9—H9B109.8
C3—C2—H2120.5O3—C9—H9B109.8
C1—C2—H2120.5H9A—C9—H9B108.2
C4—C3—C2121.3 (2)C9—C10—H10A109.5
C4—C3—H3119.4C9—C10—H10B109.5
C2—C3—H3119.4H10A—C10—H10B109.5
C3—C4—O1115.4 (3)C9—C10—H10C109.5
C3—C4—C5119.9 (2)H10A—C10—H10C109.5
O1—C4—C5124.8 (3)H10B—C10—H10C109.5
C4—C5—C6119.1 (3)O1—C11—H11A109.5
C4—C5—H5120.5O1—C11—H11B109.5
C6—C5—H5120.5H11A—C11—H11B109.5
C1—C6—C5120.9 (2)O1—C11—H11C109.5
C1—C6—H6119.6H11A—C11—H11C109.5
C5—C6—H6119.6H11B—C11—H11C109.5
C1—N1—N2—C7177.1 (2)C2—C1—C6—C50.1 (4)
N2—N1—C1—C6178.3 (2)N1—C1—C6—C5179.6 (3)
N2—N1—C1—C22.2 (4)C4—C5—C6—C10.1 (4)
C6—C1—C2—C30.2 (4)N1—N2—C7—C8179.7 (2)
N1—C1—C2—C3179.4 (3)N1—N2—C7—Cl10.6 (4)
C1—C2—C3—C40.5 (5)C9—O3—C8—O21.8 (4)
C2—C3—C4—O1179.4 (3)C9—O3—C8—C7177.3 (3)
C2—C3—C4—C50.4 (5)N2—C7—C8—O2179.3 (3)
C11—O1—C4—C3175.0 (3)Cl1—C7—C8—O21.5 (4)
C11—O1—C4—C54.9 (5)N2—C7—C8—O31.6 (4)
C3—C4—C5—C60.1 (5)Cl1—C7—C8—O3177.6 (2)
O1—C4—C5—C6179.7 (3)C8—O3—C9—C10176.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.97 (4)2.11 (4)3.053 (3)164 (3)
C6—H6···O2i0.932.593.368 (3)141
Symmetry code: (i) x+2, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaC11H13ClN2O3
Mr256.68
Crystal system, space groupMonoclinic, P21
Temperature (K)296
a, b, c (Å)4.7480 (2), 9.9256 (4), 13.3084 (4)
β (°) 91.468 (3)
V3)626.98 (4)
Z2
Radiation typeCu Kα
µ (mm1)2.71
Crystal size (mm)0.23 × 0.11 × 0.06
Data collection
DiffractometerAgilent SuperNova (Dual, Cu at zero, Atlas) CCD
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.860, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
3153, 1824, 1685
Rint0.018
(sin θ/λ)max1)0.629
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.109, 1.07
No. of reflections1824
No. of parameters159
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.20
Absolute structureFlack (1983), 466 Friedel pairs
Absolute structure parameter0.01 (2)

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.97 (4)2.11 (4)3.053 (3)164 (3)
C6—H6···O2i0.932.593.368 (3)141
Symmetry code: (i) x+2, y1/2, z+1.
 

Acknowledgements

We would like to thank the Deanship of Scientific Research at King Abdulaziz University for the support of this research via a Research Group Track Grant (No. 3-102/428).

References

First citationAgilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.
First citationAsiri, A. M., Al-Youbi, A. O., Zayed, M. E. M. & Ng, S. W. (2011a). Acta Cryst. E67, o1961.  Web of Science CSD CrossRef IUCr Journals
First citationAsiri, A. M., Al-Youbi, A. O., Zayed, M. E. M. & Ng, S. W. (2011b). Acta Cryst. E67, o1964.  Web of Science CSD CrossRef IUCr Journals
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.  CrossRef CAS Web of Science
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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