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The title compound, C16H14Cl2N2O2, was synthesized by the reaction of 1-(5-chloro-2-hydroxy­phen­yl)ethanone with hydrazine hydrate. The mol­ecule sits on a crystallographic center of symmetry at the mid-point of the central N—N bond and both N atoms are acceptors in an intra­molecular hydrogen bond. In the crystal structure, the planar mol­ecules are arranged in a sheet-like motif with one C—H...O bond linking mol­ecules within the sheets and a second C—H...O inter­action between neighboring sheets. There is also a close Cl...Cl inter­molecular approach of 3.54 (1) Å within the sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042870/fl2158sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042870/fl2158Isup2.hkl
Contains datablock I

CCDC reference: 663707

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.036
  • wR factor = 0.081
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H8C .. O1 .. 2.63 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Recently, a number of azine compounds containing both a diimine linkage and N—N bonding have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen et al., 1999;). As an extension of work on the structural characterization of azine derivatives,the title compound, (I),was synthesized and its crystal structure is reported here.

In the title compound, there is a crystallographic center of symmetry at the midpoint of the N—N bond (Fig. 1.). The molecule displays an (E, E) conformation with respect to the symmetry related C=N double bonds. This configuration agrees with those commonly found in similar compounds (Glaser et al., 1995; Hunig et al., 2000). In the crystal the planar molecules are arranged in a sheet like motif with one C—H···O bond linking molecules within the sheets and a second C—H···O interaction between neighboring sheets. There is also a close Cl—Cl intermolecular approach of 3.54 (1) Å within the sheets. (Table 1 and Fig. 2).

Related literature top

For further details of the chemistry, see: Kundu et al. (2005); Kesslen et al. (1999). For similar structures, see: Glaser et al. (1995); Hunig et al. (2000).

Experimental top

An ethanol solution (50 ml) of hydrazine (0.02 mol) and 1-(5-chloro-2-hydroxyphenyl)ethanone(0.04 mol) was refluxed and stirred for 3 h. The mixture was cooled and the resulting solid product, (I), was collected by filtration. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone.

Refinement top

All H atoms were positioned geometrically and treated as riding on their parent atoms,with CH(methyl) = 0.96 Å, C—H(aromatic) = 0.93 Å,O—H = 0.82 Å and with Uiso(H) = 1.5Ueq(Cmethyl,O) anddn3057 1.2Ueq(Caromatic).

Structure description top

Recently, a number of azine compounds containing both a diimine linkage and N—N bonding have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen et al., 1999;). As an extension of work on the structural characterization of azine derivatives,the title compound, (I),was synthesized and its crystal structure is reported here.

In the title compound, there is a crystallographic center of symmetry at the midpoint of the N—N bond (Fig. 1.). The molecule displays an (E, E) conformation with respect to the symmetry related C=N double bonds. This configuration agrees with those commonly found in similar compounds (Glaser et al., 1995; Hunig et al., 2000). In the crystal the planar molecules are arranged in a sheet like motif with one C—H···O bond linking molecules within the sheets and a second C—H···O interaction between neighboring sheets. There is also a close Cl—Cl intermolecular approach of 3.54 (1) Å within the sheets. (Table 1 and Fig. 2).

For further details of the chemistry, see: Kundu et al. (2005); Kesslen et al. (1999). For similar structures, see: Glaser et al. (1995); Hunig et al. (2000).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level·Dashed lines show intramolecular hydrogen bonds.
[Figure 2] Fig. 2. Packing diagram of (I), showing intermolecular C—H···O hydrogen bonds.(dashed lines).
(E,E)-4,4'-Dichloro-2,2'-(1,1'-azinodiethylene)diphenol top
Crystal data top
C16H14Cl2N2O2Z = 1
Mr = 337.19F(000) = 174
Triclinic, P1Dx = 1.504 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 3.9105 (2) ÅCell parameters from 1047 reflections
b = 6.2985 (4) Åθ = 2.7–23.0°
c = 15.1479 (9) ŵ = 0.44 mm1
α = 89.520 (2)°T = 273 K
β = 88.792 (1)°Plate, colorless
γ = 86.164 (2)°0.25 × 0.18 × 0.12 mm
V = 372.17 (4) Å3
Data collection top
Bruker APEX II CCD area-detector
diffractometer
1315 independent reflections
Radiation source: fine-focus sealed tube1010 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
phi and ω scansθmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 44
Tmin = 0.897, Tmax = 0.949k = 77
4295 measured reflectionsl = 1718
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0223P)2 + 0.229P]
where P = (Fo2 + 2Fc2)/3
1315 reflections(Δ/σ)max = 0.003
102 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H14Cl2N2O2γ = 86.164 (2)°
Mr = 337.19V = 372.17 (4) Å3
Triclinic, P1Z = 1
a = 3.9105 (2) ÅMo Kα radiation
b = 6.2985 (4) ŵ = 0.44 mm1
c = 15.1479 (9) ÅT = 273 K
α = 89.520 (2)°0.25 × 0.18 × 0.12 mm
β = 88.792 (1)°
Data collection top
Bruker APEX II CCD area-detector
diffractometer
1315 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1010 reflections with I > 2σ(I)
Tmin = 0.897, Tmax = 0.949Rint = 0.025
4295 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.00Δρmax = 0.21 e Å3
1315 reflectionsΔρmin = 0.18 e Å3
102 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
Cl10.07776 (19)0.29780 (11)0.07597 (4)0.0668 (3)
O10.6578 (4)0.3076 (2)0.33622 (10)0.0531 (4)
H10.65530.25650.38590.080*
N10.5071 (4)0.0325 (3)0.45587 (10)0.0392 (4)
C10.5138 (5)0.1637 (3)0.27931 (13)0.0408 (5)
C20.3675 (5)0.0368 (3)0.30718 (13)0.0357 (5)
C30.2340 (5)0.1759 (3)0.24204 (13)0.0409 (5)
H30.13870.30950.25810.049*
C40.2415 (6)0.1185 (4)0.15515 (14)0.0458 (6)
C50.3773 (6)0.0796 (4)0.12886 (14)0.0525 (6)
H50.37710.11820.06970.063*
C60.5124 (6)0.2187 (4)0.19101 (14)0.0509 (6)
H60.60460.35210.17360.061*
C70.3551 (5)0.0988 (3)0.40064 (12)0.0347 (5)
C80.1725 (6)0.3052 (3)0.42815 (14)0.0450 (6)
H8A0.06900.28880.48560.068*
H8B0.00200.34550.38640.068*
H8C0.33350.41360.43000.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0850 (5)0.0718 (5)0.0411 (3)0.0148 (4)0.0136 (3)0.0121 (3)
O10.0727 (12)0.0382 (9)0.0462 (9)0.0140 (8)0.0056 (8)0.0026 (7)
N10.0479 (11)0.0350 (10)0.0339 (8)0.0045 (8)0.0053 (8)0.0026 (7)
C10.0436 (13)0.0364 (12)0.0418 (12)0.0005 (10)0.0021 (10)0.0051 (9)
C20.0367 (12)0.0343 (11)0.0360 (11)0.0007 (9)0.0035 (9)0.0029 (9)
C30.0423 (13)0.0381 (12)0.0415 (12)0.0042 (10)0.0050 (9)0.0025 (9)
C40.0487 (14)0.0502 (14)0.0380 (12)0.0026 (11)0.0061 (10)0.0068 (10)
C50.0630 (16)0.0585 (16)0.0356 (12)0.0004 (12)0.0030 (11)0.0049 (11)
C60.0621 (16)0.0440 (13)0.0453 (13)0.0068 (12)0.0010 (11)0.0057 (10)
C70.0344 (12)0.0312 (11)0.0383 (11)0.0005 (9)0.0034 (9)0.0038 (9)
C80.0510 (14)0.0393 (12)0.0432 (12)0.0099 (10)0.0053 (10)0.0017 (10)
Geometric parameters (Å, º) top
Cl1—C41.743 (2)C3—H30.9300
O1—C11.350 (2)C4—C51.382 (3)
O1—H10.8200C5—C61.370 (3)
N1—C71.297 (2)C5—H50.9300
N1—N1i1.400 (3)C6—H60.9300
C1—C61.385 (3)C7—C81.499 (3)
C1—C21.415 (3)C8—H8A0.9600
C2—C31.400 (3)C8—H8B0.9600
C2—C71.471 (3)C8—H8C0.9600
C3—C41.367 (3)
C1—O1—H1109.5C6—C5—H5120.4
C7—N1—N1i115.28 (19)C4—C5—H5120.4
O1—C1—C6117.51 (19)C5—C6—C1121.1 (2)
O1—C1—C2122.30 (18)C5—C6—H6119.5
C6—C1—C2120.19 (19)C1—C6—H6119.5
C3—C2—C1117.37 (18)N1—C7—C2116.84 (17)
C3—C2—C7120.79 (18)N1—C7—C8123.10 (18)
C1—C2—C7121.85 (17)C2—C7—C8120.06 (17)
C4—C3—C2121.11 (19)C7—C8—H8A109.5
C4—C3—H3119.4C7—C8—H8B109.5
C2—C3—H3119.4H8A—C8—H8B109.5
C3—C4—C5121.08 (19)C7—C8—H8C109.5
C3—C4—Cl1119.64 (17)H8A—C8—H8C109.5
C5—C4—Cl1119.27 (17)H8B—C8—H8C109.5
C6—C5—C4119.2 (2)
O1—C1—C2—C3178.2 (2)C4—C5—C6—C10.2 (4)
C6—C1—C2—C31.9 (3)O1—C1—C6—C5178.6 (2)
O1—C1—C2—C71.7 (3)C2—C1—C6—C51.4 (4)
C6—C1—C2—C7178.2 (2)N1i—N1—C7—C2179.4 (2)
C1—C2—C3—C40.8 (3)N1i—N1—C7—C80.7 (3)
C7—C2—C3—C4179.3 (2)C3—C2—C7—N1174.95 (19)
C2—C3—C4—C50.8 (4)C1—C2—C7—N14.9 (3)
C2—C3—C4—Cl1179.15 (17)C3—C2—C7—C85.1 (3)
C3—C4—C5—C61.3 (4)C1—C2—C7—C8175.0 (2)
Cl1—C4—C5—C6178.66 (19)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.832.551 (2)146
C8—H8B···O1ii0.962.603.368 (2)137
C8—H8C···O1iii0.962.633.455 (3)145
Symmetry codes: (ii) x1, y+1, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC16H14Cl2N2O2
Mr337.19
Crystal system, space groupTriclinic, P1
Temperature (K)273
a, b, c (Å)3.9105 (2), 6.2985 (4), 15.1479 (9)
α, β, γ (°)89.520 (2), 88.792 (1), 86.164 (2)
V3)372.17 (4)
Z1
Radiation typeMo Kα
µ (mm1)0.44
Crystal size (mm)0.25 × 0.18 × 0.12
Data collection
DiffractometerBruker APEX II CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.897, 0.949
No. of measured, independent and
observed [I > 2σ(I)] reflections
4295, 1315, 1010
Rint0.025
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.081, 1.00
No. of reflections1315
No. of parameters102
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.18

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.832.551 (2)146.3
C8—H8B···O1i0.962.603.368 (2)137.4
C8—H8C···O1ii0.962.633.455 (3)144.9
Symmetry codes: (i) x1, y+1, z; (ii) x, y+1, z.
 

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