Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042870/fl2158sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042870/fl2158Isup2.hkl |
CCDC reference: 663707
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (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
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).
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.
All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(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).
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).
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).
C16H14Cl2N2O2 | Z = 1 |
Mr = 337.19 | F(000) = 174 |
Triclinic, P1 | Dx = 1.504 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9105 (2) Å | Cell parameters from 1047 reflections |
b = 6.2985 (4) Å | θ = 2.7–23.0° |
c = 15.1479 (9) Å | µ = 0.44 mm−1 |
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 |
Bruker APEX II CCD area-detector diffractometer | 1315 independent reflections |
Radiation source: fine-focus sealed tube | 1010 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
phi and ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −4→4 |
Tmin = 0.897, Tmax = 0.949 | k = −7→7 |
4295 measured reflections | l = −17→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-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 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C16H14Cl2N2O2 | γ = 86.164 (2)° |
Mr = 337.19 | V = 372.17 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 3.9105 (2) Å | Mo Kα radiation |
b = 6.2985 (4) Å | µ = 0.44 mm−1 |
c = 15.1479 (9) Å | T = 273 K |
α = 89.520 (2)° | 0.25 × 0.18 × 0.12 mm |
β = 88.792 (1)° |
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 = 0.949 | Rint = 0.025 |
4295 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.21 e Å−3 |
1315 reflections | Δρmin = −0.18 e Å−3 |
102 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.07776 (19) | 0.29780 (11) | 0.07597 (4) | 0.0668 (3) | |
O1 | 0.6578 (4) | −0.3076 (2) | 0.33622 (10) | 0.0531 (4) | |
H1 | 0.6553 | −0.2565 | 0.3859 | 0.080* | |
N1 | 0.5071 (4) | −0.0325 (3) | 0.45587 (10) | 0.0392 (4) | |
C1 | 0.5138 (5) | −0.1637 (3) | 0.27931 (13) | 0.0408 (5) | |
C2 | 0.3675 (5) | 0.0368 (3) | 0.30718 (13) | 0.0357 (5) | |
C3 | 0.2340 (5) | 0.1759 (3) | 0.24204 (13) | 0.0409 (5) | |
H3 | 0.1387 | 0.3095 | 0.2581 | 0.049* | |
C4 | 0.2415 (6) | 0.1185 (4) | 0.15515 (14) | 0.0458 (6) | |
C5 | 0.3773 (6) | −0.0796 (4) | 0.12886 (14) | 0.0525 (6) | |
H5 | 0.3771 | −0.1182 | 0.0697 | 0.063* | |
C6 | 0.5124 (6) | −0.2187 (4) | 0.19101 (14) | 0.0509 (6) | |
H6 | 0.6046 | −0.3521 | 0.1736 | 0.061* | |
C7 | 0.3551 (5) | 0.0988 (3) | 0.40064 (12) | 0.0347 (5) | |
C8 | 0.1725 (6) | 0.3052 (3) | 0.42815 (14) | 0.0450 (6) | |
H8A | 0.0690 | 0.2888 | 0.4856 | 0.068* | |
H8B | −0.0020 | 0.3455 | 0.3864 | 0.068* | |
H8C | 0.3335 | 0.4136 | 0.4300 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0850 (5) | 0.0718 (5) | 0.0411 (3) | 0.0148 (4) | −0.0136 (3) | 0.0121 (3) |
O1 | 0.0727 (12) | 0.0382 (9) | 0.0462 (9) | 0.0140 (8) | −0.0056 (8) | 0.0026 (7) |
N1 | 0.0479 (11) | 0.0350 (10) | 0.0339 (8) | 0.0045 (8) | −0.0053 (8) | 0.0026 (7) |
C1 | 0.0436 (13) | 0.0364 (12) | 0.0418 (12) | 0.0005 (10) | −0.0021 (10) | 0.0051 (9) |
C2 | 0.0367 (12) | 0.0343 (11) | 0.0360 (11) | −0.0007 (9) | −0.0035 (9) | 0.0029 (9) |
C3 | 0.0423 (13) | 0.0381 (12) | 0.0415 (12) | 0.0042 (10) | −0.0050 (9) | 0.0025 (9) |
C4 | 0.0487 (14) | 0.0502 (14) | 0.0380 (12) | 0.0026 (11) | −0.0061 (10) | 0.0068 (10) |
C5 | 0.0630 (16) | 0.0585 (16) | 0.0356 (12) | 0.0004 (12) | −0.0030 (11) | −0.0049 (11) |
C6 | 0.0621 (16) | 0.0440 (13) | 0.0453 (13) | 0.0068 (12) | −0.0010 (11) | −0.0057 (10) |
C7 | 0.0344 (12) | 0.0312 (11) | 0.0383 (11) | −0.0005 (9) | −0.0034 (9) | 0.0038 (9) |
C8 | 0.0510 (14) | 0.0393 (12) | 0.0432 (12) | 0.0099 (10) | −0.0053 (10) | 0.0017 (10) |
Cl1—C4 | 1.743 (2) | C3—H3 | 0.9300 |
O1—C1 | 1.350 (2) | C4—C5 | 1.382 (3) |
O1—H1 | 0.8200 | C5—C6 | 1.370 (3) |
N1—C7 | 1.297 (2) | C5—H5 | 0.9300 |
N1—N1i | 1.400 (3) | C6—H6 | 0.9300 |
C1—C6 | 1.385 (3) | C7—C8 | 1.499 (3) |
C1—C2 | 1.415 (3) | C8—H8A | 0.9600 |
C2—C3 | 1.400 (3) | C8—H8B | 0.9600 |
C2—C7 | 1.471 (3) | C8—H8C | 0.9600 |
C3—C4 | 1.367 (3) | ||
C1—O1—H1 | 109.5 | C6—C5—H5 | 120.4 |
C7—N1—N1i | 115.28 (19) | C4—C5—H5 | 120.4 |
O1—C1—C6 | 117.51 (19) | C5—C6—C1 | 121.1 (2) |
O1—C1—C2 | 122.30 (18) | C5—C6—H6 | 119.5 |
C6—C1—C2 | 120.19 (19) | C1—C6—H6 | 119.5 |
C3—C2—C1 | 117.37 (18) | N1—C7—C2 | 116.84 (17) |
C3—C2—C7 | 120.79 (18) | N1—C7—C8 | 123.10 (18) |
C1—C2—C7 | 121.85 (17) | C2—C7—C8 | 120.06 (17) |
C4—C3—C2 | 121.11 (19) | C7—C8—H8A | 109.5 |
C4—C3—H3 | 119.4 | C7—C8—H8B | 109.5 |
C2—C3—H3 | 119.4 | H8A—C8—H8B | 109.5 |
C3—C4—C5 | 121.08 (19) | C7—C8—H8C | 109.5 |
C3—C4—Cl1 | 119.64 (17) | H8A—C8—H8C | 109.5 |
C5—C4—Cl1 | 119.27 (17) | H8B—C8—H8C | 109.5 |
C6—C5—C4 | 119.2 (2) | ||
O1—C1—C2—C3 | 178.2 (2) | C4—C5—C6—C1 | 0.2 (4) |
C6—C1—C2—C3 | −1.9 (3) | O1—C1—C6—C5 | −178.6 (2) |
O1—C1—C2—C7 | −1.7 (3) | C2—C1—C6—C5 | 1.4 (4) |
C6—C1—C2—C7 | 178.2 (2) | N1i—N1—C7—C2 | 179.4 (2) |
C1—C2—C3—C4 | 0.8 (3) | N1i—N1—C7—C8 | −0.7 (3) |
C7—C2—C3—C4 | −179.3 (2) | C3—C2—C7—N1 | −174.95 (19) |
C2—C3—C4—C5 | 0.8 (4) | C1—C2—C7—N1 | 4.9 (3) |
C2—C3—C4—Cl1 | −179.15 (17) | C3—C2—C7—C8 | 5.1 (3) |
C3—C4—C5—C6 | −1.3 (4) | C1—C2—C7—C8 | −175.0 (2) |
Cl1—C4—C5—C6 | 178.66 (19) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.83 | 2.551 (2) | 146 |
C8—H8B···O1ii | 0.96 | 2.60 | 3.368 (2) | 137 |
C8—H8C···O1iii | 0.96 | 2.63 | 3.455 (3) | 145 |
Symmetry codes: (ii) x−1, y+1, z; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C16H14Cl2N2O2 |
Mr | 337.19 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 372.17 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.25 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker APEX II CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.897, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4295, 1315, 1010 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.081, 1.00 |
No. of reflections | 1315 |
No. of parameters | 102 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.18 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.83 | 2.551 (2) | 146.3 |
C8—H8B···O1i | 0.96 | 2.60 | 3.368 (2) | 137.4 |
C8—H8C···O1ii | 0.96 | 2.63 | 3.455 (3) | 144.9 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y+1, z. |
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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).