Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031339/hg2250sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031339/hg2250Isup2.hkl |
CCDC reference: 657654
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.059
- wR factor = 0.181
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.330 0.758 Tmin(prime) and Tmax expected: 0.672 0.943 RR(prime) = 0.611 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.56
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.24
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 1.244 Tmax scaled 0.943 Tmin scaled 0.411 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 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 3 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 related literature, see: Kumbhar & Dewang (2001); Pelizzi & Pelizzi (1980); Rastogi et al. (1979); Satapathy & Sahoo (1970); Sinn & Harris (1969); Yamada et al. (1968).
A solution of hydrazine hydrate (0.001 M) was added to a solution 2-formyl thymol (0.002 M) in ethanol (50 ml) and mixture was heated on a water bath for 8 hr. Yellow crystals deposited at room temperature which were filtered and recrystallized from ethanol, (yield 83%). Yellow crystals suitable for x- ray diffraction were obtained.
Elemental analysis - Found (cal) C - 75.15 (74.96), H - 8.76 (8.33), N - 7.64 (7.97). IR (KBr, cm -1) 3420 (–OH), 1600 (–C=N–). NMR- (CDCl3, dppm)- 1.22 (d, 12H, gem CH3), 2.37 (S, 6H, Ar- CH3) 3.33 {(heptane, 2H, CH)}, 6.68–7.110 (d, 4H, Ar—H), 9.1 (S, 2H, CH=N).
The H atoms were idealized with an O—H distance of 0.82 and C—H distances of 0.93 (aromatic C—H), 0.96 (CH3), and 0.98 (CH) Å and Uiso(H) = 1.2Ueq(C) (1.5Ueq(C) for the CH3 protons).
Hydrazides have interesting ligational properties due to presence of several potential coordination sites and transitional metal complexes of this ligand have been studied (Rastogi et al., 1979; Pelizzi & Pelizzi, 1980). Selection of the title compound was based on its broad spectrum activity and important role in plants as well as natural occurrence of the parent compound thymol (2-hydroxy-3-isopropyl-6-methylbenzene) (Kumbhar & Dewang, 2001). Hydrazones are a class of compounds obtained by condensation of aldehyde or ketone with appropriate amines. The types of hydrazone produced depend upon the amines used and may include simple amines like aniline or hydrazine. When the terminal NH2 group is condensed with aldehydes or ketones, the proton of NH group become more labile and acyl hydrazones react with metal ions in the enol form (Satapathy & Sahoo, 1970; Yamada et al., 1968; Sinn & Harris, 1969).
Elemental analysis of title compound gave a satisfactory fit to the formula C22H28N2O2. Table 1 contains selected bond lengths and angles. Views of the molecule and unit-cell contents are shown in Figs 1 and 2 respectively.
Hydrogen bonding is major feature of the structure of phenolic hydrazines. Invariably, the phenolic H atom forms an intramolecular hydrogen bond to the N atom of hydrazine group, giving a six membered ring. This interaction is usually characterized in terms of phenolic O to hydrazine N separation. This distance varies little between structures, with maximum value of 2.65 Å and minimum of 2.51 Å. In all free ligand structures, the molecules associate via intramolecular hydrogen bonding.
The structure of the title compound C22H28N2O2 exhibits intramolecular hydrogen bonding (Table 2) where the H atom of the phenolic hydroxyl group forms a strong O—H······N intramolecular hydrogen bond with an O···.N distance 2.578 (2)Å which is in the middle of expected range of such hydrogen bonds.
For related literature, see: Kumbhar & Dewang (2001); Pelizzi & Pelizzi (1980); Rastogi et al. (1979); Satapathy & Sahoo (1970); Sinn & Harris (1969); Yamada et al. (1968).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C22H28N2O2 | F(000) = 380 |
Mr = 352.46 | Dx = 1.158 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 65 reflections |
a = 11.925 (2) Å | θ = 3.2–28.0° |
b = 6.0622 (12) Å | µ = 0.58 mm−1 |
c = 14.152 (2) Å | T = 293 K |
β = 98.763 (10)° | Plate, yellow |
V = 1011.2 (3) Å3 | 0.60 × 0.55 × 0.10 mm |
Z = 2 |
Bruker P4 diffractometer | 1507 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 69.0°, θmin = 7.5° |
ω scans | h = −14→0 |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | k = 0→7 |
Tmin = 0.330, Tmax = 0.758 | l = −16→17 |
1958 measured reflections | 3 standard reflections every 97 reflections |
1869 independent reflections | intensity decay: none |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0834P)2 + 0.14P] where P = (Fo2 + 2Fc2)/3 |
1869 reflections | (Δ/σ)max = 0.001 |
122 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.10 e Å−3 |
C22H28N2O2 | V = 1011.2 (3) Å3 |
Mr = 352.46 | Z = 2 |
Monoclinic, P21/n | Cu Kα radiation |
a = 11.925 (2) Å | µ = 0.58 mm−1 |
b = 6.0622 (12) Å | T = 293 K |
c = 14.152 (2) Å | 0.60 × 0.55 × 0.10 mm |
β = 98.763 (10)° |
Bruker P4 diffractometer | 1507 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scans (North et al., 1968) | Rint = 0.036 |
Tmin = 0.330, Tmax = 0.758 | 3 standard reflections every 97 reflections |
1958 measured reflections | intensity decay: none |
1869 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.13 e Å−3 |
1869 reflections | Δρmin = −0.10 e Å−3 |
122 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 | ||
O | 0.22448 (12) | 0.2919 (2) | 0.98676 (12) | 0.0945 (5) | |
H1O | 0.1826 | 0.1917 | 0.9987 | 0.142* | |
N | 0.03674 (14) | 0.0815 (3) | 0.98764 (12) | 0.0828 (5) | |
C1 | 0.16522 (16) | 0.4342 (3) | 0.92369 (13) | 0.0746 (5) | |
C2 | 0.04839 (16) | 0.4043 (3) | 0.89208 (13) | 0.0745 (5) | |
C21 | −0.01234 (18) | 0.2229 (3) | 0.92723 (14) | 0.0799 (6) | |
H21A | −0.0896 | 0.2079 | 0.9054 | 0.096* | |
C3 | −0.00895 (17) | 0.5556 (4) | 0.82627 (13) | 0.0812 (6) | |
C31 | −0.13374 (19) | 0.5317 (5) | 0.78758 (18) | 0.1100 (8) | |
H31A | −0.1566 | 0.6481 | 0.7428 | 0.165* | |
H31B | −0.1771 | 0.5401 | 0.8393 | 0.165* | |
H31C | −0.1468 | 0.3917 | 0.7561 | 0.165* | |
C4 | 0.05091 (19) | 0.7293 (4) | 0.79547 (15) | 0.0882 (6) | |
H4A | 0.0137 | 0.8309 | 0.7524 | 0.106* | |
C5 | 0.16609 (19) | 0.7543 (3) | 0.82806 (15) | 0.0844 (6) | |
H5A | 0.2042 | 0.8726 | 0.8057 | 0.101* | |
C6 | 0.22623 (17) | 0.6100 (3) | 0.89244 (13) | 0.0757 (5) | |
C61 | 0.35080 (17) | 0.6367 (4) | 0.93133 (15) | 0.0864 (6) | |
H61A | 0.3843 | 0.4888 | 0.9364 | 0.104* | |
C62 | 0.3655 (2) | 0.7337 (5) | 1.03203 (17) | 0.1066 (8) | |
H62A | 0.3250 | 0.6448 | 1.0717 | 0.160* | |
H62B | 0.3362 | 0.8814 | 1.0294 | 0.160* | |
H62C | 0.4446 | 0.7358 | 1.0583 | 0.160* | |
C63 | 0.4165 (2) | 0.7718 (5) | 0.8680 (2) | 0.1156 (9) | |
H63A | 0.4026 | 0.7148 | 0.8039 | 0.173* | |
H63B | 0.4961 | 0.7630 | 0.8919 | 0.173* | |
H63C | 0.3924 | 0.9228 | 0.8679 | 0.173* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O | 0.0887 (9) | 0.0828 (9) | 0.1125 (11) | −0.0062 (7) | 0.0172 (8) | 0.0219 (8) |
N | 0.0919 (11) | 0.0713 (10) | 0.0910 (11) | −0.0131 (8) | 0.0326 (8) | −0.0045 (8) |
C1 | 0.0848 (12) | 0.0698 (10) | 0.0714 (10) | −0.0033 (9) | 0.0190 (8) | −0.0002 (8) |
C2 | 0.0846 (12) | 0.0719 (11) | 0.0704 (10) | −0.0072 (9) | 0.0221 (9) | −0.0069 (8) |
C21 | 0.0863 (12) | 0.0783 (12) | 0.0796 (12) | −0.0087 (9) | 0.0268 (9) | −0.0095 (10) |
C3 | 0.0874 (12) | 0.0900 (13) | 0.0682 (10) | −0.0044 (10) | 0.0183 (9) | −0.0037 (9) |
C31 | 0.0914 (15) | 0.136 (2) | 0.1000 (16) | −0.0058 (14) | 0.0078 (12) | 0.0137 (15) |
C4 | 0.1015 (15) | 0.0890 (14) | 0.0735 (12) | −0.0008 (11) | 0.0113 (10) | 0.0087 (10) |
C5 | 0.1018 (15) | 0.0780 (12) | 0.0757 (11) | −0.0094 (10) | 0.0211 (10) | 0.0034 (9) |
C6 | 0.0855 (11) | 0.0711 (10) | 0.0735 (10) | −0.0079 (9) | 0.0214 (9) | −0.0027 (9) |
C61 | 0.0828 (12) | 0.0834 (13) | 0.0963 (14) | −0.0080 (10) | 0.0241 (10) | 0.0047 (11) |
C62 | 0.0906 (14) | 0.131 (2) | 0.0956 (16) | −0.0111 (14) | 0.0072 (11) | −0.0023 (14) |
C63 | 0.1092 (17) | 0.124 (2) | 0.1194 (19) | −0.0348 (15) | 0.0353 (14) | 0.0092 (16) |
O—C1 | 1.359 (2) | C4—C5 | 1.389 (3) |
O—H1O | 0.8200 | C4—H4A | 0.9300 |
N—C21 | 1.287 (3) | C5—C6 | 1.382 (3) |
N—Ni | 1.400 (3) | C5—H5A | 0.9300 |
C1—C6 | 1.400 (3) | C6—C61 | 1.512 (3) |
C1—C2 | 1.409 (3) | C61—C63 | 1.518 (3) |
C2—C3 | 1.408 (3) | C61—C62 | 1.527 (3) |
C2—C21 | 1.446 (3) | C61—H61A | 0.9800 |
C21—H21A | 0.9300 | C62—H62A | 0.9600 |
C3—C4 | 1.380 (3) | C62—H62B | 0.9600 |
C3—C31 | 1.512 (3) | C62—H62C | 0.9600 |
C31—H31A | 0.9600 | C63—H63A | 0.9600 |
C31—H31B | 0.9600 | C63—H63B | 0.9600 |
C31—H31C | 0.9600 | C63—H63C | 0.9600 |
C1—O—H1O | 109.5 | C6—C5—H5A | 118.7 |
C21—N—Ni | 113.4 (2) | C4—C5—H5A | 118.7 |
O—C1—C6 | 116.59 (18) | C5—C6—C1 | 116.59 (19) |
O—C1—C2 | 121.14 (17) | C5—C6—C61 | 123.68 (18) |
C6—C1—C2 | 122.27 (18) | C1—C6—C61 | 119.70 (18) |
C3—C2—C1 | 118.94 (17) | C6—C61—C63 | 114.18 (19) |
C3—C2—C21 | 120.31 (18) | C6—C61—C62 | 110.35 (17) |
C1—C2—C21 | 120.75 (18) | C63—C61—C62 | 110.4 (2) |
N—C21—C2 | 122.29 (19) | C6—C61—H61A | 107.2 |
N—C21—H21A | 118.9 | C63—C61—H61A | 107.2 |
C2—C21—H21A | 118.9 | C62—C61—H61A | 107.2 |
C4—C3—C2 | 118.93 (18) | C61—C62—H62A | 109.5 |
C4—C3—C31 | 119.1 (2) | C61—C62—H62B | 109.5 |
C2—C3—C31 | 121.95 (19) | H62A—C62—H62B | 109.5 |
C3—C31—H31A | 109.5 | C61—C62—H62C | 109.5 |
C3—C31—H31B | 109.5 | H62A—C62—H62C | 109.5 |
H31A—C31—H31B | 109.5 | H62B—C62—H62C | 109.5 |
C3—C31—H31C | 109.5 | C61—C63—H63A | 109.5 |
H31A—C31—H31C | 109.5 | C61—C63—H63B | 109.5 |
H31B—C31—H31C | 109.5 | H63A—C63—H63B | 109.5 |
C3—C4—C5 | 120.7 (2) | C61—C63—H63C | 109.5 |
C3—C4—H4A | 119.6 | H63A—C63—H63C | 109.5 |
C5—C4—H4A | 119.6 | H63B—C63—H63C | 109.5 |
C6—C5—C4 | 122.52 (19) | ||
O—C1—C2—C3 | −179.61 (17) | C31—C3—C4—C5 | −178.8 (2) |
C6—C1—C2—C3 | 0.5 (3) | C3—C4—C5—C6 | −0.4 (3) |
O—C1—C2—C21 | 1.0 (3) | C4—C5—C6—C1 | 0.2 (3) |
C6—C1—C2—C21 | −178.88 (17) | C4—C5—C6—C61 | −178.17 (19) |
Ni—N—C21—C2 | −179.80 (17) | O—C1—C6—C5 | 179.78 (16) |
C3—C2—C21—N | −179.75 (17) | C2—C1—C6—C5 | −0.3 (3) |
C1—C2—C21—N | −0.4 (3) | O—C1—C6—C61 | −1.7 (3) |
C1—C2—C3—C4 | −0.6 (3) | C2—C1—C6—C61 | 178.18 (17) |
C21—C2—C3—C4 | 178.78 (17) | C5—C6—C61—C63 | −23.7 (3) |
C1—C2—C3—C31 | 178.73 (18) | C1—C6—C61—C63 | 158.0 (2) |
C21—C2—C3—C31 | −1.9 (3) | C5—C6—C61—C62 | 101.3 (2) |
C2—C3—C4—C5 | 0.5 (3) | C1—C6—C61—C62 | −77.0 (2) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C22H28N2O2 |
Mr | 352.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.925 (2), 6.0622 (12), 14.152 (2) |
β (°) | 98.763 (10) |
V (Å3) | 1011.2 (3) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.60 × 0.55 × 0.10 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | Empirical (using intensity measurements) via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.330, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1958, 1869, 1507 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.181, 1.06 |
No. of reflections | 1869 |
No. of parameters | 122 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.10 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
O—C1 | 1.359 (2) | N—Ni | 1.400 (3) |
N—C21 | 1.287 (3) | ||
C21—N—Ni | 113.4 (2) | O—C1—C2 | 121.14 (17) |
O—C1—C6 | 116.59 (18) |
Symmetry code: (i) −x, −y, −z+2. |
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Hydrazides have interesting ligational properties due to presence of several potential coordination sites and transitional metal complexes of this ligand have been studied (Rastogi et al., 1979; Pelizzi & Pelizzi, 1980). Selection of the title compound was based on its broad spectrum activity and important role in plants as well as natural occurrence of the parent compound thymol (2-hydroxy-3-isopropyl-6-methylbenzene) (Kumbhar & Dewang, 2001). Hydrazones are a class of compounds obtained by condensation of aldehyde or ketone with appropriate amines. The types of hydrazone produced depend upon the amines used and may include simple amines like aniline or hydrazine. When the terminal NH2 group is condensed with aldehydes or ketones, the proton of NH group become more labile and acyl hydrazones react with metal ions in the enol form (Satapathy & Sahoo, 1970; Yamada et al., 1968; Sinn & Harris, 1969).
Elemental analysis of title compound gave a satisfactory fit to the formula C22H28N2O2. Table 1 contains selected bond lengths and angles. Views of the molecule and unit-cell contents are shown in Figs 1 and 2 respectively.
Hydrogen bonding is major feature of the structure of phenolic hydrazines. Invariably, the phenolic H atom forms an intramolecular hydrogen bond to the N atom of hydrazine group, giving a six membered ring. This interaction is usually characterized in terms of phenolic O to hydrazine N separation. This distance varies little between structures, with maximum value of 2.65 Å and minimum of 2.51 Å. In all free ligand structures, the molecules associate via intramolecular hydrogen bonding.
The structure of the title compound C22H28N2O2 exhibits intramolecular hydrogen bonding (Table 2) where the H atom of the phenolic hydroxyl group forms a strong O—H······N intramolecular hydrogen bond with an O···.N distance 2.578 (2)Å which is in the middle of expected range of such hydrogen bonds.