Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034599/at2341sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034599/at2341Isup2.hkl |
CCDC reference: 657804
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.031
- wR factor = 0.087
- Data-to-parameter ratio = 8.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.66 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.30 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C12
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.53 From the CIF: _reflns_number_total 1539 Count of symmetry unique reflns 1543 Completeness (_total/calc) 99.74% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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 structures, see: Narayana et al. (2007); Yathirajan, Sarojini et al. (2007); Yathirajan, Narayana et al. (2007); Sarojini et al. (2007). For related literature, see: Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Liu et al. (2006); Flack (1983); Narayana, Ashalatha et al. (2005); Narayana, Vijayaraj et al. (2005).
Hydrazine hydrate (100%) (2 ml) was added to methyl 6-methoxy-2-naphthoate (4.3 g, 0.02 mol) in 20 ml e thanol and refluxed for 4 h on a water bath. The precipitate formed was collected and recrystallized from ethyl acetate. X-ray quality crystals were obtained from a mixture of acetone and DMF(1:1) and the compound obtained was a Schiff base of the hydrazide with acetone, C15H16N2O2 (m.p.: 445–447 K). Analysis for C15H16N2O2: Found (Calculated): C 70.20 (70.29), H 6.22 (6.29), N 10.87% (10.93%).
H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95Å and Uiso(H) = 1.2Ueq(C) [C—H = 0.98Å and Uiso(H) = 1.5Ueq(C) for the methyl groups, which were allowed to rotate but not to tip]. The amino H atom was freely refined. In the absence of anomalous scatterers, the Flack [(1983). Acta Cryst. A39, 876–881] parameter is meaningless and therefore, Friedel pairs had been merged prior to refinement.
Hydrazides and the corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems. Some substituted hydrazides are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. Some substituted hydrazides and their Schiff bases are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. It is also used as an intermediate in many pharmaceutically important compounds. A new Schiff base of the hydrazide, C15H16N2O2, was accidentally formed, when the synthesized hydrazide was recrystallized using a 1:1 mixture of acetone and dimethyl formamide. The crystal structure of the newly formed compound is reported.
Geometric parameters of the title compound (Fig. 1) are in the usual ranges. The crystal packing is characterized by chains of molecules connected by N—H···O hydrogen bonds running along the c axis (Fig. 2).
For related structures, see: Narayana et al. (2007); Yathirajan, Sarojini et al. (2007); Yathirajan, Narayana et al. (2007); Sarojini et al. (2007). For related literature, see: Misra et al. (1981); Agarwal et al. (1983); Varma et al. (1986); Singh & Dash (1988); Liu et al. (2006); Flack (1983); Narayana, Ashalatha et al. (2005); Narayana, Vijayaraj et al. (2005).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
C15H16N2O2 | F(000) = 544 |
Mr = 256.30 | Dx = 1.270 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 8050 reflections |
a = 24.037 (3) Å | θ = 3.6–27.2° |
b = 5.9957 (4) Å | µ = 0.09 mm−1 |
c = 9.3014 (10) Å | T = 173 K |
β = 91.673 (9)° | Rod, colourless |
V = 1339.9 (2) Å3 | 0.38 × 0.24 × 0.24 mm |
Z = 4 |
Stoe IPDS II two-circle diffractometer | 1506 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 27.5°, θmin = 3.5° |
ω scans | h = −27→30 |
8435 measured reflections | k = −7→7 |
1539 independent reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.1264P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
1539 reflections | Δρmax = 0.24 e Å−3 |
180 parameters | Δρmin = −0.15 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (3) |
C15H16N2O2 | V = 1339.9 (2) Å3 |
Mr = 256.30 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 24.037 (3) Å | µ = 0.09 mm−1 |
b = 5.9957 (4) Å | T = 173 K |
c = 9.3014 (10) Å | 0.38 × 0.24 × 0.24 mm |
β = 91.673 (9)° |
Stoe IPDS II two-circle diffractometer | 1506 reflections with I > 2σ(I) |
8435 measured reflections | Rint = 0.037 |
1539 independent reflections |
R[F2 > 2σ(F2)] = 0.031 | 2 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.24 e Å−3 |
1539 reflections | Δρmin = −0.15 e Å−3 |
180 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 | ||
N1 | 0.61518 (6) | 0.6094 (2) | 0.48733 (13) | 0.0305 (3) | |
H1 | 0.6241 (8) | 0.630 (3) | 0.398 (2) | 0.033 (5)* | |
N2 | 0.56452 (7) | 0.6965 (3) | 0.53277 (15) | 0.0438 (4) | |
O1 | 0.62273 (6) | 0.3857 (2) | 0.68512 (13) | 0.0409 (3) | |
O2 | 0.93004 (5) | 0.1401 (2) | 0.23424 (16) | 0.0483 (4) | |
C1 | 0.69319 (6) | 0.3547 (2) | 0.51132 (14) | 0.0274 (3) | |
C2 | 0.72496 (6) | 0.4663 (2) | 0.41240 (16) | 0.0282 (3) | |
H2 | 0.7124 | 0.6055 | 0.3751 | 0.034* | |
C3 | 0.77597 (6) | 0.3761 (2) | 0.36589 (15) | 0.0276 (3) | |
C4 | 0.80881 (7) | 0.4902 (3) | 0.26298 (18) | 0.0338 (3) | |
H4 | 0.7960 | 0.6276 | 0.2234 | 0.041* | |
C5 | 0.85828 (7) | 0.4036 (3) | 0.22131 (19) | 0.0373 (4) | |
H5 | 0.8792 | 0.4789 | 0.1510 | 0.045* | |
C6 | 0.87878 (7) | 0.2009 (3) | 0.28263 (18) | 0.0363 (4) | |
C7 | 0.84830 (7) | 0.0842 (3) | 0.38110 (17) | 0.0344 (3) | |
H7 | 0.8622 | −0.0514 | 0.4208 | 0.041* | |
C8 | 0.79556 (6) | 0.1691 (2) | 0.42301 (15) | 0.0284 (3) | |
C9 | 0.76168 (7) | 0.0543 (2) | 0.52314 (16) | 0.0315 (3) | |
H9 | 0.7735 | −0.0858 | 0.5607 | 0.038* | |
C10 | 0.71221 (7) | 0.1449 (2) | 0.56560 (15) | 0.0308 (3) | |
H10 | 0.6903 | 0.0663 | 0.6323 | 0.037* | |
C11 | 0.64049 (6) | 0.4497 (3) | 0.56888 (14) | 0.0291 (3) | |
C12 | 0.54904 (7) | 0.8804 (3) | 0.47282 (16) | 0.0365 (4) | |
C13 | 0.49405 (11) | 0.9730 (6) | 0.5149 (3) | 0.0729 (9) | |
H13A | 0.4769 | 0.8719 | 0.5835 | 0.109* | |
H13B | 0.4697 | 0.9880 | 0.4291 | 0.109* | |
H13C | 0.4996 | 1.1196 | 0.5596 | 0.109* | |
C14 | 0.58033 (8) | 1.0116 (3) | 0.3649 (2) | 0.0425 (4) | |
H14A | 0.6202 | 1.0062 | 0.3895 | 0.064* | |
H14B | 0.5676 | 1.1669 | 0.3655 | 0.064* | |
H14C | 0.5736 | 0.9478 | 0.2690 | 0.064* | |
C15 | 0.95677 (9) | −0.0466 (4) | 0.3035 (3) | 0.0538 (5) | |
H15A | 0.9593 | −0.0207 | 0.4075 | 0.081* | |
H15B | 0.9942 | −0.0649 | 0.2664 | 0.081* | |
H15C | 0.9350 | −0.1820 | 0.2838 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0336 (7) | 0.0371 (7) | 0.0210 (6) | 0.0077 (5) | 0.0070 (5) | 0.0023 (5) |
N2 | 0.0427 (8) | 0.0602 (10) | 0.0294 (6) | 0.0208 (7) | 0.0142 (6) | 0.0113 (6) |
O1 | 0.0504 (7) | 0.0507 (7) | 0.0218 (5) | 0.0072 (5) | 0.0062 (4) | 0.0086 (5) |
O2 | 0.0358 (7) | 0.0496 (8) | 0.0601 (8) | 0.0133 (6) | 0.0107 (6) | 0.0061 (6) |
C1 | 0.0316 (7) | 0.0270 (7) | 0.0235 (6) | −0.0004 (5) | −0.0019 (5) | −0.0013 (5) |
C2 | 0.0310 (7) | 0.0249 (7) | 0.0287 (7) | 0.0011 (5) | −0.0019 (5) | 0.0027 (5) |
C3 | 0.0276 (7) | 0.0251 (7) | 0.0301 (7) | −0.0007 (5) | −0.0019 (5) | 0.0011 (5) |
C4 | 0.0310 (7) | 0.0307 (7) | 0.0395 (8) | 0.0011 (6) | 0.0007 (6) | 0.0088 (6) |
C5 | 0.0306 (8) | 0.0377 (8) | 0.0438 (9) | −0.0010 (6) | 0.0038 (6) | 0.0070 (6) |
C6 | 0.0317 (8) | 0.0357 (8) | 0.0414 (8) | 0.0051 (6) | 0.0013 (6) | −0.0001 (7) |
C7 | 0.0358 (8) | 0.0283 (7) | 0.0392 (8) | 0.0064 (6) | 0.0006 (6) | −0.0008 (6) |
C8 | 0.0317 (8) | 0.0238 (6) | 0.0294 (7) | 0.0005 (5) | −0.0028 (5) | −0.0013 (5) |
C9 | 0.0393 (8) | 0.0225 (6) | 0.0326 (8) | 0.0016 (5) | −0.0030 (6) | 0.0031 (5) |
C10 | 0.0390 (8) | 0.0271 (7) | 0.0261 (6) | −0.0018 (5) | 0.0005 (5) | 0.0029 (5) |
C11 | 0.0356 (7) | 0.0321 (7) | 0.0196 (6) | −0.0007 (6) | 0.0007 (5) | −0.0010 (5) |
C12 | 0.0372 (8) | 0.0485 (9) | 0.0241 (7) | 0.0111 (7) | 0.0017 (5) | −0.0021 (6) |
C13 | 0.0629 (15) | 0.099 (2) | 0.0581 (13) | 0.0480 (14) | 0.0258 (11) | 0.0284 (13) |
C14 | 0.0404 (8) | 0.0315 (8) | 0.0555 (10) | 0.0012 (6) | −0.0009 (8) | 0.0041 (7) |
C15 | 0.0437 (11) | 0.0486 (11) | 0.0692 (13) | 0.0189 (8) | 0.0049 (9) | 0.0008 (10) |
N1—C11 | 1.355 (2) | C6—C7 | 1.380 (2) |
N1—N2 | 1.4017 (18) | C7—C8 | 1.431 (2) |
N1—H1 | 0.88 (2) | C7—H7 | 0.9500 |
N2—C12 | 1.286 (2) | C8—C9 | 1.431 (2) |
O1—C11 | 1.2352 (19) | C9—C10 | 1.376 (2) |
O2—C6 | 1.3733 (19) | C9—H9 | 0.9500 |
O2—C15 | 1.434 (2) | C10—H10 | 0.9500 |
C1—C2 | 1.385 (2) | C12—C14 | 1.496 (3) |
C1—C10 | 1.426 (2) | C12—C13 | 1.496 (2) |
C1—C11 | 1.502 (2) | C13—H13A | 0.9800 |
C2—C3 | 1.419 (2) | C13—H13B | 0.9800 |
C2—H2 | 0.9500 | C13—H13C | 0.9800 |
C3—C8 | 1.4245 (18) | C14—H14A | 0.9800 |
C3—C4 | 1.432 (2) | C14—H14B | 0.9800 |
C4—C5 | 1.364 (2) | C14—H14C | 0.9800 |
C4—H4 | 0.9500 | C15—H15A | 0.9800 |
C5—C6 | 1.424 (2) | C15—H15B | 0.9800 |
C5—H5 | 0.9500 | C15—H15C | 0.9800 |
C11—N1—N2 | 118.32 (12) | C10—C9—H9 | 119.7 |
C11—N1—H1 | 121.1 (13) | C8—C9—H9 | 119.7 |
N2—N1—H1 | 118.2 (13) | C9—C10—C1 | 121.18 (13) |
C12—N2—N1 | 115.58 (13) | C9—C10—H10 | 119.4 |
C6—O2—C15 | 117.03 (15) | C1—C10—H10 | 119.4 |
C2—C1—C10 | 118.95 (14) | O1—C11—N1 | 123.28 (15) |
C2—C1—C11 | 122.73 (13) | O1—C11—C1 | 120.72 (14) |
C10—C1—C11 | 118.26 (12) | N1—C11—C1 | 115.98 (12) |
C1—C2—C3 | 121.09 (13) | N2—C12—C14 | 126.69 (15) |
C1—C2—H2 | 119.5 | N2—C12—C13 | 116.84 (16) |
C3—C2—H2 | 119.5 | C14—C12—C13 | 116.47 (16) |
C2—C3—C8 | 119.83 (12) | C12—C13—H13A | 109.5 |
C2—C3—C4 | 121.29 (13) | C12—C13—H13B | 109.5 |
C8—C3—C4 | 118.87 (13) | H13A—C13—H13B | 109.5 |
C5—C4—C3 | 120.66 (14) | C12—C13—H13C | 109.5 |
C5—C4—H4 | 119.7 | H13A—C13—H13C | 109.5 |
C3—C4—H4 | 119.7 | H13B—C13—H13C | 109.5 |
C4—C5—C6 | 120.35 (15) | C12—C14—H14A | 109.5 |
C4—C5—H5 | 119.8 | C12—C14—H14B | 109.5 |
C6—C5—H5 | 119.8 | H14A—C14—H14B | 109.5 |
O2—C6—C7 | 125.58 (15) | C12—C14—H14C | 109.5 |
O2—C6—C5 | 113.48 (14) | H14A—C14—H14C | 109.5 |
C7—C6—C5 | 120.94 (14) | H14B—C14—H14C | 109.5 |
C6—C7—C8 | 119.49 (14) | O2—C15—H15A | 109.5 |
C6—C7—H7 | 120.3 | O2—C15—H15B | 109.5 |
C8—C7—H7 | 120.3 | H15A—C15—H15B | 109.5 |
C3—C8—C7 | 119.61 (13) | O2—C15—H15C | 109.5 |
C3—C8—C9 | 118.25 (13) | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 122.13 (13) | H15B—C15—H15C | 109.5 |
C10—C9—C8 | 120.66 (13) | ||
C11—N1—N2—C12 | 164.11 (15) | C4—C3—C8—C9 | −178.54 (15) |
C10—C1—C2—C3 | −0.6 (2) | C6—C7—C8—C3 | −1.9 (2) |
C11—C1—C2—C3 | 176.83 (12) | C6—C7—C8—C9 | 179.15 (14) |
C1—C2—C3—C8 | −1.0 (2) | C3—C8—C9—C10 | −1.6 (2) |
C1—C2—C3—C4 | 179.63 (15) | C7—C8—C9—C10 | 177.36 (13) |
C2—C3—C4—C5 | 178.74 (14) | C8—C9—C10—C1 | 0.1 (2) |
C8—C3—C4—C5 | −0.7 (2) | C2—C1—C10—C9 | 1.0 (2) |
C3—C4—C5—C6 | −1.7 (3) | C11—C1—C10—C9 | −176.49 (13) |
C15—O2—C6—C7 | −7.3 (3) | N2—N1—C11—O1 | −4.0 (2) |
C15—O2—C6—C5 | 172.53 (17) | N2—N1—C11—C1 | 177.15 (14) |
C4—C5—C6—O2 | −177.47 (15) | C2—C1—C11—O1 | −157.24 (15) |
C4—C5—C6—C7 | 2.3 (3) | C10—C1—C11—O1 | 20.2 (2) |
O2—C6—C7—C8 | 179.27 (14) | C2—C1—C11—N1 | 21.6 (2) |
C5—C6—C7—C8 | −0.5 (2) | C10—C1—C11—N1 | −160.97 (13) |
C2—C3—C8—C7 | −176.96 (13) | N1—N2—C12—C14 | −2.2 (3) |
C4—C3—C8—C7 | 2.4 (2) | N1—N2—C12—C13 | 177.68 (19) |
C2—C3—C8—C9 | 2.07 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 (2) | 1.98 (2) | 2.8222 (17) | 161.3 (19) |
Symmetry code: (i) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H16N2O2 |
Mr | 256.30 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 173 |
a, b, c (Å) | 24.037 (3), 5.9957 (4), 9.3014 (10) |
β (°) | 91.673 (9) |
V (Å3) | 1339.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.38 × 0.24 × 0.24 |
Data collection | |
Diffractometer | Stoe IPDS II two-circle |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8435, 1539, 1506 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.087, 1.07 |
No. of reflections | 1539 |
No. of parameters | 180 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.15 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 (2) | 1.98 (2) | 2.8222 (17) | 161.3 (19) |
Symmetry code: (i) x, −y+1, z−1/2. |
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Hydrazides and the corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems. Some substituted hydrazides are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. Some substituted hydrazides and their Schiff bases are reported to exhibit carcinostatic activity against several types of tumors and also possess antimicrobial activity. It is also used as an intermediate in many pharmaceutically important compounds. A new Schiff base of the hydrazide, C15H16N2O2, was accidentally formed, when the synthesized hydrazide was recrystallized using a 1:1 mixture of acetone and dimethyl formamide. The crystal structure of the newly formed compound is reported.
Geometric parameters of the title compound (Fig. 1) are in the usual ranges. The crystal packing is characterized by chains of molecules connected by N—H···O hydrogen bonds running along the c axis (Fig. 2).