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organic compounds
N′-tert-Butyl-N′-(3,5-dimethylbenzoyl)-2,2-dimethyl-4-oxochroman-6-carbohydrazide
aSchool of Pharmaceutical Sciences, Southern Medical University, Guangzhou 510515, People's Republic of China
*Correspondence e-mail: peiliangzhao1999@yahoo.com.cn
In the 25H30N2O4, the steric size of the tert-butyl group causes the 3,5-dimethylphenyl ring to adopt a transoid geometry with respect to the N—C(O) bond. The six-membered heterocyclic ring is disordered over two sites, with occupancies of 0.553 (4) and 0.447 (4). Intramolecular C—H⋯O interactions are present. In the crystal, molecules are linked by intermolecular N—H⋯O and C—H⋯O hydrogen bonds.
of the title compound, CRelated literature
For general background to dibenzoylhydrazines and their derivatives, see: Sawada et al. (2003). For a related structure, see: Zhao et al. (2005
). For the preparation of the title compound, see: Zhao et al. (2007
); Mao et al. (2008
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809028815/fj2236sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809028815/fj2236Isup2.hkl
To A solution of 2,2-Dimethyl-4-oxo-chroman-6-carboxylic acid N'-tert-butyl-hydrazide (1.5 mmol) in 10 ml of dichloromethane was added dropwise to a stirred mixture of 3,5-dimethylbenzoyl chloride (1.5 mmol), triethylamine (1.6 mmol) and dichloromethane (5 ml) in an ice bath.After stirring the mixture at room temperature for 3 h,ethyl acetate (30 ml) was added to the reaction mixture. The organic layer was separated and washed successively with water (15 ml) and brine (15 ml), and then dried with anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by
on silicagel using hexane/ethyl acetate (9:1 v/v) as to afford (I) (yield 80%, m.p. 435 K) Spectroscopic analysis: 1H NMR(CDCl3, 400 MHz) 8.06 (s, 1H, N—H), 7.74 (d, 2H, C10—H, C11—H), 7.05 (s, 2H, C19—H, C23—H), 6.81 (m, 2H, C8—H, C21—H), 2.70 (s, 2H, C2—H), 2.21 (s, 6H, C24—H, C25—H), 1.57 (s, 9H, C14—H, C15—H,C16—H),1.44 (s, 6H, C6—H,C7—H); MS (EI 70 eV)m/z(%):422 (16), 367 (95), 349 (35), 203 (62), 146 (20),133 (100), 105 (49),102 (19). Crystals suitable for an X-ray diffraction study were grown from methanol at 292 K.All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry with C—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C), but each group was allowed to rotate freely about its C—C bond. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.97 Å,an N—H distance of 0.86 Å and Uiso(H) = 1.2Ueq(C,N).
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C25H30N2O4 | F(000) = 904 |
Mr = 422.51 | Dx = 1.211 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5293 reflections |
a = 14.1260 (12) Å | θ = 2.3–27.9° |
b = 10.6964 (9) Å | µ = 0.08 mm−1 |
c = 15.4370 (13) Å | T = 297 K |
β = 96.426 (2)° | Block, colorless |
V = 2317.8 (3) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 5043 independent reflections |
Radiation source: fine-focus sealed tube | 3983 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2005) | h = −18→18 |
Tmin = 0.976, Tmax = 0.984 | k = −13→13 |
13199 measured reflections | l = −19→11 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0739P)2 + 0.3537P] where P = (Fo2 + 2Fc2)/3 |
5043 reflections | (Δ/σ)max = 0.027 |
338 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C25H30N2O4 | V = 2317.8 (3) Å3 |
Mr = 422.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.1260 (12) Å | µ = 0.08 mm−1 |
b = 10.6964 (9) Å | T = 297 K |
c = 15.4370 (13) Å | 0.30 × 0.20 × 0.20 mm |
β = 96.426 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 5043 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2005) | 3983 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.984 | Rint = 0.020 |
13199 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.142 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.22 e Å−3 |
5043 reflections | Δρmin = −0.17 e Å−3 |
338 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 | Occ. (<1) | |
C3 | 0.66849 (13) | 1.10349 (14) | −0.10449 (11) | 0.0605 (4) | |
C4 | 0.67622 (12) | 0.88189 (13) | −0.00473 (10) | 0.0514 (4) | |
C5 | 0.68639 (11) | 0.87969 (14) | −0.09323 (9) | 0.0494 (3) | |
C1 | 0.6450 (5) | 0.9997 (11) | 0.0354 (8) | 0.065 (2) | 0.553 (4) |
O1 | 0.6346 (7) | 1.0033 (10) | 0.1119 (7) | 0.114 (3) | 0.553 (4) |
C2 | 0.6193 (3) | 1.1038 (3) | −0.0289 (2) | 0.0658 (10) | 0.553 (4) |
H2A | 0.5515 | 1.0993 | −0.0475 | 0.079* | 0.553 (4) |
H2B | 0.6314 | 1.1830 | 0.0009 | 0.079* | 0.553 (4) |
C6 | 0.6317 (4) | 1.1921 (4) | −0.1762 (3) | 0.0794 (12) | 0.553 (4) |
H6A | 0.5657 | 1.1746 | −0.1940 | 0.119* | 0.553 (4) |
H6B | 0.6676 | 1.1816 | −0.2249 | 0.119* | 0.553 (4) |
H6C | 0.6382 | 1.2765 | −0.1553 | 0.119* | 0.553 (4) |
C7 | 0.7797 (3) | 1.1317 (4) | −0.0800 (3) | 0.0873 (13) | 0.553 (4) |
H7A | 0.7875 | 1.2129 | −0.0537 | 0.131* | 0.553 (4) |
H7B | 0.8112 | 1.1295 | −0.1319 | 0.131* | 0.553 (4) |
H7C | 0.8069 | 1.0696 | −0.0398 | 0.131* | 0.553 (4) |
C1' | 0.6818 (6) | 1.0036 (14) | 0.0428 (10) | 0.060 (2) | 0.447 (4) |
O1' | 0.6711 (7) | 1.0167 (11) | 0.1174 (8) | 0.0697 (17) | 0.447 (4) |
C2' | 0.7037 (4) | 1.1160 (4) | −0.0090 (3) | 0.0685 (13) | 0.447 (4) |
H2'1 | 0.7721 | 1.1291 | −0.0027 | 0.082* | 0.447 (4) |
H2'2 | 0.6746 | 1.1890 | 0.0143 | 0.082* | 0.447 (4) |
C7' | 0.5527 (3) | 1.0980 (4) | −0.1099 (3) | 0.0755 (13) | 0.447 (4) |
H7'1 | 0.5340 | 1.0260 | −0.0789 | 0.113* | 0.447 (4) |
H7'2 | 0.5262 | 1.0926 | −0.1698 | 0.113* | 0.447 (4) |
H7'3 | 0.5297 | 1.1722 | −0.0843 | 0.113* | 0.447 (4) |
C6' | 0.6941 (6) | 1.2082 (6) | −0.1583 (4) | 0.0936 (19) | 0.447 (4) |
H6'1 | 0.6725 | 1.2850 | −0.1350 | 0.140* | 0.447 (4) |
H6'2 | 0.6645 | 1.1974 | −0.2169 | 0.140* | 0.447 (4) |
H6'3 | 0.7620 | 1.2110 | −0.1583 | 0.140* | 0.447 (4) |
C8 | 0.68071 (12) | 0.77025 (13) | 0.04199 (10) | 0.0515 (4) | |
H8 | 0.6738 | 0.7719 | 0.1012 | 0.062* | |
C9 | 0.69514 (10) | 0.65732 (12) | 0.00237 (9) | 0.0440 (3) | |
C10 | 0.70566 (10) | 0.65759 (14) | −0.08622 (9) | 0.0499 (3) | |
H10 | 0.7153 | 0.5823 | −0.1141 | 0.060* | |
C11 | 0.70207 (11) | 0.76656 (15) | −0.13332 (10) | 0.0544 (4) | |
H11 | 0.7102 | 0.7646 | −0.1923 | 0.065* | |
C12 | 0.69536 (10) | 0.53436 (12) | 0.04860 (10) | 0.0468 (3) | |
C13 | 0.59930 (11) | 0.41391 (14) | 0.21344 (11) | 0.0538 (4) | |
C14 | 0.53721 (13) | 0.52843 (17) | 0.18794 (15) | 0.0753 (5) | |
H14A | 0.5673 | 0.6019 | 0.2140 | 0.113* | |
H14B | 0.4759 | 0.5178 | 0.2082 | 0.113* | |
H14C | 0.5296 | 0.5373 | 0.1257 | 0.113* | |
C15 | 0.60593 (14) | 0.39710 (18) | 0.31198 (13) | 0.0715 (5) | |
H15A | 0.6370 | 0.3193 | 0.3279 | 0.107* | |
H15B | 0.5430 | 0.3967 | 0.3299 | 0.107* | |
H15C | 0.6420 | 0.4647 | 0.3401 | 0.107* | |
C16 | 0.55686 (12) | 0.29932 (16) | 0.16431 (14) | 0.0702 (5) | |
H16A | 0.5496 | 0.3161 | 0.1028 | 0.105* | |
H16B | 0.4957 | 0.2808 | 0.1828 | 0.105* | |
H16C | 0.5985 | 0.2291 | 0.1764 | 0.105* | |
C17 | 0.76979 (10) | 0.35224 (11) | 0.20322 (9) | 0.0419 (3) | |
C18 | 0.86257 (9) | 0.37282 (12) | 0.16645 (9) | 0.0426 (3) | |
C19 | 0.91465 (10) | 0.48329 (13) | 0.17253 (10) | 0.0475 (3) | |
H19 | 0.8915 | 0.5525 | 0.2000 | 0.057* | |
C20 | 1.00090 (11) | 0.49090 (14) | 0.13791 (10) | 0.0530 (4) | |
C21 | 1.03369 (11) | 0.38643 (16) | 0.09734 (11) | 0.0582 (4) | |
H21 | 1.0906 | 0.3920 | 0.0725 | 0.070* | |
C22 | 0.98488 (11) | 0.27454 (15) | 0.09244 (11) | 0.0561 (4) | |
C23 | 0.89924 (10) | 0.26895 (13) | 0.12762 (10) | 0.0494 (3) | |
H23 | 0.8655 | 0.1942 | 0.1253 | 0.059* | |
C24 | 1.05961 (13) | 0.60902 (17) | 0.14489 (14) | 0.0745 (5) | |
H24A | 1.0845 | 0.6224 | 0.2046 | 0.112* | |
H24B | 1.0203 | 0.6786 | 0.1246 | 0.112* | |
H24C | 1.1113 | 0.6011 | 0.1099 | 0.112* | |
C25 | 1.02483 (16) | 0.16056 (19) | 0.05138 (16) | 0.0862 (6) | |
H25A | 1.0685 | 0.1864 | 0.0114 | 0.129* | |
H25B | 0.9737 | 0.1137 | 0.0206 | 0.129* | |
H25C | 1.0577 | 0.1092 | 0.0961 | 0.129* | |
N1 | 0.71169 (8) | 0.54096 (10) | 0.13664 (8) | 0.0442 (3) | |
H1 | 0.7207 (11) | 0.6105 (16) | 0.1645 (11) | 0.053* | |
N2 | 0.69837 (8) | 0.43704 (10) | 0.18823 (8) | 0.0448 (3) | |
O2 | 0.68091 (10) | 0.98341 (11) | −0.14408 (8) | 0.0697 (4) | |
O3 | 0.68252 (10) | 0.43588 (10) | 0.00964 (8) | 0.0680 (3) | |
O4 | 0.75822 (7) | 0.25569 (9) | 0.24413 (7) | 0.0527 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.0823 (11) | 0.0413 (8) | 0.0569 (9) | −0.0035 (7) | 0.0036 (8) | 0.0097 (7) |
C4 | 0.0704 (9) | 0.0384 (7) | 0.0462 (8) | 0.0063 (6) | 0.0101 (7) | 0.0034 (6) |
C5 | 0.0560 (8) | 0.0456 (8) | 0.0478 (8) | 0.0026 (6) | 0.0105 (6) | 0.0064 (6) |
C1 | 0.100 (5) | 0.040 (2) | 0.059 (4) | 0.013 (4) | 0.027 (5) | 0.004 (2) |
O1 | 0.236 (10) | 0.046 (3) | 0.070 (4) | 0.024 (5) | 0.064 (6) | 0.004 (2) |
C2 | 0.092 (3) | 0.0395 (14) | 0.069 (2) | 0.0125 (15) | 0.0221 (18) | 0.0105 (13) |
C6 | 0.114 (4) | 0.053 (2) | 0.070 (2) | 0.005 (2) | 0.007 (3) | 0.0194 (18) |
C7 | 0.080 (2) | 0.066 (2) | 0.115 (3) | −0.0203 (18) | 0.006 (2) | 0.008 (2) |
C1' | 0.088 (6) | 0.043 (3) | 0.049 (3) | 0.014 (5) | 0.007 (5) | 0.0066 (19) |
O1' | 0.121 (4) | 0.042 (3) | 0.045 (2) | 0.010 (2) | 0.008 (3) | −0.0031 (18) |
C2' | 0.090 (3) | 0.047 (2) | 0.066 (2) | −0.0059 (19) | −0.003 (2) | −0.0011 (17) |
C7' | 0.073 (3) | 0.078 (3) | 0.074 (3) | 0.015 (2) | 0.002 (2) | 0.008 (2) |
C6' | 0.138 (6) | 0.068 (3) | 0.079 (4) | −0.023 (4) | 0.030 (4) | 0.018 (3) |
C8 | 0.0718 (10) | 0.0418 (7) | 0.0416 (7) | 0.0084 (7) | 0.0097 (7) | 0.0023 (6) |
C9 | 0.0468 (7) | 0.0375 (7) | 0.0467 (7) | 0.0039 (5) | 0.0010 (6) | 0.0006 (6) |
C10 | 0.0540 (8) | 0.0450 (8) | 0.0503 (8) | 0.0081 (6) | 0.0043 (6) | −0.0066 (6) |
C11 | 0.0645 (9) | 0.0576 (9) | 0.0427 (8) | 0.0072 (7) | 0.0129 (7) | 0.0002 (7) |
C12 | 0.0518 (8) | 0.0355 (7) | 0.0519 (8) | 0.0041 (6) | 0.0012 (6) | −0.0016 (6) |
C13 | 0.0501 (8) | 0.0415 (7) | 0.0715 (10) | 0.0016 (6) | 0.0140 (7) | −0.0001 (7) |
C14 | 0.0567 (10) | 0.0608 (10) | 0.1105 (16) | 0.0147 (8) | 0.0189 (10) | 0.0057 (10) |
C15 | 0.0796 (12) | 0.0646 (10) | 0.0756 (12) | 0.0033 (9) | 0.0318 (9) | 0.0017 (9) |
C16 | 0.0560 (9) | 0.0571 (10) | 0.0980 (14) | −0.0107 (8) | 0.0109 (9) | −0.0075 (9) |
C17 | 0.0512 (7) | 0.0313 (6) | 0.0425 (7) | 0.0004 (5) | 0.0026 (6) | −0.0010 (5) |
C18 | 0.0481 (7) | 0.0369 (6) | 0.0416 (7) | 0.0041 (5) | −0.0002 (5) | 0.0023 (5) |
C19 | 0.0535 (8) | 0.0378 (7) | 0.0508 (8) | 0.0004 (6) | 0.0034 (6) | −0.0028 (6) |
C20 | 0.0506 (8) | 0.0504 (8) | 0.0570 (9) | −0.0030 (6) | 0.0012 (6) | 0.0018 (7) |
C21 | 0.0483 (8) | 0.0636 (10) | 0.0640 (10) | 0.0033 (7) | 0.0114 (7) | −0.0005 (8) |
C22 | 0.0562 (9) | 0.0530 (9) | 0.0592 (9) | 0.0098 (7) | 0.0069 (7) | −0.0067 (7) |
C23 | 0.0544 (8) | 0.0381 (7) | 0.0549 (8) | 0.0028 (6) | 0.0025 (6) | −0.0028 (6) |
C24 | 0.0652 (10) | 0.0628 (11) | 0.0964 (14) | −0.0170 (8) | 0.0124 (10) | −0.0043 (10) |
C25 | 0.0850 (13) | 0.0685 (12) | 0.1098 (16) | 0.0131 (10) | 0.0317 (12) | −0.0227 (11) |
N1 | 0.0548 (7) | 0.0272 (5) | 0.0495 (7) | 0.0011 (5) | 0.0016 (5) | 0.0022 (5) |
N2 | 0.0496 (6) | 0.0315 (5) | 0.0539 (7) | 0.0017 (5) | 0.0079 (5) | 0.0049 (5) |
O2 | 0.1092 (10) | 0.0515 (6) | 0.0522 (6) | 0.0076 (6) | 0.0257 (6) | 0.0124 (5) |
O3 | 0.1024 (9) | 0.0384 (6) | 0.0610 (7) | 0.0002 (6) | −0.0009 (6) | −0.0085 (5) |
O4 | 0.0645 (6) | 0.0345 (5) | 0.0598 (6) | 0.0032 (4) | 0.0096 (5) | 0.0099 (4) |
C3—C2 | 1.423 (4) | C11—H11 | 0.9300 |
C3—O2 | 1.4416 (19) | C12—O3 | 1.2165 (17) |
C3—C6' | 1.464 (5) | C12—N1 | 1.3547 (19) |
C3—C6 | 1.504 (4) | C13—N2 | 1.5143 (18) |
C3—C2' | 1.509 (4) | C13—C15 | 1.524 (3) |
C3—C7 | 1.602 (4) | C13—C16 | 1.528 (2) |
C3—C7' | 1.629 (5) | C13—C14 | 1.532 (2) |
C4—C5 | 1.390 (2) | C14—H14A | 0.9600 |
C4—C8 | 1.3928 (19) | C14—H14B | 0.9600 |
C4—C1 | 1.492 (11) | C14—H14C | 0.9600 |
C4—C1' | 1.492 (15) | C15—H15A | 0.9600 |
C5—O2 | 1.3562 (17) | C15—H15B | 0.9600 |
C5—C11 | 1.388 (2) | C15—H15C | 0.9600 |
C1—O1 | 1.207 (16) | C16—H16A | 0.9600 |
C1—C2 | 1.509 (12) | C16—H16B | 0.9600 |
C2—H2A | 0.9700 | C16—H16C | 0.9600 |
C2—H2B | 0.9700 | C17—O4 | 1.2310 (15) |
C6—H6A | 0.9600 | C17—N2 | 1.3572 (17) |
C6—H6B | 0.9600 | C17—C18 | 1.5016 (19) |
C6—H6C | 0.9600 | C18—C19 | 1.3896 (19) |
C7—H7A | 0.9600 | C18—C23 | 1.3898 (19) |
C7—H7B | 0.9600 | C19—C20 | 1.387 (2) |
C7—H7C | 0.9600 | C19—H19 | 0.9300 |
C1'—O1' | 1.186 (19) | C20—C21 | 1.386 (2) |
C1'—C2' | 1.495 (15) | C20—C24 | 1.509 (2) |
C2'—H2'1 | 0.9700 | C21—C22 | 1.379 (2) |
C2'—H2'2 | 0.9700 | C21—H21 | 0.9300 |
C7'—H7'1 | 0.9600 | C22—C23 | 1.382 (2) |
C7'—H7'2 | 0.9600 | C22—C25 | 1.512 (2) |
C7'—H7'3 | 0.9600 | C23—H23 | 0.9300 |
C6'—H6'1 | 0.9600 | C24—H24A | 0.9600 |
C6'—H6'2 | 0.9600 | C24—H24B | 0.9600 |
C6'—H6'3 | 0.9600 | C24—H24C | 0.9600 |
C8—C9 | 1.3794 (19) | C25—H25A | 0.9600 |
C8—H8 | 0.9300 | C25—H25B | 0.9600 |
C9—C10 | 1.392 (2) | C25—H25C | 0.9600 |
C9—C12 | 1.4962 (18) | N1—N2 | 1.3924 (15) |
C10—C11 | 1.372 (2) | N1—H1 | 0.862 (17) |
C10—H10 | 0.9300 | ||
C2—C3—O2 | 116.33 (16) | C9—C10—H10 | 119.3 |
C2—C3—C6' | 129.6 (3) | C10—C11—C5 | 120.18 (13) |
O2—C3—C6' | 113.1 (3) | C10—C11—H11 | 119.9 |
C2—C3—C6 | 116.2 (3) | C5—C11—H11 | 119.9 |
O2—C3—C6 | 107.3 (2) | O3—C12—N1 | 122.71 (13) |
C2—C3—C2' | 48.4 (2) | O3—C12—C9 | 122.21 (13) |
O2—C3—C2' | 116.81 (19) | N1—C12—C9 | 115.07 (11) |
C6'—C3—C2' | 114.3 (3) | N2—C13—C15 | 108.69 (13) |
C6—C3—C2' | 135.4 (3) | N2—C13—C16 | 109.02 (12) |
C2—C3—C7 | 111.2 (3) | C15—C13—C16 | 112.19 (14) |
O2—C3—C7 | 96.03 (19) | N2—C13—C14 | 108.80 (12) |
C6'—C3—C7 | 72.1 (4) | C15—C13—C14 | 108.68 (15) |
C6—C3—C7 | 107.7 (3) | C16—C13—C14 | 109.40 (15) |
C2'—C3—C7 | 62.9 (3) | C13—C14—H14A | 109.5 |
C2—C3—C7' | 57.5 (2) | C13—C14—H14B | 109.5 |
O2—C3—C7' | 96.6 (2) | H14A—C14—H14B | 109.5 |
C6'—C3—C7' | 108.0 (4) | C13—C14—H14C | 109.5 |
C6—C3—C7' | 73.9 (3) | H14A—C14—H14C | 109.5 |
C2'—C3—C7' | 105.9 (3) | H14B—C14—H14C | 109.5 |
C7—C3—C7' | 166.1 (3) | C13—C15—H15A | 109.5 |
C5—C4—C8 | 119.40 (13) | C13—C15—H15B | 109.5 |
C5—C4—C1 | 119.3 (5) | H15A—C15—H15B | 109.5 |
C8—C4—C1 | 120.5 (5) | C13—C15—H15C | 109.5 |
C5—C4—C1' | 119.5 (6) | H15A—C15—H15C | 109.5 |
C8—C4—C1' | 119.8 (6) | H15B—C15—H15C | 109.5 |
O2—C5—C11 | 117.17 (13) | C13—C16—H16A | 109.5 |
O2—C5—C4 | 123.34 (13) | C13—C16—H16B | 109.5 |
C11—C5—C4 | 119.48 (13) | H16A—C16—H16B | 109.5 |
O1—C1—C4 | 120.5 (10) | C13—C16—H16C | 109.5 |
O1—C1—C2 | 125.0 (10) | H16A—C16—H16C | 109.5 |
C4—C1—C2 | 114.3 (8) | H16B—C16—H16C | 109.5 |
C3—C2—C1 | 115.7 (4) | O4—C17—N2 | 120.62 (12) |
C3—C2—H2A | 108.4 | O4—C17—C18 | 119.25 (12) |
C1—C2—H2A | 108.4 | N2—C17—C18 | 120.08 (11) |
C3—C2—H2B | 108.4 | C19—C18—C23 | 119.26 (13) |
C1—C2—H2B | 108.4 | C19—C18—C17 | 125.24 (12) |
H2A—C2—H2B | 107.4 | C23—C18—C17 | 115.41 (12) |
C3—C6—H6A | 109.5 | C20—C19—C18 | 120.35 (13) |
C3—C6—H6B | 109.5 | C20—C19—H19 | 119.8 |
C3—C6—H6C | 109.5 | C18—C19—H19 | 119.8 |
C3—C7—H7A | 109.5 | C21—C20—C19 | 118.65 (14) |
C3—C7—H7B | 109.5 | C21—C20—C24 | 119.92 (15) |
C3—C7—H7C | 109.5 | C19—C20—C24 | 121.42 (14) |
O1'—C1'—C4 | 125.0 (12) | C22—C21—C20 | 122.29 (14) |
O1'—C1'—C2' | 118.7 (12) | C22—C21—H21 | 118.9 |
C4—C1'—C2' | 116.2 (10) | C20—C21—H21 | 118.9 |
C1'—C2'—C3 | 112.6 (6) | C21—C22—C23 | 118.06 (14) |
C1'—C2'—H2'1 | 109.1 | C21—C22—C25 | 120.98 (15) |
C3—C2'—H2'1 | 109.1 | C23—C22—C25 | 120.94 (15) |
C1'—C2'—H2'2 | 109.1 | C22—C23—C18 | 121.33 (13) |
C3—C2'—H2'2 | 109.1 | C22—C23—H23 | 119.3 |
H2'1—C2'—H2'2 | 107.8 | C18—C23—H23 | 119.3 |
C3—C7'—H7'1 | 109.5 | C20—C24—H24A | 109.5 |
C3—C7'—H7'2 | 109.5 | C20—C24—H24B | 109.5 |
H7'1—C7'—H7'2 | 109.5 | H24A—C24—H24B | 109.5 |
C3—C7'—H7'3 | 109.5 | C20—C24—H24C | 109.5 |
H7'1—C7'—H7'3 | 109.5 | H24A—C24—H24C | 109.5 |
H7'2—C7'—H7'3 | 109.5 | H24B—C24—H24C | 109.5 |
C3—C6'—H6'1 | 109.5 | C22—C25—H25A | 109.5 |
C3—C6'—H6'2 | 109.5 | C22—C25—H25B | 109.5 |
H6'1—C6'—H6'2 | 109.5 | H25A—C25—H25B | 109.5 |
C3—C6'—H6'3 | 109.5 | C22—C25—H25C | 109.5 |
H6'1—C6'—H6'3 | 109.5 | H25A—C25—H25C | 109.5 |
H6'2—C6'—H6'3 | 109.5 | H25B—C25—H25C | 109.5 |
C9—C8—C4 | 121.44 (13) | C12—N1—N2 | 120.89 (11) |
C9—C8—H8 | 119.3 | C12—N1—H1 | 123.0 (11) |
C4—C8—H8 | 119.3 | N2—N1—H1 | 115.2 (11) |
C8—C9—C10 | 118.11 (12) | C17—N2—N1 | 119.06 (11) |
C8—C9—C12 | 123.42 (12) | C17—N2—C13 | 122.53 (11) |
C10—C9—C12 | 118.41 (12) | N1—N2—C13 | 117.73 (10) |
C11—C10—C9 | 121.39 (13) | C5—O2—C3 | 119.03 (12) |
C11—C10—H10 | 119.3 | ||
C8—C4—C5—O2 | 178.51 (15) | C4—C5—C11—C10 | 1.2 (2) |
C1—C4—C5—O2 | 8.4 (4) | C8—C9—C12—O3 | 159.80 (15) |
C1'—C4—C5—O2 | −14.6 (4) | C10—C9—C12—O3 | −17.1 (2) |
C8—C4—C5—C11 | −0.8 (2) | C8—C9—C12—N1 | −20.8 (2) |
C1—C4—C5—C11 | −170.9 (4) | C10—C9—C12—N1 | 162.30 (13) |
C1'—C4—C5—C11 | 166.0 (4) | O4—C17—C18—C19 | −134.18 (14) |
C5—C4—C1—O1 | 179.1 (7) | N2—C17—C18—C19 | 48.51 (19) |
C8—C4—C1—O1 | 9.2 (9) | O4—C17—C18—C23 | 42.43 (18) |
C1'—C4—C1—O1 | −85 (3) | N2—C17—C18—C23 | −134.88 (13) |
C5—C4—C1—C2 | 5.0 (7) | C23—C18—C19—C20 | 1.9 (2) |
C8—C4—C1—C2 | −164.9 (4) | C17—C18—C19—C20 | 178.41 (13) |
C1'—C4—C1—C2 | 101 (3) | C18—C19—C20—C21 | 0.0 (2) |
O2—C3—C2—C1 | 41.7 (5) | C18—C19—C20—C24 | −179.00 (15) |
C6'—C3—C2—C1 | −150.7 (6) | C19—C20—C21—C22 | −1.9 (2) |
C6—C3—C2—C1 | 169.6 (5) | C24—C20—C21—C22 | 177.18 (17) |
C2'—C3—C2—C1 | −61.8 (5) | C20—C21—C22—C23 | 1.7 (2) |
C7—C3—C2—C1 | −66.8 (5) | C20—C21—C22—C25 | −177.15 (17) |
C7'—C3—C2—C1 | 122.4 (5) | C21—C22—C23—C18 | 0.4 (2) |
O1—C1—C2—C3 | 156.6 (8) | C25—C22—C23—C18 | 179.19 (16) |
C4—C1—C2—C3 | −29.6 (7) | C19—C18—C23—C22 | −2.1 (2) |
C5—C4—C1'—O1' | 177.5 (8) | C17—C18—C23—C22 | −178.97 (13) |
C8—C4—C1'—O1' | −15.7 (11) | O3—C12—N1—N2 | −11.2 (2) |
C1—C4—C1'—O1' | 82 (3) | C9—C12—N1—N2 | 169.32 (11) |
C5—C4—C1'—C2' | −3.3 (8) | O4—C17—N2—N1 | −175.61 (12) |
C8—C4—C1'—C2' | 163.5 (4) | C18—C17—N2—N1 | 1.66 (18) |
C1—C4—C1'—C2' | −99 (3) | O4—C17—N2—C13 | −5.3 (2) |
O1'—C1'—C2'—C3 | −151.4 (8) | C18—C17—N2—C13 | 171.97 (12) |
C4—C1'—C2'—C3 | 29.4 (8) | C12—N1—N2—C17 | 84.40 (16) |
C2—C3—C2'—C1' | 61.4 (5) | C12—N1—N2—C13 | −86.37 (16) |
O2—C3—C2'—C1' | −41.0 (6) | C15—C13—N2—C17 | 61.36 (17) |
C6'—C3—C2'—C1' | −176.2 (6) | C16—C13—N2—C17 | −61.21 (18) |
C6—C3—C2'—C1' | 148.0 (6) | C14—C13—N2—C17 | 179.54 (14) |
C7—C3—C2'—C1' | −123.8 (6) | C15—C13—N2—N1 | −128.22 (13) |
C7'—C3—C2'—C1' | 65.1 (6) | C16—C13—N2—N1 | 109.21 (14) |
C5—C4—C8—C9 | 0.1 (2) | C14—C13—N2—N1 | −10.03 (19) |
C1—C4—C8—C9 | 170.0 (4) | C11—C5—O2—C3 | −177.56 (14) |
C1'—C4—C8—C9 | −166.8 (4) | C4—C5—O2—C3 | 3.1 (2) |
C4—C8—C9—C10 | 0.3 (2) | C2—C3—O2—C5 | −28.9 (3) |
C4—C8—C9—C12 | −176.65 (14) | C6'—C3—O2—C5 | 161.4 (4) |
C8—C9—C10—C11 | 0.1 (2) | C6—C3—O2—C5 | −160.9 (3) |
C12—C9—C10—C11 | 177.22 (13) | C2'—C3—O2—C5 | 25.7 (3) |
C9—C10—C11—C5 | −0.9 (2) | C7—C3—O2—C5 | 88.4 (2) |
O2—C5—C11—C10 | −178.14 (14) | C7'—C3—O2—C5 | −85.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16C···O4 | 0.96 | 2.39 | 3.007 (2) | 121 |
C15—H15A···O4 | 0.96 | 2.36 | 2.918 (2) | 117 |
C8—H8···O4i | 0.93 | 2.48 | 3.3214 (18) | 151 |
N1—H1···O4i | 0.862 (17) | 2.096 (18) | 2.9442 (15) | 167.8 (15) |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C25H30N2O4 |
Mr | 422.51 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 297 |
a, b, c (Å) | 14.1260 (12), 10.6964 (9), 15.4370 (13) |
β (°) | 96.426 (2) |
V (Å3) | 2317.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2005) |
Tmin, Tmax | 0.976, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13199, 5043, 3983 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.142, 1.04 |
No. of reflections | 5043 |
No. of parameters | 338 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.17 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16C···O4 | 0.96 | 2.39 | 3.007 (2) | 121 |
C15—H15A···O4 | 0.96 | 2.36 | 2.918 (2) | 117 |
C8—H8···O4i | 0.93 | 2.48 | 3.3214 (18) | 151 |
N1—H1···O4i | 0.862 (17) | 2.096 (18) | 2.9442 (15) | 167.8 (15) |
Symmetry code: (i) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
The authors acknowledge financial support from the Science Foundation of the Southern Medical University for New Excellent Talents (No. B1000374).
References
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mao, C. H., Wang, K. L., Wang, Z. M., Qu, X., Huang, R. & Wang, Q. M. (2008). Bioorg. Med. Chem. 16, 488–494. Web of Science CrossRef PubMed CAS Google Scholar
Sawada, Y., Yanai, T., Nakagawa, H., Kajino, F., Tsukamoto, Y., Yokoi, S., Yanagi, M., Sugizaki, H., Toya, T. & Masui, A. (2003). Pest Manag. Sci. 59, 49–57. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2005). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, P.-L., Huang, W. & Yang, G.-F. (2005). Acta Cryst. E61, o2139–o2141. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhao, P. L., Li, J. & Yang, G. F. (2007). Bioorg. Med. Chem. 15, 1888–1895. Web of Science CrossRef PubMed CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Dibenzoylhydrazines are well known as nonsteroidal ecdysone agonists that have the potential to control the Lepidopteran pests while exerting only a low toxicity against non-target insects. (Sawada et al., 2003). While chroman derivatives also have broad-spectrum biological activity. Hence, to search for novel lead compounds for crop protection, The title compound, (I), was designed and synthesized in our laboratory. In this paper, we present the X-ray crystallographic analysis of (I).
As shown in Fig. 1, the six-membered heterocyclic ring adopts a half-chair conformation. the dihedral angle between the phenyl ring and the benzene ring of the chromanone is 58.14 (2)°. The six-memebered heterocyclic ring is disordered over two sites with occupancies of 0.553 (4) and 0.447 (4). The steric size of the N-tert-butyl group causes the 3,5-dimethylphenyl group to be directed away from it.
One intermolecular N—H···O hydrogen bond and one intermolecular C—H···O hydrogen bonds exist in the crystal structure (Table 1 and Fig. 2), atoms N1 and C8 in the molecule act as donors, via the H atoms H1 and H8, to the O4 of a adjacent molecule(Tabel 2). As a result, an seven-membered ring is formed between molecules (Fig. 2). No π-π stacking interactions are observed in the crystal structure.