Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039097/wn2002sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039097/wn2002Isup2.hkl |
CCDC reference: 296695
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.008 Å
- R factor = 0.051
- wR factor = 0.146
- Data-to-parameter ratio = 6.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 6.73 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C31 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8
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 25.00 From the CIF: _reflns_number_total 2820 Count of symmetry unique reflns 2852 Completeness (_total/calc) 98.88% 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
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 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
An anhydrous ethanol solution of 4-ethoxy-3-methoxybenzaldehyde (1.80 g, 10 mmol) was added to an anhydrous ethanol solution of 1-(4-nitrophenyl)hydrazine (1.53 g, 10 mmol) and the mixture stirred at 350 K for 5 h under nitrogen. A yellow precipitate appeared which was isolated, recrystallized from acetonitrile, and then dried in a vacuum to give the pure compound in 83% yield. Yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an acetonitrile solution.
The H atoms were included in calculated positions and refined using a riding-model approximation. Constrained C—H and N—H bond lengths and Uiso(H) parameters: 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic CH; 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene CH2; 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl CH3; 0.86 Å and Uiso(H) = 1.2Ueq(N) for imino NH. In the absence of significant anomalous dispersion effects, Friedel pairs were averaged.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.
Fig. 1. The structure of (I), with displacement ellipsoids for non-H atoms drawn at the 30% probability level. | |
Fig. 2. Packing diagram for (I), with H bonds drawn as dashed lines. |
C16H17N3O4 | F(000) = 664 |
Mr = 315.33 | Dx = 1.324 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 1909 reflections |
a = 7.589 (2) Å | θ = 2.8–22.1° |
b = 23.491 (7) Å | µ = 0.10 mm−1 |
c = 8.929 (2) Å | T = 294 K |
β = 96.287 (5)° | Block, yellow |
V = 1582.2 (7) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2820 independent reflections |
Radiation source: fine-focus sealed tube | 1741 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→6 |
Tmin = 0.962, Tmax = 0.983 | k = −27→27 |
7919 measured reflections | l = −10→10 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.072P)2] where P = (Fo2 + 2Fc2)/3 |
2820 reflections | (Δ/σ)max = 0.021 |
419 parameters | Δρmax = 0.31 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C16H17N3O4 | V = 1582.2 (7) Å3 |
Mr = 315.33 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.589 (2) Å | µ = 0.10 mm−1 |
b = 23.491 (7) Å | T = 294 K |
c = 8.929 (2) Å | 0.22 × 0.20 × 0.18 mm |
β = 96.287 (5)° |
Bruker SMART APEX CCD area-detector diffractometer | 2820 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1741 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.983 | Rint = 0.044 |
7919 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.31 e Å−3 |
2820 reflections | Δρmin = −0.21 e Å−3 |
419 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 > 2σ(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 | ||
O1 | 0.8873 (6) | 0.24430 (17) | 0.4654 (5) | 0.0704 (12) | |
O2 | 1.1357 (5) | 0.30101 (18) | 0.3632 (5) | 0.0658 (11) | |
O3 | −0.2396 (6) | 0.2677 (2) | 0.9379 (7) | 0.0978 (16) | |
O4 | −0.2808 (8) | 0.3407 (2) | 1.0737 (7) | 0.117 (2) | |
O5 | 0.4675 (6) | −0.00804 (16) | 0.9106 (4) | 0.0666 (11) | |
O6 | 0.5682 (5) | 0.05007 (16) | 1.1448 (4) | 0.0559 (10) | |
O7 | −0.1223 (9) | 0.0948 (2) | −0.2717 (6) | 0.113 (2) | |
O8 | −0.0312 (7) | 0.0137 (2) | −0.1896 (5) | 0.0936 (16) | |
N1 | 0.5232 (6) | 0.38797 (19) | 0.7327 (5) | 0.0520 (12) | |
N2 | 0.4168 (6) | 0.41536 (19) | 0.8219 (5) | 0.0548 (12) | |
H2 | 0.4413 | 0.4497 | 0.8503 | 0.066* | |
N3 | −0.1920 (8) | 0.3142 (3) | 0.9913 (7) | 0.0760 (16) | |
N4 | 0.2437 (6) | 0.13593 (19) | 0.5003 (5) | 0.0513 (12) | |
N5 | 0.1626 (6) | 0.16531 (19) | 0.3824 (5) | 0.0570 (13) | |
H5 | 0.1463 | 0.2013 | 0.3916 | 0.068* | |
N6 | −0.0572 (8) | 0.0645 (3) | −0.1722 (6) | 0.0689 (15) | |
C1 | 0.7653 (7) | 0.3287 (2) | 0.5710 (6) | 0.0495 (13) | |
H1 | 0.6744 | 0.3079 | 0.6065 | 0.059* | |
C2 | 0.8847 (8) | 0.3021 (2) | 0.4928 (6) | 0.0520 (14) | |
C3 | 1.0213 (8) | 0.3324 (2) | 0.4362 (6) | 0.0518 (14) | |
C4 | 1.0322 (8) | 0.3903 (2) | 0.4600 (7) | 0.0592 (16) | |
H4 | 1.1203 | 0.4115 | 0.4214 | 0.071* | |
C5 | 0.9113 (8) | 0.4164 (2) | 0.5416 (7) | 0.0582 (15) | |
H5A | 0.9208 | 0.4554 | 0.5584 | 0.070* | |
C6 | 0.7775 (7) | 0.3873 (2) | 0.5989 (6) | 0.0493 (14) | |
C7 | 0.6565 (7) | 0.4152 (2) | 0.6905 (6) | 0.0500 (13) | |
H7 | 0.6754 | 0.4530 | 0.7189 | 0.060* | |
C8 | 0.2718 (7) | 0.3890 (2) | 0.8668 (5) | 0.0443 (13) | |
C9 | 0.2276 (8) | 0.3330 (2) | 0.8240 (6) | 0.0519 (14) | |
H9 | 0.3008 | 0.3123 | 0.7671 | 0.062* | |
C10 | 0.0782 (8) | 0.3091 (2) | 0.8655 (7) | 0.0578 (16) | |
H10 | 0.0483 | 0.2721 | 0.8355 | 0.069* | |
C11 | −0.0302 (8) | 0.3388 (2) | 0.9516 (6) | 0.0558 (15) | |
C12 | 0.0137 (8) | 0.3935 (3) | 0.9973 (7) | 0.0567 (15) | |
H12 | −0.0588 | 0.4134 | 1.0565 | 0.068* | |
C13 | 0.1628 (8) | 0.4183 (2) | 0.9561 (6) | 0.0523 (14) | |
H13 | 0.1923 | 0.4552 | 0.9878 | 0.063* | |
C14 | 0.7678 (9) | 0.2091 (3) | 0.5353 (8) | 0.0741 (19) | |
H14A | 0.7851 | 0.2147 | 0.6424 | 0.111* | |
H14B | 0.7893 | 0.1700 | 0.5127 | 0.111* | |
H14C | 0.6481 | 0.2189 | 0.4980 | 0.111* | |
C15 | 1.2930 (8) | 0.3273 (3) | 0.3220 (7) | 0.0691 (18) | |
H15A | 1.3643 | 0.3416 | 0.4108 | 0.083* | |
H15B | 1.2629 | 0.3589 | 0.2541 | 0.083* | |
C16 | 1.3937 (9) | 0.2830 (4) | 0.2459 (8) | 0.096 (3) | |
H16A | 1.4302 | 0.2533 | 0.3163 | 0.144* | |
H16B | 1.4963 | 0.3000 | 0.2102 | 0.144* | |
H16C | 1.3190 | 0.2673 | 0.1623 | 0.144* | |
C17 | 0.4268 (7) | 0.1661 (2) | 0.8828 (6) | 0.0544 (14) | |
H17 | 0.4189 | 0.2056 | 0.8799 | 0.065* | |
C18 | 0.4976 (8) | 0.1399 (2) | 1.0161 (6) | 0.0528 (14) | |
H18 | 0.5366 | 0.1617 | 1.1003 | 0.063* | |
C19 | 0.5091 (7) | 0.0814 (2) | 1.0216 (5) | 0.0428 (13) | |
C20 | 0.4521 (7) | 0.0498 (2) | 0.8919 (6) | 0.0447 (13) | |
C21 | 0.3839 (7) | 0.0760 (2) | 0.7615 (6) | 0.0457 (13) | |
H21 | 0.3478 | 0.0544 | 0.6765 | 0.055* | |
C22 | 0.3683 (7) | 0.1357 (2) | 0.7557 (6) | 0.0485 (14) | |
C23 | 0.2874 (7) | 0.1635 (2) | 0.6196 (6) | 0.0495 (14) | |
H23 | 0.2676 | 0.2025 | 0.6207 | 0.059* | |
C24 | 0.1055 (7) | 0.1394 (2) | 0.2486 (6) | 0.0462 (13) | |
C25 | 0.1382 (7) | 0.0813 (2) | 0.2251 (6) | 0.0483 (14) | |
H25 | 0.1959 | 0.0592 | 0.3018 | 0.058* | |
C26 | 0.0837 (8) | 0.0579 (2) | 0.0875 (6) | 0.0545 (15) | |
H26 | 0.1065 | 0.0197 | 0.0709 | 0.065* | |
C27 | −0.0029 (8) | 0.0893 (2) | −0.0253 (6) | 0.0491 (14) | |
C28 | −0.0387 (8) | 0.1466 (2) | −0.0040 (7) | 0.0560 (15) | |
H28 | −0.0981 | 0.1682 | −0.0810 | 0.067* | |
C29 | 0.0154 (7) | 0.1704 (2) | 0.1326 (6) | 0.0532 (14) | |
H29 | −0.0089 | 0.2086 | 0.1482 | 0.064* | |
C30 | 0.4288 (12) | −0.0428 (3) | 0.7795 (7) | 0.088 (2) | |
H30A | 0.3054 | −0.0393 | 0.7431 | 0.132* | |
H30B | 0.4553 | −0.0818 | 0.8048 | 0.132* | |
H30C | 0.4995 | −0.0306 | 0.7027 | 0.132* | |
C31 | 0.6331 (9) | 0.0801 (3) | 1.2804 (6) | 0.0589 (16) | |
H31A | 0.5400 | 0.1037 | 1.3137 | 0.071* | |
H31B | 0.7316 | 0.1044 | 1.2618 | 0.071* | |
C32 | 0.6916 (11) | 0.0371 (3) | 1.3976 (7) | 0.095 (3) | |
H32A | 0.5914 | 0.0152 | 1.4208 | 0.142* | |
H32B | 0.7436 | 0.0561 | 1.4868 | 0.142* | |
H32C | 0.7777 | 0.0123 | 1.3608 | 0.142* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.080 (3) | 0.042 (2) | 0.095 (3) | −0.006 (2) | 0.035 (2) | −0.003 (2) |
O2 | 0.063 (3) | 0.063 (3) | 0.077 (3) | 0.000 (2) | 0.029 (2) | 0.002 (2) |
O3 | 0.084 (3) | 0.054 (3) | 0.158 (5) | −0.017 (3) | 0.023 (3) | 0.003 (3) |
O4 | 0.111 (4) | 0.102 (4) | 0.151 (5) | −0.025 (3) | 0.076 (4) | −0.017 (4) |
O5 | 0.105 (3) | 0.042 (2) | 0.049 (2) | 0.008 (2) | −0.012 (2) | −0.0050 (19) |
O6 | 0.073 (3) | 0.055 (2) | 0.038 (2) | 0.002 (2) | −0.0051 (19) | −0.0018 (18) |
O7 | 0.174 (6) | 0.082 (4) | 0.071 (3) | 0.013 (4) | −0.038 (4) | 0.007 (3) |
O8 | 0.145 (5) | 0.056 (3) | 0.077 (3) | −0.009 (3) | −0.004 (3) | −0.009 (3) |
N1 | 0.054 (3) | 0.045 (3) | 0.056 (3) | 0.007 (2) | 0.004 (2) | −0.006 (2) |
N2 | 0.057 (3) | 0.043 (3) | 0.066 (3) | −0.001 (2) | 0.013 (3) | −0.013 (2) |
N3 | 0.068 (4) | 0.065 (4) | 0.099 (5) | −0.002 (3) | 0.027 (3) | 0.013 (3) |
N4 | 0.061 (3) | 0.048 (3) | 0.046 (3) | 0.010 (2) | 0.012 (2) | 0.015 (2) |
N5 | 0.077 (3) | 0.043 (3) | 0.050 (3) | 0.016 (2) | 0.004 (2) | 0.002 (2) |
N6 | 0.080 (4) | 0.066 (4) | 0.059 (3) | −0.012 (3) | 0.001 (3) | 0.002 (3) |
C1 | 0.052 (3) | 0.042 (3) | 0.056 (3) | −0.003 (3) | 0.014 (3) | 0.002 (3) |
C2 | 0.060 (4) | 0.034 (3) | 0.063 (4) | −0.003 (3) | 0.011 (3) | 0.004 (3) |
C3 | 0.054 (3) | 0.046 (4) | 0.057 (4) | 0.004 (3) | 0.010 (3) | 0.000 (3) |
C4 | 0.059 (4) | 0.046 (4) | 0.074 (4) | −0.009 (3) | 0.012 (3) | 0.009 (3) |
C5 | 0.062 (4) | 0.037 (3) | 0.076 (4) | −0.003 (3) | 0.007 (3) | −0.006 (3) |
C6 | 0.052 (3) | 0.040 (3) | 0.056 (3) | 0.002 (3) | 0.002 (3) | 0.001 (3) |
C7 | 0.053 (3) | 0.041 (3) | 0.055 (3) | 0.003 (3) | 0.002 (3) | −0.006 (3) |
C8 | 0.048 (3) | 0.041 (3) | 0.042 (3) | −0.001 (3) | −0.002 (2) | 0.004 (2) |
C9 | 0.062 (4) | 0.033 (3) | 0.061 (4) | 0.006 (3) | 0.008 (3) | −0.005 (3) |
C10 | 0.067 (4) | 0.033 (3) | 0.073 (4) | −0.003 (3) | 0.003 (3) | 0.003 (3) |
C11 | 0.064 (4) | 0.043 (4) | 0.060 (4) | 0.007 (3) | 0.004 (3) | 0.004 (3) |
C12 | 0.054 (4) | 0.057 (4) | 0.060 (4) | 0.003 (3) | 0.010 (3) | −0.001 (3) |
C13 | 0.060 (4) | 0.039 (3) | 0.058 (3) | 0.005 (3) | 0.004 (3) | −0.013 (3) |
C14 | 0.088 (5) | 0.043 (4) | 0.093 (5) | −0.011 (3) | 0.019 (4) | 0.001 (3) |
C15 | 0.056 (4) | 0.086 (5) | 0.069 (4) | −0.004 (3) | 0.021 (3) | 0.022 (4) |
C16 | 0.070 (5) | 0.124 (7) | 0.101 (5) | 0.004 (5) | 0.045 (4) | 0.009 (5) |
C17 | 0.068 (4) | 0.036 (3) | 0.059 (4) | 0.008 (3) | 0.007 (3) | 0.000 (3) |
C18 | 0.065 (4) | 0.045 (3) | 0.046 (3) | −0.002 (3) | −0.003 (3) | −0.008 (3) |
C19 | 0.045 (3) | 0.046 (3) | 0.038 (3) | 0.000 (2) | 0.004 (2) | 0.002 (2) |
C20 | 0.054 (3) | 0.035 (3) | 0.046 (3) | 0.000 (3) | 0.008 (3) | 0.001 (3) |
C21 | 0.055 (4) | 0.040 (3) | 0.043 (3) | 0.000 (2) | 0.007 (3) | −0.004 (2) |
C22 | 0.058 (4) | 0.046 (4) | 0.043 (3) | 0.001 (3) | 0.011 (3) | 0.004 (3) |
C23 | 0.058 (4) | 0.042 (3) | 0.050 (3) | 0.012 (3) | 0.014 (3) | 0.004 (3) |
C24 | 0.045 (3) | 0.050 (4) | 0.044 (3) | 0.004 (3) | 0.007 (3) | 0.009 (3) |
C25 | 0.051 (3) | 0.039 (3) | 0.055 (4) | 0.007 (3) | 0.007 (3) | 0.008 (3) |
C26 | 0.060 (4) | 0.050 (4) | 0.053 (3) | 0.000 (3) | 0.002 (3) | 0.004 (3) |
C27 | 0.058 (4) | 0.045 (4) | 0.044 (3) | −0.004 (3) | 0.004 (3) | 0.003 (3) |
C28 | 0.063 (4) | 0.058 (4) | 0.047 (3) | 0.000 (3) | 0.005 (3) | 0.011 (3) |
C29 | 0.061 (4) | 0.049 (3) | 0.051 (3) | 0.015 (3) | 0.012 (3) | 0.006 (3) |
C30 | 0.157 (7) | 0.041 (4) | 0.062 (4) | 0.013 (4) | −0.005 (4) | −0.011 (3) |
C31 | 0.059 (4) | 0.062 (4) | 0.055 (4) | −0.009 (3) | 0.002 (3) | −0.010 (3) |
C32 | 0.137 (7) | 0.081 (5) | 0.057 (4) | −0.018 (5) | −0.032 (4) | 0.003 (4) |
O1—C2 | 1.380 (6) | C12—H12 | 0.9300 |
O1—C14 | 1.421 (7) | C13—H13 | 0.9300 |
O2—C3 | 1.358 (6) | C14—H14A | 0.9600 |
O2—C15 | 1.428 (7) | C14—H14B | 0.9600 |
O3—N3 | 1.231 (7) | C14—H14C | 0.9600 |
O4—N3 | 1.221 (7) | C15—C16 | 1.498 (9) |
O5—C20 | 1.372 (6) | C15—H15A | 0.9700 |
O5—C30 | 1.431 (7) | C15—H15B | 0.9700 |
O6—C19 | 1.358 (6) | C16—H16A | 0.9600 |
O6—C31 | 1.440 (6) | C16—H16B | 0.9600 |
O7—N6 | 1.201 (6) | C16—H16C | 0.9600 |
O8—N6 | 1.222 (6) | C17—C22 | 1.374 (8) |
N1—C7 | 1.288 (7) | C17—C18 | 1.394 (7) |
N1—N2 | 1.356 (6) | C17—H17 | 0.9300 |
N2—C8 | 1.361 (7) | C18—C19 | 1.379 (7) |
N2—H2 | 0.8600 | C18—H18 | 0.9300 |
N3—C11 | 1.436 (8) | C19—C20 | 1.403 (7) |
N4—C23 | 1.259 (6) | C20—C21 | 1.368 (7) |
N4—N5 | 1.350 (6) | C21—C22 | 1.406 (7) |
N5—C24 | 1.368 (7) | C21—H21 | 0.9300 |
N5—H5 | 0.8600 | C22—C23 | 1.455 (7) |
N6—C27 | 1.453 (7) | C23—H23 | 0.9300 |
C1—C2 | 1.355 (8) | C24—C29 | 1.383 (7) |
C1—C6 | 1.400 (7) | C24—C25 | 1.408 (7) |
C1—H1 | 0.9300 | C25—C26 | 1.367 (7) |
C2—C3 | 1.397 (8) | C25—H25 | 0.9300 |
C3—C4 | 1.378 (7) | C26—C27 | 1.358 (7) |
C4—C5 | 1.377 (8) | C26—H26 | 0.9300 |
C4—H4 | 0.9300 | C27—C28 | 1.391 (7) |
C5—C6 | 1.368 (8) | C28—C29 | 1.363 (8) |
C5—H5A | 0.9300 | C28—H28 | 0.9300 |
C6—C7 | 1.451 (8) | C29—H29 | 0.9300 |
C7—H7 | 0.9300 | C30—H30A | 0.9600 |
C8—C13 | 1.392 (7) | C30—H30B | 0.9600 |
C8—C9 | 1.401 (7) | C30—H30C | 0.9600 |
C9—C10 | 1.353 (8) | C31—C32 | 1.485 (8) |
C9—H9 | 0.9300 | C31—H31A | 0.9700 |
C10—C11 | 1.377 (8) | C31—H31B | 0.9700 |
C10—H10 | 0.9300 | C32—H32A | 0.9600 |
C11—C12 | 1.377 (8) | C32—H32B | 0.9600 |
C12—C13 | 1.360 (8) | C32—H32C | 0.9600 |
C2—O1—C14 | 118.1 (5) | O2—C15—H15B | 110.2 |
C3—O2—C15 | 119.0 (5) | C16—C15—H15B | 110.2 |
C20—O5—C30 | 117.3 (4) | H15A—C15—H15B | 108.5 |
C19—O6—C31 | 117.9 (4) | C15—C16—H16A | 109.5 |
C7—N1—N2 | 118.2 (4) | C15—C16—H16B | 109.5 |
N1—N2—C8 | 120.7 (4) | H16A—C16—H16B | 109.5 |
N1—N2—H2 | 119.7 | C15—C16—H16C | 109.5 |
C8—N2—H2 | 119.7 | H16A—C16—H16C | 109.5 |
O4—N3—O3 | 121.9 (6) | H16B—C16—H16C | 109.5 |
O4—N3—C11 | 119.1 (6) | C22—C17—C18 | 122.4 (5) |
O3—N3—C11 | 119.0 (6) | C22—C17—H17 | 118.8 |
C23—N4—N5 | 116.9 (5) | C18—C17—H17 | 118.8 |
N4—N5—C24 | 121.9 (5) | C19—C18—C17 | 119.2 (5) |
N4—N5—H5 | 119.1 | C19—C18—H18 | 120.4 |
C24—N5—H5 | 119.1 | C17—C18—H18 | 120.4 |
O7—N6—O8 | 122.9 (6) | O6—C19—C18 | 125.7 (5) |
O7—N6—C27 | 118.9 (6) | O6—C19—C20 | 115.3 (5) |
O8—N6—C27 | 118.2 (6) | C18—C19—C20 | 119.1 (5) |
C2—C1—C6 | 120.7 (5) | C21—C20—O5 | 124.7 (5) |
C2—C1—H1 | 119.7 | C21—C20—C19 | 121.2 (5) |
C6—C1—H1 | 119.7 | O5—C20—C19 | 114.1 (5) |
C1—C2—O1 | 124.7 (5) | C20—C21—C22 | 120.2 (5) |
C1—C2—C3 | 121.0 (5) | C20—C21—H21 | 119.9 |
O1—C2—C3 | 114.3 (5) | C22—C21—H21 | 119.9 |
O2—C3—C4 | 125.4 (5) | C17—C22—C21 | 118.0 (5) |
O2—C3—C2 | 115.9 (5) | C17—C22—C23 | 121.7 (5) |
C4—C3—C2 | 118.8 (5) | C21—C22—C23 | 120.3 (5) |
C5—C4—C3 | 119.3 (6) | N4—C23—C22 | 121.6 (5) |
C5—C4—H4 | 120.4 | N4—C23—H23 | 119.2 |
C3—C4—H4 | 120.4 | C22—C23—H23 | 119.2 |
C4—C5—C6 | 122.7 (5) | N5—C24—C29 | 120.2 (5) |
C4—C5—H5A | 118.7 | N5—C24—C25 | 121.1 (5) |
C6—C5—H5A | 118.7 | C29—C24—C25 | 118.6 (5) |
C5—C6—C1 | 117.5 (5) | C26—C25—C24 | 118.8 (5) |
C5—C6—C7 | 121.8 (5) | C26—C25—H25 | 120.6 |
C1—C6—C7 | 120.7 (5) | C24—C25—H25 | 120.6 |
N1—C7—C6 | 120.4 (5) | C27—C26—C25 | 121.6 (5) |
N1—C7—H7 | 119.8 | C27—C26—H26 | 119.2 |
C6—C7—H7 | 119.8 | C25—C26—H26 | 119.2 |
N2—C8—C13 | 119.6 (5) | C26—C27—C28 | 120.6 (5) |
N2—C8—C9 | 121.6 (5) | C26—C27—N6 | 121.3 (5) |
C13—C8—C9 | 118.8 (5) | C28—C27—N6 | 118.1 (5) |
C10—C9—C8 | 119.9 (5) | C29—C28—C27 | 118.3 (5) |
C10—C9—H9 | 120.1 | C29—C28—H28 | 120.8 |
C8—C9—H9 | 120.1 | C27—C28—H28 | 120.8 |
C9—C10—C11 | 120.8 (5) | C28—C29—C24 | 122.0 (6) |
C9—C10—H10 | 119.6 | C28—C29—H29 | 119.0 |
C11—C10—H10 | 119.6 | C24—C29—H29 | 119.0 |
C12—C11—C10 | 120.0 (6) | O5—C30—H30A | 109.5 |
C12—C11—N3 | 119.2 (6) | O5—C30—H30B | 109.5 |
C10—C11—N3 | 120.8 (6) | H30A—C30—H30B | 109.5 |
C13—C12—C11 | 120.1 (6) | O5—C30—H30C | 109.5 |
C13—C12—H12 | 120.0 | H30A—C30—H30C | 109.5 |
C11—C12—H12 | 120.0 | H30B—C30—H30C | 109.5 |
C12—C13—C8 | 120.5 (5) | O6—C31—C32 | 108.0 (5) |
C12—C13—H13 | 119.8 | O6—C31—H31A | 110.1 |
C8—C13—H13 | 119.8 | C32—C31—H31A | 110.1 |
O1—C14—H14A | 109.5 | O6—C31—H31B | 110.1 |
O1—C14—H14B | 109.5 | C32—C31—H31B | 110.1 |
H14A—C14—H14B | 109.5 | H31A—C31—H31B | 108.4 |
O1—C14—H14C | 109.5 | C31—C32—H32A | 109.5 |
H14A—C14—H14C | 109.5 | C31—C32—H32B | 109.5 |
H14B—C14—H14C | 109.5 | H32A—C32—H32B | 109.5 |
O2—C15—C16 | 107.4 (6) | C31—C32—H32C | 109.5 |
O2—C15—H15A | 110.2 | H32A—C32—H32C | 109.5 |
C16—C15—H15A | 110.2 | H32B—C32—H32C | 109.5 |
C7—N1—N2—C8 | 178.5 (4) | C3—O2—C15—C16 | 179.3 (5) |
C23—N4—N5—C24 | −178.4 (5) | C22—C17—C18—C19 | −0.3 (9) |
C6—C1—C2—O1 | 177.2 (5) | C31—O6—C19—C18 | −3.3 (8) |
C6—C1—C2—C3 | −0.9 (8) | C31—O6—C19—C20 | 178.3 (4) |
C14—O1—C2—C1 | −6.2 (8) | C17—C18—C19—O6 | −177.2 (5) |
C14—O1—C2—C3 | 172.0 (5) | C17—C18—C19—C20 | 1.2 (8) |
C15—O2—C3—C4 | 8.0 (8) | C30—O5—C20—C21 | 7.7 (8) |
C15—O2—C3—C2 | −170.8 (5) | C30—O5—C20—C19 | −173.9 (5) |
C1—C2—C3—O2 | 178.3 (5) | O6—C19—C20—C21 | 177.8 (5) |
O1—C2—C3—O2 | 0.0 (7) | C18—C19—C20—C21 | −0.8 (8) |
C1—C2—C3—C4 | −0.5 (9) | O6—C19—C20—O5 | −0.7 (7) |
O1—C2—C3—C4 | −178.9 (5) | C18—C19—C20—O5 | −179.2 (5) |
O2—C3—C4—C5 | −177.3 (5) | O5—C20—C21—C22 | 177.8 (5) |
C2—C3—C4—C5 | 1.5 (9) | C19—C20—C21—C22 | −0.5 (8) |
C3—C4—C5—C6 | −1.0 (9) | C18—C17—C22—C21 | −1.0 (8) |
C4—C5—C6—C1 | −0.5 (8) | C18—C17—C22—C23 | 177.2 (5) |
C4—C5—C6—C7 | 177.1 (5) | C20—C21—C22—C17 | 1.4 (8) |
C2—C1—C6—C5 | 1.4 (8) | C20—C21—C22—C23 | −176.8 (5) |
C2—C1—C6—C7 | −176.2 (5) | N5—N4—C23—C22 | 177.2 (4) |
N2—N1—C7—C6 | 178.1 (5) | C17—C22—C23—N4 | 175.6 (5) |
C5—C6—C7—N1 | 174.3 (5) | C21—C22—C23—N4 | −6.2 (8) |
C1—C6—C7—N1 | −8.3 (8) | N4—N5—C24—C29 | 177.0 (5) |
N1—N2—C8—C13 | −178.9 (5) | N4—N5—C24—C25 | −3.7 (8) |
N1—N2—C8—C9 | 0.4 (7) | N5—C24—C25—C26 | −177.8 (5) |
N2—C8—C9—C10 | −177.2 (5) | C29—C24—C25—C26 | 1.6 (7) |
C13—C8—C9—C10 | 2.1 (8) | C24—C25—C26—C27 | −1.0 (8) |
C8—C9—C10—C11 | −1.0 (8) | C25—C26—C27—C28 | 0.1 (9) |
C9—C10—C11—C12 | −0.4 (8) | C25—C26—C27—N6 | 178.7 (5) |
C9—C10—C11—N3 | 177.8 (5) | O7—N6—C27—C26 | −174.8 (6) |
O4—N3—C11—C12 | −5.2 (9) | O8—N6—C27—C26 | 3.8 (9) |
O3—N3—C11—C12 | 172.8 (6) | O7—N6—C27—C28 | 3.8 (9) |
O4—N3—C11—C10 | 176.6 (6) | O8—N6—C27—C28 | −177.6 (6) |
O3—N3—C11—C10 | −5.4 (9) | C26—C27—C28—C29 | 0.0 (9) |
C10—C11—C12—C13 | 0.8 (8) | N6—C27—C28—C29 | −178.6 (5) |
N3—C11—C12—C13 | −177.5 (5) | C27—C28—C29—C24 | 0.6 (8) |
C11—C12—C13—C8 | 0.4 (8) | N5—C24—C29—C28 | 177.9 (5) |
N2—C8—C13—C12 | 177.5 (5) | C25—C24—C29—C28 | −1.4 (8) |
C9—C8—C13—C12 | −1.8 (8) | C19—O6—C31—C32 | −179.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O5i | 0.86 | 2.39 | 3.042 (6) | 133 |
N2—H2···O6i | 0.86 | 2.36 | 3.179 (6) | 160 |
N5—H5···O1ii | 0.86 | 2.37 | 2.949 (6) | 125 |
N5—H5···O2ii | 0.86 | 2.36 | 3.198 (7) | 166 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H17N3O4 |
Mr | 315.33 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 294 |
a, b, c (Å) | 7.589 (2), 23.491 (7), 8.929 (2) |
β (°) | 96.287 (5) |
V (Å3) | 1582.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.962, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7919, 2820, 1741 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.146, 1.14 |
No. of reflections | 2820 |
No. of parameters | 419 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.21 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O5i | 0.86 | 2.39 | 3.042 (6) | 133 |
N2—H2···O6i | 0.86 | 2.36 | 3.179 (6) | 160 |
N5—H5···O1ii | 0.86 | 2.37 | 2.949 (6) | 125 |
N5—H5···O2ii | 0.86 | 2.36 | 3.198 (7) | 166 |
Symmetry codes: (i) −x+1, y+1/2, −z+2; (ii) x−1, y, z. |
Metal complexes based on Schiff bases have attracted much attention because of their biological activity (Kahwa et al., 1986). Consequently, a large number of Schiff base derivatives have been synthesized and employed to develop protein and enzyme mimics, such as models to mimic hydrolase in the hydrolysis of p-nitrophenyl picolinate (Li et al., 2005).
In order to investigate their crystal structures, which will provide useful information for the coordination properties of Schiff bases functioning as ligands, in the present study we report the synthesis and molecular structure of the nitrophenylhydrazine Schiff base derivative (I) (Fig. 1).
The asymmetric unit of (I) consists of two independent molecules, which are quite similar to each other. In molecule 1, the vanillin group (C1–C7/O1/O2) is planar, with an r.m.s. deviation, δ, from the mean plane of 0.029 Å, and it makes a dihedral angle of 11.29 (18)° with the phenylhydrazine residue (C8–C13/N1/N2). In molecule 2, the vanillin group (C17–C23/O5/O6) is also planar, with δ = 0.027 Å, and it makes a dihedral angle of 10.87 (13)° with the phenylhydrazine residue (C24–C29/N4/N5). The nitro group and its attached aromatic ring are not coplanar, with dihedral angles of 7.23 (9) (for O3/N3/O4) and 4.61 (6)° (for O7/N6/O8). Furthermore, the phenylhydrazine residues of the two independent molecules are almost perpendicular to each other, with a dihedral angle of 86.36 (9)°, while the dihedral angle between the two vanillin groups is 77.10 (9)°. All bond lengths and angles are within normal ranges (Allen et al., 1987).
Two bifurcated intermolecular N—H···(O,O) hydrogen-bond systems are found in (I) (Table 1 and Fig. 2), which help to consolidate the crystal packing. The hydrogen bonds link adjacent molecules, forming infinite chains.