In the title compound, C
21H
19N
3O
6S, the vanillin group makes dihedral angles of 56.00 (7)° and 7.22 (8)° with the 4-methylbenzene ring and the nitrophenylhydrazine ring, respectively. The crystal packing is stabilized by intermolecular N—H
O hydrogen bonds and weak, non-classical intermolecular C—H
O hydrogen bonds that link adjacent molecules into one-dimensional extended chains.
Supporting information
CCDC reference: 627643
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.039
- wR factor = 0.098
- Data-to-parameter ratio = 12.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - O5 .. 5.36 su
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C18
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 26.40
From the CIF: _reflns_number_total 3643
Count of symmetry unique reflns 2217
Completeness (_total/calc) 164.32%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1426
Fraction of Friedel pairs measured 0.643
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 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
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
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.
Crystal data top
C21H19N3O6S | F(000) = 460 |
Mr = 441.46 | Dx = 1.404 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2106 reflections |
a = 6.343 (2) Å | θ = 2.7–24.5° |
b = 15.305 (5) Å | µ = 0.20 mm−1 |
c = 10.780 (4) Å | T = 294 K |
β = 93.727 (6)° | Block, orange |
V = 1044.3 (6) Å3 | 0.40 × 0.32 × 0.20 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX CCD area detector diffractometer | 3643 independent reflections |
Radiation source: fine-focus sealed tube | 2567 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 26.4°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.912, Tmax = 0.961 | k = −17→19 |
5892 measured reflections | l = −8→13 |
Refinement top
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.075P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
3643 reflections | Δρmax = 0.14 e Å−3 |
282 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.12 (8) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.24341 (14) | 1.12009 (5) | 0.55822 (8) | 0.0630 (3) | |
O1 | 1.3556 (4) | 0.45905 (15) | 0.0491 (2) | 0.0746 (7) | |
O2 | 1.6306 (4) | 0.51669 (16) | −0.0254 (2) | 0.0756 (7) | |
O3 | 0.3167 (3) | 0.91758 (13) | 0.42565 (19) | 0.0616 (6) | |
O4 | 0.2480 (3) | 1.09007 (13) | 0.41529 (18) | 0.0546 (5) | |
O5 | 0.4552 (4) | 1.13225 (17) | 0.6079 (2) | 0.0841 (8) | |
O6 | 0.0974 (5) | 1.18976 (17) | 0.5530 (3) | 0.1009 (10) | |
N1 | 1.4610 (5) | 0.52306 (18) | 0.0228 (2) | 0.0559 (7) | |
N2 | 1.1756 (4) | 0.85700 (15) | 0.1220 (2) | 0.0540 (7) | |
H2 | 1.2512 | 0.8998 | 0.0984 | 0.065* | |
N3 | 0.9952 (4) | 0.87500 (16) | 0.1805 (2) | 0.0491 (6) | |
C1 | 1.3839 (5) | 0.60934 (19) | 0.0499 (2) | 0.0468 (7) | |
C2 | 1.5046 (5) | 0.6804 (2) | 0.0229 (3) | 0.0522 (8) | |
H2A | 1.6338 | 0.6727 | −0.0119 | 0.063* | |
C3 | 1.4338 (5) | 0.7626 (2) | 0.0476 (3) | 0.0532 (8) | |
H3 | 1.5148 | 0.8111 | 0.0295 | 0.064* | |
C4 | 1.2399 (4) | 0.77383 (18) | 0.0998 (2) | 0.0448 (7) | |
C5 | 1.1201 (5) | 0.70048 (19) | 0.1279 (3) | 0.0507 (7) | |
H5 | 0.9915 | 0.7074 | 0.1635 | 0.061* | |
C6 | 1.1921 (4) | 0.6189 (2) | 0.1029 (2) | 0.0507 (7) | |
H6 | 1.1130 | 0.5700 | 0.1213 | 0.061* | |
C7 | 0.9609 (5) | 0.9551 (2) | 0.1987 (3) | 0.0490 (7) | |
H7 | 1.0570 | 0.9955 | 0.1713 | 0.059* | |
C8 | 0.7786 (5) | 0.98790 (18) | 0.2607 (3) | 0.0446 (7) | |
C9 | 0.7482 (5) | 1.07714 (19) | 0.2661 (3) | 0.0492 (7) | |
H9 | 0.8452 | 1.1147 | 0.2331 | 0.059* | |
C10 | 0.5748 (5) | 1.1106 (2) | 0.3202 (2) | 0.0498 (7) | |
H10 | 0.5538 | 1.1707 | 0.3227 | 0.060* | |
C11 | 0.4344 (4) | 1.05564 (18) | 0.3699 (2) | 0.0443 (7) | |
C12 | 0.4636 (4) | 0.96450 (19) | 0.3694 (2) | 0.0452 (7) | |
C13 | 0.6369 (4) | 0.93158 (18) | 0.3137 (2) | 0.0446 (7) | |
H13 | 0.6591 | 0.8716 | 0.3116 | 0.054* | |
C14 | 0.3462 (6) | 0.8252 (2) | 0.4364 (3) | 0.0696 (10) | |
H14A | 0.3526 | 0.8002 | 0.3550 | 0.104* | |
H14B | 0.2301 | 0.8000 | 0.4767 | 0.104* | |
H14C | 0.4756 | 0.8134 | 0.4846 | 0.104* | |
C15 | 0.1323 (5) | 1.0297 (2) | 0.6287 (3) | 0.0505 (7) | |
C16 | −0.0757 (5) | 1.0076 (2) | 0.6011 (3) | 0.0609 (9) | |
H16 | −0.1611 | 1.0424 | 0.5478 | 0.073* | |
C17 | −0.1557 (5) | 0.9340 (2) | 0.6529 (3) | 0.0665 (9) | |
H17 | −0.2962 | 0.9192 | 0.6335 | 0.080* | |
C18 | −0.0345 (6) | 0.8811 (2) | 0.7328 (3) | 0.0636 (9) | |
C19 | 0.1728 (6) | 0.9051 (3) | 0.7608 (3) | 0.0751 (10) | |
H19 | 0.2573 | 0.8710 | 0.8154 | 0.090* | |
C20 | 0.2572 (6) | 0.9789 (3) | 0.7094 (3) | 0.0661 (9) | |
H20 | 0.3973 | 0.9942 | 0.7290 | 0.079* | |
C21 | −0.1261 (8) | 0.8003 (3) | 0.7877 (4) | 0.0983 (14) | |
H21A | −0.1059 | 0.7514 | 0.7340 | 0.147* | |
H21B | −0.2744 | 0.8087 | 0.7964 | 0.147* | |
H21C | −0.0563 | 0.7891 | 0.8679 | 0.147* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0703 (6) | 0.0476 (5) | 0.0742 (5) | 0.0001 (4) | 0.0298 (4) | −0.0110 (4) |
O1 | 0.0972 (19) | 0.0418 (14) | 0.0863 (17) | 0.0032 (14) | 0.0169 (14) | −0.0056 (12) |
O2 | 0.0797 (17) | 0.0588 (15) | 0.0908 (17) | 0.0220 (13) | 0.0251 (14) | −0.0064 (12) |
O3 | 0.0648 (14) | 0.0436 (13) | 0.0796 (14) | −0.0064 (11) | 0.0292 (11) | 0.0009 (10) |
O4 | 0.0496 (11) | 0.0549 (14) | 0.0608 (12) | 0.0135 (10) | 0.0149 (9) | 0.0033 (9) |
O5 | 0.0771 (17) | 0.095 (2) | 0.0823 (17) | −0.0377 (15) | 0.0180 (12) | −0.0309 (14) |
O6 | 0.120 (2) | 0.0527 (16) | 0.139 (3) | 0.0251 (16) | 0.0721 (18) | 0.0007 (15) |
N1 | 0.0735 (19) | 0.0426 (15) | 0.0524 (15) | 0.0099 (15) | 0.0090 (14) | −0.0020 (13) |
N2 | 0.0549 (16) | 0.0384 (15) | 0.0720 (17) | 0.0035 (12) | 0.0289 (13) | 0.0003 (11) |
N3 | 0.0503 (15) | 0.0436 (15) | 0.0552 (15) | 0.0058 (12) | 0.0177 (11) | −0.0014 (11) |
C1 | 0.0584 (17) | 0.0381 (16) | 0.0443 (15) | 0.0087 (14) | 0.0068 (13) | −0.0028 (13) |
C2 | 0.0501 (17) | 0.0482 (19) | 0.060 (2) | 0.0056 (15) | 0.0183 (14) | −0.0027 (15) |
C3 | 0.0550 (19) | 0.0409 (17) | 0.0665 (19) | −0.0001 (15) | 0.0242 (15) | −0.0009 (14) |
C4 | 0.0494 (17) | 0.0377 (16) | 0.0488 (16) | 0.0005 (13) | 0.0144 (13) | 0.0012 (12) |
C5 | 0.0490 (17) | 0.0484 (19) | 0.0566 (18) | 0.0028 (15) | 0.0179 (14) | 0.0024 (14) |
C6 | 0.0581 (17) | 0.0402 (16) | 0.0552 (16) | −0.0047 (16) | 0.0149 (13) | 0.0018 (14) |
C7 | 0.0488 (17) | 0.0426 (18) | 0.0567 (19) | 0.0016 (14) | 0.0129 (13) | −0.0015 (14) |
C8 | 0.0463 (16) | 0.0417 (17) | 0.0467 (16) | 0.0031 (13) | 0.0097 (13) | −0.0010 (12) |
C9 | 0.0515 (18) | 0.0411 (17) | 0.0565 (18) | −0.0026 (14) | 0.0138 (13) | 0.0029 (13) |
C10 | 0.0586 (17) | 0.0363 (16) | 0.0560 (17) | 0.0093 (15) | 0.0143 (13) | 0.0059 (14) |
C11 | 0.0465 (16) | 0.0431 (17) | 0.0442 (17) | 0.0087 (13) | 0.0096 (13) | 0.0022 (12) |
C12 | 0.0477 (17) | 0.0435 (17) | 0.0450 (16) | −0.0025 (14) | 0.0070 (13) | −0.0017 (13) |
C13 | 0.0480 (16) | 0.0366 (16) | 0.0503 (16) | 0.0027 (13) | 0.0102 (13) | −0.0032 (12) |
C14 | 0.089 (3) | 0.046 (2) | 0.076 (2) | −0.0112 (18) | 0.0190 (19) | 0.0069 (16) |
C15 | 0.0504 (18) | 0.0538 (18) | 0.0485 (17) | 0.0031 (15) | 0.0121 (14) | −0.0058 (14) |
C16 | 0.0517 (19) | 0.069 (2) | 0.062 (2) | 0.0051 (17) | 0.0066 (15) | 0.0078 (17) |
C17 | 0.0541 (19) | 0.076 (2) | 0.069 (2) | −0.0140 (19) | 0.0052 (17) | −0.0060 (19) |
C18 | 0.080 (3) | 0.056 (2) | 0.0554 (19) | −0.0013 (19) | 0.0119 (18) | −0.0070 (16) |
C19 | 0.084 (3) | 0.077 (3) | 0.063 (2) | 0.018 (2) | −0.0056 (19) | 0.0134 (19) |
C20 | 0.056 (2) | 0.081 (3) | 0.061 (2) | 0.0010 (19) | −0.0002 (16) | 0.0005 (18) |
C21 | 0.137 (4) | 0.064 (3) | 0.095 (3) | −0.019 (3) | 0.023 (3) | 0.005 (2) |
Geometric parameters (Å, º) top
S1—O6 | 1.411 (3) | C8—C9 | 1.381 (4) |
S1—O5 | 1.426 (3) | C8—C13 | 1.394 (4) |
S1—O4 | 1.610 (2) | C9—C10 | 1.377 (4) |
S1—C15 | 1.749 (3) | C9—H9 | 0.9300 |
O1—N1 | 1.230 (4) | C10—C11 | 1.361 (4) |
O2—N1 | 1.229 (3) | C10—H10 | 0.9300 |
O3—C12 | 1.351 (3) | C11—C12 | 1.407 (4) |
O3—C14 | 1.430 (4) | C12—C13 | 1.381 (4) |
O4—C11 | 1.411 (3) | C13—H13 | 0.9300 |
N1—C1 | 1.445 (4) | C14—H14A | 0.9600 |
N2—C4 | 1.362 (4) | C14—H14B | 0.9600 |
N2—N3 | 1.370 (3) | C14—H14C | 0.9600 |
N2—H2 | 0.8600 | C15—C16 | 1.375 (4) |
N3—C7 | 1.263 (4) | C15—C20 | 1.377 (4) |
C1—C2 | 1.372 (4) | C16—C17 | 1.369 (5) |
C1—C6 | 1.385 (4) | C16—H16 | 0.9300 |
C2—C3 | 1.368 (4) | C17—C18 | 1.380 (5) |
C2—H2A | 0.9300 | C17—H17 | 0.9300 |
C3—C4 | 1.396 (4) | C18—C19 | 1.380 (5) |
C3—H3 | 0.9300 | C18—C21 | 1.504 (5) |
C4—C5 | 1.400 (4) | C19—C20 | 1.381 (5) |
C5—C6 | 1.363 (4) | C19—H19 | 0.9300 |
C5—H5 | 0.9300 | C20—H20 | 0.9300 |
C6—H6 | 0.9300 | C21—H21A | 0.9600 |
C7—C8 | 1.461 (4) | C21—H21B | 0.9600 |
C7—H7 | 0.9300 | C21—H21C | 0.9600 |
| | | |
O6—S1—O5 | 121.07 (18) | C11—C10—C9 | 119.8 (3) |
O6—S1—O4 | 103.33 (15) | C11—C10—H10 | 120.1 |
O5—S1—O4 | 108.76 (13) | C9—C10—H10 | 120.1 |
O6—S1—C15 | 109.46 (16) | C10—C11—C12 | 121.5 (3) |
O5—S1—C15 | 109.66 (16) | C10—C11—O4 | 119.4 (2) |
O4—S1—C15 | 102.89 (13) | C12—C11—O4 | 119.0 (2) |
C12—O3—C14 | 118.1 (3) | O3—C12—C13 | 126.3 (3) |
C11—O4—S1 | 120.44 (16) | O3—C12—C11 | 115.5 (2) |
O2—N1—O1 | 122.6 (3) | C13—C12—C11 | 118.2 (3) |
O2—N1—C1 | 118.4 (3) | C12—C13—C8 | 120.3 (3) |
O1—N1—C1 | 119.0 (3) | C12—C13—H13 | 119.8 |
C4—N2—N3 | 122.5 (2) | C8—C13—H13 | 119.8 |
C4—N2—H2 | 118.8 | O3—C14—H14A | 109.5 |
N3—N2—H2 | 118.8 | O3—C14—H14B | 109.5 |
C7—N3—N2 | 115.1 (2) | H14A—C14—H14B | 109.5 |
C2—C1—C6 | 121.4 (3) | O3—C14—H14C | 109.5 |
C2—C1—N1 | 118.7 (3) | H14A—C14—H14C | 109.5 |
C6—C1—N1 | 119.9 (3) | H14B—C14—H14C | 109.5 |
C3—C2—C1 | 119.5 (3) | C16—C15—C20 | 120.2 (3) |
C3—C2—H2A | 120.2 | C16—C15—S1 | 120.5 (2) |
C1—C2—H2A | 120.2 | C20—C15—S1 | 119.3 (3) |
C2—C3—C4 | 120.1 (3) | C17—C16—C15 | 119.3 (3) |
C2—C3—H3 | 120.0 | C17—C16—H16 | 120.4 |
C4—C3—H3 | 120.0 | C15—C16—H16 | 120.4 |
N2—C4—C3 | 117.9 (3) | C16—C17—C18 | 122.1 (3) |
N2—C4—C5 | 122.6 (2) | C16—C17—H17 | 118.9 |
C3—C4—C5 | 119.6 (3) | C18—C17—H17 | 118.9 |
C6—C5—C4 | 119.9 (3) | C19—C18—C17 | 117.6 (3) |
C6—C5—H5 | 120.0 | C19—C18—C21 | 121.3 (4) |
C4—C5—H5 | 120.0 | C17—C18—C21 | 121.0 (3) |
C5—C6—C1 | 119.6 (3) | C18—C19—C20 | 121.3 (3) |
C5—C6—H6 | 120.2 | C18—C19—H19 | 119.4 |
C1—C6—H6 | 120.2 | C20—C19—H19 | 119.4 |
N3—C7—C8 | 123.7 (3) | C15—C20—C19 | 119.5 (3) |
N3—C7—H7 | 118.2 | C15—C20—H20 | 120.3 |
C8—C7—H7 | 118.2 | C19—C20—H20 | 120.3 |
C9—C8—C13 | 119.9 (3) | C18—C21—H21A | 109.5 |
C9—C8—C7 | 118.4 (3) | C18—C21—H21B | 109.5 |
C13—C8—C7 | 121.7 (3) | H21A—C21—H21B | 109.5 |
C10—C9—C8 | 120.3 (3) | C18—C21—H21C | 109.5 |
C10—C9—H9 | 119.9 | H21A—C21—H21C | 109.5 |
C8—C9—H9 | 119.9 | H21B—C21—H21C | 109.5 |
| | | |
O6—S1—O4—C11 | 148.4 (2) | S1—O4—C11—C10 | −90.4 (3) |
O5—S1—O4—C11 | 18.5 (3) | S1—O4—C11—C12 | 93.9 (3) |
C15—S1—O4—C11 | −97.7 (2) | C14—O3—C12—C13 | 4.0 (4) |
C4—N2—N3—C7 | 177.3 (3) | C14—O3—C12—C11 | −175.4 (3) |
O2—N1—C1—C2 | −1.2 (4) | C10—C11—C12—O3 | 177.7 (3) |
O1—N1—C1—C2 | 178.5 (3) | O4—C11—C12—O3 | −6.7 (4) |
O2—N1—C1—C6 | 179.3 (3) | C10—C11—C12—C13 | −1.7 (4) |
O1—N1—C1—C6 | −1.0 (4) | O4—C11—C12—C13 | 173.9 (2) |
C6—C1—C2—C3 | −0.7 (4) | O3—C12—C13—C8 | −178.9 (3) |
N1—C1—C2—C3 | 179.8 (3) | C11—C12—C13—C8 | 0.5 (4) |
C1—C2—C3—C4 | 0.0 (5) | C9—C8—C13—C12 | 1.4 (4) |
N3—N2—C4—C3 | −175.6 (3) | C7—C8—C13—C12 | −178.7 (3) |
N3—N2—C4—C5 | 4.1 (4) | O6—S1—C15—C16 | 41.3 (3) |
C2—C3—C4—N2 | −179.7 (3) | O5—S1—C15—C16 | 176.3 (2) |
C2—C3—C4—C5 | 0.7 (5) | O4—S1—C15—C16 | −68.1 (3) |
N2—C4—C5—C6 | 179.6 (3) | O6—S1—C15—C20 | −140.8 (3) |
C3—C4—C5—C6 | −0.7 (4) | O5—S1—C15—C20 | −5.8 (3) |
C4—C5—C6—C1 | 0.0 (4) | O4—S1—C15—C20 | 109.8 (3) |
C2—C1—C6—C5 | 0.7 (4) | C20—C15—C16—C17 | −1.1 (5) |
N1—C1—C6—C5 | −179.9 (2) | S1—C15—C16—C17 | 176.7 (2) |
N2—N3—C7—C8 | −179.4 (2) | C15—C16—C17—C18 | 0.4 (5) |
N3—C7—C8—C9 | −174.6 (3) | C16—C17—C18—C19 | 0.6 (5) |
N3—C7—C8—C13 | 5.4 (4) | C16—C17—C18—C21 | −179.6 (3) |
C13—C8—C9—C10 | −2.1 (5) | C17—C18—C19—C20 | −0.9 (5) |
C7—C8—C9—C10 | 178.0 (3) | C21—C18—C19—C20 | 179.4 (3) |
C8—C9—C10—C11 | 0.9 (4) | C16—C15—C20—C19 | 0.9 (5) |
C9—C10—C11—C12 | 1.1 (4) | S1—C15—C20—C19 | −177.0 (2) |
C9—C10—C11—O4 | −174.5 (2) | C18—C19—C20—C15 | 0.1 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.86 | 2.11 | 2.956 (3) | 167 |
C3—H3···O1i | 0.93 | 2.57 | 3.477 (4) | 165 |
Symmetry code: (i) −x+3, y+1/2, −z. |