


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808036015/at2666sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808036015/at2666Isup2.hkl |
CCDC reference: 712403
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.044
- wR factor = 0.132
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level C Value of measurement temperature given = 294.000 Value of melting point given = 0.000 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 300 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
An anhydrous acetonitrile solution (100 ml) of 4-hydroxy-3-methoxybenzaldehyde (1.52 g, 10 mmol) was added dropwise to a solution (50 ml) of 1-(bromomethyl)-4-nitrobenzene (2.16 g, 10 mmol) and pyridine (0.79 g, 10 mmol) in acetonitrile, in 30 min., and the mixture refluxed for 24 h under nitrogen atmosphere. The solvent was removed and the resultant mixture poured into ice-water (100 ml). The yellow precipitate was then isolated and recrystallized from acetonitrile, and then dried in a vacuum to give the pure compound in 74% yield. Pale-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 bond lengths and isotropic U parameters: 0.93 Å and Uiso(H) = 1.2Ueq(C) for Csp2—H; 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene C—H; 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl C—H.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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).
![]() | 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. |
C15H13NO5 | F(000) = 1200 |
Mr = 287.26 | Dx = 1.353 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3156 reflections |
a = 13.743 (3) Å | θ = 2.2–26.5° |
b = 12.526 (3) Å | µ = 0.10 mm−1 |
c = 16.384 (3) Å | T = 294 K |
V = 2820.4 (10) Å3 | Block, pale-yellow |
Z = 8 | 0.23 × 0.18 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2877 independent reflections |
Radiation source: fine-focus sealed tube | 1540 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→17 |
Tmin = 0.932, Tmax = 0.988 | k = −14→15 |
15172 measured reflections | l = −20→18 |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0424P)2 + 1.1393P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.001 |
2877 reflections | Δρmax = 0.16 e Å−3 |
192 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (5) |
C15H13NO5 | V = 2820.4 (10) Å3 |
Mr = 287.26 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.743 (3) Å | µ = 0.10 mm−1 |
b = 12.526 (3) Å | T = 294 K |
c = 16.384 (3) Å | 0.23 × 0.18 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2877 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1540 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.988 | Rint = 0.045 |
15172 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.16 e Å−3 |
2877 reflections | Δρmin = −0.17 e Å−3 |
192 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 | ||
N1 | 0.14273 (18) | −0.3678 (2) | 1.20564 (17) | 0.0880 (7) | |
O1 | 0.1166 (2) | −0.34357 (19) | 1.27401 (14) | 0.1320 (9) | |
O2 | 0.1674 (2) | −0.45767 (19) | 1.18670 (15) | 0.1303 (9) | |
O3 | 0.11868 (11) | 0.05467 (12) | 0.99132 (8) | 0.0671 (5) | |
O4 | 0.07376 (11) | 0.23118 (12) | 1.05892 (9) | 0.0705 (5) | |
O5 | 0.1082 (2) | 0.5139 (2) | 0.82786 (17) | 0.1500 (12) | |
C1 | 0.09685 (14) | 0.23830 (18) | 0.97787 (13) | 0.0570 (5) | |
C2 | 0.09799 (15) | 0.33013 (19) | 0.93261 (15) | 0.0671 (6) | |
H2 | 0.0826 | 0.3950 | 0.9570 | 0.081* | |
C3 | 0.12223 (16) | 0.3267 (2) | 0.84953 (16) | 0.0739 (7) | |
C4 | 0.14582 (18) | 0.2313 (2) | 0.81422 (15) | 0.0772 (7) | |
H4 | 0.1626 | 0.2294 | 0.7592 | 0.093* | |
C5 | 0.14517 (17) | 0.1375 (2) | 0.85877 (14) | 0.0704 (7) | |
H5 | 0.1610 | 0.0730 | 0.8340 | 0.085* | |
C6 | 0.12076 (15) | 0.14069 (17) | 0.94062 (13) | 0.0572 (6) | |
C7 | 0.1230 (2) | 0.4259 (3) | 0.8018 (2) | 0.1087 (12) | |
H7 | 0.1361 | 0.4199 | 0.7463 | 0.130* | |
C8 | 0.0516 (2) | 0.3282 (2) | 1.10024 (16) | 0.0976 (10) | |
H8A | 0.1071 | 0.3747 | 1.0985 | 0.146* | |
H8B | 0.0354 | 0.3130 | 1.1560 | 0.146* | |
H8C | −0.0027 | 0.3623 | 1.0741 | 0.146* | |
C9 | 0.14047 (18) | −0.04690 (17) | 0.95782 (13) | 0.0680 (6) | |
H9A | 0.2033 | −0.0447 | 0.9309 | 0.082* | |
H9B | 0.0917 | −0.0660 | 0.9176 | 0.082* | |
C10 | 0.14211 (15) | −0.12841 (17) | 1.02476 (13) | 0.0562 (5) | |
C11 | 0.16208 (16) | −0.23375 (19) | 1.00431 (14) | 0.0665 (6) | |
H11 | 0.1746 | −0.2516 | 0.9502 | 0.080* | |
C12 | 0.16355 (17) | −0.31198 (19) | 1.06322 (16) | 0.0707 (7) | |
H12 | 0.1777 | −0.3824 | 1.0496 | 0.085* | |
C13 | 0.14380 (16) | −0.28411 (19) | 1.14254 (15) | 0.0637 (6) | |
C14 | 0.12433 (18) | −0.18140 (19) | 1.16476 (14) | 0.0709 (7) | |
H14 | 0.1117 | −0.1644 | 1.2190 | 0.085* | |
C15 | 0.12358 (17) | −0.10322 (19) | 1.10550 (14) | 0.0668 (6) | |
H15 | 0.1105 | −0.0329 | 1.1200 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0997 (17) | 0.0762 (17) | 0.0882 (18) | −0.0093 (13) | −0.0130 (14) | 0.0156 (14) |
O1 | 0.212 (3) | 0.1117 (17) | 0.0727 (14) | −0.0042 (16) | 0.0010 (16) | 0.0221 (13) |
O2 | 0.177 (2) | 0.0729 (15) | 0.141 (2) | 0.0080 (15) | 0.0028 (17) | 0.0271 (14) |
O3 | 0.0910 (12) | 0.0563 (10) | 0.0541 (9) | 0.0010 (8) | 0.0058 (8) | −0.0018 (7) |
O4 | 0.0939 (12) | 0.0657 (10) | 0.0520 (9) | 0.0107 (8) | 0.0013 (8) | −0.0026 (8) |
O5 | 0.175 (3) | 0.1065 (19) | 0.169 (2) | 0.0499 (18) | 0.0663 (19) | 0.0703 (18) |
C1 | 0.0525 (12) | 0.0661 (15) | 0.0524 (12) | −0.0001 (10) | −0.0015 (10) | 0.0039 (11) |
C2 | 0.0595 (14) | 0.0662 (15) | 0.0757 (16) | 0.0055 (11) | 0.0020 (12) | 0.0117 (12) |
C3 | 0.0561 (14) | 0.0888 (19) | 0.0768 (17) | 0.0040 (13) | 0.0062 (12) | 0.0297 (15) |
C4 | 0.0726 (16) | 0.104 (2) | 0.0555 (14) | −0.0001 (15) | 0.0069 (12) | 0.0140 (15) |
C5 | 0.0762 (16) | 0.0778 (17) | 0.0573 (14) | −0.0025 (13) | 0.0029 (12) | −0.0004 (13) |
C6 | 0.0584 (13) | 0.0597 (14) | 0.0536 (13) | −0.0043 (10) | −0.0026 (10) | 0.0043 (11) |
C7 | 0.090 (2) | 0.122 (3) | 0.114 (2) | 0.029 (2) | 0.0266 (18) | 0.057 (2) |
C8 | 0.148 (3) | 0.0751 (19) | 0.0700 (16) | 0.0201 (18) | −0.0029 (17) | −0.0147 (14) |
C9 | 0.0865 (17) | 0.0611 (15) | 0.0563 (13) | 0.0032 (12) | 0.0080 (12) | −0.0068 (11) |
C10 | 0.0538 (12) | 0.0587 (14) | 0.0562 (13) | −0.0018 (10) | 0.0038 (10) | −0.0046 (10) |
C11 | 0.0712 (15) | 0.0645 (16) | 0.0640 (14) | 0.0029 (12) | 0.0158 (11) | −0.0088 (12) |
C12 | 0.0698 (15) | 0.0577 (15) | 0.0847 (18) | 0.0049 (11) | 0.0114 (13) | −0.0043 (13) |
C13 | 0.0598 (13) | 0.0628 (15) | 0.0685 (15) | −0.0028 (11) | −0.0047 (12) | 0.0070 (12) |
C14 | 0.0905 (18) | 0.0715 (17) | 0.0509 (13) | −0.0038 (13) | −0.0053 (12) | −0.0051 (12) |
C15 | 0.0865 (17) | 0.0584 (14) | 0.0555 (14) | −0.0008 (12) | −0.0029 (12) | −0.0085 (11) |
N1—O1 | 1.215 (3) | C7—H7 | 0.9300 |
N1—O2 | 1.216 (3) | C8—H8A | 0.9600 |
N1—C13 | 1.472 (3) | C8—H8B | 0.9600 |
O3—C6 | 1.361 (2) | C8—H8C | 0.9600 |
O3—C9 | 1.418 (2) | C9—C10 | 1.499 (3) |
O4—C1 | 1.368 (2) | C9—H9A | 0.9700 |
O4—C8 | 1.424 (3) | C9—H9B | 0.9700 |
O5—C7 | 1.199 (4) | C10—C15 | 1.384 (3) |
C1—C2 | 1.369 (3) | C10—C11 | 1.389 (3) |
C1—C6 | 1.406 (3) | C11—C12 | 1.376 (3) |
C2—C3 | 1.402 (3) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C12—C13 | 1.373 (3) |
C3—C4 | 1.367 (3) | C12—H12 | 0.9300 |
C3—C7 | 1.468 (4) | C13—C14 | 1.364 (3) |
C4—C5 | 1.383 (3) | C14—C15 | 1.379 (3) |
C4—H4 | 0.9300 | C14—H14 | 0.9300 |
C5—C6 | 1.383 (3) | C15—H15 | 0.9300 |
C5—H5 | 0.9300 | ||
O1—N1—O2 | 123.3 (3) | H8A—C8—H8B | 109.5 |
O1—N1—C13 | 118.2 (3) | O4—C8—H8C | 109.5 |
O2—N1—C13 | 118.5 (3) | H8A—C8—H8C | 109.5 |
C6—O3—C9 | 118.02 (16) | H8B—C8—H8C | 109.5 |
C1—O4—C8 | 117.09 (18) | O3—C9—C10 | 109.34 (17) |
O4—C1—C2 | 125.7 (2) | O3—C9—H9A | 109.8 |
O4—C1—C6 | 114.77 (19) | C10—C9—H9A | 109.8 |
C2—C1—C6 | 119.5 (2) | O3—C9—H9B | 109.8 |
C1—C2—C3 | 120.2 (2) | C10—C9—H9B | 109.8 |
C1—C2—H2 | 119.9 | H9A—C9—H9B | 108.3 |
C3—C2—H2 | 119.9 | C15—C10—C11 | 118.9 (2) |
C4—C3—C2 | 119.6 (2) | C15—C10—C9 | 122.8 (2) |
C4—C3—C7 | 120.9 (3) | C11—C10—C9 | 118.28 (19) |
C2—C3—C7 | 119.5 (3) | C12—C11—C10 | 120.7 (2) |
C3—C4—C5 | 121.2 (2) | C12—C11—H11 | 119.6 |
C3—C4—H4 | 119.4 | C10—C11—H11 | 119.6 |
C5—C4—H4 | 119.4 | C13—C12—C11 | 118.7 (2) |
C4—C5—C6 | 119.3 (2) | C13—C12—H12 | 120.7 |
C4—C5—H5 | 120.4 | C11—C12—H12 | 120.7 |
C6—C5—H5 | 120.4 | C14—C13—C12 | 122.1 (2) |
O3—C6—C5 | 125.1 (2) | C14—C13—N1 | 118.8 (2) |
O3—C6—C1 | 114.76 (19) | C12—C13—N1 | 119.1 (2) |
C5—C6—C1 | 120.2 (2) | C13—C14—C15 | 118.9 (2) |
O5—C7—C3 | 126.0 (3) | C13—C14—H14 | 120.5 |
O5—C7—H7 | 117.0 | C15—C14—H14 | 120.5 |
C3—C7—H7 | 117.0 | C14—C15—C10 | 120.7 (2) |
O4—C8—H8A | 109.5 | C14—C15—H15 | 119.7 |
O4—C8—H8B | 109.5 | C10—C15—H15 | 119.7 |
C8—O4—C1—C2 | −1.8 (3) | C2—C3—C7—O5 | 3.3 (5) |
C8—O4—C1—C6 | 178.3 (2) | C6—O3—C9—C10 | 175.41 (18) |
O4—C1—C2—C3 | −179.5 (2) | O3—C9—C10—C15 | 0.6 (3) |
C6—C1—C2—C3 | 0.4 (3) | O3—C9—C10—C11 | 179.86 (19) |
C1—C2—C3—C4 | −0.8 (3) | C15—C10—C11—C12 | −0.1 (3) |
C1—C2—C3—C7 | 179.9 (2) | C9—C10—C11—C12 | −179.4 (2) |
C2—C3—C4—C5 | 0.7 (4) | C10—C11—C12—C13 | 0.7 (3) |
C7—C3—C4—C5 | −179.9 (2) | C11—C12—C13—C14 | −1.0 (4) |
C3—C4—C5—C6 | −0.4 (4) | C11—C12—C13—N1 | 178.4 (2) |
C9—O3—C6—C5 | −1.8 (3) | O1—N1—C13—C14 | 6.0 (4) |
C9—O3—C6—C1 | 179.01 (19) | O2—N1—C13—C14 | −174.4 (2) |
C4—C5—C6—O3 | −179.1 (2) | O1—N1—C13—C12 | −173.5 (3) |
C4—C5—C6—C1 | 0.0 (3) | O2—N1—C13—C12 | 6.1 (4) |
O4—C1—C6—O3 | −1.0 (3) | C12—C13—C14—C15 | 0.6 (4) |
C2—C1—C6—O3 | 179.12 (19) | N1—C13—C14—C15 | −178.8 (2) |
O4—C1—C6—C5 | 179.83 (19) | C13—C14—C15—C10 | 0.1 (4) |
C2—C1—C6—C5 | −0.1 (3) | C11—C10—C15—C14 | −0.4 (3) |
C4—C3—C7—O5 | −176.1 (3) | C9—C10—C15—C14 | 178.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O5i | 0.93 | 2.60 | 3.405 (3) | 146 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H13NO5 |
Mr | 287.26 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 13.743 (3), 12.526 (3), 16.384 (3) |
V (Å3) | 2820.4 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.23 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.932, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15172, 2877, 1540 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.132, 0.99 |
No. of reflections | 2877 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O5i | 0.93 | 2.60 | 3.405 (3) | 146 |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Schiff-base ligands have received a good deal of attention in biology and chemistry (Kahwa et al., 1986). Many Schiff base derivatives have been synthesized and employed to develop protein and enzyme mimics (Santos et al., 2001). As a part of our interest in the coordination properties of Schiff bases functioning as ligands, we investigated the title compound, (I), used as a precursor in the preparation of Schiff bases.
In the title molecule (Fig. 1), bond lengths and angles are within normal ranges (Allen et al., 1987). The vanillin group (C1—C7/O3/O4) is essentially planar (except the methyl H atoms), with an r.m.s. deviation for fitted atoms of 0.035 (3) Å. This group makes a dihedral angle of 4.95 (8)° with the benzene ring (C10—C15) of the nitrobenzene group.
The crystal packing is stabilized by weak, non-classical intermolecular C14—H14···O5═C7 interactions that link adjacent molecules into one-dimensional chains running along the c axis (Table 1, Fig. 2).