Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040676/xu2306sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040676/xu2306Isup2.hkl |
CCDC reference: 663679
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.051
- wR factor = 0.139
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C8 - C9 ... 1.53 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 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 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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
All reagents were of AR grade and obtained commercially without further purification. The title compound was prepared according to Matović et al. (2005). A THF (THF= tetrahydrofuran) solution (8 ml) of ethyl oxalyl chloride (1.11 ml, 10 mmol) was added dropwise into a THF solution (10 ml) of anthranilic acid (1.37 g, 10 mmol) with continuous stirring. The mixture was stirred quickly for 1 h and then 20 ml absolute ethanol was further added and the mixture was added dropwise into the absolute ethanol solution (10 ml) of 3-dimethylamino-propylamine (1.02 g, 10 mmol) with stirring and kept the temperature at 273 K for 8 h. The title compound was precipitated as a white powder and washed with absolute ethanol for several times and dried under vacuum. Yield: 1.79 g (75%). Colorless crystals of the compound suitable for X-ray analysis were obtained from an ethanol/water (1:1) mixture by slow evaporation for one week at room temperature.
The H atom on protonated tertiary nitrogen atom N3 was located in a different Fourier map and refined with a restraint of N—H = 0.91 Å, final Uiso(H) value being 0.046 (9) Å2. Other H atoms were placed in calculated positions with C—H = 0.97 Å (methylene), 0.96 Å (methyl), 0.93 Å (aromatic) and N—H = 0.86 Å, and included in the final cycles of refinement in riding mode. Torsion angles for methyl groups were refined with Uiso(H) = 1.5Ueq(C). For other H atoms, Uiso(H) = 1.2Ueq(C,N).
N,N'-disubstituted oxamidate derivatives are known to be versatile organic ligands, which can chelate as well as bridge the metal ions to construct discrete and extend structures (Ojima & Nonoyama, 1988). Compared with the symmetrical substituted derivatives, the design and synthesis of those unsymmetrical substituted are rather limited owing to the relative difficulty of synthesizing new compounds (Matović et al., 2005; Pei et al., 1991; Zang et al., 2003). Herein, we report the synthesis and X-ray structural of the title oxamidate compound.
The title compound occurs as a zwitterion with the tertiary N atom (N3) protonated and the carboxyl group deprotonated (Fig. 1). There is an intramolecular hydrogen bond between amido nitrogen atom (N1) and carboxyl oxygen atom (O2). The zwitterion has a transoid conformation, and six atoms of oxamido group are almost coplanar, which is similar to other oxamido compounds (Perić et al., 2001; Su et al., 1999; Sun et al., 2006). The dihedral angle between the oxamide and the benzene ring is 27.05 (12)°, and that between the benzene ring and carboxyl group is 23.9 (4)°.
As shown in Fig. 2, the zwitterions are linked into a 1-D ribbon along the b axis by the hydrogen bonding (Table 1).
For general background, see: Ojima & Nonoyama (1988); Matović et al. (2005); Pei et al. (1991); Zang et al. (2003). For related structures, see: Perić et al. (2001); Su et al. (1999); Sun et al. (2006). For synthesis, see: Matović et al. (2005).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1999).
C14H19N3O4 | F(000) = 624 |
Mr = 293.32 | Dx = 1.341 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1356 reflections |
a = 14.780 (5) Å | θ = 2.4–22.7° |
b = 8.762 (3) Å | µ = 0.10 mm−1 |
c = 11.576 (4) Å | T = 298 K |
β = 104.193 (5)° | Block, colourless |
V = 1453.4 (9) Å3 | 0.24 × 0.23 × 0.10 mm |
Z = 4 |
Bruker APEX area-detector diffractometer | 1374 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.059 |
Graphite monochromator | θmax = 25.2°, θmin = 1.4° |
φ and ω scans | h = −17→17 |
7492 measured reflections | k = −10→8 |
2628 independent reflections | l = −13→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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0558P)2 + 0.0967P] where P = (Fo2 + 2Fc2)/3 |
2628 reflections | (Δ/σ)max < 0.001 |
196 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C14H19N3O4 | V = 1453.4 (9) Å3 |
Mr = 293.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.780 (5) Å | µ = 0.10 mm−1 |
b = 8.762 (3) Å | T = 298 K |
c = 11.576 (4) Å | 0.24 × 0.23 × 0.10 mm |
β = 104.193 (5)° |
Bruker APEX area-detector diffractometer | 1374 reflections with I > 2σ(I) |
7492 measured reflections | Rint = 0.059 |
2628 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.23 e Å−3 |
2628 reflections | Δρmin = −0.21 e Å−3 |
196 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 | ||
C1 | 0.8415 (2) | 0.5075 (3) | 0.5747 (3) | 0.0353 (7) | |
C2 | 0.81197 (19) | 0.3653 (3) | 0.4998 (3) | 0.0337 (7) | |
C3 | 0.8755 (2) | 0.3010 (3) | 0.4428 (3) | 0.0394 (8) | |
H3 | 0.9354 | 0.3413 | 0.4566 | 0.047* | |
C4 | 0.8514 (2) | 0.1781 (4) | 0.3659 (3) | 0.0460 (9) | |
H4 | 0.8943 | 0.1380 | 0.3272 | 0.055* | |
C5 | 0.7636 (2) | 0.1161 (3) | 0.3474 (3) | 0.0454 (8) | |
H5 | 0.7471 | 0.0340 | 0.2955 | 0.055* | |
C6 | 0.6995 (2) | 0.1739 (3) | 0.4047 (3) | 0.0419 (8) | |
H6 | 0.6409 | 0.1292 | 0.3929 | 0.050* | |
C7 | 0.72259 (19) | 0.2997 (3) | 0.4806 (3) | 0.0335 (7) | |
C8 | 0.5848 (2) | 0.2933 (3) | 0.5658 (3) | 0.0377 (8) | |
C9 | 0.53513 (19) | 0.3990 (3) | 0.6361 (3) | 0.0361 (7) | |
C10 | 0.41422 (19) | 0.4063 (4) | 0.7457 (3) | 0.0462 (9) | |
H10A | 0.4076 | 0.5132 | 0.7235 | 0.055* | |
H10B | 0.4460 | 0.4002 | 0.8295 | 0.055* | |
C11 | 0.31874 (19) | 0.3339 (3) | 0.7258 (3) | 0.0402 (8) | |
H11A | 0.3249 | 0.2307 | 0.7571 | 0.048* | |
H11B | 0.2900 | 0.3286 | 0.6410 | 0.048* | |
C12 | 0.25722 (19) | 0.4261 (3) | 0.7870 (3) | 0.0398 (8) | |
H12A | 0.2923 | 0.4511 | 0.8671 | 0.048* | |
H12B | 0.2405 | 0.5211 | 0.7441 | 0.048* | |
C13 | 0.1151 (2) | 0.4356 (4) | 0.8607 (3) | 0.0593 (11) | |
H13A | 0.1554 | 0.4706 | 0.9340 | 0.089* | |
H13B | 0.0665 | 0.3734 | 0.8777 | 0.089* | |
H13C | 0.0880 | 0.5217 | 0.8135 | 0.089* | |
C14 | 0.1101 (2) | 0.2974 (4) | 0.6764 (3) | 0.0513 (9) | |
H14A | 0.0570 | 0.2423 | 0.6884 | 0.077* | |
H14B | 0.1451 | 0.2334 | 0.6360 | 0.077* | |
H14C | 0.0893 | 0.3866 | 0.6292 | 0.077* | |
N1 | 0.65712 (15) | 0.3637 (3) | 0.5368 (2) | 0.0376 (7) | |
H1 | 0.6642 | 0.4589 | 0.5547 | 0.045* | |
N2 | 0.46907 (16) | 0.3289 (3) | 0.6754 (2) | 0.0460 (7) | |
H2 | 0.4583 | 0.2341 | 0.6585 | 0.055* | |
N3 | 0.17012 (16) | 0.3439 (3) | 0.7937 (2) | 0.0366 (6) | |
H3A | 0.1880 (18) | 0.2573 (18) | 0.837 (2) | 0.046 (9)* | |
O1 | 0.92471 (14) | 0.5334 (2) | 0.6149 (2) | 0.0555 (7) | |
O2 | 0.77507 (13) | 0.5939 (2) | 0.58818 (19) | 0.0461 (6) | |
O3 | 0.56068 (15) | 0.1614 (2) | 0.5449 (2) | 0.0553 (7) | |
O4 | 0.55702 (13) | 0.5330 (2) | 0.6540 (2) | 0.0500 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0358 (18) | 0.0429 (18) | 0.0285 (19) | −0.0025 (14) | 0.0101 (15) | 0.0036 (15) |
C2 | 0.0326 (17) | 0.0388 (17) | 0.0301 (19) | 0.0015 (13) | 0.0084 (15) | 0.0052 (14) |
C3 | 0.0334 (17) | 0.0502 (19) | 0.037 (2) | 0.0040 (14) | 0.0120 (16) | 0.0007 (16) |
C4 | 0.046 (2) | 0.054 (2) | 0.043 (2) | 0.0096 (16) | 0.0200 (18) | −0.0051 (17) |
C5 | 0.049 (2) | 0.0469 (19) | 0.040 (2) | 0.0044 (16) | 0.0110 (18) | −0.0097 (16) |
C6 | 0.0395 (19) | 0.0470 (19) | 0.038 (2) | −0.0047 (14) | 0.0075 (17) | −0.0086 (16) |
C7 | 0.0325 (17) | 0.0398 (17) | 0.0291 (19) | 0.0044 (13) | 0.0091 (15) | 0.0029 (14) |
C8 | 0.0328 (17) | 0.0424 (18) | 0.039 (2) | 0.0023 (14) | 0.0110 (16) | 0.0034 (16) |
C9 | 0.0282 (16) | 0.0434 (18) | 0.036 (2) | 0.0001 (14) | 0.0056 (15) | 0.0014 (16) |
C10 | 0.0375 (19) | 0.058 (2) | 0.048 (2) | −0.0008 (15) | 0.0190 (17) | −0.0008 (18) |
C11 | 0.0347 (17) | 0.0447 (18) | 0.044 (2) | 0.0019 (14) | 0.0155 (16) | 0.0024 (16) |
C12 | 0.0345 (17) | 0.0401 (18) | 0.046 (2) | −0.0016 (13) | 0.0126 (16) | 0.0038 (15) |
C13 | 0.049 (2) | 0.070 (2) | 0.068 (3) | 0.0075 (18) | 0.031 (2) | −0.008 (2) |
C14 | 0.0417 (19) | 0.068 (2) | 0.042 (2) | −0.0041 (17) | 0.0056 (18) | 0.0009 (18) |
N1 | 0.0324 (14) | 0.0404 (15) | 0.0424 (17) | −0.0034 (11) | 0.0138 (13) | −0.0063 (13) |
N2 | 0.0410 (16) | 0.0436 (15) | 0.061 (2) | −0.0060 (12) | 0.0264 (15) | −0.0056 (14) |
N3 | 0.0325 (14) | 0.0412 (16) | 0.0376 (17) | 0.0005 (12) | 0.0115 (13) | 0.0058 (13) |
O1 | 0.0293 (13) | 0.0661 (15) | 0.0691 (18) | −0.0068 (11) | 0.0079 (12) | −0.0197 (13) |
O2 | 0.0377 (12) | 0.0439 (12) | 0.0578 (16) | 0.0002 (10) | 0.0138 (12) | −0.0144 (11) |
O3 | 0.0600 (15) | 0.0385 (13) | 0.0772 (19) | −0.0097 (11) | 0.0352 (14) | −0.0068 (12) |
O4 | 0.0460 (14) | 0.0407 (13) | 0.0689 (18) | −0.0055 (10) | 0.0252 (13) | −0.0074 (12) |
C1—O1 | 1.224 (3) | C10—C11 | 1.512 (4) |
C1—O2 | 1.279 (3) | C10—H10A | 0.9700 |
C1—C2 | 1.520 (4) | C10—H10B | 0.9700 |
C2—C3 | 1.393 (4) | C11—C12 | 1.516 (4) |
C2—C7 | 1.407 (4) | C11—H11A | 0.9700 |
C3—C4 | 1.386 (4) | C11—H11B | 0.9700 |
C3—H3 | 0.9300 | C12—N3 | 1.494 (3) |
C4—C5 | 1.375 (4) | C12—H12A | 0.9700 |
C4—H4 | 0.9300 | C12—H12B | 0.9700 |
C5—C6 | 1.379 (4) | C13—N3 | 1.489 (3) |
C5—H5 | 0.9300 | C13—H13A | 0.9600 |
C6—C7 | 1.399 (4) | C13—H13B | 0.9600 |
C6—H6 | 0.9300 | C13—H13C | 0.9600 |
C7—N1 | 1.408 (3) | C14—N3 | 1.485 (4) |
C8—C9 | 1.534 (4) | C14—H14A | 0.9600 |
C8—O3 | 1.217 (3) | C14—H14B | 0.9600 |
C9—O4 | 1.222 (3) | C14—H14C | 0.9600 |
C8—N1 | 1.345 (3) | N1—H1 | 0.8600 |
C9—N2 | 1.325 (3) | N2—H2 | 0.8600 |
C10—N2 | 1.451 (3) | N3—H3A | 0.912 (19) |
O1—C1—O2 | 125.0 (3) | C12—C11—H11A | 109.6 |
O1—C1—C2 | 119.3 (3) | C10—C11—H11B | 109.6 |
O2—C1—C2 | 115.7 (3) | C12—C11—H11B | 109.6 |
C3—C2—C7 | 118.4 (3) | H11A—C11—H11B | 108.1 |
C3—C2—C1 | 118.0 (3) | N3—C12—C11 | 113.0 (2) |
C7—C2—C1 | 123.5 (2) | N3—C12—H12A | 109.0 |
C4—C3—C2 | 121.4 (3) | C11—C12—H12A | 109.0 |
C4—C3—H3 | 119.3 | N3—C12—H12B | 109.0 |
C2—C3—H3 | 119.3 | C11—C12—H12B | 109.0 |
C5—C4—C3 | 119.4 (3) | H12A—C12—H12B | 107.8 |
C5—C4—H4 | 120.3 | N3—C13—H13A | 109.5 |
C3—C4—H4 | 120.3 | N3—C13—H13B | 109.5 |
C4—C5—C6 | 120.9 (3) | H13A—C13—H13B | 109.5 |
C4—C5—H5 | 119.6 | N3—C13—H13C | 109.5 |
C6—C5—H5 | 119.6 | H13A—C13—H13C | 109.5 |
C5—C6—C7 | 120.1 (3) | H13B—C13—H13C | 109.5 |
C5—C6—H6 | 120.0 | N3—C14—H14A | 109.5 |
C7—C6—H6 | 120.0 | N3—C14—H14B | 109.5 |
C6—C7—C2 | 119.7 (3) | H14A—C14—H14B | 109.5 |
C6—C7—N1 | 121.0 (3) | N3—C14—H14C | 109.5 |
C2—C7—N1 | 119.3 (3) | H14A—C14—H14C | 109.5 |
O3—C8—N1 | 126.7 (3) | H14B—C14—H14C | 109.5 |
O3—C8—C9 | 121.6 (3) | C8—N1—C7 | 127.7 (2) |
N1—C8—C9 | 111.6 (3) | C8—N1—H1 | 116.2 |
O4—C9—N2 | 125.0 (3) | C7—N1—H1 | 116.2 |
O4—C9—C8 | 121.9 (3) | C9—N2—C10 | 122.5 (3) |
N2—C9—C8 | 113.0 (3) | C9—N2—H2 | 118.8 |
N2—C10—C11 | 110.3 (3) | C10—N2—H2 | 118.8 |
N2—C10—H10A | 109.6 | C14—N3—C13 | 110.1 (2) |
C11—C10—H10A | 109.6 | C14—N3—C12 | 114.5 (2) |
N2—C10—H10B | 109.6 | C13—N3—C12 | 110.8 (2) |
C11—C10—H10B | 109.6 | C14—N3—H3A | 107.4 (18) |
H10A—C10—H10B | 108.1 | C13—N3—H3A | 106.8 (17) |
C10—C11—C12 | 110.4 (2) | C12—N3—H3A | 107.0 (18) |
C10—C11—H11A | 109.6 | ||
O1—C1—C2—C3 | −23.4 (4) | O3—C8—C9—O4 | −177.5 (3) |
O2—C1—C2—C3 | 154.9 (3) | O3—C8—C9—N2 | 3.5 (4) |
O1—C1—C2—C7 | 159.7 (3) | N1—C8—C9—N2 | −174.2 (3) |
O2—C1—C2—C7 | −22.0 (4) | N1—C8—C9—O4 | 4.8 (4) |
C7—C2—C3—C4 | 1.9 (4) | N2—C10—C11—C12 | −173.0 (2) |
C1—C2—C3—C4 | −175.2 (3) | C10—C11—C12—N3 | −167.4 (3) |
C2—C3—C4—C5 | −1.5 (5) | O3—C8—N1—C7 | −2.7 (5) |
C3—C4—C5—C6 | −0.3 (5) | C9—C8—N1—C7 | 174.9 (3) |
C4—C5—C6—C7 | 1.6 (5) | C2—C7—N1—C8 | −154.0 (3) |
C5—C6—C7—C2 | −1.1 (4) | C6—C7—N1—C8 | 27.0 (4) |
C5—C6—C7—N1 | 177.8 (3) | O4—C9—N2—C10 | 0.0 (5) |
C3—C2—C7—C6 | −0.6 (4) | C8—C9—N2—C10 | 178.9 (3) |
C1—C2—C7—C6 | 176.3 (3) | C11—C10—N2—C9 | 151.3 (3) |
C3—C2—C7—N1 | −179.6 (2) | C11—C12—N3—C14 | −58.1 (3) |
C1—C2—C7—N1 | −2.7 (4) | C11—C12—N3—C13 | 176.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.98 | 2.637 (3) | 132 |
N3—H3A···O2i | 0.91 (2) | 1.69 (2) | 2.604 (3) | 177 (3) |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C14H19N3O4 |
Mr | 293.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 14.780 (5), 8.762 (3), 11.576 (4) |
β (°) | 104.193 (5) |
V (Å3) | 1453.4 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.24 × 0.23 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7492, 2628, 1374 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.139, 1.03 |
No. of reflections | 2628 |
No. of parameters | 196 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.98 | 2.637 (3) | 132 |
N3—H3A···O2i | 0.912 (19) | 1.693 (18) | 2.604 (3) | 177 (3) |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
N,N'-disubstituted oxamidate derivatives are known to be versatile organic ligands, which can chelate as well as bridge the metal ions to construct discrete and extend structures (Ojima & Nonoyama, 1988). Compared with the symmetrical substituted derivatives, the design and synthesis of those unsymmetrical substituted are rather limited owing to the relative difficulty of synthesizing new compounds (Matović et al., 2005; Pei et al., 1991; Zang et al., 2003). Herein, we report the synthesis and X-ray structural of the title oxamidate compound.
The title compound occurs as a zwitterion with the tertiary N atom (N3) protonated and the carboxyl group deprotonated (Fig. 1). There is an intramolecular hydrogen bond between amido nitrogen atom (N1) and carboxyl oxygen atom (O2). The zwitterion has a transoid conformation, and six atoms of oxamido group are almost coplanar, which is similar to other oxamido compounds (Perić et al., 2001; Su et al., 1999; Sun et al., 2006). The dihedral angle between the oxamide and the benzene ring is 27.05 (12)°, and that between the benzene ring and carboxyl group is 23.9 (4)°.
As shown in Fig. 2, the zwitterions are linked into a 1-D ribbon along the b axis by the hydrogen bonding (Table 1).