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The title compound, C14H19N3O4, exists as a zwitterion, with a tertiary N atom protonated and a carboxyl group deprotonated. In the crystal structure, the planar oxamide group displays a transoid conformation. The mol­ecules link to each other via hydrogen bonding, resulting in an extended supra­molecular chain along the b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040676/xu2306sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040676/xu2306Isup2.hkl
Contains datablock I

CCDC reference: 663679

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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).

Structure description top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids. Dashed line indicates hydrogen bond.
[Figure 2] Fig. 2. The packing diagram for (I), viewed down the c axis. The H-bonds are shown as dashed lines; H atoms not involved in hydrogen bonding were omitted for clarity [symmetry codes: (i) 1 - x, y - 1/2, 3/2 - z; (ii) 1 - x, y + 1/2, 3/2 - z].
2-{N'-[3-(Dimethylammonio)propyl]oxamido}benzoate top
Crystal data top
C14H19N3O4F(000) = 624
Mr = 293.32Dx = 1.341 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1356 reflections
a = 14.780 (5) Åθ = 2.4–22.7°
b = 8.762 (3) ŵ = 0.10 mm1
c = 11.576 (4) ÅT = 298 K
β = 104.193 (5)°Block, colourless
V = 1453.4 (9) Å30.24 × 0.23 × 0.10 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer
1374 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.059
Graphite monochromatorθmax = 25.2°, θmin = 1.4°
φ and ω scansh = 1717
7492 measured reflectionsk = 108
2628 independent reflectionsl = 1311
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H 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 parametersΔρmax = 0.23 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C14H19N3O4V = 1453.4 (9) Å3
Mr = 293.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.780 (5) ŵ = 0.10 mm1
b = 8.762 (3) ÅT = 298 K
c = 11.576 (4) Å0.24 × 0.23 × 0.10 mm
β = 104.193 (5)°
Data collection top
Bruker APEX area-detector
diffractometer
1374 reflections with I > 2σ(I)
7492 measured reflectionsRint = 0.059
2628 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.23 e Å3
2628 reflectionsΔρmin = 0.21 e Å3
196 parameters
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8415 (2)0.5075 (3)0.5747 (3)0.0353 (7)
C20.81197 (19)0.3653 (3)0.4998 (3)0.0337 (7)
C30.8755 (2)0.3010 (3)0.4428 (3)0.0394 (8)
H30.93540.34130.45660.047*
C40.8514 (2)0.1781 (4)0.3659 (3)0.0460 (9)
H40.89430.13800.32720.055*
C50.7636 (2)0.1161 (3)0.3474 (3)0.0454 (8)
H50.74710.03400.29550.055*
C60.6995 (2)0.1739 (3)0.4047 (3)0.0419 (8)
H60.64090.12920.39290.050*
C70.72259 (19)0.2997 (3)0.4806 (3)0.0335 (7)
C80.5848 (2)0.2933 (3)0.5658 (3)0.0377 (8)
C90.53513 (19)0.3990 (3)0.6361 (3)0.0361 (7)
C100.41422 (19)0.4063 (4)0.7457 (3)0.0462 (9)
H10A0.40760.51320.72350.055*
H10B0.44600.40020.82950.055*
C110.31874 (19)0.3339 (3)0.7258 (3)0.0402 (8)
H11A0.32490.23070.75710.048*
H11B0.29000.32860.64100.048*
C120.25722 (19)0.4261 (3)0.7870 (3)0.0398 (8)
H12A0.29230.45110.86710.048*
H12B0.24050.52110.74410.048*
C130.1151 (2)0.4356 (4)0.8607 (3)0.0593 (11)
H13A0.15540.47060.93400.089*
H13B0.06650.37340.87770.089*
H13C0.08800.52170.81350.089*
C140.1101 (2)0.2974 (4)0.6764 (3)0.0513 (9)
H14A0.05700.24230.68840.077*
H14B0.14510.23340.63600.077*
H14C0.08930.38660.62920.077*
N10.65712 (15)0.3637 (3)0.5368 (2)0.0376 (7)
H10.66420.45890.55470.045*
N20.46907 (16)0.3289 (3)0.6754 (2)0.0460 (7)
H20.45830.23410.65850.055*
N30.17012 (16)0.3439 (3)0.7937 (2)0.0366 (6)
H3A0.1880 (18)0.2573 (18)0.837 (2)0.046 (9)*
O10.92471 (14)0.5334 (2)0.6149 (2)0.0555 (7)
O20.77507 (13)0.5939 (2)0.58818 (19)0.0461 (6)
O30.56068 (15)0.1614 (2)0.5449 (2)0.0553 (7)
O40.55702 (13)0.5330 (2)0.6540 (2)0.0500 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0358 (18)0.0429 (18)0.0285 (19)0.0025 (14)0.0101 (15)0.0036 (15)
C20.0326 (17)0.0388 (17)0.0301 (19)0.0015 (13)0.0084 (15)0.0052 (14)
C30.0334 (17)0.0502 (19)0.037 (2)0.0040 (14)0.0120 (16)0.0007 (16)
C40.046 (2)0.054 (2)0.043 (2)0.0096 (16)0.0200 (18)0.0051 (17)
C50.049 (2)0.0469 (19)0.040 (2)0.0044 (16)0.0110 (18)0.0097 (16)
C60.0395 (19)0.0470 (19)0.038 (2)0.0047 (14)0.0075 (17)0.0086 (16)
C70.0325 (17)0.0398 (17)0.0291 (19)0.0044 (13)0.0091 (15)0.0029 (14)
C80.0328 (17)0.0424 (18)0.039 (2)0.0023 (14)0.0110 (16)0.0034 (16)
C90.0282 (16)0.0434 (18)0.036 (2)0.0001 (14)0.0056 (15)0.0014 (16)
C100.0375 (19)0.058 (2)0.048 (2)0.0008 (15)0.0190 (17)0.0008 (18)
C110.0347 (17)0.0447 (18)0.044 (2)0.0019 (14)0.0155 (16)0.0024 (16)
C120.0345 (17)0.0401 (18)0.046 (2)0.0016 (13)0.0126 (16)0.0038 (15)
C130.049 (2)0.070 (2)0.068 (3)0.0075 (18)0.031 (2)0.008 (2)
C140.0417 (19)0.068 (2)0.042 (2)0.0041 (17)0.0056 (18)0.0009 (18)
N10.0324 (14)0.0404 (15)0.0424 (17)0.0034 (11)0.0138 (13)0.0063 (13)
N20.0410 (16)0.0436 (15)0.061 (2)0.0060 (12)0.0264 (15)0.0056 (14)
N30.0325 (14)0.0412 (16)0.0376 (17)0.0005 (12)0.0115 (13)0.0058 (13)
O10.0293 (13)0.0661 (15)0.0691 (18)0.0068 (11)0.0079 (12)0.0197 (13)
O20.0377 (12)0.0439 (12)0.0578 (16)0.0002 (10)0.0138 (12)0.0144 (11)
O30.0600 (15)0.0385 (13)0.0772 (19)0.0097 (11)0.0352 (14)0.0068 (12)
O40.0460 (14)0.0407 (13)0.0689 (18)0.0055 (10)0.0252 (13)0.0074 (12)
Geometric parameters (Å, º) top
C1—O11.224 (3)C10—C111.512 (4)
C1—O21.279 (3)C10—H10A0.9700
C1—C21.520 (4)C10—H10B0.9700
C2—C31.393 (4)C11—C121.516 (4)
C2—C71.407 (4)C11—H11A0.9700
C3—C41.386 (4)C11—H11B0.9700
C3—H30.9300C12—N31.494 (3)
C4—C51.375 (4)C12—H12A0.9700
C4—H40.9300C12—H12B0.9700
C5—C61.379 (4)C13—N31.489 (3)
C5—H50.9300C13—H13A0.9600
C6—C71.399 (4)C13—H13B0.9600
C6—H60.9300C13—H13C0.9600
C7—N11.408 (3)C14—N31.485 (4)
C8—C91.534 (4)C14—H14A0.9600
C8—O31.217 (3)C14—H14B0.9600
C9—O41.222 (3)C14—H14C0.9600
C8—N11.345 (3)N1—H10.8600
C9—N21.325 (3)N2—H20.8600
C10—N21.451 (3)N3—H3A0.912 (19)
O1—C1—O2125.0 (3)C12—C11—H11A109.6
O1—C1—C2119.3 (3)C10—C11—H11B109.6
O2—C1—C2115.7 (3)C12—C11—H11B109.6
C3—C2—C7118.4 (3)H11A—C11—H11B108.1
C3—C2—C1118.0 (3)N3—C12—C11113.0 (2)
C7—C2—C1123.5 (2)N3—C12—H12A109.0
C4—C3—C2121.4 (3)C11—C12—H12A109.0
C4—C3—H3119.3N3—C12—H12B109.0
C2—C3—H3119.3C11—C12—H12B109.0
C5—C4—C3119.4 (3)H12A—C12—H12B107.8
C5—C4—H4120.3N3—C13—H13A109.5
C3—C4—H4120.3N3—C13—H13B109.5
C4—C5—C6120.9 (3)H13A—C13—H13B109.5
C4—C5—H5119.6N3—C13—H13C109.5
C6—C5—H5119.6H13A—C13—H13C109.5
C5—C6—C7120.1 (3)H13B—C13—H13C109.5
C5—C6—H6120.0N3—C14—H14A109.5
C7—C6—H6120.0N3—C14—H14B109.5
C6—C7—C2119.7 (3)H14A—C14—H14B109.5
C6—C7—N1121.0 (3)N3—C14—H14C109.5
C2—C7—N1119.3 (3)H14A—C14—H14C109.5
O3—C8—N1126.7 (3)H14B—C14—H14C109.5
O3—C8—C9121.6 (3)C8—N1—C7127.7 (2)
N1—C8—C9111.6 (3)C8—N1—H1116.2
O4—C9—N2125.0 (3)C7—N1—H1116.2
O4—C9—C8121.9 (3)C9—N2—C10122.5 (3)
N2—C9—C8113.0 (3)C9—N2—H2118.8
N2—C10—C11110.3 (3)C10—N2—H2118.8
N2—C10—H10A109.6C14—N3—C13110.1 (2)
C11—C10—H10A109.6C14—N3—C12114.5 (2)
N2—C10—H10B109.6C13—N3—C12110.8 (2)
C11—C10—H10B109.6C14—N3—H3A107.4 (18)
H10A—C10—H10B108.1C13—N3—H3A106.8 (17)
C10—C11—C12110.4 (2)C12—N3—H3A107.0 (18)
C10—C11—H11A109.6
O1—C1—C2—C323.4 (4)O3—C8—C9—O4177.5 (3)
O2—C1—C2—C3154.9 (3)O3—C8—C9—N23.5 (4)
O1—C1—C2—C7159.7 (3)N1—C8—C9—N2174.2 (3)
O2—C1—C2—C722.0 (4)N1—C8—C9—O44.8 (4)
C7—C2—C3—C41.9 (4)N2—C10—C11—C12173.0 (2)
C1—C2—C3—C4175.2 (3)C10—C11—C12—N3167.4 (3)
C2—C3—C4—C51.5 (5)O3—C8—N1—C72.7 (5)
C3—C4—C5—C60.3 (5)C9—C8—N1—C7174.9 (3)
C4—C5—C6—C71.6 (5)C2—C7—N1—C8154.0 (3)
C5—C6—C7—C21.1 (4)C6—C7—N1—C827.0 (4)
C5—C6—C7—N1177.8 (3)O4—C9—N2—C100.0 (5)
C3—C2—C7—C60.6 (4)C8—C9—N2—C10178.9 (3)
C1—C2—C7—C6176.3 (3)C11—C10—N2—C9151.3 (3)
C3—C2—C7—N1179.6 (2)C11—C12—N3—C1458.1 (3)
C1—C2—C7—N12.7 (4)C11—C12—N3—C13176.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.861.982.637 (3)132
N3—H3A···O2i0.91 (2)1.69 (2)2.604 (3)177 (3)
Symmetry code: (i) x+1, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC14H19N3O4
Mr293.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)14.780 (5), 8.762 (3), 11.576 (4)
β (°) 104.193 (5)
V3)1453.4 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.24 × 0.23 × 0.10
Data collection
DiffractometerBruker APEX area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7492, 2628, 1374
Rint0.059
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.139, 1.03
No. of reflections2628
No. of parameters196
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.861.982.637 (3)132
N3—H3A···O2i0.912 (19)1.693 (18)2.604 (3)177 (3)
Symmetry code: (i) x+1, y1/2, z+3/2.
 

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