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N-Carbamylmaleamic acid (malur) undergoes cyclodehydration under favourable conditions, as expected, to give N-carbamyl maleimide. N-(Carboxymethyl) maleamic acid (malgly), however, does not undergo a similar cyclization reaction. Strong π bonding between the C and N of the amide group as well as two intramolecular hydrogen bonds makes malgly a planar molecule, as revealed by single-crystal X-ray studies.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614018952/eb5032sup1.cif
Contains datablocks tpr375, emku145

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614018952/eb5032tpr375sup2.hkl
Contains datablock tpr375

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614018952/eb5032emku145sup3.hkl
Contains datablock emku145

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614018952/eb5032sup4.pdf
This file include the crystallographic and NMR data of malgly and malur along with DFT calculations on selected conformers

CCDC references: 1020675; 1020676

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Data collection: Bruker SMART for tpr375; CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) for emku145. Cell refinement: Bruker SMART for tpr375; CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) for emku145. Data reduction: Bruker SAINT for tpr375; CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) for emku145. For both compounds, program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1]
[Figure 2]
(tpr375) top
Crystal data top
C12H14N2O10Z = 2
Mr = 346.25F(000) = 360
Triclinic, P1Dx = 1.611 Mg m3
a = 8.1895 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.8902 (9) ÅCell parameters from 5586 reflections
c = 10.6709 (9) Åθ = 0.00–0.00°
α = 113.376 (1)°µ = 0.14 mm1
β = 104.250 (1)°T = 273 K
γ = 103.472 (1)°0.42 × 0.40 × 0.26 mm
V = 713.87 (11) Å3
Data collection top
CCD area detector
diffractometer
2770 independent reflections
Radiation source: fine-focus sealed tube2485 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
phi and ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan
SADABS
h = 1010
Tmin = 0.942, Tmax = 0.964k = 1212
7343 measured reflectionsl = 1313
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0624P)2 + 0.111P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2770 reflectionsΔρmax = 0.19 e Å3
236 parametersΔρmin = 0.22 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (4)
Crystal data top
C12H14N2O10γ = 103.472 (1)°
Mr = 346.25V = 713.87 (11) Å3
Triclinic, P1Z = 2
a = 8.1895 (7) ÅMo Kα radiation
b = 9.8902 (9) ŵ = 0.14 mm1
c = 10.6709 (9) ÅT = 273 K
α = 113.376 (1)°0.42 × 0.40 × 0.26 mm
β = 104.250 (1)°
Data collection top
CCD area detector
diffractometer
2770 independent reflections
Absorption correction: multi-scan
SADABS
2485 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.964Rint = 0.023
7343 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.19 e Å3
2770 reflectionsΔρmin = 0.22 e Å3
236 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
xyzUiso*/Ueq
C10.30523 (16)0.38307 (15)0.27100 (14)0.0359 (3)
C20.38612 (16)0.54886 (15)0.30038 (14)0.0369 (3)
H2A0.30180.59060.27250.044*
C30.55791 (17)0.64788 (15)0.35951 (14)0.0365 (3)
H30.57560.74780.36770.044*
C40.72464 (16)0.62028 (14)0.41404 (13)0.0337 (3)
C51.05012 (16)0.72501 (15)0.52427 (16)0.0404 (3)
H5A1.05840.63430.44870.048*
H5B1.05530.70710.60800.048*
C61.20698 (16)0.87195 (15)0.57111 (14)0.0353 (3)
C70.19123 (16)0.15212 (15)0.75852 (14)0.0371 (3)
C80.11311 (17)0.04642 (14)0.79785 (14)0.0379 (3)
H80.19880.04740.77790.046*
C90.05829 (17)0.06284 (15)0.85670 (14)0.0381 (3)
H90.07420.02040.87170.046*
C100.22671 (16)0.19506 (14)0.90154 (13)0.0348 (3)
C110.55194 (16)0.30275 (15)1.00200 (15)0.0387 (3)
H11A0.55650.40221.07570.046*
H11B0.56190.31580.91840.046*
C120.70842 (16)0.26459 (15)1.06553 (14)0.0368 (3)
H1X0.883 (2)0.823 (2)0.4682 (18)0.055 (5)*
H3X1.460 (3)0.953 (2)0.6475 (19)0.071 (5)*
H10X0.960 (3)0.350 (2)1.153 (2)0.077 (6)*
H2Y0.382 (2)0.100 (2)0.9632 (18)0.063 (5)*
N10.87948 (14)0.73978 (13)0.46740 (12)0.0367 (3)
N20.38042 (14)0.17905 (13)0.95489 (12)0.0376 (3)
O10.14090 (12)0.31373 (12)0.21363 (12)0.0521 (3)
O20.40728 (12)0.31060 (11)0.30544 (12)0.0478 (3)
H2X0.51420.36970.34210.072*
O30.72413 (12)0.49293 (11)0.41169 (12)0.0456 (3)
O41.19149 (12)0.98929 (11)0.56895 (11)0.0464 (3)
O51.36132 (12)0.85533 (12)0.61524 (13)0.0525 (3)
O60.35560 (12)0.11275 (12)0.70682 (12)0.0516 (3)
O70.08702 (12)0.28594 (11)0.77821 (13)0.0496 (3)
H7X0.01930.30110.81940.074*
O80.22971 (12)0.31704 (11)0.89144 (12)0.0481 (3)
O90.69398 (13)0.14374 (12)1.07034 (13)0.0554 (3)
O100.86250 (13)0.38047 (12)1.11300 (13)0.0561 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0241 (6)0.0358 (6)0.0467 (6)0.0086 (5)0.0074 (5)0.0237 (5)
C20.0258 (6)0.0359 (6)0.0536 (7)0.0134 (5)0.0103 (5)0.0274 (6)
C30.0295 (6)0.0300 (6)0.0526 (7)0.0113 (5)0.0115 (5)0.0246 (5)
C40.0249 (6)0.0305 (6)0.0438 (6)0.0075 (5)0.0086 (5)0.0205 (5)
C50.0231 (6)0.0364 (7)0.0628 (8)0.0084 (5)0.0086 (5)0.0309 (6)
C60.0254 (6)0.0332 (6)0.0473 (7)0.0095 (5)0.0098 (5)0.0224 (5)
C70.0251 (6)0.0335 (6)0.0506 (7)0.0093 (5)0.0097 (5)0.0220 (5)
C80.0280 (6)0.0294 (6)0.0542 (7)0.0064 (5)0.0113 (5)0.0231 (5)
C90.0309 (6)0.0316 (6)0.0544 (7)0.0117 (5)0.0115 (5)0.0258 (6)
C100.0264 (6)0.0328 (6)0.0438 (6)0.0110 (5)0.0087 (5)0.0198 (5)
C110.0257 (6)0.0349 (6)0.0555 (7)0.0102 (5)0.0091 (5)0.0260 (6)
C120.0267 (6)0.0349 (6)0.0487 (7)0.0109 (5)0.0096 (5)0.0232 (5)
N10.0236 (5)0.0308 (5)0.0556 (6)0.0075 (4)0.0086 (5)0.0260 (5)
N20.0254 (6)0.0330 (6)0.0542 (6)0.0101 (4)0.0083 (5)0.0251 (5)
O10.0233 (5)0.0473 (6)0.0793 (7)0.0063 (4)0.0042 (4)0.0374 (5)
O20.0239 (4)0.0361 (5)0.0798 (7)0.0068 (4)0.0052 (4)0.0355 (5)
O30.0245 (4)0.0337 (5)0.0772 (6)0.0086 (4)0.0079 (4)0.0334 (5)
O40.0295 (5)0.0350 (5)0.0742 (6)0.0110 (4)0.0116 (4)0.0312 (5)
O50.0225 (5)0.0434 (6)0.0914 (8)0.0105 (4)0.0096 (5)0.0402 (5)
O60.0232 (5)0.0470 (5)0.0826 (7)0.0093 (4)0.0093 (4)0.0378 (5)
O70.0243 (4)0.0391 (5)0.0850 (7)0.0088 (4)0.0072 (4)0.0391 (5)
O80.0259 (4)0.0358 (5)0.0805 (7)0.0090 (4)0.0077 (4)0.0347 (5)
O90.0310 (5)0.0437 (6)0.0929 (8)0.0116 (4)0.0093 (5)0.0437 (6)
O100.0241 (5)0.0458 (6)0.0951 (8)0.0063 (4)0.0074 (5)0.0434 (6)
Geometric parameters (Å, º) top
C1—O11.2196 (15)C8—C91.3304 (18)
C1—O21.2977 (15)C8—H80.9300
C1—C21.4864 (17)C9—C101.4763 (17)
C2—C31.3294 (17)C9—H90.9300
C2—H2A0.9300C10—O81.2483 (15)
C3—C41.4785 (17)C10—N21.3211 (16)
C3—H30.9300C11—N21.4444 (16)
C4—O31.2488 (15)C11—C121.4983 (17)
C4—N11.3196 (16)C11—H11A0.9700
C5—N11.4459 (16)C11—H11B0.9700
C5—C61.4999 (17)C12—O91.1963 (16)
C5—H5A0.9700C12—O101.3089 (16)
C5—H5B0.9700N1—H1X0.814 (19)
C6—O41.2048 (15)N2—H2Y0.83 (2)
C6—O51.3083 (15)O2—H2X0.8200
C7—O61.2197 (16)O5—H3X0.97 (2)
C7—O71.2996 (15)O7—H7X0.8200
C7—C81.4851 (17)O10—H10X0.98 (2)
O1—C1—O2119.35 (12)C7—C8—H8114.4
O1—C1—C2119.79 (11)C8—C9—C10128.92 (11)
O2—C1—C2120.86 (11)C8—C9—H9115.5
C3—C2—C1131.26 (11)C10—C9—H9115.5
C3—C2—H2A114.4O8—C10—N2119.96 (12)
C1—C2—H2A114.4O8—C10—C9123.81 (11)
C2—C3—C4128.65 (11)N2—C10—C9116.23 (11)
C2—C3—H3115.7N2—C11—C12111.43 (11)
C4—C3—H3115.7N2—C11—H11A109.3
O3—C4—N1120.25 (11)C12—C11—H11A109.3
O3—C4—C3123.57 (11)N2—C11—H11B109.3
N1—C4—C3116.18 (11)C12—C11—H11B109.3
N1—C5—C6110.85 (11)H11A—C11—H11B108.0
N1—C5—H5A109.5O9—C12—O10124.84 (12)
C6—C5—H5A109.5O9—C12—C11124.43 (12)
N1—C5—H5B109.5O10—C12—C11110.72 (11)
C6—C5—H5B109.5C4—N1—C5120.44 (11)
H5A—C5—H5B108.1C4—N1—H1X121.7 (12)
O4—C6—O5125.04 (11)C5—N1—H1X117.9 (13)
O4—C6—C5124.12 (11)C10—N2—C11120.08 (11)
O5—C6—C5110.84 (11)C10—N2—H2Y121.6 (13)
O6—C7—O7119.47 (12)C11—N2—H2Y118.3 (13)
O6—C7—C8119.56 (11)C1—O2—H2X109.5
O7—C7—C8120.97 (11)C6—O5—H3X108.7 (12)
C9—C8—C7131.11 (12)C7—O7—H7X109.5
C9—C8—H8114.4C12—O10—H10X107.6 (12)
(emku145) top
Crystal data top
C5H6N2O4Dx = 1.597 Mg m3
Mr = 158.12Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 1214 reflections
a = 10.4325 (8) Åθ = 3.3–28.6°
b = 6.7755 (12) ŵ = 0.14 mm1
c = 18.6056 (14) ÅT = 293 K
V = 1315.1 (3) Å3Block, colorless
Z = 80.42 × 0.38 × 0.31 mm
F(000) = 656
Data collection top
Xcalibur, Eos, Gemini
diffractometer
1345 independent reflections
Radiation source: Enhance (Mo) X-ray Source1124 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 26.4°, θmin = 2.9°
Absorption correction: multi-scan
CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
h = 1213
Tmin = 0.944, Tmax = 0.958k = 48
3214 measured reflectionsl = 2313
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 0.97 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
1345 reflections(Δ/σ)max = 0.001
109 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C5H6N2O4V = 1315.1 (3) Å3
Mr = 158.12Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 10.4325 (8) ŵ = 0.14 mm1
b = 6.7755 (12) ÅT = 293 K
c = 18.6056 (14) Å0.42 × 0.38 × 0.31 mm
Data collection top
Xcalibur, Eos, Gemini
diffractometer
1345 independent reflections
Absorption correction: multi-scan
CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
1124 reflections with I > 2σ(I)
Tmin = 0.944, Tmax = 0.958Rint = 0.024
3214 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.21 e Å3
1345 reflectionsΔρmin = 0.19 e Å3
109 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
xyzUiso*/Ueq
H2A0.138 (2)0.136 (3)0.2670 (12)0.047 (6)*
H2B0.146 (2)0.201 (3)0.1884 (14)0.058 (7)*
C10.60903 (17)0.4391 (3)0.10008 (9)0.0355 (5)
C20.55302 (17)0.3068 (3)0.04661 (9)0.0377 (5)
H20.60130.27960.00580.045*
C30.43954 (17)0.2232 (3)0.05173 (10)0.0363 (5)
H30.41680.14240.01340.044*
C40.34293 (16)0.2388 (2)0.10956 (9)0.0321 (4)
C50.30376 (16)0.1547 (3)0.23569 (9)0.0310 (4)
N10.38049 (14)0.1807 (2)0.17645 (7)0.0315 (4)
H10.46090.15780.18220.038*
N20.17948 (14)0.1686 (3)0.22836 (10)0.0396 (4)
O10.54714 (11)0.5343 (2)0.14280 (7)0.0439 (4)
O20.73458 (11)0.4433 (2)0.09632 (7)0.0476 (4)
H2C0.76310.50830.12990.071*
O30.23415 (11)0.2908 (2)0.09558 (7)0.0441 (4)
O40.35592 (11)0.1137 (2)0.29397 (6)0.0404 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0298 (8)0.0427 (10)0.0341 (9)0.0012 (8)0.0038 (7)0.0033 (8)
C20.0363 (10)0.0496 (11)0.0274 (9)0.0030 (9)0.0030 (7)0.0024 (8)
C30.0366 (10)0.0429 (10)0.0295 (9)0.0018 (8)0.0036 (7)0.0074 (8)
C40.0305 (9)0.0339 (9)0.0319 (9)0.0022 (7)0.0050 (7)0.0036 (7)
C50.0276 (8)0.0334 (9)0.0320 (9)0.0039 (7)0.0037 (7)0.0045 (7)
N10.0222 (7)0.0404 (8)0.0320 (8)0.0014 (6)0.0025 (6)0.0018 (6)
N20.0249 (8)0.0571 (11)0.0367 (9)0.0023 (7)0.0000 (7)0.0025 (8)
O10.0320 (7)0.0521 (8)0.0476 (8)0.0003 (6)0.0047 (6)0.0122 (7)
O20.0299 (7)0.0645 (10)0.0484 (8)0.0074 (6)0.0087 (5)0.0118 (7)
O30.0304 (7)0.0626 (9)0.0393 (7)0.0075 (6)0.0062 (5)0.0027 (6)
O40.0300 (7)0.0603 (9)0.0311 (7)0.0078 (6)0.0036 (5)0.0008 (6)
Geometric parameters (Å, º) top
C1—O11.210 (2)C4—N11.363 (2)
C1—O21.312 (2)C5—O41.245 (2)
C1—C21.461 (2)C5—N21.307 (2)
C2—C31.316 (2)C5—N11.373 (2)
C2—H20.9300N1—H10.8600
C3—C41.478 (2)N2—H2A0.87 (2)
C3—H30.9300N2—H2B0.85 (3)
C4—O31.216 (2)O2—H2C0.8200
O1—C1—O2123.76 (17)N1—C4—C3116.61 (15)
O1—C1—C2124.12 (16)O4—C5—N2122.73 (17)
O2—C1—C2112.12 (15)O4—C5—N1118.22 (15)
C3—C2—C1125.07 (16)N2—C5—N1119.02 (16)
C3—C2—H2117.5C4—N1—C5127.03 (15)
C1—C2—H2117.5C4—N1—H1116.5
C2—C3—C4129.44 (16)C5—N1—H1116.5
C2—C3—H3115.3C5—N2—H2A112.9 (15)
C4—C3—H3115.3C5—N2—H2B121.2 (18)
O3—C4—N1123.17 (17)H2A—N2—H2B126 (2)
O3—C4—C3120.09 (16)C1—O2—H2C109.5

Experimental details

(tpr375)(emku145)
Crystal data
Chemical formulaC12H14N2O10C5H6N2O4
Mr346.25158.12
Crystal system, space groupTriclinic, P1Orthorhombic, Pbcn
Temperature (K)273293
a, b, c (Å)8.1895 (7), 9.8902 (9), 10.6709 (9)10.4325 (8), 6.7755 (12), 18.6056 (14)
α, β, γ (°)113.376 (1), 104.250 (1), 103.472 (1)90, 90, 90
V3)713.87 (11)1315.1 (3)
Z28
Radiation typeMo KαMo Kα
µ (mm1)0.140.14
Crystal size (mm)0.42 × 0.40 × 0.260.42 × 0.38 × 0.31
Data collection
DiffractometerCCD area detector
diffractometer
Xcalibur, Eos, Gemini
diffractometer
Absorption correctionMulti-scan
SADABS
Multi-scan
CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax0.942, 0.9640.944, 0.958
No. of measured, independent and
observed [I > 2σ(I)] reflections
7343, 2770, 2485 3214, 1345, 1124
Rint0.0230.024
(sin θ/λ)max1)0.6170.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.103, 1.05 0.041, 0.140, 0.97
No. of reflections27701345
No. of parameters236109
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.220.21, 0.19

Computer programs: Bruker SMART, CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44), Bruker SAINT, SHELXL97 (Sheldrick, 2008).

 

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