This paper reports the synthesis, X-ray and NMR investigations of chiral and
meso dinitriles of tartaric acid (tartarodinitriles) and their
O,
O′-diacetyl and
O,
O′-dibenzoyl derivatives. While in chiral tartaric acid its esters and NH amides the four-atom carbon chain is overwhelmingly
trans, it is
gauche in chiral tartarodinitriles. Conversely,
meso-tartaric acid, its esters and amides display a tendency for the
gauche conformation, but
meso-tartarodinitriles usually have the
trans conformation. The NMR studies of tartarodinitriles reveal the presence of a conformational equilibrium in solution with a preference for those conformers found in crystals. The
gauche conformation of
meso-tartarodinitriles seems to be stabilized by local dipolar interactions, intramolecular C—H
O hydrogen bonds and by a tendency for maximization of the
gauche effect, the latter effect also operating in chiral tartarodinitriles. Stabilization of the
trans conformers of tartarodinitriles in the crystals seems to originate from specific intermolecular interactions.
Supporting information
CCDC references: 699601; 699602; 699603; 699604
For all compounds, data collection: CrysAlis CCD v.1.171 (Oxford Diffraction,2007); cell refinement: CrysAlis PRO v.1.171 (Oxford Diffraction,2007); data reduction: CrysAlis PRO v.1.171 (Oxford Diffraction,2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Simens Analytical X-Ray Instruments (1989), Mercury (Bruno, et al. 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Crystal data top
C4H4N2O2 | Dx = 1.519 Mg m−3 |
Mr = 112.09 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 478 reflections |
a = 7.2155 (15) Å | θ = 3.8–26.1° |
b = 6.2725 (12) Å | µ = 0.13 mm−1 |
c = 10.828 (2) Å | T = 130 K |
V = 490.04 (17) Å3 | Prismatic, colourless |
Z = 4 | 0.50 × 0.35 × 0.20 mm |
F(000) = 232 | |
Data collection top
Kuma KM4CCD κ-geometry diffractometer | 352 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.039 |
Graphite monochromator | θmax = 26.1°, θmin = 3.8° |
ω scans | h = −8→5 |
2811 measured reflections | k = −7→7 |
478 independent reflections | l = −13→13 |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | Riding |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0645P)2] where P = (Fo2 + 2Fc2)/3 |
478 reflections | (Δ/σ)max < 0.001 |
41 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.1068 (3) | 0.1971 (3) | 0.39095 (19) | 0.0213 (5) | |
C2 | 0.0641 (3) | 0.0965 (3) | 0.51150 (17) | 0.0196 (6) | |
H2A | −0.0003 | 0.2018 | 0.5659 | 0.024* | |
N1 | 0.1434 (2) | 0.2728 (3) | 0.29811 (14) | 0.0269 (5) | |
O2 | 0.23079 (18) | 0.0297 (2) | 0.56832 (13) | 0.0220 (5) | |
H2O | 0.229 (3) | 0.085 (4) | 0.642 (2) | 0.045 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0228 (11) | 0.0190 (11) | 0.0222 (11) | 0.0014 (8) | −0.0010 (9) | −0.0021 (9) |
C2 | 0.0216 (11) | 0.0213 (11) | 0.0158 (10) | 0.0020 (8) | 0.0001 (8) | −0.0008 (8) |
N1 | 0.0317 (10) | 0.0293 (10) | 0.0196 (10) | −0.0036 (8) | 0.0017 (8) | 0.0011 (8) |
O2 | 0.0250 (8) | 0.0248 (8) | 0.0161 (8) | 0.0014 (6) | −0.0034 (6) | −0.0023 (6) |
Geometric parameters (Å, º) top
C1—N1 | 1.143 (2) | C2—C2i | 1.544 (4) |
C1—C2 | 1.482 (3) | C2—H2A | 1.0000 |
C2—O2 | 1.414 (2) | O2—H2O | 0.87 (3) |
| | | |
N1—C1—C2 | 178.6 (2) | O2—C2—H2A | 109.5 |
O2—C2—C1 | 109.40 (15) | C1—C2—H2A | 109.5 |
O2—C2—C2i | 110.34 (19) | C2i—C2—H2A | 109.5 |
C1—C2—C2i | 108.45 (19) | C2—O2—H2O | 105.5 (16) |
Symmetry code: (i) −x, −y, −z+1. |
Crystal data top
C8H8N2O4 | Dx = 1.361 Mg m−3 |
Mr = 196.16 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1892 reflections |
a = 12.4510 (4) Å | θ = 2.8–26.1° |
b = 8.5089 (3) Å | µ = 0.11 mm−1 |
c = 18.0764 (5) Å | T = 130 K |
V = 1915.09 (11) Å3 | Cube, colourless |
Z = 8 | 0.60 × 0.40 × 0.40 mm |
F(000) = 816 | |
Data collection top
Kuma KM4CCD κ-geometry diffractometer | 1438 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 26.1°, θmin = 2.8° |
ω scans | h = −14→15 |
7983 measured reflections | k = −5→10 |
1892 independent reflections | l = −18→22 |
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)] = 0.029 | Riding |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.1378P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1892 reflections | Δρmax = 0.15 e Å−3 |
128 parameters | Δρmin = −0.21 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: 0.0030 (7) |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.28613 (10) | 0.68999 (15) | 0.20264 (6) | 0.0303 (3) | |
C2 | 0.39887 (9) | 0.66610 (13) | 0.17984 (6) | 0.0235 (3) | |
H2A | 0.4425 | 0.6308 | 0.2232 | 0.028* | |
C3 | 0.44618 (9) | 0.81709 (14) | 0.14802 (6) | 0.0235 (3) | |
H3A | 0.4502 | 0.8992 | 0.1875 | 0.028* | |
C4 | 0.38312 (9) | 0.87712 (14) | 0.08435 (6) | 0.0254 (3) | |
N1 | 0.19831 (9) | 0.71034 (15) | 0.21825 (6) | 0.0446 (3) | |
O2 | 0.39879 (6) | 0.54666 (9) | 0.12411 (4) | 0.0241 (2) | |
O3 | 0.55178 (6) | 0.77781 (9) | 0.12351 (4) | 0.0260 (2) | |
N4 | 0.33504 (9) | 0.92360 (13) | 0.03556 (6) | 0.0393 (3) | |
C20 | 0.46945 (9) | 0.42452 (14) | 0.13412 (6) | 0.0238 (3) | |
O20 | 0.52640 (6) | 0.41396 (11) | 0.18723 (4) | 0.0300 (2) | |
C21 | 0.46398 (10) | 0.31504 (15) | 0.07021 (7) | 0.0333 (3) | |
H21A | 0.4974 | 0.3642 | 0.0269 | 0.040* | 0.70 |
H21B | 0.3887 | 0.2910 | 0.0592 | 0.040* | 0.70 |
H21C | 0.5022 | 0.2177 | 0.0824 | 0.040* | 0.70 |
H21D | 0.4227 | 0.2220 | 0.0848 | 0.040* | 0.30 |
H21E | 0.5366 | 0.2841 | 0.0552 | 0.040* | 0.30 |
H21F | 0.4292 | 0.3669 | 0.0281 | 0.040* | 0.30 |
C30 | 0.62837 (9) | 0.89243 (13) | 0.13243 (6) | 0.0240 (3) | |
O30 | 0.60689 (7) | 1.01851 (10) | 0.15784 (5) | 0.0328 (2) | |
C31 | 0.73445 (9) | 0.83722 (15) | 0.10555 (7) | 0.0312 (3) | |
H31A | 0.7493 | 0.7325 | 0.1257 | 0.037* | 0.70 |
H31B | 0.7905 | 0.9104 | 0.1217 | 0.037* | 0.70 |
H31C | 0.7336 | 0.8322 | 0.0514 | 0.037* | 0.70 |
H31D | 0.7650 | 0.9168 | 0.0725 | 0.037* | 0.30 |
H31E | 0.7260 | 0.7377 | 0.0789 | 0.037* | 0.30 |
H31F | 0.7828 | 0.8196 | 0.1475 | 0.037* | 0.30 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0349 (7) | 0.0330 (7) | 0.0229 (6) | 0.0041 (6) | −0.0007 (5) | 0.0024 (5) |
C2 | 0.0265 (6) | 0.0244 (6) | 0.0196 (5) | 0.0042 (5) | −0.0025 (4) | −0.0018 (5) |
C3 | 0.0235 (6) | 0.0239 (6) | 0.0230 (6) | 0.0031 (5) | −0.0030 (4) | −0.0062 (5) |
C4 | 0.0291 (7) | 0.0212 (6) | 0.0259 (6) | 0.0007 (5) | 0.0014 (5) | −0.0028 (5) |
N1 | 0.0356 (7) | 0.0605 (9) | 0.0377 (6) | 0.0093 (6) | 0.0050 (5) | 0.0041 (6) |
O2 | 0.0278 (4) | 0.0217 (4) | 0.0227 (4) | 0.0019 (3) | −0.0038 (3) | −0.0020 (3) |
O3 | 0.0225 (4) | 0.0235 (5) | 0.0321 (4) | 0.0017 (3) | −0.0010 (3) | −0.0069 (4) |
N4 | 0.0466 (7) | 0.0379 (7) | 0.0333 (6) | 0.0075 (5) | −0.0065 (5) | 0.0040 (5) |
C20 | 0.0230 (6) | 0.0228 (6) | 0.0257 (6) | −0.0008 (5) | 0.0049 (5) | 0.0037 (5) |
O20 | 0.0282 (4) | 0.0365 (5) | 0.0252 (4) | 0.0074 (4) | −0.0018 (3) | 0.0020 (4) |
C21 | 0.0417 (8) | 0.0261 (7) | 0.0322 (7) | 0.0024 (6) | −0.0005 (5) | −0.0038 (5) |
C30 | 0.0295 (6) | 0.0231 (7) | 0.0194 (5) | −0.0009 (5) | −0.0052 (4) | 0.0040 (5) |
O30 | 0.0400 (5) | 0.0234 (5) | 0.0350 (5) | −0.0045 (4) | 0.0048 (4) | −0.0043 (4) |
C31 | 0.0267 (7) | 0.0317 (7) | 0.0353 (6) | 0.0023 (5) | −0.0020 (5) | 0.0048 (6) |
Geometric parameters (Å, º) top
C1—N1 | 1.1424 (15) | C21—H21B | 0.9799 |
C1—C2 | 1.4771 (17) | C21—H21C | 0.9800 |
C2—O2 | 1.4310 (13) | C21—H21D | 0.9799 |
C2—C3 | 1.5259 (16) | C21—H21E | 0.9801 |
C2—H2A | 1.0000 | C21—H21F | 0.9801 |
C3—O3 | 1.4272 (14) | C30—O30 | 1.1973 (14) |
C3—C4 | 1.4839 (16) | C30—C31 | 1.4837 (16) |
C3—H3A | 1.0000 | C31—H31A | 0.9801 |
C4—N4 | 1.1369 (14) | C31—H31B | 0.9800 |
O2—C20 | 1.3737 (13) | C31—H31C | 0.9798 |
O3—C30 | 1.3735 (14) | C31—H31D | 0.9799 |
C20—O20 | 1.1969 (13) | C31—H31E | 0.9800 |
C20—C21 | 1.4857 (16) | C31—H31F | 0.9800 |
C21—H21A | 0.9800 | | |
| | | |
N1—C1—C2 | 177.95 (13) | H21C—C21—H21E | 52.2 |
O2—C2—C1 | 107.07 (9) | H21D—C21—H21E | 109.9 |
O2—C2—C3 | 109.45 (8) | C20—C21—H21F | 109.9 |
C1—C2—C3 | 110.87 (10) | H21A—C21—H21F | 51.4 |
O2—C2—H2A | 109.8 | H21B—C21—H21F | 60.9 |
C1—C2—H2A | 109.8 | H21C—C21—H21F | 140.3 |
C3—C2—H2A | 109.8 | H21D—C21—H21F | 109.9 |
O3—C3—C4 | 109.10 (9) | H21E—C21—H21F | 108.3 |
O3—C3—C2 | 105.99 (9) | O30—C30—O3 | 121.75 (10) |
C4—C3—C2 | 112.21 (9) | O30—C30—C31 | 127.46 (11) |
O3—C3—H3A | 109.8 | O3—C30—C31 | 110.78 (10) |
C4—C3—H3A | 109.8 | C30—C31—H31A | 109.5 |
C2—C3—H3A | 109.8 | C30—C31—H31B | 109.6 |
N4—C4—C3 | 179.74 (14) | H31A—C31—H31B | 109.5 |
C20—O2—C2 | 116.36 (8) | C30—C31—H31C | 109.4 |
C30—O3—C3 | 115.91 (9) | H31A—C31—H31C | 109.5 |
O20—C20—O2 | 122.82 (11) | H31B—C31—H31C | 109.5 |
O20—C20—C21 | 127.14 (11) | C30—C31—H31D | 109.0 |
O2—C20—C21 | 110.03 (9) | H31A—C31—H31D | 141.4 |
C20—C21—H21A | 109.5 | H31B—C31—H31D | 57.8 |
C20—C21—H21B | 109.5 | H31C—C31—H31D | 54.9 |
H21A—C21—H21B | 109.5 | C30—C31—H31E | 109.8 |
C20—C21—H21C | 109.5 | H31A—C31—H31E | 54.3 |
H21A—C21—H21C | 109.5 | H31B—C31—H31E | 140.6 |
H21B—C21—H21C | 109.5 | H31C—C31—H31E | 58.0 |
C20—C21—H21D | 108.8 | H31D—C31—H31E | 109.9 |
H21A—C21—H21D | 141.5 | C30—C31—H31F | 110.0 |
H21B—C21—H21D | 52.0 | H31A—C31—H31F | 57.2 |
H21C—C21—H21D | 60.8 | H31B—C31—H31F | 55.2 |
C20—C21—H21E | 109.9 | H31C—C31—H31F | 140.6 |
H21A—C21—H21E | 60.1 | H31D—C31—H31F | 109.9 |
H21B—C21—H21E | 140.4 | H31E—C31—H31F | 108.3 |
| | | |
O2—C2—C3—O3 | −58.33 (11) | C4—C3—O3—C30 | 94.79 (11) |
C1—C2—C3—O3 | −176.21 (9) | C2—C3—O3—C30 | −144.19 (9) |
O2—C2—C3—C4 | 60.66 (12) | C2—O2—C20—O20 | 2.15 (15) |
C1—C2—C3—C4 | −57.22 (12) | C2—O2—C20—C21 | −177.08 (9) |
C1—C2—O2—C20 | −129.58 (9) | C3—O3—C30—O30 | −1.49 (15) |
C3—C2—O2—C20 | 110.19 (10) | C3—O3—C30—C31 | 179.53 (9) |
Crystal data top
C18H12N2O4 | Z = 1 |
Mr = 320.30 | F(000) = 166 |
Triclinic, P1 | Dx = 1.354 Mg m−3 |
a = 5.7840 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.3241 (18) Å | Cell parameters from 690 reflections |
c = 10.229 (3) Å | θ = 2.2–26.0° |
α = 106.26 (2)° | µ = 0.10 mm−1 |
β = 105.30 (2)° | T = 295 K |
γ = 96.55 (2)° | Plate, colourless |
V = 392.90 (18) Å3 | 0.40 × 0.20 × 0.10 mm |
Data collection top
Kuma KM4CCD κ-geometry diffractometer | 720 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 26.0°, θmin = 2.2° |
ω scans | h = −7→7 |
3310 measured reflections | k = −9→8 |
1526 independent reflections | l = −12→12 |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | Riding |
S = 0.87 | w = 1/[σ2(Fo2) + (0.0602P)2] where P = (Fo2 + 2Fc2)/3 |
1526 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.7067 (4) | 0.3356 (4) | −0.0651 (2) | 0.1004 (8) | |
C1 | 0.6776 (4) | 0.2093 (4) | −0.0243 (2) | 0.0733 (7) | |
C2 | 0.6353 (3) | 0.0443 (3) | 0.02731 (18) | 0.0582 (6) | |
H2A | 0.7299 | −0.0526 | −0.0042 | 0.070* | |
O2 | 0.6942 (2) | 0.10852 (19) | 0.17988 (12) | 0.0571 (4) | |
C20 | 0.9385 (4) | 0.1618 (3) | 0.25485 (18) | 0.0484 (5) | |
O20 | 1.0897 (3) | 0.1597 (2) | 0.19460 (14) | 0.0721 (5) | |
C21 | 0.9803 (3) | 0.2197 (2) | 0.41001 (17) | 0.0425 (5) | |
C22 | 1.2117 (4) | 0.3173 (3) | 0.4994 (2) | 0.0521 (5) | |
H22A | 1.3350 | 0.3450 | 0.4609 | 0.063* | |
C23 | 1.2594 (4) | 0.3735 (3) | 0.6457 (2) | 0.0634 (6) | |
H23A | 1.4145 | 0.4408 | 0.7060 | 0.076* | |
C24 | 1.0797 (5) | 0.3305 (3) | 0.7026 (2) | 0.0649 (6) | |
H24A | 1.1132 | 0.3679 | 0.8014 | 0.078* | |
C25 | 0.8507 (4) | 0.2327 (3) | 0.6147 (2) | 0.0601 (6) | |
H25A | 0.7290 | 0.2033 | 0.6539 | 0.072* | |
C26 | 0.8002 (4) | 0.1778 (3) | 0.4680 (2) | 0.0516 (5) | |
H26A | 0.6440 | 0.1123 | 0.4083 | 0.062* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0971 (17) | 0.126 (2) | 0.0553 (13) | −0.0152 (16) | 0.0036 (12) | 0.0280 (13) |
C1 | 0.0633 (16) | 0.103 (2) | 0.0341 (12) | −0.0084 (15) | 0.0072 (11) | 0.0106 (12) |
C2 | 0.0433 (11) | 0.0877 (16) | 0.0270 (10) | 0.0052 (12) | 0.0070 (9) | −0.0002 (10) |
O2 | 0.0389 (8) | 0.0883 (10) | 0.0280 (7) | 0.0079 (7) | 0.0046 (6) | 0.0016 (6) |
C20 | 0.0393 (12) | 0.0567 (12) | 0.0397 (12) | 0.0105 (10) | 0.0074 (10) | 0.0054 (9) |
O20 | 0.0454 (9) | 0.1107 (13) | 0.0463 (9) | 0.0106 (8) | 0.0160 (7) | 0.0042 (8) |
C21 | 0.0386 (11) | 0.0491 (11) | 0.0328 (10) | 0.0124 (9) | 0.0047 (9) | 0.0069 (9) |
C22 | 0.0433 (12) | 0.0538 (12) | 0.0481 (12) | 0.0083 (10) | 0.0044 (10) | 0.0093 (10) |
C23 | 0.0570 (15) | 0.0632 (14) | 0.0458 (13) | 0.0070 (12) | −0.0088 (11) | 0.0059 (11) |
C24 | 0.0811 (18) | 0.0686 (14) | 0.0352 (11) | 0.0196 (14) | 0.0069 (12) | 0.0105 (10) |
C25 | 0.0656 (15) | 0.0707 (15) | 0.0449 (13) | 0.0155 (13) | 0.0190 (12) | 0.0176 (11) |
C26 | 0.0439 (12) | 0.0593 (12) | 0.0427 (12) | 0.0065 (11) | 0.0063 (10) | 0.0112 (10) |
Geometric parameters (Å, º) top
N1—C1 | 1.130 (3) | C22—C23 | 1.377 (2) |
C1—C2 | 1.468 (3) | C22—H22A | 0.9300 |
C2—O2 | 1.430 (2) | C23—C24 | 1.365 (3) |
C2—C2i | 1.512 (4) | C23—H23A | 0.9300 |
C2—H2A | 0.9800 | C24—C25 | 1.367 (3) |
O2—C20 | 1.368 (2) | C24—H24A | 0.9300 |
C20—O20 | 1.195 (2) | C25—C26 | 1.380 (2) |
C20—C21 | 1.468 (2) | C25—H25A | 0.9300 |
C21—C26 | 1.373 (2) | C26—H26A | 0.9300 |
C21—C22 | 1.382 (2) | | |
| | | |
N1—C1—C2 | 179.0 (3) | C23—C22—H22A | 120.1 |
O2—C2—C1 | 110.77 (16) | C21—C22—H22A | 120.1 |
O2—C2—C2i | 104.71 (17) | C24—C23—C22 | 120.20 (19) |
C1—C2—C2i | 109.1 (2) | C24—C23—H23A | 119.9 |
O2—C2—H2A | 110.7 | C22—C23—H23A | 119.9 |
C1—C2—H2A | 110.7 | C23—C24—C25 | 120.29 (19) |
C2i—C2—H2A | 110.7 | C23—C24—H24A | 119.9 |
C20—O2—C2 | 115.70 (13) | C25—C24—H24A | 119.9 |
O20—C20—O2 | 121.10 (16) | C24—C25—C26 | 119.98 (19) |
O20—C20—C21 | 127.29 (18) | C24—C25—H25A | 120.0 |
O2—C20—C21 | 111.61 (15) | C26—C25—H25A | 120.0 |
C26—C21—C22 | 119.61 (16) | C21—C26—C25 | 120.07 (18) |
C26—C21—C20 | 122.50 (17) | C21—C26—H26A | 120.0 |
C22—C21—C20 | 117.89 (17) | C25—C26—H26A | 120.0 |
C23—C22—C21 | 119.84 (18) | | |
| | | |
C1—C2—O2—C20 | −74.2 (2) | C26—C21—C22—C23 | −0.7 (3) |
C2i—C2—O2—C20 | 168.31 (19) | C20—C21—C22—C23 | −179.67 (16) |
C2—O2—C20—O20 | 2.3 (3) | C21—C22—C23—C24 | 1.0 (3) |
C2—O2—C20—C21 | −178.29 (15) | C22—C23—C24—C25 | −0.5 (3) |
O20—C20—C21—C26 | −165.4 (2) | C23—C24—C25—C26 | −0.3 (3) |
O2—C20—C21—C26 | 15.2 (2) | C22—C21—C26—C25 | −0.1 (3) |
O20—C20—C21—C22 | 13.5 (3) | C20—C21—C26—C25 | 178.87 (17) |
O2—C20—C21—C22 | −165.85 (16) | C24—C25—C26—C21 | 0.6 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Crystal data top
C8H8N2O4 | Dx = 1.307 Mg m−3 |
Mr = 196.16 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 1149 reflections |
a = 8.6112 (3) Å | θ = 3.2–26.0° |
b = 9.8185 (3) Å | µ = 0.11 mm−1 |
c = 11.7898 (3) Å | T = 295 K |
V = 996.82 (5) Å3 | Cube, colourless |
Z = 4 | 0.55 × 0.50 × 0.40 mm |
F(000) = 408 | |
Data collection top
Kuma KM4CCD κ-geometry diffractometer | 980 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −8→10 |
7153 measured reflections | k = −12→11 |
1149 independent reflections | l = −14→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)] = 0.035 | Riding |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0755P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1149 reflections | Δρmax = 0.19 e Å−3 |
129 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0 (10) |
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 | x | y | z | Uiso*/Ueq | |
N1 | −0.0675 (3) | 0.6798 (3) | 0.25884 (18) | 0.0840 (7) | |
C1 | −0.0507 (3) | 0.5911 (2) | 0.19802 (17) | 0.0518 (5) | |
C2 | −0.0346 (2) | 0.47826 (19) | 0.11753 (15) | 0.0440 (4) | |
H2 | 0.0133 | 0.4001 | 0.1556 | 0.053* | |
C3 | −0.1917 (2) | 0.4360 (2) | 0.06801 (16) | 0.0461 (5) | |
H3 | −0.1777 | 0.3589 | 0.0163 | 0.055* | |
C4 | −0.2644 (2) | 0.5505 (3) | 0.00702 (17) | 0.0576 (6) | |
N4 | −0.3176 (3) | 0.6410 (3) | −0.0378 (3) | 0.0898 (8) | |
O2 | 0.05725 (14) | 0.51668 (14) | 0.02206 (11) | 0.0481 (4) | |
C20 | 0.2150 (2) | 0.5150 (2) | 0.03972 (19) | 0.0529 (5) | |
O20 | 0.26812 (19) | 0.4952 (2) | 0.13107 (14) | 0.0737 (5) | |
C21 | 0.3002 (3) | 0.5398 (3) | −0.0676 (2) | 0.0705 (7) | |
H211 | 0.3414 | 0.6307 | −0.0674 | 0.085* | |
H212 | 0.2306 | 0.5293 | −0.1306 | 0.085* | |
H213 | 0.3838 | 0.4756 | −0.0744 | 0.085* | |
O3 | −0.28422 (17) | 0.39526 (15) | 0.16257 (11) | 0.0550 (4) | |
C30 | −0.4056 (2) | 0.3105 (2) | 0.13934 (18) | 0.0514 (5) | |
O30 | −0.4366 (2) | 0.28067 (19) | 0.04418 (15) | 0.0760 (5) | |
C31 | −0.4855 (3) | 0.2673 (3) | 0.2438 (2) | 0.0736 (7) | |
H311 | −0.5877 | 0.2352 | 0.2253 | 0.088* | |
H312 | −0.4932 | 0.3431 | 0.2948 | 0.088* | |
H313 | −0.4276 | 0.1954 | 0.2793 | 0.088* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.1129 (19) | 0.0706 (13) | 0.0685 (12) | −0.0044 (15) | −0.0085 (13) | −0.0210 (11) |
C1 | 0.0551 (12) | 0.0498 (11) | 0.0507 (10) | −0.0009 (10) | −0.0094 (9) | −0.0005 (9) |
C2 | 0.0400 (9) | 0.0409 (10) | 0.0512 (9) | 0.0009 (8) | −0.0020 (8) | 0.0030 (8) |
C3 | 0.0426 (10) | 0.0465 (10) | 0.0492 (9) | −0.0055 (9) | 0.0034 (8) | −0.0055 (8) |
C4 | 0.0403 (10) | 0.0726 (14) | 0.0600 (11) | −0.0070 (11) | −0.0051 (9) | 0.0050 (11) |
N4 | 0.0602 (13) | 0.1009 (17) | 0.1084 (17) | −0.0027 (13) | −0.0188 (13) | 0.0371 (16) |
O2 | 0.0366 (7) | 0.0524 (8) | 0.0551 (7) | −0.0024 (6) | −0.0012 (6) | 0.0050 (6) |
C20 | 0.0363 (10) | 0.0533 (11) | 0.0689 (11) | 0.0012 (9) | −0.0054 (9) | 0.0034 (10) |
O20 | 0.0499 (9) | 0.0967 (13) | 0.0746 (9) | −0.0008 (9) | −0.0141 (8) | 0.0168 (10) |
C21 | 0.0454 (12) | 0.0897 (17) | 0.0764 (14) | −0.0015 (13) | 0.0053 (11) | 0.0112 (14) |
O3 | 0.0508 (8) | 0.0640 (9) | 0.0502 (7) | −0.0121 (7) | 0.0049 (6) | −0.0051 (7) |
C30 | 0.0433 (10) | 0.0453 (10) | 0.0656 (12) | −0.0033 (9) | 0.0030 (9) | 0.0013 (10) |
O30 | 0.0719 (12) | 0.0816 (11) | 0.0744 (10) | −0.0318 (10) | 0.0036 (9) | −0.0185 (9) |
C31 | 0.0597 (14) | 0.0829 (18) | 0.0783 (14) | −0.0083 (14) | 0.0081 (12) | 0.0221 (13) |
Geometric parameters (Å, º) top
N1—C1 | 1.137 (3) | C20—C21 | 1.483 (3) |
C1—C2 | 1.465 (3) | C21—H211 | 0.9600 |
C2—O2 | 1.426 (2) | C21—H212 | 0.9600 |
C2—C3 | 1.531 (3) | C21—H213 | 0.9600 |
C2—H2 | 0.9800 | O3—C30 | 1.364 (2) |
C3—O3 | 1.428 (2) | C30—O30 | 1.190 (3) |
C3—C4 | 1.474 (3) | C30—C31 | 1.473 (3) |
C3—H3 | 0.9800 | C31—H311 | 0.9600 |
C4—N4 | 1.130 (3) | C31—H312 | 0.9600 |
O2—C20 | 1.374 (2) | C31—H313 | 0.9600 |
C20—O20 | 1.186 (3) | | |
| | | |
N1—C1—C2 | 177.9 (3) | O2—C20—C21 | 110.97 (18) |
O2—C2—C1 | 111.32 (16) | C20—C21—H211 | 109.5 |
O2—C2—C3 | 105.11 (14) | C20—C21—H212 | 109.5 |
C1—C2—C3 | 111.58 (15) | H211—C21—H212 | 109.5 |
O2—C2—H2 | 109.6 | C20—C21—H213 | 109.5 |
C1—C2—H2 | 109.6 | H211—C21—H213 | 109.5 |
C3—C2—H2 | 109.6 | H212—C21—H213 | 109.5 |
O3—C3—C4 | 110.95 (16) | C30—O3—C3 | 116.23 (14) |
O3—C3—C2 | 105.75 (14) | O30—C30—O3 | 120.76 (19) |
C4—C3—C2 | 110.80 (16) | O30—C30—C31 | 127.8 (2) |
O3—C3—H3 | 109.8 | O3—C30—C31 | 111.5 (2) |
C4—C3—H3 | 109.8 | C30—C31—H311 | 109.5 |
C2—C3—H3 | 109.8 | C30—C31—H312 | 109.5 |
N4—C4—C3 | 177.9 (3) | H311—C31—H312 | 109.5 |
C20—O2—C2 | 115.17 (15) | C30—C31—H313 | 109.5 |
O20—C20—O2 | 121.40 (19) | H311—C31—H313 | 109.5 |
O20—C20—C21 | 127.63 (18) | H312—C31—H313 | 109.5 |
| | | |
O2—C2—C3—O3 | 179.14 (14) | C2—O2—C20—O20 | −6.7 (3) |
C1—C2—C3—O3 | −60.1 (2) | C2—O2—C20—C21 | 173.09 (19) |
O2—C2—C3—C4 | −60.56 (19) | C4—C3—O3—C30 | 82.0 (2) |
C1—C2—C3—C4 | 60.2 (2) | C2—C3—O3—C30 | −157.76 (15) |
C1—C2—O2—C20 | 79.8 (2) | C3—O3—C30—O30 | −4.8 (3) |
C3—C2—O2—C20 | −159.25 (16) | C3—O3—C30—C31 | 175.84 (19) |