The case of prototropic annular tautomerism in an imidazole derivative has been found. The crystal structure contains a 50:50 mixture of two tautomers: 4-nitro-5-methoxyimidazole and 5-nitro-4-methoxyimidazole. The X-ray experiment actually shows the superposition of these compounds; it appears as if the structure is centrosymmetric and the N—H hydrogen atoms are disordered over two ring N atoms. Owing to the hydrogen-bond pattern, the values of their site occupation factors have to be exactly equal to 1/2. The molecules are connected into a three-dimensional network by means of N—H
N and C—H
O hydrogen bonds.
Supporting information
CCDC references: 237249; 237250
For both compounds, data collection: CrysAlis CCD v.169; cell refinement: CrysAlis CCD v.169; data reduction: CrysAlis RED v.169; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
(1) 4(5)-nitro-5(4)-methoxy-1
H-imidazole
top
Crystal data top
C4H5N3O3 | F(000) = 592 |
Mr = 143.11 | Dx = 1.660 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4048 reflections |
a = 7.5542 (6) Å | θ = 4–22° |
b = 11.3112 (9) Å | µ = 0.14 mm−1 |
c = 13.4773 (10) Å | T = 90 K |
β = 95.920 (6)° | Prism, colourless |
V = 1145.45 (15) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 8 | |
Data collection top
KUMA KM4CCD four-circle diffractometer | 1513 independent reflections |
Radiation source: fine-focus sealed tube | 1266 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
/w scan | θmax = 29.0°, θmin = 3.3° |
Absorption correction: multi-scan SORTAV (Blessing, 1989) | h = −10→7 |
Tmin = 0.983, Tmax = 0.984 | k = −15→15 |
7556 measured reflections | l = −17→18 |
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)] = 0.031 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.080 | All H-atom parameters refined |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0464P)2 + 0.0996P] where P = (Fo2 + 2Fc2)/3 |
1567 reflections | (Δ/σ)max < 0.001 |
115 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C4H5N3O3 | V = 1145.45 (15) Å3 |
Mr = 143.11 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 7.5542 (6) Å | µ = 0.14 mm−1 |
b = 11.3112 (9) Å | T = 90 K |
c = 13.4773 (10) Å | 0.2 × 0.2 × 0.1 mm |
β = 95.920 (6)° | |
Data collection top
KUMA KM4CCD four-circle diffractometer | 1513 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1989) | 1266 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.984 | Rint = 0.030 |
7556 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.080 | All H-atom parameters refined |
S = 1.10 | Δρmax = 0.26 e Å−3 |
1567 reflections | Δρmin = −0.26 e Å−3 |
115 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.59381 (11) | 0.92865 (7) | 0.34804 (6) | 0.01395 (19) | |
H1 | 0.533 (3) | 0.927 (2) | 0.2932 (18) | 0.017 (6)* | 0.50 |
C2 | 0.75692 (13) | 0.98053 (9) | 0.36613 (7) | 0.0155 (2) | |
H2 | 0.8117 (15) | 1.0230 (11) | 0.3179 (9) | 0.018 (3)* | |
N3 | 0.82832 (11) | 0.96510 (7) | 0.45830 (6) | 0.01428 (19) | |
H3 | 0.936 (3) | 0.988 (2) | 0.4810 (19) | 0.017 (6)* | 0.50 |
C4 | 0.70651 (12) | 0.89944 (8) | 0.50417 (7) | 0.0134 (2) | |
N4 | 0.73546 (11) | 0.86677 (7) | 0.60484 (6) | 0.01406 (18) | |
O41 | 0.62036 (10) | 0.80732 (7) | 0.64056 (5) | 0.02048 (19) | |
O42 | 0.87603 (9) | 0.89940 (7) | 0.65360 (5) | 0.01926 (18) | |
C5 | 0.56102 (12) | 0.87666 (8) | 0.43511 (7) | 0.0129 (2) | |
O5 | 0.41617 (9) | 0.81572 (6) | 0.45016 (5) | 0.01594 (17) | |
C51 | 0.28526 (14) | 0.80036 (10) | 0.36430 (7) | 0.0184 (2) | |
H51A | 0.1936 (17) | 0.7555 (11) | 0.3893 (10) | 0.020 (3)* | |
H51B | 0.3403 (18) | 0.7604 (11) | 0.3098 (10) | 0.024 (3)* | |
H51C | 0.2343 (18) | 0.8776 (11) | 0.3405 (11) | 0.026 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0140 (4) | 0.0166 (4) | 0.0109 (4) | −0.0006 (3) | −0.0006 (3) | 0.0007 (3) |
C2 | 0.0164 (5) | 0.0173 (5) | 0.0125 (5) | −0.0017 (4) | 0.0004 (3) | 0.0007 (3) |
N3 | 0.0134 (4) | 0.0174 (4) | 0.0118 (4) | −0.0013 (3) | 0.0002 (3) | −0.0003 (3) |
C4 | 0.0131 (4) | 0.0157 (4) | 0.0111 (4) | 0.0001 (3) | 0.0005 (3) | 0.0000 (3) |
N4 | 0.0126 (4) | 0.0167 (4) | 0.0126 (4) | 0.0007 (3) | 0.0000 (3) | −0.0009 (3) |
O41 | 0.0166 (4) | 0.0290 (4) | 0.0160 (4) | −0.0047 (3) | 0.0020 (3) | 0.0043 (3) |
O42 | 0.0153 (4) | 0.0277 (4) | 0.0137 (4) | −0.0030 (3) | −0.0038 (3) | −0.0007 (3) |
C5 | 0.0134 (4) | 0.0135 (4) | 0.0118 (4) | 0.0014 (3) | 0.0015 (3) | −0.0009 (3) |
O5 | 0.0128 (3) | 0.0222 (4) | 0.0124 (3) | −0.0049 (3) | −0.0009 (2) | 0.0010 (3) |
C51 | 0.0149 (5) | 0.0246 (5) | 0.0147 (5) | −0.0056 (4) | −0.0034 (4) | 0.0017 (4) |
Geometric parameters (Å, º) top
N1—C5 | 1.3580 (12) | C4—N4 | 1.4014 (12) |
N1—C2 | 1.3638 (13) | N4—O41 | 1.2354 (10) |
N1—H1 | 0.83 (2) | N4—O42 | 1.2457 (11) |
C2—N3 | 1.3139 (12) | C5—O5 | 1.3265 (12) |
C2—H2 | 0.938 (12) | O5—C51 | 1.4530 (11) |
N3—C4 | 1.3776 (12) | C51—H51A | 0.948 (13) |
N3—H3 | 0.87 (2) | C51—H51B | 0.991 (13) |
C4—C5 | 1.3891 (13) | C51—H51C | 0.995 (13) |
| | | |
C5—N1—C2 | 105.89 (8) | O41—N4—C4 | 118.36 (8) |
C5—N1—H1 | 128.6 (17) | O42—N4—C4 | 118.17 (8) |
C2—N1—H1 | 125.4 (17) | O5—C5—N1 | 125.74 (8) |
N3—C2—N1 | 112.77 (9) | O5—C5—C4 | 127.02 (8) |
N3—C2—H2 | 123.7 (8) | N1—C5—C4 | 107.25 (8) |
N1—C2—H2 | 123.5 (7) | C5—O5—C51 | 116.40 (7) |
C2—N3—C4 | 105.53 (8) | O5—C51—H51A | 104.1 (8) |
C2—N3—H3 | 124.5 (17) | O5—C51—H51B | 110.0 (8) |
C4—N3—H3 | 129.7 (17) | H51A—C51—H51B | 113.4 (11) |
N3—C4—C5 | 108.56 (8) | O5—C51—H51C | 111.2 (8) |
N3—C4—N4 | 122.13 (8) | H51A—C51—H51C | 108.2 (10) |
C5—C4—N4 | 129.31 (9) | H51B—C51—H51C | 109.9 (11) |
O41—N4—O42 | 123.47 (8) | | |
| | | |
C5—N1—C2—N3 | −0.20 (11) | C2—N1—C5—O5 | −179.69 (9) |
N1—C2—N3—C4 | 0.01 (11) | C2—N1—C5—C4 | 0.31 (10) |
C2—N3—C4—C5 | 0.19 (11) | N3—C4—C5—O5 | 179.68 (9) |
C2—N3—C4—N4 | −178.97 (9) | N4—C4—C5—O5 | −1.24 (17) |
N3—C4—N4—O41 | −179.65 (8) | N3—C4—C5—N1 | −0.31 (11) |
C5—C4—N4—O41 | 1.39 (15) | N4—C4—C5—N1 | 178.76 (9) |
N3—C4—N4—O42 | 0.44 (13) | N1—C5—O5—C51 | 2.38 (14) |
C5—C4—N4—O42 | −178.53 (9) | C4—C5—O5—C51 | −177.62 (9) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N1i | 0.83 (2) | 2.04 (3) | 2.8670 (16) | 174 (2) |
C2—H2···O42ii | 0.938 (12) | 2.477 (12) | 3.3749 (12) | 160.4 (10) |
C2—H2···O42iii | 0.938 (12) | 2.509 (12) | 3.1235 (13) | 123.3 (9) |
N3—H3···N3iii | 0.87 (2) | 1.96 (2) | 2.8307 (17) | 176 (2) |
C51—H51A···O41iv | 0.948 (13) | 2.469 (13) | 3.2918 (13) | 145.2 (11) |
C51—H51A···O5iv | 0.948 (13) | 2.528 (13) | 3.3283 (13) | 142.3 (11) |
C51—H51C···O42v | 0.995 (13) | 2.660 (13) | 3.6077 (14) | 159.3 (11) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, −y+2, z−1/2; (iii) −x+2, −y+2, −z+1; (iv) −x+1/2, −y+3/2, −z+1; (v) −x+1, −y+2, −z+1. |
(2) 4(5)-nitro-5(4)-methoxy-1
H-imidazole
top
Crystal data top
C4H5N3O3 | F(000) = 592 |
Mr = 143.11 | Dx = 1.660 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 4048 reflections |
a = 7.5542 (6) Å | θ = 4–22° |
b = 11.3112 (9) Å | µ = 0.14 mm−1 |
c = 13.4773 (10) Å | T = 90 K |
β = 95.920 (6)° | Prism, colourless |
V = 1145.45 (15) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 8 | |
Data collection top
KUMA KM4CCD four-circle diffractometer | 2380 independent reflections |
Radiation source: fine-focus sealed tube | 1876 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
/w scan | θmax = 29.9°, θmin = 3.0° |
Absorption correction: multi-scan SORTAV (Blessing, 1989) | h = −10→7 |
Tmin = 0.983, Tmax = 0.984 | k = −15→15 |
7556 measured reflections | l = −17→18 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full with fixed elements per cycle | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.043P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.120 |
2380 reflections | Δρmax = 0.22 e Å−3 |
193 parameters | Δρmin = −0.26 e Å−3 |
2 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 1 (2) |
Crystal data top
C4H5N3O3 | V = 1145.45 (15) Å3 |
Mr = 143.11 | Z = 8 |
Monoclinic, Cc | Mo Kα radiation |
a = 7.5542 (6) Å | µ = 0.14 mm−1 |
b = 11.3112 (9) Å | T = 90 K |
c = 13.4773 (10) Å | 0.2 × 0.2 × 0.1 mm |
β = 95.920 (6)° | |
Data collection top
KUMA KM4CCD four-circle diffractometer | 2380 independent reflections |
Absorption correction: multi-scan SORTAV (Blessing, 1989) | 1876 reflections with I > 2σ(I) |
Tmin = 0.983, Tmax = 0.984 | Rint = 0.030 |
7556 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | (Δ/σ)max = 0.120 |
S = 1.06 | Δρmax = 0.22 e Å−3 |
2380 reflections | Δρmin = −0.26 e Å−3 |
193 parameters | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
2 restraints | Absolute structure parameter: 1 (2) |
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 | |
N1A | 0.66219 (18) | 0.57146 (11) | 0.62985 (9) | 0.0131 (3) | |
H1A | 0.599 (2) | 0.5720 (16) | 0.5774 (14) | 0.016* | |
C2A | 0.8234 (2) | 0.52011 (13) | 0.64684 (11) | 0.0161 (3) | |
H2A | 0.887 (2) | 0.4872 (16) | 0.5987 (14) | 0.019* | |
N3A | 0.89693 (17) | 0.53538 (11) | 0.74040 (9) | 0.0136 (3) | |
C4A | 0.7737 (2) | 0.59970 (13) | 0.78532 (11) | 0.0150 (3) | |
N4A | 0.80112 (18) | 0.63272 (11) | 0.88544 (10) | 0.0166 (3) | |
O41A | 0.94363 (15) | 0.60129 (10) | 0.93578 (8) | 0.0195 (3) | |
O42A | 0.68542 (16) | 0.69258 (10) | 0.92218 (9) | 0.0228 (3) | |
C5A | 0.6291 (2) | 0.62301 (13) | 0.71860 (10) | 0.0147 (3) | |
O5A | 0.48477 (14) | 0.68369 (9) | 0.73264 (7) | 0.0148 (3) | |
C51A | 0.3524 (2) | 0.70014 (14) | 0.64674 (11) | 0.0178 (3) | |
H51A | 0.3028 | 0.6232 | 0.6250 | 0.023* | |
H51B | 0.4088 | 0.7368 | 0.5921 | 0.023* | |
H51C | 0.2567 | 0.7514 | 0.6655 | 0.023* | |
N1B | 0.24025 (18) | 0.53451 (11) | 0.32375 (10) | 0.0153 (3) | |
H1B | 0.132 (2) | 0.5114 (16) | 0.2996 (14) | 0.018* | |
C2B | 0.3096 (2) | 0.51884 (13) | 0.41458 (12) | 0.0149 (3) | |
H2B | 0.260 (2) | 0.4701 (15) | 0.4623 (14) | 0.018* | |
N3B | 0.47439 (17) | 0.57134 (12) | 0.43354 (9) | 0.0153 (3) | |
C4B | 0.50660 (19) | 0.62351 (12) | 0.34835 (11) | 0.0116 (3) | |
O4B | 0.65256 (15) | 0.68485 (9) | 0.33247 (8) | 0.0173 (3) | |
C41B | 0.7821 (2) | 0.69912 (15) | 0.41801 (11) | 0.0194 (4) | |
H41A | 0.7284 | 0.7426 | 0.4702 | 0.025* | |
H41B | 0.8847 | 0.7432 | 0.3986 | 0.025* | |
H41C | 0.8211 | 0.6212 | 0.4434 | 0.025* | |
C5B | 0.36094 (19) | 0.60132 (13) | 0.27712 (10) | 0.0121 (3) | |
N5B | 0.33021 (17) | 0.63350 (10) | 0.17595 (9) | 0.0118 (3) | |
O51B | 0.44495 (15) | 0.69273 (10) | 0.14108 (8) | 0.0186 (3) | |
O52B | 0.19160 (15) | 0.59979 (10) | 0.12861 (8) | 0.0196 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0165 (7) | 0.0131 (6) | 0.0098 (6) | 0.0040 (5) | 0.0025 (5) | −0.0021 (4) |
C2A | 0.0209 (9) | 0.0162 (7) | 0.0104 (7) | −0.0025 (6) | −0.0025 (6) | −0.0035 (5) |
N3A | 0.0111 (6) | 0.0204 (6) | 0.0088 (6) | 0.0009 (5) | −0.0020 (5) | 0.0001 (5) |
C4A | 0.0211 (9) | 0.0139 (7) | 0.0101 (7) | −0.0049 (6) | 0.0014 (6) | −0.0001 (5) |
N4A | 0.0118 (6) | 0.0209 (7) | 0.0168 (7) | 0.0030 (5) | −0.0002 (5) | 0.0077 (5) |
O41A | 0.0121 (6) | 0.0296 (6) | 0.0156 (6) | 0.0030 (5) | −0.0036 (4) | −0.0045 (4) |
O42A | 0.0193 (6) | 0.0301 (7) | 0.0195 (6) | 0.0039 (5) | 0.0046 (5) | −0.0040 (5) |
C5A | 0.0216 (8) | 0.0159 (7) | 0.0081 (6) | −0.0032 (6) | 0.0088 (6) | −0.0042 (5) |
O5A | 0.0133 (5) | 0.0222 (6) | 0.0079 (5) | 0.0035 (4) | −0.0032 (4) | 0.0005 (4) |
C51A | 0.0150 (8) | 0.0219 (8) | 0.0155 (8) | 0.0039 (6) | −0.0027 (6) | −0.0016 (6) |
N1B | 0.0157 (7) | 0.0149 (6) | 0.0156 (6) | −0.0016 (5) | 0.0027 (5) | −0.0003 (5) |
C2B | 0.0126 (7) | 0.0181 (7) | 0.0143 (7) | −0.0055 (6) | 0.0027 (6) | −0.0022 (5) |
N3B | 0.0124 (6) | 0.0208 (6) | 0.0118 (6) | 0.0025 (5) | −0.0033 (5) | −0.0007 (5) |
C4B | 0.0065 (7) | 0.0113 (6) | 0.0158 (7) | 0.0001 (5) | −0.0043 (5) | −0.0061 (5) |
O4B | 0.0124 (6) | 0.0222 (6) | 0.0173 (6) | −0.0063 (4) | 0.0018 (4) | 0.0020 (4) |
C41B | 0.0162 (8) | 0.0271 (9) | 0.0138 (7) | −0.0074 (6) | −0.0043 (6) | 0.0021 (6) |
C5B | 0.0067 (7) | 0.0176 (7) | 0.0118 (7) | −0.0043 (5) | 0.0000 (5) | −0.0002 (5) |
N5B | 0.0129 (6) | 0.0128 (6) | 0.0096 (5) | 0.0042 (5) | 0.0004 (5) | 0.0051 (4) |
O51B | 0.0141 (6) | 0.0282 (6) | 0.0131 (5) | −0.0054 (5) | −0.0002 (4) | 0.0045 (4) |
O52B | 0.0189 (6) | 0.0270 (6) | 0.0117 (5) | −0.0031 (5) | −0.0043 (4) | −0.0054 (4) |
Geometric parameters (Å, º) top
N1A—C2A | 1.347 (2) | N1B—C2B | 1.293 (2) |
N1A—C5A | 1.3766 (18) | N1B—C5B | 1.3840 (19) |
N1A—H1A | 0.810 (18) | N1B—H1B | 0.890 (16) |
C2A—N3A | 1.3355 (19) | C2B—N3B | 1.379 (2) |
C2A—H2A | 0.925 (19) | C2B—H2B | 0.951 (18) |
N3A—C4A | 1.3705 (19) | N3B—C4B | 1.335 (2) |
C4A—C5A | 1.367 (2) | C4B—O4B | 1.3385 (18) |
C4A—N4A | 1.3948 (19) | C4B—C5B | 1.4063 (19) |
N4A—O42A | 1.2477 (17) | O4B—C41B | 1.4420 (18) |
N4A—O41A | 1.2629 (16) | C41B—H41A | 0.9800 |
C5A—O5A | 1.3183 (19) | C41B—H41B | 0.9800 |
O5A—C51A | 1.4616 (17) | C41B—H41C | 0.9800 |
C51A—H51A | 0.9800 | C5B—N5B | 1.4071 (18) |
C51A—H51B | 0.9800 | N5B—O51B | 1.2267 (16) |
C51A—H51C | 0.9800 | N5B—O52B | 1.2293 (16) |
| | | |
C2A—N1A—C5A | 106.08 (13) | C2B—N1B—C5B | 106.45 (13) |
C2A—N1A—H1A | 126.2 (13) | C2B—N1B—H1B | 125.0 (13) |
C5A—N1A—H1A | 127.7 (13) | C5B—N1B—H1B | 128.3 (13) |
N3A—C2A—N1A | 112.66 (14) | N1B—C2B—N3B | 112.72 (14) |
N3A—C2A—H2A | 121.2 (11) | N1B—C2B—H2B | 124.8 (11) |
N1A—C2A—H2A | 125.5 (11) | N3B—C2B—H2B | 122.2 (11) |
C2A—N3A—C4A | 104.51 (13) | C4B—N3B—C2B | 105.78 (12) |
C5A—C4A—N3A | 110.18 (12) | N3B—C4B—O4B | 126.35 (13) |
C5A—C4A—N4A | 127.83 (14) | N3B—C4B—C5B | 108.00 (13) |
N3A—C4A—N4A | 122.00 (14) | O4B—C4B—C5B | 125.65 (13) |
O42A—N4A—O41A | 122.19 (13) | C4B—O4B—C41B | 115.61 (11) |
O42A—N4A—C4A | 119.29 (13) | O4B—C41B—H41A | 109.5 |
O41A—N4A—C4A | 118.52 (13) | O4B—C41B—H41B | 109.5 |
O5A—C5A—C4A | 128.51 (13) | H41A—C41B—H41B | 109.5 |
O5A—C5A—N1A | 124.91 (14) | O4B—C41B—H41C | 109.5 |
C4A—C5A—N1A | 106.58 (13) | H41A—C41B—H41C | 109.5 |
C5A—O5A—C51A | 117.46 (11) | H41B—C41B—H41C | 109.5 |
O5A—C51A—H51A | 109.5 | N1B—C5B—C4B | 107.05 (13) |
O5A—C51A—H51B | 109.5 | N1B—C5B—N5B | 122.05 (13) |
H51A—C51A—H51B | 109.5 | C4B—C5B—N5B | 130.89 (14) |
O5A—C51A—H51C | 109.5 | O51B—N5B—O52B | 124.63 (12) |
H51A—C51A—H51C | 109.5 | O51B—N5B—C5B | 117.39 (12) |
H51B—C51A—H51C | 109.5 | O52B—N5B—C5B | 117.98 (12) |
| | | |
C5A—N1A—C2A—N3A | −0.25 (18) | C5B—N1B—C2B—N3B | −0.32 (18) |
N1A—C2A—N3A—C4A | 0.43 (17) | N1B—C2B—N3B—C4B | 0.59 (18) |
C2A—N3A—C4A—C5A | −0.45 (17) | C2B—N3B—C4B—O4B | −179.71 (14) |
C2A—N3A—C4A—N4A | 179.18 (14) | C2B—N3B—C4B—C5B | −0.60 (16) |
C5A—C4A—N4A—O42A | −1.3 (2) | N3B—C4B—O4B—C41B | −2.9 (2) |
N3A—C4A—N4A—O42A | 179.09 (13) | C5B—C4B—O4B—C41B | 178.12 (14) |
C5A—C4A—N4A—O41A | 179.07 (14) | C2B—N1B—C5B—C4B | −0.06 (16) |
N3A—C4A—N4A—O41A | −0.5 (2) | C2B—N1B—C5B—N5B | 178.74 (14) |
N3A—C4A—C5A—O5A | −178.83 (14) | N3B—C4B—C5B—N1B | 0.43 (16) |
N4A—C4A—C5A—O5A | 1.6 (3) | O4B—C4B—C5B—N1B | 179.55 (13) |
N3A—C4A—C5A—N1A | 0.31 (17) | N3B—C4B—C5B—N5B | −178.23 (14) |
N4A—C4A—C5A—N1A | −179.29 (14) | O4B—C4B—C5B—N5B | 0.9 (3) |
C2A—N1A—C5A—O5A | 179.14 (14) | N1B—C5B—N5B—O51B | −179.91 (13) |
C2A—N1A—C5A—C4A | −0.05 (16) | C4B—C5B—N5B—O51B | −1.4 (2) |
C4A—C5A—O5A—C51A | 177.22 (15) | N1B—C5B—N5B—O52B | −0.4 (2) |
N1A—C5A—O5A—C51A | −1.8 (2) | C4B—C5B—N5B—O52B | 178.05 (14) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···N3B | 0.810 (18) | 2.067 (19) | 2.8702 (13) | 171.3 (19) |
C2A—H2A···O52Bi | 0.925 (19) | 2.496 (18) | 3.1268 (17) | 125.7 (14) |
C51A—H51A···O52Bii | 0.98 | 2.66 | 3.6032 (16) | 161 |
C51A—H51C···O51Biii | 0.98 | 2.43 | 3.3013 (16) | 148 |
C51A—H51C···O4Biii | 0.98 | 2.56 | 3.3190 (16) | 134 |
C51A—H51B···O52Biv | 0.98 | 2.83 | 3.4463 (17) | 122 |
N1B—H1B···N3Av | 0.890 (16) | 1.941 (17) | 2.8306 (14) | 177.1 (19) |
C2B—H2B···O52Bii | 0.951 (18) | 2.482 (18) | 3.3832 (19) | 158.1 (15) |
C41B—H41A···O51Biv | 0.98 | 2.78 | 3.3595 (19) | 118 |
C41B—H41B···O42Avi | 0.98 | 2.38 | 3.2792 (17) | 153 |
C41B—H41B···O5Avi | 0.98 | 2.57 | 3.3366 (16) | 135 |
C41B—H41C···O41Avii | 0.98 | 2.69 | 3.6101 (18) | 157 |
Symmetry codes: (i) x+1, −y+1, z+1/2; (ii) x, −y+1, z+1/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) x+1/2, −y+3/2, z+1/2; (v) x−1, −y+1, z−1/2; (vi) x+1/2, −y+3/2, z−1/2; (vii) x, −y+1, z−1/2. |
Experimental details
| (1) | (2) |
Crystal data |
Chemical formula | C4H5N3O3 | C4H5N3O3 |
Mr | 143.11 | 143.11 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, Cc |
Temperature (K) | 90 | 90 |
a, b, c (Å) | 7.5542 (6), 11.3112 (9), 13.4773 (10) | 7.5542 (6), 11.3112 (9), 13.4773 (10) |
β (°) | 95.920 (6) | 95.920 (6) |
V (Å3) | 1145.45 (15) | 1145.45 (15) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.14 | 0.14 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 | 0.2 × 0.2 × 0.1 |
|
Data collection |
Diffractometer | KUMA KM4CCD four-circle diffractometer | KUMA KM4CCD four-circle diffractometer |
Absorption correction | Multi-scan SORTAV (Blessing, 1989) | Multi-scan SORTAV (Blessing, 1989) |
Tmin, Tmax | 0.983, 0.984 | 0.983, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7556, 1513, 1266 | 7556, 2380, 1876 |
Rint | 0.030 | 0.030 |
(sin θ/λ)max (Å−1) | 0.682 | 0.701 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.080, 1.10 | 0.029, 0.074, 1.06 |
No. of reflections | 1567 | 2380 |
No. of parameters | 115 | 193 |
No. of restraints | 0 | 2 |
H-atom treatment | All H-atom parameters refined | H atoms treated by a mixture of independent and constrained refinement |
(Δ/σ)max | < 0.001 | 0.120 |
Δρmax, Δρmin (e Å−3) | 0.26, −0.26 | 0.22, −0.26 |
Absolute structure | ? | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | ? | 1 (2) |
Selected geometric parameters (Å, º) for (1) topN1—C5 | 1.3580 (12) | N3—C4 | 1.3776 (12) |
N1—C2 | 1.3638 (13) | N4—O41 | 1.2354 (10) |
C2—N3 | 1.3139 (12) | N4—O42 | 1.2457 (11) |
| | | |
C5—N1—C2 | 105.89 (8) | C2—N3—C4 | 105.53 (8) |
Hydrogen-bond geometry (Å, º) for (1) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N1i | 0.83 (2) | 2.04 (3) | 2.8670 (16) | 174 (2) |
C2—H2···O42ii | 0.938 (12) | 2.477 (12) | 3.3749 (12) | 160.4 (10) |
C2—H2···O42iii | 0.938 (12) | 2.509 (12) | 3.1235 (13) | 123.3 (9) |
N3—H3···N3iii | 0.87 (2) | 1.96 (2) | 2.8307 (17) | 176 (2) |
C51—H51A···O41iv | 0.948 (13) | 2.469 (13) | 3.2918 (13) | 145.2 (11) |
C51—H51A···O5iv | 0.948 (13) | 2.528 (13) | 3.3283 (13) | 142.3 (11) |
C51—H51C···O42v | 0.995 (13) | 2.660 (13) | 3.6077 (14) | 159.3 (11) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, −y+2, z−1/2; (iii) −x+2, −y+2, −z+1; (iv) −x+1/2, −y+3/2, −z+1; (v) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) for (2) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···N3B | 0.810 (18) | 2.067 (19) | 2.8702 (13) | 171.3 (19) |
C2A—H2A···O52Bi | 0.925 (19) | 2.496 (18) | 3.1268 (17) | 125.7 (14) |
C51A—H51A···O52Bii | 0.98 | 2.66 | 3.6032 (16) | 161.4 |
C51A—H51C···O51Biii | 0.98 | 2.43 | 3.3013 (16) | 148.2 |
C51A—H51C···O4Biii | 0.98 | 2.56 | 3.3190 (16) | 134.0 |
C51A—H51B···O52Biv | 0.98 | 2.83 | 3.4463 (17) | 121.7 |
N1B—H1B···N3Av | 0.890 (16) | 1.941 (17) | 2.8306 (14) | 177.1 (19) |
C2B—H2B···O52Bii | 0.951 (18) | 2.482 (18) | 3.3832 (19) | 158.1 (15) |
C41B—H41A···O51Biv | 0.98 | 2.78 | 3.3595 (19) | 118.3 |
C41B—H41B···O42Avi | 0.98 | 2.38 | 3.2792 (17) | 153.1 |
C41B—H41B···O5Avi | 0.98 | 2.57 | 3.3366 (16) | 135.1 |
C41B—H41C···O41Avii | 0.98 | 2.69 | 3.6101 (18) | 157.2 |
Symmetry codes: (i) x+1, −y+1, z+1/2; (ii) x, −y+1, z+1/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) x+1/2, −y+3/2, z+1/2; (v) x−1, −y+1, z−1/2; (vi) x+1/2, −y+3/2, z−1/2; (vii) x, −y+1, z−1/2. |