Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017444/sk1591sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017444/sk1591Isup2.hkl |
CCDC reference: 199430
A sample of (I) was purchased from Aldrich and converted into 2-amino-4,6-dimethoxy-5-nitrosopyrimidine according to the method of Marchal et al. (2002). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone.
Compound (IV) is triclinic and space group P1 was assumed and confirmed by the analysis. H atoms were treated as riding atoms, with distances C—H 0.98 Å, N—H 0.88 Å and O—H 1.00 Å. In the absence of any significant anomalous scatterers, the Friedel equivalents were merged; the absolute structure could not be established.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
4C6H8N4O3·3H2O | Z = 1 |
Mr = 790.70 | F(000) = 414 |
Triclinic, P1 | Dx = 1.563 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9588 (4) Å | Cell parameters from 6738 reflections |
b = 7.1984 (4) Å | θ = 2.9–27.4° |
c = 17.4239 (11) Å | µ = 0.13 mm−1 |
α = 101.181 (2)° | T = 120 K |
β = 98.559 (2)° | Plate, blue |
γ = 95.360 (4)° | 0.20 × 0.20 × 0.04 mm |
V = 839.95 (9) Å3 |
Nonius KappaCCD diffractometer | 3638 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2498 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ϕ scans, and ω scans with κ offsets | θmax = 27.4°, θmin = 2.9° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −8→8 |
Tmin = 0.964, Tmax = 0.992 | k = −9→9 |
10707 measured reflections | l = −22→22 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0793P)2] where P = (Fo2 + 2Fc2)/3 |
3638 reflections | (Δ/σ)max < 0.001 |
504 parameters | Δρmax = 0.32 e Å−3 |
3 restraints | Δρmin = −0.38 e Å−3 |
4C6H8N4O3·3H2O | γ = 95.360 (4)° |
Mr = 790.70 | V = 839.95 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.9588 (4) Å | Mo Kα radiation |
b = 7.1984 (4) Å | µ = 0.13 mm−1 |
c = 17.4239 (11) Å | T = 120 K |
α = 101.181 (2)° | 0.20 × 0.20 × 0.04 mm |
β = 98.559 (2)° |
Nonius KappaCCD diffractometer | 3638 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2498 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.992 | Rint = 0.076 |
10707 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 3 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.32 e Å−3 |
3638 reflections | Δρmin = −0.38 e Å−3 |
504 parameters |
x | y | z | Uiso*/Ueq | ||
N11 | 1.0461 (6) | 0.8843 (6) | 0.8538 (2) | 0.0208 (10) | |
C12 | 0.9963 (7) | 0.7835 (7) | 0.7781 (3) | 0.0195 (11) | |
N12 | 1.1247 (6) | 0.7907 (7) | 0.7309 (3) | 0.0257 (11) | |
N13 | 0.8217 (6) | 0.6718 (6) | 0.7459 (3) | 0.0218 (10) | |
C14 | 0.6949 (7) | 0.6648 (7) | 0.7939 (3) | 0.0191 (11) | |
O14 | 0.5197 (5) | 0.5605 (5) | 0.7671 (2) | 0.0240 (8) | |
C141 | 0.4732 (8) | 0.4730 (8) | 0.6830 (3) | 0.0265 (12) | |
C15 | 0.7294 (8) | 0.7597 (7) | 0.8745 (3) | 0.0179 (11) | |
O15 | 0.6139 (5) | 0.8287 (5) | 0.9895 (2) | 0.0262 (9) | |
N15 | 0.5842 (6) | 0.7378 (6) | 0.9175 (3) | 0.0227 (10) | |
C16 | 0.9187 (8) | 0.8709 (8) | 0.9004 (3) | 0.0230 (12) | |
C161 | 1.1548 (8) | 1.0770 (9) | 0.9991 (4) | 0.0331 (15) | |
O16 | 0.9622 (5) | 0.9659 (5) | 0.9762 (2) | 0.0244 (9) | |
N21 | 0.0168 (6) | 0.2605 (6) | 0.7490 (3) | 0.0201 (10) | |
C22 | 0.0231 (8) | 0.3416 (7) | 0.8264 (3) | 0.0204 (12) | |
N22 | 0.1855 (6) | 0.4547 (6) | 0.8634 (3) | 0.0248 (11) | |
N23 | −0.1189 (6) | 0.3222 (6) | 0.8711 (3) | 0.0212 (10) | |
C24 | −0.2801 (7) | 0.2114 (7) | 0.8338 (3) | 0.0184 (11) | |
C241 | −0.3974 (8) | 0.2785 (8) | 0.9556 (3) | 0.0277 (13) | |
O24 | −0.4264 (5) | 0.1860 (5) | 0.8731 (2) | 0.0243 (9) | |
C25 | −0.3093 (7) | 0.1153 (7) | 0.7535 (3) | 0.0185 (11) | |
O25 | −0.5175 (5) | −0.0782 (5) | 0.6516 (2) | 0.0247 (9) | |
N25 | −0.4858 (6) | 0.0056 (6) | 0.7233 (3) | 0.0200 (10) | |
C26 | −0.1468 (8) | 0.1513 (7) | 0.7139 (3) | 0.0194 (11) | |
C261 | 0.0020 (8) | 0.1045 (8) | 0.5987 (3) | 0.0249 (12) | |
O26 | −0.1656 (5) | 0.0698 (5) | 0.6371 (2) | 0.0227 (8) | |
N31 | −0.0981 (7) | −0.3167 (6) | 0.2526 (3) | 0.0212 (10) | |
N32 | −0.2559 (6) | −0.3078 (6) | 0.3586 (3) | 0.0239 (11) | |
C32 | −0.0962 (8) | −0.2551 (7) | 0.3313 (3) | 0.0194 (11) | |
N33 | 0.0519 (6) | −0.1488 (6) | 0.3860 (3) | 0.0215 (10) | |
C34 | 0.2110 (7) | −0.1007 (7) | 0.3581 (3) | 0.0193 (11) | |
O34 | 0.3660 (5) | 0.0008 (5) | 0.4081 (2) | 0.0230 (8) | |
C341 | 0.3460 (8) | 0.0513 (9) | 0.4917 (3) | 0.0298 (13) | |
C35 | 0.2319 (8) | −0.1465 (8) | 0.2768 (3) | 0.0204 (12) | |
N35 | 0.4031 (7) | −0.0768 (7) | 0.2580 (3) | 0.0239 (10) | |
O35 | 0.4262 (5) | −0.1179 (5) | 0.1866 (2) | 0.0261 (9) | |
C36 | 0.0624 (7) | −0.2615 (8) | 0.2260 (3) | 0.0193 (12) | |
O36 | 0.0703 (5) | −0.3116 (5) | 0.1499 (2) | 0.0234 (9) | |
C361 | −0.1002 (8) | −0.4246 (8) | 0.0976 (3) | 0.0270 (13) | |
N41 | 0.8734 (6) | 0.1885 (6) | 0.2813 (3) | 0.0197 (10) | |
C42 | 0.9329 (7) | 0.1611 (7) | 0.2100 (3) | 0.0182 (11) | |
N42 | 0.8068 (7) | 0.0500 (6) | 0.1504 (3) | 0.0243 (11) | |
N43 | 1.1060 (6) | 0.2345 (6) | 0.1939 (3) | 0.0205 (10) | |
C44 | 1.2283 (8) | 0.3395 (7) | 0.2559 (3) | 0.0172 (11) | |
C441 | 1.4523 (9) | 0.3745 (9) | 0.1675 (3) | 0.0292 (13) | |
O44 | 1.4008 (5) | 0.4173 (5) | 0.2467 (2) | 0.0233 (9) | |
C45 | 1.1857 (8) | 0.3770 (8) | 0.3346 (3) | 0.0209 (12) | |
N45 | 1.3313 (6) | 0.4828 (6) | 0.3914 (3) | 0.0214 (10) | |
O45 | 1.3037 (5) | 0.5177 (6) | 0.4626 (2) | 0.0268 (9) | |
C46 | 0.9977 (7) | 0.2940 (7) | 0.3418 (3) | 0.0204 (12) | |
C461 | 0.7494 (7) | 0.2398 (8) | 0.4176 (3) | 0.0241 (12) | |
O46 | 0.9452 (5) | 0.3241 (5) | 0.4129 (2) | 0.0221 (8) | |
O1 | 1.0196 (6) | 0.5837 (6) | 0.5724 (2) | 0.0323 (9) | |
O2 | 0.2974 (6) | 0.6369 (6) | 1.0270 (2) | 0.0329 (10) | |
O3 | −0.3319 (5) | −0.2749 (5) | 0.5232 (2) | 0.0289 (9) | |
H12A | 1.2396 | 0.8596 | 0.7486 | 0.031* | |
H12B | 1.0962 | 0.7266 | 0.6814 | 0.031* | |
H14A | 0.4585 | 0.5727 | 0.6521 | 0.040* | |
H14B | 0.3506 | 0.3864 | 0.6724 | 0.040* | |
H14C | 0.5792 | 0.4010 | 0.6677 | 0.040* | |
H16A | 1.2551 | 0.9937 | 0.9877 | 0.050* | |
H16B | 1.1769 | 1.1338 | 1.0560 | 0.050* | |
H16C | 1.1621 | 1.1785 | 0.9690 | 0.050* | |
H22A | 0.2825 | 0.4739 | 0.8375 | 0.030* | |
H22B | 0.1962 | 0.5105 | 0.9137 | 0.030* | |
H24A | −0.2885 | 0.2302 | 0.9849 | 0.042* | |
H24B | −0.5170 | 0.2517 | 0.9771 | 0.042* | |
H24C | −0.3671 | 0.4166 | 0.9609 | 0.042* | |
H26A | 0.0231 | 0.2400 | 0.5969 | 0.037* | |
H26B | −0.0230 | 0.0272 | 0.5445 | 0.037* | |
H26C | 0.1188 | 0.0697 | 0.6288 | 0.037* | |
H32A | −0.3561 | −0.3792 | 0.3260 | 0.029* | |
H32B | −0.2618 | −0.2714 | 0.4093 | 0.029* | |
H34A | 0.2535 | 0.1455 | 0.4984 | 0.045* | |
H34B | 0.4739 | 0.1056 | 0.5239 | 0.045* | |
H34C | 0.2971 | −0.0633 | 0.5089 | 0.045* | |
H36A | −0.1244 | −0.5474 | 0.1131 | 0.041* | |
H36B | −0.0765 | −0.4466 | 0.0427 | 0.041* | |
H36C | −0.2146 | −0.3559 | 0.1018 | 0.041* | |
H42A | 0.6936 | 0.0000 | 0.1589 | 0.029* | |
H42B | 0.8364 | 0.0263 | 0.1023 | 0.029* | |
H44A | 1.4455 | 0.2359 | 0.1495 | 0.044* | |
H44B | 1.5857 | 0.4344 | 0.1692 | 0.044* | |
H44C | 1.3604 | 0.4242 | 0.1306 | 0.044* | |
H46A | 0.6526 | 0.2788 | 0.3790 | 0.036* | |
H46B | 0.7215 | 0.2835 | 0.4712 | 0.036* | |
H46C | 0.7427 | 0.1003 | 0.4059 | 0.036* | |
H11 | 0.8884 | 0.6188 | 0.5528 | 0.039* | |
H12 | 1.0864 | 0.5611 | 0.5251 | 0.039* | |
H21 | 0.2654 | 0.7272 | 1.0733 | 0.039* | |
H22 | 0.4216 | 0.6986 | 1.0155 | 0.039* | |
H31 | −0.3527 | −0.1728 | 0.5679 | 0.035* | |
H32 | −0.4589 | −0.3604 | 0.5066 | 0.035* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N11 | 0.025 (3) | 0.020 (2) | 0.018 (2) | 0.004 (2) | 0.0068 (19) | 0.0021 (19) |
C12 | 0.018 (3) | 0.019 (3) | 0.021 (3) | 0.003 (2) | 0.001 (2) | 0.005 (2) |
N12 | 0.021 (3) | 0.034 (3) | 0.024 (3) | 0.003 (2) | 0.008 (2) | 0.008 (2) |
N13 | 0.021 (2) | 0.024 (2) | 0.022 (3) | 0.008 (2) | 0.0034 (19) | 0.0051 (19) |
C14 | 0.018 (3) | 0.015 (3) | 0.024 (3) | 0.000 (2) | 0.003 (2) | 0.005 (2) |
O14 | 0.019 (2) | 0.029 (2) | 0.020 (2) | −0.0062 (16) | 0.0000 (15) | 0.0019 (16) |
C141 | 0.026 (3) | 0.032 (3) | 0.020 (3) | 0.002 (2) | −0.001 (2) | 0.004 (2) |
C15 | 0.020 (3) | 0.015 (3) | 0.020 (3) | −0.001 (2) | 0.005 (2) | 0.007 (2) |
O15 | 0.029 (2) | 0.031 (2) | 0.018 (2) | −0.0027 (17) | 0.0070 (15) | 0.0020 (17) |
N15 | 0.026 (3) | 0.025 (2) | 0.017 (2) | 0.003 (2) | 0.0050 (18) | 0.005 (2) |
C16 | 0.028 (3) | 0.023 (3) | 0.018 (3) | 0.013 (2) | 0.001 (2) | 0.003 (2) |
C161 | 0.023 (3) | 0.041 (4) | 0.025 (3) | −0.006 (3) | −0.007 (2) | −0.007 (3) |
O16 | 0.0206 (19) | 0.028 (2) | 0.020 (2) | −0.0057 (16) | 0.0040 (15) | −0.0027 (16) |
N21 | 0.025 (3) | 0.021 (2) | 0.015 (2) | 0.0064 (19) | 0.0032 (18) | 0.0028 (19) |
C22 | 0.021 (3) | 0.016 (3) | 0.024 (3) | 0.005 (2) | 0.001 (2) | 0.005 (2) |
N22 | 0.021 (3) | 0.031 (3) | 0.023 (3) | 0.005 (2) | 0.0053 (19) | 0.004 (2) |
N23 | 0.020 (2) | 0.022 (2) | 0.022 (2) | 0.0047 (19) | 0.0038 (18) | 0.0050 (19) |
C24 | 0.017 (3) | 0.018 (3) | 0.022 (3) | 0.008 (2) | 0.004 (2) | 0.004 (2) |
C241 | 0.029 (3) | 0.031 (3) | 0.020 (3) | 0.001 (2) | 0.007 (2) | −0.003 (2) |
O24 | 0.0208 (19) | 0.032 (2) | 0.017 (2) | −0.0004 (17) | 0.0047 (15) | −0.0001 (16) |
C25 | 0.020 (3) | 0.015 (3) | 0.021 (3) | 0.005 (2) | 0.000 (2) | 0.004 (2) |
O25 | 0.024 (2) | 0.031 (2) | 0.017 (2) | −0.0001 (17) | 0.0009 (16) | 0.0030 (17) |
N25 | 0.020 (2) | 0.020 (2) | 0.020 (3) | 0.0017 (19) | 0.0011 (18) | 0.0054 (19) |
C26 | 0.025 (3) | 0.016 (3) | 0.019 (3) | 0.003 (2) | 0.004 (2) | 0.006 (2) |
C261 | 0.021 (3) | 0.030 (3) | 0.023 (3) | −0.002 (2) | 0.006 (2) | 0.004 (2) |
O26 | 0.023 (2) | 0.026 (2) | 0.017 (2) | −0.0047 (16) | 0.0053 (15) | 0.0032 (16) |
N31 | 0.027 (3) | 0.020 (2) | 0.019 (3) | 0.004 (2) | 0.0084 (19) | 0.0068 (19) |
N32 | 0.023 (3) | 0.032 (3) | 0.017 (3) | 0.000 (2) | 0.0032 (19) | 0.008 (2) |
C32 | 0.017 (3) | 0.017 (3) | 0.027 (3) | 0.008 (2) | 0.007 (2) | 0.007 (2) |
N33 | 0.026 (2) | 0.018 (2) | 0.023 (3) | 0.0058 (19) | 0.0069 (19) | 0.0069 (19) |
C34 | 0.018 (3) | 0.020 (3) | 0.022 (3) | 0.006 (2) | 0.001 (2) | 0.008 (2) |
O34 | 0.024 (2) | 0.031 (2) | 0.0131 (19) | −0.0001 (17) | 0.0029 (14) | 0.0037 (16) |
C341 | 0.031 (3) | 0.038 (3) | 0.015 (3) | 0.000 (3) | 0.003 (2) | −0.002 (2) |
C35 | 0.026 (3) | 0.022 (3) | 0.014 (3) | 0.006 (2) | 0.000 (2) | 0.005 (2) |
N35 | 0.019 (2) | 0.034 (3) | 0.020 (3) | 0.004 (2) | 0.0053 (19) | 0.009 (2) |
O35 | 0.026 (2) | 0.031 (2) | 0.019 (2) | 0.0016 (18) | 0.0064 (16) | 0.0000 (17) |
C36 | 0.019 (3) | 0.024 (3) | 0.017 (3) | 0.008 (2) | 0.004 (2) | 0.007 (2) |
O36 | 0.023 (2) | 0.032 (2) | 0.013 (2) | 0.0018 (16) | 0.0028 (15) | 0.0005 (16) |
C361 | 0.028 (3) | 0.030 (3) | 0.018 (3) | −0.005 (3) | −0.001 (2) | 0.002 (2) |
N41 | 0.016 (2) | 0.021 (2) | 0.022 (3) | 0.0019 (19) | 0.0037 (18) | 0.0040 (19) |
C42 | 0.020 (3) | 0.011 (2) | 0.025 (3) | −0.001 (2) | 0.004 (2) | 0.006 (2) |
N42 | 0.020 (2) | 0.021 (2) | 0.028 (3) | −0.0078 (19) | 0.005 (2) | 0.001 (2) |
N43 | 0.017 (2) | 0.018 (2) | 0.023 (3) | 0.0007 (19) | 0.0004 (18) | 0.0006 (19) |
C44 | 0.019 (3) | 0.007 (2) | 0.025 (3) | −0.002 (2) | 0.001 (2) | 0.007 (2) |
C441 | 0.034 (3) | 0.035 (3) | 0.021 (3) | 0.005 (3) | 0.013 (3) | 0.004 (3) |
O44 | 0.018 (2) | 0.027 (2) | 0.022 (2) | −0.0061 (16) | 0.0057 (15) | 0.0016 (16) |
C45 | 0.018 (3) | 0.026 (3) | 0.020 (3) | 0.001 (2) | 0.006 (2) | 0.006 (2) |
N45 | 0.021 (2) | 0.022 (2) | 0.020 (3) | 0.002 (2) | 0.0026 (18) | 0.0022 (19) |
O45 | 0.026 (2) | 0.035 (2) | 0.018 (2) | 0.0022 (17) | 0.0038 (15) | 0.0026 (17) |
C46 | 0.019 (3) | 0.018 (3) | 0.025 (3) | 0.002 (2) | 0.004 (2) | 0.006 (2) |
C461 | 0.013 (3) | 0.031 (3) | 0.028 (3) | −0.002 (2) | 0.010 (2) | 0.004 (3) |
O46 | 0.0206 (19) | 0.030 (2) | 0.015 (2) | 0.0032 (16) | 0.0026 (14) | 0.0022 (16) |
O1 | 0.030 (2) | 0.042 (2) | 0.023 (2) | 0.0067 (19) | 0.0048 (16) | 0.0012 (18) |
O2 | 0.032 (2) | 0.041 (2) | 0.021 (2) | −0.0085 (18) | 0.0085 (16) | −0.0007 (18) |
O3 | 0.026 (2) | 0.031 (2) | 0.026 (2) | −0.0043 (17) | 0.0068 (16) | 0.0012 (17) |
N11—C12 | 1.354 (7) | C34—C35 | 1.424 (7) |
C12—N13 | 1.370 (7) | C35—C36 | 1.443 (7) |
N13—C14 | 1.308 (7) | C36—N31 | 1.328 (7) |
C14—C15 | 1.411 (7) | C32—N32 | 1.325 (7) |
C15—C16 | 1.437 (8) | C35—N35 | 1.360 (7) |
C16—N11 | 1.296 (7) | N35—O35 | 1.259 (6) |
C12—N12 | 1.306 (7) | N32—H32A | 0.88 |
C15—N15 | 1.360 (7) | N32—H32B | 0.88 |
N15—O15 | 1.275 (6) | C34—O34 | 1.335 (6) |
N12—H12A | 0.88 | C341—O34 | 1.462 (6) |
N12—H12B | 0.88 | C341—H34A | 0.98 |
C14—O14 | 1.339 (6) | C341—H34B | 0.98 |
O14—C141 | 1.453 (6) | C341—H34C | 0.98 |
C141—H14A | 0.98 | C36—O36 | 1.315 (6) |
C141—H14B | 0.98 | O36—C361 | 1.453 (6) |
C141—H14C | 0.98 | C361—H36A | 0.98 |
C16—O16 | 1.340 (6) | C361—H36B | 0.98 |
C161—O16 | 1.453 (7) | C361—H36C | 0.98 |
C161—H16A | 0.98 | N41—C42 | 1.353 (7) |
C161—H16B | 0.98 | C42—N43 | 1.359 (7) |
C161—H16C | 0.98 | N43—C44 | 1.323 (6) |
N21—C22 | 1.354 (7) | C44—C45 | 1.427 (7) |
C22—N23 | 1.359 (7) | C45—C46 | 1.420 (7) |
N23—C24 | 1.315 (7) | C46—N41 | 1.316 (7) |
C24—C25 | 1.411 (7) | C42—N42 | 1.328 (7) |
C25—C26 | 1.439 (7) | C45—N45 | 1.361 (7) |
C26—N21 | 1.314 (7) | N45—O45 | 1.263 (6) |
C22—N22 | 1.328 (7) | N42—H42A | 0.88 |
C25—N25 | 1.369 (7) | N42—H42B | 0.88 |
N25—O25 | 1.255 (6) | C44—O44 | 1.322 (6) |
N22—H22A | 0.88 | C441—O44 | 1.460 (7) |
N22—H22B | 0.88 | C441—H44A | 0.98 |
C24—O24 | 1.327 (6) | C441—H44B | 0.98 |
C241—O24 | 1.437 (6) | C441—H44C | 0.98 |
C241—H24A | 0.98 | C46—O46 | 1.326 (6) |
C241—H24B | 0.98 | C461—O46 | 1.459 (6) |
C241—H24C | 0.98 | C461—H46A | 0.98 |
C26—O26 | 1.335 (6) | C461—H46B | 0.98 |
C261—O26 | 1.453 (6) | C461—H46C | 0.98 |
C261—H26A | 0.98 | O1—H11 | 0.9981 |
C261—H26B | 0.98 | O1—H12 | 0.9992 |
C261—H26C | 0.98 | O2—H21 | 0.9992 |
N31—C32 | 1.353 (7) | O2—H22 | 1.0001 |
C32—N33 | 1.355 (7) | O3—H31 | 0.9994 |
N33—C34 | 1.317 (7) | O3—H32 | 0.9983 |
C16—N11—C12 | 117.1 (5) | C32—N32—H32B | 120.0 |
N12—C12—N11 | 118.1 (5) | H32A—N32—H32B | 120.0 |
N12—C12—N13 | 116.2 (5) | N32—C32—N31 | 116.6 (5) |
N11—C12—N13 | 125.8 (5) | N32—C32—N33 | 115.8 (5) |
C12—N12—H12A | 120.0 | N31—C32—N33 | 127.6 (5) |
C12—N12—H12B | 120.0 | C34—N33—C32 | 115.0 (5) |
H12A—N12—H12B | 120.0 | N33—C34—O34 | 119.2 (5) |
C14—N13—C12 | 115.6 (5) | N33—C34—C35 | 124.9 (5) |
N13—C14—O14 | 119.5 (5) | O34—C34—C35 | 115.9 (4) |
N13—C14—C15 | 124.4 (5) | C34—O34—C341 | 116.6 (4) |
O14—C14—C15 | 116.1 (4) | O34—C341—H34A | 109.5 |
C14—O14—C141 | 117.5 (4) | O34—C341—H34B | 109.5 |
O14—C141—H14A | 109.5 | H34A—C341—H34B | 109.5 |
O14—C141—H14B | 109.5 | O34—C341—H34C | 109.5 |
H14A—C141—H14B | 109.5 | H34A—C341—H34C | 109.5 |
O14—C141—H14C | 109.5 | H34B—C341—H34C | 109.5 |
H14A—C141—H14C | 109.5 | N35—C35—C34 | 117.0 (5) |
H14B—C141—H14C | 109.5 | N35—C35—C36 | 129.6 (5) |
N15—C15—C14 | 117.9 (4) | C34—C35—C36 | 113.4 (5) |
N15—C15—C16 | 128.1 (5) | O35—N35—C35 | 118.1 (4) |
C14—C15—C16 | 114.0 (4) | O36—C36—N31 | 119.6 (5) |
O15—N15—C15 | 117.6 (4) | O36—C36—C35 | 117.3 (5) |
N11—C16—O16 | 119.3 (5) | N31—C36—C35 | 123.1 (5) |
N11—C16—C15 | 123.1 (5) | C36—O36—C361 | 118.1 (4) |
O16—C16—C15 | 117.5 (5) | O36—C361—H36A | 109.5 |
O16—C161—H16A | 109.5 | O36—C361—H36B | 109.5 |
O16—C161—H16B | 109.5 | H36A—C361—H36B | 109.5 |
H16A—C161—H16B | 109.5 | O36—C361—H36C | 109.5 |
O16—C161—H16C | 109.5 | H36A—C361—H36C | 109.5 |
H16A—C161—H16C | 109.5 | H36B—C361—H36C | 109.5 |
H16B—C161—H16C | 109.5 | C46—N41—C42 | 116.6 (5) |
C16—O16—C161 | 115.3 (4) | N42—C42—N41 | 115.3 (5) |
C26—N21—C22 | 115.3 (4) | N42—C42—N43 | 117.9 (5) |
N22—C22—N21 | 116.8 (5) | N41—C42—N43 | 126.8 (5) |
N22—C22—N23 | 115.6 (5) | C42—N42—H42A | 120.0 |
N21—C22—N23 | 127.5 (5) | C42—N42—H42B | 120.0 |
C22—N22—H22A | 120.0 | H42A—N42—H42B | 120.0 |
C22—N22—H22B | 120.0 | C44—N43—C42 | 115.3 (5) |
H22A—N22—H22B | 120.0 | O44—C44—N43 | 120.1 (5) |
C24—N23—C22 | 115.3 (5) | O44—C44—C45 | 116.2 (4) |
N23—C24—O24 | 119.1 (5) | N43—C44—C45 | 123.7 (5) |
N23—C24—C25 | 124.2 (5) | O44—C441—H44A | 109.5 |
O24—C24—C25 | 116.7 (5) | O44—C441—H44B | 109.5 |
O24—C241—H24A | 109.5 | H44A—C441—H44B | 109.5 |
O24—C241—H24B | 109.5 | O44—C441—H44C | 109.5 |
H24A—C241—H24B | 109.5 | H44A—C441—H44C | 109.5 |
O24—C241—H24C | 109.5 | H44B—C441—H44C | 109.5 |
H24A—C241—H24C | 109.5 | C44—O44—C441 | 117.4 (4) |
H24B—C241—H24C | 109.5 | N45—C45—C46 | 129.8 (5) |
C24—O24—C241 | 117.6 (4) | N45—C45—C44 | 115.7 (5) |
N25—C25—C24 | 117.2 (5) | C46—C45—C44 | 114.5 (5) |
N25—C25—C26 | 128.8 (5) | O45—N45—C45 | 118.6 (4) |
C24—C25—C26 | 114.0 (5) | N41—C46—O46 | 118.5 (5) |
O25—N25—C25 | 118.6 (4) | N41—C46—C45 | 123.1 (5) |
N21—C26—O26 | 118.8 (4) | O46—C46—C45 | 118.4 (5) |
N21—C26—C25 | 123.6 (5) | O46—C461—H46A | 109.5 |
O26—C26—C25 | 117.6 (4) | O46—C461—H46B | 109.5 |
O26—C261—H26A | 109.5 | H46A—C461—H46B | 109.5 |
O26—C261—H26B | 109.5 | O46—C461—H46C | 109.5 |
H26A—C261—H26B | 109.5 | H46A—C461—H46C | 109.5 |
O26—C261—H26C | 109.5 | H46B—C461—H46C | 109.5 |
H26A—C261—H26C | 109.5 | C46—O46—C461 | 116.8 (4) |
H26B—C261—H26C | 109.5 | H11—O1—H12 | 105.6 |
C26—O26—C261 | 116.7 (4) | H21—O2—H22 | 105.3 |
C36—N31—C32 | 115.9 (4) | H31—O3—H32 | 105.5 |
C32—N32—H32A | 120.0 | ||
C16—N11—C12—N12 | −178.1 (5) | C36—N31—C32—N32 | 179.5 (4) |
C16—N11—C12—N13 | 1.4 (8) | C36—N31—C32—N33 | −2.0 (7) |
N12—C12—N13—C14 | 179.6 (4) | N32—C32—N33—C34 | 178.8 (4) |
N11—C12—N13—C14 | 0.1 (8) | N31—C32—N33—C34 | 0.3 (7) |
C12—N13—C14—O14 | 179.3 (4) | C32—N33—C34—O34 | −178.6 (4) |
C12—N13—C14—C15 | −1.4 (7) | C32—N33—C34—C35 | 2.3 (7) |
N13—C14—O14—C141 | −5.4 (7) | N33—C34—O34—C341 | 0.1 (7) |
C15—C14—O14—C141 | 175.3 (4) | C35—C34—O34—C341 | 179.2 (4) |
N13—C14—C15—N15 | −179.4 (5) | N33—C34—C35—N35 | 176.6 (5) |
O14—C14—C15—N15 | −0.1 (7) | O34—C34—C35—N35 | −2.4 (7) |
N13—C14—C15—C16 | 1.2 (7) | N33—C34—C35—C36 | −2.8 (7) |
O14—C14—C15—C16 | −179.5 (4) | O34—C34—C35—C36 | 178.1 (4) |
C14—C15—N15—O15 | −177.8 (4) | C34—C35—N35—O35 | 178.9 (4) |
C16—C15—N15—O15 | 1.6 (8) | C36—C35—N35—O35 | −1.7 (8) |
C12—N11—C16—O16 | 179.1 (4) | C32—N31—C36—O36 | −178.4 (5) |
C12—N11—C16—C15 | −1.6 (8) | C32—N31—C36—C35 | 1.3 (7) |
N15—C15—C16—N11 | −179.0 (5) | N35—C35—C36—O36 | 1.2 (8) |
C14—C15—C16—N11 | 0.4 (8) | C34—C35—C36—O36 | −179.4 (4) |
N15—C15—C16—O16 | 0.4 (8) | N35—C35—C36—N31 | −178.5 (5) |
C14—C15—C16—O16 | 179.8 (4) | C34—C35—C36—N31 | 0.8 (7) |
N11—C16—O16—C161 | −0.3 (7) | N31—C36—O36—C361 | 0.8 (7) |
C15—C16—O16—C161 | −179.6 (5) | C35—C36—O36—C361 | −179.0 (5) |
C26—N21—C22—N22 | −179.2 (5) | C46—N41—C42—N42 | 178.3 (4) |
C26—N21—C22—N23 | 0.2 (8) | C46—N41—C42—N43 | −1.5 (7) |
N22—C22—N23—C24 | 179.4 (4) | N42—C42—N43—C44 | −178.1 (4) |
N21—C22—N23—C24 | 0.0 (8) | N41—C42—N43—C44 | 1.7 (7) |
C22—N23—C24—O24 | −179.5 (4) | C42—N43—C44—O44 | 179.9 (4) |
C22—N23—C24—C25 | 0.5 (7) | C42—N43—C44—C45 | −0.4 (7) |
N23—C24—O24—C241 | −1.6 (7) | N43—C44—O44—C441 | −3.0 (7) |
C25—C24—O24—C241 | 178.3 (4) | C45—C44—O44—C441 | 177.3 (5) |
N23—C24—C25—N25 | −179.8 (5) | O44—C44—C45—N45 | −2.4 (6) |
O24—C24—C25—N25 | 0.3 (7) | N43—C44—C45—N45 | 177.9 (5) |
N23—C24—C25—C26 | −1.1 (7) | O44—C44—C45—C46 | 178.9 (4) |
O24—C24—C25—C26 | 178.9 (4) | N43—C44—C45—C46 | −0.8 (7) |
C24—C25—N25—O25 | 178.5 (4) | C46—C45—N45—O45 | −0.2 (8) |
C26—C25—N25—O25 | 0.1 (8) | C44—C45—N45—O45 | −178.7 (4) |
C22—N21—C26—O26 | 178.5 (4) | C42—N41—C46—O46 | −179.9 (4) |
C22—N21—C26—C25 | −0.9 (7) | C42—N41—C46—C45 | 0.0 (7) |
N25—C25—C26—N21 | 179.7 (5) | N45—C45—C46—N41 | −177.5 (5) |
C24—C25—C26—N21 | 1.3 (7) | C44—C45—C46—N41 | 1.0 (7) |
N25—C25—C26—O26 | 0.3 (8) | N45—C45—C46—O46 | 2.4 (8) |
C24—C25—C26—O26 | −178.1 (4) | C44—C45—C46—O46 | −179.1 (4) |
N21—C26—O26—C261 | 1.9 (6) | N41—C46—O46—C461 | −1.3 (6) |
C25—C26—O26—C261 | −178.6 (4) | C45—C46—O46—C461 | 178.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H12···O45 | 1.00 | 2.00 | 2.957 (5) | 159 |
O1—H12···O46 | 1.00 | 2.35 | 2.977 (5) | 120 |
N42—H42A···O35 | 0.88 | 2.13 | 3.011 (6) | 177 |
N32—H32B···O3 | 0.88 | 2.12 | 2.962 (6) | 161 |
O3—H31···O25 | 1.00 | 2.04 | 2.941 (5) | 149 |
O3—H31···O26 | 1.00 | 2.12 | 2.882 (5) | 132 |
N22—H22A···O14 | 0.88 | 2.31 | 3.183 (6) | 172 |
N22—H22B···O2 | 0.88 | 2.00 | 2.855 (6) | 165 |
O2—H22···O15 | 1.00 | 1.73 | 2.719 (6) | 171 |
O2—H22···N15 | 1.00 | 2.23 | 3.090 (6) | 143 |
N12—H12B···O1 | 0.88 | 1.95 | 2.825 (6) | 177 |
O1—H11···O3i | 1.00 | 1.82 | 2.817 (5) | 170 |
O2—H21···O36ii | 1.00 | 2.08 | 2.834 (5) | 131 |
O2—H21···O35ii | 1.00 | 2.16 | 2.951 (5) | 135 |
N42—H42B···O15iii | 0.88 | 2.43 | 2.991 (6) | 122 |
N42—H42B···O16iii | 0.88 | 2.46 | 3.337 (6) | 173 |
N12—H12A···N25iv | 0.88 | 2.24 | 3.027 (6) | 149 |
O3—H32···O45v | 1.00 | 1.78 | 2.767 (5) | 168 |
O3—H32···N45v | 1.00 | 2.32 | 3.145 (6) | 139 |
N32—H32A···O44v | 0.88 | 2.23 | 3.108 (6) | 175 |
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z+1; (iii) x, y−1, z−1; (iv) x+2, y+1, z; (v) x−2, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | 4C6H8N4O3·3H2O |
Mr | 790.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 6.9588 (4), 7.1984 (4), 17.4239 (11) |
α, β, γ (°) | 101.181 (2), 98.559 (2), 95.360 (4) |
V (Å3) | 839.95 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.20 × 0.20 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.964, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10707, 3638, 2498 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.140, 1.00 |
No. of reflections | 3638 |
No. of parameters | 504 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.38 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).
N11—C12 | 1.354 (7) | N31—C32 | 1.353 (7) |
C12—N13 | 1.370 (7) | C32—N33 | 1.355 (7) |
N13—C14 | 1.308 (7) | N33—C34 | 1.317 (7) |
C14—C15 | 1.411 (7) | C34—C35 | 1.424 (7) |
C15—C16 | 1.437 (8) | C35—C36 | 1.443 (7) |
C16—N11 | 1.296 (7) | C36—N31 | 1.328 (7) |
C12—N12 | 1.306 (7) | C32—N32 | 1.325 (7) |
C15—N15 | 1.360 (7) | C35—N35 | 1.360 (7) |
N15—O15 | 1.275 (6) | N35—O35 | 1.259 (6) |
N21—C22 | 1.354 (7) | N41—C42 | 1.353 (7) |
C22—N23 | 1.359 (7) | C42—N43 | 1.359 (7) |
N23—C24 | 1.315 (7) | N43—C44 | 1.323 (6) |
C24—C25 | 1.411 (7) | C44—C45 | 1.427 (7) |
C25—C26 | 1.439 (7) | C45—C46 | 1.420 (7) |
C26—N21 | 1.314 (7) | C46—N41 | 1.316 (7) |
C22—N22 | 1.328 (7) | C42—N42 | 1.328 (7) |
C25—N25 | 1.369 (7) | C45—N45 | 1.361 (7) |
N25—O25 | 1.255 (6) | N45—O45 | 1.263 (6) |
N13—C14—O14—C141 | −5.4 (7) | N33—C34—O34—C341 | 0.1 (7) |
N11—C16—O16—C161 | −0.3 (7) | N31—C36—O36—C361 | 0.8 (7) |
N23—C24—O24—C241 | −1.6 (7) | N43—C44—O44—C441 | −3.0 (7) |
N21—C26—O26—C261 | 1.9 (6) | N41—C46—O46—C461 | −1.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H12···O45 | 1.00 | 2.00 | 2.957 (5) | 159 |
O1—H12···O46 | 1.00 | 2.35 | 2.977 (5) | 120 |
N42—H42A···O35 | 0.88 | 2.13 | 3.011 (6) | 177 |
N32—H32B···O3 | 0.88 | 2.12 | 2.962 (6) | 161 |
O3—H31···O25 | 1.00 | 2.04 | 2.941 (5) | 149 |
O3—H31···O26 | 1.00 | 2.12 | 2.882 (5) | 132 |
N22—H22A···O14 | 0.88 | 2.31 | 3.183 (6) | 172 |
N22—H22B···O2 | 0.88 | 2.00 | 2.855 (6) | 165 |
O2—H22···O15 | 1.00 | 1.73 | 2.719 (6) | 171 |
O2—H22···N15 | 1.00 | 2.23 | 3.090 (6) | 143 |
N12—H12B···O1 | 0.88 | 1.95 | 2.825 (6) | 177 |
O1—H11···O3i | 1.00 | 1.82 | 2.817 (5) | 170 |
O2—H21···O36ii | 1.00 | 2.08 | 2.834 (5) | 131 |
O2—H21···O35ii | 1.00 | 2.16 | 2.951 (5) | 135 |
N42—H42B···O15iii | 0.88 | 2.43 | 2.991 (6) | 122 |
N42—H42B···O16iii | 0.88 | 2.46 | 3.337 (6) | 173 |
N12—H12A···N25iv | 0.88 | 2.24 | 3.027 (6) | 149 |
O3—H32···O45v | 1.00 | 1.78 | 2.767 (5) | 168 |
O3—H32···N45v | 1.00 | 2.32 | 3.145 (6) | 139 |
N32—H32A···O44v | 0.88 | 2.23 | 3.108 (6) | 175 |
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z+1; (iii) x, y−1, z−1; (iv) x+2, y+1, z; (v) x−2, y−1, z. |
In 2-amino-4,6-dimethoxypyrimidine, (I), both N—H bonds are involved in the formation of N—H···N hydrogen bonds, so forming a chain of edge-fused rings containing two distinct R22(8) motifs (Low et al., 2002). The benzyloxy analogue 2-amino-4,6-bis(benzyloxy)pyrimidine, (II), on the other hand, utilizes only one of the N—H bonds in forming an N—H···N hydrogen bond, again forming an R22(8) motif, while the other N—H bond forms an N—H···O hydrogen bond which generates a simple C(6) chain motif; the combination of the ring and chain motifs generates a molecular ladder (Quesada, Marchal et al., 2002). There are no R22(8) rings in 2-amino-4,6-bis(benzyloxy)-5-nitrosopyrimidine, (III), the nitrosated analogue of (II) (Quesada, Low et al., 2002). Instead, one N—H bond participates in a three-centre N—H···(N,O) hydrogen bond, while the other forms an N—H···π(arene) hydrogen bond; the overall supramolecular structure is again one-dimensional. Thus, the supramolecular structures of (I)-(III) involve two, one or zero distinct R22(8) rings, respectively, containing paired N—H···N hydrogen bonds. Intrigued by the differences in structural behaviour, not only between (I) and (II), but also between (II) and (III), we have now investigated the nitrosated analogue of (I), namely 2-amino-4,6-dimethoxy-5-nitrosopyrimidine, which upon crystallization from acetone, as used for (I) and (III), yields the stoichiometric hydrate 4C6H8N4O3·3H2O, (IV).
Compound (IV) (Fig. 1) crystallizes in the non-centrosymmetric triclinic space group P1 with four pyrimidine molecules and three water molecules in the asymmetric unit. Each of the pyrimidine molecules adopts a conformation in which the two methyl C atoms are essentially in the plane of the ring, but directed away from the nitroso substituent, just as in (III) (Quesada, Low et al., 2002). In each of the pyrimidine molecules in (IV), the Nn1—Cn6 and Nn3—Cn4 bonds (n = 1 - 4) are short for their type (Allen et al., 1987) and the Cn2—Nn2 bonds are much shorter than both the Nn1—Cn2 and Cn2—Nn3 bonds (Table 1); in addition, the Cn5—Nn5 bonds are shorter and the Nn5—On5 bonds longer than the corresponding bonds in simple unpolarized Ar—NO compounds. All of these distances point to the charge-separated form (IVa) as an important contributor to the overall molecular-electronic structure.
The seven independent molecular components in (IV) are linked into a three-dimensional framework by a combination of six three-centre hydrogen bonds, of which four are of O—H···(O)2 type and one each are of O—H···(N,O) and N—H···(O)2 types, and eight two-centre hydrogen bonds, one each of the O—H···O and N—H···N types and six of the N—H···O type (Table 2). The three-centre systems are, in general, distinctly asymmetric, but most are nearly planar; their angle sums at H range from 340 to 359°, with a mean value of 351°. The D—H···A angles in the two-centre hydrogen bonds range from 149 to 177°, with a mean of 168°, and all are reasonably short, and thus reasonably strong, for their types.
In supramolecular systems such as this, the selection of the asymmetric unit is, to a large extent, arbitrary; however, in (IV), it is possible to select a compact cyclic asymmetric unit bounded by an R77(38) motif (Fig. 1) which incorporates three of the three-centre hydrogen bonds and five of the two-centre hydrogen bonds, leaving just six hydrogen bonds to link these cyclic aggregates into the continuous framework. The interior of this cyclic unit is occupied by four methoxy groups, one from each of the pyrimidine molecules. Because translation is the only symmetry operation available in P1, the formation of the framework itself can be readily analyzed in terms of just three chain motifs linking the cyclic aggregates.
In the simplest of these chain motifs, the O1 water molecule in the aggregate at (x, y, z) acts as hydrogen-bond donor, via H11, to water atom O3 at (1 + x, 1 + y, z), so generating a chain parallel to the [110] direction (Fig. 2). The second chain motif utilizes two different three-centre hydrogen bonds with which to link the cyclic aggregates; the O2 water molecule acts as hydrogen-bond donor, via H21, to both methoxy atom O36 and nitroso atom O35 in the pyrimidine molecule at (x, 1 + y, 1 + z), while the N42 amino group acts as donor, via H42B, to methoxy atom O16 and nitroso atom O15 at (x, -1 + y, -1 + z), and these three-centre interactions combine to generate a chain running parallel to [011] (Fig. 3). Finally, in the most complex of the chains, the N12 amino group acts as donor, via H12A, to nitroso atom N25 at (2 + x, 1 + y, z), while the N32 amino group acts as donor, via H32A, to methoxy atom O44 at (-2 + x, -1 + y, z), each hydrogen bond thus forming a chain along [210]; additionally, the O3 water molecule acts as donor, via H32, to both N45 and O45 at (-2 + x, -1 + y, z), providing the final component of the [210] chain (Fig. 3). The combination of the [011] and [210] ladders generates a very elegant (122) sheet (Fig. 3), while the combination of [110], [011] and [210] chains suffices to generate a single three-dimensional framework.