Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107005677/ob3031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005677/ob3031Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005677/ob3031IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107005677/ob3031IIIsup4.hkl |
CCDC references: 605380; 605381; 606029
Compounds (I) and (II) were prepared by mixing a hot methanol solution (20 ml) of 2-amino-4,6-dimethoxypyrimidine (38 mg, Aldrich) with a hot aqueous solution of the corresponding acid [4-hydroxybenzoic acid (34 mg, Loba Chemie) or dipicolinic acid (41 mg, Loba Chemie)] in a 1:1 molar ratio, and warmed for half an hour over a water bath. Each solution was cooled slowly and kept at room temperature. After a few days, colourless plate-like crystals were obtained [yield 69 and 64% for (I) and (II), respectively]. Compound (III) was prepared by mixing a hot methanol solution (20 ml) of 2-amino-4,6-dimethoxypyrimidine (76 mg) and L-(+)-tartaric acid (37 mg, Loba Chemie) in a 2:1 molar ratio, and crystallized as described above (yield 58%). Compound (III) was obtained even if the starting materials were in a 1:1 molar ratio.
The H atoms of the water molecules were located in difference Fourier maps and refined as riding in their as-found relative positions. The other H atoms were positioned geometrically, and treated as riding with N—H, O—H and C—H bond lengths of 0.86, 0.82 and 0.93–0.98 Å, respectively, and with Uiso(H) values of 1.5Ueq(C,O) for OH groups in (I) and (II) and for all methyl groups, or 1.2Ueq(C,N,O). For (III), Friedel pairs were averaged in the absence of significant anomalous scattering effects, and the absolute structure was assigned based on the known absolute configuration of L-(+)-tartaric acid (Bijvoet et al., 1951; Hope & de la Camp, 1972).
For all compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
C6H10N3O2+·C7H5O3−·H2O | F(000) = 656 |
Mr = 311.30 | Dx = 1.484 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3172 reflections |
a = 6.9710 (2) Å | θ = 3.5–27.5° |
b = 10.9014 (3) Å | µ = 0.12 mm−1 |
c = 18.3749 (6) Å | T = 120 K |
β = 93.631 (2)° | Plate-like, colourless |
V = 1393.57 (7) Å3 | 0.48 × 0.30 × 0.14 mm |
Z = 4 |
Bruker–Nonius KappaCCD area-detector diffractometer | 2415 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.036 |
Graphite monochromator | θmax = 27.6°, θmin = 3.5° |
ϕ and ω scans | h = −8→9 |
12896 measured reflections | k = −14→9 |
3172 independent reflections | l = −23→22 |
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)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0837P)2 + 0.1403P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3172 reflections | Δρmax = 0.58 e Å−3 |
203 parameters | Δρmin = −0.65 e Å−3 |
3 restraints | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.053 (5) |
C6H10N3O2+·C7H5O3−·H2O | V = 1393.57 (7) Å3 |
Mr = 311.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9710 (2) Å | µ = 0.12 mm−1 |
b = 10.9014 (3) Å | T = 120 K |
c = 18.3749 (6) Å | 0.48 × 0.30 × 0.14 mm |
β = 93.631 (2)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 2415 reflections with I > 2σ(I) |
12896 measured reflections | Rint = 0.036 |
3172 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 3 restraints |
wR(F2) = 0.140 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.58 e Å−3 |
3172 reflections | Δρmin = −0.65 e Å−3 |
203 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.40962 (16) | 0.85957 (10) | 0.51255 (6) | 0.0207 (3) | |
O2 | 0.26432 (16) | 0.80476 (10) | 0.26006 (6) | 0.0206 (3) | |
N1 | 0.34431 (18) | 0.65078 (12) | 0.33471 (7) | 0.0172 (4) | |
N2 | 0.42097 (19) | 0.48035 (13) | 0.40256 (7) | 0.0215 (4) | |
N3 | 0.42694 (18) | 0.66807 (12) | 0.46101 (7) | 0.0166 (4) | |
C2 | 0.3974 (2) | 0.60079 (15) | 0.40033 (8) | 0.0156 (4) | |
C4 | 0.3935 (2) | 0.78774 (15) | 0.45418 (9) | 0.0166 (5) | |
C5 | 0.3390 (2) | 0.84720 (14) | 0.38839 (9) | 0.0183 (5) | |
C6 | 0.3155 (2) | 0.77336 (14) | 0.32874 (9) | 0.0168 (4) | |
C7 | 0.4645 (3) | 0.80425 (16) | 0.58223 (9) | 0.0228 (5) | |
C8 | 0.2401 (2) | 0.93355 (15) | 0.24485 (10) | 0.0231 (5) | |
O3 | 0.26439 (17) | 0.34335 (10) | 0.27838 (6) | 0.0225 (4) | |
O4 | 0.26345 (16) | 0.52068 (10) | 0.21800 (6) | 0.0203 (3) | |
O5 | 0.01317 (18) | 0.16590 (10) | −0.04400 (6) | 0.0235 (4) | |
C9 | 0.1800 (2) | 0.34106 (14) | 0.15073 (8) | 0.0148 (4) | |
C10 | 0.1605 (2) | 0.40701 (15) | 0.08591 (9) | 0.0166 (4) | |
C11 | 0.1067 (2) | 0.35042 (14) | 0.02052 (9) | 0.0170 (5) | |
C12 | 0.0690 (2) | 0.22490 (14) | 0.01898 (8) | 0.0164 (4) | |
C13 | 0.0887 (2) | 0.15670 (15) | 0.08311 (9) | 0.0184 (5) | |
C14 | 0.1441 (2) | 0.21491 (14) | 0.14802 (9) | 0.0175 (5) | |
C15 | 0.2394 (2) | 0.40424 (15) | 0.22074 (9) | 0.0166 (4) | |
O1W | 0.04316 (17) | 0.17595 (11) | 0.34496 (6) | 0.0244 (4) | |
H1 | 0.32880 | 0.60470 | 0.29680 | 0.0210* | |
H2A | 0.45540 | 0.44490 | 0.44310 | 0.0260* | |
H2B | 0.40180 | 0.43760 | 0.36350 | 0.0260* | |
H5 | 0.32000 | 0.93160 | 0.38570 | 0.0220* | |
H7A | 0.37930 | 0.73740 | 0.59100 | 0.0340* | |
H7B | 0.45690 | 0.86440 | 0.62010 | 0.0340* | |
H7C | 0.59390 | 0.77410 | 0.58190 | 0.0340* | |
H8A | 0.14510 | 0.96680 | 0.27490 | 0.0350* | |
H8B | 0.19880 | 0.94450 | 0.19440 | 0.0350* | |
H8C | 0.36010 | 0.97520 | 0.25500 | 0.0350* | |
H5A | 0.01630 | 0.21380 | −0.07830 | 0.0350* | |
H10 | 0.18420 | 0.49100 | 0.08660 | 0.0200* | |
H11 | 0.09560 | 0.39600 | −0.02230 | 0.0200* | |
H13 | 0.06480 | 0.07280 | 0.08230 | 0.0220* | |
H14 | 0.15780 | 0.16910 | 0.19070 | 0.0210* | |
H1W | −0.06570 | 0.14160 | 0.32000 | 0.0290* | |
H2W | 0.11260 | 0.22130 | 0.31310 | 0.0290* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0249 (6) | 0.0185 (6) | 0.0183 (6) | 0.0032 (5) | −0.0020 (5) | −0.0043 (5) |
O2 | 0.0257 (6) | 0.0174 (6) | 0.0184 (6) | 0.0013 (5) | −0.0017 (5) | 0.0020 (5) |
N1 | 0.0190 (7) | 0.0171 (7) | 0.0153 (7) | 0.0004 (5) | −0.0007 (5) | −0.0016 (5) |
N2 | 0.0335 (9) | 0.0164 (7) | 0.0139 (7) | 0.0017 (6) | −0.0038 (6) | −0.0009 (6) |
N3 | 0.0149 (7) | 0.0178 (7) | 0.0171 (7) | 0.0003 (5) | 0.0001 (5) | −0.0026 (6) |
C2 | 0.0128 (7) | 0.0185 (8) | 0.0155 (8) | −0.0009 (6) | 0.0001 (6) | −0.0006 (6) |
C4 | 0.0115 (7) | 0.0198 (8) | 0.0186 (9) | −0.0012 (6) | 0.0013 (6) | −0.0038 (7) |
C5 | 0.0175 (8) | 0.0151 (7) | 0.0224 (9) | 0.0009 (6) | 0.0022 (6) | −0.0009 (7) |
C6 | 0.0118 (7) | 0.0194 (8) | 0.0193 (8) | 0.0001 (6) | 0.0009 (6) | 0.0037 (7) |
C7 | 0.0266 (9) | 0.0235 (9) | 0.0180 (9) | 0.0041 (7) | −0.0021 (7) | −0.0045 (7) |
C8 | 0.0255 (9) | 0.0183 (8) | 0.0252 (9) | 0.0027 (7) | −0.0001 (7) | 0.0058 (7) |
O3 | 0.0308 (7) | 0.0202 (6) | 0.0158 (6) | −0.0036 (5) | −0.0032 (5) | 0.0033 (5) |
O4 | 0.0279 (6) | 0.0158 (6) | 0.0167 (6) | −0.0008 (5) | −0.0014 (5) | −0.0010 (5) |
O5 | 0.0334 (7) | 0.0217 (6) | 0.0149 (6) | −0.0020 (5) | −0.0018 (5) | −0.0025 (5) |
C9 | 0.0107 (7) | 0.0173 (8) | 0.0163 (8) | 0.0003 (6) | 0.0010 (6) | −0.0016 (6) |
C10 | 0.0171 (8) | 0.0144 (7) | 0.0186 (8) | −0.0012 (6) | 0.0024 (6) | 0.0005 (6) |
C11 | 0.0173 (8) | 0.0194 (8) | 0.0143 (8) | 0.0016 (6) | 0.0012 (6) | 0.0029 (6) |
C12 | 0.0142 (7) | 0.0200 (8) | 0.0151 (8) | 0.0020 (6) | 0.0010 (6) | −0.0042 (6) |
C13 | 0.0188 (8) | 0.0156 (8) | 0.0210 (9) | 0.0010 (6) | 0.0019 (7) | −0.0002 (7) |
C14 | 0.0196 (8) | 0.0179 (8) | 0.0149 (8) | 0.0011 (6) | 0.0011 (6) | 0.0012 (6) |
C15 | 0.0134 (7) | 0.0185 (8) | 0.0181 (8) | 0.0003 (6) | 0.0017 (6) | 0.0002 (7) |
O1W | 0.0287 (7) | 0.0286 (7) | 0.0154 (6) | −0.0069 (5) | −0.0016 (5) | 0.0024 (5) |
O1—C4 | 1.327 (2) | C5—C6 | 1.361 (2) |
O1—C7 | 1.445 (2) | C5—H5 | 0.9304 |
O2—C6 | 1.334 (2) | C7—H7C | 0.9604 |
O2—C8 | 1.439 (2) | C7—H7A | 0.9602 |
O3—C15 | 1.253 (2) | C7—H7B | 0.9600 |
O4—C15 | 1.282 (2) | C8—H8B | 0.9606 |
O5—C12 | 1.3592 (18) | C8—H8C | 0.9597 |
O5—H5A | 0.8198 | C8—H8A | 0.9598 |
O1W—H1W | 0.9393 | C9—C14 | 1.398 (2) |
O1W—H2W | 0.9259 | C9—C10 | 1.390 (2) |
N1—C2 | 1.353 (2) | C9—C15 | 1.494 (2) |
N1—C6 | 1.355 (2) | C10—C11 | 1.381 (2) |
N2—C2 | 1.324 (2) | C11—C12 | 1.393 (2) |
N3—C4 | 1.330 (2) | C12—C13 | 1.393 (2) |
N3—C2 | 1.340 (2) | C13—C14 | 1.384 (2) |
N1—H1 | 0.8601 | C10—H10 | 0.9303 |
N2—H2A | 0.8598 | C11—H11 | 0.9296 |
N2—H2B | 0.8591 | C13—H13 | 0.9296 |
C4—C5 | 1.403 (2) | C14—H14 | 0.9295 |
C4—O1—C7 | 118.30 (13) | H7A—C7—H7C | 109.42 |
C6—O2—C8 | 117.06 (12) | O2—C8—H8C | 109.49 |
C12—O5—H5A | 109.45 | O2—C8—H8A | 109.48 |
H1W—O1W—H2W | 110.04 | O2—C8—H8B | 109.45 |
C2—N1—C6 | 120.01 (14) | H8B—C8—H8C | 109.45 |
C2—N3—C4 | 116.22 (14) | H8A—C8—H8B | 109.43 |
C2—N1—H1 | 119.98 | H8A—C8—H8C | 109.53 |
C6—N1—H1 | 120.01 | C10—C9—C15 | 120.38 (14) |
C2—N2—H2A | 120.00 | C14—C9—C15 | 121.55 (14) |
H2A—N2—H2B | 120.01 | C10—C9—C14 | 118.07 (14) |
C2—N2—H2B | 119.99 | C9—C10—C11 | 121.37 (15) |
N2—C2—N3 | 120.34 (14) | C10—C11—C12 | 119.79 (15) |
N1—C2—N3 | 122.69 (14) | O5—C12—C11 | 121.70 (14) |
N1—C2—N2 | 116.97 (14) | C11—C12—C13 | 119.91 (14) |
O1—C4—C5 | 115.36 (14) | O5—C12—C13 | 118.38 (14) |
N3—C4—C5 | 124.82 (15) | C12—C13—C14 | 119.44 (15) |
O1—C4—N3 | 119.82 (14) | C9—C14—C13 | 121.41 (15) |
C4—C5—C6 | 115.65 (14) | O3—C15—C9 | 119.98 (14) |
O2—C6—C5 | 128.40 (14) | O3—C15—O4 | 123.12 (15) |
N1—C6—C5 | 120.56 (15) | O4—C15—C9 | 116.90 (14) |
O2—C6—N1 | 111.04 (13) | C9—C10—H10 | 119.31 |
C6—C5—H5 | 122.17 | C11—C10—H10 | 119.32 |
C4—C5—H5 | 122.18 | C12—C11—H11 | 120.15 |
O1—C7—H7C | 109.47 | C10—C11—H11 | 120.06 |
O1—C7—H7A | 109.49 | C12—C13—H13 | 120.24 |
O1—C7—H7B | 109.49 | C14—C13—H13 | 120.32 |
H7B—C7—H7C | 109.47 | C9—C14—H14 | 119.33 |
H7A—C7—H7B | 109.49 | C13—C14—H14 | 119.26 |
C7—O1—C4—N3 | 0.3 (2) | C4—C5—C6—O2 | 179.81 (14) |
C7—O1—C4—C5 | 179.74 (14) | C14—C9—C10—C11 | 0.2 (2) |
C8—O2—C6—C5 | 3.8 (2) | C15—C9—C14—C13 | 179.86 (13) |
C8—O2—C6—N1 | −176.39 (12) | C10—C9—C15—O3 | −177.03 (14) |
C2—N1—C6—O2 | 179.96 (13) | C10—C9—C15—O4 | 2.6 (2) |
C2—N1—C6—C5 | −0.2 (2) | C14—C9—C15—O3 | 2.4 (2) |
C6—N1—C2—N2 | 179.22 (13) | C14—C9—C15—O4 | −177.99 (13) |
C6—N1—C2—N3 | −1.2 (2) | C15—C9—C10—C11 | 179.67 (13) |
C4—N3—C2—N2 | −177.77 (13) | C10—C9—C14—C13 | −0.7 (2) |
C2—N3—C4—C5 | −3.0 (2) | C9—C10—C11—C12 | 0.6 (2) |
C4—N3—C2—N1 | 2.7 (2) | C10—C11—C12—O5 | 179.10 (13) |
C2—N3—C4—O1 | 176.44 (13) | C10—C11—C12—C13 | −1.0 (2) |
O1—C4—C5—C6 | −177.74 (13) | C11—C12—C13—C14 | 0.6 (2) |
N3—C4—C5—C6 | 1.7 (2) | O5—C12—C13—C14 | −179.55 (13) |
C4—C5—C6—N1 | 0.0 (2) | C12—C13—C14—C9 | 0.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4 | 0.86 | 1.75 | 2.6029 (17) | 172 |
O1W—H1W···O4i | 0.94 | 2.00 | 2.9084 (16) | 162 |
N2—H2A···N3ii | 0.86 | 2.26 | 3.1128 (19) | 171 |
N2—H2B···O3 | 0.86 | 2.06 | 2.8832 (17) | 161 |
O1W—H2W···O3 | 0.93 | 1.84 | 2.7284 (16) | 160 |
O5—H5A···O1Wiii | 0.82 | 1.87 | 2.6894 (16) | 176 |
C11—H11···O1Wiii | 0.93 | 2.57 | 3.241 (2) | 130 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
C6H10N3O2+·C7H4NO4−·H2O | Z = 2 |
Mr = 340.30 | F(000) = 356 |
Triclinic, P1 | Dx = 1.514 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8247 (6) Å | Cell parameters from 3384 reflections |
b = 7.9273 (5) Å | θ = 3.2–27.6° |
c = 14.4038 (10) Å | µ = 0.13 mm−1 |
α = 82.558 (5)° | T = 120 K |
β = 88.133 (4)° | Plate-like, colourless |
γ = 75.075 (5)° | 0.40 × 0.25 × 0.10 mm |
V = 746.63 (10) Å3 |
Bruker–Nonius KappaCCD area-detector diffractometer | 2397 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.062 |
Graphite monochromator | θmax = 27.6°, θmin = 3.2° |
ϕ and ω scans | h = −8→8 |
14555 measured reflections | k = −10→10 |
3384 independent reflections | l = −18→18 |
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)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.175 | w = 1/[σ2(Fo2) + (0.108P)2 + 0.0561P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3384 reflections | Δρmax = 0.53 e Å−3 |
221 parameters | Δρmin = −0.62 e Å−3 |
3 restraints | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.090 (13) |
C6H10N3O2+·C7H4NO4−·H2O | γ = 75.075 (5)° |
Mr = 340.30 | V = 746.63 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8247 (6) Å | Mo Kα radiation |
b = 7.9273 (5) Å | µ = 0.13 mm−1 |
c = 14.4038 (10) Å | T = 120 K |
α = 82.558 (5)° | 0.40 × 0.25 × 0.10 mm |
β = 88.133 (4)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 2397 reflections with I > 2σ(I) |
14555 measured reflections | Rint = 0.062 |
3384 independent reflections |
R[F2 > 2σ(F2)] = 0.064 | 3 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.53 e Å−3 |
3384 reflections | Δρmin = −0.62 e Å−3 |
221 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9563 (2) | −0.25025 (17) | 1.16681 (9) | 0.0274 (4) | |
O2 | 0.7551 (2) | −0.17070 (16) | 0.84995 (9) | 0.0267 (4) | |
N1 | 0.6917 (2) | 0.04888 (19) | 0.93715 (11) | 0.0228 (5) | |
N2 | 0.6231 (2) | 0.2887 (2) | 1.01707 (11) | 0.0275 (5) | |
N3 | 0.7901 (2) | 0.0229 (2) | 1.09597 (11) | 0.0248 (5) | |
C2 | 0.7029 (3) | 0.1180 (2) | 1.01778 (13) | 0.0231 (6) | |
C4 | 0.8653 (3) | −0.1477 (2) | 1.09173 (13) | 0.0236 (6) | |
C5 | 0.8596 (3) | −0.2310 (2) | 1.01190 (13) | 0.0248 (6) | |
C6 | 0.7729 (3) | −0.1246 (2) | 0.93434 (13) | 0.0236 (6) | |
C7 | 0.9634 (3) | −0.1690 (3) | 1.25092 (14) | 0.0302 (6) | |
C8 | 0.8446 (3) | −0.3522 (3) | 0.83754 (14) | 0.0292 (6) | |
O3 | 0.4188 (2) | 0.47450 (17) | 0.85149 (9) | 0.0319 (4) | |
O4 | 0.5196 (2) | 0.22687 (17) | 0.78647 (9) | 0.0298 (4) | |
O5 | 0.2275 (2) | 0.43641 (19) | 0.38006 (9) | 0.0346 (5) | |
O6 | 0.3302 (2) | 0.19762 (18) | 0.48598 (10) | 0.0342 (5) | |
N4 | 0.3479 (2) | 0.3902 (2) | 0.62073 (11) | 0.0234 (5) | |
C9 | 0.3479 (3) | 0.4868 (2) | 0.69062 (13) | 0.0235 (6) | |
C10 | 0.2774 (3) | 0.6692 (2) | 0.68014 (14) | 0.0277 (6) | |
C11 | 0.2059 (3) | 0.7554 (3) | 0.59367 (15) | 0.0324 (6) | |
C12 | 0.2036 (3) | 0.6579 (3) | 0.52110 (14) | 0.0291 (6) | |
C13 | 0.2739 (3) | 0.4766 (3) | 0.53802 (13) | 0.0255 (6) | |
C14 | 0.4354 (3) | 0.3896 (2) | 0.78357 (13) | 0.0238 (5) | |
C15 | 0.2737 (3) | 0.3692 (3) | 0.45903 (14) | 0.0271 (6) | |
O1W | 0.6166 (3) | 0.0172 (2) | 0.63786 (12) | 0.0554 (6) | |
H1 | 0.63360 | 0.11500 | 0.88850 | 0.0270* | |
H2A | 0.62760 | 0.33760 | 1.06660 | 0.0330* | |
H2B | 0.56660 | 0.35110 | 0.96700 | 0.0330* | |
H5 | 0.91190 | −0.35150 | 1.01200 | 0.0300* | |
H7A | 1.02810 | −0.07450 | 1.23720 | 0.0450* | |
H7B | 1.03890 | −0.25510 | 1.29850 | 0.0450* | |
H7C | 0.82800 | −0.12380 | 1.27270 | 0.0450* | |
H8A | 0.98720 | −0.38130 | 0.85090 | 0.0440* | |
H8B | 0.82500 | −0.36940 | 0.77410 | 0.0440* | |
H8C | 0.78130 | −0.42680 | 0.87940 | 0.0440* | |
H6 | 0.34210 | 0.14480 | 0.43990 | 0.0510* | |
H10 | 0.27850 | 0.73180 | 0.73040 | 0.0330* | |
H11 | 0.15990 | 0.87750 | 0.58440 | 0.0390* | |
H12 | 0.15590 | 0.71280 | 0.46220 | 0.0350* | |
H1W | 0.61800 | 0.00800 | 0.70470 | 0.0670* | |
H2W | 0.53550 | 0.12620 | 0.61940 | 0.0670* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0364 (8) | 0.0249 (7) | 0.0195 (7) | −0.0033 (6) | −0.0066 (6) | −0.0052 (5) |
O2 | 0.0388 (8) | 0.0217 (7) | 0.0187 (7) | −0.0023 (6) | −0.0025 (6) | −0.0093 (5) |
N1 | 0.0296 (8) | 0.0192 (8) | 0.0183 (8) | −0.0020 (6) | −0.0041 (6) | −0.0048 (6) |
N2 | 0.0381 (10) | 0.0223 (8) | 0.0204 (9) | −0.0020 (7) | −0.0053 (7) | −0.0072 (6) |
N3 | 0.0297 (9) | 0.0233 (8) | 0.0215 (8) | −0.0046 (7) | −0.0023 (7) | −0.0068 (6) |
C2 | 0.0268 (10) | 0.0237 (10) | 0.0201 (10) | −0.0069 (8) | −0.0007 (8) | −0.0069 (7) |
C4 | 0.0281 (10) | 0.0226 (9) | 0.0204 (10) | −0.0064 (8) | −0.0003 (8) | −0.0039 (8) |
C5 | 0.0311 (10) | 0.0210 (9) | 0.0221 (10) | −0.0042 (8) | −0.0008 (8) | −0.0065 (7) |
C6 | 0.0256 (10) | 0.0252 (10) | 0.0210 (10) | −0.0056 (8) | 0.0012 (7) | −0.0091 (7) |
C7 | 0.0395 (11) | 0.0319 (11) | 0.0190 (10) | −0.0066 (9) | −0.0052 (8) | −0.0068 (8) |
C8 | 0.0400 (11) | 0.0244 (10) | 0.0221 (10) | −0.0022 (8) | −0.0009 (8) | −0.0112 (8) |
O3 | 0.0487 (9) | 0.0248 (7) | 0.0211 (7) | −0.0032 (6) | −0.0068 (6) | −0.0097 (6) |
O4 | 0.0418 (8) | 0.0226 (7) | 0.0219 (7) | 0.0003 (6) | −0.0058 (6) | −0.0074 (5) |
O5 | 0.0457 (9) | 0.0387 (8) | 0.0183 (8) | −0.0071 (7) | −0.0053 (6) | −0.0062 (6) |
O6 | 0.0507 (9) | 0.0312 (8) | 0.0207 (7) | −0.0069 (7) | −0.0047 (7) | −0.0097 (6) |
N4 | 0.0281 (9) | 0.0242 (8) | 0.0183 (8) | −0.0058 (7) | 0.0004 (6) | −0.0059 (6) |
C9 | 0.0271 (10) | 0.0243 (10) | 0.0192 (10) | −0.0054 (8) | 0.0007 (7) | −0.0054 (7) |
C10 | 0.0366 (11) | 0.0243 (10) | 0.0223 (10) | −0.0046 (8) | 0.0004 (8) | −0.0096 (8) |
C11 | 0.0412 (12) | 0.0226 (10) | 0.0298 (11) | −0.0014 (9) | −0.0020 (9) | −0.0031 (8) |
C12 | 0.0338 (11) | 0.0301 (11) | 0.0211 (10) | −0.0045 (8) | −0.0028 (8) | −0.0019 (8) |
C13 | 0.0270 (10) | 0.0297 (10) | 0.0206 (10) | −0.0070 (8) | −0.0001 (8) | −0.0063 (8) |
C14 | 0.0301 (10) | 0.0222 (9) | 0.0200 (9) | −0.0062 (8) | −0.0023 (8) | −0.0066 (7) |
C15 | 0.0276 (10) | 0.0324 (11) | 0.0215 (10) | −0.0069 (8) | −0.0009 (8) | −0.0059 (8) |
O1W | 0.0894 (14) | 0.0365 (9) | 0.0303 (9) | 0.0106 (9) | −0.0165 (9) | −0.0173 (7) |
O1—C4 | 1.331 (2) | N4—C9 | 1.341 (2) |
O1—C7 | 1.452 (2) | C4—C5 | 1.404 (3) |
O2—C6 | 1.332 (2) | C5—C6 | 1.361 (3) |
O2—C8 | 1.443 (3) | C5—H5 | 0.9295 |
O3—C14 | 1.244 (2) | C7—H7A | 0.9600 |
O4—C14 | 1.266 (2) | C7—H7B | 0.9601 |
O5—C15 | 1.207 (2) | C7—H7C | 0.9594 |
O6—C15 | 1.324 (3) | C8—H8C | 0.9603 |
O6—H6 | 0.8206 | C8—H8B | 0.9597 |
O1W—H1W | 0.9562 | C8—H8A | 0.9604 |
O1W—H2W | 0.9096 | C9—C14 | 1.513 (3) |
N1—C6 | 1.349 (2) | C9—C10 | 1.391 (2) |
N1—C2 | 1.359 (2) | C10—C11 | 1.380 (3) |
N2—C2 | 1.321 (2) | C11—C12 | 1.381 (3) |
N3—C2 | 1.335 (2) | C12—C13 | 1.385 (3) |
N3—C4 | 1.326 (2) | C13—C15 | 1.507 (3) |
N1—H1 | 0.8596 | C10—H10 | 0.9305 |
N2—H2B | 0.8608 | C11—H11 | 0.9306 |
N2—H2A | 0.8599 | C12—H12 | 0.9298 |
N4—C13 | 1.339 (2) | ||
C4—O1—C7 | 117.71 (15) | H7B—C7—H7C | 109.47 |
C6—O2—C8 | 116.85 (14) | O2—C8—H8C | 109.48 |
C15—O6—H6 | 109.45 | O2—C8—H8B | 109.49 |
H1W—O1W—H2W | 104.58 | H8B—C8—H8C | 109.48 |
C2—N1—C6 | 119.25 (15) | H8A—C8—H8B | 109.43 |
C2—N3—C4 | 115.98 (16) | H8A—C8—H8C | 109.44 |
C6—N1—H1 | 120.41 | O2—C8—H8A | 109.50 |
C2—N1—H1 | 120.35 | C10—C9—C14 | 119.72 (16) |
C2—N2—H2A | 120.05 | N4—C9—C14 | 117.18 (14) |
H2A—N2—H2B | 119.94 | N4—C9—C10 | 123.07 (17) |
C2—N2—H2B | 120.02 | C9—C10—C11 | 118.64 (18) |
C9—N4—C13 | 117.15 (17) | C10—C11—C12 | 119.1 (2) |
N2—C2—N3 | 119.34 (16) | C11—C12—C13 | 118.51 (19) |
N1—C2—N3 | 123.48 (15) | N4—C13—C12 | 123.55 (19) |
N1—C2—N2 | 117.17 (16) | C12—C13—C15 | 118.89 (18) |
O1—C4—C5 | 116.16 (14) | N4—C13—C15 | 117.53 (19) |
N3—C4—C5 | 124.59 (17) | O4—C14—C9 | 117.30 (15) |
O1—C4—N3 | 119.24 (16) | O3—C14—O4 | 124.73 (17) |
C4—C5—C6 | 115.95 (15) | O3—C14—C9 | 117.96 (14) |
N1—C6—C5 | 120.71 (16) | O6—C15—C13 | 112.86 (17) |
O2—C6—C5 | 127.33 (15) | O5—C15—O6 | 125.0 (2) |
O2—C6—N1 | 111.96 (15) | O5—C15—C13 | 122.2 (2) |
C4—C5—H5 | 122.06 | C11—C10—H10 | 120.68 |
C6—C5—H5 | 121.99 | C9—C10—H10 | 120.68 |
O1—C7—H7A | 109.51 | C10—C11—H11 | 120.46 |
O1—C7—H7B | 109.45 | C12—C11—H11 | 120.49 |
O1—C7—H7C | 109.45 | C11—C12—H12 | 120.73 |
H7A—C7—H7B | 109.45 | C13—C12—H12 | 120.76 |
H7A—C7—H7C | 109.50 | ||
C7—O1—C4—N3 | 1.6 (3) | O1—C4—C5—C6 | −177.74 (18) |
C7—O1—C4—C5 | −179.43 (17) | C4—C5—C6—O2 | 177.75 (19) |
C8—O2—C6—N1 | 177.39 (16) | C4—C5—C6—N1 | −2.4 (3) |
C8—O2—C6—C5 | −2.8 (3) | N4—C9—C14—O3 | −173.15 (18) |
C6—N1—C2—N2 | 179.37 (17) | N4—C9—C14—O4 | 6.5 (3) |
C6—N1—C2—N3 | −0.3 (3) | C14—C9—C10—C11 | 177.41 (19) |
C2—N1—C6—O2 | −178.08 (16) | C10—C9—C14—O4 | −171.69 (19) |
C2—N1—C6—C5 | 2.1 (3) | C10—C9—C14—O3 | 8.7 (3) |
C4—N3—C2—N1 | −0.9 (3) | N4—C9—C10—C11 | −0.7 (3) |
C2—N3—C4—O1 | 179.31 (17) | C9—C10—C11—C12 | 1.1 (3) |
C2—N3—C4—C5 | 0.4 (3) | C10—C11—C12—C13 | −0.1 (3) |
C4—N3—C2—N2 | 179.43 (18) | C11—C12—C13—C15 | −179.47 (19) |
C9—N4—C13—C12 | 1.7 (3) | C11—C12—C13—N4 | −1.3 (3) |
C9—N4—C13—C15 | 179.87 (18) | N4—C13—C15—O5 | −173.08 (19) |
C13—N4—C9—C10 | −0.7 (3) | C12—C13—C15—O6 | −175.29 (19) |
C13—N4—C9—C14 | −178.80 (18) | N4—C13—C15—O6 | 6.4 (3) |
N3—C4—C5—C6 | 1.2 (3) | C12—C13—C15—O5 | 5.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4 | 0.86 | 1.71 | 2.569 (2) | 174 |
N2—H2A···O3i | 0.86 | 1.97 | 2.793 (2) | 159 |
N2—H2B···O3 | 0.86 | 1.98 | 2.837 (2) | 173 |
O1W—H1W···O2 | 0.96 | 2.44 | 3.275 (2) | 146 |
O1W—H1W···O4 | 0.96 | 2.17 | 2.836 (2) | 125 |
O1W—H2W···O6 | 0.91 | 2.34 | 2.946 (2) | 124 |
O1W—H2W···N4 | 0.91 | 2.16 | 3.035 (2) | 162 |
O6—H6···O1Wii | 0.82 | 1.77 | 2.577 (2) | 165 |
C7—H7B···O5iii | 0.96 | 2.60 | 3.507 (3) | 158 |
C8—H8B···O5ii | 0.96 | 2.41 | 3.365 (2) | 175 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1; (iii) x+1, y−1, z+1. |
C6H10N3O2+·C4H5O6−·C6H9N3O2 | F(000) = 484 |
Mr = 460.41 | Dx = 1.531 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2378 reflections |
a = 7.3245 (2) Å | θ = 3.2–27.5° |
b = 15.8349 (6) Å | µ = 0.13 mm−1 |
c = 8.9264 (3) Å | T = 120 K |
β = 105.251 (2)° | Plate-like, colourless |
V = 998.85 (6) Å3 | 0.42 × 0.28 × 0.18 mm |
Z = 2 |
Bruker–Nonius KappaCCD area-detector diffractometer | 2122 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.035 |
Graphite monochromator | θmax = 27.6°, θmin = 3.2° |
ϕ and ω scans | h = −9→9 |
13297 measured reflections | k = −20→19 |
2378 independent reflections | l = −11→11 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.049 | w = 1/[σ2(Fo2) + (0.0752P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.110 | (Δ/σ)max < 0.001 |
S = 1.15 | Δρmax = 0.69 e Å−3 |
2378 reflections | Δρmin = −0.70 e Å−3 |
297 parameters | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
1 restraint | Extinction coefficient: 0.134 (10) |
Primary atom site location: structure-invariant direct methods | Absolute structure: see text |
Secondary atom site location: difference Fourier map |
C6H10N3O2+·C4H5O6−·C6H9N3O2 | V = 998.85 (6) Å3 |
Mr = 460.41 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.3245 (2) Å | µ = 0.13 mm−1 |
b = 15.8349 (6) Å | T = 120 K |
c = 8.9264 (3) Å | 0.42 × 0.28 × 0.18 mm |
β = 105.251 (2)° |
Bruker–Nonius KappaCCD area-detector diffractometer | 2122 reflections with I > 2σ(I) |
13297 measured reflections | Rint = 0.035 |
2378 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 1 restraint |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.69 e Å−3 |
2378 reflections | Δρmin = −0.70 e Å−3 |
297 parameters | Absolute structure: see text |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
O1A | 0.8255 (3) | 0.30102 (12) | 0.8077 (2) | 0.0233 (6) | |
O2A | 0.9013 (3) | 0.28021 (12) | 0.3002 (2) | 0.0216 (5) | |
N1A | 0.8302 (3) | 0.16913 (14) | 0.4276 (2) | 0.0176 (6) | |
N2A | 0.7712 (3) | 0.04769 (15) | 0.5515 (2) | 0.0214 (7) | |
N3A | 0.7951 (3) | 0.17312 (15) | 0.6842 (2) | 0.0183 (6) | |
C2A | 0.7990 (4) | 0.13015 (17) | 0.5558 (3) | 0.0165 (7) | |
C4A | 0.8300 (3) | 0.25513 (17) | 0.6841 (3) | 0.0174 (7) | |
C5A | 0.8723 (4) | 0.29968 (17) | 0.5611 (3) | 0.0204 (7) | |
C6A | 0.8686 (4) | 0.25293 (16) | 0.4314 (3) | 0.0170 (7) | |
C7A | 0.7670 (4) | 0.25969 (19) | 0.9324 (3) | 0.0257 (8) | |
C8A | 0.9477 (4) | 0.36861 (18) | 0.2948 (3) | 0.0226 (8) | |
O1B | 0.7584 (3) | −0.41862 (12) | −0.8001 (2) | 0.0233 (6) | |
O2B | 0.6580 (3) | −0.41577 (11) | −0.2988 (2) | 0.0202 (5) | |
N1B | 0.6495 (3) | −0.29710 (14) | −0.4353 (2) | 0.0175 (6) | |
N2B | 0.6246 (3) | −0.17413 (14) | −0.5729 (3) | 0.0220 (7) | |
N3B | 0.6941 (3) | −0.29419 (15) | −0.6915 (2) | 0.0180 (6) | |
C2B | 0.6575 (3) | −0.25731 (17) | −0.5666 (3) | 0.0177 (7) | |
C4B | 0.7212 (4) | −0.37671 (18) | −0.6810 (3) | 0.0184 (7) | |
C5B | 0.7116 (4) | −0.42544 (17) | −0.5533 (3) | 0.0193 (8) | |
C6B | 0.6748 (4) | −0.38140 (16) | −0.4309 (3) | 0.0167 (7) | |
C7B | 0.7603 (4) | −0.3709 (2) | −0.9380 (3) | 0.0254 (8) | |
C8B | 0.6900 (4) | −0.50529 (17) | −0.2811 (3) | 0.0231 (8) | |
O3 | 0.7964 (3) | −0.04317 (12) | 0.2868 (2) | 0.0225 (5) | |
O4 | 0.8116 (3) | 0.07902 (12) | 0.1635 (2) | 0.0251 (6) | |
O5 | 0.7913 (3) | 0.00720 (13) | −0.1059 (2) | 0.0277 (6) | |
O6 | 0.4496 (3) | −0.05678 (13) | −0.0305 (2) | 0.0228 (6) | |
O7 | 0.5031 (3) | −0.11616 (13) | −0.3020 (2) | 0.0241 (5) | |
O8 | 0.6988 (3) | −0.21546 (13) | −0.1709 (2) | 0.0226 (6) | |
C9 | 0.7984 (3) | 0.00022 (18) | 0.1696 (3) | 0.0193 (8) | |
C10 | 0.7918 (4) | −0.04866 (17) | 0.0184 (3) | 0.0195 (7) | |
C11 | 0.6141 (4) | −0.10387 (17) | −0.0251 (3) | 0.0180 (7) | |
C12 | 0.5988 (3) | −0.14634 (17) | −0.1812 (3) | 0.0178 (7) | |
H1A | 0.82550 | 0.14040 | 0.34490 | 0.0210* | |
H5A | 0.90080 | 0.35700 | 0.56750 | 0.0240* | |
H21A | 0.75070 | 0.02220 | 0.63060 | 0.0260* | |
H22A | 0.77340 | 0.01950 | 0.46970 | 0.0260* | |
H71A | 0.65640 | 0.22620 | 0.88970 | 0.0310* | |
H72A | 0.73870 | 0.30160 | 1.00080 | 0.0310* | |
H73A | 0.86730 | 0.22400 | 0.98940 | 0.0310* | |
H81A | 0.84100 | 0.40220 | 0.30130 | 0.0270* | |
H82A | 0.97890 | 0.38050 | 0.19900 | 0.0270* | |
H83A | 1.05390 | 0.38180 | 0.38050 | 0.0270* | |
H5B | 0.72880 | −0.48370 | −0.55070 | 0.0230* | |
H21B | 0.59980 | −0.14880 | −0.49530 | 0.0260* | |
H22B | 0.62820 | −0.14600 | −0.65450 | 0.0260* | |
H71B | 0.63270 | −0.35940 | −0.99630 | 0.0300* | |
H72B | 0.82330 | −0.40300 | −1.00080 | 0.0300* | |
H73B | 0.82620 | −0.31860 | −0.90850 | 0.0300* | |
H81B | 0.60190 | −0.53450 | −0.36350 | 0.0280* | |
H82B | 0.67260 | −0.52310 | −0.18300 | 0.0280* | |
H83B | 0.81680 | −0.51800 | −0.28500 | 0.0280* | |
H5 | 0.79360 | 0.05610 | −0.07540 | 0.0330* | |
H6 | 0.42440 | −0.02700 | −0.10840 | 0.0270* | |
H8 | 0.67150 | −0.23990 | −0.25480 | 0.0270* | |
H10 | 0.90350 | −0.08510 | 0.03590 | 0.0230* | |
H11 | 0.62600 | −0.14790 | 0.05400 | 0.0220* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0349 (11) | 0.0202 (10) | 0.0160 (9) | 0.0000 (8) | 0.0086 (8) | −0.0046 (7) |
O2A | 0.0312 (10) | 0.0190 (10) | 0.0166 (8) | −0.0008 (8) | 0.0100 (8) | 0.0000 (8) |
N1A | 0.0235 (10) | 0.0169 (11) | 0.0128 (9) | 0.0016 (9) | 0.0056 (8) | −0.0029 (8) |
N2A | 0.0318 (12) | 0.0187 (12) | 0.0152 (10) | −0.0012 (10) | 0.0090 (9) | −0.0017 (9) |
N3A | 0.0208 (10) | 0.0182 (12) | 0.0157 (10) | 0.0008 (9) | 0.0044 (8) | −0.0022 (8) |
C2A | 0.0170 (12) | 0.0168 (13) | 0.0150 (11) | 0.0017 (10) | 0.0032 (10) | −0.0007 (9) |
C4A | 0.0201 (12) | 0.0160 (13) | 0.0152 (12) | 0.0032 (10) | 0.0030 (10) | −0.0032 (9) |
C5A | 0.0261 (13) | 0.0162 (13) | 0.0186 (12) | −0.0006 (11) | 0.0054 (10) | −0.0022 (10) |
C6A | 0.0184 (11) | 0.0155 (13) | 0.0173 (12) | 0.0025 (10) | 0.0049 (10) | 0.0002 (10) |
C7A | 0.0338 (15) | 0.0272 (16) | 0.0174 (12) | 0.0014 (12) | 0.0089 (11) | −0.0028 (11) |
C8A | 0.0276 (13) | 0.0202 (14) | 0.0203 (12) | −0.0029 (12) | 0.0068 (11) | 0.0008 (11) |
O1B | 0.0370 (11) | 0.0211 (11) | 0.0145 (9) | −0.0006 (9) | 0.0118 (8) | −0.0024 (7) |
O2B | 0.0330 (10) | 0.0149 (10) | 0.0153 (8) | −0.0012 (8) | 0.0107 (8) | 0.0005 (7) |
N1B | 0.0228 (10) | 0.0154 (11) | 0.0147 (9) | −0.0025 (9) | 0.0057 (8) | −0.0023 (9) |
N2B | 0.0341 (13) | 0.0158 (11) | 0.0186 (10) | 0.0036 (10) | 0.0113 (10) | 0.0018 (9) |
N3B | 0.0204 (10) | 0.0186 (12) | 0.0150 (9) | −0.0018 (9) | 0.0049 (8) | −0.0020 (8) |
C2B | 0.0158 (11) | 0.0197 (13) | 0.0164 (12) | −0.0011 (10) | 0.0020 (10) | −0.0007 (10) |
C4B | 0.0181 (12) | 0.0207 (14) | 0.0161 (12) | −0.0013 (10) | 0.0039 (10) | −0.0036 (10) |
C5B | 0.0270 (14) | 0.0150 (13) | 0.0171 (12) | −0.0002 (11) | 0.0080 (11) | −0.0019 (9) |
C6B | 0.0178 (12) | 0.0167 (14) | 0.0150 (11) | −0.0020 (10) | 0.0031 (10) | −0.0013 (10) |
C7B | 0.0342 (15) | 0.0286 (16) | 0.0148 (12) | −0.0031 (12) | 0.0090 (11) | 0.0013 (11) |
C8B | 0.0356 (15) | 0.0153 (13) | 0.0207 (12) | −0.0016 (11) | 0.0114 (12) | 0.0007 (10) |
O3 | 0.0322 (10) | 0.0197 (10) | 0.0163 (8) | −0.0020 (8) | 0.0076 (8) | −0.0020 (7) |
O4 | 0.0404 (12) | 0.0174 (11) | 0.0192 (9) | −0.0040 (9) | 0.0106 (9) | −0.0029 (7) |
O5 | 0.0469 (12) | 0.0207 (11) | 0.0182 (9) | −0.0093 (10) | 0.0135 (9) | −0.0019 (8) |
O6 | 0.0272 (10) | 0.0238 (10) | 0.0191 (9) | 0.0042 (8) | 0.0093 (8) | −0.0002 (8) |
O7 | 0.0308 (10) | 0.0244 (10) | 0.0156 (8) | 0.0048 (9) | 0.0033 (7) | −0.0015 (8) |
O8 | 0.0357 (11) | 0.0171 (10) | 0.0145 (8) | 0.0049 (8) | 0.0057 (8) | −0.0017 (7) |
C9 | 0.0210 (13) | 0.0202 (15) | 0.0168 (12) | −0.0023 (11) | 0.0053 (10) | −0.0032 (10) |
C10 | 0.0282 (13) | 0.0171 (13) | 0.0156 (11) | −0.0003 (10) | 0.0099 (11) | −0.0022 (10) |
C11 | 0.0249 (12) | 0.0162 (13) | 0.0143 (11) | 0.0026 (10) | 0.0078 (10) | −0.0008 (10) |
C12 | 0.0206 (12) | 0.0158 (13) | 0.0179 (12) | −0.0031 (10) | 0.0065 (10) | −0.0026 (10) |
O1A—C4A | 1.329 (3) | N3B—C4B | 1.321 (4) |
O1A—C7A | 1.450 (3) | N3B—C2B | 1.347 (3) |
O2A—C6A | 1.328 (3) | N2B—H22B | 0.8601 |
O2A—C8A | 1.444 (3) | N2B—H21B | 0.8602 |
O1B—C7B | 1.448 (3) | C4A—C5A | 1.406 (4) |
O1B—C4B | 1.341 (3) | C5A—C6A | 1.368 (4) |
O2B—C6B | 1.333 (3) | C5A—H5A | 0.9297 |
O2B—C8B | 1.439 (3) | C7A—H73A | 0.9599 |
O3—C9 | 1.255 (3) | C7A—H71A | 0.9593 |
O4—C9 | 1.254 (3) | C7A—H72A | 0.9606 |
O5—C10 | 1.418 (3) | C8A—H81A | 0.9596 |
O6—C11 | 1.407 (4) | C8A—H82A | 0.9601 |
O7—C12 | 1.219 (3) | C8A—H83A | 0.9596 |
O8—C12 | 1.307 (3) | C4B—C5B | 1.394 (4) |
O5—H5 | 0.8195 | C5B—C6B | 1.381 (4) |
O6—H6 | 0.8200 | C5B—H5B | 0.9306 |
O8—H8 | 0.8197 | C7B—H73B | 0.9599 |
N1A—C6A | 1.355 (3) | C7B—H71B | 0.9600 |
N1A—C2A | 1.371 (3) | C7B—H72B | 0.9600 |
N2A—C2A | 1.321 (4) | C8B—H83B | 0.9598 |
N3A—C2A | 1.340 (3) | C8B—H82B | 0.9598 |
N3A—C4A | 1.324 (4) | C8B—H81B | 0.9600 |
N1A—H1A | 0.8601 | C9—C10 | 1.546 (4) |
N2A—H22A | 0.8596 | C10—C11 | 1.531 (4) |
N2A—H21A | 0.8601 | C11—C12 | 1.525 (4) |
N1B—C2B | 1.345 (3) | C10—H10 | 0.9795 |
N1B—C6B | 1.347 (3) | C11—H11 | 0.9797 |
N2B—C2B | 1.338 (3) | ||
C4A—O1A—C7A | 117.9 (2) | N1B—C2B—N2B | 116.7 (2) |
C6A—O2A—C8A | 116.3 (2) | N1B—C2B—N3B | 125.6 (2) |
C4B—O1B—C7B | 117.7 (2) | N2B—C2B—N3B | 117.7 (2) |
C6B—O2B—C8B | 116.7 (2) | O1B—C4B—N3B | 119.4 (2) |
C10—O5—H5 | 109.50 | N3B—C4B—C5B | 124.5 (2) |
C11—O6—H6 | 109.48 | O1B—C4B—C5B | 116.0 (2) |
C12—O8—H8 | 109.49 | C4B—C5B—C6B | 115.5 (2) |
C2A—N1A—C6A | 119.9 (2) | O2B—C6B—N1B | 112.7 (2) |
C2A—N3A—C4A | 116.8 (2) | O2B—C6B—C5B | 125.2 (2) |
C6A—N1A—H1A | 120.04 | N1B—C6B—C5B | 122.1 (2) |
C2A—N1A—H1A | 120.02 | C4B—C5B—H5B | 122.26 |
H21A—N2A—H22A | 120.00 | C6B—C5B—H5B | 122.29 |
C2A—N2A—H21A | 119.94 | O1B—C7B—H71B | 109.53 |
C2A—N2A—H22A | 120.07 | O1B—C7B—H72B | 109.50 |
C2B—N1B—C6B | 116.9 (2) | H72B—C7B—H73B | 109.44 |
C2B—N3B—C4B | 115.4 (2) | O1B—C7B—H73B | 109.50 |
H21B—N2B—H22B | 120.03 | H71B—C7B—H72B | 109.44 |
C2B—N2B—H21B | 119.95 | H71B—C7B—H73B | 109.43 |
C2B—N2B—H22B | 120.02 | O2B—C8B—H81B | 109.47 |
N1A—C2A—N3A | 122.1 (2) | O2B—C8B—H82B | 109.44 |
N1A—C2A—N2A | 118.6 (2) | O2B—C8B—H83B | 109.50 |
N2A—C2A—N3A | 119.3 (2) | H82B—C8B—H83B | 109.48 |
N3A—C4A—C5A | 125.1 (2) | H81B—C8B—H82B | 109.49 |
O1A—C4A—C5A | 115.6 (2) | H81B—C8B—H83B | 109.45 |
O1A—C4A—N3A | 119.3 (2) | O3—C9—C10 | 116.7 (2) |
C4A—C5A—C6A | 115.4 (2) | O3—C9—O4 | 126.8 (2) |
N1A—C6A—C5A | 120.6 (2) | O4—C9—C10 | 116.5 (2) |
O2A—C6A—C5A | 127.0 (2) | O5—C10—C9 | 111.3 (2) |
O2A—C6A—N1A | 112.4 (2) | O5—C10—C11 | 109.3 (2) |
C6A—C5A—H5A | 122.29 | C9—C10—C11 | 109.7 (2) |
C4A—C5A—H5A | 122.26 | C10—C11—C12 | 109.7 (2) |
O1A—C7A—H72A | 109.45 | O6—C11—C10 | 111.7 (2) |
O1A—C7A—H71A | 109.49 | O6—C11—C12 | 110.2 (2) |
O1A—C7A—H73A | 109.46 | O7—C12—O8 | 124.9 (2) |
H71A—C7A—H72A | 109.49 | O7—C12—C11 | 121.5 (2) |
H71A—C7A—H73A | 109.49 | O8—C12—C11 | 113.6 (2) |
H72A—C7A—H73A | 109.44 | O5—C10—H10 | 108.80 |
H82A—C8A—H83A | 109.54 | C9—C10—H10 | 108.83 |
H81A—C8A—H82A | 109.49 | C11—C10—H10 | 108.83 |
O2A—C8A—H83A | 109.44 | O6—C11—H11 | 108.35 |
O2A—C8A—H82A | 109.45 | C10—C11—H11 | 108.37 |
O2A—C8A—H81A | 109.43 | C12—C11—H11 | 108.42 |
H81A—C8A—H83A | 109.48 | ||
C7A—O1A—C4A—N3A | −4.9 (3) | C4B—N3B—C2B—N2B | −178.5 (2) |
C7A—O1A—C4A—C5A | 174.9 (2) | C2B—N3B—C4B—O1B | 180.0 (2) |
C8A—O2A—C6A—N1A | −178.7 (2) | O1A—C4A—C5A—C6A | −177.2 (2) |
C8A—O2A—C6A—C5A | 0.7 (4) | N3A—C4A—C5A—C6A | 2.6 (4) |
C7B—O1B—C4B—N3B | −2.2 (4) | C4A—C5A—C6A—N1A | −1.4 (4) |
C7B—O1B—C4B—C5B | 177.0 (3) | C4A—C5A—C6A—O2A | 179.3 (3) |
C8B—O2B—C6B—N1B | −177.7 (2) | O1B—C4B—C5B—C6B | 179.5 (3) |
C8B—O2B—C6B—C5B | 3.1 (4) | N3B—C4B—C5B—C6B | −1.4 (4) |
C2A—N1A—C6A—O2A | 177.9 (2) | C4B—C5B—C6B—O2B | 179.3 (3) |
C2A—N1A—C6A—C5A | −1.5 (4) | C4B—C5B—C6B—N1B | 0.2 (4) |
C6A—N1A—C2A—N3A | 3.6 (4) | O3—C9—C10—O5 | 178.9 (2) |
C6A—N1A—C2A—N2A | −176.7 (3) | O3—C9—C10—C11 | 57.8 (3) |
C2A—N3A—C4A—C5A | −0.7 (4) | O4—C9—C10—O5 | −3.4 (3) |
C4A—N3A—C2A—N2A | 177.8 (2) | O4—C9—C10—C11 | −124.5 (2) |
C2A—N3A—C4A—O1A | 179.1 (2) | O5—C10—C11—C12 | 52.9 (3) |
C4A—N3A—C2A—N1A | −2.5 (4) | C9—C10—C11—O6 | 52.7 (3) |
C2B—N1B—C6B—O2B | −177.8 (2) | C9—C10—C11—C12 | 175.2 (2) |
C6B—N1B—C2B—N3B | −2.1 (4) | O5—C10—C11—O6 | −69.6 (3) |
C2B—N1B—C6B—C5B | 1.4 (4) | O6—C11—C12—O7 | 27.9 (3) |
C6B—N1B—C2B—N2B | 177.3 (2) | C10—C11—C12—O7 | −95.5 (3) |
C2B—N3B—C4B—C5B | 0.9 (4) | C10—C11—C12—O8 | 83.5 (3) |
C4B—N3B—C2B—N1B | 1.0 (4) | O6—C11—C12—O8 | −153.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O4 | 0.86 | 1.87 | 2.728 (3) | 179 |
O5—H5···O4 | 0.82 | 2.13 | 2.629 (3) | 119 |
O6—H6···O7 | 0.82 | 2.42 | 2.722 (3) | 103 |
O6—H6···O1Bi | 0.82 | 2.20 | 2.860 (3) | 138 |
O8—H8···N1B | 0.82 | 1.82 | 2.631 (3) | 171 |
N2A—H21A···O5ii | 0.86 | 2.30 | 3.090 (3) | 152 |
N2B—H21B···O7 | 0.86 | 2.09 | 2.935 (3) | 165 |
N2A—H22A···O3 | 0.86 | 1.96 | 2.814 (3) | 176 |
N2B—H22B···O3iii | 0.86 | 2.19 | 2.878 (3) | 137 |
C8A—H81A···O7iv | 0.96 | 2.54 | 3.328 (4) | 140 |
C8B—H82B···O6v | 0.96 | 2.37 | 3.308 (3) | 166 |
Symmetry codes: (i) −x+1, y+1/2, −z−1; (ii) x, y, z+1; (iii) x, y, z−1; (iv) −x+1, y+1/2, −z; (v) −x+1, y−1/2, −z. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C6H10N3O2+·C7H5O3−·H2O | C6H10N3O2+·C7H4NO4−·H2O | C6H10N3O2+·C4H5O6−·C6H9N3O2 |
Mr | 311.30 | 340.30 | 460.41 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 6.9710 (2), 10.9014 (3), 18.3749 (6) | 6.8247 (6), 7.9273 (5), 14.4038 (10) | 7.3245 (2), 15.8349 (6), 8.9264 (3) |
α, β, γ (°) | 90, 93.631 (2), 90 | 82.558 (5), 88.133 (4), 75.075 (5) | 90, 105.251 (2), 90 |
V (Å3) | 1393.57 (7) | 746.63 (10) | 998.85 (6) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.12 | 0.13 | 0.13 |
Crystal size (mm) | 0.48 × 0.30 × 0.14 | 0.40 × 0.25 × 0.10 | 0.42 × 0.28 × 0.18 |
Data collection | |||
Diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer | Bruker–Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12896, 3172, 2415 | 14555, 3384, 2397 | 13297, 2378, 2122 |
Rint | 0.036 | 0.062 | 0.035 |
(sin θ/λ)max (Å−1) | 0.651 | 0.651 | 0.651 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.140, 1.09 | 0.064, 0.175, 1.07 | 0.049, 0.110, 1.15 |
No. of reflections | 3172 | 3384 | 2378 |
No. of parameters | 203 | 221 | 297 |
No. of restraints | 3 | 3 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.65 | 0.53, −0.62 | 0.69, −0.70 |
Absolute structure | ? | ? | See text |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.
O3—C15 | 1.253 (2) | N1—C6 | 1.355 (2) |
O4—C15 | 1.282 (2) | N2—C2 | 1.324 (2) |
O5—C12 | 1.3592 (18) | N3—C4 | 1.330 (2) |
N1—C2 | 1.353 (2) | N3—C2 | 1.340 (2) |
C2—N1—C6 | 120.01 (14) | C2—N3—C4 | 116.22 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4 | 0.86 | 1.75 | 2.6029 (17) | 172 |
O1W—H1W···O4i | 0.94 | 2.00 | 2.9084 (16) | 162 |
N2—H2A···N3ii | 0.86 | 2.26 | 3.1128 (19) | 171 |
N2—H2B···O3 | 0.86 | 2.06 | 2.8832 (17) | 161 |
O1W—H2W···O3 | 0.93 | 1.84 | 2.7284 (16) | 160 |
O5—H5A···O1Wiii | 0.82 | 1.87 | 2.6894 (16) | 176 |
C11—H11···O1Wiii | 0.93 | 2.57 | 3.241 (2) | 130 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
O3—C14 | 1.244 (2) | N2—C2 | 1.321 (2) |
O4—C14 | 1.266 (2) | N3—C2 | 1.335 (2) |
O5—C15 | 1.207 (2) | N3—C4 | 1.326 (2) |
O6—C15 | 1.324 (3) | N4—C13 | 1.339 (2) |
N1—C6 | 1.349 (2) | N4—C9 | 1.341 (2) |
N1—C2 | 1.359 (2) | ||
C2—N1—C6 | 119.25 (15) | C9—N4—C13 | 117.15 (17) |
C2—N3—C4 | 115.98 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4 | 0.86 | 1.71 | 2.569 (2) | 174 |
N2—H2A···O3i | 0.86 | 1.97 | 2.793 (2) | 159 |
N2—H2B···O3 | 0.86 | 1.98 | 2.837 (2) | 173 |
O1W—H1W···O2 | 0.96 | 2.44 | 3.275 (2) | 146 |
O1W—H1W···O4 | 0.96 | 2.17 | 2.836 (2) | 125 |
O1W—H2W···O6 | 0.91 | 2.34 | 2.946 (2) | 124 |
O1W—H2W···N4 | 0.91 | 2.16 | 3.035 (2) | 162 |
O6—H6···O1Wii | 0.82 | 1.77 | 2.577 (2) | 165 |
C7—H7B···O5iii | 0.96 | 2.60 | 3.507 (3) | 158 |
C8—H8B···O5ii | 0.96 | 2.41 | 3.365 (2) | 175 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1; (iii) x+1, y−1, z+1. |
O3—C9 | 1.255 (3) | N2A—C2A | 1.321 (4) |
O4—C9 | 1.254 (3) | N3A—C2A | 1.340 (3) |
O5—C10 | 1.418 (3) | N3A—C4A | 1.324 (4) |
O6—C11 | 1.407 (4) | N1B—C2B | 1.345 (3) |
O7—C12 | 1.219 (3) | N1B—C6B | 1.347 (3) |
O8—C12 | 1.307 (3) | N2B—C2B | 1.338 (3) |
N1A—C6A | 1.355 (3) | N3B—C4B | 1.321 (4) |
N1A—C2A | 1.371 (3) | N3B—C2B | 1.347 (3) |
C2A—N1A—C6A | 119.9 (2) | C2B—N1B—C6B | 116.9 (2) |
C2A—N3A—C4A | 116.8 (2) | C2B—N3B—C4B | 115.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O4 | 0.8600 | 1.8700 | 2.728 (3) | 179.00 |
O5—H5···O4 | 0.8200 | 2.1300 | 2.629 (3) | 119.00 |
O6—H6···O7 | 0.8200 | 2.4200 | 2.722 (3) | 103.00 |
O6—H6···O1Bi | 0.8200 | 2.2000 | 2.860 (3) | 138.00 |
O8—H8···N1B | 0.8200 | 1.8200 | 2.631 (3) | 171.00 |
N2A—H21A···O5ii | 0.8600 | 2.3000 | 3.090 (3) | 152.00 |
N2B—H21B···O7 | 0.8600 | 2.0900 | 2.935 (3) | 165.00 |
N2A—H22A···O3 | 0.8600 | 1.9600 | 2.814 (3) | 176.00 |
N2B—H22B···O3iii | 0.8600 | 2.1900 | 2.878 (3) | 137.00 |
C8A—H81A···O7iv | 0.9600 | 2.5400 | 3.328 (4) | 140.00 |
C8B—H82B···O6v | 0.9600 | 2.3700 | 3.308 (3) | 166.00 |
Symmetry codes: (i) −x+1, y+1/2, −z−1; (ii) x, y, z+1; (iii) x, y, z−1; (iv) −x+1, y+1/2, −z; (v) −x+1, y−1/2, −z. |
Pyrimidine and aminopyrimidine derivatives are biologically very important compounds as they occur in nature as components of nucleic acids. Some aminopyrimidine derivatives are used as antifolate drugs (Hunt et al., 1980; Baker & Santi, 1965). Hydrogen bonding plays a key role in molecular recognition and crystal engineering research (Desiraju, 1989). 2-Aminopyrimidine forms 1:1 adducts with different mono- and dicarboxylic acids (Etter & Adsmond, 1990) rather than individual self-assembly compounds (Scheinbeim & Schempp, 1976). The adducts of carboxylic acids with 2-aminoheterocylic ring systems form a graph-set motif of R22(8) (Lynch & Jones, 2004). This motif is very robust in aminopyrimidine carboxylic acid/carboxylate systems. The crystal structures of aminopyrimidine derivatives (Schwalbe & Williams, 1982), aminopyrimidine carboxylates (Muthiah, Francis et al., 2006) and cocrystals (Chinnakali et al., 1999) have been reported. The crystal structure of 2-amino-4,6-dimethoxy pyrimidine [abbreviated as (MeO)2-ampy] has also been reported (Low et al., 2002). The crystal structures of (MeO)2-ampy–4-aminobenzoic acid (1/1) (Thanigaimani et al., 2006), Me2-Hampy bromide Me2-ampy monohydrate [Me2-Hampy = 2-amino-4,6-dimethylpyrimidinium; Panneerselvam et al., 2004], Me2-Hampy hydrogen sulfate (Hemamalini et al., 2005), Me2-ampy–cinnamic acid (1/2) (Balasubramani et al., 2005), Me2-Hampy picrate (Subashini et al., 2006) and Me2-Hampy salicylate (Muthiah, Balasubramani et al., 2006) have been recently reported from our laboratorAy. We are interested in the network of hydrogen-bonding patterns in the carboxylate–aminopyrimidine interactions under a variety of molecular environments. In the present study, 4-hydroxybenzoic acid, dipicolinic acid (pyridine-2,6-dicarboxylic acid) and tartaric acid are selected to form adducts with (MeO)2-ampy. The crystal structures of 4-hydroxybenzoic acid monohydrate (Colapietro et al., 1979; Fukuyama et al., 1973), Me2-ampy–4-hydroxybenzoic acid (1/1) (Balasubramani et al., 2006), dipicolinic acid (Carranza Téllez et al., 2002) and (+)-tartaric acid (Stern & Beevers, 1950) are also known.
ORTEP (Johnson, 1976) views of the title compounds, (I)–(III), are shown in Figs. 1–3. In (I), the asymmetric unit contains an (MeO)2-Hampy+ cation, a 4-hydroxybenzoate anion and a water molecule. In (II), the asymmetric unit contains an (MeO)2-Hampy+ cation, a hydrogen dipicolinate anion and a water molecule. In (III), one (MeO)2-Hampy+ cation, a hydrogen L-tartrate anion and a neutral (MeO)2-ampy molecule constitute the asymmetric unit. In all the compounds, the pyrimidine rings are protonated at the atom N1. Protonation of the pyrimidine base on the N1 site is reflected by the increase in bond angle at N1 [C2—N1—C6 = 120.01 (14)° in (I), 119.25 (15)° in (II) and 119.9 (2)° in cation A of (III)] when compared with that of the unprotonated atom N3 [C2—N3—C4 = 116.22 (14)° in (I), 115.98 (16)° in (II) and 116.8 (2)° in (III)]. In all the crystal structures (I)–(III), the carboxylate group of the respective anions (4-hydroxybenzoate, hydrogen dipicolinate and hydrogen L-tartrate) interacts with the aminopyrimidinium cation through a pair of N—H···O hydrogen bonds to form an eight-membered R22(8) ring motif (Etter, 1990; Bernstein et al., 1995).
In (I), the (MeO)2-Hampy+ cations are centrosymmetrically paired through a pair of N2—H2A···N3(-x + 1, -y + 1, -z + 1) hydrogen bonds (Table 2) to form an R22(8) ring motif (Fig. 4). Two inversion-related 4-hydroxybenzoate anions are connected by water molecules via O—H···O and C—H···O1W hydrogen bonds, forming an R44(16) ring motif. A similar type of C—H···Owater hydrogen bonds have been investigated on the basis of the structural data determined by neutron diffraction (Steiner & Saenger, 1993). The carboxylate groups are bridged by the intervening water molecules via O—H···O hydrogen bonds, resulting in a supramolecular chain along the b axis. The water molecules act as hydrogen-bond donors to the carboxylate group of the 4-hydroxybenzoate and also act as hydrogen-bond acceptors to the hydroxy group of the 4-hydroxybenzoate ion to form an O—H···O hydrogen-bonded sheet parallel to the (011) plane.
In (II), inversion-related R22(8) motifs (amino pyrimidine–carboxylate motifs) are further bridged by N—H···O hydrogen bonds (Table 4) on either side forming the DDAA array of quadruple hydrogen bonds (Fig. 5). This array is extended further on either side by Owater—H···Omethoxy hydrogen bonds, resulting in an array of six hydrogen bonds (ADDAAD). The water molecule plays a pivotal role, and five hydrogen-bonded fused rings are formed around the water molecule. Two inversion-related water molecules are bridged by two inversion-related carboxyl OH groups, generating an R44(8) ring motif. Each H atom of the water molecule acts as a bifurcated donor and the O atom acts as a single acceptor. The water molecule–dipicolinate interaction via O—H···O and O—H···N hydrogen bonds leads to two hydrogen-bonded rings R12(5) and R22(7). Furthermore, these arrays are connected via a pair of C—H···O hydrogen bonds involving one of the O atoms of the carboxylate group and the methoxy group (C7 and C8) of the pyrimidinium cation, resulting in the formation of a 20-membered ring R42(20).
In (III), the carboxyl group of the tartrate anion interacts with atom N1B and the 2-amino group of the neutral (MeO)2-ampy molecule (B) through N—H···O and O—H···N hydrogen bonds (Table 6) to form an eight-membered ring [R22(8)] (Fig. 6). The 2-amino group of the (MeO)2-Hampy+ cation (A) interacts with hydroxy group O5 through an N—H···O hydrogen bond, and the 2-amino group of molecule B interacts with one of the carboxylate anions, O3, through an N—H···O hydrogen bond, forming a cyclic R43(12) hydrogen-bonded motif. These types of interactions are extended along the c axis to form a hydrogen-bonded supramolecular ribbon. In addition, both the carboxylate groups interact with adjacent hydroxy groups via intramolecular O—H···O hydrogen bonds, leading to a five-membered ring [S(5)]. Furthermore, these arrays are connected via C—H···O hydrogen bonds, resulting in a two-dimensional network.
In all the crystal structures (I)–(III), π–π stacking interactions between aromatic rings are observed. In (I), the pyrimidine ring of the (MeO)2-Hampy+ cation stacks with the benzene ring of the 4-hydroxybenzoate anion, with interplanar and centroid-to-centroid distances of 3.317 and 3.554 Å, respectively, and a slip angle (angle between the centroid vector and the normal to the plane) of 18.9°. In (II), a π–π interaction is observed between two (MeO)2-Hampy+ cations related by an inversion centre. The centroid-to-centroid distance and interplanar distance are 3.310 and 3.253 Å, respectively, the slip angle being 10.7°. In (III), the pyrimidine rings of the (MeO)2-Hampy+ cation A form stacking interactions with the (MeO)2-ampy molecule B; the centroid-to-centroid distance and interplanar distances are 3.625 and 3.335 Å, respectively, the slip angle being 21.2°. These are typical aromatic stacking values (Hunter, 1994).