Hydantoin-5-acetic acid [2-(2,5-dioxoimidazolidin-4-yl)acetic acid] and orotic acid (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid) each contain one rigid acceptor-donor-acceptor hydrogen-bonding site and a flexible side chain, which can adopt different conformations. Since both compounds may be used as coformers for supramolecular complexes, they have been crystallized in order to examine their conformational preferences, giving solvent-free hydantoin-5-acetic acid, C5H6N2O4, (I), and three crystals containing orotic acid, namely, orotic acid dimethyl sulfoxide monosolvate, C5H4N2O4·C2H6OS, (IIa), dimethylammonium orotate-orotic acid (1/1), C2H8N+·C5H3N2O4-·C5H4N2O4, (IIb), and dimethylammonium orotate-orotic acid (3/1), 3C2H8N+·3C5H3N2O4-·C5H4N2O4, (IIc). The crystal structure of (I) shows a three-dimensional network, with the acid function located perpendicular to the ring. Interestingly, the hydroxy O atom acts as an acceptor, even though the carbonyl O atom is not involved in any hydrogen bonds. However, in (IIa), (IIb) and (IIc), the acid functions are only slightly twisted out of the ring planes. All H atoms of the acidic functions are directed away from the rings and, with respect to the carbonyl O atoms, they show an antiperiplanar conformation in (I) and synperiplanar conformations in (IIa), (IIb) and (IIc). Furthermore, in (IIa), (IIb) and (IIc), different conformations of the acid O=C-C-N torsion angle are observed, leading to different hydrogen-bonding arrangements depending on their conformation and composition.
Supporting information
CCDC references: 867030; 867031; 867032; 867033
Solvent evaporation experiments with a racemic mixture of commercially
available hydantoin-5-acetic acid (5.2 mg, 0.033 mmol) in H2O (250 µl) at
room temperature yielded one crystal, (I). Three single crystals of (II) were
obtained during crystallization attempts with commercially available orotic
acid [(IIa): 2.1 mg, 0.014 mmol in DMSO (50 µl) at room temperature;
(IIb): 1.7 mg, 0.011 mmol in DMF (150 µl) at room temperature;
(IIc): 4.5 mg, 0.029 mmol in DMF (450 µl) at 277 K].
The H atoms of (I), (IIa) and (IIb) were initially located in
difference Fourier syntheses, while in (IIc) the H atom of the
carboxylic acid group between molecules B and D, and two of the
six DMC H atoms, could not be observed. Since both molecules B and
D show bond lengths indicative of single and double bonds, the H atom
of the carboxylic acid group was placed in the middle of the two O atoms, with
Uiso(H) = 1.5Ueq(O43B).
H atoms bonded to C atoms in all structures were refined using a riding model,
with methyl C—H = 0.98, secondary C—H = 0.99 and aromatic C—H = 0.95 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H or
1.2Ueq(C) for secondary and aromatic H. In (I), (IIa) and
(IIb), H atoms bonded to N and O atoms were refined isotropically,
while in (IIc) they were refined using a riding model, with amide N—H
= 0.88 Å and protonated N—H = 0.92 Å, and with Uiso(H) =
1.2Ueq(N).
Due to the weak anomalous signals in the racemic mixture of (I) and in
(IIc), 452 Friedel pairs for (I) and 2966 Friedel pairs for
(IIc) were merged before refinement. The absolute structures of (I) and
(IIc) were not determined.
The displacement ellipsoids of (IIc) (Fig. 8) are significantly
enlarged, although the data for this compound were definitely collected at 173 K. The only explanation we have for this is that the molecules in the crystals
are not perfectly ordered but adopt slightly different positions in different
unit cells.
Data collection: X-AREA (Stoe & Cie, 2001) for (I), (IIa), (IIc); SMART (Siemens, 1994) for (IIb). Cell refinement: X-AREA (Stoe & Cie, 2001) for (I), (IIa), (IIc); SAINT (Siemens, 1994) for (IIb). Data reduction: X-AREA (Stoe & Cie, 2001) for (I), (IIa), (IIc); SAINT (Siemens, 1994) for (IIb). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
(I) 2-(2,5-dioxoimidazolidin-4-yl)acetic acid
top
Crystal data top
C5H6N2O4 | F(000) = 328 |
Mr = 158.12 | Dx = 1.725 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7026 reflections |
a = 7.6148 (5) Å | θ = 3.2–26.0° |
b = 8.5592 (6) Å | µ = 0.15 mm−1 |
c = 9.3406 (6) Å | T = 173 K |
V = 608.79 (7) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.10 × 0.10 mm |
Data collection top
Stoe IPDS II two-circle diffractometer | 607 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.107 |
Graphite monochromator | θmax = 25.7°, θmin = 3.2° |
ω scans | h = −9→9 |
10371 measured reflections | k = −10→10 |
692 independent reflections | l = −11→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0331P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
692 reflections | Δρmax = 0.14 e Å−3 |
113 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.074 (8) |
Crystal data top
C5H6N2O4 | V = 608.79 (7) Å3 |
Mr = 158.12 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.6148 (5) Å | µ = 0.15 mm−1 |
b = 8.5592 (6) Å | T = 173 K |
c = 9.3406 (6) Å | 0.50 × 0.10 × 0.10 mm |
Data collection top
Stoe IPDS II two-circle diffractometer | 607 reflections with I > 2σ(I) |
10371 measured reflections | Rint = 0.107 |
692 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.14 e Å−3 |
692 reflections | Δρmin = −0.15 e Å−3 |
113 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 | |
N1 | 0.7709 (2) | 0.3562 (2) | 0.39865 (18) | 0.0166 (4) | |
H1 | 0.754 (3) | 0.262 (3) | 0.371 (3) | 0.028 (7)* | |
C2 | 0.9253 (3) | 0.4268 (2) | 0.3742 (2) | 0.0169 (5) | |
O21 | 1.05432 (19) | 0.37022 (17) | 0.31350 (16) | 0.0237 (4) | |
N3 | 0.9153 (2) | 0.57583 (19) | 0.43026 (18) | 0.0169 (4) | |
H3 | 1.005 (3) | 0.646 (3) | 0.425 (3) | 0.027 (7)* | |
C4 | 0.7561 (3) | 0.6037 (2) | 0.4920 (2) | 0.0159 (4) | |
O41 | 0.71109 (19) | 0.72508 (17) | 0.54961 (16) | 0.0219 (4) | |
C5 | 0.6520 (3) | 0.4518 (2) | 0.4832 (2) | 0.0148 (4) | |
H5 | 0.6433 | 0.4060 | 0.5814 | 0.018* | |
C51 | 0.4675 (3) | 0.4669 (2) | 0.4217 (2) | 0.0153 (5) | |
H51A | 0.4159 | 0.3613 | 0.4122 | 0.018* | |
H51B | 0.3940 | 0.5264 | 0.4901 | 0.018* | |
C52 | 0.4614 (3) | 0.5467 (2) | 0.2786 (2) | 0.0148 (4) | |
O53 | 0.58083 (19) | 0.62326 (17) | 0.22980 (16) | 0.0230 (4) | |
O54 | 0.31095 (19) | 0.53338 (18) | 0.20578 (15) | 0.0195 (4) | |
H54 | 0.224 (4) | 0.466 (4) | 0.261 (4) | 0.066 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0142 (9) | 0.0115 (9) | 0.0240 (9) | −0.0006 (7) | −0.0015 (7) | −0.0023 (8) |
C2 | 0.0158 (11) | 0.0159 (10) | 0.0191 (10) | 0.0013 (9) | −0.0040 (9) | 0.0003 (8) |
O21 | 0.0129 (7) | 0.0236 (8) | 0.0345 (8) | 0.0015 (7) | 0.0029 (7) | −0.0079 (7) |
N3 | 0.0129 (8) | 0.0144 (9) | 0.0233 (9) | −0.0007 (7) | −0.0012 (7) | −0.0015 (7) |
C4 | 0.0143 (10) | 0.0155 (10) | 0.0180 (9) | 0.0009 (8) | −0.0032 (8) | 0.0011 (8) |
O41 | 0.0172 (7) | 0.0188 (7) | 0.0297 (8) | 0.0020 (6) | −0.0006 (7) | −0.0071 (7) |
C5 | 0.0141 (10) | 0.0144 (10) | 0.0159 (10) | 0.0003 (8) | −0.0005 (8) | 0.0020 (9) |
C51 | 0.0128 (9) | 0.0167 (10) | 0.0164 (10) | −0.0013 (8) | −0.0001 (8) | 0.0022 (9) |
C52 | 0.0135 (9) | 0.0145 (10) | 0.0165 (10) | 0.0025 (8) | 0.0013 (8) | −0.0011 (9) |
O53 | 0.0192 (8) | 0.0266 (8) | 0.0233 (8) | −0.0028 (7) | 0.0018 (6) | 0.0070 (7) |
O54 | 0.0174 (7) | 0.0223 (8) | 0.0187 (7) | 0.0001 (6) | −0.0048 (6) | 0.0011 (7) |
Geometric parameters (Å, º) top
N1—C2 | 1.341 (3) | C5—C51 | 1.523 (3) |
N1—C5 | 1.454 (3) | C5—H5 | 1.0000 |
N1—H1 | 0.86 (3) | C51—C52 | 1.502 (3) |
C2—O21 | 1.233 (3) | C51—H51A | 0.9900 |
C2—N3 | 1.381 (3) | C51—H51B | 0.9900 |
N3—C4 | 1.363 (3) | C52—O53 | 1.210 (2) |
N3—H3 | 0.91 (3) | C52—O54 | 1.337 (3) |
C4—O41 | 1.219 (3) | O54—H54 | 1.02 (4) |
C4—C5 | 1.525 (3) | | |
| | | |
C2—N1—C5 | 112.65 (17) | C51—C5—C4 | 115.33 (17) |
C2—N1—H1 | 120.3 (16) | N1—C5—H5 | 108.6 |
C5—N1—H1 | 126.9 (16) | C51—C5—H5 | 108.6 |
O21—C2—N1 | 126.87 (19) | C4—C5—H5 | 108.6 |
O21—C2—N3 | 125.50 (19) | C52—C51—C5 | 113.74 (17) |
N1—C2—N3 | 107.63 (18) | C52—C51—H51A | 108.8 |
C4—N3—C2 | 111.78 (17) | C5—C51—H51A | 108.8 |
C4—N3—H3 | 125.1 (16) | C52—C51—H51B | 108.8 |
C2—N3—H3 | 123.1 (16) | C5—C51—H51B | 108.8 |
O41—C4—N3 | 125.84 (18) | H51A—C51—H51B | 107.7 |
O41—C4—C5 | 127.18 (19) | O53—C52—O54 | 119.92 (18) |
N3—C4—C5 | 106.88 (16) | O53—C52—C51 | 123.91 (19) |
N1—C5—C51 | 114.69 (16) | O54—C52—C51 | 116.14 (18) |
N1—C5—C4 | 100.69 (16) | C52—O54—H54 | 110 (2) |
| | | |
C5—N1—C2—O21 | 175.3 (2) | O41—C4—C5—N1 | 178.0 (2) |
C5—N1—C2—N3 | −4.4 (2) | N3—C4—C5—N1 | −5.6 (2) |
O21—C2—N3—C4 | −179.3 (2) | O41—C4—C5—C51 | 53.9 (3) |
N1—C2—N3—C4 | 0.3 (2) | N3—C4—C5—C51 | −129.59 (17) |
C2—N3—C4—O41 | −180.0 (2) | N1—C5—C51—C52 | −63.1 (2) |
C2—N3—C4—C5 | 3.5 (2) | C4—C5—C51—C52 | 53.2 (2) |
C2—N1—C5—C51 | 130.58 (18) | C5—C51—C52—O53 | −16.0 (3) |
C2—N1—C5—C4 | 6.1 (2) | C5—C51—C52—O54 | 166.01 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O54i | 0.86 (3) | 2.14 (3) | 2.996 (2) | 175 (2) |
N3—H3···O41ii | 0.91 (3) | 1.93 (3) | 2.831 (2) | 168 (2) |
O54—H54···O21iii | 1.02 (4) | 1.61 (4) | 2.604 (2) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1, y, z. |
(IIa) 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid
dimethyl sulfoxide monosolvate
top
Crystal data top
C5H4N2O4·C2H6OS | F(000) = 488 |
Mr = 234.23 | Dx = 1.570 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9844 reflections |
a = 9.3710 (6) Å | θ = 3.4–26.0° |
b = 5.9752 (3) Å | µ = 0.33 mm−1 |
c = 17.8433 (13) Å | T = 173 K |
β = 97.447 (6)° | Block, colourless |
V = 990.68 (11) Å3 | 0.35 × 0.25 × 0.20 mm |
Z = 4 | |
Data collection top
Stoe IPDS II two-circle diffractometer | 1865 independent reflections |
Radiation source: fine-focus sealed tube | 1383 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω scans | θmax = 25.6°, θmin = 3.4° |
Absorption correction: multi-scan (MULABS; Blessing, 1995; Spek, 2009) | h = −11→11 |
Tmin = 0.893, Tmax = 0.937 | k = −7→7 |
18676 measured reflections | l = −21→21 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0406P)2] where P = (Fo2 + 2Fc2)/3 |
1865 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C5H4N2O4·C2H6OS | V = 990.68 (11) Å3 |
Mr = 234.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3710 (6) Å | µ = 0.33 mm−1 |
b = 5.9752 (3) Å | T = 173 K |
c = 17.8433 (13) Å | 0.35 × 0.25 × 0.20 mm |
β = 97.447 (6)° | |
Data collection top
Stoe IPDS II two-circle diffractometer | 1865 independent reflections |
Absorption correction: multi-scan (MULABS; Blessing, 1995; Spek, 2009) | 1383 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.937 | Rint = 0.076 |
18676 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.17 e Å−3 |
1865 reflections | Δρmin = −0.32 e Å−3 |
150 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 | |
N1 | 0.89572 (19) | −0.2416 (3) | 0.51608 (8) | 0.0217 (4) | |
H1 | 0.960 (3) | −0.319 (4) | 0.5367 (13) | 0.038 (7)* | |
C2 | 0.8290 (2) | −0.3166 (3) | 0.44711 (10) | 0.0226 (4) | |
O21 | 0.86777 (16) | −0.4924 (2) | 0.41954 (7) | 0.0319 (4) | |
C3 | 0.7156 (2) | −0.1743 (3) | 0.41215 (10) | 0.0233 (4) | |
H3 | 0.6658 | −0.2119 | 0.3640 | 0.028* | |
C4 | 0.68033 (19) | 0.0119 (3) | 0.44777 (9) | 0.0195 (4) | |
C41 | 0.5632 (2) | 0.1634 (3) | 0.41131 (10) | 0.0211 (4) | |
O42 | 0.50315 (17) | 0.1265 (3) | 0.34854 (8) | 0.0407 (4) | |
O43 | 0.53739 (16) | 0.3326 (2) | 0.45316 (7) | 0.0321 (4) | |
H43 | 0.465 (3) | 0.428 (5) | 0.4243 (15) | 0.062 (8)* | |
N5 | 0.74985 (17) | 0.0713 (3) | 0.51739 (8) | 0.0212 (3) | |
H5 | 0.720 (3) | 0.201 (4) | 0.5416 (13) | 0.043 (7)* | |
C6 | 0.86277 (19) | −0.0504 (3) | 0.55333 (9) | 0.0199 (4) | |
O61 | 0.92976 (15) | 0.0044 (2) | 0.61383 (7) | 0.0271 (3) | |
C1X | 0.1119 (3) | 0.4769 (4) | 0.29052 (12) | 0.0419 (6) | |
H1X1 | 0.1014 | 0.3275 | 0.3117 | 0.063* | |
H1X2 | 0.0711 | 0.4776 | 0.2371 | 0.063* | |
H1X3 | 0.0610 | 0.5864 | 0.3182 | 0.063* | |
S2X | 0.29746 (6) | 0.54840 (9) | 0.29868 (3) | 0.03026 (15) | |
O21X | 0.34198 (15) | 0.5853 (2) | 0.38341 (7) | 0.0321 (4) | |
C3X | 0.2768 (2) | 0.8194 (4) | 0.25787 (11) | 0.0320 (5) | |
H3X1 | 0.2198 | 0.9128 | 0.2879 | 0.048* | |
H3X2 | 0.2276 | 0.8075 | 0.2061 | 0.048* | |
H3X3 | 0.3718 | 0.8873 | 0.2570 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0236 (9) | 0.0208 (8) | 0.0195 (8) | 0.0085 (7) | −0.0023 (7) | −0.0004 (6) |
C2 | 0.0247 (10) | 0.0212 (10) | 0.0212 (9) | 0.0041 (8) | −0.0002 (8) | −0.0013 (8) |
O21 | 0.0368 (8) | 0.0266 (8) | 0.0293 (7) | 0.0146 (6) | −0.0073 (6) | −0.0092 (6) |
C3 | 0.0244 (10) | 0.0240 (11) | 0.0201 (9) | 0.0031 (8) | −0.0030 (7) | −0.0015 (7) |
C4 | 0.0187 (9) | 0.0202 (11) | 0.0195 (8) | 0.0016 (7) | 0.0021 (7) | 0.0019 (7) |
C41 | 0.0196 (10) | 0.0210 (10) | 0.0223 (9) | 0.0023 (8) | 0.0010 (7) | 0.0014 (7) |
O42 | 0.0487 (10) | 0.0369 (9) | 0.0304 (8) | 0.0162 (7) | −0.0183 (7) | −0.0087 (7) |
O43 | 0.0352 (9) | 0.0357 (9) | 0.0227 (7) | 0.0210 (7) | −0.0069 (6) | −0.0067 (6) |
N5 | 0.0224 (9) | 0.0208 (9) | 0.0195 (7) | 0.0057 (7) | −0.0007 (6) | −0.0006 (7) |
C6 | 0.0219 (10) | 0.0191 (9) | 0.0187 (9) | 0.0041 (8) | 0.0021 (7) | 0.0024 (8) |
O61 | 0.0317 (8) | 0.0263 (8) | 0.0208 (6) | 0.0051 (6) | −0.0058 (5) | −0.0038 (5) |
C1X | 0.0525 (15) | 0.0376 (14) | 0.0309 (11) | −0.0141 (11) | −0.0122 (10) | 0.0080 (10) |
S2X | 0.0388 (3) | 0.0310 (3) | 0.0189 (2) | 0.0155 (2) | −0.00447 (19) | −0.0020 (2) |
O21X | 0.0366 (9) | 0.0380 (9) | 0.0186 (7) | 0.0187 (7) | −0.0083 (6) | −0.0033 (6) |
C3X | 0.0335 (12) | 0.0346 (12) | 0.0264 (10) | 0.0003 (10) | −0.0012 (9) | 0.0037 (9) |
Geometric parameters (Å, º) top
N1—C6 | 1.377 (2) | N5—C6 | 1.372 (2) |
N1—C2 | 1.381 (2) | N5—H5 | 0.95 (3) |
N1—H1 | 0.81 (3) | C6—O61 | 1.221 (2) |
C2—O21 | 1.235 (2) | C1X—S2X | 1.778 (2) |
C2—C3 | 1.438 (3) | C1X—H1X1 | 0.9800 |
C3—C4 | 1.344 (3) | C1X—H1X2 | 0.9800 |
C3—H3 | 0.9500 | C1X—H1X3 | 0.9800 |
C4—N5 | 1.373 (2) | S2X—O21X | 1.5313 (12) |
C4—C41 | 1.504 (2) | S2X—C3X | 1.775 (2) |
C41—O42 | 1.207 (2) | C3X—H3X1 | 0.9800 |
C41—O43 | 1.298 (2) | C3X—H3X2 | 0.9800 |
O43—H43 | 0.98 (3) | C3X—H3X3 | 0.9800 |
| | | |
C6—N1—C2 | 126.55 (16) | O61—C6—N5 | 123.24 (17) |
C6—N1—H1 | 116.9 (17) | O61—C6—N1 | 121.83 (17) |
C2—N1—H1 | 116.5 (17) | N5—C6—N1 | 114.93 (15) |
O21—C2—N1 | 120.57 (17) | S2X—C1X—H1X1 | 109.5 |
O21—C2—C3 | 124.69 (16) | S2X—C1X—H1X2 | 109.5 |
N1—C2—C3 | 114.74 (16) | H1X1—C1X—H1X2 | 109.5 |
C4—C3—C2 | 119.84 (16) | S2X—C1X—H1X3 | 109.5 |
C4—C3—H3 | 120.1 | H1X1—C1X—H1X3 | 109.5 |
C2—C3—H3 | 120.1 | H1X2—C1X—H1X3 | 109.5 |
C3—C4—N5 | 121.67 (16) | O21X—S2X—C3X | 105.96 (9) |
C3—C4—C41 | 120.30 (16) | O21X—S2X—C1X | 104.71 (9) |
N5—C4—C41 | 118.03 (15) | C3X—S2X—C1X | 97.59 (10) |
O42—C41—O43 | 125.26 (17) | S2X—C3X—H3X1 | 109.5 |
O42—C41—C4 | 121.16 (16) | S2X—C3X—H3X2 | 109.5 |
O43—C41—C4 | 113.57 (15) | H3X1—C3X—H3X2 | 109.5 |
C41—O43—H43 | 108.7 (16) | S2X—C3X—H3X3 | 109.5 |
C4—N5—C6 | 122.19 (16) | H3X1—C3X—H3X3 | 109.5 |
C4—N5—H5 | 119.2 (14) | H3X2—C3X—H3X3 | 109.5 |
C6—N5—H5 | 118.6 (14) | | |
| | | |
C6—N1—C2—O21 | −179.51 (18) | C3—C4—C41—O43 | 177.81 (17) |
C6—N1—C2—C3 | 0.9 (3) | N5—C4—C41—O43 | −2.9 (2) |
O21—C2—C3—C4 | 178.84 (19) | C3—C4—N5—C6 | 2.6 (3) |
N1—C2—C3—C4 | −1.6 (3) | C41—C4—N5—C6 | −176.69 (16) |
C2—C3—C4—N5 | −0.1 (3) | C4—N5—C6—O61 | 176.99 (17) |
C2—C3—C4—C41 | 179.23 (17) | C4—N5—C6—N1 | −3.2 (3) |
C3—C4—C41—O42 | −3.2 (3) | C2—N1—C6—O61 | −178.73 (18) |
N5—C4—C41—O42 | 176.17 (18) | C2—N1—C6—N5 | 1.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21i | 0.81 (3) | 2.04 (3) | 2.846 (2) | 175 (2) |
N5—H5···O21Xii | 0.95 (3) | 1.99 (3) | 2.912 (2) | 164 (2) |
O43—H43···O21X | 0.98 (3) | 1.59 (3) | 2.5675 (18) | 176 (2) |
Symmetry codes: (i) −x+2, −y−1, −z+1; (ii) −x+1, −y+1, −z+1. |
(IIb) dimethylammonium 2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylate
2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid
top
Crystal data top
C2H8N+·C5H3N2O4−·C5H4N2O4 | Z = 2 |
Mr = 357.29 | F(000) = 372 |
Triclinic, P1 | Dx = 1.615 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.111 (1) Å | Cell parameters from 1108 reflections |
b = 8.9503 (11) Å | θ = 3.0–25.0° |
c = 11.6804 (15) Å | µ = 0.14 mm−1 |
α = 112.366 (3)° | T = 173 K |
β = 97.263 (2)° | Block, colourless |
γ = 104.621 (2)° | 0.20 × 0.20 × 0.10 mm |
V = 734.94 (16) Å3 | |
Data collection top
Siemens SMART three-circle diffractometer | 1341 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.072 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −9→9 |
4208 measured reflections | k = −10→9 |
2555 independent reflections | l = 0→13 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0314P)2] where P = (Fo2 + 2Fc2)/3 |
2555 reflections | (Δ/σ)max = 0.001 |
254 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C2H8N+·C5H3N2O4−·C5H4N2O4 | γ = 104.621 (2)° |
Mr = 357.29 | V = 734.94 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.111 (1) Å | Mo Kα radiation |
b = 8.9503 (11) Å | µ = 0.14 mm−1 |
c = 11.6804 (15) Å | T = 173 K |
α = 112.366 (3)° | 0.20 × 0.20 × 0.10 mm |
β = 97.263 (2)° | |
Data collection top
Siemens SMART three-circle diffractometer | 1341 reflections with I > 2σ(I) |
4208 measured reflections | Rint = 0.072 |
2555 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.86 | Δρmax = 0.25 e Å−3 |
2555 reflections | Δρmin = −0.30 e Å−3 |
254 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | 0.3067 (3) | 0.5065 (3) | 0.9463 (2) | 0.0156 (5) | |
H1A | 0.246 (5) | 0.516 (4) | 1.011 (3) | 0.051 (12)* | |
C2A | 0.2633 (3) | 0.3452 (3) | 0.8476 (2) | 0.0157 (5) | |
O21A | 0.1483 (3) | 0.2228 (2) | 0.84705 (18) | 0.0226 (5) | |
C3A | 0.3581 (4) | 0.3324 (4) | 0.7507 (3) | 0.0173 (5) | |
H3A | 0.3389 | 0.2247 | 0.6820 | 0.021* | |
C4A | 0.4745 (4) | 0.4744 (3) | 0.7582 (3) | 0.0183 (6) | |
C41A | 0.5780 (4) | 0.4822 (3) | 0.6587 (2) | 0.0187 (6) | |
O42A | 0.6688 (3) | 0.6239 (2) | 0.6744 (2) | 0.0270 (5) | |
O43A | 0.5591 (2) | 0.3367 (2) | 0.56875 (19) | 0.0216 (4) | |
N5A | 0.5078 (3) | 0.6319 (3) | 0.8588 (2) | 0.0167 (5) | |
H5A | 0.585 (4) | 0.716 (4) | 0.859 (3) | 0.022 (8)* | |
C6A | 0.4281 (3) | 0.6537 (3) | 0.9579 (2) | 0.0151 (5) | |
O61A | 0.4608 (2) | 0.7915 (2) | 1.04936 (17) | 0.0218 (5) | |
N1B | 0.9550 (3) | 0.2335 (3) | 0.0314 (2) | 0.0189 (5) | |
H1B | 1.003 (4) | 0.230 (4) | −0.033 (3) | 0.034 (10)* | |
C2B | 1.0178 (3) | 0.3844 (3) | 0.1408 (2) | 0.0172 (6) | |
O21B | 1.1311 (2) | 0.5086 (2) | 0.14177 (16) | 0.0216 (4) | |
C3B | 0.9408 (4) | 0.3862 (3) | 0.2447 (2) | 0.0192 (6) | |
H3B | 0.9767 | 0.4867 | 0.3228 | 0.023* | |
C4B | 0.8181 (3) | 0.2451 (3) | 0.2306 (2) | 0.0161 (5) | |
C41B | 0.7279 (3) | 0.2328 (3) | 0.3331 (3) | 0.0193 (6) | |
O42B | 0.6337 (3) | 0.0945 (3) | 0.3206 (2) | 0.0401 (6) | |
O43B | 0.7568 (3) | 0.3775 (2) | 0.4296 (2) | 0.0317 (5) | |
H43 | 0.654 (6) | 0.361 (5) | 0.485 (4) | 0.075 (14)* | |
N5B | 0.7646 (3) | 0.0966 (3) | 0.1194 (2) | 0.0200 (5) | |
H5B | 0.684 (5) | 0.010 (4) | 0.109 (3) | 0.041 (10)* | |
C6B | 0.8285 (3) | 0.0856 (3) | 0.0153 (2) | 0.0164 (6) | |
O61B | 0.7798 (2) | −0.0441 (2) | −0.08620 (17) | 0.0226 (4) | |
C1X | 0.7368 (4) | 0.0946 (4) | −0.3393 (3) | 0.0408 (9) | |
H1X1 | 0.6390 | 0.1187 | −0.3027 | 0.061* | |
H1X2 | 0.7205 | 0.0947 | −0.4238 | 0.061* | |
H1X3 | 0.8478 | 0.1826 | −0.2832 | 0.061* | |
N2X | 0.7416 (3) | −0.0753 (3) | −0.3516 (3) | 0.0283 (6) | |
H2X1 | 0.749 (6) | −0.073 (6) | −0.260 (5) | 0.105 (18)* | |
H2X2 | 0.633 (5) | −0.152 (4) | −0.402 (3) | 0.041 (10)* | |
C3X | 0.8856 (4) | −0.1228 (4) | −0.4060 (3) | 0.0344 (7) | |
H3X1 | 0.8823 | −0.2354 | −0.4111 | 0.052* | |
H3X2 | 0.9988 | −0.0377 | −0.3511 | 0.052* | |
H3X3 | 0.8714 | −0.1267 | −0.4918 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0139 (12) | 0.0143 (12) | 0.0151 (13) | −0.0001 (9) | 0.0087 (10) | 0.0040 (11) |
C2A | 0.0110 (12) | 0.0172 (12) | 0.0199 (13) | 0.0045 (8) | 0.0087 (10) | 0.0075 (11) |
O21A | 0.0230 (11) | 0.0191 (9) | 0.0241 (11) | 0.0024 (7) | 0.0153 (9) | 0.0074 (8) |
C3A | 0.0213 (12) | 0.0164 (11) | 0.0178 (13) | 0.0039 (8) | 0.0130 (10) | 0.0102 (11) |
C4A | 0.0203 (14) | 0.0201 (12) | 0.0108 (12) | 0.0073 (10) | 0.0025 (10) | 0.0029 (9) |
C41A | 0.0147 (11) | 0.0252 (13) | 0.0146 (14) | 0.0055 (8) | 0.0021 (10) | 0.0082 (11) |
O42A | 0.0303 (12) | 0.0188 (9) | 0.0290 (11) | 0.0009 (8) | 0.0166 (9) | 0.0090 (9) |
O43A | 0.0231 (10) | 0.0197 (8) | 0.0177 (11) | 0.0043 (6) | 0.0127 (8) | 0.0029 (8) |
N5A | 0.0145 (11) | 0.0151 (11) | 0.0178 (12) | −0.0009 (8) | 0.0089 (9) | 0.0062 (9) |
C6A | 0.0120 (13) | 0.0184 (12) | 0.0148 (13) | 0.0035 (9) | 0.0027 (10) | 0.0080 (10) |
O61A | 0.0243 (10) | 0.0161 (10) | 0.0197 (10) | 0.0030 (7) | 0.0104 (8) | 0.0029 (8) |
N1B | 0.0222 (13) | 0.0189 (11) | 0.0136 (12) | 0.0053 (9) | 0.0102 (11) | 0.0041 (9) |
C2B | 0.0192 (14) | 0.0171 (12) | 0.0149 (12) | 0.0073 (11) | 0.0049 (11) | 0.0054 (9) |
O21B | 0.0242 (11) | 0.0185 (9) | 0.0166 (10) | −0.0009 (7) | 0.0084 (8) | 0.0058 (9) |
C3B | 0.0220 (14) | 0.0188 (14) | 0.0098 (14) | 0.0063 (10) | 0.0052 (11) | −0.0013 (12) |
C4B | 0.0178 (12) | 0.0161 (11) | 0.0105 (13) | 0.0057 (9) | 0.0034 (9) | 0.0019 (9) |
C41B | 0.0149 (14) | 0.0245 (12) | 0.0175 (15) | 0.0056 (9) | 0.0108 (11) | 0.0064 (12) |
O42B | 0.0513 (16) | 0.0246 (11) | 0.0344 (13) | −0.0036 (9) | 0.0303 (11) | 0.0066 (9) |
O43B | 0.0286 (11) | 0.0259 (11) | 0.0273 (12) | −0.0045 (8) | 0.0187 (9) | 0.0026 (9) |
N5B | 0.0199 (14) | 0.0160 (10) | 0.0197 (13) | −0.0009 (9) | 0.0090 (11) | 0.0062 (9) |
C6B | 0.0188 (15) | 0.0150 (11) | 0.0192 (15) | 0.0045 (10) | 0.0125 (13) | 0.0094 (11) |
O61B | 0.0252 (11) | 0.0147 (9) | 0.0178 (11) | −0.0009 (7) | 0.0116 (8) | −0.0008 (9) |
C1X | 0.0339 (17) | 0.0243 (14) | 0.066 (3) | 0.0073 (11) | 0.0125 (18) | 0.0230 (17) |
N2X | 0.0256 (14) | 0.0259 (11) | 0.0305 (16) | 0.0010 (9) | 0.0079 (12) | 0.0137 (11) |
C3X | 0.0266 (18) | 0.0341 (15) | 0.039 (2) | 0.0054 (11) | 0.0147 (15) | 0.0129 (15) |
Geometric parameters (Å, º) top
N1A—C6A | 1.378 (3) | C3B—H3B | 0.9500 |
N1A—C2A | 1.383 (3) | C4B—N5B | 1.376 (3) |
N1A—H1A | 0.95 (4) | C4B—C41B | 1.504 (4) |
C2A—O21A | 1.244 (3) | C41B—O42B | 1.222 (3) |
C2A—C3A | 1.432 (4) | C41B—O43B | 1.293 (3) |
C3A—C4A | 1.343 (3) | O43B—H43 | 1.13 (4) |
C3A—H3A | 0.9500 | N5B—C6B | 1.360 (4) |
C4A—N5A | 1.381 (3) | N5B—H5B | 0.83 (3) |
C4A—C41A | 1.529 (4) | C6B—O61B | 1.230 (3) |
C41A—O42A | 1.226 (3) | C1X—N2X | 1.482 (3) |
C41A—O43A | 1.281 (3) | C1X—H1X1 | 0.9800 |
N5A—C6A | 1.370 (4) | C1X—H1X2 | 0.9800 |
N5A—H5A | 0.84 (3) | C1X—H1X3 | 0.9800 |
C6A—O61A | 1.222 (3) | N2X—C3X | 1.478 (4) |
N1B—C2B | 1.375 (3) | N2X—H2X1 | 1.06 (5) |
N1B—C6B | 1.384 (3) | N2X—H2X2 | 0.92 (3) |
N1B—H1B | 0.88 (3) | C3X—H3X1 | 0.9800 |
C2B—O21B | 1.246 (3) | C3X—H3X2 | 0.9800 |
C2B—C3B | 1.430 (4) | C3X—H3X3 | 0.9800 |
C3B—C4B | 1.334 (3) | | |
| | | |
C6A—N1A—C2A | 126.2 (2) | C3B—C4B—N5B | 122.0 (2) |
C6A—N1A—H1A | 117 (2) | C3B—C4B—C41B | 123.7 (2) |
C2A—N1A—H1A | 116 (2) | N5B—C4B—C41B | 114.3 (2) |
O21A—C2A—N1A | 120.0 (2) | O42B—C41B—O43B | 125.1 (3) |
O21A—C2A—C3A | 124.3 (3) | O42B—C41B—C4B | 120.4 (2) |
N1A—C2A—C3A | 115.7 (2) | O43B—C41B—C4B | 114.5 (2) |
C4A—C3A—C2A | 119.3 (3) | C41B—O43B—H43 | 109 (2) |
C4A—C3A—H3A | 120.4 | C6B—N5B—C4B | 122.4 (2) |
C2A—C3A—H3A | 120.4 | C6B—N5B—H5B | 115 (2) |
C3A—C4A—N5A | 121.4 (3) | C4B—N5B—H5B | 122 (3) |
C3A—C4A—C41A | 125.2 (2) | O61B—C6B—N5B | 123.7 (2) |
N5A—C4A—C41A | 113.4 (2) | O61B—C6B—N1B | 121.5 (2) |
O42A—C41A—O43A | 128.0 (3) | N5B—C6B—N1B | 114.8 (2) |
O42A—C41A—C4A | 117.2 (2) | N2X—C1X—H1X1 | 109.5 |
O43A—C41A—C4A | 114.8 (2) | N2X—C1X—H1X2 | 109.5 |
C41A—O43A—H43 | 109.2 (16) | H1X1—C1X—H1X2 | 109.5 |
C6A—N5A—C4A | 122.8 (2) | N2X—C1X—H1X3 | 109.5 |
C6A—N5A—H5A | 120 (2) | H1X1—C1X—H1X3 | 109.5 |
C4A—N5A—H5A | 117 (2) | H1X2—C1X—H1X3 | 109.5 |
O61A—C6A—N5A | 123.3 (2) | C1X—N2X—C3X | 113.4 (2) |
O61A—C6A—N1A | 122.2 (3) | C1X—N2X—H2X1 | 107 (2) |
N5A—C6A—N1A | 114.4 (2) | C3X—N2X—H2X1 | 112 (3) |
C2B—N1B—C6B | 125.8 (2) | C1X—N2X—H2X2 | 105.6 (19) |
C2B—N1B—H1B | 117 (2) | C3X—N2X—H2X2 | 111 (2) |
C6B—N1B—H1B | 117 (2) | H2X1—N2X—H2X2 | 107 (3) |
O21B—C2B—N1B | 119.1 (2) | N2X—C3X—H3X1 | 109.5 |
O21B—C2B—C3B | 125.1 (2) | N2X—C3X—H3X2 | 109.5 |
N1B—C2B—C3B | 115.8 (2) | H3X1—C3X—H3X2 | 109.5 |
C4B—C3B—C2B | 119.2 (2) | N2X—C3X—H3X3 | 109.5 |
C4B—C3B—H3B | 120.4 | H3X1—C3X—H3X3 | 109.5 |
C2B—C3B—H3B | 120.4 | H3X2—C3X—H3X3 | 109.5 |
| | | |
C6A—N1A—C2A—O21A | −178.5 (2) | C6B—N1B—C2B—O21B | −179.4 (2) |
C6A—N1A—C2A—C3A | 1.6 (4) | C6B—N1B—C2B—C3B | −1.3 (3) |
O21A—C2A—C3A—C4A | 177.3 (2) | O21B—C2B—C3B—C4B | 178.8 (2) |
N1A—C2A—C3A—C4A | −2.8 (4) | N1B—C2B—C3B—C4B | 0.9 (3) |
C2A—C3A—C4A—N5A | 1.5 (4) | C2B—C3B—C4B—N5B | 0.8 (4) |
C2A—C3A—C4A—C41A | −176.6 (2) | C2B—C3B—C4B—C41B | −179.68 (19) |
C3A—C4A—C41A—O42A | 174.4 (3) | C3B—C4B—C41B—O42B | −170.5 (3) |
N5A—C4A—C41A—O42A | −3.9 (3) | N5B—C4B—C41B—O42B | 9.0 (3) |
C3A—C4A—C41A—O43A | −6.3 (4) | C3B—C4B—C41B—O43B | 10.7 (3) |
N5A—C4A—C41A—O43A | 175.5 (2) | N5B—C4B—C41B—O43B | −169.8 (2) |
C3A—C4A—N5A—C6A | 1.2 (3) | C3B—C4B—N5B—C6B | −2.3 (4) |
C41A—C4A—N5A—C6A | 179.6 (2) | C41B—C4B—N5B—C6B | 178.1 (2) |
C4A—N5A—C6A—O61A | 177.6 (2) | C4B—N5B—C6B—O61B | −178.2 (2) |
C4A—N5A—C6A—N1A | −2.4 (3) | C4B—N5B—C6B—N1B | 1.8 (4) |
C2A—N1A—C6A—O61A | −179.0 (2) | C2B—N1B—C6B—O61B | 180.0 (2) |
C2A—N1A—C6A—N5A | 1.0 (3) | C2B—N1B—C6B—N5B | 0.0 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O21Bi | 0.95 (4) | 1.90 (4) | 2.836 (3) | 172 (3) |
N5A—H5A···O61Bii | 0.84 (3) | 2.12 (3) | 2.947 (3) | 165 (3) |
N1B—H1B···O21Aiii | 0.88 (3) | 1.94 (3) | 2.807 (3) | 169 (3) |
O43B—H43···O43A | 1.13 (4) | 1.37 (4) | 2.482 (3) | 167 (4) |
N5B—H5B···O61Aiv | 0.83 (3) | 2.11 (3) | 2.931 (3) | 169 (3) |
N2X—H2X1···O61B | 1.06 (5) | 1.92 (5) | 2.973 (3) | 174 (4) |
N2X—H2X2···O43Av | 0.92 (3) | 2.11 (3) | 2.982 (3) | 159 (3) |
Symmetry codes: (i) x−1, y, z+1; (ii) x, y+1, z+1; (iii) x+1, y, z−1; (iv) x, y−1, z−1; (v) −x+1, −y, −z. |
(IIc) tris(dimethylammonium)
tris(2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylate)
2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylic acid
top
Crystal data top
3C2H8N+·3C5H3N2O4−·C5H4N2O4 | F(000) = 796 |
Mr = 759.67 | Dx = 1.551 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 7480 reflections |
a = 7.0176 (14) Å | θ = 3.4–25.9° |
b = 18.026 (4) Å | µ = 0.13 mm−1 |
c = 12.906 (3) Å | T = 173 K |
β = 94.94 (3)° | Plate, colourless |
V = 1626.5 (6) Å3 | 0.18 × 0.16 × 0.06 mm |
Z = 2 | |
Data collection top
Stoe IPDS II two-circle diffractometer | 2207 reflections with I > 2σ(I) |
Radiation source: Genix 3D IµS microfocus X-ray source | Rint = 0.091 |
Genix 3D multilayer optics monochromator | θmax = 25.0°, θmin = 3.4° |
ω scans | h = −8→8 |
15886 measured reflections | k = −21→21 |
2968 independent reflections | l = −15→15 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.0963P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2968 reflections | Δρmax = 0.30 e Å−3 |
479 parameters | Δρmin = −0.31 e Å−3 |
1 restraint | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.024 (4) |
Crystal data top
3C2H8N+·3C5H3N2O4−·C5H4N2O4 | V = 1626.5 (6) Å3 |
Mr = 759.67 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.0176 (14) Å | µ = 0.13 mm−1 |
b = 18.026 (4) Å | T = 173 K |
c = 12.906 (3) Å | 0.18 × 0.16 × 0.06 mm |
β = 94.94 (3)° | |
Data collection top
Stoe IPDS II two-circle diffractometer | 2207 reflections with I > 2σ(I) |
15886 measured reflections | Rint = 0.091 |
2968 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 1 restraint |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.30 e Å−3 |
2968 reflections | Δρmin = −0.31 e Å−3 |
479 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 | |
N1A | 0.5478 (9) | 0.1209 (3) | 0.8501 (5) | 0.0726 (14) | |
H1A | 0.5689 | 0.0877 | 0.8998 | 0.087* | |
C2A | 0.4817 (11) | 0.1885 (4) | 0.8787 (5) | 0.0698 (15) | |
O21A | 0.4495 (9) | 0.1988 (3) | 0.9713 (4) | 0.0786 (13) | |
C3A | 0.4514 (11) | 0.2422 (4) | 0.7965 (5) | 0.0706 (15) | |
H3A | 0.4078 | 0.2907 | 0.8106 | 0.085* | |
C4A | 0.4857 (11) | 0.2226 (4) | 0.6998 (6) | 0.0707 (15) | |
C41A | 0.4582 (11) | 0.2755 (4) | 0.6077 (6) | 0.0728 (16) | |
O42A | 0.4646 (10) | 0.2489 (3) | 0.5195 (4) | 0.0869 (15) | |
O43A | 0.4359 (9) | 0.3425 (3) | 0.6311 (4) | 0.0804 (13) | |
N5A | 0.5457 (9) | 0.1528 (3) | 0.6766 (5) | 0.0709 (13) | |
H5A | 0.5598 | 0.1417 | 0.6113 | 0.085* | |
C6A | 0.5849 (12) | 0.0994 (4) | 0.7515 (6) | 0.0744 (17) | |
O61A | 0.6483 (9) | 0.0386 (3) | 0.7327 (4) | 0.0813 (13) | |
N1B | 0.9926 (10) | 0.6659 (3) | −0.0180 (5) | 0.0709 (13) | |
H1B | 1.0160 | 0.6991 | −0.0652 | 0.085* | |
C2B | 0.9659 (11) | 0.5947 (4) | −0.0513 (6) | 0.0721 (16) | |
O21B | 0.9672 (8) | 0.5786 (3) | −0.1452 (4) | 0.0777 (12) | |
C3B | 0.9387 (11) | 0.5408 (4) | 0.0285 (5) | 0.0710 (16) | |
H3B | 0.9240 | 0.4898 | 0.0114 | 0.085* | |
C4B | 0.9344 (11) | 0.5636 (3) | 0.1280 (5) | 0.0683 (15) | |
C41B | 0.8977 (11) | 0.5112 (4) | 0.2152 (6) | 0.0711 (16) | |
O42B | 0.8692 (9) | 0.5348 (3) | 0.3000 (4) | 0.0810 (13) | |
O43B | 0.8973 (8) | 0.4426 (3) | 0.1851 (4) | 0.0745 (12) | |
H43B | 0.8915 | 0.3914 | 0.2457 | 0.112* | |
N5B | 0.9566 (9) | 0.6366 (3) | 0.1554 (5) | 0.0711 (14) | |
H5B | 0.9518 | 0.6495 | 0.2209 | 0.085* | |
C6B | 0.9865 (12) | 0.6908 (4) | 0.0821 (6) | 0.0750 (17) | |
O61B | 1.0074 (10) | 0.7572 (3) | 0.1050 (4) | 0.0865 (15) | |
N1C | 0.4892 (9) | 0.6574 (3) | 0.6523 (5) | 0.0708 (13) | |
H1C | 0.5159 | 0.6901 | 0.6050 | 0.085* | |
C2C | 0.4150 (10) | 0.5909 (4) | 0.6170 (6) | 0.0704 (15) | |
O21C | 0.3860 (8) | 0.5797 (3) | 0.5216 (4) | 0.0784 (13) | |
C3C | 0.3769 (11) | 0.5376 (4) | 0.6964 (5) | 0.0714 (16) | |
H3C | 0.3298 | 0.4897 | 0.6776 | 0.086* | |
C4C | 0.4087 (10) | 0.5566 (4) | 0.7966 (6) | 0.0686 (15) | |
C41C | 0.3723 (10) | 0.5057 (4) | 0.8854 (6) | 0.0695 (15) | |
O42C | 0.4194 (9) | 0.5276 (3) | 0.9757 (4) | 0.0809 (14) | |
O43C | 0.2976 (8) | 0.4428 (3) | 0.8593 (4) | 0.0749 (12) | |
N5C | 0.4787 (9) | 0.6252 (3) | 0.8262 (5) | 0.0692 (13) | |
H5C | 0.4940 | 0.6360 | 0.8929 | 0.083* | |
C6C | 0.5261 (12) | 0.6778 (4) | 0.7553 (6) | 0.0725 (16) | |
O61C | 0.5984 (9) | 0.7377 (3) | 0.7812 (4) | 0.0838 (14) | |
N1D | 1.0712 (9) | 0.1202 (3) | 0.5173 (5) | 0.0725 (14) | |
H1D | 1.1101 | 0.0880 | 0.5659 | 0.087* | |
C2D | 1.0083 (11) | 0.1883 (4) | 0.5484 (6) | 0.0760 (17) | |
O21D | 1.0007 (10) | 0.2003 (3) | 0.6430 (4) | 0.0858 (15) | |
C3D | 0.9573 (12) | 0.2411 (4) | 0.4673 (6) | 0.0748 (17) | |
H3D | 0.9185 | 0.2898 | 0.4840 | 0.090* | |
C4D | 0.9649 (10) | 0.2209 (4) | 0.3675 (6) | 0.0678 (15) | |
C41D | 0.9167 (11) | 0.2723 (4) | 0.2781 (5) | 0.0694 (15) | |
O42D | 0.9107 (8) | 0.2489 (3) | 0.1882 (4) | 0.0787 (13) | |
O43D | 0.8839 (8) | 0.3396 (3) | 0.3062 (4) | 0.0768 (13) | |
N5D | 1.0226 (9) | 0.1513 (3) | 0.3408 (5) | 0.0701 (13) | |
H5D | 1.0249 | 0.1397 | 0.2747 | 0.084* | |
C6D | 1.0772 (11) | 0.0991 (4) | 0.4157 (6) | 0.0720 (16) | |
O61D | 1.1343 (9) | 0.0365 (3) | 0.3941 (4) | 0.0819 (14) | |
C1X | 1.2307 (11) | −0.0877 (4) | 0.1829 (6) | 0.0783 (18) | |
H1X1 | 1.2492 | −0.0466 | 0.1351 | 0.117* | |
H1X2 | 1.2043 | −0.1334 | 0.1430 | 0.117* | |
H1X3 | 1.3467 | −0.0943 | 0.2300 | 0.117* | |
N2X | 1.0695 (9) | −0.0711 (3) | 0.2435 (5) | 0.0734 (14) | |
H2X1 | 0.9616 | −0.0637 | 0.1989 | 0.088* | |
H2X2 | 1.0941 | −0.0279 | 0.2802 | 0.088* | |
C3X | 1.0335 (14) | −0.1311 (4) | 0.3163 (7) | 0.086 (2) | |
H3X1 | 0.9241 | −0.1179 | 0.3549 | 0.129* | |
H3X2 | 1.1469 | −0.1382 | 0.3651 | 0.129* | |
H3X3 | 1.0054 | −0.1770 | 0.2774 | 0.129* | |
C1Y | 0.5844 (15) | 0.4151 (6) | 0.4069 (9) | 0.101 (3) | |
H1Y1 | 0.6984 | 0.4326 | 0.4491 | 0.152* | |
H1Y2 | 0.5739 | 0.4409 | 0.3399 | 0.152* | |
H1Y3 | 0.5949 | 0.3616 | 0.3953 | 0.152* | |
N2Y | 0.4141 (9) | 0.4303 (3) | 0.4615 (5) | 0.0730 (13) | |
H2Y1 | 0.4264 | 0.4067 | 0.5249 | 0.088* | |
H2Y2 | 0.4074 | 0.4805 | 0.4738 | 0.088* | |
C3Y | 0.2354 (14) | 0.4064 (6) | 0.4043 (8) | 0.098 (3) | |
H3Y1 | 0.1275 | 0.4187 | 0.4446 | 0.147* | |
H3Y2 | 0.2390 | 0.3527 | 0.3932 | 0.147* | |
H3Y3 | 0.2201 | 0.4318 | 0.3370 | 0.147* | |
C1Z | 0.5618 (12) | 0.3634 (6) | 1.0729 (8) | 0.091 (2) | |
H1Z1 | 0.6548 | 0.3459 | 1.0259 | 0.136* | |
H1Z2 | 0.5839 | 0.3380 | 1.1400 | 0.136* | |
H1Z3 | 0.5767 | 0.4170 | 1.0832 | 0.136* | |
N2Z | 0.3659 (9) | 0.3472 (3) | 1.0269 (5) | 0.0734 (14) | |
H2Z1 | 0.3474 | 0.3705 | 0.9634 | 0.088* | |
H2Z2 | 0.3547 | 0.2969 | 1.0155 | 0.088* | |
C3Z | 0.2167 (12) | 0.3706 (4) | 1.0912 (7) | 0.0815 (19) | |
H3Z1 | 0.0912 | 0.3585 | 1.0560 | 0.122* | |
H3Z2 | 0.2256 | 0.4243 | 1.1026 | 0.122* | |
H3Z3 | 0.2326 | 0.3449 | 1.1583 | 0.122* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.087 (4) | 0.069 (3) | 0.063 (3) | 0.012 (3) | 0.008 (3) | −0.001 (2) |
C2A | 0.078 (4) | 0.065 (3) | 0.066 (4) | 0.003 (3) | 0.004 (3) | 0.003 (3) |
O21A | 0.095 (4) | 0.076 (3) | 0.065 (3) | 0.006 (2) | 0.009 (2) | −0.003 (2) |
C3A | 0.081 (4) | 0.067 (3) | 0.063 (3) | 0.006 (3) | 0.000 (3) | 0.005 (3) |
C4A | 0.075 (4) | 0.063 (3) | 0.073 (4) | 0.002 (3) | 0.002 (3) | 0.001 (3) |
C41A | 0.078 (4) | 0.071 (3) | 0.070 (4) | 0.005 (3) | 0.005 (3) | 0.007 (3) |
O42A | 0.117 (5) | 0.078 (3) | 0.065 (3) | 0.009 (3) | 0.010 (3) | −0.002 (2) |
O43A | 0.095 (4) | 0.074 (3) | 0.072 (3) | 0.000 (2) | 0.004 (3) | 0.002 (2) |
N5A | 0.078 (4) | 0.067 (3) | 0.067 (3) | 0.010 (3) | 0.003 (3) | 0.001 (2) |
C6A | 0.082 (5) | 0.074 (4) | 0.067 (4) | 0.007 (3) | 0.005 (3) | 0.001 (3) |
O61A | 0.097 (4) | 0.074 (3) | 0.073 (3) | 0.011 (3) | 0.003 (3) | −0.001 (2) |
N1B | 0.082 (4) | 0.065 (3) | 0.066 (3) | −0.002 (2) | 0.006 (3) | −0.006 (2) |
C2B | 0.079 (4) | 0.069 (3) | 0.068 (4) | 0.000 (3) | 0.006 (3) | 0.003 (3) |
O21B | 0.089 (3) | 0.076 (3) | 0.068 (3) | 0.003 (2) | 0.009 (2) | 0.000 (2) |
C3B | 0.081 (4) | 0.067 (3) | 0.066 (4) | −0.004 (3) | 0.008 (3) | 0.002 (3) |
C4B | 0.079 (4) | 0.063 (3) | 0.063 (3) | −0.003 (3) | 0.004 (3) | 0.005 (2) |
C41B | 0.075 (4) | 0.065 (3) | 0.073 (4) | −0.004 (3) | 0.005 (3) | 0.000 (3) |
O42B | 0.096 (4) | 0.078 (3) | 0.071 (3) | −0.009 (3) | 0.014 (3) | 0.000 (2) |
O43B | 0.093 (3) | 0.063 (2) | 0.066 (3) | −0.001 (2) | 0.006 (2) | −0.001 (2) |
N5B | 0.082 (4) | 0.057 (3) | 0.074 (3) | −0.003 (2) | 0.008 (3) | 0.001 (2) |
C6B | 0.085 (5) | 0.074 (4) | 0.067 (4) | 0.000 (3) | 0.009 (3) | 0.006 (3) |
O61B | 0.121 (5) | 0.064 (2) | 0.075 (3) | −0.009 (3) | 0.011 (3) | −0.002 (2) |
N1C | 0.071 (3) | 0.074 (3) | 0.067 (3) | −0.006 (2) | 0.002 (2) | 0.000 (2) |
C2C | 0.066 (4) | 0.071 (3) | 0.073 (4) | −0.006 (3) | 0.001 (3) | 0.002 (3) |
O21C | 0.093 (4) | 0.080 (3) | 0.062 (3) | −0.004 (2) | 0.001 (2) | −0.002 (2) |
C3C | 0.079 (4) | 0.065 (3) | 0.068 (4) | −0.005 (3) | −0.002 (3) | −0.002 (3) |
C4C | 0.067 (4) | 0.066 (3) | 0.072 (4) | −0.005 (3) | 0.002 (3) | 0.001 (3) |
C41C | 0.066 (4) | 0.071 (3) | 0.070 (4) | −0.001 (3) | −0.002 (3) | 0.005 (3) |
O42C | 0.098 (4) | 0.077 (3) | 0.066 (3) | −0.004 (3) | −0.003 (2) | −0.004 (2) |
O43C | 0.077 (3) | 0.070 (2) | 0.077 (3) | −0.007 (2) | 0.001 (2) | −0.002 (2) |
N5C | 0.073 (3) | 0.072 (3) | 0.062 (3) | −0.006 (3) | 0.002 (2) | −0.003 (2) |
C6C | 0.082 (5) | 0.068 (3) | 0.068 (4) | −0.005 (3) | 0.006 (3) | −0.004 (3) |
O61C | 0.100 (4) | 0.071 (3) | 0.080 (3) | −0.015 (2) | 0.005 (3) | −0.004 (2) |
N1D | 0.079 (4) | 0.071 (3) | 0.068 (3) | 0.006 (3) | 0.005 (3) | −0.001 (2) |
C2D | 0.079 (5) | 0.076 (4) | 0.071 (4) | 0.005 (3) | −0.003 (3) | 0.000 (3) |
O21D | 0.118 (5) | 0.073 (3) | 0.067 (3) | 0.006 (3) | 0.006 (3) | −0.001 (2) |
C3D | 0.089 (5) | 0.069 (4) | 0.066 (4) | 0.006 (3) | 0.006 (3) | 0.003 (3) |
C4D | 0.066 (4) | 0.065 (3) | 0.072 (4) | 0.000 (3) | 0.006 (3) | 0.003 (3) |
C41D | 0.079 (4) | 0.068 (3) | 0.060 (3) | 0.005 (3) | 0.003 (3) | 0.003 (3) |
O42D | 0.091 (4) | 0.072 (3) | 0.071 (3) | 0.011 (2) | −0.001 (2) | −0.001 (2) |
O43D | 0.095 (4) | 0.062 (2) | 0.073 (3) | 0.001 (2) | 0.009 (3) | 0.002 (2) |
N5D | 0.073 (4) | 0.069 (3) | 0.067 (3) | 0.006 (2) | 0.002 (3) | 0.006 (2) |
C6D | 0.076 (4) | 0.073 (4) | 0.064 (3) | 0.001 (3) | −0.008 (3) | 0.005 (3) |
O61D | 0.102 (4) | 0.067 (2) | 0.075 (3) | 0.015 (3) | 0.001 (3) | −0.002 (2) |
C1X | 0.076 (5) | 0.082 (4) | 0.078 (4) | 0.005 (3) | 0.009 (3) | 0.005 (3) |
N2X | 0.075 (4) | 0.075 (3) | 0.070 (3) | −0.001 (3) | 0.007 (3) | 0.005 (3) |
C3X | 0.096 (6) | 0.075 (4) | 0.087 (5) | −0.008 (4) | 0.007 (4) | 0.008 (3) |
C1Y | 0.091 (6) | 0.103 (6) | 0.113 (7) | 0.015 (5) | 0.023 (5) | 0.022 (5) |
N2Y | 0.079 (4) | 0.070 (3) | 0.069 (3) | −0.003 (3) | 0.001 (3) | −0.001 (2) |
C3Y | 0.090 (6) | 0.100 (6) | 0.101 (6) | −0.012 (4) | −0.010 (5) | 0.020 (5) |
C1Z | 0.073 (5) | 0.096 (5) | 0.101 (6) | −0.007 (4) | −0.010 (4) | 0.019 (4) |
N2Z | 0.072 (4) | 0.075 (3) | 0.073 (3) | 0.002 (3) | 0.006 (3) | 0.003 (3) |
C3Z | 0.081 (5) | 0.083 (4) | 0.081 (4) | 0.012 (3) | 0.012 (4) | 0.007 (3) |
Geometric parameters (Å, º) top
N1A—C2A | 1.367 (9) | N1D—C2D | 1.377 (9) |
N1A—C6A | 1.376 (9) | N1D—H1D | 0.8800 |
N1A—H1A | 0.8800 | C2D—O21D | 1.245 (9) |
C2A—O21A | 1.249 (8) | C2D—C3D | 1.437 (10) |
C2A—C3A | 1.438 (9) | C3D—C4D | 1.343 (10) |
C3A—C4A | 1.339 (10) | C3D—H3D | 0.9500 |
C3A—H3A | 0.9500 | C4D—N5D | 1.371 (9) |
C4A—N5A | 1.368 (9) | C4D—C41D | 1.496 (9) |
C4A—C41A | 1.523 (10) | C41D—O42D | 1.232 (9) |
C41A—O42A | 1.240 (9) | C41D—O43D | 1.294 (8) |
C41A—O43A | 1.258 (9) | O43D—H43B | 1.2216 |
N5A—C6A | 1.374 (9) | N5D—C6D | 1.379 (9) |
N5A—H5A | 0.8800 | N5D—H5D | 0.8800 |
C6A—O61A | 1.215 (9) | C6D—O61D | 1.238 (9) |
N1B—C2B | 1.361 (9) | C1X—N2X | 1.461 (9) |
N1B—C6B | 1.371 (9) | C1X—H1X1 | 0.9800 |
N1B—H1B | 0.8800 | C1X—H1X2 | 0.9800 |
C2B—O21B | 1.247 (9) | C1X—H1X3 | 0.9800 |
C2B—C3B | 1.441 (9) | N2X—C3X | 1.468 (9) |
C3B—C4B | 1.351 (10) | N2X—H2X1 | 0.9200 |
C3B—H3B | 0.9500 | N2X—H2X2 | 0.9200 |
C4B—N5B | 1.367 (8) | C3X—H3X1 | 0.9800 |
C4B—C41B | 1.507 (9) | C3X—H3X2 | 0.9800 |
C41B—O42B | 1.207 (9) | C3X—H3X3 | 0.9800 |
C41B—O43B | 1.297 (8) | C1Y—N2Y | 1.465 (11) |
O43B—H43B | 1.2118 | C1Y—H1Y1 | 0.9800 |
N5B—C6B | 1.389 (9) | C1Y—H1Y2 | 0.9800 |
N5B—H5B | 0.8800 | C1Y—H1Y3 | 0.9800 |
C6B—O61B | 1.239 (9) | N2Y—C3Y | 1.464 (12) |
N1C—C2C | 1.369 (9) | N2Y—H2Y1 | 0.9200 |
N1C—C6C | 1.382 (9) | N2Y—H2Y2 | 0.9200 |
N1C—H1C | 0.8800 | C3Y—H3Y1 | 0.9800 |
C2C—O21C | 1.247 (9) | C3Y—H3Y2 | 0.9800 |
C2C—C3C | 1.446 (9) | C3Y—H3Y3 | 0.9800 |
C3C—C4C | 1.338 (10) | C1Z—N2Z | 1.479 (11) |
C3C—H3C | 0.9500 | C1Z—H1Z1 | 0.9800 |
C4C—N5C | 1.373 (8) | C1Z—H1Z2 | 0.9800 |
C4C—C41C | 1.506 (9) | C1Z—H1Z3 | 0.9800 |
C41C—O42C | 1.248 (9) | N2Z—C3Z | 1.454 (9) |
C41C—O43C | 1.282 (9) | N2Z—H2Z1 | 0.9200 |
N5C—C6C | 1.378 (9) | N2Z—H2Z2 | 0.9200 |
N5C—H5C | 0.8800 | C3Z—H3Z1 | 0.9800 |
C6C—O61C | 1.226 (9) | C3Z—H3Z2 | 0.9800 |
N1D—C6D | 1.368 (10) | C3Z—H3Z3 | 0.9800 |
| | | |
C2A—N1A—C6A | 126.6 (6) | C4D—C3D—C2D | 119.4 (7) |
C2A—N1A—H1A | 116.7 | C4D—C3D—H3D | 120.3 |
C6A—N1A—H1A | 116.7 | C2D—C3D—H3D | 120.3 |
O21A—C2A—N1A | 119.0 (6) | C3D—C4D—N5D | 121.8 (7) |
O21A—C2A—C3A | 125.3 (6) | C3D—C4D—C41D | 123.1 (6) |
N1A—C2A—C3A | 115.6 (6) | N5D—C4D—C41D | 115.1 (6) |
C4A—C3A—C2A | 119.0 (6) | O42D—C41D—O43D | 126.3 (6) |
C4A—C3A—H3A | 120.5 | O42D—C41D—C4D | 120.2 (6) |
C2A—C3A—H3A | 120.5 | O43D—C41D—C4D | 113.5 (6) |
C3A—C4A—N5A | 122.0 (7) | C41D—O43D—H43B | 121.2 |
C3A—C4A—C41A | 122.8 (6) | C4D—N5D—C6D | 121.2 (6) |
N5A—C4A—C41A | 115.2 (6) | C4D—N5D—H5D | 119.4 |
O42A—C41A—O43A | 127.4 (7) | C6D—N5D—H5D | 119.4 |
O42A—C41A—C4A | 117.5 (6) | O61D—C6D—N1D | 120.4 (7) |
O43A—C41A—C4A | 115.1 (7) | O61D—C6D—N5D | 122.7 (7) |
C4A—N5A—C6A | 122.5 (6) | N1D—C6D—N5D | 116.9 (6) |
C4A—N5A—H5A | 118.8 | N2X—C1X—H1X1 | 109.5 |
C6A—N5A—H5A | 118.8 | N2X—C1X—H1X2 | 109.5 |
O61A—C6A—N5A | 123.1 (7) | H1X1—C1X—H1X2 | 109.5 |
O61A—C6A—N1A | 122.6 (7) | N2X—C1X—H1X3 | 109.5 |
N5A—C6A—N1A | 114.3 (6) | H1X1—C1X—H1X3 | 109.5 |
C2B—N1B—C6B | 126.3 (6) | H1X2—C1X—H1X3 | 109.5 |
C2B—N1B—H1B | 116.9 | C1X—N2X—C3X | 112.1 (6) |
C6B—N1B—H1B | 116.9 | C1X—N2X—H2X1 | 109.2 |
O21B—C2B—N1B | 121.0 (6) | C3X—N2X—H2X1 | 109.2 |
O21B—C2B—C3B | 123.3 (6) | C1X—N2X—H2X2 | 109.2 |
N1B—C2B—C3B | 115.6 (6) | C3X—N2X—H2X2 | 109.2 |
C4B—C3B—C2B | 119.3 (6) | H2X1—N2X—H2X2 | 107.9 |
C4B—C3B—H3B | 120.3 | N2X—C3X—H3X1 | 109.5 |
C2B—C3B—H3B | 120.3 | N2X—C3X—H3X2 | 109.5 |
C3B—C4B—N5B | 121.8 (6) | H3X1—C3X—H3X2 | 109.5 |
C3B—C4B—C41B | 122.5 (6) | N2X—C3X—H3X3 | 109.5 |
N5B—C4B—C41B | 115.7 (6) | H3X1—C3X—H3X3 | 109.5 |
O42B—C41B—O43B | 127.7 (7) | H3X2—C3X—H3X3 | 109.5 |
O42B—C41B—C4B | 120.5 (6) | N2Y—C1Y—H1Y1 | 109.5 |
O43B—C41B—C4B | 111.8 (6) | N2Y—C1Y—H1Y2 | 109.5 |
C41B—O43B—H43B | 122.2 | H1Y1—C1Y—H1Y2 | 109.5 |
C4B—N5B—C6B | 121.5 (6) | N2Y—C1Y—H1Y3 | 109.5 |
C4B—N5B—H5B | 119.3 | H1Y1—C1Y—H1Y3 | 109.5 |
C6B—N5B—H5B | 119.3 | H1Y2—C1Y—H1Y3 | 109.5 |
O61B—C6B—N1B | 121.9 (7) | C3Y—N2Y—C1Y | 113.7 (8) |
O61B—C6B—N5B | 122.7 (7) | C3Y—N2Y—H2Y1 | 108.8 |
N1B—C6B—N5B | 115.5 (6) | C1Y—N2Y—H2Y1 | 108.8 |
C2C—N1C—C6C | 126.0 (6) | C3Y—N2Y—H2Y2 | 108.8 |
C2C—N1C—H1C | 117.0 | C1Y—N2Y—H2Y2 | 108.8 |
C6C—N1C—H1C | 117.0 | H2Y1—N2Y—H2Y2 | 107.7 |
O21C—C2C—N1C | 119.7 (6) | N2Y—C3Y—H3Y1 | 109.5 |
O21C—C2C—C3C | 124.6 (6) | N2Y—C3Y—H3Y2 | 109.5 |
N1C—C2C—C3C | 115.7 (6) | H3Y1—C3Y—H3Y2 | 109.5 |
C4C—C3C—C2C | 119.3 (6) | N2Y—C3Y—H3Y3 | 109.5 |
C4C—C3C—H3C | 120.3 | H3Y1—C3Y—H3Y3 | 109.5 |
C2C—C3C—H3C | 120.3 | H3Y2—C3Y—H3Y3 | 109.5 |
C3C—C4C—N5C | 121.6 (6) | N2Z—C1Z—H1Z1 | 109.5 |
C3C—C4C—C41C | 123.7 (6) | N2Z—C1Z—H1Z2 | 109.5 |
N5C—C4C—C41C | 114.7 (6) | H1Z1—C1Z—H1Z2 | 109.5 |
O42C—C41C—O43C | 126.5 (7) | N2Z—C1Z—H1Z3 | 109.5 |
O42C—C41C—C4C | 117.9 (6) | H1Z1—C1Z—H1Z3 | 109.5 |
O43C—C41C—C4C | 115.5 (6) | H1Z2—C1Z—H1Z3 | 109.5 |
C4C—N5C—C6C | 122.5 (6) | C3Z—N2Z—C1Z | 113.8 (7) |
C4C—N5C—H5C | 118.8 | C3Z—N2Z—H2Z1 | 108.8 |
C6C—N5C—H5C | 118.8 | C1Z—N2Z—H2Z1 | 108.8 |
O61C—C6C—N5C | 122.8 (7) | C3Z—N2Z—H2Z2 | 108.8 |
O61C—C6C—N1C | 122.4 (7) | C1Z—N2Z—H2Z2 | 108.8 |
N5C—C6C—N1C | 114.7 (6) | H2Z1—N2Z—H2Z2 | 107.7 |
C6D—N1D—C2D | 124.3 (7) | N2Z—C3Z—H3Z1 | 109.5 |
C6D—N1D—H1D | 117.8 | N2Z—C3Z—H3Z2 | 109.5 |
C2D—N1D—H1D | 117.8 | H3Z1—C3Z—H3Z2 | 109.5 |
O21D—C2D—N1D | 118.9 (7) | N2Z—C3Z—H3Z3 | 109.5 |
O21D—C2D—C3D | 124.8 (7) | H3Z1—C3Z—H3Z3 | 109.5 |
N1D—C2D—C3D | 116.3 (7) | H3Z2—C3Z—H3Z3 | 109.5 |
| | | |
C6A—N1A—C2A—O21A | 177.8 (7) | C6C—N1C—C2C—O21C | 179.0 (7) |
C6A—N1A—C2A—C3A | −1.0 (12) | C6C—N1C—C2C—C3C | −1.4 (11) |
O21A—C2A—C3A—C4A | −177.6 (8) | O21C—C2C—C3C—C4C | −178.2 (8) |
N1A—C2A—C3A—C4A | 1.1 (11) | N1C—C2C—C3C—C4C | 2.3 (10) |
C2A—C3A—C4A—N5A | 1.0 (12) | C2C—C3C—C4C—N5C | −0.7 (11) |
C2A—C3A—C4A—C41A | −179.9 (7) | C2C—C3C—C4C—C41C | 179.4 (7) |
C3A—C4A—C41A—O42A | −168.9 (8) | C3C—C4C—C41C—O42C | 175.3 (7) |
N5A—C4A—C41A—O42A | 10.2 (11) | N5C—C4C—C41C—O42C | −4.6 (10) |
C3A—C4A—C41A—O43A | 12.7 (12) | C3C—C4C—C41C—O43C | −3.6 (11) |
N5A—C4A—C41A—O43A | −168.1 (7) | N5C—C4C—C41C—O43C | 176.5 (6) |
C3A—C4A—N5A—C6A | −3.6 (12) | C3C—C4C—N5C—C6C | −2.1 (11) |
C41A—C4A—N5A—C6A | 177.2 (7) | C41C—C4C—N5C—C6C | 177.8 (7) |
C4A—N5A—C6A—O61A | −175.8 (8) | C4C—N5C—C6C—O61C | −175.9 (7) |
C4A—N5A—C6A—N1A | 3.6 (11) | C4C—N5C—C6C—N1C | 2.9 (10) |
C2A—N1A—C6A—O61A | 178.1 (8) | C2C—N1C—C6C—O61C | 177.7 (8) |
C2A—N1A—C6A—N5A | −1.3 (12) | C2C—N1C—C6C—N5C | −1.1 (11) |
C6B—N1B—C2B—O21B | 177.2 (8) | C6D—N1D—C2D—O21D | 176.7 (7) |
C6B—N1B—C2B—C3B | −3.4 (12) | C6D—N1D—C2D—C3D | −3.8 (11) |
O21B—C2B—C3B—C4B | −178.3 (8) | O21D—C2D—C3D—C4D | −177.6 (8) |
N1B—C2B—C3B—C4B | 2.3 (11) | N1D—C2D—C3D—C4D | 2.9 (11) |
C2B—C3B—C4B—N5B | −0.5 (12) | C2D—C3D—C4D—N5D | −0.9 (12) |
C2B—C3B—C4B—C41B | 177.2 (7) | C2D—C3D—C4D—C41D | −179.3 (7) |
C3B—C4B—C41B—O42B | −169.9 (8) | C3D—C4D—C41D—O42D | −173.9 (8) |
N5B—C4B—C41B—O42B | 7.9 (11) | N5D—C4D—C41D—O42D | 7.6 (11) |
C3B—C4B—C41B—O43B | 8.6 (11) | C3D—C4D—C41D—O43D | 5.9 (11) |
N5B—C4B—C41B—O43B | −173.6 (7) | N5D—C4D—C41D—O43D | −172.6 (7) |
C3B—C4B—N5B—C6B | −0.6 (12) | C3D—C4D—N5D—C6D | −0.6 (11) |
C41B—C4B—N5B—C6B | −178.4 (7) | C41D—C4D—N5D—C6D | 177.9 (7) |
C2B—N1B—C6B—O61B | −178.0 (8) | C2D—N1D—C6D—O61D | −179.4 (7) |
C2B—N1B—C6B—N5B | 2.4 (12) | C2D—N1D—C6D—N5D | 2.5 (11) |
C4B—N5B—C6B—O61B | −179.8 (8) | C4D—N5D—C6D—O61D | −178.2 (7) |
C4B—N5B—C6B—N1B | −0.2 (11) | C4D—N5D—C6D—N1D | −0.1 (11) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O42Ci | 0.88 | 1.93 | 2.801 (8) | 168 |
N5A—H5A···O21Cii | 0.88 | 2.11 | 2.953 (8) | 161 |
N1B—H1B···O42Diii | 0.88 | 1.93 | 2.790 (8) | 165 |
N5B—H5B···O21Div | 0.88 | 1.98 | 2.837 (8) | 163 |
O43B—H43B···O43D | 1.21 | 1.22 | 2.433 (6) | 179 |
N1C—H1C···O42Av | 0.88 | 1.94 | 2.805 (8) | 167 |
N5C—H5C···O21Avi | 0.88 | 2.10 | 2.936 (8) | 159 |
N1D—H1D···O42Bvii | 0.88 | 1.97 | 2.817 (8) | 160 |
N5D—H5D···O21Bviii | 0.88 | 2.01 | 2.852 (8) | 160 |
N2X—H2X1···O43Cii | 0.92 | 1.91 | 2.805 (9) | 164 |
N2X—H2X2···O61D | 0.92 | 1.88 | 2.755 (8) | 159 |
N2Y—H2Y1···O43A | 0.92 | 1.79 | 2.695 (8) | 167 |
N2Y—H2Y2···O21C | 0.92 | 1.90 | 2.813 (8) | 171 |
N2Z—H2Z1···O43C | 0.92 | 1.88 | 2.776 (8) | 163 |
N2Z—H2Z2···O21A | 0.92 | 1.99 | 2.843 (8) | 154 |
Symmetry codes: (i) −x+1, y−1/2, −z+2; (ii) −x+1, y−1/2, −z+1; (iii) −x+2, y+1/2, −z; (iv) −x+2, y+1/2, −z+1; (v) −x+1, y+1/2, −z+1; (vi) −x+1, y+1/2, −z+2; (vii) −x+2, y−1/2, −z+1; (viii) −x+2, y−1/2, −z. |
Experimental details
| (I) | (IIa) | (IIb) | (IIc) |
Crystal data |
Chemical formula | C5H6N2O4 | C5H4N2O4·C2H6OS | C2H8N+·C5H3N2O4−·C5H4N2O4 | 3C2H8N+·3C5H3N2O4−·C5H4N2O4 |
Mr | 158.12 | 234.23 | 357.29 | 759.67 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 173 | 173 | 173 | 173 |
a, b, c (Å) | 7.6148 (5), 8.5592 (6), 9.3406 (6) | 9.3710 (6), 5.9752 (3), 17.8433 (13) | 8.111 (1), 8.9503 (11), 11.6804 (15) | 7.0176 (14), 18.026 (4), 12.906 (3) |
α, β, γ (°) | 90, 90, 90 | 90, 97.447 (6), 90 | 112.366 (3), 97.263 (2), 104.621 (2) | 90, 94.94 (3), 90 |
V (Å3) | 608.79 (7) | 990.68 (11) | 734.94 (16) | 1626.5 (6) |
Z | 4 | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.15 | 0.33 | 0.14 | 0.13 |
Crystal size (mm) | 0.50 × 0.10 × 0.10 | 0.35 × 0.25 × 0.20 | 0.20 × 0.20 × 0.10 | 0.18 × 0.16 × 0.06 |
|
Data collection |
Diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer | Siemens SMART three-circle diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | – | Multi-scan (MULABS; Blessing, 1995; Spek, 2009) | – | – |
Tmin, Tmax | – | 0.893, 0.937 | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10371, 692, 607 | 18676, 1865, 1383 | 4208, 2555, 1341 | 15886, 2968, 2207 |
Rint | 0.107 | 0.076 | 0.072 | 0.091 |
(sin θ/λ)max (Å−1) | 0.610 | 0.609 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.055, 0.99 | 0.032, 0.072, 0.91 | 0.061, 0.104, 0.86 | 0.065, 0.169, 1.02 |
No. of reflections | 692 | 1865 | 2555 | 2968 |
No. of parameters | 113 | 150 | 254 | 479 |
No. of restraints | 0 | 0 | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 | 0.17, −0.32 | 0.25, −0.30 | 0.30, −0.31 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O54i | 0.86 (3) | 2.14 (3) | 2.996 (2) | 175 (2) |
N3—H3···O41ii | 0.91 (3) | 1.93 (3) | 2.831 (2) | 168 (2) |
O54—H54···O21iii | 1.02 (4) | 1.61 (4) | 2.604 (2) | 165 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21i | 0.81 (3) | 2.04 (3) | 2.846 (2) | 175 (2) |
N5—H5···O21Xii | 0.95 (3) | 1.99 (3) | 2.912 (2) | 164 (2) |
O43—H43···O21X | 0.98 (3) | 1.59 (3) | 2.5675 (18) | 176 (2) |
Symmetry codes: (i) −x+2, −y−1, −z+1; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O21Bi | 0.95 (4) | 1.90 (4) | 2.836 (3) | 172 (3) |
N5A—H5A···O61Bii | 0.84 (3) | 2.12 (3) | 2.947 (3) | 165 (3) |
N1B—H1B···O21Aiii | 0.88 (3) | 1.94 (3) | 2.807 (3) | 169 (3) |
O43B—H43···O43A | 1.13 (4) | 1.37 (4) | 2.482 (3) | 167 (4) |
N5B—H5B···O61Aiv | 0.83 (3) | 2.11 (3) | 2.931 (3) | 169 (3) |
N2X—H2X1···O61B | 1.06 (5) | 1.92 (5) | 2.973 (3) | 174 (4) |
N2X—H2X2···O43Av | 0.92 (3) | 2.11 (3) | 2.982 (3) | 159 (3) |
Symmetry codes: (i) x−1, y, z+1; (ii) x, y+1, z+1; (iii) x+1, y, z−1; (iv) x, y−1, z−1; (v) −x+1, −y, −z. |
Hydrogen-bond geometry (Å, º) for (IIc) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O42Ci | 0.88 | 1.93 | 2.801 (8) | 168 |
N5A—H5A···O21Cii | 0.88 | 2.11 | 2.953 (8) | 161 |
N1B—H1B···O42Diii | 0.88 | 1.93 | 2.790 (8) | 165 |
N5B—H5B···O21Div | 0.88 | 1.98 | 2.837 (8) | 163 |
O43B—H43B···O43D | 1.21 | 1.22 | 2.433 (6) | 179 |
N1C—H1C···O42Av | 0.88 | 1.94 | 2.805 (8) | 167 |
N5C—H5C···O21Avi | 0.88 | 2.10 | 2.936 (8) | 159 |
N1D—H1D···O42Bvii | 0.88 | 1.97 | 2.817 (8) | 160 |
N5D—H5D···O21Bviii | 0.88 | 2.01 | 2.852 (8) | 160 |
N2X—H2X1···O43Cii | 0.92 | 1.91 | 2.805 (9) | 164 |
N2X—H2X2···O61D | 0.92 | 1.88 | 2.755 (8) | 159 |
N2Y—H2Y1···O43A | 0.92 | 1.79 | 2.695 (8) | 167 |
N2Y—H2Y2···O21C | 0.92 | 1.90 | 2.813 (8) | 171 |
N2Z—H2Z1···O43C | 0.92 | 1.88 | 2.776 (8) | 163 |
N2Z—H2Z2···O21A | 0.92 | 1.99 | 2.843 (8) | 154 |
Symmetry codes: (i) −x+1, y−1/2, −z+2; (ii) −x+1, y−1/2, −z+1; (iii) −x+2, y+1/2, −z; (iv) −x+2, y+1/2, −z+1; (v) −x+1, y+1/2, −z+1; (vi) −x+1, y+1/2, −z+2; (vii) −x+2, y−1/2, −z+1; (viii) −x+2, y−1/2, −z. |
Active pharmaceutical ingredients (APIs) usually contain functional groups that are involved in recognition processes. Their polymorphic nature often leads to new opportunities in drug development. APIs are mostly administered as salts or together with a pharmaceutically inactive carrier compound, which possibly changes the desired pharmaceutical effects (Almarsson & Zaworotko, 2004). The design of cocrystals with an API presents an alternative route to obtain new dosage forms without affecting the pharmaceutical activity (Ghosh et al., 2011; Vishweshwar et al., 2005). The most promising approach for the design of cocrystals deals with supramolecular synthons (Blagden et al., 2008). The most-studied synthon is that formed between an amide and a carboxylic acid (Rodríguez-Cuamatzi et al., 2007). Since carboxylic acids form robust and directed hydrogen bonds (Blagden et al., 2007) they are ideal candidates as coformers for APIs (Almarsson & Zaworotko, 2004). Although carboxylic acids are able to improve the stability of API-containing complexes (Seaton & Parkin, 2011), they show conformational polymorphism. Therefore, the possible conformations of carboxylic acids must be examined prior to their use as coformers for APIs. For this reason, we crystallized hydantoin-5-acetic acid, (I), and orotic acid, (II), under several different sets of conditions.
Compounds (I) and (II) contain heterocyclic ring structures, rigid ADA (A = acceptor, D = donor) hydrogen-bonding sites and rotatable acid functionalities. Various crystallization attempts with hydantoin-5-acetic acid yielded only the solvent-free structure, (I), while crystallization experiments with (II) resulted in three structures, namely a dimethyl sulfoxide monosolvate, (IIa), and two dimethylammonium orotate–orotic acid compounds with varying compositions, (IIb) and (IIc). Both (IIb) and (IIc) crystallized from dimethylformamide but at different temperatures [(IIb) at room temperature and (IIc) at 277 K].
Compound (I) crystallizes in the orthorhombic space group P212121 with one molecule in the asymmetric unit. The molecule contains a centre of chirality at C5, the absolute configuration of which was not determined due to the absence of significant anomalous scatterers (Fig. 1). The planar side chain (r.m.s. deviation for all non-H atoms = 0.006 Å) is perpendicular [dihedral angle = 89.28 (6)°] to the planar hydantoin ring (r.m.s deviation = 0.026 Å for all non-H atoms). Hydroxyl atom H54 points away from the hydantoin ring and the O—H bond is trans to the C═O bond [O53—C52—O54—H54 = 180 (2)°].
The crystal packing of (I) shows sheets of hydantoin-5-acetic acid molecules, which are parallel to the (012) plane (Fig. 2). The sheets are characterized by R33(15) interactions (Bernstein et al., 1995) with one O—H···O and two N—H···O hydrogen bonds (Table 1). Adjacent sheets are connected via R44(20) patterns which consist of two N—H···O and two O—H···O bonds, building a three-dimensional network in the form of a zigzag pattern (Fig. 3). Interestingly, the N—H···O interactions of the R44(20) patterns are connected via atom O54 of the carboxyl group and not via carbonyl atom O53.
The orotic acid dimethyl sulfoxide (DMSO) monosolvate (IIa) crystallizes in the monoclinic space group P21/c, with one planar orotic acid molecule (r.m.s deviation = 0.038 Å for all non-H atoms) and one DMSO molecule in the asymmetric unit (Fig. 4). The carbonyl O atom of the acid functionality is located in an antiperiplanar arrangement with respect to atom N5 [torsion angle N5—C4—C41—O42 = 176.17 (18)°] and is synperiplanar to atom H43. In the asymmetric unit, the DMSO and orotic acid molecules are connected via an O—H···O hydrogen bond.
In the packing of (IIa), two orotic acid molecules are connected to form a centrosymmetric dimer. These dimers are further connected via DMSO molecules by N—H···O and O—H···O hydrogen bonds (Table 2) to form chains running in the [120] and [120] directions, respectively (Fig. 5).
Compound (IIb) crystallizes from dimethylformamide (DMF) in the triclinic space group P1. Since we did not use a water-free solvent, acidic hydrolysis of DMF, followed by an acid–base reaction with orotic acid, has taken place, resulting in the formation of a dimethylammonium cation (DMC) and an orotate anion. The asymmetric unit of (IIb) contains an orotic acid molecule (A) and an orotate anion (B), both of which are planar (r.m.s deviation for all non-H atoms of molecule A = 0.054 Å; r.m.s deviation of all non-H atoms of anion B = 0.081 Å), and one DMC cation [angle C1X—N2X—C3X = 113.4 (2)°] (Fig. 6). In the asymmetric unit, the molecule A and anion B are connected through a short O—H···O acid bridge [D···A = 2.482 (3) Å; Table 3], while the DMC forms an N—H···O hydrogen bond with anion B. Both molecule A and anion B show slightly twisted acid functionalities, with dihedral angles between the COO groups and the ring planes [r.m.s deviations for all non-H atoms of the ring = 0.018 Å (molecule A) and 0.009 Å (anion B)] of 6.5 (5)° in molecule A and 10.7 (4)° in anion B. Moreover, molecule A and anion B are oriented at an angle of 9.25 (5)° (for all non-H atoms of A and B) with respect to each other. Both molecule A and cation B contain bond lengths of their COO groups which are indicative of double [C41A—O42A = 1.226 (3) Å and C41B—O42B = 1.222 (3) Å] and single bonds [C41A—O43A = 1.281 (3) Å and C41B—O43B = 1.293 (3) Å]. The torsion angle N5A—C4A—C41A—O42A is -3.9 (3)°, while the corresponding angle in anion B is N5B—C4B—C41B—O42B = 9.0 (3)°. In contrast with (IIa), anion B prefers a synperiplanar conformation between atoms N5 and O42 in (IIb).
The crystal packing of (IIb) shows slightly rippled chains (r.m.s deviation of all non-H atoms of the rings = 0.087 Å) of molecules A and anions B, in turn characterized by an R22(8) pattern of two N—H···O bonds and, alternately, one O—H···O interaction. Adjacent chains are connected via R22(8) patterns of two N—H···O hydrogen bonds, resulting in honeycomb-shaped layers parallel to (111). In addition, the DMC connects molecule A and anion B via two N—H···O interactions. Furthermore, `double layers' are formed between adjacent layers by N—H···O interactions between the DMCs and molecules A and anions B, respectively (Fig. 7).
The second dimethylammonium orotate–orotic acid (3/1), (IIc), crystallizes in the monoclinic space group P21. As in (IIb), acid hydrolysis of DMF followed by an acid–base reaction with orotic acid have taken place, yielding three DMCs [angles 112.1 (6) (cation X), 113.7 (8) (cation Y) and 113.8 (7)° (cation Z)], two orotate anions (A and C) and, interestingly, two partially deprotonated orotic acid molecules (B and D), sharing one H atom of the acidic function, within the asymmetric unit (Fig. 8). All orotate anions and orotic acid molecules are essentially planar [r.m.s. deviations of all non-H atoms = 0.103 (anion A), 0.070 (molecule B), 0.027 (anion C) and 0.063 Å (molecule D)] and contain slightly twisted acid functionalities, with dihedral angles between the COO groups and the ring planes [r.m.s. deviations of all non-H atoms of the ring = 0.021 (anion A), 0.014 (molecule B), 0.020 (anion C) and 0.017 Å (molecule D)] of 13.4 (6)° in A, 9.2 (6)° in B, 2.9 (7)° in C and 7.9 (6)° in D. In A and C, similar bond lengths of both carboxy O atoms indicate delocalized charges [C41A—O42A = 1.240 (9) Å and C41A—O43A = 1.258 (9) Å, and C41C—O42C = 1.248 (9) Å and C41C—O43C = 1.282 (9) Å], while in B and D the bond lengths of atoms O42 and O43 are indicative of single [C41B—O43B = 1.297 (8) Å and C41D—O43D = 1.294 (8) Å] and double [C41B—O42B = 1.207 (9) Å and C41D—O42D = 1.232 (9) Å] bonds. In accordance with (IIb) and in contrast with (IIa), molecules B and D in (IIc) prefer a synperiplanar conformation between atoms N5 and O42 [N5B—C4B—C41B—O42B = 7.9 (11)° and N5D—C4D—C41D—O42D = 7.6 (11)°]. In the asymmetric unit, A is connected to C via two bridging DMCs (Y and Z), providing an R44(18) pattern with four N—H···O hydrogen bonds, while the third DMC, X, interacts with molecule D through one N—H···O hydrogen bond. Molecules B and D are connected via a short O—H···O acid bridge formed between atoms O43B and O43D [O···O = 2.433 (6) Å; Table 4].
In the crystal packing of (IIc), two different alternating layer structures parallel to (100), built by entities A, C, Y and Z in one case and entities B, D and X in the other, can be observed. The former layer structure contains chains running along [001] of alternating A and C entities, characterized by N—H···O-bonded R22(8) patterns. In addition, adjacent chains of A and C entities are connected to form rippled layers [r.m.s deviation of all non-H atoms of the rings of A and C = 0.487 Å] through DMCs Y and Z, providing N—H···O-bonded R44(18) patterns and R86(24) interactions of eight N—H···O bonds in turn (Fig. 9). In the second case, distorted honeycomb-shaped and slightly rippled layers [r.m.s deviation of all non-H atoms of the rings of entities B and D = 0.283 Å], which are related to those in (IIb), are observed (Fig. 10). Molecules B and D are arranged alternately and form hydrogen-bonded chains, characterized by R22(8) N—H···O interactions, running in the direction of the c axis. In contrast with (IIb), adjacent chains are linked to form layers by O—H···O interactions of the short acid bridge. Furthermore, the DMCs X in (IIc) connect both layer structures via two N—H···O interactions to form a three-dimensional network, while in (IIb) double layers are formed.
In order to study the preferred conformation of the CH—CH2—═O torsion angle in (I) and the N—C—C═O torsion angle in (II), a Cambridge Structural Database (CSD, Version 5.32 of November 2010 plus five updates; Allen, 2002) substructure search for hydantoin derivatives [(I)] and for orotic acid [(II)] was undertaken. The search for (I) did not yield comparable structures, while for (II), excluding metal-coordinated orotic acid molecules, four entries containing orotate [CSD refcodes AMOROT (Solbakk, 1971), HOXHEI (Nichol & Clegg, 2009), KEDZEZ (Nichol & Clegg, 2006) and TUWCOE (Portalone, 2010)] and two entries with orotic acid molecules [OROTAC (Takusagawa & Shimada, 1973) and OROTAC01 (Portalone, 2008)] were found. In addition, a cocrystal of orotate [Neutral orotic acid?] with pyrimethamine has been reported recently by our group (Tutughamiarso & Bolte, 2011). All CSD entries confirm the synperiplanar conformation between the N atom and the carbonyl O atom, as shown in (IIb) and (IIc). This result is in agreement with a DFT calculation (Bekiroglu & Kristiansson, 2002). In contrast, only the antiperiplanar conformation could be observed in (IIa).