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Multicomponent crystals or cocrystals play a significant role in crystal engineering, the main objective of which is to understand the role of inter­molecular inter­actions and to utilize such understanding in the design of novel crystal structures. Mol­ecules possessing carb­oxy­lic acid and amide functional groups are good candidates for forming cocrystals. β-Resorcylic acid monohydrate, C7H6O4·H2O, (I), crystallizes in the triclinic space group P\overline{1} with one β-resorcylic acid mol­ecule and one water mol­ecule in the asymmetric unit. The cocrystal thymine–β-resorcylic acid–water (1/1/1), C5H6N2O2·C7H6O4·H2O, (II), crystallizes in the ortho­rhom­bic space group Pca21, with one mol­ecule each of thymine, β-resorcylic acid and water in the asymmetric unit. All available donor and acceptor atoms in (I) and (II) are utilized for hydrogen bonding. The acid and amide functional groups are well known for the formation of self-complementary acid–acid and amide–amide homosynthons. In (I), an acid–acid homosynthon is observed, while in (II), an amide–acid heterosynthon is present. In (I), the β-resorcylic acid mol­ecule exhibits the expected intra­molecular S(6) motif between the hy­droxy and carbonyl O atoms, and an inter­molecular R22(8) dimer motif between the carb­oxy­lic acid groups; only the former motif is observed in (II). The water solvent mol­ecule in (I) propagates the discrete dimers into two-dimensional hydrogen-bonded sheets. In (II), thymine and β-resorcylic acid molecules do not form self-complementary amide–amide and acid–acid homo­syn­thons; instead, a thymine–β-resorcylic acid heterosynthon is observed. With the help of the water mol­ecule, this heterosynthon is aggregated into a three-dimensional hydrogen-bonded network. The absence of thymine base pairing in (II) might be linked to the availability of additional functional groups and the preference of the donor and acceptor hydrogen-bond combinations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615020628/cu3091sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020628/cu3091Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020628/cu3091IIsup3.hkl
Contains datablock II

CCDC references: 1434567; 1434566

Introduction top

The main objective of crystal engineering is to understand the role of inter­molecular inter­actions and to utilize such understanding in the design of novel crystal structures. Hydrogen bonding has been recognized as one of the most effective tools for generating supra­molecular assemblies from discrete ionic or molecular building blocks due to its strength and directionality (Steed & Atwood, 2000; Desiraju, 1989, 1996). Multicomponent crystals or cocrystals play a significant role in the context of crystal engineering. Good candidates for forming cocrystals are molecules possessing carb­oxy­lic acid and/or amide functional groups. Both of these functional groups are well known for the formation of self-complementary acid–acid and amide–amide homosynthons. They are also present in several biological systems and drug molecules. Thymine is a pyrimidine-based nucleobase possessing both donor and acceptor atoms and is well known for the formation of amide–amide homosynthon base pairing (Ozeki et al., 1969; Portalone et al., 1999). Similarly, β-resorcylic acid (or 2,4-di­hydroxy­benzoic acid) also forms an acid–acid homosynthon (Parkin et al., 2007). Our intention here is to study whether or not the two donor- and acceptor-rich molecules retain their self-complementary synthons on cocrystallization. Accordingly, the nucleobases cytosine and thymine were taken to cocrystallize with β-resorcylic acid. Unexpectedly, the hydrated form, (I), of β-resorcylic acid was obtained from the cocrystallization of cytosine–β-resorcylic acid, while thymine–β-resorcylic acid, (II), was obtained from the cocrystallization of thymine with β-resorcylic acid. The crystal structures of (I) and (II) are reported in order to study and understand their molecular assemblies in the solid state.

Experimental top

Synthesis and crystallization top

Cytosine, thymine (both from Sigma–Aldrich India) and β-resorcylic acid (Himedia Laboratories, Hyderabad) were used as received for the attempted preparation of cocrystals in a methanol–water mixture. Cytosine (0.025 g, 0.23 mmol) and β-resorcylic acid (0.035 g, 0.23 mmol) were dissolved in a mixture of methanol and water (20 ml, 1:1 v/v). The resulting solution was warmed [To what temperature?] and allowed to stand for slow evaporation at room temperature. On completion of the evaporation of the solvent, we found very few transparent crystals, which were later found to be the β-resorcylic acid hydrate, (I), by single-crystal X-ray diffraction analysis. Thymine (0.25 g, 0.20 mmol) and β-resorcylic acid (0.031 g, 0.20 mmol) were dissolved in a mixture of methanol and water (25 ml, 2:1 v/v). The resulting solution was warmed [To what temperature?] and allowed to stand for slow evaporation at room temperature. Crystals of (II) formed over a period of 10 d.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. The O-bound H atoms of the β-resorcylic acid and water molecules of (I) and (II) and the N-bound H atoms of the thymine molecule of (II) were located in difference-density maps and refined isotropically. The C-bound H atoms were also located in difference-density maps, but were positioned geometrically and included as riding atoms, with C—H = 0.93 Å for aromatic and C—H = 0.96 Å for methyl H atoms, and with Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for the other H atoms.

Results and discussion top

β-Resorcylic acid monohydrate, (I), crystallizes in the triclinic space group P1 with one β-resorcylic acid molecule and one water molecule in the asymmetric unit (Fig. 1). The structures of the parent β-resorcylic acid (Parkin et al., 2007; measured at 90, 100, 110 and 150 K) and of its hemihydrate (Horneffer et al., 1999; Braun et al., 2011) have been reported previously. The molecular geometry of (I) is in good agreement with these reported structures. The thymine–β-resorcylic acid–water (1/1/1) cocrystal, (II) (orthorhombic space group Pca21), has one molecule each of thymine, β-resorcylic acid and water in the asymmetric unit (Fig. 2). The molecular geometry of (II) is within the normal ranges (Allen et al., 1987) and similar to reported values (Ozeki et al., 1969; Portalone et al., 1999; Gerdil, 1961). The β-resorcylic acid molecule can exist in either a cis or a trans conformation based on the ortho-hy­droxy H-atom positions (C5—C4—O4—H). Of these two conformations, trans is considered to be the global minimum conformer compared with cis (Braun et al., 2011). The structures of the parent β-resorcylic acid and (I) and (II) reveal the trans conformation [-175.6, 176 (2) and -178 (2)°, respectively], while the hemihydrate structure prefers both cis [-5(2)°] and trans [178 (2)°] conformations.

In (I), the β-resorcylic acid molecule exhibits an intra­molecular S(6) motif (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995) between the hy­droxy O3 and carbonyl O2 atoms, and an inter­molecular carb­oxy­lic acid R22(8) dimer motif (O1—H1O···O2i; for symmetry, see Table 2). The water molecule , as donor and acceptor, links the β-resorcylic acid molecule into a two-dimensional supra­molecular hydrogen-bonded network. The water molecule links the β-resorcylic acid molecules in two ways. Firstly, as donor and acceptor, the water molecule links the β-resorcylic acid molecule and its inversion-related counterpart via hy­droxy atom O4 and forms a tetra­meric R44(8) motif. The R44(8) and R22(8) motifs are arranged alternately and generate an infinite one-dimensional chain along the b axis. Secondly, the remaining donor H atom of the water molecule inter­links adjacent chains via hy­droxy atom O3 of the β-resorcylic acid molecule and forms tetra­meric R44(16) and hexameric R66(32) motifs. Thus, the water molecule propagates the discrete β-resorcylic acid dimer into two-dimensional hydrogen-bonded sheets along the (001) plane (Fig. 3)

In the thymine–β-resorcylic acid–water (1/1/1) cocrystal, (II), O—H···O and N—H···O hydrogen bonds (Table 3) are responsible for the formation of three-dimensional hydrogen-bonded networks. As observed in (I), the β-resorcylic acid molecule forms an intra­molecular S(6) motif in (II). Both N atoms (N1 and N2) of the thymine molecule link carbonyl atom O2 of the β-resorcylic acid molecule and hy­droxy atom O3 of the screw-related molecule at (-x + 1, -y, z + 1/2) into an infinite zigzag chain along the c axis. Hy­droxy atom O4 of the β-resorcylic acid molecule, in turn, links the screw-related (-x + 1, -y - 1, z - 1/2) carbonyl atom O5 of the thymine molecule and generates a hexameric R66(32) motif. Thus, the thymine and β-resorcylic acid molecules link with each other in a zigzag fashion and produce a two-dimensional hydrogen-bonded network along the (100) plane. The water molecule plays a dual role as donor and acceptor, and links the thymine and β-resorcylic acid molecules. As donor, the water molecule links the thymine molecule and its glide-related counterpart at (-x + 3/2, y, z - 1/2) through carbonyl atom O6, while as acceptor it is connected to atom O1 of the β-resorcylic acid molecule. Thus, the water molecule bridges the thymine and β-resorcylic acid zigzag chains with an adjacent chain along the c axis [is this clear enough?], leading to the formation of a three-dimensional hydrogen-bonded network along the (100) plane (Fig. 4).

Thymine–thymine base pairing (Fig. 5a) is considered to be one of the robust amide–amide homosynthons observed in the structures of the parent thymine (Ozeki et al., 1969; Portalone et al., 1999), thymine monohydrate (Gerdil, 1961) and thymine complexes. Except for the adenine–thymine–water (2/1/4) cocrystal (Chandrasekhar et al., 2010), all other reported thymine complexes, including our four recently published cocrystals of thymine with phenolic coformers (Sridhar et al., 2015), have the above-mentioned base pair. In the former case, the thymine molecule links the adenine base pair. Structure (II) differs from the previously reported thymine complexes in that an amide–acid heterosynthon (Fig. 5b) is observed instead of the robust amide–amide homosynthon. The results for (II) are in line with our earlier study (Sridhar et al., 2015) showing that the utilization of the donor and acceptor atoms of thymine may vary according to the coformer and its ability to form robust hydrogen-bonding motifs.

The parent, hemihydrate and hydrated, i.e. (I), structures of β-resorcyclic acid follow the hydrogen-bonding rules described by Etter (1990, 1991), who established the anti­cipated hydrogen-bond patterns for several well studied functional groups. According to this rule: (i) all good H-atom donors and acceptors are used in hydrogen bonding; (ii) intra­molecular six-membered ring hydrogen bonds form in preference to inter­molecular hydrogen bonds; and (iii) the best H-atom donors and acceptors remaining after intra­molecular hydrogen-bond formation form inter­molecular hydrogen bonds. In the above three structures, the propagation of the R22(8) dimer into a one-dimensional chain is seen. However, in the parent and hemihydrated structures, the propagation is achieved through the hy­droxy atoms (Figs. 5c and 5d), while in hydrated structure (I) the propagation is completed with the help of the water molecule (Fig. 5e). As stated by Etter, in all three structures, firstly all donor and acceptor atoms are utilized in hydrogen bonding, followed by the formation of intra­molecular S(6) and inter­molecular R22(8) dimer motifs. The remaining donor and acceptor atoms [hy­droxy groups in the parent β-resorcylic acid molecule, a hy­droxy group and a water molecule in the hemihydrate, and a water molecule in (I)] are involved in inter­molecular hydrogen bonding to aggregate the molecules into two- or three-dimensional networks in the crystal packing.

In cocrystal (II), the intra­molecular S(6) motif is observed in the β-resorcylic acid molecule, which is followed by thymine–resorcylic acid and thymine–water–resorcylic acid heterosynthon inter­actions. When the Etter rule is applied to (II), the first two points are well established, as all the donor and acceptor atoms are utilized for hydrogen bonding and governed by intra­molecular and inter­molecular inter­actions. Based on rule (iii), there are six donor NH atoms from pyrimidine, [three?] OH atoms from carb­oxy­lic acid, hy­droxy and water groups, and three carbonyl acceptor O atoms from thymine and resorcylic acid. The best donor–acceptor pairing of (II) involves the hy­droxy OH group and carbonyl O atom, followed by the pyrimidine NH group and hy­droxy and carbonyl O atoms. This is clearly reflected in resorcylic acid–water, resorcylic acid–thymine and water–thymine inter­actions through carb­oxy–water O—H···O, hy­droxy–carbonyl O—H···O and water–carbonyl O—H···O hydrogen bonds. The remaining donor–acceptor pair forms a further inter­action, viz. pyrimidine–carbonyl N—H···O and pyrimidine–hy­droxy N—H···O, between thymine and resorcylic acid. [Not totally clear?] It is evident from these observations that rule (iii) might be the deciding factor, particularly for cocrystal formation. Thus, in (II), both thymine and β-resorcylic acid do not form the expected self-associated acid–acid and amide–amide pairs because of the presence of the functional groups and the preferences of the donor and acceptor combinations.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top
[Figure 1] Fig. 1. The molecular components of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The molecular components of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the discrete acid–acid [R22(8) motif] homosynthon of β-resorcylic acid, further propagated by water molecules into two-dimensional hydrogen-bonded sheets. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding are labelled. [Symmetry codes: (i) -x + 1, -y + 2, -z + 1; (ii) -x - 1, -y + 2, -z; (iii) -x - 1, -y + 1, -z.]
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing adjacent thymine–β-resorcylic acid linkages connected by water molecules, thereby generating three-dimensional hydrogen-bonded networks. The encircled area represents the hexameric R66(32) motif formed by the thymine and β-resorcylic acid linkage, shown on the right in a different orientation for a better view. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding are labelled. [Symmetry codes: (i) -x + 1, -y - 1, z - 1/2; (ii) -x + 1, -y, z + 1/2; (iii) -x + 3/2, y, z - 1/2.]
[Figure 5] Fig. 5. (a) Thymine–thymine base pairing in the parent thymine. (b) Thymine–β-resorcylic acid heterosynthon interactions in (II). (c) The propagation of the R22(8) dimer in the parent β-resorcylic acid, (d) in the hemihydrate and (e) in monohydrate (I). Hydroxy groups aggregate the dimers into a one-dimensional chain in parts (a) and (b). Also in part (b), water molecules interlink the one-dimensional chains. In part (d), water molecules help to achieve the propagation, and A and B represent two independent thymine molecules.
(I) 2,4-Dihydroxybenzoic acid monohydrate top
Crystal data top
C7H6O4·H2OZ = 2
Mr = 172.13F(000) = 180
Triclinic, P1Dx = 1.498 Mg m3
a = 3.8229 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.972 (3) ÅCell parameters from 2030 reflections
c = 11.645 (4) Åθ = 2.4–27.7°
α = 75.011 (6)°µ = 0.13 mm1
β = 89.036 (6)°T = 294 K
γ = 81.735 (6)°Block, colourless
V = 381.7 (3) Å30.17 × 0.14 × 0.09 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1571 reflections with I > 2σ(I)
ω scansRint = 0.016
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
θmax = 28.4°, θmin = 1.8°
Tmin = 0.92, Tmax = 0.98h = 54
4459 measured reflectionsk = 1111
1769 independent reflectionsl = 1414
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133 w = 1/[σ2(Fo2) + (0.0687P)2 + 0.0752P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1769 reflectionsΔρmax = 0.27 e Å3
129 parametersΔρmin = 0.22 e Å3
Crystal data top
C7H6O4·H2Oγ = 81.735 (6)°
Mr = 172.13V = 381.7 (3) Å3
Triclinic, P1Z = 2
a = 3.8229 (15) ÅMo Kα radiation
b = 8.972 (3) ŵ = 0.13 mm1
c = 11.645 (4) ÅT = 294 K
α = 75.011 (6)°0.17 × 0.14 × 0.09 mm
β = 89.036 (6)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1769 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1571 reflections with I > 2σ(I)
Tmin = 0.92, Tmax = 0.98Rint = 0.016
4459 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.27 e Å3
1769 reflectionsΔρmin = 0.22 e Å3
129 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1659 (4)0.79777 (16)0.32778 (12)0.0338 (3)
C20.0494 (4)0.87721 (16)0.21148 (12)0.0338 (3)
C30.0823 (4)0.79938 (16)0.13703 (12)0.0359 (3)
H30.16210.85310.06050.043*
C40.0942 (4)0.64093 (16)0.17770 (13)0.0362 (3)
C50.0226 (4)0.55906 (16)0.29266 (13)0.0405 (4)
H50.01470.45260.31930.049*
C60.1490 (4)0.63753 (17)0.36562 (13)0.0383 (3)
H60.22580.58310.44240.046*
C70.3064 (4)0.88088 (17)0.40467 (12)0.0372 (3)
O10.4016 (3)0.79804 (14)0.51283 (9)0.0506 (3)
H1O0.477 (6)0.863 (3)0.5503 (19)0.065 (6)*
O20.3361 (3)1.02112 (13)0.37074 (10)0.0494 (3)
O30.0611 (3)1.03181 (12)0.16616 (10)0.0474 (3)
H2O0.164 (7)1.060 (3)0.220 (2)0.081 (7)*
O40.2164 (3)0.56037 (13)0.10760 (11)0.0495 (3)
H3O0.294 (6)0.620 (2)0.043 (2)0.062 (6)*
O1W0.4806 (4)0.70954 (17)0.10993 (13)0.0622 (4)
H1W0.643 (7)0.788 (3)0.122 (2)0.089 (8)*
H2W0.569 (6)0.655 (3)0.139 (2)0.063 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0356 (7)0.0371 (7)0.0294 (7)0.0070 (5)0.0008 (5)0.0089 (5)
C20.0379 (7)0.0315 (6)0.0322 (7)0.0080 (5)0.0004 (5)0.0069 (5)
C30.0428 (8)0.0362 (7)0.0290 (7)0.0086 (6)0.0044 (5)0.0069 (5)
C40.0378 (7)0.0366 (7)0.0381 (7)0.0090 (6)0.0002 (6)0.0145 (6)
C50.0483 (8)0.0310 (7)0.0419 (8)0.0089 (6)0.0018 (6)0.0070 (6)
C60.0429 (8)0.0370 (7)0.0321 (7)0.0071 (6)0.0044 (6)0.0029 (6)
C70.0410 (8)0.0394 (7)0.0326 (7)0.0078 (6)0.0020 (6)0.0106 (6)
O10.0748 (8)0.0476 (7)0.0314 (6)0.0177 (6)0.0124 (5)0.0082 (5)
O20.0708 (8)0.0414 (6)0.0387 (6)0.0142 (5)0.0140 (5)0.0112 (5)
O30.0714 (8)0.0333 (6)0.0375 (6)0.0154 (5)0.0150 (5)0.0040 (4)
O40.0696 (8)0.0393 (6)0.0449 (7)0.0149 (5)0.0119 (6)0.0157 (5)
O1W0.0790 (10)0.0390 (7)0.0690 (9)0.0126 (7)0.0185 (7)0.0111 (6)
Geometric parameters (Å, º) top
C1—C61.401 (2)C5—H50.9300
C1—C21.404 (2)C6—H60.9300
C1—C71.457 (2)C7—O21.2387 (18)
C2—O31.3574 (18)C7—O11.3133 (18)
C2—C31.3864 (19)O1—H1O0.89 (2)
C3—C41.384 (2)O3—H2O0.86 (3)
C3—H30.9300O4—H3O0.84 (2)
C4—O41.3500 (17)O1W—H1W0.86 (3)
C4—C51.396 (2)O1W—H2W0.78 (3)
C5—C61.368 (2)
C6—C1—C2118.04 (13)C6—C5—H5120.4
C6—C1—C7121.77 (13)C4—C5—H5120.4
C2—C1—C7120.18 (13)C5—C6—C1121.73 (13)
O3—C2—C3116.86 (12)C5—C6—H6119.1
O3—C2—C1122.34 (13)C1—C6—H6119.1
C3—C2—C1120.80 (13)O2—C7—O1121.58 (13)
C4—C3—C2119.40 (13)O2—C7—C1122.44 (13)
C4—C3—H3120.3O1—C7—C1115.98 (13)
C2—C3—H3120.3C7—O1—H1O106.6 (13)
O4—C4—C3121.29 (13)C2—O3—H2O105.0 (16)
O4—C4—C5117.83 (13)C4—O4—H3O110.9 (15)
C3—C4—C5120.88 (13)H1W—O1W—H2W100 (2)
C6—C5—C4119.14 (13)
C6—C1—C2—O3178.86 (13)C3—C4—C5—C60.2 (2)
C7—C1—C2—O30.1 (2)C4—C5—C6—C10.3 (2)
C6—C1—C2—C30.8 (2)C2—C1—C6—C50.2 (2)
C7—C1—C2—C3179.50 (13)C7—C1—C6—C5178.87 (14)
O3—C2—C3—C4178.78 (13)C6—C1—C7—O2177.01 (14)
C1—C2—C3—C40.9 (2)C2—C1—C7—O21.7 (2)
C2—C3—C4—O4179.17 (13)C6—C1—C7—O12.8 (2)
C2—C3—C4—C50.4 (2)C2—C1—C7—O1178.52 (13)
O4—C4—C5—C6179.79 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.89 (2)1.78 (2)2.6697 (17)174 (2)
O3—H2O···O20.86 (3)1.81 (3)2.5938 (17)151 (2)
O4—H3O···O1W0.84 (2)1.86 (2)2.678 (2)167 (2)
O1W—H1W···O3ii0.86 (3)2.07 (3)2.919 (2)173 (2)
O1W—H2W···O4iii0.78 (3)2.15 (3)2.824 (2)145 (2)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x1, y+2, z; (iii) x1, y+1, z.
(II) 5-Methylpyrimidine-2,4(1H,3H)-dione–2,4-dihydroxybenzoic acid–water (1/1/1) top
Crystal data top
C5H6N2O2·C7H6O4·H2ODx = 1.500 Mg m3
Mr = 298.25Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca21Cell parameters from 9090 reflections
a = 26.534 (2) Åθ = 2.7–28.2°
b = 6.5377 (6) ŵ = 0.13 mm1
c = 7.6136 (7) ÅT = 294 K
V = 1320.7 (2) Å3Block, colourless
Z = 40.18 × 0.16 × 0.07 mm
F(000) = 624
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3077 reflections with I > 2σ(I)
ω scansRint = 0.020
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
θmax = 28.3°, θmin = 3.1°
Tmin = 0.92, Tmax = 0.98h = 3534
14627 measured reflectionsk = 88
3194 independent reflectionsl = 109
Refinement top
Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.033 w = 1/[σ2(Fo2) + (0.053P)2 + 0.1622P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.087(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.20 e Å3
3194 reflectionsΔρmin = 0.18 e Å3
219 parametersAbsolute structure: Flack x parameter determined using 1341 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons et al., 2013)
1 restraintAbsolute structure parameter: 0.2 (2)
Crystal data top
C5H6N2O2·C7H6O4·H2OV = 1320.7 (2) Å3
Mr = 298.25Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 26.534 (2) ŵ = 0.13 mm1
b = 6.5377 (6) ÅT = 294 K
c = 7.6136 (7) Å0.18 × 0.16 × 0.07 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3194 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
3077 reflections with I > 2σ(I)
Tmin = 0.92, Tmax = 0.98Rint = 0.020
14627 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.087Δρmax = 0.20 e Å3
S = 1.04Δρmin = 0.18 e Å3
3194 reflectionsAbsolute structure: Flack x parameter determined using 1341 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons et al., 2013)
219 parametersAbsolute structure parameter: 0.2 (2)
1 restraint
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.63245 (7)0.5232 (3)0.4515 (3)0.0334 (4)
C20.57978 (7)0.5484 (3)0.4630 (2)0.0329 (4)
C30.55696 (7)0.7213 (3)0.3949 (3)0.0371 (4)
H30.52220.73640.40200.045*
C40.58584 (7)0.8720 (3)0.3161 (3)0.0371 (4)
C50.63837 (7)0.8518 (3)0.3066 (3)0.0401 (4)
H50.65780.95430.25590.048*
C60.66070 (7)0.6794 (3)0.3727 (3)0.0380 (4)
H60.69550.66560.36520.046*
C70.65617 (7)0.3381 (3)0.5213 (3)0.0360 (4)
O10.70436 (6)0.3226 (3)0.4899 (3)0.0564 (5)
H1O0.7157 (11)0.224 (4)0.531 (4)0.055 (8)*
O20.63225 (5)0.2077 (2)0.6020 (2)0.0444 (3)
O30.54974 (5)0.4069 (2)0.5413 (2)0.0427 (3)
H2O0.5671 (11)0.313 (4)0.579 (4)0.061 (8)*
O40.56536 (6)1.0424 (2)0.2458 (3)0.0508 (4)
H3O0.5345 (14)1.034 (4)0.256 (5)0.062 (8)*
C80.56507 (7)0.1577 (3)0.8385 (3)0.0380 (4)
C90.65187 (7)0.2824 (3)0.8660 (2)0.0362 (4)
C100.63331 (8)0.4669 (3)0.9465 (3)0.0377 (4)
C110.58350 (8)0.4807 (3)0.9724 (3)0.0421 (4)
H110.57080.59721.02680.050*
C120.67010 (9)0.6289 (4)0.9997 (3)0.0508 (5)
H12A0.65220.74331.04820.076*
H12B0.68890.67260.89880.076*
H12C0.69280.57461.08630.076*
N10.55043 (6)0.3306 (3)0.9222 (3)0.0427 (4)
H1N0.5187 (11)0.341 (4)0.948 (4)0.048 (7)*
N20.61612 (6)0.1422 (3)0.8138 (2)0.0382 (4)
H2N0.6252 (10)0.035 (4)0.761 (4)0.047 (7)*
O50.53593 (6)0.0250 (2)0.7877 (3)0.0522 (4)
O60.69704 (5)0.2450 (3)0.8414 (2)0.0488 (4)
O1W0.74793 (7)0.0080 (3)0.6003 (3)0.0515 (4)
H1W0.7303 (12)0.082 (5)0.661 (4)0.059 (9)*
H2W0.7615 (13)0.081 (5)0.527 (5)0.067 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0255 (8)0.0359 (8)0.0388 (8)0.0007 (6)0.0007 (7)0.0047 (7)
C20.0251 (8)0.0369 (9)0.0368 (8)0.0022 (6)0.0013 (7)0.0048 (7)
C30.0244 (7)0.0413 (9)0.0456 (9)0.0035 (7)0.0004 (7)0.0046 (8)
C40.0334 (9)0.0350 (8)0.0430 (9)0.0032 (7)0.0004 (8)0.0044 (7)
C50.0325 (9)0.0368 (9)0.0509 (11)0.0039 (7)0.0049 (8)0.0024 (8)
C60.0248 (8)0.0409 (9)0.0485 (10)0.0003 (7)0.0011 (7)0.0058 (8)
C70.0284 (8)0.0393 (9)0.0402 (9)0.0018 (7)0.0033 (7)0.0044 (7)
O10.0294 (7)0.0537 (9)0.0862 (13)0.0104 (6)0.0037 (7)0.0182 (9)
O20.0367 (7)0.0434 (7)0.0530 (8)0.0030 (6)0.0005 (6)0.0074 (7)
O30.0257 (6)0.0441 (7)0.0584 (9)0.0008 (6)0.0002 (6)0.0085 (7)
O40.0403 (8)0.0411 (7)0.0709 (10)0.0073 (6)0.0037 (8)0.0095 (7)
C80.0286 (8)0.0417 (10)0.0435 (10)0.0038 (7)0.0008 (7)0.0080 (8)
C90.0290 (8)0.0425 (10)0.0371 (9)0.0023 (7)0.0018 (7)0.0024 (8)
C100.0359 (9)0.0376 (9)0.0395 (9)0.0030 (7)0.0025 (8)0.0020 (7)
C110.0396 (10)0.0386 (9)0.0480 (11)0.0047 (7)0.0022 (8)0.0002 (8)
C120.0498 (12)0.0474 (11)0.0553 (13)0.0119 (9)0.0059 (10)0.0041 (10)
N10.0262 (7)0.0468 (9)0.0552 (10)0.0020 (7)0.0036 (7)0.0047 (8)
N20.0297 (7)0.0374 (8)0.0476 (9)0.0012 (6)0.0013 (7)0.0029 (7)
O50.0342 (7)0.0530 (8)0.0694 (11)0.0134 (6)0.0015 (7)0.0004 (8)
O60.0270 (6)0.0599 (9)0.0594 (9)0.0000 (6)0.0004 (6)0.0089 (7)
O1W0.0364 (7)0.0541 (8)0.0639 (11)0.0074 (7)0.0056 (7)0.0082 (9)
Geometric parameters (Å, º) top
C1—C61.402 (3)C8—O51.225 (2)
C1—C21.410 (2)C8—N11.354 (3)
C1—C71.464 (3)C8—N21.372 (2)
C2—O31.359 (2)C9—O61.238 (2)
C2—C31.383 (3)C9—N21.378 (2)
C3—C41.385 (3)C9—C101.440 (3)
C3—H30.9300C10—C111.339 (3)
C4—O41.350 (2)C10—C121.496 (3)
C4—C51.402 (3)C11—N11.371 (3)
C5—C61.369 (3)C11—H110.9300
C5—H50.9300C12—H12A0.9600
C6—H60.9300C12—H12B0.9600
C7—O21.228 (2)C12—H12C0.9600
C7—O11.305 (2)N1—H1N0.87 (3)
O1—H1O0.78 (3)N2—H2N0.84 (3)
O3—H2O0.82 (3)O1W—H1W0.82 (3)
O4—H3O0.82 (4)O1W—H2W0.82 (4)
C6—C1—C2118.13 (16)O5—C8—N2121.9 (2)
C6—C1—C7121.85 (16)N1—C8—N2114.18 (17)
C2—C1—C7120.02 (17)O6—C9—N2119.44 (18)
O3—C2—C3117.64 (16)O6—C9—C10124.15 (18)
O3—C2—C1121.94 (16)N2—C9—C10116.41 (16)
C3—C2—C1120.42 (17)C11—C10—C9117.19 (17)
C2—C3—C4120.09 (16)C11—C10—C12123.78 (19)
C2—C3—H3120.0C9—C10—C12119.02 (18)
C4—C3—H3120.0C10—C11—N1122.84 (18)
O4—C4—C3122.42 (17)C10—C11—H11118.6
O4—C4—C5117.21 (18)N1—C11—H11118.6
C3—C4—C5120.38 (18)C10—C12—H12A109.5
C6—C5—C4119.25 (18)C10—C12—H12B109.5
C6—C5—H5120.4H12A—C12—H12B109.5
C4—C5—H5120.4C10—C12—H12C109.5
C5—C6—C1121.72 (16)H12A—C12—H12C109.5
C5—C6—H6119.1H12B—C12—H12C109.5
C1—C6—H6119.1C8—N1—C11123.03 (17)
O2—C7—O1122.98 (18)C8—N1—H1N116.9 (19)
O2—C7—C1122.24 (17)C11—N1—H1N120.0 (19)
O1—C7—C1114.79 (17)C8—N2—C9126.24 (18)
C7—O1—H1O112 (2)C8—N2—H2N114.2 (19)
C2—O3—H2O109 (2)C9—N2—H2N119.6 (19)
C4—O4—H3O108 (2)H1W—O1W—H2W107 (3)
O5—C8—N1123.97 (18)
C6—C1—C2—O3178.27 (18)C6—C1—C7—O15.9 (3)
C7—C1—C2—O31.5 (3)C2—C1—C7—O1174.24 (19)
C6—C1—C2—C31.2 (3)O6—C9—C10—C11176.6 (2)
C7—C1—C2—C3178.96 (18)N2—C9—C10—C113.7 (3)
O3—C2—C3—C4178.97 (18)O6—C9—C10—C122.1 (3)
C1—C2—C3—C40.6 (3)N2—C9—C10—C12177.65 (19)
C2—C3—C4—O4179.17 (19)C9—C10—C11—N11.5 (3)
C2—C3—C4—C50.8 (3)C12—C10—C11—N1179.9 (2)
O4—C4—C5—C6178.6 (2)O5—C8—N1—C11177.6 (2)
C3—C4—C5—C61.4 (3)N2—C8—N1—C112.2 (3)
C4—C5—C6—C10.7 (3)C10—C11—N1—C81.6 (3)
C2—C1—C6—C50.6 (3)O5—C8—N2—C9179.9 (2)
C7—C1—C6—C5179.57 (19)N1—C8—N2—C90.3 (3)
C6—C1—C7—O2174.42 (19)O6—C9—N2—C8177.1 (2)
C2—C1—C7—O25.4 (3)C10—C9—N2—C83.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O1W0.78 (3)1.82 (3)2.591 (2)172 (3)
O3—H2O···O20.82 (3)1.87 (3)2.589 (2)146 (3)
O4—H3O···O5i0.82 (4)1.89 (4)2.709 (2)177 (3)
N1—H1N···O3ii0.87 (3)2.00 (3)2.852 (2)169 (3)
N2—H2N···O20.84 (3)2.01 (3)2.831 (2)167 (3)
O1W—H1W···O60.82 (3)1.95 (4)2.755 (3)169 (3)
O1W—H2W···O6iii0.82 (4)2.09 (4)2.902 (3)174 (3)
Symmetry codes: (i) x+1, y1, z1/2; (ii) x+1, y, z+1/2; (iii) x+3/2, y, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC7H6O4·H2OC5H6N2O2·C7H6O4·H2O
Mr172.13298.25
Crystal system, space groupTriclinic, P1Orthorhombic, Pca21
Temperature (K)294294
a, b, c (Å)3.8229 (15), 8.972 (3), 11.645 (4)26.534 (2), 6.5377 (6), 7.6136 (7)
α, β, γ (°)75.011 (6), 89.036 (6), 81.735 (6)90, 90, 90
V3)381.7 (3)1320.7 (2)
Z24
Radiation typeMo KαMo Kα
µ (mm1)0.130.13
Crystal size (mm)0.17 × 0.14 × 0.090.18 × 0.16 × 0.07
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Multi-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.92, 0.980.92, 0.98
No. of measured, independent and
observed [I > 2σ(I)] reflections
4459, 1769, 1571 14627, 3194, 3077
Rint0.0160.020
(sin θ/λ)max1)0.6680.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.133, 1.10 0.033, 0.087, 1.04
No. of reflections17693194
No. of parameters129219
No. of restraints01
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.220.20, 0.18
Absolute structure?Flack x parameter determined using 1341 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons et al., 2013)
Absolute structure parameter?0.2 (2)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.89 (2)1.78 (2)2.6697 (17)174 (2)
O3—H2O···O20.86 (3)1.81 (3)2.5938 (17)151 (2)
O4—H3O···O1W0.84 (2)1.86 (2)2.678 (2)167 (2)
O1W—H1W···O3ii0.86 (3)2.07 (3)2.919 (2)173 (2)
O1W—H2W···O4iii0.78 (3)2.15 (3)2.824 (2)145 (2)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x1, y+2, z; (iii) x1, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O1W0.78 (3)1.82 (3)2.591 (2)172 (3)
O3—H2O···O20.82 (3)1.87 (3)2.589 (2)146 (3)
O4—H3O···O5i0.82 (4)1.89 (4)2.709 (2)177 (3)
N1—H1N···O3ii0.87 (3)2.00 (3)2.852 (2)169 (3)
N2—H2N···O20.84 (3)2.01 (3)2.831 (2)167 (3)
O1W—H1W···O60.82 (3)1.95 (4)2.755 (3)169 (3)
O1W—H2W···O6iii0.82 (4)2.09 (4)2.902 (3)174 (3)
Symmetry codes: (i) x+1, y1, z1/2; (ii) x+1, y, z+1/2; (iii) x+3/2, y, z1/2.
 

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