Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615020628/cu3091sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020628/cu3091Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615020628/cu3091IIsup3.hkl |
CCDC references: 1434567; 1434566
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.
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.
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.
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.
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).
C7H6O4·H2O | Z = 2 |
Mr = 172.13 | F(000) = 180 |
Triclinic, P1 | Dx = 1.498 Mg m−3 |
a = 3.8229 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.972 (3) Å | Cell parameters from 2030 reflections |
c = 11.645 (4) Å | θ = 2.4–27.7° |
α = 75.011 (6)° | µ = 0.13 mm−1 |
β = 89.036 (6)° | T = 294 K |
γ = 81.735 (6)° | Block, colourless |
V = 381.7 (3) Å3 | 0.17 × 0.14 × 0.09 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1571 reflections with I > 2σ(I) |
ω scans | Rint = 0.016 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | θmax = 28.4°, θmin = 1.8° |
Tmin = 0.92, Tmax = 0.98 | h = −5→4 |
4459 measured reflections | k = −11→11 |
1769 independent reflections | l = −14→14 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H 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 reflections | Δρmax = 0.27 e Å−3 |
129 parameters | Δρmin = −0.22 e Å−3 |
C7H6O4·H2O | γ = 81.735 (6)° |
Mr = 172.13 | V = 381.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 3.8229 (15) Å | Mo Kα radiation |
b = 8.972 (3) Å | µ = 0.13 mm−1 |
c = 11.645 (4) Å | T = 294 K |
α = 75.011 (6)° | 0.17 × 0.14 × 0.09 mm |
β = 89.036 (6)° |
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 = 0.98 | Rint = 0.016 |
4459 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.27 e Å−3 |
1769 reflections | Δρmin = −0.22 e Å−3 |
129 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1659 (4) | 0.79777 (16) | 0.32778 (12) | 0.0338 (3) | |
C2 | 0.0494 (4) | 0.87721 (16) | 0.21148 (12) | 0.0338 (3) | |
C3 | −0.0823 (4) | 0.79938 (16) | 0.13703 (12) | 0.0359 (3) | |
H3 | −0.1621 | 0.8531 | 0.0605 | 0.043* | |
C4 | −0.0942 (4) | 0.64093 (16) | 0.17770 (13) | 0.0362 (3) | |
C5 | 0.0226 (4) | 0.55906 (16) | 0.29266 (13) | 0.0405 (4) | |
H5 | 0.0147 | 0.4526 | 0.3193 | 0.049* | |
C6 | 0.1490 (4) | 0.63753 (17) | 0.36562 (13) | 0.0383 (3) | |
H6 | 0.2258 | 0.5831 | 0.4424 | 0.046* | |
C7 | 0.3064 (4) | 0.88088 (17) | 0.40467 (12) | 0.0372 (3) | |
O1 | 0.4016 (3) | 0.79804 (14) | 0.51283 (9) | 0.0506 (3) | |
H1O | 0.477 (6) | 0.863 (3) | 0.5503 (19) | 0.065 (6)* | |
O2 | 0.3361 (3) | 1.02112 (13) | 0.37074 (10) | 0.0494 (3) | |
O3 | 0.0611 (3) | 1.03181 (12) | 0.16616 (10) | 0.0474 (3) | |
H2O | 0.164 (7) | 1.060 (3) | 0.220 (2) | 0.081 (7)* | |
O4 | −0.2164 (3) | 0.56037 (13) | 0.10760 (11) | 0.0495 (3) | |
H3O | −0.294 (6) | 0.620 (2) | 0.043 (2) | 0.062 (6)* | |
O1W | −0.4806 (4) | 0.70954 (17) | −0.10993 (13) | 0.0622 (4) | |
H1W | −0.643 (7) | 0.788 (3) | −0.122 (2) | 0.089 (8)* | |
H2W | −0.569 (6) | 0.655 (3) | −0.139 (2) | 0.063 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0356 (7) | 0.0371 (7) | 0.0294 (7) | −0.0070 (5) | −0.0008 (5) | −0.0089 (5) |
C2 | 0.0379 (7) | 0.0315 (6) | 0.0322 (7) | −0.0080 (5) | −0.0004 (5) | −0.0069 (5) |
C3 | 0.0428 (8) | 0.0362 (7) | 0.0290 (7) | −0.0086 (6) | −0.0044 (5) | −0.0069 (5) |
C4 | 0.0378 (7) | 0.0366 (7) | 0.0381 (7) | −0.0090 (6) | 0.0002 (6) | −0.0145 (6) |
C5 | 0.0483 (8) | 0.0310 (7) | 0.0419 (8) | −0.0089 (6) | −0.0018 (6) | −0.0070 (6) |
C6 | 0.0429 (8) | 0.0370 (7) | 0.0321 (7) | −0.0071 (6) | −0.0044 (6) | −0.0029 (6) |
C7 | 0.0410 (8) | 0.0394 (7) | 0.0326 (7) | −0.0078 (6) | −0.0020 (6) | −0.0106 (6) |
O1 | 0.0748 (8) | 0.0476 (7) | 0.0314 (6) | −0.0177 (6) | −0.0124 (5) | −0.0082 (5) |
O2 | 0.0708 (8) | 0.0414 (6) | 0.0387 (6) | −0.0142 (5) | −0.0140 (5) | −0.0112 (5) |
O3 | 0.0714 (8) | 0.0333 (6) | 0.0375 (6) | −0.0154 (5) | −0.0150 (5) | −0.0040 (4) |
O4 | 0.0696 (8) | 0.0393 (6) | 0.0449 (7) | −0.0149 (5) | −0.0119 (6) | −0.0157 (5) |
O1W | 0.0790 (10) | 0.0390 (7) | 0.0690 (9) | −0.0126 (7) | −0.0185 (7) | −0.0111 (6) |
C1—C6 | 1.401 (2) | C5—H5 | 0.9300 |
C1—C2 | 1.404 (2) | C6—H6 | 0.9300 |
C1—C7 | 1.457 (2) | C7—O2 | 1.2387 (18) |
C2—O3 | 1.3574 (18) | C7—O1 | 1.3133 (18) |
C2—C3 | 1.3864 (19) | O1—H1O | 0.89 (2) |
C3—C4 | 1.384 (2) | O3—H2O | 0.86 (3) |
C3—H3 | 0.9300 | O4—H3O | 0.84 (2) |
C4—O4 | 1.3500 (17) | O1W—H1W | 0.86 (3) |
C4—C5 | 1.396 (2) | O1W—H2W | 0.78 (3) |
C5—C6 | 1.368 (2) | ||
C6—C1—C2 | 118.04 (13) | C6—C5—H5 | 120.4 |
C6—C1—C7 | 121.77 (13) | C4—C5—H5 | 120.4 |
C2—C1—C7 | 120.18 (13) | C5—C6—C1 | 121.73 (13) |
O3—C2—C3 | 116.86 (12) | C5—C6—H6 | 119.1 |
O3—C2—C1 | 122.34 (13) | C1—C6—H6 | 119.1 |
C3—C2—C1 | 120.80 (13) | O2—C7—O1 | 121.58 (13) |
C4—C3—C2 | 119.40 (13) | O2—C7—C1 | 122.44 (13) |
C4—C3—H3 | 120.3 | O1—C7—C1 | 115.98 (13) |
C2—C3—H3 | 120.3 | C7—O1—H1O | 106.6 (13) |
O4—C4—C3 | 121.29 (13) | C2—O3—H2O | 105.0 (16) |
O4—C4—C5 | 117.83 (13) | C4—O4—H3O | 110.9 (15) |
C3—C4—C5 | 120.88 (13) | H1W—O1W—H2W | 100 (2) |
C6—C5—C4 | 119.14 (13) | ||
C6—C1—C2—O3 | −178.86 (13) | C3—C4—C5—C6 | 0.2 (2) |
C7—C1—C2—O3 | −0.1 (2) | C4—C5—C6—C1 | −0.3 (2) |
C6—C1—C2—C3 | 0.8 (2) | C2—C1—C6—C5 | −0.2 (2) |
C7—C1—C2—C3 | 179.50 (13) | C7—C1—C6—C5 | −178.87 (14) |
O3—C2—C3—C4 | 178.78 (13) | C6—C1—C7—O2 | 177.01 (14) |
C1—C2—C3—C4 | −0.9 (2) | C2—C1—C7—O2 | −1.7 (2) |
C2—C3—C4—O4 | −179.17 (13) | C6—C1—C7—O1 | −2.8 (2) |
C2—C3—C4—C5 | 0.4 (2) | C2—C1—C7—O1 | 178.52 (13) |
O4—C4—C5—C6 | 179.79 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.89 (2) | 1.78 (2) | 2.6697 (17) | 174 (2) |
O3—H2O···O2 | 0.86 (3) | 1.81 (3) | 2.5938 (17) | 151 (2) |
O4—H3O···O1W | 0.84 (2) | 1.86 (2) | 2.678 (2) | 167 (2) |
O1W—H1W···O3ii | 0.86 (3) | 2.07 (3) | 2.919 (2) | 173 (2) |
O1W—H2W···O4iii | 0.78 (3) | 2.15 (3) | 2.824 (2) | 145 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x−1, −y+2, −z; (iii) −x−1, −y+1, −z. |
C5H6N2O2·C7H6O4·H2O | Dx = 1.500 Mg m−3 |
Mr = 298.25 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 9090 reflections |
a = 26.534 (2) Å | θ = 2.7–28.2° |
b = 6.5377 (6) Å | µ = 0.13 mm−1 |
c = 7.6136 (7) Å | T = 294 K |
V = 1320.7 (2) Å3 | Block, colourless |
Z = 4 | 0.18 × 0.16 × 0.07 mm |
F(000) = 624 |
Bruker SMART APEX CCD area-detector diffractometer | 3077 reflections with I > 2σ(I) |
ω scans | Rint = 0.020 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | θmax = 28.3°, θmin = 3.1° |
Tmin = 0.92, Tmax = 0.98 | h = −35→34 |
14627 measured reflections | k = −8→8 |
3194 independent reflections | l = −10→9 |
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H 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 = 1.04 | Δρmax = 0.20 e Å−3 |
3194 reflections | Δρmin = −0.18 e Å−3 |
219 parameters | Absolute structure: Flack x parameter determined using 1341 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: 0.2 (2) |
C5H6N2O2·C7H6O4·H2O | V = 1320.7 (2) Å3 |
Mr = 298.25 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 26.534 (2) Å | µ = 0.13 mm−1 |
b = 6.5377 (6) Å | T = 294 K |
c = 7.6136 (7) Å | 0.18 × 0.16 × 0.07 mm |
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 = 0.98 | Rint = 0.020 |
14627 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.087 | Δρmax = 0.20 e Å−3 |
S = 1.04 | Δρmin = −0.18 e Å−3 |
3194 reflections | Absolute structure: Flack x parameter determined using 1341 quotients [(I+) - (I-)]/[(I+) + (I-)] (Parsons et al., 2013) |
219 parameters | Absolute structure parameter: 0.2 (2) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.63245 (7) | −0.5232 (3) | 0.4515 (3) | 0.0334 (4) | |
C2 | 0.57978 (7) | −0.5484 (3) | 0.4630 (2) | 0.0329 (4) | |
C3 | 0.55696 (7) | −0.7213 (3) | 0.3949 (3) | 0.0371 (4) | |
H3 | 0.5222 | −0.7364 | 0.4020 | 0.045* | |
C4 | 0.58584 (7) | −0.8720 (3) | 0.3161 (3) | 0.0371 (4) | |
C5 | 0.63837 (7) | −0.8518 (3) | 0.3066 (3) | 0.0401 (4) | |
H5 | 0.6578 | −0.9543 | 0.2559 | 0.048* | |
C6 | 0.66070 (7) | −0.6794 (3) | 0.3727 (3) | 0.0380 (4) | |
H6 | 0.6955 | −0.6656 | 0.3652 | 0.046* | |
C7 | 0.65617 (7) | −0.3381 (3) | 0.5213 (3) | 0.0360 (4) | |
O1 | 0.70436 (6) | −0.3226 (3) | 0.4899 (3) | 0.0564 (5) | |
H1O | 0.7157 (11) | −0.224 (4) | 0.531 (4) | 0.055 (8)* | |
O2 | 0.63225 (5) | −0.2077 (2) | 0.6020 (2) | 0.0444 (3) | |
O3 | 0.54974 (5) | −0.4069 (2) | 0.5413 (2) | 0.0427 (3) | |
H2O | 0.5671 (11) | −0.313 (4) | 0.579 (4) | 0.061 (8)* | |
O4 | 0.56536 (6) | −1.0424 (2) | 0.2458 (3) | 0.0508 (4) | |
H3O | 0.5345 (14) | −1.034 (4) | 0.256 (5) | 0.062 (8)* | |
C8 | 0.56507 (7) | 0.1577 (3) | 0.8385 (3) | 0.0380 (4) | |
C9 | 0.65187 (7) | 0.2824 (3) | 0.8660 (2) | 0.0362 (4) | |
C10 | 0.63331 (8) | 0.4669 (3) | 0.9465 (3) | 0.0377 (4) | |
C11 | 0.58350 (8) | 0.4807 (3) | 0.9724 (3) | 0.0421 (4) | |
H11 | 0.5708 | 0.5972 | 1.0268 | 0.050* | |
C12 | 0.67010 (9) | 0.6289 (4) | 0.9997 (3) | 0.0508 (5) | |
H12A | 0.6522 | 0.7433 | 1.0482 | 0.076* | |
H12B | 0.6889 | 0.6726 | 0.8988 | 0.076* | |
H12C | 0.6928 | 0.5746 | 1.0863 | 0.076* | |
N1 | 0.55043 (6) | 0.3306 (3) | 0.9222 (3) | 0.0427 (4) | |
H1N | 0.5187 (11) | 0.341 (4) | 0.948 (4) | 0.048 (7)* | |
N2 | 0.61612 (6) | 0.1422 (3) | 0.8138 (2) | 0.0382 (4) | |
H2N | 0.6252 (10) | 0.035 (4) | 0.761 (4) | 0.047 (7)* | |
O5 | 0.53593 (6) | 0.0250 (2) | 0.7877 (3) | 0.0522 (4) | |
O6 | 0.69704 (5) | 0.2450 (3) | 0.8414 (2) | 0.0488 (4) | |
O1W | 0.74793 (7) | 0.0080 (3) | 0.6003 (3) | 0.0515 (4) | |
H1W | 0.7303 (12) | 0.082 (5) | 0.661 (4) | 0.059 (9)* | |
H2W | 0.7615 (13) | 0.081 (5) | 0.527 (5) | 0.067 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0255 (8) | 0.0359 (8) | 0.0388 (8) | −0.0007 (6) | −0.0007 (7) | 0.0047 (7) |
C2 | 0.0251 (8) | 0.0369 (9) | 0.0368 (8) | 0.0022 (6) | −0.0013 (7) | 0.0048 (7) |
C3 | 0.0244 (7) | 0.0413 (9) | 0.0456 (9) | −0.0035 (7) | −0.0004 (7) | 0.0046 (8) |
C4 | 0.0334 (9) | 0.0350 (8) | 0.0430 (9) | −0.0032 (7) | 0.0004 (8) | 0.0044 (7) |
C5 | 0.0325 (9) | 0.0368 (9) | 0.0509 (11) | 0.0039 (7) | 0.0049 (8) | 0.0024 (8) |
C6 | 0.0248 (8) | 0.0409 (9) | 0.0485 (10) | 0.0003 (7) | 0.0011 (7) | 0.0058 (8) |
C7 | 0.0284 (8) | 0.0393 (9) | 0.0402 (9) | −0.0018 (7) | −0.0033 (7) | 0.0044 (7) |
O1 | 0.0294 (7) | 0.0537 (9) | 0.0862 (13) | −0.0104 (6) | 0.0037 (7) | −0.0182 (9) |
O2 | 0.0367 (7) | 0.0434 (7) | 0.0530 (8) | −0.0030 (6) | −0.0005 (6) | −0.0074 (7) |
O3 | 0.0257 (6) | 0.0441 (7) | 0.0584 (9) | 0.0008 (6) | 0.0002 (6) | −0.0085 (7) |
O4 | 0.0403 (8) | 0.0411 (7) | 0.0709 (10) | −0.0073 (6) | 0.0037 (8) | −0.0095 (7) |
C8 | 0.0286 (8) | 0.0417 (10) | 0.0435 (10) | −0.0038 (7) | −0.0008 (7) | 0.0080 (8) |
C9 | 0.0290 (8) | 0.0425 (10) | 0.0371 (9) | −0.0023 (7) | −0.0018 (7) | 0.0024 (8) |
C10 | 0.0359 (9) | 0.0376 (9) | 0.0395 (9) | −0.0030 (7) | −0.0025 (8) | 0.0020 (7) |
C11 | 0.0396 (10) | 0.0386 (9) | 0.0480 (11) | 0.0047 (7) | 0.0022 (8) | −0.0002 (8) |
C12 | 0.0498 (12) | 0.0474 (11) | 0.0553 (13) | −0.0119 (9) | −0.0059 (10) | −0.0041 (10) |
N1 | 0.0262 (7) | 0.0468 (9) | 0.0552 (10) | 0.0020 (7) | 0.0036 (7) | 0.0047 (8) |
N2 | 0.0297 (7) | 0.0374 (8) | 0.0476 (9) | −0.0012 (6) | 0.0013 (7) | −0.0029 (7) |
O5 | 0.0342 (7) | 0.0530 (8) | 0.0694 (11) | −0.0134 (6) | −0.0015 (7) | 0.0004 (8) |
O6 | 0.0270 (6) | 0.0599 (9) | 0.0594 (9) | 0.0000 (6) | 0.0004 (6) | −0.0089 (7) |
O1W | 0.0364 (7) | 0.0541 (8) | 0.0639 (11) | −0.0074 (7) | 0.0056 (7) | −0.0082 (9) |
C1—C6 | 1.402 (3) | C8—O5 | 1.225 (2) |
C1—C2 | 1.410 (2) | C8—N1 | 1.354 (3) |
C1—C7 | 1.464 (3) | C8—N2 | 1.372 (2) |
C2—O3 | 1.359 (2) | C9—O6 | 1.238 (2) |
C2—C3 | 1.383 (3) | C9—N2 | 1.378 (2) |
C3—C4 | 1.385 (3) | C9—C10 | 1.440 (3) |
C3—H3 | 0.9300 | C10—C11 | 1.339 (3) |
C4—O4 | 1.350 (2) | C10—C12 | 1.496 (3) |
C4—C5 | 1.402 (3) | C11—N1 | 1.371 (3) |
C5—C6 | 1.369 (3) | C11—H11 | 0.9300 |
C5—H5 | 0.9300 | C12—H12A | 0.9600 |
C6—H6 | 0.9300 | C12—H12B | 0.9600 |
C7—O2 | 1.228 (2) | C12—H12C | 0.9600 |
C7—O1 | 1.305 (2) | N1—H1N | 0.87 (3) |
O1—H1O | 0.78 (3) | N2—H2N | 0.84 (3) |
O3—H2O | 0.82 (3) | O1W—H1W | 0.82 (3) |
O4—H3O | 0.82 (4) | O1W—H2W | 0.82 (4) |
C6—C1—C2 | 118.13 (16) | O5—C8—N2 | 121.9 (2) |
C6—C1—C7 | 121.85 (16) | N1—C8—N2 | 114.18 (17) |
C2—C1—C7 | 120.02 (17) | O6—C9—N2 | 119.44 (18) |
O3—C2—C3 | 117.64 (16) | O6—C9—C10 | 124.15 (18) |
O3—C2—C1 | 121.94 (16) | N2—C9—C10 | 116.41 (16) |
C3—C2—C1 | 120.42 (17) | C11—C10—C9 | 117.19 (17) |
C2—C3—C4 | 120.09 (16) | C11—C10—C12 | 123.78 (19) |
C2—C3—H3 | 120.0 | C9—C10—C12 | 119.02 (18) |
C4—C3—H3 | 120.0 | C10—C11—N1 | 122.84 (18) |
O4—C4—C3 | 122.42 (17) | C10—C11—H11 | 118.6 |
O4—C4—C5 | 117.21 (18) | N1—C11—H11 | 118.6 |
C3—C4—C5 | 120.38 (18) | C10—C12—H12A | 109.5 |
C6—C5—C4 | 119.25 (18) | C10—C12—H12B | 109.5 |
C6—C5—H5 | 120.4 | H12A—C12—H12B | 109.5 |
C4—C5—H5 | 120.4 | C10—C12—H12C | 109.5 |
C5—C6—C1 | 121.72 (16) | H12A—C12—H12C | 109.5 |
C5—C6—H6 | 119.1 | H12B—C12—H12C | 109.5 |
C1—C6—H6 | 119.1 | C8—N1—C11 | 123.03 (17) |
O2—C7—O1 | 122.98 (18) | C8—N1—H1N | 116.9 (19) |
O2—C7—C1 | 122.24 (17) | C11—N1—H1N | 120.0 (19) |
O1—C7—C1 | 114.79 (17) | C8—N2—C9 | 126.24 (18) |
C7—O1—H1O | 112 (2) | C8—N2—H2N | 114.2 (19) |
C2—O3—H2O | 109 (2) | C9—N2—H2N | 119.6 (19) |
C4—O4—H3O | 108 (2) | H1W—O1W—H2W | 107 (3) |
O5—C8—N1 | 123.97 (18) | ||
C6—C1—C2—O3 | 178.27 (18) | C6—C1—C7—O1 | 5.9 (3) |
C7—C1—C2—O3 | −1.5 (3) | C2—C1—C7—O1 | −174.24 (19) |
C6—C1—C2—C3 | −1.2 (3) | O6—C9—C10—C11 | −176.6 (2) |
C7—C1—C2—C3 | 178.96 (18) | N2—C9—C10—C11 | 3.7 (3) |
O3—C2—C3—C4 | −178.97 (18) | O6—C9—C10—C12 | 2.1 (3) |
C1—C2—C3—C4 | 0.6 (3) | N2—C9—C10—C12 | −177.65 (19) |
C2—C3—C4—O4 | −179.17 (19) | C9—C10—C11—N1 | −1.5 (3) |
C2—C3—C4—C5 | 0.8 (3) | C12—C10—C11—N1 | 179.9 (2) |
O4—C4—C5—C6 | 178.6 (2) | O5—C8—N1—C11 | −177.6 (2) |
C3—C4—C5—C6 | −1.4 (3) | N2—C8—N1—C11 | 2.2 (3) |
C4—C5—C6—C1 | 0.7 (3) | C10—C11—N1—C8 | −1.6 (3) |
C2—C1—C6—C5 | 0.6 (3) | O5—C8—N2—C9 | −179.9 (2) |
C7—C1—C6—C5 | −179.57 (19) | N1—C8—N2—C9 | 0.3 (3) |
C6—C1—C7—O2 | −174.42 (19) | O6—C9—N2—C8 | 177.1 (2) |
C2—C1—C7—O2 | 5.4 (3) | C10—C9—N2—C8 | −3.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O1W | 0.78 (3) | 1.82 (3) | 2.591 (2) | 172 (3) |
O3—H2O···O2 | 0.82 (3) | 1.87 (3) | 2.589 (2) | 146 (3) |
O4—H3O···O5i | 0.82 (4) | 1.89 (4) | 2.709 (2) | 177 (3) |
N1—H1N···O3ii | 0.87 (3) | 2.00 (3) | 2.852 (2) | 169 (3) |
N2—H2N···O2 | 0.84 (3) | 2.01 (3) | 2.831 (2) | 167 (3) |
O1W—H1W···O6 | 0.82 (3) | 1.95 (4) | 2.755 (3) | 169 (3) |
O1W—H2W···O6iii | 0.82 (4) | 2.09 (4) | 2.902 (3) | 174 (3) |
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. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C7H6O4·H2O | C5H6N2O2·C7H6O4·H2O |
Mr | 172.13 | 298.25 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pca21 |
Temperature (K) | 294 | 294 |
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 |
V (Å3) | 381.7 (3) | 1320.7 (2) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.13 |
Crystal size (mm) | 0.17 × 0.14 × 0.09 | 0.18 × 0.16 × 0.07 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.92, 0.98 | 0.92, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4459, 1769, 1571 | 14627, 3194, 3077 |
Rint | 0.016 | 0.020 |
(sin θ/λ)max (Å−1) | 0.668 | 0.668 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.133, 1.10 | 0.033, 0.087, 1.04 |
No. of reflections | 1769 | 3194 |
No. of parameters | 129 | 219 |
No. of restraints | 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 |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 | 0.20, −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).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.89 (2) | 1.78 (2) | 2.6697 (17) | 174 (2) |
O3—H2O···O2 | 0.86 (3) | 1.81 (3) | 2.5938 (17) | 151 (2) |
O4—H3O···O1W | 0.84 (2) | 1.86 (2) | 2.678 (2) | 167 (2) |
O1W—H1W···O3ii | 0.86 (3) | 2.07 (3) | 2.919 (2) | 173 (2) |
O1W—H2W···O4iii | 0.78 (3) | 2.15 (3) | 2.824 (2) | 145 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x−1, −y+2, −z; (iii) −x−1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O1W | 0.78 (3) | 1.82 (3) | 2.591 (2) | 172 (3) |
O3—H2O···O2 | 0.82 (3) | 1.87 (3) | 2.589 (2) | 146 (3) |
O4—H3O···O5i | 0.82 (4) | 1.89 (4) | 2.709 (2) | 177 (3) |
N1—H1N···O3ii | 0.87 (3) | 2.00 (3) | 2.852 (2) | 169 (3) |
N2—H2N···O2 | 0.84 (3) | 2.01 (3) | 2.831 (2) | 167 (3) |
O1W—H1W···O6 | 0.82 (3) | 1.95 (4) | 2.755 (3) | 169 (3) |
O1W—H2W···O6iii | 0.82 (4) | 2.09 (4) | 2.902 (3) | 174 (3) |
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. |