Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616007403/sk3624sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007403/sk3624Isup5.hkl | |
Chemdraw file https://doi.org/10.1107/S2053229616007403/sk3624Isup7.cdx | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616007403/sk3624IIsup6.hkl |
CCDC references: 1477887; 1477886
4-Hydroxypyrimidine derivatives are an important class of biomolecules which includes nucleobases (e.g. thymine, uracil and cytosine) and many pharmaceuticals (Sharma et al., 2014). In solution, 4-hydroxypyrimidines are known to undergo keto–enol tautomerization to the pyrimidin-4(1H)-one and pyrimidin-4(3H)-one forms. The relative stability of pyrimidine tautomers has been assessed both computationally and experimentally and can vary based on the functionality and position of other ring substitutents (Sanchez et al., 2007; Giuliano et al., 2010; Galvão et al., 2013). The frequency with which different tautomeric forms of 4-hydroxypyrimidines are observed in the solid state varies greatly, but generally reflects their relative stability.
The original goal of this study was to cocrystallize the less stable 4-hydroxy tautomer of 2-amino-5,6-dimethylpyrimidin-4-one with a molecule that has a complementary hydrogen-bond acceptor–donor–acceptor motif. A similar approach to isolating less stable tautomeric forms has been used recently for other systems (Epa et al., 2013; Juribašić et al., 2014). Though our efforts to cocrystallize 2-amino-5,6-dimethyl-4-hydroxypyrimidine (ADP) and uric acid (UA) were not successful, crystallization from aqueous solutions with and without uric acid resulted in different tautomeric forms. Triclinic ADP crystals, form (I), were obtained from aqueous or ethanolic solutions of pure ADP, while monoclinic ADP crystals, form (II), formed from aqueous solutions containing a 4:1 ratio of ADP and UA.
2-Amino-5,6-dimethyl-4-hydroxypyrimidine (ADP, 96%) and uric acid (UA, 99+%) were purchased from Sigma–Aldrich. Ethyl alcohol (190 proof) was purchased from Warner–Graham Company. All reagents were used as received. Deionized water was filtered through a Barnstead deionizing cartridge and distilled prior to use. Crystallization of aqueous solutions of ADP at room temperature yielded triclinic single crystals of form (I). Crystallization from ethanol also yielded fine powder of (I). 4:1 Molar ratios of ADP and UA were ground using a mortar and pestle and dissolved in water. Slow evaporation of this solution at room temperature yielded prismatic monoclinic crystals of form (II).
Differential scanning calorimetry (DSC) showed that each material undergoes melting/decomposition above 573 K with no other observable phase changes at lower temperature. IR spectra were collected using a Nicolet 380 FT–IR spectrometer (Thermo Electron Corporation) with removable KBr optics. The spectra were collected from 4000 to 400 cm-1 averaged over 16 scans with a resolution of 1 cm-1. The OMNIC (Thermo Nicolet Analytical Instruments, Madison, Wisconsin) software package was used for analysis.
Powder X-ray diffraction data were collected on a Rigaku Rapid/XRD diffractometer with Cu Kα radiation (λ = 1.5418 Å) at a tube voltage of 40 kV and a current of 30 mA, and analyzed with JADE software (Materials Data, 2003). Data was collected over a 2θ range of 5–40° at a scan speed of 1.0 ° min-1.
Crystal data, data collection and structure refinement details are summarized in Table 1. The ADP (I) structural model consists of one 1H molecule per asymmetric unit.H atoms on N atoms were located in difference maps and their positions refined to good hydrogen-bonding locations. The N1—H13 distance was restrained to 0.96 (2) Å. Methyl H-atom positions were optimized by rotation about Me—C bonds, with idealized C—H, Me—H, and H···H distances. Methyl and amine H atom Uiso values were assigned as 1.5 times Ueq of the carrier atom; remaining H atom Uiso values were assigned as 1.2 times the carrier Ueq.
The ADP (II) structural model consists of two 1H and two 3H molecules per asymmetric unit.H atoms on N atoms were located in a difference map and their positions refined to good hydrogen-bonding locations. Methyl H-atom positions were optimized by rotation about Me—C bonds, with idealized C—H, Me—H, and H···H distances. Methyl and amine H atom Uiso values were assigned as 1.5 times Ueq of the carrier atom.
Single-crystal X-ray diffraction on an ADP crystal obtained by recrystallization from water gave a triclinic structure, form (I), with an asymmetric unit consisting of one 2-amino-5,6-dimethylpyrimidin-4(1H)-one molecule (Fig. 1). Pyrimidin-4(1H)-one molecules assemble into one-dimensional hydrogen-bonded ribbons in the [100] direction (Fig. 2). Each O atom hydrogen bonds to both H—N1 and H2N(C2) to form an [MISSING] motif and is also part of a C(6) motif along the a axis. Molecules in adjacent antiparallel C(6) chains also form cyclic [MISSING] dimers between atom N3 and the H2N(C2) group. Adjacent ribbons form π–π stacks along the b axis with a centroid–centroid distance between N1—C2—N3—C4—C5—C6 rings of 3.680 (18) Å.
The size of the displacement ellipsoids on the C, N and O atoms and the C═O bond length [1.259 (4) Å] suggest the presence of only one tautomer at low temperature. However, the IR spectra of the crystalline material show an intense broad signal in the range 2900–3300 cm-1, indicative of O—H stretching (Fig. 3). We therefore suspect that some intermolecular H-atom transfer between N1—H···O and N1···H—O [N1···O = 2.784 (4) Å] likely occurs, even if it is not observed in the X-ray diffraction data. Differences in the temperature at which data were collected (X-ray at 100 K and IR at 298 K) may also be a factor. Notably, powder X-ray diffraction patterns of ADP recrystallized from water or ethanol and unrecrystallized ADP are all in good agreement with the simulated PXRD pattern of form (I) (Fig. 4). No additional diffraction lines are present which suggest the presence of phase impurities.
Our efforts to isolate the 4-hydroxy tautomer through cocrystallization with uric acid, which is most stable in its diketo form, were not successful. Instead, aqueous solutions containing both components yielded ADP form (II). The asymmetric unit of ADP (II) consists of four unique molecules, including two 4(1H)-tautomers (molecules B and C) and two 4(3H)-tautomers (molecules A and D). The complementary nature of the donor–acceptor–acceptor groups in the 4(1H)-tautomer and the acceptor–donor–donor groups in the 4(3H)-tautomer allows pairs of A and B molecules (or C and D molecules) to triply hydrogen bond to one another in a Watson–Crick-like motif (Fig. 5). Two of the three hydrogen bonds are of the form (C4)O···H—N(C2), with the third between the central N3···H—N3. This triply hydrogen-bonded motif can only be achieved with a 1:1 mixture of the 4(1H)- and 4(3H)-tautomeric forms and is not possible if only one tautomer is present.
Each (0k0) layer consists of either A and B molecules or C and D molecules. Within a given layer, the triply hydrogen-bonded dimers form a two-dimensional network of π–π stacks. The Cg1···Cg2 centroid–centroid distance (Cg1 is the centroid of the N1A—C2A—N3A—C4A—C5A—C6A ring and Cg2 is the centroid of the N1B—C2B—N3B—C4B—C5B—C6B ring) is 3.8162 (16) Å and the Cg3···Cg4 centroid–centroid distance (Cg3 is the centroid of the N1C—C2C—N3C—C4C—C5C—C6C ring and Cg4 is the centroid of the N1D—C2D—N3D—C4D—C5D—C6D ring) is 3.4844 (16) Å. The π-stacking direction alternates in adjacent layers. In layers formed from A and B molecules, the π-stack direction is parallel to (101). In layers formed from C and D molecules, the π-stack direction is parallel to (100). Hydrogen bonds between O···H—N1 and O···H—N(C2) serve to connect adjacent AB and CD layers along the b axis, forming a three-dimensional hydrogen-bond network.
In the packing arrangements of both ADP forms (I) and (II), all donor and acceptor atoms are satisfied. Form (I) (157.3 Å3 per molecule) is slightly more dense than form (II) (164.59 Å3 per molecule), however, differential scanning calorimetry did not show any solid-state transformations in either material before their eventual decomposition at around 573 K.
A search of the Cambridge Structure Database (Version 5.37, November 2015; Groom & Allen, 2014) yielded only 12 entries for 4-hydroxypyrimidines, 42 entries for pyrimidin-4(1H)-ones, and 168 entries for pyrimidin-4(3H)-ones, after excluding larger heterocycles. Closer analysis showed that like ADP, 63% of the entries possess an amino substituent at the C2 position. This makes the distribution of tautomers all the more interesting. Of the pyrimidin-4(3H)-one and 4-hydroxypyrimidine tautomers in the CSD, 96/168 (57%) and 6/12 (50%) have an amino group at C2, respectively. In contrast, 40/42 (95%) of the pyrimidin-4(1H)-one tautomer structures in the CSD have an amino group in the 2-position [only CERZEF (Maistralis et al., 1991) and TAGVIG (Xiong et al., 2006) do not]. This suggests that the 2-amino group affords special opportunities to achieve favorable packing motifs between 1H-tautomers or between 11H- and 3H-tautomers that may not be possible with other substituted pyrimidin-4-ones. 13 CSD entries have both pyrimidin-4(3H)-one and pyrimidin-4(1H)-one tautomers present within the same lattice [refcodes CERZEF (Xiong et al., 2006), ICYTIN (Sharma & McConnell, 1965), ICYTIN01 (Portalone & Colapietro, 2007), LEJLAN, LEJLOB, LEJMES, and LEJMIW (Bannister et al., 1994), MECXUP (Tutughamiarso & Egert, 2012), MINVIP01 (Portalone & Irrera, 2011), OQURAU and OQUREY (Gerhardt et al., 2011), QOBCIV (Radhakrishnan et al., 2014) and ZERMIS (Toledo et al., 1995)]. The same kind of triple hydrogen-bonding motif seen in Fig. 6 between 1H- and 3H-tautomers is observed in 11/13 cases. The only exceptions are CERZEF (Xiong et al., 2006), which does not have an amino group at C2, and possibly ZERMIS (Toledo et al., 1995), for which three-dimensional coordinates are not given.
We believe that the isolation of the 4-hydroxy tautomer of the title compound through crystallization, either in a single component or cocrystal form, remains an open possibility assuming the right solution conditions can be identified. For other 4-hydroxypyrimidines with 2-amino substituents, efforts to isolate the 4-hydroxy tautomer may also simultaneously need to consider ways to inhibit the cocrystallization of the 4(3H) and 4(1H) tautomers with one another.
4-Hydroxypyrimidine derivatives are an important class of biomolecules which includes nucleobases (e.g. thymine, uracil and cytosine) and many pharmaceuticals (Sharma et al., 2014). In solution, 4-hydroxypyrimidines are known to undergo keto–enol tautomerization to the pyrimidin-4(1H)-one and pyrimidin-4(3H)-one forms. The relative stability of pyrimidine tautomers has been assessed both computationally and experimentally and can vary based on the functionality and position of other ring substitutents (Sanchez et al., 2007; Giuliano et al., 2010; Galvão et al., 2013). The frequency with which different tautomeric forms of 4-hydroxypyrimidines are observed in the solid state varies greatly, but generally reflects their relative stability.
The original goal of this study was to cocrystallize the less stable 4-hydroxy tautomer of 2-amino-5,6-dimethylpyrimidin-4-one with a molecule that has a complementary hydrogen-bond acceptor–donor–acceptor motif. A similar approach to isolating less stable tautomeric forms has been used recently for other systems (Epa et al., 2013; Juribašić et al., 2014). Though our efforts to cocrystallize 2-amino-5,6-dimethyl-4-hydroxypyrimidine (ADP) and uric acid (UA) were not successful, crystallization from aqueous solutions with and without uric acid resulted in different tautomeric forms. Triclinic ADP crystals, form (I), were obtained from aqueous or ethanolic solutions of pure ADP, while monoclinic ADP crystals, form (II), formed from aqueous solutions containing a 4:1 ratio of ADP and UA.
Differential scanning calorimetry (DSC) showed that each material undergoes melting/decomposition above 573 K with no other observable phase changes at lower temperature. IR spectra were collected using a Nicolet 380 FT–IR spectrometer (Thermo Electron Corporation) with removable KBr optics. The spectra were collected from 4000 to 400 cm-1 averaged over 16 scans with a resolution of 1 cm-1. The OMNIC (Thermo Nicolet Analytical Instruments, Madison, Wisconsin) software package was used for analysis.
Powder X-ray diffraction data were collected on a Rigaku Rapid/XRD diffractometer with Cu Kα radiation (λ = 1.5418 Å) at a tube voltage of 40 kV and a current of 30 mA, and analyzed with JADE software (Materials Data, 2003). Data was collected over a 2θ range of 5–40° at a scan speed of 1.0 ° min-1.
Single-crystal X-ray diffraction on an ADP crystal obtained by recrystallization from water gave a triclinic structure, form (I), with an asymmetric unit consisting of one 2-amino-5,6-dimethylpyrimidin-4(1H)-one molecule (Fig. 1). Pyrimidin-4(1H)-one molecules assemble into one-dimensional hydrogen-bonded ribbons in the [100] direction (Fig. 2). Each O atom hydrogen bonds to both H—N1 and H2N(C2) to form an [MISSING] motif and is also part of a C(6) motif along the a axis. Molecules in adjacent antiparallel C(6) chains also form cyclic [MISSING] dimers between atom N3 and the H2N(C2) group. Adjacent ribbons form π–π stacks along the b axis with a centroid–centroid distance between N1—C2—N3—C4—C5—C6 rings of 3.680 (18) Å.
The size of the displacement ellipsoids on the C, N and O atoms and the C═O bond length [1.259 (4) Å] suggest the presence of only one tautomer at low temperature. However, the IR spectra of the crystalline material show an intense broad signal in the range 2900–3300 cm-1, indicative of O—H stretching (Fig. 3). We therefore suspect that some intermolecular H-atom transfer between N1—H···O and N1···H—O [N1···O = 2.784 (4) Å] likely occurs, even if it is not observed in the X-ray diffraction data. Differences in the temperature at which data were collected (X-ray at 100 K and IR at 298 K) may also be a factor. Notably, powder X-ray diffraction patterns of ADP recrystallized from water or ethanol and unrecrystallized ADP are all in good agreement with the simulated PXRD pattern of form (I) (Fig. 4). No additional diffraction lines are present which suggest the presence of phase impurities.
Our efforts to isolate the 4-hydroxy tautomer through cocrystallization with uric acid, which is most stable in its diketo form, were not successful. Instead, aqueous solutions containing both components yielded ADP form (II). The asymmetric unit of ADP (II) consists of four unique molecules, including two 4(1H)-tautomers (molecules B and C) and two 4(3H)-tautomers (molecules A and D). The complementary nature of the donor–acceptor–acceptor groups in the 4(1H)-tautomer and the acceptor–donor–donor groups in the 4(3H)-tautomer allows pairs of A and B molecules (or C and D molecules) to triply hydrogen bond to one another in a Watson–Crick-like motif (Fig. 5). Two of the three hydrogen bonds are of the form (C4)O···H—N(C2), with the third between the central N3···H—N3. This triply hydrogen-bonded motif can only be achieved with a 1:1 mixture of the 4(1H)- and 4(3H)-tautomeric forms and is not possible if only one tautomer is present.
Each (0k0) layer consists of either A and B molecules or C and D molecules. Within a given layer, the triply hydrogen-bonded dimers form a two-dimensional network of π–π stacks. The Cg1···Cg2 centroid–centroid distance (Cg1 is the centroid of the N1A—C2A—N3A—C4A—C5A—C6A ring and Cg2 is the centroid of the N1B—C2B—N3B—C4B—C5B—C6B ring) is 3.8162 (16) Å and the Cg3···Cg4 centroid–centroid distance (Cg3 is the centroid of the N1C—C2C—N3C—C4C—C5C—C6C ring and Cg4 is the centroid of the N1D—C2D—N3D—C4D—C5D—C6D ring) is 3.4844 (16) Å. The π-stacking direction alternates in adjacent layers. In layers formed from A and B molecules, the π-stack direction is parallel to (101). In layers formed from C and D molecules, the π-stack direction is parallel to (100). Hydrogen bonds between O···H—N1 and O···H—N(C2) serve to connect adjacent AB and CD layers along the b axis, forming a three-dimensional hydrogen-bond network.
In the packing arrangements of both ADP forms (I) and (II), all donor and acceptor atoms are satisfied. Form (I) (157.3 Å3 per molecule) is slightly more dense than form (II) (164.59 Å3 per molecule), however, differential scanning calorimetry did not show any solid-state transformations in either material before their eventual decomposition at around 573 K.
A search of the Cambridge Structure Database (Version 5.37, November 2015; Groom & Allen, 2014) yielded only 12 entries for 4-hydroxypyrimidines, 42 entries for pyrimidin-4(1H)-ones, and 168 entries for pyrimidin-4(3H)-ones, after excluding larger heterocycles. Closer analysis showed that like ADP, 63% of the entries possess an amino substituent at the C2 position. This makes the distribution of tautomers all the more interesting. Of the pyrimidin-4(3H)-one and 4-hydroxypyrimidine tautomers in the CSD, 96/168 (57%) and 6/12 (50%) have an amino group at C2, respectively. In contrast, 40/42 (95%) of the pyrimidin-4(1H)-one tautomer structures in the CSD have an amino group in the 2-position [only CERZEF (Maistralis et al., 1991) and TAGVIG (Xiong et al., 2006) do not]. This suggests that the 2-amino group affords special opportunities to achieve favorable packing motifs between 1H-tautomers or between 11H- and 3H-tautomers that may not be possible with other substituted pyrimidin-4-ones. 13 CSD entries have both pyrimidin-4(3H)-one and pyrimidin-4(1H)-one tautomers present within the same lattice [refcodes CERZEF (Xiong et al., 2006), ICYTIN (Sharma & McConnell, 1965), ICYTIN01 (Portalone & Colapietro, 2007), LEJLAN, LEJLOB, LEJMES, and LEJMIW (Bannister et al., 1994), MECXUP (Tutughamiarso & Egert, 2012), MINVIP01 (Portalone & Irrera, 2011), OQURAU and OQUREY (Gerhardt et al., 2011), QOBCIV (Radhakrishnan et al., 2014) and ZERMIS (Toledo et al., 1995)]. The same kind of triple hydrogen-bonding motif seen in Fig. 6 between 1H- and 3H-tautomers is observed in 11/13 cases. The only exceptions are CERZEF (Xiong et al., 2006), which does not have an amino group at C2, and possibly ZERMIS (Toledo et al., 1995), for which three-dimensional coordinates are not given.
We believe that the isolation of the 4-hydroxy tautomer of the title compound through crystallization, either in a single component or cocrystal form, remains an open possibility assuming the right solution conditions can be identified. For other 4-hydroxypyrimidines with 2-amino substituents, efforts to isolate the 4-hydroxy tautomer may also simultaneously need to consider ways to inhibit the cocrystallization of the 4(3H) and 4(1H) tautomers with one another.
2-Amino-5,6-dimethyl-4-hydroxypyrimidine (ADP, 96%) and uric acid (UA, 99+%) were purchased from Sigma–Aldrich. Ethyl alcohol (190 proof) was purchased from Warner–Graham Company. All reagents were used as received. Deionized water was filtered through a Barnstead deionizing cartridge and distilled prior to use. Crystallization of aqueous solutions of ADP at room temperature yielded triclinic single crystals of form (I). Crystallization from ethanol also yielded fine powder of (I). 4:1 Molar ratios of ADP and UA were ground using a mortar and pestle and dissolved in water. Slow evaporation of this solution at room temperature yielded prismatic monoclinic crystals of form (II).
Crystal data, data collection and structure refinement details are summarized in Table 1. The ADP (I) structural model consists of one 1H molecule per asymmetric unit.H atoms on N atoms were located in difference maps and their positions refined to good hydrogen-bonding locations. The N1—H13 distance was restrained to 0.96 (2) Å. Methyl H-atom positions were optimized by rotation about Me—C bonds, with idealized C—H, Me—H, and H···H distances. Methyl and amine H atom Uiso values were assigned as 1.5 times Ueq of the carrier atom; remaining H atom Uiso values were assigned as 1.2 times the carrier Ueq.
The ADP (II) structural model consists of two 1H and two 3H molecules per asymmetric unit.H atoms on N atoms were located in a difference map and their positions refined to good hydrogen-bonding locations. Methyl H-atom positions were optimized by rotation about Me—C bonds, with idealized C—H, Me—H, and H···H distances. Methyl and amine H atom Uiso values were assigned as 1.5 times Ueq of the carrier atom.
For both compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT, XPREP, and SADABS (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2014). Software used to prepare material for publication: XCIF (Bruker, 2014) and publCIF (Westrip, 2010) for (I); XCIF (Bruker, 2014) for (II).
C6H9N3O | Z = 2 |
Mr = 139.16 | F(000) = 148 |
Triclinic, P1 | Dx = 1.469 Mg m−3 |
a = 6.613 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.018 (3) Å | Cell parameters from 1892 reflections |
c = 7.078 (3) Å | θ = 2.9–28.6° |
α = 97.374 (10)° | µ = 0.11 mm−1 |
β = 104.521 (9)° | T = 100 K |
γ = 92.038 (10)° | Prism, colorless |
V = 314.6 (2) Å3 | 0.35 × 0.06 × 0.02 mm |
Bruker Kappa/APEXII CCD diffractometer | 1096 independent reflections |
Radiation source: microfocus sealed tube | 794 reflections with I > 2σ(I) |
Multilayer mirrors monochromator | Rint = 0.056 |
profile data from φ and ω scans | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −7→7 |
Tmin = 0.854, Tmax = 0.977 | k = −8→8 |
4211 measured reflections | l = −8→8 |
Refinement on F2 | 1 restraint |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.228 | w = 1/[σ2(Fo2) + (0.1559P)2 + 0.0319P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1096 reflections | Δρmax = 0.50 e Å−3 |
102 parameters | Δρmin = −0.31 e Å−3 |
C6H9N3O | γ = 92.038 (10)° |
Mr = 139.16 | V = 314.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.613 (2) Å | Mo Kα radiation |
b = 7.018 (3) Å | µ = 0.11 mm−1 |
c = 7.078 (3) Å | T = 100 K |
α = 97.374 (10)° | 0.35 × 0.06 × 0.02 mm |
β = 104.521 (9)° |
Bruker Kappa/APEXII CCD diffractometer | 1096 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 794 reflections with I > 2σ(I) |
Tmin = 0.854, Tmax = 0.977 | Rint = 0.056 |
4211 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 1 restraint |
wR(F2) = 0.228 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.50 e Å−3 |
1096 reflections | Δρmin = −0.31 e Å−3 |
102 parameters |
Experimental. One distinct cell was identified using APEX2 (Bruker, 2014). Six frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2014) then corrected for absorption by integration using SAINT/SADABS v2014/4 (Bruker, 2014) to sort, merge, and scale the combined data. No decay correction was applied. |
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. Structure was phased by direct methods (Sheldrick, 2015). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude and resolution. |
x | y | z | Uiso*/Ueq | ||
N3 | 0.3585 (4) | 0.3790 (4) | 0.2614 (4) | 0.0143 (7) | |
N1 | 0.5735 (4) | 0.2759 (4) | 0.0536 (4) | 0.0130 (7) | |
H13 | 0.719 (3) | 0.273 (5) | 0.055 (5) | 0.020* | |
O9 | 0.0084 (3) | 0.3244 (3) | 0.1458 (3) | 0.0186 (7) | |
C5 | 0.2078 (5) | 0.2263 (4) | −0.0796 (5) | 0.0141 (8) | |
N10 | 0.7190 (5) | 0.4194 (4) | 0.3730 (4) | 0.0169 (8) | |
H11 | 0.854 (7) | 0.416 (5) | 0.353 (6) | 0.025* | |
H12 | 0.705 (6) | 0.485 (5) | 0.482 (6) | 0.025* | |
C6 | 0.4050 (5) | 0.2090 (4) | −0.1002 (5) | 0.0133 (8) | |
C4 | 0.1864 (5) | 0.3122 (4) | 0.1130 (5) | 0.0142 (8) | |
C8 | 0.0142 (5) | 0.1676 (5) | −0.2415 (5) | 0.0211 (9) | |
H14 | −0.0874 | 0.2655 | −0.2379 | 0.032* | |
H15 | −0.0465 | 0.0437 | −0.2239 | 0.032* | |
H16 | 0.0493 | 0.1552 | −0.3688 | 0.032* | |
C2 | 0.5471 (5) | 0.3598 (4) | 0.2305 (5) | 0.0125 (8) | |
C7 | 0.4579 (5) | 0.1211 (4) | −0.2867 (5) | 0.0159 (8) | |
H17 | 0.3373 | 0.0396 | −0.3708 | 0.024* | |
H18 | 0.5781 | 0.0428 | −0.2529 | 0.024* | |
H19 | 0.4927 | 0.2238 | −0.3573 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N3 | 0.0131 (16) | 0.0152 (14) | 0.0163 (15) | 0.0009 (11) | 0.0057 (13) | 0.0042 (12) |
N1 | 0.0095 (15) | 0.0167 (14) | 0.0141 (15) | 0.0017 (11) | 0.0049 (12) | 0.0028 (11) |
O9 | 0.0112 (13) | 0.0205 (13) | 0.0259 (15) | 0.0006 (9) | 0.0082 (11) | 0.0037 (11) |
C5 | 0.0158 (19) | 0.0110 (15) | 0.0161 (18) | −0.0003 (13) | 0.0041 (15) | 0.0036 (13) |
N10 | 0.0156 (17) | 0.0239 (16) | 0.0105 (15) | 0.0017 (12) | 0.0033 (13) | 0.0004 (12) |
C6 | 0.0163 (19) | 0.0097 (15) | 0.0150 (17) | 0.0002 (13) | 0.0050 (14) | 0.0036 (13) |
C4 | 0.0147 (19) | 0.0105 (15) | 0.0192 (19) | 0.0015 (12) | 0.0055 (15) | 0.0072 (13) |
C8 | 0.018 (2) | 0.0194 (17) | 0.024 (2) | −0.0002 (14) | 0.0021 (16) | 0.0007 (15) |
C2 | 0.0137 (18) | 0.0093 (15) | 0.0146 (18) | 0.0023 (13) | 0.0014 (15) | 0.0059 (13) |
C7 | 0.0158 (19) | 0.0169 (16) | 0.0159 (18) | 0.0013 (13) | 0.0059 (14) | 0.0015 (14) |
N3—C2 | 1.328 (4) | N10—H11 | 0.94 (5) |
N3—C4 | 1.362 (4) | N10—H12 | 0.87 (4) |
N1—C6 | 1.368 (4) | C6—C7 | 1.511 (4) |
N1—C2 | 1.369 (4) | C8—H14 | 0.9800 |
N1—H13 | 0.961 (18) | C8—H15 | 0.9800 |
O9—C4 | 1.259 (4) | C8—H16 | 0.9800 |
C5—C6 | 1.356 (5) | C7—H17 | 0.9800 |
C5—C4 | 1.461 (5) | C7—H18 | 0.9800 |
C5—C8 | 1.492 (4) | C7—H19 | 0.9800 |
N10—C2 | 1.330 (4) | ||
C2—N3—C4 | 119.0 (3) | C5—C8—H14 | 109.5 |
C6—N1—C2 | 121.0 (3) | C5—C8—H15 | 109.5 |
C6—N1—H13 | 127 (2) | H14—C8—H15 | 109.5 |
C2—N1—H13 | 112 (2) | C5—C8—H16 | 109.5 |
C6—C5—C4 | 117.1 (3) | H14—C8—H16 | 109.5 |
C6—C5—C8 | 124.2 (3) | H15—C8—H16 | 109.5 |
C4—C5—C8 | 118.7 (3) | N3—C2—N10 | 120.8 (3) |
C2—N10—H11 | 123 (2) | N3—C2—N1 | 121.9 (3) |
C2—N10—H12 | 118 (3) | N10—C2—N1 | 117.3 (3) |
H11—N10—H12 | 118 (4) | C6—C7—H17 | 109.5 |
C5—C6—N1 | 120.2 (3) | C6—C7—H18 | 109.5 |
C5—C6—C7 | 124.7 (3) | H17—C7—H18 | 109.5 |
N1—C6—C7 | 115.2 (3) | C6—C7—H19 | 109.5 |
O9—C4—N3 | 118.6 (3) | H17—C7—H19 | 109.5 |
O9—C4—C5 | 120.7 (3) | H18—C7—H19 | 109.5 |
N3—C4—C5 | 120.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···O9i | 0.96 (2) | 1.87 (2) | 2.784 (4) | 159 (3) |
N10—H11···O9i | 0.94 (5) | 2.04 (4) | 2.837 (4) | 142 (3) |
N10—H12···N3ii | 0.87 (4) | 2.09 (4) | 2.956 (4) | 173 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
C6H9N3O | F(000) = 1184 |
Mr = 139.16 | Dx = 1.404 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1880 (7) Å | Cell parameters from 9541 reflections |
b = 28.047 (3) Å | θ = 2.7–25.5° |
c = 13.3265 (15) Å | µ = 0.10 mm−1 |
β = 101.414 (3)° | T = 100 K |
V = 2633.5 (5) Å3 | Needle, colorless |
Z = 16 | 0.26 × 0.05 × 0.01 mm |
Bruker Kappa/APEXII CCD diffractometer | 4745 independent reflections |
Radiation source: microfocus sealed tube | 3217 reflections with I > 2σ(I) |
Multilayer mirrors monochromator | Rint = 0.067 |
profile data from φ and ω scans | θmax = 25.4°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −8→7 |
Tmin = 0.700, Tmax = 0.746 | k = −33→33 |
33593 measured reflections | l = −16→16 |
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)] = 0.062 | w = 1/[σ2(Fo2) + (0.0387P)2 + 3.4581P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.130 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.30 e Å−3 |
4745 reflections | Δρmin = −0.32 e Å−3 |
406 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0022 (3) |
C6H9N3O | V = 2633.5 (5) Å3 |
Mr = 139.16 | Z = 16 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1880 (7) Å | µ = 0.10 mm−1 |
b = 28.047 (3) Å | T = 100 K |
c = 13.3265 (15) Å | 0.26 × 0.05 × 0.01 mm |
β = 101.414 (3)° |
Bruker Kappa/APEXII CCD diffractometer | 4745 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 3217 reflections with I > 2σ(I) |
Tmin = 0.700, Tmax = 0.746 | Rint = 0.067 |
33593 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.30 e Å−3 |
4745 reflections | Δρmin = −0.32 e Å−3 |
406 parameters |
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. Structure was phased by direct methods (Sheldrick, 2015). Systematic conditions suggested the ambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F2. The final map had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude and resolution. |
x | y | z | Uiso*/Ueq | ||
N1A | −0.0812 (3) | 0.42666 (8) | 0.84144 (17) | 0.0173 (6) | |
N3A | 0.1001 (4) | 0.49006 (8) | 0.79636 (18) | 0.0152 (6) | |
H13A | 0.201 (4) | 0.5002 (10) | 0.765 (2) | 0.023* | |
N10A | 0.1790 (4) | 0.41269 (9) | 0.7674 (2) | 0.0197 (6) | |
H11A | 0.180 (4) | 0.3822 (12) | 0.787 (2) | 0.029* | |
H12A | 0.271 (5) | 0.4248 (11) | 0.741 (2) | 0.029* | |
O9A | 0.0389 (3) | 0.56753 (7) | 0.82337 (15) | 0.0229 (5) | |
C2A | 0.0627 (4) | 0.44259 (10) | 0.8028 (2) | 0.0163 (7) | |
C4A | −0.0039 (4) | 0.52512 (10) | 0.8327 (2) | 0.0166 (7) | |
C5A | −0.1533 (4) | 0.50838 (10) | 0.8800 (2) | 0.0165 (7) | |
C6A | −0.1857 (4) | 0.46038 (10) | 0.8813 (2) | 0.0173 (7) | |
C7A | −0.3402 (5) | 0.43983 (11) | 0.9285 (2) | 0.0260 (8) | |
H17A | −0.4394 | 0.4638 | 0.9281 | 0.039* | |
H18A | −0.2878 | 0.4303 | 0.9992 | 0.039* | |
H19A | −0.3945 | 0.4119 | 0.8891 | 0.039* | |
C8A | −0.2650 (4) | 0.54501 (11) | 0.9260 (2) | 0.0241 (8) | |
H14A | −0.2235 | 0.5770 | 0.9110 | 0.036* | |
H15A | −0.2438 | 0.5404 | 1.0003 | 0.036* | |
H16A | −0.4004 | 0.5413 | 0.8967 | 0.036* | |
N1B | 0.4155 (3) | 0.41654 (8) | 0.35107 (17) | 0.0144 (6) | |
H13B | 0.396 (4) | 0.3853 (11) | 0.360 (2) | 0.022* | |
N3B | 0.5926 (3) | 0.47807 (7) | 0.29715 (17) | 0.0132 (6) | |
N10B | 0.6578 (4) | 0.39999 (9) | 0.2660 (2) | 0.0183 (6) | |
H11B | 0.635 (4) | 0.3695 (12) | 0.264 (2) | 0.027* | |
H12B | 0.755 (5) | 0.4102 (11) | 0.237 (2) | 0.027* | |
O9B | 0.5210 (3) | 0.55418 (6) | 0.32720 (14) | 0.0172 (5) | |
C2B | 0.5557 (4) | 0.43199 (10) | 0.3048 (2) | 0.0134 (7) | |
C4B | 0.4849 (4) | 0.51066 (10) | 0.3359 (2) | 0.0135 (7) | |
C5B | 0.3353 (4) | 0.49529 (10) | 0.3865 (2) | 0.0144 (7) | |
C6B | 0.3040 (4) | 0.44786 (10) | 0.3924 (2) | 0.0147 (7) | |
C7B | 0.1543 (4) | 0.42572 (10) | 0.4408 (2) | 0.0202 (7) | |
H17B | 0.1565 | 0.3910 | 0.4323 | 0.030* | |
H18B | 0.0295 | 0.4381 | 0.4079 | 0.030* | |
H19B | 0.1787 | 0.4336 | 0.5139 | 0.030* | |
C8B | 0.2232 (4) | 0.53208 (10) | 0.4308 (2) | 0.0215 (7) | |
H14B | 0.1275 | 0.5162 | 0.4622 | 0.032* | |
H15B | 0.1603 | 0.5534 | 0.3762 | 0.032* | |
H16B | 0.3087 | 0.5506 | 0.4828 | 0.032* | |
N1C | 0.7489 (3) | 0.16943 (8) | 0.28326 (18) | 0.0145 (6) | |
H13C | 0.781 (4) | 0.1418 (11) | 0.297 (2) | 0.022* | |
N3C | 0.6124 (3) | 0.22543 (8) | 0.15957 (17) | 0.0125 (5) | |
N10C | 0.5930 (4) | 0.14538 (9) | 0.1233 (2) | 0.0174 (6) | |
H11C | 0.589 (4) | 0.1153 (12) | 0.147 (2) | 0.026* | |
H12C | 0.523 (4) | 0.1543 (11) | 0.061 (2) | 0.026* | |
O9C | 0.6333 (3) | 0.30361 (7) | 0.19908 (14) | 0.0184 (5) | |
C2C | 0.6500 (4) | 0.18054 (9) | 0.1889 (2) | 0.0122 (6) | |
C4C | 0.6700 (4) | 0.26143 (10) | 0.2274 (2) | 0.0138 (7) | |
C5C | 0.7721 (4) | 0.25050 (10) | 0.3299 (2) | 0.0147 (7) | |
C6C | 0.8095 (4) | 0.20426 (10) | 0.3551 (2) | 0.0133 (6) | |
C7C | 0.9109 (4) | 0.18694 (11) | 0.4573 (2) | 0.0200 (7) | |
H17C | 1.0137 | 0.2091 | 0.4851 | 0.030* | |
H18C | 0.9640 | 0.1552 | 0.4500 | 0.030* | |
H19C | 0.8216 | 0.1851 | 0.5040 | 0.030* | |
C8C | 0.8342 (4) | 0.29091 (10) | 0.4029 (2) | 0.0220 (7) | |
H14C | 0.7223 | 0.3075 | 0.4173 | 0.033* | |
H15C | 0.9115 | 0.3133 | 0.3722 | 0.033* | |
H16C | 0.9094 | 0.2783 | 0.4669 | 0.033* | |
N1D | 0.2877 (3) | 0.18802 (8) | 0.33794 (17) | 0.0159 (6) | |
N3D | 0.4040 (3) | 0.24697 (8) | 0.45903 (19) | 0.0139 (6) | |
H13D | 0.470 (4) | 0.2554 (10) | 0.520 (2) | 0.021* | |
N10D | 0.4384 (4) | 0.16790 (9) | 0.5025 (2) | 0.0190 (6) | |
H11D | 0.410 (4) | 0.1381 (12) | 0.487 (2) | 0.029* | |
H12D | 0.498 (4) | 0.1754 (11) | 0.565 (3) | 0.029* | |
O9D | 0.3804 (3) | 0.32568 (6) | 0.42509 (14) | 0.0182 (5) | |
C2D | 0.3744 (4) | 0.20068 (10) | 0.4304 (2) | 0.0142 (7) | |
C4D | 0.3427 (4) | 0.28422 (9) | 0.3930 (2) | 0.0132 (6) | |
C5D | 0.2438 (4) | 0.27161 (10) | 0.2942 (2) | 0.0146 (7) | |
C6D | 0.2247 (4) | 0.22386 (10) | 0.2707 (2) | 0.0151 (7) | |
C7D | 0.1307 (4) | 0.20763 (11) | 0.1659 (2) | 0.0222 (7) | |
H17D | 0.2049 | 0.2185 | 0.1160 | 0.033* | |
H18D | 0.0025 | 0.2210 | 0.1486 | 0.033* | |
H19D | 0.1233 | 0.1727 | 0.1646 | 0.033* | |
C8D | 0.1664 (4) | 0.31038 (10) | 0.2197 (2) | 0.0216 (7) | |
H14D | 0.1681 | 0.3407 | 0.2563 | 0.032* | |
H15D | 0.0357 | 0.3026 | 0.1866 | 0.032* | |
H16D | 0.2449 | 0.3131 | 0.1676 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0175 (15) | 0.0171 (13) | 0.0182 (14) | −0.0003 (11) | 0.0057 (11) | 0.0023 (11) |
N3A | 0.0137 (15) | 0.0153 (14) | 0.0175 (14) | −0.0016 (11) | 0.0052 (11) | 0.0003 (10) |
N10A | 0.0203 (17) | 0.0102 (13) | 0.0309 (16) | −0.0002 (12) | 0.0111 (13) | 0.0031 (12) |
O9A | 0.0225 (13) | 0.0150 (12) | 0.0332 (13) | −0.0009 (9) | 0.0100 (10) | −0.0018 (9) |
C2A | 0.0178 (18) | 0.0156 (16) | 0.0141 (15) | −0.0009 (14) | 0.0000 (13) | 0.0007 (12) |
C4A | 0.0167 (18) | 0.0153 (17) | 0.0158 (16) | 0.0005 (13) | −0.0019 (13) | −0.0010 (13) |
C5A | 0.0130 (18) | 0.0224 (17) | 0.0133 (15) | 0.0014 (13) | 0.0010 (13) | 0.0003 (13) |
C6A | 0.0141 (18) | 0.0233 (17) | 0.0138 (16) | −0.0004 (13) | 0.0009 (13) | 0.0032 (13) |
C7A | 0.027 (2) | 0.0259 (18) | 0.0272 (19) | −0.0032 (15) | 0.0091 (15) | 0.0003 (14) |
C8A | 0.0193 (19) | 0.0300 (19) | 0.0232 (17) | 0.0002 (14) | 0.0046 (14) | −0.0026 (14) |
N1B | 0.0180 (15) | 0.0076 (12) | 0.0181 (14) | −0.0037 (11) | 0.0048 (11) | −0.0006 (10) |
N3B | 0.0157 (14) | 0.0083 (13) | 0.0160 (13) | −0.0015 (10) | 0.0042 (11) | −0.0002 (10) |
N10B | 0.0181 (16) | 0.0094 (13) | 0.0304 (15) | −0.0027 (11) | 0.0119 (12) | −0.0017 (12) |
O9B | 0.0203 (12) | 0.0089 (11) | 0.0242 (12) | −0.0010 (9) | 0.0086 (9) | −0.0009 (9) |
C2B | 0.0139 (17) | 0.0137 (16) | 0.0116 (15) | −0.0012 (13) | −0.0004 (13) | −0.0019 (12) |
C4B | 0.0165 (18) | 0.0109 (16) | 0.0113 (15) | 0.0018 (13) | −0.0014 (13) | −0.0016 (12) |
C5B | 0.0159 (17) | 0.0135 (16) | 0.0141 (15) | 0.0008 (13) | 0.0035 (13) | −0.0003 (12) |
C6B | 0.0124 (17) | 0.0183 (16) | 0.0127 (15) | 0.0013 (12) | 0.0007 (13) | −0.0008 (12) |
C7B | 0.0194 (19) | 0.0173 (16) | 0.0255 (18) | −0.0006 (13) | 0.0081 (14) | 0.0011 (13) |
C8B | 0.023 (2) | 0.0185 (17) | 0.0244 (17) | 0.0025 (14) | 0.0092 (14) | −0.0007 (13) |
N1C | 0.0155 (15) | 0.0096 (12) | 0.0179 (14) | 0.0016 (11) | 0.0025 (11) | 0.0009 (11) |
N3C | 0.0130 (14) | 0.0102 (12) | 0.0147 (13) | −0.0007 (10) | 0.0039 (11) | −0.0011 (10) |
N10C | 0.0261 (17) | 0.0092 (13) | 0.0152 (14) | −0.0014 (12) | 0.0002 (12) | 0.0020 (11) |
O9C | 0.0218 (13) | 0.0123 (11) | 0.0195 (11) | 0.0008 (9) | 0.0003 (9) | −0.0008 (9) |
C2C | 0.0110 (16) | 0.0118 (15) | 0.0144 (16) | −0.0008 (12) | 0.0041 (13) | 0.0001 (12) |
C4C | 0.0109 (17) | 0.0122 (16) | 0.0193 (16) | 0.0009 (12) | 0.0055 (13) | −0.0011 (13) |
C5C | 0.0115 (17) | 0.0169 (16) | 0.0163 (16) | −0.0015 (12) | 0.0038 (13) | −0.0029 (13) |
C6C | 0.0095 (17) | 0.0159 (16) | 0.0153 (15) | −0.0010 (12) | 0.0043 (13) | −0.0008 (12) |
C7C | 0.0201 (19) | 0.0238 (17) | 0.0162 (16) | −0.0010 (14) | 0.0039 (14) | 0.0020 (13) |
C8C | 0.024 (2) | 0.0199 (17) | 0.0198 (17) | 0.0005 (14) | −0.0017 (14) | −0.0040 (13) |
N1D | 0.0180 (15) | 0.0166 (13) | 0.0138 (13) | −0.0027 (11) | 0.0043 (11) | −0.0029 (11) |
N3D | 0.0129 (15) | 0.0137 (13) | 0.0151 (13) | −0.0025 (10) | 0.0026 (11) | −0.0023 (11) |
N10D | 0.0256 (17) | 0.0114 (13) | 0.0183 (14) | −0.0016 (12) | −0.0001 (12) | −0.0014 (12) |
O9D | 0.0229 (13) | 0.0132 (11) | 0.0175 (11) | −0.0015 (9) | 0.0018 (9) | −0.0002 (9) |
C2D | 0.0128 (17) | 0.0128 (15) | 0.0184 (16) | −0.0019 (13) | 0.0065 (13) | −0.0020 (13) |
C4D | 0.0132 (17) | 0.0104 (15) | 0.0171 (16) | −0.0002 (12) | 0.0060 (13) | 0.0008 (12) |
C5D | 0.0101 (17) | 0.0195 (16) | 0.0144 (16) | −0.0002 (13) | 0.0032 (13) | 0.0025 (12) |
C6D | 0.0111 (17) | 0.0206 (16) | 0.0144 (16) | −0.0011 (13) | 0.0044 (13) | −0.0012 (13) |
C7D | 0.026 (2) | 0.0233 (17) | 0.0170 (17) | −0.0023 (14) | 0.0031 (14) | −0.0012 (13) |
C8D | 0.0224 (19) | 0.0205 (17) | 0.0208 (17) | 0.0002 (14) | 0.0015 (14) | 0.0011 (13) |
N1A—C2A | 1.321 (4) | N1C—C2C | 1.352 (4) |
N1A—C6A | 1.378 (4) | N1C—C6C | 1.377 (3) |
N3A—C2A | 1.365 (4) | N1C—H13C | 0.82 (3) |
N3A—C4A | 1.380 (4) | N3C—C2C | 1.330 (3) |
N3A—H13A | 0.94 (3) | N3C—C4C | 1.364 (3) |
N10A—C2A | 1.334 (4) | N10C—C2C | 1.328 (3) |
N10A—H11A | 0.89 (3) | N10C—H11C | 0.91 (3) |
N10A—H12A | 0.88 (3) | N10C—H12C | 0.91 (3) |
O9A—C4A | 1.241 (3) | O9C—C4C | 1.254 (3) |
C4A—C5A | 1.428 (4) | C4C—C5C | 1.449 (4) |
C5A—C6A | 1.367 (4) | C5C—C6C | 1.353 (4) |
C5A—C8A | 1.507 (4) | C5C—C8C | 1.503 (4) |
C6A—C7A | 1.496 (4) | C6C—C7C | 1.493 (4) |
C7A—H17A | 0.9800 | C7C—H17C | 0.9800 |
C7A—H18A | 0.9800 | C7C—H18C | 0.9800 |
C7A—H19A | 0.9800 | C7C—H19C | 0.9800 |
C8A—H14A | 0.9800 | C8C—H14C | 0.9800 |
C8A—H15A | 0.9800 | C8C—H15C | 0.9800 |
C8A—H16A | 0.9800 | C8C—H16C | 0.9800 |
N1B—C2B | 1.353 (4) | N1D—C2D | 1.315 (4) |
N1B—C6B | 1.376 (4) | N1D—C6D | 1.363 (4) |
N1B—H13B | 0.90 (3) | N3D—C2D | 1.358 (3) |
N3B—C2B | 1.327 (3) | N3D—C4D | 1.380 (3) |
N3B—C4B | 1.363 (3) | N3D—H13D | 0.89 (3) |
N10B—C2B | 1.327 (4) | N10D—C2D | 1.344 (4) |
N10B—H11B | 0.87 (3) | N10D—H11D | 0.87 (3) |
N10B—H12B | 0.91 (3) | N10D—H12D | 0.89 (3) |
O9B—C4B | 1.258 (3) | O9D—C4D | 1.250 (3) |
C4B—C5B | 1.444 (4) | C4D—C5D | 1.412 (4) |
C5B—C6B | 1.354 (4) | C5D—C6D | 1.376 (4) |
C5B—C8B | 1.500 (4) | C5D—C8D | 1.503 (4) |
C6B—C7B | 1.495 (4) | C6D—C7D | 1.497 (4) |
C7B—H17B | 0.9800 | C7D—H17D | 0.9800 |
C7B—H18B | 0.9800 | C7D—H18D | 0.9800 |
C7B—H19B | 0.9800 | C7D—H19D | 0.9800 |
C8B—H14B | 0.9800 | C8D—H14D | 0.9800 |
C8B—H15B | 0.9800 | C8D—H15D | 0.9800 |
C8B—H16B | 0.9800 | C8D—H16D | 0.9800 |
C2A—N1A—C6A | 116.5 (2) | C2C—N1C—C6C | 121.3 (2) |
C2A—N3A—C4A | 123.1 (3) | C2C—N1C—H13C | 120 (2) |
C2A—N3A—H13A | 119.9 (18) | C6C—N1C—H13C | 119 (2) |
C4A—N3A—H13A | 116.9 (18) | C2C—N3C—C4C | 119.2 (2) |
C2A—N10A—H11A | 118 (2) | C2C—N10C—H11C | 119.0 (19) |
C2A—N10A—H12A | 118 (2) | C2C—N10C—H12C | 115.8 (19) |
H11A—N10A—H12A | 122 (3) | H11C—N10C—H12C | 122 (3) |
N1A—C2A—N10A | 121.3 (3) | N10C—C2C—N3C | 119.4 (3) |
N1A—C2A—N3A | 122.3 (3) | N10C—C2C—N1C | 118.6 (2) |
N10A—C2A—N3A | 116.5 (3) | N3C—C2C—N1C | 122.0 (2) |
O9A—C4A—N3A | 119.1 (3) | O9C—C4C—N3C | 118.7 (2) |
O9A—C4A—C5A | 125.6 (3) | O9C—C4C—C5C | 121.4 (2) |
N3A—C4A—C5A | 115.3 (3) | N3C—C4C—C5C | 119.9 (2) |
C6A—C5A—C4A | 118.3 (3) | C6C—C5C—C4C | 118.4 (3) |
C6A—C5A—C8A | 124.1 (3) | C6C—C5C—C8C | 122.9 (3) |
C4A—C5A—C8A | 117.6 (3) | C4C—C5C—C8C | 118.7 (2) |
C5A—C6A—N1A | 124.3 (3) | C5C—C6C—N1C | 119.1 (3) |
C5A—C6A—C7A | 121.8 (3) | C5C—C6C—C7C | 125.1 (3) |
N1A—C6A—C7A | 113.9 (3) | N1C—C6C—C7C | 115.7 (2) |
C6A—C7A—H17A | 109.5 | C6C—C7C—H17C | 109.5 |
C6A—C7A—H18A | 109.5 | C6C—C7C—H18C | 109.5 |
H17A—C7A—H18A | 109.5 | H17C—C7C—H18C | 109.5 |
C6A—C7A—H19A | 109.5 | C6C—C7C—H19C | 109.5 |
H17A—C7A—H19A | 109.5 | H17C—C7C—H19C | 109.5 |
H18A—C7A—H19A | 109.5 | H18C—C7C—H19C | 109.5 |
C5A—C8A—H14A | 109.5 | C5C—C8C—H14C | 109.5 |
C5A—C8A—H15A | 109.5 | C5C—C8C—H15C | 109.5 |
H14A—C8A—H15A | 109.5 | H14C—C8C—H15C | 109.5 |
C5A—C8A—H16A | 109.5 | C5C—C8C—H16C | 109.5 |
H14A—C8A—H16A | 109.5 | H14C—C8C—H16C | 109.5 |
H15A—C8A—H16A | 109.5 | H15C—C8C—H16C | 109.5 |
C2B—N1B—C6B | 121.6 (2) | C2D—N1D—C6D | 116.8 (2) |
C2B—N1B—H13B | 121.4 (19) | C2D—N3D—C4D | 122.1 (2) |
C6B—N1B—H13B | 116.9 (19) | C2D—N3D—H13D | 122.4 (19) |
C2B—N3B—C4B | 119.1 (2) | C4D—N3D—H13D | 115.4 (19) |
C2B—N10B—H11B | 124 (2) | C2D—N10D—H11D | 117 (2) |
C2B—N10B—H12B | 119 (2) | C2D—N10D—H12D | 123 (2) |
H11B—N10B—H12B | 117 (3) | H11D—N10D—H12D | 120 (3) |
N10B—C2B—N3B | 119.6 (3) | N1D—C2D—N10D | 121.2 (3) |
N10B—C2B—N1B | 118.7 (3) | N1D—C2D—N3D | 122.7 (3) |
N3B—C2B—N1B | 121.7 (3) | N10D—C2D—N3D | 116.1 (3) |
O9B—C4B—N3B | 118.2 (2) | O9D—C4D—N3D | 117.8 (2) |
O9B—C4B—C5B | 121.3 (2) | O9D—C4D—C5D | 125.9 (3) |
N3B—C4B—C5B | 120.5 (2) | N3D—C4D—C5D | 116.3 (2) |
C6B—C5B—C4B | 117.9 (3) | C6D—C5D—C4D | 117.7 (3) |
C6B—C5B—C8B | 123.0 (3) | C6D—C5D—C8D | 123.1 (3) |
C4B—C5B—C8B | 119.1 (2) | C4D—C5D—C8D | 119.2 (2) |
C5B—C6B—N1B | 119.2 (3) | N1D—C6D—C5D | 124.3 (3) |
C5B—C6B—C7B | 125.1 (3) | N1D—C6D—C7D | 114.8 (2) |
N1B—C6B—C7B | 115.7 (2) | C5D—C6D—C7D | 121.0 (3) |
C6B—C7B—H17B | 109.5 | C6D—C7D—H17D | 109.5 |
C6B—C7B—H18B | 109.5 | C6D—C7D—H18D | 109.5 |
H17B—C7B—H18B | 109.5 | H17D—C7D—H18D | 109.5 |
C6B—C7B—H19B | 109.5 | C6D—C7D—H19D | 109.5 |
H17B—C7B—H19B | 109.5 | H17D—C7D—H19D | 109.5 |
H18B—C7B—H19B | 109.5 | H18D—C7D—H19D | 109.5 |
C5B—C8B—H14B | 109.5 | C5D—C8D—H14D | 109.5 |
C5B—C8B—H15B | 109.5 | C5D—C8D—H15D | 109.5 |
H14B—C8B—H15B | 109.5 | H14D—C8D—H15D | 109.5 |
C5B—C8B—H16B | 109.5 | C5D—C8D—H16D | 109.5 |
H14B—C8B—H16B | 109.5 | H14D—C8D—H16D | 109.5 |
H15B—C8B—H16B | 109.5 | H15D—C8D—H16D | 109.5 |
C6A—N1A—C2A—N10A | 176.3 (3) | C4C—N3C—C2C—N10C | 179.6 (3) |
C6A—N1A—C2A—N3A | −4.0 (4) | C4C—N3C—C2C—N1C | −2.0 (4) |
C4A—N3A—C2A—N1A | 2.4 (4) | C6C—N1C—C2C—N10C | −179.1 (3) |
C4A—N3A—C2A—N10A | −177.9 (3) | C6C—N1C—C2C—N3C | 2.5 (4) |
C2A—N3A—C4A—O9A | −179.7 (3) | C2C—N3C—C4C—O9C | −179.8 (2) |
C2A—N3A—C4A—C5A | 1.2 (4) | C2C—N3C—C4C—C5C | 0.4 (4) |
O9A—C4A—C5A—C6A | 178.1 (3) | O9C—C4C—C5C—C6C | −179.0 (3) |
N3A—C4A—C5A—C6A | −2.8 (4) | N3C—C4C—C5C—C6C | 0.8 (4) |
O9A—C4A—C5A—C8A | −2.3 (4) | O9C—C4C—C5C—C8C | 0.0 (4) |
N3A—C4A—C5A—C8A | 176.9 (2) | N3C—C4C—C5C—C8C | 179.8 (3) |
C4A—C5A—C6A—N1A | 1.2 (4) | C4C—C5C—C6C—N1C | −0.3 (4) |
C8A—C5A—C6A—N1A | −178.4 (3) | C8C—C5C—C6C—N1C | −179.4 (3) |
C4A—C5A—C6A—C7A | −179.5 (3) | C4C—C5C—C6C—C7C | −179.3 (3) |
C8A—C5A—C6A—C7A | 0.9 (4) | C8C—C5C—C6C—C7C | 1.7 (5) |
C2A—N1A—C6A—C5A | 2.2 (4) | C2C—N1C—C6C—C5C | −1.2 (4) |
C2A—N1A—C6A—C7A | −177.1 (2) | C2C—N1C—C6C—C7C | 177.8 (3) |
C4B—N3B—C2B—N10B | 179.0 (3) | C6D—N1D—C2D—N10D | 178.8 (3) |
C4B—N3B—C2B—N1B | −0.8 (4) | C6D—N1D—C2D—N3D | −0.9 (4) |
C6B—N1B—C2B—N10B | −179.7 (3) | C4D—N3D—C2D—N1D | 0.8 (4) |
C6B—N1B—C2B—N3B | 0.1 (4) | C4D—N3D—C2D—N10D | −178.9 (3) |
C2B—N3B—C4B—O9B | −179.4 (2) | C2D—N3D—C4D—O9D | −178.2 (3) |
C2B—N3B—C4B—C5B | 1.3 (4) | C2D—N3D—C4D—C5D | 1.2 (4) |
O9B—C4B—C5B—C6B | 179.7 (3) | O9D—C4D—C5D—C6D | 176.4 (3) |
N3B—C4B—C5B—C6B | −1.1 (4) | N3D—C4D—C5D—C6D | −2.9 (4) |
O9B—C4B—C5B—C8B | −0.9 (4) | O9D—C4D—C5D—C8D | −3.0 (4) |
N3B—C4B—C5B—C8B | 178.3 (3) | N3D—C4D—C5D—C8D | 177.7 (2) |
C4B—C5B—C6B—N1B | 0.4 (4) | C2D—N1D—C6D—C5D | −1.1 (4) |
C8B—C5B—C6B—N1B | −179.0 (3) | C2D—N1D—C6D—C7D | 178.7 (3) |
C4B—C5B—C6B—C7B | −179.3 (3) | C4D—C5D—C6D—N1D | 3.0 (4) |
C8B—C5B—C6B—C7B | 1.3 (5) | C8D—C5D—C6D—N1D | −177.6 (3) |
C2B—N1B—C6B—C5B | 0.1 (4) | C4D—C5D—C6D—C7D | −176.8 (3) |
C2B—N1B—C6B—C7B | 179.8 (2) | C8D—C5D—C6D—C7D | 2.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3A—H13A···N3Bi | 0.94 (3) | 1.94 (3) | 2.885 (3) | 179 (3) |
N10A—H11A···N1Dii | 0.89 (3) | 2.18 (3) | 3.030 (3) | 160 (3) |
N10A—H12A···O9Bi | 0.88 (3) | 1.99 (3) | 2.860 (3) | 174 (3) |
N1B—H13B···O9D | 0.90 (3) | 1.90 (3) | 2.762 (3) | 160 (3) |
N10B—H11B···O9C | 0.87 (3) | 2.04 (3) | 2.841 (3) | 153 (3) |
N10B—H12B···O9Ai | 0.91 (3) | 1.93 (3) | 2.834 (3) | 179 (3) |
N1C—H13C···N1Aiii | 0.82 (3) | 2.19 (3) | 2.997 (3) | 170 (3) |
N10C—H11C···O9Biv | 0.91 (3) | 1.94 (3) | 2.804 (3) | 158 (3) |
N10C—H12C···O9Dv | 0.91 (3) | 1.98 (3) | 2.893 (3) | 178 (3) |
N3D—H13D···N3Cii | 0.89 (3) | 2.01 (3) | 2.898 (3) | 179 (3) |
N10D—H12D···O9Cii | 0.89 (3) | 1.95 (3) | 2.830 (3) | 176 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x+1, −y+1/2, z−1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C6H9N3O | C6H9N3O |
Mr | 139.16 | 139.16 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 6.613 (2), 7.018 (3), 7.078 (3) | 7.1880 (7), 28.047 (3), 13.3265 (15) |
α, β, γ (°) | 97.374 (10), 104.521 (9), 92.038 (10) | 90, 101.414 (3), 90 |
V (Å3) | 314.6 (2) | 2633.5 (5) |
Z | 2 | 16 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.10 |
Crystal size (mm) | 0.35 × 0.06 × 0.02 | 0.26 × 0.05 × 0.01 |
Data collection | ||
Diffractometer | Bruker Kappa/APEXII CCD | Bruker Kappa/APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2014) | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.854, 0.977 | 0.700, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4211, 1096, 794 | 33593, 4745, 3217 |
Rint | 0.056 | 0.067 |
(sin θ/λ)max (Å−1) | 0.594 | 0.602 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.228, 1.06 | 0.062, 0.130, 1.06 |
No. of reflections | 1096 | 4745 |
No. of parameters | 102 | 406 |
No. of restraints | 1 | 0 |
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) | 0.50, −0.31 | 0.30, −0.32 |
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), SAINT, XPREP, and SADABS (Bruker, 2014), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), SHELXTL (Bruker, 2014), XCIF (Bruker, 2014) and publCIF (Westrip, 2010), XCIF (Bruker, 2014).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H13···O9i | 0.961 (18) | 1.87 (2) | 2.784 (4) | 159 (3) |
N10—H11···O9i | 0.94 (5) | 2.04 (4) | 2.837 (4) | 142 (3) |
N10—H12···N3ii | 0.87 (4) | 2.09 (4) | 2.956 (4) | 173 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3A—H13A···N3Bi | 0.94 (3) | 1.94 (3) | 2.885 (3) | 179 (3) |
N10A—H11A···N1Dii | 0.89 (3) | 2.18 (3) | 3.030 (3) | 160 (3) |
N10A—H12A···O9Bi | 0.88 (3) | 1.99 (3) | 2.860 (3) | 174 (3) |
N1B—H13B···O9D | 0.90 (3) | 1.90 (3) | 2.762 (3) | 160 (3) |
N10B—H11B···O9C | 0.87 (3) | 2.04 (3) | 2.841 (3) | 153 (3) |
N10B—H12B···O9Ai | 0.91 (3) | 1.93 (3) | 2.834 (3) | 179 (3) |
N1C—H13C···N1Aiii | 0.82 (3) | 2.19 (3) | 2.997 (3) | 170 (3) |
N10C—H11C···O9Biv | 0.91 (3) | 1.94 (3) | 2.804 (3) | 158 (3) |
N10C—H12C···O9Dv | 0.91 (3) | 1.98 (3) | 2.893 (3) | 178 (3) |
N3D—H13D···N3Cii | 0.89 (3) | 2.01 (3) | 2.898 (3) | 179 (3) |
N10D—H12D···O9Cii | 0.89 (3) | 1.95 (3) | 2.830 (3) | 176 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) x+1, −y+1/2, z−1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+1/2, z−1/2. |