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The anti­biotic trimethoprim [5-(3,4,5-tri­meth­oxy­benz­yl)pyrimidine-2,4-di­amine] was cocrystallized with glutarimide (piperidine-2,6-dione) and its 3,3-dimethyl derivative (4,4-di­methyl­piperidine-2,6-dione). The cocrystals, viz. trimethoprim-glutarimide (1/1), C14H18N4O3·C5H7NO2, (I), and trimethoprim-3,3-di­methyl­glutarimide (1/1), C14H18N4O3·C7H11NO2, (II), are held together by three neighbouring hydrogen bonds (one central N-H...N and two N-H...O) between the pyrimidine ring of trimethoprim and the imide group of glutarimide, with an ADA/DAD pattern (A = acceptor and D = donor). These heterodimers resemble two known cocrystals of trimethoprim with barbituric acid and its 5,5-diethyl derivative. Trimethoprim shows a conformation in which the planes of the pyrimidine and benzene rings are approximately perpendicular to one another. In its glutarimide coformer, five of the six ring atoms lie in a common plane; the C atom opposite the N atom deviates by about 0.6 Å. The crystal packing of each of the two cocrystals is characterized by an extended network of hydrogen bonds and contains centrosymmetrically related trimethoprim homodimers formed by a pair of N-H...N hydrogen bonds. This structural motif occurs in five of the nine published crystal structures in which neutral trimethoprim is present.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614027193/sk3574sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614027193/sk3574Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614027193/sk3574IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614027193/sk3574Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614027193/sk3574IIsup5.cml
Supplementary material

CCDC references: 1038889; 1038888

Introduction top

The pyrimidine derivative trimethoprim inhibits the enzyme di­hydro­folate redu­ctase (DHFR), which catalyzes the vital reduction of di­hydro­folate to tetra­hydro­folate and whose inhibition leads eventually to cell death. Since trimethoprim shows a remarkable specificity for bacterial (as compared to mammalian) DHFR, it has been used as an anti­biotic against bacterial infections for decades (Feeney, 2000). The combination of trimethoprim with sulfamethoxazole, known as cotrimoxazole, has frequently been used against Pneumocystis carinii pneumonia (Hughes et al., 1974; Hughes, 1987). The crystal structures of trimethoprim bound to E. coli and chicken DHFR suggested that the loss of one hydrogen bond between an amino group of trimethoprim and a carbonyl group of DHFR may cause the observed specificity (Matthews et al., 1985), but the crystal structure of trimethoprim complexed with mouse DHFR and the cofactor NADPH (the reduced form of nicotinamide adenine dinucleotide phosphate) urged some caution concerning the exact binding mode (Groom et al., 1991). There is also a large co-operative effect between trimethoprim and NADPH, which has been investigated by multidimensional NMR spectroscopy (Kovalevskaya et al., 2007).

As a simple model of molecular recognition, we have studied a number of cocrystals of the anti­fungal drug 5-fluoro­cytosine, which exhibit an unsymmetric AAD/DDA pattern (A = acceptor and D = donor) of three neighbouring hydrogen bonds (Tutughamiarso et al., 2012; Tutughamiarso & Egert, 2012). In the course of a systematic study of cocrystals between pairs of compounds held together by a symmetric ADA/DAD pattern (Ton & Egert, 2015), we became inter­ested in trimethoprim because of its DAD arrangement, with a pyrimidine N atom as a hydrogen-bond acceptor located between two amino substituents as donor groups. Therefore, we crystallized trimethoprim with glutarimide and two of its derivatives, which all possess the appropriate ADA arrangement of functional groups, and were successful with glutarimide itself and 3,3-di­methyl­glutarimide, whereas the cocrystallization experiments with the spiro compound 3,3-tetra­methyl­eneglutarimide yielded only crystals of lower quality (Ton, 2010).

We also hoped that we would gain better insight into the hydrogen-bond inter­actions between the different components in the solid state. Since hydrogen bonds play a key role for the formation of supra­molecular complexes between a drug and its receptor, the structures of suitable cocrystals can be very helpful for the design of new active pharmaceutical ingredients (APIs) in the form of cocrystals with improved physical properties and better bioavailability (Vishweshwar et al., 2006; Yadav et al., 2009). Also the development of new APIs often makes use of the information about inter­actions between API candidates and their protein-binding pocket (Böhm & Klebe, 1996).

Experimental top

Crystallization top

Trimethoprim–glutarimide (1/1), (I) top

Trimethoprim (0.03 mmol, 8.7 mg) and glutarimide (0.03 mmol, 3.3 mg) were dissolved separately in a small amount (20 drops from a Pasteur pipette) of di­methyl sulfoxide (DMSO). The solutions were joined in a flask with a screw shutter and the mixture was kept at 323 K. After several days, crystals of (I) were obtained as colourless blocks.

Trimethoprim–3,3-di­methyl­glutarimide (1/1), (II) top

Trimethoprim (0.03 mmol, 8.7 mg) and 3,3-di­methyl­glutarimide (0.03 mmol, 4.2 mg) were dissolved separately in 40 drops of methanol and the resulting solution diluted with a further 15 drops. The solutions were joined in a flask with a screw shutter and the mixture was kept at room temperature. After several days, crystals of (II) were obtained as colourless blocks.

Refinement top

All H atoms were located unequivocally by difference Fourier synthesis. Subsequently, H atoms bonded to C atoms were refined using a riding model, with C—H = 0.98 (methyl), 0.99 (methyl­ene) or 0.95 Å (aromatic). Methyl groups were allowed to rotate about their local threefold axis. H atoms bonded to N atoms were refined isotropically. For all riding H atoms, fixed individual displacement parameters were employed, with Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for all other H atoms.

In (I), glutarimide atom C4' is disordered, with a site-occupation factor of 0.879 (7) for the major-occupied site. The two minor-disorder bonds involving atom C4'B were restrained to a distance of 1.49 Å. In (II), the refinement of an extinction coefficient improved the agreement between structure model and experimental data significantly.

Comment top

Cocrystal (I) crystallized in the space group P21/n with one molecule of trimethoprim and one molecule of glutarimide in the asymmetric unit, which form the expected heterodimer [the angle between component rings atoms N1/N3/C2/C4–C6 and N1'/C2'/C5'/C6' is 23.99 (9)°] held together by three hydrogen bonds, one central N—H···N and two neighbouring N—H···O hydrogen bonds (Fig. 1). The planar pyrimidine and benzene rings of trimethoprim (r.m.s. deviations = 0.014 and 0.003 Å, respectively, for all non-H atoms) form an angle of 86.35 (5)° caused by the dihedral angles about the two single bonds connecting these groups [ϕ1 (C4—C5—C7—C8) = -74.68 (17)° and ϕ2 (C5—C7—C8—C9) = -34.70 (18)°]. The neighbouring meth­oxy substituents of the benzene ring show the usual conformational behaviour: while the methyl groups of the outer substituents take the electronically favoured position in the plane of the benzene ring, steric reasons prevent such a conformation for the central meth­oxy substituent, whose O—CH3 bond is approximately perpendicular to the plane of the ring [C10—C11—O11—C15 = -96.84 (16)°]. In the glutarimide molecule, five of the six ring atoms form a planar arrangement (r.m.s. deviation = 0.013 Å), from which the two disordered positions of atom C4', which is opposite to the ring N atom, deviate to either side. The crystal packing is stabilized by further hydrogen bonds through inversion centres, with participation of the trimethoprim N—H bonds which are not involved in inter­actions with glutarimide, viz. N2—H···N1 hydrogen bonds leading to the formation of trimethoprim homodimers with an R22(8) pattern in graph-set notation (Bernstein et al., 1995), and somewhat longer N—H···O inter­actions from atom N4 to the central meth­oxy group, which generate trimethoprim homodimers with an R22(20) pattern. This gives rise to an extended network of hydrogen bonds (Fig. 2 and Table 2).

Cocrystal (II) crystallized in the space group P1, also with one planar heterodimer [angle between the pyrimidine ring and glutarimide = 3.97 (8)°] in the asymmetric unit (Fig. 3). The hydrogen-bond pattern of the heterodimer and the conformations of its constituents compare well with (I). The angle of 72.21 (5)° between the planar pyrimidine and benzene rings [r.m.s. deviations = 0.007 and 0.010 Å, respectively; dihedral angles ϕ1 = -86.60 (15)° and ϕ2 = 35.83 (16)°], the orientation of the meth­oxy substituents with the central meth­oxy group approximately perpendicular to the plane of the benzene ring [C10—C11—O11—C15 = -97.87 (13)°] and also the conformation of the glutarimide ring with five atoms in a plane (r.m.s. deviation = 0.022 Å) and atom C4' deviating by 0.624 (2) Å are very similar. Again an extended network of hydrogen bonds is observed in the crystal with hydrogen-bonded ribbons running in the [110] direction, approximately parallel to (114). As in (I), R22(8) trimethoprim homodimers formed by a pair of N2—H···N1 hydrogen bonds across an inversion centre and inter­molecular N—H···O hydrogen bonds from the trimethoprim amino group at atom C4 are observed, but this time the latter are accepted by carbonyl atom O6' of 3,3-di­methyl­glutarimide (which is also involved in the formation of the heterodimer); this gives rise to an R42(8) motif with four N—H···O hydrogen bonds, also across an inversion centre (Fig. 4 and Table 3).

Although the quality of the crystals obtained from the cocrystallization experiments of trimethoprim with 3,3-tetra­methyl­eneglutarimide was not satisfactory, the crystal structure could be solved (Ton, 2010) and showed features similar to those of cocrystals (I) and (II), viz. a heterodimer held together by three hydrogen bonds, the additional formation of R22(8) trimethoprim homodimers and an extended hydrogen-bond network. A search of the Cambridge Structural Database (CSD, Version 5.35 of November 2013, plus two updates; Groom & Allen, 2014) yielded nine structures containing neutral trimethoprim (not protonated at the pyrimidine ring), excluding metal complexes. Most of these structures show R22(8) heterodimers [CSD refcodes QAXHEX (Bettinetti et al., 2000) and SMZTMP (Giuseppetti et al., 1980)] or R22(8) trimethoprim homodimers [BEXVOP (Shimizu & Nishigaki, 1982), LIBCOQ (Delori & Jones, 2011) and RIWLOY (Sardone et al., 1997)]; the crystal structure of the 1:1 molecular complex between trimethoprim and sulfadimidine (RASSUZ; Bettinetti & Sardone, 1997) contains both. Also the crystal structure of trimethoprim itself (AMXBPM10; Koetzle & Williams, 1976) shows R22(8) homodimers across inversion centres. Only two cocrystals [BIGCUP (Shimizu et al., 1982) and GIGQIX (Thomas Mu­thiah et al., 2007)] contain heterodimers with an ADA/DAD hydrogen-bond pattern, the coformers being barbituric acid (GIGQIX) and its 5,5-di­ethyl derivative (BIGCUP), respectively, the constitution of which is very similar to that of the glutarimides employed by us.

In order to obtain cocrystals with a specific inter­action pattern, for example, ADA/DAD, as in the present investigation, the molecules constituting the supra­molecular complex must not only possess a certain kind and geometrical arrangement of the inter­acting functional groups, but have to meet other conditions as well (e.g. they should show similar solubility properties). Thus, the molecular components to be employed must be carefully selected. Nevertheless, the crystallization experiments and the investigation of potential cocrystals can be very tedious and time-consuming. Therefore, we have developed and successfully applied a strategy for obtaining cocrystals in a systematic way, in which the most promising combinations of components are detected as early as possible (Ton & Egert, 2015).

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A perspective view of cocrystal (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probality level. Dashed lines indicate hydrogen bonds. Only the major occupied site of the glutarimide ring is shown.
[Figure 2] Fig. 2. A partial packing diagram of cocrystal (I). Only the major occupied site of the glutarimide ring is shown. Hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+2.]
[Figure 3] Fig. 3. A perspective view of cocrystal (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probality level. Dashed lines indicate hydrogen bonds.
[Figure 4] Fig. 4. A partial packing diagram of cocrystal (II). Hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y, -z+1.]
(I) 5-(3,4,5-Trimethoxybenzyl)pyrimidine-2,4-diamine–piperidine-2,6-dione (1/1) top
Crystal data top
C14H18N4O3·C5H7NO2Z = 4
Mr = 403.44F(000) = 856
Monoclinic, P21/nDx = 1.293 Mg m3
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.774 (2) ŵ = 0.10 mm1
b = 17.046 (3) ÅT = 173 K
c = 14.168 (3) ÅBlock, colourless
β = 102.04 (3)°0.38 × 0.31 × 0.25 mm
V = 2072.4 (7) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
3128 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
Graphite monochromatorθmax = 25.8°, θmin = 3.6°
phi scansh = 1010
27135 measured reflectionsk = 2020
3885 independent reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.18 w = 1/[σ2(Fo2) + (0.058P)2]
where P = (Fo2 + 2Fc2)/3
3885 reflections(Δ/σ)max = 0.001
290 parametersΔρmax = 0.31 e Å3
2 restraintsΔρmin = 0.22 e Å3
Crystal data top
C14H18N4O3·C5H7NO2V = 2072.4 (7) Å3
Mr = 403.44Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.774 (2) ŵ = 0.10 mm1
b = 17.046 (3) ÅT = 173 K
c = 14.168 (3) Å0.38 × 0.31 × 0.25 mm
β = 102.04 (3)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3128 reflections with I > 2σ(I)
27135 measured reflectionsRint = 0.063
3885 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.18Δρmax = 0.31 e Å3
3885 reflectionsΔρmin = 0.22 e Å3
290 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.35985 (13)0.50636 (7)0.57770 (8)0.0251 (3)
C20.46253 (16)0.55371 (8)0.63566 (10)0.0230 (3)
N20.60173 (15)0.56461 (8)0.61140 (10)0.0309 (3)
H2A0.666 (2)0.6001 (12)0.6448 (14)0.042 (5)*
H2B0.613 (2)0.5460 (11)0.5549 (15)0.040 (5)*
N30.43890 (14)0.58999 (7)0.71665 (8)0.0248 (3)
C40.29946 (16)0.57890 (8)0.74043 (10)0.0240 (3)
N40.27641 (17)0.61399 (8)0.82188 (10)0.0338 (3)
H4A0.350 (2)0.6451 (12)0.8541 (14)0.043 (5)*
H4B0.196 (2)0.6035 (11)0.8472 (13)0.039 (5)*
C50.17950 (16)0.53359 (8)0.68165 (9)0.0227 (3)
C60.22041 (16)0.49896 (8)0.60289 (10)0.0242 (3)
H60.14430.46720.56290.029*
C70.01762 (16)0.52871 (8)0.70136 (10)0.0258 (3)
H7A0.05310.50820.64280.031*
H7B0.01740.58250.71250.031*
C80.00020 (16)0.47757 (8)0.78714 (9)0.0238 (3)
C90.08865 (17)0.40970 (8)0.80935 (10)0.0260 (3)
H90.16410.39610.77280.031*
C100.06690 (17)0.36149 (8)0.88542 (10)0.0275 (3)
O100.15032 (13)0.29384 (6)0.91296 (8)0.0371 (3)
C110.04298 (17)0.38206 (8)0.94015 (10)0.0274 (3)
O110.05919 (13)0.33722 (6)1.01941 (7)0.0328 (3)
C120.13137 (16)0.45052 (8)0.91736 (10)0.0263 (3)
O120.23431 (12)0.46624 (6)0.97554 (8)0.0338 (3)
C130.11032 (16)0.49815 (8)0.84050 (10)0.0256 (3)
H130.17100.54430.82490.031*
C140.2669 (2)0.27369 (10)0.85991 (13)0.0439 (4)
H14A0.21810.26720.79160.066*
H14B0.31740.22450.88500.066*
H14C0.34490.31560.86680.066*
C150.1843 (2)0.28144 (10)0.99616 (12)0.0374 (4)
H15A0.28100.30890.96760.056*
H15B0.19700.25441.05510.056*
H15C0.16000.24300.95000.056*
C160.32823 (19)0.53548 (10)0.95372 (12)0.0372 (4)
H16A0.26080.58080.95070.056*
H16B0.38770.54401.00420.056*
H16C0.40030.52890.89130.056*
N1'0.65530 (16)0.72199 (8)0.80898 (10)0.0325 (3)
H1'0.598 (2)0.6804 (13)0.7864 (15)0.049 (5)*
C2'0.78363 (18)0.73759 (9)0.77020 (11)0.0307 (3)
O2'0.81893 (13)0.69207 (7)0.71155 (8)0.0388 (3)
C3'0.8712 (2)0.81218 (11)0.80146 (12)0.0438 (4)
H3'10.83250.85390.75390.053*0.879 (7)
H3'20.98300.80390.80190.053*0.879 (7)
H3'30.97450.79720.84010.053*0.121 (7)
H3'40.88970.83840.74250.053*0.121 (7)
C4'A0.8543 (2)0.83987 (11)0.90221 (15)0.0351 (6)0.879 (7)
H4'10.91320.80420.95190.042*0.879 (7)
H4'20.89890.89320.91450.042*0.879 (7)
C4'B0.8079 (18)0.8691 (7)0.8552 (12)0.044 (5)*0.121 (7)
H4'30.76000.91100.81040.053*0.121 (7)
H4'40.89490.89310.90210.053*0.121 (7)
C5'0.6882 (2)0.84107 (10)0.90966 (12)0.0424 (4)
H5'10.63490.88450.86950.051*0.879 (7)
H5'20.68230.85190.97740.051*0.879 (7)
H5'30.74070.83520.97830.051*0.121 (7)
H5'40.60940.88300.90660.051*0.121 (7)
C6'0.60338 (19)0.76596 (10)0.87836 (12)0.0365 (4)
O6'0.49030 (16)0.74405 (9)0.90849 (11)0.0598 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0279 (6)0.0263 (6)0.0218 (6)0.0019 (5)0.0070 (5)0.0033 (5)
C20.0269 (7)0.0226 (6)0.0198 (6)0.0024 (5)0.0056 (5)0.0008 (5)
N20.0272 (7)0.0411 (7)0.0264 (7)0.0062 (6)0.0102 (5)0.0113 (6)
N30.0273 (6)0.0270 (6)0.0212 (6)0.0021 (5)0.0073 (5)0.0035 (5)
C40.0299 (7)0.0214 (6)0.0219 (7)0.0005 (5)0.0084 (5)0.0012 (5)
N40.0367 (8)0.0394 (7)0.0298 (7)0.0119 (6)0.0170 (6)0.0139 (6)
C50.0269 (7)0.0209 (6)0.0206 (6)0.0000 (5)0.0058 (5)0.0048 (5)
C60.0279 (7)0.0233 (7)0.0211 (7)0.0030 (5)0.0043 (5)0.0002 (5)
C70.0269 (7)0.0266 (7)0.0246 (7)0.0005 (6)0.0068 (6)0.0032 (6)
C80.0257 (7)0.0250 (7)0.0203 (7)0.0058 (5)0.0037 (5)0.0010 (5)
C90.0278 (7)0.0283 (7)0.0231 (7)0.0016 (6)0.0082 (6)0.0005 (5)
C100.0330 (8)0.0246 (7)0.0232 (7)0.0021 (6)0.0022 (6)0.0004 (5)
O100.0484 (7)0.0311 (6)0.0338 (6)0.0083 (5)0.0133 (5)0.0087 (5)
C110.0319 (8)0.0309 (7)0.0185 (7)0.0081 (6)0.0034 (6)0.0021 (5)
O110.0411 (6)0.0347 (6)0.0222 (5)0.0089 (5)0.0061 (4)0.0049 (4)
C120.0256 (7)0.0333 (8)0.0206 (7)0.0059 (6)0.0060 (6)0.0033 (6)
O120.0354 (6)0.0417 (6)0.0276 (5)0.0002 (5)0.0141 (4)0.0009 (5)
C130.0259 (7)0.0274 (7)0.0229 (7)0.0017 (5)0.0039 (5)0.0002 (6)
C140.0566 (11)0.0382 (9)0.0393 (9)0.0184 (8)0.0158 (8)0.0064 (7)
C150.0410 (9)0.0356 (9)0.0369 (9)0.0080 (7)0.0112 (7)0.0026 (7)
C160.0321 (8)0.0495 (10)0.0316 (8)0.0046 (7)0.0101 (6)0.0038 (7)
N1'0.0339 (7)0.0293 (7)0.0339 (7)0.0057 (6)0.0064 (6)0.0075 (6)
C2'0.0343 (8)0.0282 (7)0.0276 (7)0.0016 (6)0.0020 (6)0.0035 (6)
O2'0.0393 (6)0.0367 (6)0.0422 (7)0.0001 (5)0.0127 (5)0.0038 (5)
C3'0.0550 (11)0.0402 (9)0.0351 (9)0.0168 (8)0.0068 (8)0.0023 (7)
C4'A0.0432 (11)0.0251 (9)0.0333 (11)0.0087 (8)0.0005 (8)0.0011 (8)
C5'0.0591 (11)0.0314 (8)0.0337 (9)0.0029 (8)0.0029 (8)0.0070 (7)
C6'0.0359 (9)0.0381 (9)0.0337 (8)0.0017 (7)0.0031 (7)0.0104 (7)
O6'0.0502 (8)0.0739 (10)0.0619 (9)0.0234 (7)0.0269 (7)0.0377 (8)
Geometric parameters (Å, º) top
N1—C61.3498 (19)C14—H14B0.9800
N1—C21.3522 (18)C14—H14C0.9800
C2—N21.3489 (19)C15—H15A0.9800
C2—N31.3571 (18)C15—H15B0.9800
N2—H2A0.89 (2)C15—H15C0.9800
N2—H2B0.89 (2)C16—H16A0.9800
N3—C41.3483 (19)C16—H16B0.9800
C4—N41.3520 (19)C16—H16C0.9800
C4—C51.425 (2)N1'—C2'1.378 (2)
N4—H4A0.89 (2)N1'—C6'1.387 (2)
N4—H4B0.87 (2)N1'—H1'0.89 (2)
C5—C61.375 (2)C2'—O2'1.2230 (19)
C5—C71.506 (2)C2'—C3'1.504 (2)
C6—H60.9500C3'—C4'B1.416 (9)
C7—C81.5299 (19)C3'—C4'A1.540 (3)
C7—H7A0.9900C3'—H3'10.9900
C7—H7B0.9900C3'—H3'20.9900
C8—C131.390 (2)C3'—H3'30.9900
C8—C91.394 (2)C3'—H3'40.9900
C9—C101.400 (2)C4'A—C5'1.482 (3)
C9—H90.9500C4'A—H4'10.9900
C10—O101.3779 (18)C4'A—H4'20.9900
C10—C111.402 (2)C4'B—C5'1.504 (9)
O10—C141.432 (2)C4'B—H4'30.9900
C11—O111.3900 (17)C4'B—H4'40.9900
C11—C121.401 (2)C5'—C6'1.501 (2)
O11—C151.4374 (19)C5'—H5'10.9900
C12—O121.3702 (18)C5'—H5'20.9900
C12—C131.401 (2)C5'—H5'30.9900
O12—C161.436 (2)C5'—H5'40.9900
C13—H130.9500C6'—O6'1.218 (2)
C14—H14A0.9800
C6—N1—C2114.90 (12)H16A—C16—H16B109.5
N2—C2—N1116.84 (13)O12—C16—H16C109.5
N2—C2—N3117.32 (13)H16A—C16—H16C109.5
N1—C2—N3125.84 (13)H16B—C16—H16C109.5
C2—N2—H2A117.6 (13)C2'—N1'—C6'126.52 (14)
C2—N2—H2B117.3 (12)C2'—N1'—H1'117.3 (13)
H2A—N2—H2B123.0 (18)C6'—N1'—H1'116.2 (13)
C4—N3—C2117.00 (12)O2'—C2'—N1'119.49 (14)
N3—C4—N4117.15 (13)O2'—C2'—C3'123.39 (15)
N3—C4—C5121.86 (12)N1'—C2'—C3'117.10 (14)
N4—C4—C5120.98 (13)C4'B—C3'—C2'120.3 (5)
C4—N4—H4A118.6 (13)C2'—C3'—C4'A112.96 (14)
C4—N4—H4B122.5 (12)C4'B—C3'—H3'175.9
H4A—N4—H4B118.5 (18)C2'—C3'—H3'1109.0
C6—C5—C4114.89 (13)C4'A—C3'—H3'1109.0
C6—C5—C7122.88 (13)C4'B—C3'—H3'2126.4
C4—C5—C7122.11 (12)C2'—C3'—H3'2109.0
N1—C6—C5125.38 (13)C4'A—C3'—H3'2109.0
N1—C6—H6117.3H3'1—C3'—H3'2107.8
C5—C6—H6117.3C4'B—C3'—H3'3107.3
C5—C7—C8115.81 (12)C2'—C3'—H3'3107.3
C5—C7—H7A108.3C4'A—C3'—H3'379.7
C8—C7—H7A108.3H3'1—C3'—H3'3134.9
C5—C7—H7B108.3C4'B—C3'—H3'4107.3
C8—C7—H7B108.3C2'—C3'—H3'4107.3
H7A—C7—H7B107.4C4'A—C3'—H3'4135.1
C13—C8—C9120.40 (13)H3'2—C3'—H3'474.5
C13—C8—C7119.08 (12)H3'3—C3'—H3'4106.9
C9—C8—C7120.48 (12)C5'—C4'A—C3'110.88 (15)
C8—C9—C10120.10 (13)C5'—C4'A—H4'1109.5
C8—C9—H9119.9C3'—C4'A—H4'1109.5
C10—C9—H9119.9C5'—C4'A—H4'2109.5
O10—C10—C9124.04 (14)C3'—C4'A—H4'2109.5
O10—C10—C11116.01 (13)H4'1—C4'A—H4'2108.1
C9—C10—C11119.93 (13)C3'—C4'B—C5'116.9 (7)
C10—O10—C14116.58 (12)C3'—C4'B—H4'3108.1
O11—C11—C12119.95 (13)C5'—C4'B—H4'3108.1
O11—C11—C10120.49 (13)C3'—C4'B—H4'4108.1
C12—C11—C10119.49 (13)C5'—C4'B—H4'4108.1
C11—O11—C15112.37 (11)H4'3—C4'B—H4'4107.3
O12—C12—C11115.27 (12)C4'A—C5'—C6'113.67 (15)
O12—C12—C13124.37 (13)C6'—C5'—C4'B118.4 (4)
C11—C12—C13120.36 (13)C4'A—C5'—H5'1108.8
C12—O12—C16116.87 (12)C6'—C5'—H5'1108.8
C8—C13—C12119.71 (13)C4'B—C5'—H5'176.4
C8—C13—H13120.1C4'A—C5'—H5'2108.8
C12—C13—H13120.1C6'—C5'—H5'2108.8
O10—C14—H14A109.5C4'B—C5'—H5'2128.4
O10—C14—H14B109.5H5'1—C5'—H5'2107.7
H14A—C14—H14B109.5C4'A—C5'—H5'378.8
O10—C14—H14C109.5C6'—C5'—H5'3107.7
H14A—C14—H14C109.5C4'B—C5'—H5'3107.7
H14B—C14—H14C109.5H5'1—C5'—H5'3135.0
O11—C15—H15A109.5C4'A—C5'—H5'4134.0
O11—C15—H15B109.5C6'—C5'—H5'4107.7
H15A—C15—H15B109.5C4'B—C5'—H5'4107.7
O11—C15—H15C109.5H5'2—C5'—H5'474.4
H15A—C15—H15C109.5H5'3—C5'—H5'4107.1
H15B—C15—H15C109.5O6'—C6'—N1'119.66 (15)
O12—C16—H16A109.5O6'—C6'—C5'123.26 (15)
O12—C16—H16B109.5N1'—C6'—C5'117.03 (15)
C6—N1—C2—N2178.07 (12)C10—C11—C12—O12179.25 (12)
C6—N1—C2—N33.1 (2)O11—C11—C12—C13176.85 (12)
N2—C2—N3—C4179.94 (12)C10—C11—C12—C130.0 (2)
N1—C2—N3—C41.2 (2)C11—C12—O12—C16179.32 (12)
C2—N3—C4—N4179.01 (13)C13—C12—O12—C161.5 (2)
C2—N3—C4—C52.27 (19)C9—C8—C13—C120.3 (2)
N3—C4—C5—C63.52 (19)C7—C8—C13—C12177.99 (12)
N4—C4—C5—C6177.81 (13)O12—C12—C13—C8178.68 (12)
N3—C4—C5—C7172.70 (12)C11—C12—C13—C80.5 (2)
N4—C4—C5—C76.0 (2)C6'—N1'—C2'—O2'177.55 (15)
C2—N1—C6—C51.6 (2)C6'—N1'—C2'—C3'4.0 (2)
C4—C5—C6—N11.5 (2)O2'—C2'—C3'—C4'B168.2 (9)
C7—C5—C6—N1174.67 (13)N1'—C2'—C3'—C4'B10.3 (10)
C6—C5—C7—C8109.40 (15)O2'—C2'—C3'—C4'A154.99 (16)
C4—C5—C7—C874.68 (17)N1'—C2'—C3'—C4'A26.6 (2)
C5—C7—C8—C13147.65 (13)C4'B—C3'—C4'A—C5'60.8 (8)
C5—C7—C8—C934.70 (18)C2'—C3'—C4'A—C5'49.8 (2)
C13—C8—C9—C100.3 (2)C2'—C3'—C4'B—C5'22.1 (18)
C7—C8—C9—C10177.29 (12)C4'A—C3'—C4'B—C5'64.3 (10)
C8—C9—C10—O10179.38 (13)C3'—C4'A—C5'—C6'50.8 (2)
C8—C9—C10—C110.8 (2)C3'—C4'A—C5'—C4'B55.4 (8)
C9—C10—O10—C140.8 (2)C3'—C4'B—C5'—C4'A69.6 (11)
C11—C10—O10—C14177.80 (14)C3'—C4'B—C5'—C6'21.0 (17)
O10—C10—C11—O112.48 (19)C2'—N1'—C6'—O6'177.79 (17)
C9—C10—C11—O11176.17 (12)C2'—N1'—C6'—C5'4.6 (2)
O10—C10—C11—C12179.33 (12)C4'A—C5'—C6'—O6'153.46 (19)
C9—C10—C11—C120.7 (2)C4'B—C5'—C6'—O6'169.4 (9)
C12—C11—O11—C1586.33 (16)C4'A—C5'—C6'—N1'29.0 (2)
C10—C11—O11—C1596.84 (16)C4'B—C5'—C6'—N1'8.1 (9)
O11—C11—C12—O122.39 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N30.89 (2)2.17 (2)3.0565 (19)172.0 (18)
N2—H2A···O20.89 (2)2.15 (2)3.0393 (19)174.1 (18)
N4—H4A···O60.89 (2)2.13 (2)2.997 (2)164.3 (17)
N2—H2B···N1i0.89 (2)2.14 (2)3.0220 (18)176.3 (17)
N4—H4B···O11ii0.87 (2)2.64 (2)3.3419 (19)137.9 (15)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+2.
(II) 5-(3,4,5-Trimethoxybenzyl)pyrimidine-2,4-diamine–4,4-dimethylpiperidine-2,6-dione (1/1) top
Crystal data top
C14H18N4O3·C7H11NO2V = 1157.9 (4) Å3
Mr = 431.49Z = 2
Triclinic, P1F(000) = 460
Hall symbol: -P 1Dx = 1.238 Mg m3
a = 7.361 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.032 (2) ŵ = 0.09 mm1
c = 14.132 (3) ÅT = 173 K
α = 109.59 (3)°Block, colourless
β = 92.48 (3)°0.47 × 0.37 × 0.34 mm
γ = 99.14 (3)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3479 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 25.6°, θmin = 3.6°
phi scansh = 88
15922 measured reflectionsk = 1414
4314 independent reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0621P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
4314 reflectionsΔρmax = 0.28 e Å3
306 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.028 (3)
Crystal data top
C14H18N4O3·C7H11NO2γ = 99.14 (3)°
Mr = 431.49V = 1157.9 (4) Å3
Triclinic, P1Z = 2
a = 7.361 (2) ÅMo Kα radiation
b = 12.032 (2) ŵ = 0.09 mm1
c = 14.132 (3) ÅT = 173 K
α = 109.59 (3)°0.47 × 0.37 × 0.34 mm
β = 92.48 (3)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3479 reflections with I > 2σ(I)
15922 measured reflectionsRint = 0.048
4314 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.15Δρmax = 0.28 e Å3
4314 reflectionsΔρmin = 0.14 e Å3
306 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.00496 (17)0.33643 (10)0.45211 (8)0.0355 (3)
C20.1689 (2)0.36416 (12)0.49913 (9)0.0317 (3)
N20.2411 (2)0.48082 (11)0.54479 (10)0.0420 (3)
H2A0.353 (3)0.5024 (17)0.5830 (15)0.061 (6)*
H2B0.172 (2)0.5332 (16)0.5411 (13)0.048 (5)*
N30.27401 (16)0.28306 (10)0.50554 (8)0.0303 (3)
C40.20120 (18)0.16549 (11)0.45853 (9)0.0279 (3)
N40.31079 (18)0.08684 (11)0.46390 (9)0.0338 (3)
H4A0.428 (3)0.1189 (16)0.5029 (14)0.053 (5)*
H4B0.268 (2)0.0086 (15)0.4378 (11)0.031 (4)*
C50.02039 (19)0.12678 (12)0.40617 (9)0.0295 (3)
C60.07234 (19)0.21877 (13)0.40805 (10)0.0331 (3)
H60.19470.19660.37520.040*
C70.06721 (19)0.00315 (12)0.35179 (10)0.0318 (3)
H7A0.20310.01090.35210.038*
H7B0.02590.05160.39010.038*
C80.02350 (17)0.05609 (11)0.24254 (9)0.0260 (3)
C90.15111 (17)0.02102 (11)0.21564 (9)0.0266 (3)
H90.24200.03680.26490.032*
C100.19194 (16)0.07109 (11)0.11629 (9)0.0255 (3)
O100.35487 (12)0.03742 (9)0.08127 (7)0.0371 (3)
C110.06178 (17)0.15892 (11)0.04408 (9)0.0244 (3)
O110.10689 (12)0.21160 (8)0.05321 (6)0.0287 (2)
C120.11425 (17)0.19251 (10)0.07096 (10)0.0267 (3)
O120.23328 (13)0.27587 (8)0.00618 (8)0.0386 (3)
C130.15581 (17)0.14061 (11)0.17032 (10)0.0284 (3)
H130.27520.16340.18830.034*
C140.4816 (2)0.06485 (16)0.14772 (12)0.0487 (4)
H14A0.41690.13250.17320.073*
H14B0.58320.08650.11090.073*
H14C0.53140.04550.20460.073*
C150.04138 (19)0.15778 (12)0.12177 (10)0.0317 (3)
H15A0.09410.17080.12740.048*
H15B0.08240.19440.18840.048*
H15C0.09120.07140.09620.048*
C160.4233 (2)0.30057 (16)0.00986 (15)0.0537 (4)
H16A0.43450.33610.06290.081*
H16B0.49390.35680.05290.081*
H16C0.47210.22570.03060.081*
N1'0.63437 (17)0.36411 (10)0.63542 (9)0.0335 (3)
H1'0.522 (3)0.3398 (15)0.5955 (14)0.050 (5)*
C2'0.6890 (2)0.48679 (12)0.68843 (10)0.0337 (3)
O2'0.58454 (16)0.55520 (9)0.68556 (9)0.0485 (3)
C3'0.8773 (2)0.52742 (12)0.74509 (11)0.0361 (3)
H3'A0.87840.60290.80210.043*
H3'B0.96730.54540.69980.043*
C4'0.94108 (18)0.43534 (12)0.78683 (10)0.0317 (3)
C5'0.91750 (19)0.31542 (12)0.69934 (10)0.0330 (3)
H5'A1.01500.32140.65430.040*
H5'B0.93720.25240.72720.040*
C6'0.73329 (19)0.27654 (12)0.63749 (10)0.0310 (3)
O6'0.66948 (15)0.17077 (9)0.58926 (8)0.0417 (3)
C7'0.8208 (2)0.42118 (14)0.86976 (11)0.0425 (4)
H7'10.86100.36240.89610.064*
H7'20.69100.39340.84140.064*
H7'30.83370.49870.92460.064*
C8'1.1439 (2)0.47784 (14)0.83005 (13)0.0470 (4)
H8'11.18290.42020.85820.070*
H8'21.15870.55660.88340.070*
H8'31.22020.48400.77630.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0448 (7)0.0368 (7)0.0287 (6)0.0253 (5)0.0026 (5)0.0085 (5)
C20.0444 (8)0.0340 (7)0.0232 (6)0.0237 (6)0.0070 (6)0.0106 (5)
N20.0495 (8)0.0317 (7)0.0465 (8)0.0253 (6)0.0037 (6)0.0085 (6)
N30.0406 (6)0.0305 (6)0.0253 (5)0.0211 (5)0.0052 (5)0.0098 (5)
C40.0388 (7)0.0318 (7)0.0202 (6)0.0198 (6)0.0094 (5)0.0114 (5)
N40.0421 (7)0.0262 (6)0.0349 (6)0.0171 (5)0.0006 (5)0.0083 (5)
C50.0379 (7)0.0354 (7)0.0211 (6)0.0188 (6)0.0107 (5)0.0111 (5)
C60.0372 (7)0.0420 (8)0.0242 (6)0.0208 (6)0.0049 (5)0.0103 (6)
C70.0349 (7)0.0380 (7)0.0291 (7)0.0146 (6)0.0112 (6)0.0156 (6)
C80.0303 (6)0.0265 (6)0.0281 (6)0.0137 (5)0.0080 (5)0.0140 (5)
C90.0252 (6)0.0301 (7)0.0243 (6)0.0084 (5)0.0010 (5)0.0079 (5)
C100.0227 (6)0.0303 (7)0.0272 (6)0.0111 (5)0.0054 (5)0.0115 (5)
O100.0232 (5)0.0494 (6)0.0302 (5)0.0017 (4)0.0079 (4)0.0044 (4)
C110.0295 (6)0.0218 (6)0.0247 (6)0.0125 (5)0.0051 (5)0.0078 (5)
O110.0363 (5)0.0268 (5)0.0238 (4)0.0136 (4)0.0057 (4)0.0060 (4)
C120.0291 (6)0.0186 (6)0.0324 (7)0.0060 (5)0.0023 (5)0.0083 (5)
O120.0315 (5)0.0299 (5)0.0427 (6)0.0030 (4)0.0028 (4)0.0014 (4)
C130.0272 (6)0.0250 (6)0.0375 (7)0.0080 (5)0.0104 (5)0.0142 (5)
C140.0251 (7)0.0645 (11)0.0408 (9)0.0064 (7)0.0058 (6)0.0042 (7)
C150.0354 (7)0.0298 (7)0.0295 (7)0.0030 (6)0.0000 (5)0.0116 (5)
C160.0297 (8)0.0482 (10)0.0669 (11)0.0023 (7)0.0030 (7)0.0034 (8)
N1'0.0386 (7)0.0279 (6)0.0355 (6)0.0143 (5)0.0011 (5)0.0097 (5)
C2'0.0450 (8)0.0274 (7)0.0337 (7)0.0149 (6)0.0056 (6)0.0132 (6)
O2'0.0560 (7)0.0316 (6)0.0581 (7)0.0236 (5)0.0058 (5)0.0103 (5)
C3'0.0407 (8)0.0268 (7)0.0433 (8)0.0080 (6)0.0040 (6)0.0146 (6)
C4'0.0353 (7)0.0271 (7)0.0335 (7)0.0086 (6)0.0011 (6)0.0107 (5)
C5'0.0366 (7)0.0317 (7)0.0349 (7)0.0163 (6)0.0039 (6)0.0124 (6)
C6'0.0393 (7)0.0274 (7)0.0302 (7)0.0158 (6)0.0062 (6)0.0105 (5)
O6'0.0476 (6)0.0266 (5)0.0480 (6)0.0163 (5)0.0067 (5)0.0062 (4)
C7'0.0581 (9)0.0406 (8)0.0325 (8)0.0157 (7)0.0082 (7)0.0142 (6)
C8'0.0433 (9)0.0378 (8)0.0572 (10)0.0089 (7)0.0080 (7)0.0140 (7)
Geometric parameters (Å, º) top
N1—C61.3405 (19)C14—H14A0.9800
N1—C21.3538 (19)C14—H14B0.9800
C2—N21.340 (2)C14—H14C0.9800
C2—N31.3608 (16)C15—H15A0.9800
N2—H2A0.91 (2)C15—H15B0.9800
N2—H2B0.884 (18)C15—H15C0.9800
N3—C41.3519 (18)C16—H16A0.9800
C4—N41.3556 (16)C16—H16B0.9800
C4—C51.422 (2)C16—H16C0.9800
N4—H4A0.95 (2)N1'—C6'1.3798 (16)
N4—H4B0.886 (16)N1'—C2'1.3947 (19)
C5—C61.3833 (18)N1'—H1'0.928 (19)
C5—C71.510 (2)C2'—O2'1.2211 (16)
C6—H60.9500C2'—C3'1.493 (2)
C7—C81.5302 (17)C3'—C4'1.5411 (18)
C7—H7A0.9900C3'—H3'A0.9900
C7—H7B0.9900C3'—H3'B0.9900
C8—C131.388 (2)C4'—C8'1.527 (2)
C8—C91.3972 (18)C4'—C5'1.532 (2)
C9—C101.3969 (17)C4'—C7'1.537 (2)
C9—H90.9500C5'—C6'1.498 (2)
C10—O101.3708 (15)C5'—H5'A0.9900
C10—C111.3952 (19)C5'—H5'B0.9900
O10—C141.4319 (19)C6'—O6'1.2270 (18)
C11—O111.3872 (15)C7'—H7'10.9800
C11—C121.4021 (18)C7'—H7'20.9800
O11—C151.4388 (15)C7'—H7'30.9800
C12—O121.3663 (17)C8'—H8'10.9800
C12—C131.4018 (18)C8'—H8'20.9800
O12—C161.4275 (18)C8'—H8'30.9800
C13—H130.9500
C6—N1—C2115.20 (11)H14B—C14—H14C109.5
N2—C2—N1117.15 (12)O11—C15—H15A109.5
N2—C2—N3117.62 (13)O11—C15—H15B109.5
N1—C2—N3125.21 (13)H15A—C15—H15B109.5
C2—N2—H2A119.3 (12)O11—C15—H15C109.5
C2—N2—H2B117.4 (11)H15A—C15—H15C109.5
H2A—N2—H2B123.1 (17)H15B—C15—H15C109.5
C4—N3—C2117.39 (12)O12—C16—H16A109.5
N3—C4—N4116.12 (12)O12—C16—H16B109.5
N3—C4—C5121.85 (11)H16A—C16—H16B109.5
N4—C4—C5122.03 (13)O12—C16—H16C109.5
C4—N4—H4A117.5 (11)H16A—C16—H16C109.5
C4—N4—H4B120.3 (10)H16B—C16—H16C109.5
H4A—N4—H4B121.9 (15)C6'—N1'—C2'125.52 (12)
C6—C5—C4114.49 (13)C6'—N1'—H1'117.6 (11)
C6—C5—C7121.44 (12)C2'—N1'—H1'116.8 (11)
C4—C5—C7124.08 (11)O2'—C2'—N1'119.64 (13)
N1—C6—C5125.83 (13)O2'—C2'—C3'123.38 (13)
N1—C6—H6117.1N1'—C2'—C3'116.97 (12)
C5—C6—H6117.1C2'—C3'—C4'114.06 (12)
C5—C7—C8115.19 (11)C2'—C3'—H3'A108.7
C5—C7—H7A108.5C4'—C3'—H3'A108.7
C8—C7—H7A108.5C2'—C3'—H3'B108.7
C5—C7—H7B108.5C4'—C3'—H3'B108.7
C8—C7—H7B108.5H3'A—C3'—H3'B107.6
H7A—C7—H7B107.5C8'—C4'—C5'110.09 (12)
C13—C8—C9119.81 (11)C8'—C4'—C7'109.91 (13)
C13—C8—C7120.18 (11)C5'—C4'—C7'109.85 (12)
C9—C8—C7119.99 (12)C8'—C4'—C3'109.73 (12)
C10—C9—C8119.93 (12)C5'—C4'—C3'107.77 (11)
C10—C9—H9120.0C7'—C4'—C3'109.46 (11)
C8—C9—H9120.0C6'—C5'—C4'115.05 (11)
O10—C10—C11115.17 (11)C6'—C5'—H5'A108.5
O10—C10—C9124.22 (12)C4'—C5'—H5'A108.5
C11—C10—C9120.58 (11)C6'—C5'—H5'B108.5
C10—O10—C14117.48 (10)C4'—C5'—H5'B108.5
O11—C11—C10119.99 (11)H5'A—C5'—H5'B107.5
O11—C11—C12120.73 (12)O6'—C6'—N1'119.80 (13)
C10—C11—C12119.27 (11)O6'—C6'—C5'122.27 (12)
C11—O11—C15112.28 (9)N1'—C6'—C5'117.93 (12)
O12—C12—C13125.47 (12)C4'—C7'—H7'1109.5
O12—C12—C11114.58 (11)C4'—C7'—H7'2109.5
C13—C12—C11119.94 (12)H7'1—C7'—H7'2109.5
C12—O12—C16118.23 (12)C4'—C7'—H7'3109.5
C8—C13—C12120.39 (11)H7'1—C7'—H7'3109.5
C8—C13—H13119.8H7'2—C7'—H7'3109.5
C12—C13—H13119.8C4'—C8'—H8'1109.5
O10—C14—H14A109.5C4'—C8'—H8'2109.5
O10—C14—H14B109.5H8'1—C8'—H8'2109.5
H14A—C14—H14B109.5C4'—C8'—H8'3109.5
O10—C14—H14C109.5H8'1—C8'—H8'3109.5
H14A—C14—H14C109.5H8'2—C8'—H8'3109.5
C6—N1—C2—N2179.55 (12)C10—C11—O11—C1597.87 (13)
C6—N1—C2—N31.10 (19)C12—C11—O11—C1581.83 (13)
N2—C2—N3—C4179.38 (11)O11—C11—C12—O122.02 (16)
N1—C2—N3—C42.17 (19)C10—C11—C12—O12177.69 (10)
C2—N3—C4—N4178.32 (11)O11—C11—C12—C13178.32 (10)
C2—N3—C4—C51.43 (17)C10—C11—C12—C131.97 (17)
N3—C4—C5—C60.18 (17)C13—C12—O12—C169.77 (19)
N4—C4—C5—C6179.92 (11)C11—C12—O12—C16169.87 (13)
N3—C4—C5—C7179.55 (11)C9—C8—C13—C121.09 (17)
N4—C4—C5—C70.19 (18)C7—C8—C13—C12177.73 (11)
C2—N1—C6—C50.78 (19)O12—C12—C13—C8179.71 (11)
C4—C5—C6—N11.36 (19)C11—C12—C13—C80.10 (17)
C7—C5—C6—N1178.38 (11)C6'—N1'—C2'—O2'175.54 (13)
C6—C5—C7—C893.12 (14)C6'—N1'—C2'—C3'5.5 (2)
C4—C5—C7—C886.60 (15)O2'—C2'—C3'—C4'148.90 (14)
C5—C7—C8—C13145.35 (12)N1'—C2'—C3'—C4'32.16 (17)
C5—C7—C8—C935.83 (16)C2'—C3'—C4'—C8'172.07 (12)
C13—C8—C9—C100.02 (17)C2'—C3'—C4'—C5'52.18 (16)
C7—C8—C9—C10178.81 (11)C2'—C3'—C4'—C7'67.25 (16)
C8—C9—C10—O10175.97 (11)C8'—C4'—C5'—C6'168.30 (12)
C8—C9—C10—C112.08 (17)C7'—C4'—C5'—C6'70.54 (15)
C11—C10—O10—C14170.55 (12)C3'—C4'—C5'—C6'48.65 (15)
C9—C10—O10—C147.60 (18)C2'—N1'—C6'—O6'178.44 (13)
O10—C10—C11—O114.55 (16)C2'—N1'—C6'—C5'1.8 (2)
C9—C10—C11—O11177.23 (10)C4'—C5'—C6'—O6'155.05 (13)
O10—C10—C11—C12175.16 (10)C4'—C5'—C6'—N1'25.15 (17)
C9—C10—C11—C123.06 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···N30.928 (19)2.06 (2)2.985 (2)178.9 (17)
N2—H2A···O20.91 (2)2.06 (2)2.966 (2)172.3 (17)
N4—H4A···O60.95 (2)2.00 (2)2.946 (2)173.8 (16)
N2—H2B···N1i0.884 (18)2.121 (19)3.0027 (18)174.3 (15)
N4—H4B···O6ii0.886 (16)2.188 (16)2.9637 (16)145.9 (13)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H18N4O3·C5H7NO2C14H18N4O3·C7H11NO2
Mr403.44431.49
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)173173
a, b, c (Å)8.774 (2), 17.046 (3), 14.168 (3)7.361 (2), 12.032 (2), 14.132 (3)
α, β, γ (°)90, 102.04 (3), 90109.59 (3), 92.48 (3), 99.14 (3)
V3)2072.4 (7)1157.9 (4)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.100.09
Crystal size (mm)0.38 × 0.31 × 0.250.47 × 0.37 × 0.34
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
27135, 3885, 3128 15922, 4314, 3479
Rint0.0630.048
(sin θ/λ)max1)0.6110.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.104, 1.18 0.038, 0.106, 1.15
No. of reflections38854314
No. of parameters290306
No. of restraints20
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)0.31, 0.220.28, 0.14

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008) and XP (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1'—H1'···N30.89 (2)2.17 (2)3.0565 (19)172.0 (18)
N2—H2A···O2'0.89 (2)2.15 (2)3.0393 (19)174.1 (18)
N4—H4A···O6'0.89 (2)2.13 (2)2.997 (2)164.3 (17)
N2—H2B···N1i0.89 (2)2.14 (2)3.0220 (18)176.3 (17)
N4—H4B···O11ii0.87 (2)2.64 (2)3.3419 (19)137.9 (15)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1'—H1'···N30.928 (19)2.06 (2)2.985 (2)178.9 (17)
N2—H2A···O2'0.91 (2)2.06 (2)2.966 (2)172.3 (17)
N4—H4A···O6'0.95 (2)2.00 (2)2.946 (2)173.8 (16)
N2—H2B···N1i0.884 (18)2.121 (19)3.0027 (18)174.3 (15)
N4—H4B···O6'ii0.886 (16)2.188 (16)2.9637 (16)145.9 (13)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z+1.
 

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