Four 7-ar­yl-substituted pyrido[2,3-d]pyrimidine-2,4(1H,3H)-diones: similar mol­ecular structures but different crystal structures

Mol­ecules of 1,3-dimethyl-7-(4-methyl­phen­yl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, C₁₆H₁₅N₃O₂, (I), are linked by paired C—H...O hydrogen bonds to form centrosymmetric R₂²(10) dimers, which are linked into chains by a single π–π stacking inter­action. A single C—H...O hydrogen bond links the mol­ecules of 7-(biphenyl-4-yl)-1,3-dimethyl­pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, C₂₁H₁₇N₃O₂, (II), into C(10) chains, which are weakly linked into sheets by a π–π stacking inter­action. In 7-(4-fluoro­phen­yl)-3-methyl­pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, C₁₄H₁₀FN₃O₂, (III), an N—H...O hydrogen bond links the mol­ecules into C(6) chains, which are linked into sheets by a π–π stacking inter­action. The mol­ecules of 7-(4-methoxy­phen­yl)-3-methyl­pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, C₁₅H₁₃N₃O₃, (IV), are also linked into C(6) chains by an N—H...O hydrogen bond, but here the chains are linked into sheets by a combination of two independent C—H...π(arene) hydrogen bonds.

S1. Comment

Pyrido[2,3-d]pyrimidine heterocycles (also known as 5-deazapteridines) have received considerable attention over the past decade as a result of the wide range of biological activity that they exhibit (Devi et al., 2003; Tu et al., 2008), including for example bronchodilator, vasodilator, antiallergic, cardiotonic, antihypertensive or hepatoprotective activities, as well as for their role in the treatment of proliferative diseases (Devi et al., 2004). As part of a wide-ranging project on the synthesis and characterization of fused pyrimidine systems under solvent-free conditions, we report here the structures of four examples of 7-arylpyrido[2,3-d]pyrimidine derivatives prepared by cyclocondensation reactions between 6-aminopyrimidin-5-carboxaldehydes and acetophenones, utilizing solvent-free fusion reactions promoted by BF₃–Et₂O catalysis.

While the molecular structures of the pair of compounds 1,3-dimethyl-7-(4-methylphenyl)pyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (I), and 7-(1,1'-biphenyl-4-yl)-1,3-dimethylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (II) (Figs. 1 and 2), are broadly similar in constitution and very similar in conformation, they exhibit significant differences in their crystal structures, in particular in their space groups and in their pattern of supramolecular aggregation. Similarly, the pair of compounds 7-(4-fluorophenyl)-3-methylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (III), and 7-(4-methoxyphenyl)-3-methylpyrido[2,3-d]pyrimidine-2,4(1H,3H)-dione, (IV) (Figs. 3 and 4), which are closely related to (I) and (II), have similar constitutions and conformations, but again they crystallize in different space groups and they exhibit different patterns of supramolecular aggregation. Overall, no two of the compounds reported here crystallize in the same space group or have similar unit-cell dimensions or exhibit the same pattern of direction-specific intermolecular interactions.

The molecular conformations are straightforwardly definable in terms of the interplanar angle between the pyridine ring and the pendent aryl ring (C71–C76), with an additional angle between the two rings of the biphenyl-4-yl substituent in (II) (Table1). These angles indicate that the molecular skeletons do not much deviate from overall planarity, a point emphasized by the very small deviation, 0.012 (5) Å, of the methoxy C atom from the plane of the adjacent aryl ring in (IV). The bond distances and angles show no unexpected values.

In our analysis of the intermolecular interactions, we have discounted all intermolecular contacts involving methyl C—H bonds, on the usual grounds that these bonds are of low acidity, while the rotation about the adjacent C—C bonds of methyl groups bonded to planar rings are hindered by extremely low barriers, typically a few joules per mole (Tannenbaum et al., 1956; Naylor & Wilson, 1957), and so are likely to be undergoing very fast rotation about the adjacent C—C bonds.

In (I), there is a single C—H···O hydrogen bond utilizing a pyridine C—H bond as the donor (Table 2), and this links pairs of molecules into centrosymmetric dimers characterized by an R₂²(10) (Bernstein et al., 1995) motif. In addition, the pyridine rings of the molecules at (x, y, z) and (-x, -y + 1, -z + 1) are strictly parallel, with an interplanar spacing of 3.439 (2) Å; the corresponding ring-centroid separation is 3.693 (2) Å, with a near-ideal ring-centroid offset of 1.345 (2) Å. The combined effect of these two interactions is to link the molecules into a π-stacked chain of hydrogen-bonded dimers, running parallel to the [010] direction, with R₂²(10) rings centred at (0, n, 1/2), where n represents an integer, alternating with π–π stacking interactions across (0, n + 1/2, 1/2), where n represents an integer (Fig. 5).

The crystal structure of (II) also contains just one intermolecular C—H···O hydrogen bond, but this now involves an aryl C—H bond as the donor (Table 2), and its effect is to link molecules related by the 2₁ screw axis along (1/2, y, 3/4) into a C(10) chain running parallel to the [010] direction. The pyridine and phenyl rings in the molecules at (x, y, z) and (-x, -y + 1, -z + 1), respectively, are not parallel, but the dihedral angle between them is only 12.8 (2)°; the ring-centroid separation is 3.718 (2) Å and the interplanar distance is ca 3.53 Å, corresponding to a ring-centroid offset of ca 1.17 Å. Thus, these centrosymmetrically related molecules are weakly linked by the π–π stacking interaction and the overall effect of this is to link the hydrogen-bonded chain into a sheet parallel to (102) (Fig. 6).

In each of (III) and (IV), a single N—H···O hydrogen-bond links the molecules into a C(6) chain. Although the same hydrogen-bond donor and acceptor are utilized in each structure, the construction and orientation of the chains is different. In (III), the chain consists of molecules related by a 2₁ screw axis parallel to the [010] direction, while the chain in (IV) consists of molecules related by translation along [100]. In addition, the subsequent linking of the chains is different in the two structures. The pyridine ring in the molecule of (III) at (x, y, z) makes angles of 1.1 (2)° with the phenyl ring in each of the molecules at (x + 1/2, -y + 1/2, -z + 1) and (x - 1/2, -y + 1/2, -z + 1), with ring-centroid separations of 3.759 (2) Å and 3.748 (2) Å respectively. The interplanar spacings are ca 3.315 and ca 3.39 Å, respectively, corresponding to ring centroid offsets of ca 1.77 and ca 1.60 Å, respectively. The cooperative action of these two independent stacking interactions along [100] links the hydrogen-bonded chains along [010] into a sheet parallel to (001) (Fig. 7). In the structure of (IV), by contrast, the chains generated by the C—H···O hydrogen bond are linked by two independent C—H···π(arene) hydrogen bonds, both involving the same ring as the acceptor. The C71–C76 ring in the molecule at (x, y, z) acts as a hydrogen-bond acceptor from C72 in the molecule at (x + 1/2, -y, z) and from C75 in the molecule at (x - 1/2, -y + 1, z), so forming a chain running parallel to the [110] direction; the two C—H···π hydrogen bonds lie on opposite faces of the ring, with C···Cg···C and H···Cg···H angles of 179 and 177°, respectively. The combination of the [100] and [110] chains then generates a sheet parallel to (001) (Fig. 8).

In view of the different patterns of supramolecular aggregation found here for (I)–(IV), it is of interest briefly to compare these structures with those of the closely related compounds (V) [Cambridge Structural Database (Allen, 2002) refcode QOQQIW (Sarkhel et al., 2001)] and (VI) (XEBCUD; Wang et al., 2006). The crystal structure of (V) was described (Sarkhel et al., 2001) as containing C—H···O and C—H···Br hydrogen bonds and π–π stacking interactions, although the structural effects of these interactions were not specified. However, it is now well established that Br and Cl bonded to C are both exceptionally poor acceptors of hydrogen bonds, even from O—H and N—H units, so that the C—H···Br contacts in (V) and the C—H···Cl contacts in (VI) are likely to be no more than normal van der Waals contacts (Brammer et al., 2001; Thallypally & Nangia, 2001). Accordingly, the structure of (V) consists of C(10) hydrogen-bonded chains, running parallel to the [001] direction and built from a single C—H···O hydrogen bond; antiparallel pairs of these chains, related by inversion, are linked by the π—π stacking interaction (Fig. 9). The original report on (VI) (Wang et al., 2006) stated that `the crystal structure is stabilized by N—H···O, C—H···O and C—H···Cl hydrogen bonds', but it gave no information as to the actions of these interactions. Re-examination of this structure shows that most of the so-called hydrogen bonds listed by the authors have H···A distances far too long to be of structural significance. In the event, only two hydrogen bonds linking the heterocyclic components are significant, and they link these molecules into chains of centrosymmetric rings running parallel to the [001] direction: the dimethylformamide molecules are pendent from the chain, but they play no other role in the hydrogen bonding. Within the chain, R₂²(8) rings containing paired N—H···O hydrogen bonds are centred at (0, 0, n), where n represents an integer, and these alternate with R₂²(16) rings containing paired C—H···O hydrogen bonds, which are centred at (0, 0, 1/2 + n), where n represents an integer (Fig. 10). These chains are further linked by a π–π stacking interaction to form a sheet parallel to (100).

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Brammer et al. (2001); Devi et al. (2003, 2004); Naylor & Wilson (1957); Sarkhel et al. (2001); Tannenbaum et al. (1956); Thallypally & Nangia (2001); Tu et al. (2008); Wang et al. (2006).

S2. Experimental

Equimolar quantities of the appropriate 6-aminopyrimidine-5-carboxaldehyde, 6-amino-1,3-dimethyl-5-formylpyrimidine-2,4(1H,3H)-dione for (I) and (II) or 6-amino-2-methoxy-3-methyl-5-formylpyrimidine-4(3H)-one for (III) and (IV), and the appropriate 4-substituted acetophenone 4-RC₆H₄COCH₃, where R is Me for (I), Ph for (II), F for (III) and MeO for (IV), were mixed in the absence of solvent. Three drops of BF₃–Et₂O were added to each mixture, which was then heated in an oil bath at 443 K for 30 s. The resulting dark-brown liquids were diluted with ethanol and cooled to ambient temperature. The solid products were collected by filtration, washed with ethanol and then recrystallized to give the pure pyrido[2,3-d]pyrimidine derivatives as crystals suitable for single-crystal X-ray diffraction. For (I), yellow solid, crystallized from ethanol/DMF, yield 50%, m.p. 458–460 K; HR–MS found: 281.1159; C₁₆H₁₅N₃O₂ requires: 281.1164. For (II), yellow solid, purified by column chromatography using chloroform as eluant, and recrystallized from ethanol/DMF, yield 60%, m.p. 506–509 K; HR–MS found: 343.1313; C₂₁H₁₇N₃O₂ requires: 343.1321. For (III), yellow solid, crystallized form DMF, yield 60%, m.p. 568–570 K; HRMS found: 271.0752; C₁₄H₁₀FN₃O₂ requires: 271.0757. For (IV), yellow solid, crystallized form DMF, yield 70%, m.p. > 573 K. HR–MS found: 283.0966; C₁₅H₁₃N₃O₃ requires: 283.0957.

S3. Refinement

With the exception of the methyl H atoms bonded to C31 in compound (III), all H atoms were clearly located in difference maps. H atoms bonded to C31 in compound (III) were placed in calculated positions, and all H atoms were then treated as riding atoms in geometrically idealized positions. The H atoms bonded to three-connected C atoms in aromatic or heteroaromatic rings were placed along the external bisectors of the ring angles, with C—H distances of 0.95Å and with U_iso(H) = 1.2U_eq(C). H atoms bonded to ring N atoms were placed along the external bisectors of the ring angles, with N—H distances of 0.88Å and with U_iso(H) = 1.2U_eq(N). The methyl groups were all permitted to rotate about the adjacent C—X bonds (X = C or O) but not to tilt, with all of the X—C—H and H—C—H angles held fixed in each such group, and with C—H distances of 0.98Å and with U_iso(H) = 1.5U_eq(C). In the absence of significant resonant scattering, the Friedel-equivalent reflections were merged for compounds (III) and (IV). Hence, the absolute configuration of the molecules in (III), and the correct orientation of the structure of (IV) with respect to the polar-axis direction are both undetermined.

Computing details

For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecular structure of (III), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. The molecular structure of (IV), showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a chain of π-stacked hydrogen-bonded dimers along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a sheet parallel to (102) built from π-stacked hydrogen-bonded chains along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of (III), showing the formation of a sheet parallel to (001) built from π-stacked hydrogen-bonded chains along [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 8. A stereoview of part of the crystal structure of (IV), showing the formation of a sheet parallel to (001) built from one C—H···O hydrogen bond and two C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 9. A stereoview of part of the crystal structure of QOQQIW (Sarkhel et al., 2001), showing the formation of a π-stacked pair of C(10) hydrogen-bonded chains. The original atom coordinates have been employed and, for the sale of clarity, H atoms not involved in the motif shown have been omitted.
	Fig. 10. A stereoview of part of the crystal structure of XEBCUD (Wang et al., 2006), showing the formation of a chain of hydrogen-bonded R2^2(8) and R2^2(16) rings. The original atom coordinates have been employed and, for the sale of clarity, H atoms not involved in the motifs shown have been omitted, as have the dimethylformamide molecules.

(I) 1,3-dimethyl-7-(4-methylphenyl)pyrido[2,3-d]pyrimidine- 2,4(1H,3H)-dione

Crystal data

C16H15N3O2	Z = 2
Mr = 281.31	F(000) = 296
Triclinic, P1	Dx = 1.379 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9953 (5) Å	Cell parameters from 2989 reflections
b = 7.9221 (7) Å	θ = 3.0–27.6°
c = 12.5140 (13) Å	µ = 0.09 mm^−1
α = 93.466 (4)°	T = 120 K
β = 92.993 (6)°	Lath, yellow
γ = 101.152 (6)°	0.20 × 0.10 × 0.02 mm
V = 677.71 (11) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	2989 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1699 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
Detector resolution: 9.091 pixels mm^-1	θmax = 27.6°, θmin = 3.0°
ϕ & ω scans	h = −8→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.972, Tmax = 0.998	l = −16→16
11686 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.200	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1083P)^2] where P = (Fo^2 + 2Fc^2)/3
2989 reflections	(Δ/σ)max = 0.001
193 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

Experimental. Mass spectrum: MS (70 eV) m/z (%) = 281 (M⁺, 100), 252 (51), 169 (50). HR—MS found 281.1159 ?

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.3482 (3)	0.6338 (3)	0.60948 (16)	0.0213 (5)
C2	0.3500 (3)	0.5603 (3)	0.7078 (2)	0.0228 (6)
N3	0.2804 (3)	0.3826 (3)	0.70606 (16)	0.0228 (5)
C4	0.2060 (3)	0.2754 (3)	0.6160 (2)	0.0228 (6)
C4A	0.2009 (3)	0.3606 (3)	0.5157 (2)	0.0207 (6)
C5	0.1232 (3)	0.2714 (3)	0.4197 (2)	0.0240 (6)
H5	0.0704	0.1512	0.4171	0.029*
C6	0.1235 (3)	0.3597 (3)	0.3271 (2)	0.0240 (6)
H6	0.0681	0.3015	0.2608	0.029*
C7	0.2066 (3)	0.5360 (3)	0.33295 (19)	0.0197 (5)
N8	0.2799 (3)	0.6237 (3)	0.42589 (16)	0.0215 (5)
C8A	0.2751 (3)	0.5372 (3)	0.51497 (19)	0.0198 (6)
C11	0.4114 (4)	0.8209 (3)	0.6093 (2)	0.0282 (6)
H11A	0.5150	0.8475	0.5596	0.042*
H11B	0.4610	0.8686	0.6817	0.042*
H11C	0.3004	0.8720	0.5864	0.042*
O2	0.4081 (3)	0.6462 (2)	0.79085 (15)	0.0318 (5)
C31	0.2855 (4)	0.3030 (3)	0.8091 (2)	0.0286 (7)
H31A	0.1547	0.2828	0.8362	0.043*
H31B	0.3767	0.3803	0.8610	0.043*
H31C	0.3286	0.1929	0.7988	0.043*
O4	0.1474 (2)	0.1207 (2)	0.62202 (15)	0.0305 (5)
C71	0.2153 (3)	0.6379 (3)	0.2370 (2)	0.0221 (6)
C72	0.2021 (3)	0.5621 (3)	0.1334 (2)	0.0268 (6)
H72	0.1851	0.4403	0.1223	0.032*
C73	0.2133 (4)	0.6624 (4)	0.0456 (2)	0.0302 (6)
H73	0.2052	0.6080	−0.0247	0.036*
C74	0.2361 (3)	0.8400 (3)	0.0589 (2)	0.0277 (6)
C75	0.2518 (3)	0.9174 (3)	0.1621 (2)	0.0275 (6)
H75	0.2698	1.0394	0.1725	0.033*
C76	0.2415 (3)	0.8183 (3)	0.2511 (2)	0.0238 (6)
H76	0.2522	0.8732	0.3214	0.029*
C77	0.2436 (4)	0.9479 (4)	−0.0370 (2)	0.0353 (7)
H77A	0.3196	0.9021	−0.0914	0.053*
H77B	0.3055	1.0675	−0.0145	0.053*
H77C	0.1106	0.9441	−0.0672	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0243 (10)	0.0185 (11)	0.0216 (12)	0.0056 (8)	0.0012 (8)	0.0007 (9)
C2	0.0219 (12)	0.0248 (14)	0.0229 (15)	0.0064 (10)	0.0025 (10)	0.0032 (11)
N3	0.0233 (10)	0.0241 (12)	0.0238 (12)	0.0090 (9)	0.0044 (8)	0.0076 (9)
C4	0.0219 (12)	0.0232 (14)	0.0252 (15)	0.0069 (10)	0.0080 (10)	0.0048 (11)
C4A	0.0163 (11)	0.0205 (13)	0.0261 (15)	0.0041 (9)	0.0041 (9)	0.0036 (11)
C5	0.0210 (12)	0.0191 (13)	0.0321 (15)	0.0037 (10)	0.0043 (10)	0.0023 (11)
C6	0.0233 (12)	0.0226 (14)	0.0243 (15)	0.0008 (10)	0.0008 (10)	−0.0005 (11)
C7	0.0151 (11)	0.0231 (14)	0.0217 (14)	0.0051 (9)	0.0022 (9)	0.0017 (11)
N8	0.0198 (10)	0.0238 (12)	0.0216 (12)	0.0052 (9)	0.0028 (8)	0.0023 (9)
C8A	0.0174 (11)	0.0218 (14)	0.0212 (14)	0.0060 (10)	0.0012 (9)	0.0018 (11)
C11	0.0344 (14)	0.0219 (14)	0.0280 (16)	0.0050 (11)	0.0026 (11)	0.0008 (11)
O2	0.0411 (11)	0.0333 (11)	0.0219 (11)	0.0095 (8)	0.0014 (8)	0.0027 (9)
C31	0.0301 (14)	0.0326 (16)	0.0247 (16)	0.0060 (12)	0.0039 (11)	0.0127 (12)
O4	0.0342 (10)	0.0214 (11)	0.0370 (12)	0.0047 (8)	0.0073 (8)	0.0090 (8)
C71	0.0179 (12)	0.0265 (14)	0.0216 (14)	0.0031 (10)	−0.0009 (9)	0.0045 (11)
C72	0.0254 (13)	0.0260 (15)	0.0280 (16)	0.0038 (10)	−0.0007 (10)	0.0001 (12)
C73	0.0300 (14)	0.0383 (17)	0.0209 (15)	0.0046 (12)	−0.0012 (10)	0.0015 (12)
C74	0.0221 (13)	0.0332 (16)	0.0279 (16)	0.0040 (11)	−0.0004 (10)	0.0091 (12)
C75	0.0251 (13)	0.0263 (15)	0.0312 (16)	0.0040 (11)	0.0014 (10)	0.0066 (12)
C76	0.0208 (12)	0.0281 (15)	0.0217 (14)	0.0027 (10)	0.0005 (9)	0.0023 (11)
C77	0.0350 (15)	0.0439 (18)	0.0298 (17)	0.0107 (13)	0.0049 (12)	0.0126 (14)

Geometric parameters (Å, º)

N1—C8A	1.386 (3)	C11—H11B	0.9800
N1—C2	1.393 (3)	C11—H11C	0.9800
N1—C11	1.463 (3)	C31—H31A	0.9800
C2—O2	1.214 (3)	C31—H31B	0.9800
C2—N3	1.396 (3)	C31—H31C	0.9800
N3—C4	1.383 (3)	C71—C72	1.386 (4)
N3—C31	1.472 (3)	C71—C76	1.404 (3)
C4—O4	1.223 (3)	C72—C73	1.392 (3)
C4—C4A	1.463 (3)	C72—H72	0.9500
C4A—C5	1.386 (4)	C73—C74	1.384 (4)
C4A—C8A	1.395 (3)	C73—H73	0.9500
C5—C6	1.389 (3)	C74—C75	1.385 (4)
C5—H5	0.9500	C74—C77	1.513 (3)
C6—C7	1.401 (3)	C75—C76	1.398 (3)
C6—H6	0.9500	C75—H75	0.9500
C7—N8	1.342 (3)	C76—H76	0.9500
C7—C71	1.484 (3)	C77—H77A	0.9800
N8—C8A	1.342 (3)	C77—H77B	0.9800
C11—H11A	0.9800	C77—H77C	0.9800
C8A—N1—C2	122.0 (2)	H11A—C11—H11C	109.5
C8A—N1—C11	120.0 (2)	H11B—C11—H11C	109.5
C2—N1—C11	117.9 (2)	N3—C31—H31A	109.5
O2—C2—N1	121.8 (2)	N3—C31—H31B	109.5
O2—C2—N3	121.6 (2)	H31A—C31—H31B	109.5
N1—C2—N3	116.6 (2)	N3—C31—H31C	109.5
C4—N3—C2	125.6 (2)	H31A—C31—H31C	109.5
C4—N3—C31	117.3 (2)	H31B—C31—H31C	109.5
C2—N3—C31	117.1 (2)	C72—C71—C76	118.4 (2)
O4—C4—N3	121.2 (2)	C72—C71—C7	122.5 (2)
O4—C4—C4A	123.4 (2)	C76—C71—C7	119.1 (2)
N3—C4—C4A	115.4 (2)	C71—C72—C73	120.8 (2)
C5—C4A—C8A	118.0 (2)	C71—C72—H72	119.6
C5—C4A—C4	122.0 (2)	C73—C72—H72	119.6
C8A—C4A—C4	120.0 (2)	C74—C73—C72	121.1 (2)
C4A—C5—C6	119.2 (2)	C74—C73—H73	119.5
C4A—C5—H5	120.4	C72—C73—H73	119.5
C6—C5—H5	120.4	C73—C74—C75	118.7 (2)
C5—C6—C7	119.0 (2)	C73—C74—C77	120.8 (2)
C5—C6—H6	120.5	C75—C74—C77	120.5 (2)
C7—C6—H6	120.5	C74—C75—C76	120.8 (2)
N8—C7—C6	122.1 (2)	C74—C75—H75	119.6
N8—C7—C71	115.9 (2)	C76—C75—H75	119.6
C6—C7—C71	122.0 (2)	C75—C76—C71	120.3 (2)
C7—N8—C8A	118.1 (2)	C75—C76—H76	119.9
N8—C8A—N1	116.1 (2)	C71—C76—H76	119.9
N8—C8A—C4A	123.5 (2)	C74—C77—H77A	109.5
N1—C8A—C4A	120.4 (2)	C74—C77—H77B	109.5
N1—C11—H11A	109.5	H77A—C77—H77B	109.5
N1—C11—H11B	109.5	C74—C77—H77C	109.5
H11A—C11—H11B	109.5	H77A—C77—H77C	109.5
N1—C11—H11C	109.5	H77B—C77—H77C	109.5
C8A—N1—C2—O2	−177.5 (2)	C7—N8—C8A—C4A	1.1 (3)
C11—N1—C2—O2	−2.5 (3)	C2—N1—C8A—N8	179.36 (19)
C8A—N1—C2—N3	2.1 (3)	C11—N1—C8A—N8	4.4 (3)
C11—N1—C2—N3	177.12 (19)	C2—N1—C8A—C4A	−0.3 (3)
O2—C2—N3—C4	177.9 (2)	C11—N1—C8A—C4A	−175.2 (2)
N1—C2—N3—C4	−1.7 (3)	C5—C4A—C8A—N8	−1.9 (3)
O2—C2—N3—C31	−1.7 (3)	C4—C4A—C8A—N8	178.4 (2)
N1—C2—N3—C31	178.73 (18)	C5—C4A—C8A—N1	177.7 (2)
C2—N3—C4—O4	−179.8 (2)	C4—C4A—C8A—N1	−2.0 (3)
C31—N3—C4—O4	−0.2 (3)	N8—C7—C71—C72	160.1 (2)
C2—N3—C4—C4A	−0.5 (3)	C6—C7—C71—C72	−21.1 (3)
C31—N3—C4—C4A	179.10 (18)	N8—C7—C71—C76	−18.7 (3)
O4—C4—C4A—C5	1.9 (4)	C6—C7—C71—C76	160.1 (2)
N3—C4—C4A—C5	−177.4 (2)	C76—C71—C72—C73	−0.4 (3)
O4—C4—C4A—C8A	−178.4 (2)	C7—C71—C72—C73	−179.2 (2)
N3—C4—C4A—C8A	2.3 (3)	C71—C72—C73—C74	−0.6 (4)
C8A—C4A—C5—C6	0.5 (3)	C72—C73—C74—C75	1.3 (4)
C4—C4A—C5—C6	−179.8 (2)	C72—C73—C74—C77	−178.6 (2)
C4A—C5—C6—C7	1.5 (3)	C73—C74—C75—C76	−1.1 (3)
C5—C6—C7—N8	−2.4 (3)	C77—C74—C75—C76	178.8 (2)
C5—C6—C7—C71	178.9 (2)	C74—C75—C76—C71	0.1 (3)
C6—C7—N8—C8A	1.1 (3)	C72—C71—C76—C75	0.6 (3)
C71—C7—N8—C8A	179.90 (18)	C7—C71—C76—C75	179.5 (2)
C7—N8—C8A—N1	−178.52 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4^i	0.95	2.39	3.306 (3)	161

Symmetry code: (i) −x, −y, −z+1.

(II) 7-(biphenyl-4-yl)-1,3-dimethylpyrido[2,3-d]pyrimidine- 2,4(1H,3H)-dione

Crystal data

C21H17N3O2	F(000) = 720
Mr = 343.38	Dx = 1.450 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3613 reflections
a = 7.2314 (5) Å	θ = 3.1–27.5°
b = 17.5834 (18) Å	µ = 0.10 mm^−1
c = 12.4864 (15) Å	T = 120 K
β = 97.782 (8)°	Block, yellow
V = 1573.1 (3) Å^3	0.45 × 0.27 × 0.15 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	3612 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1851 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ϕ & ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −22→22
Tmin = 0.947, Tmax = 0.986	l = −16→16
40144 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.244	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.138P)^2 + 0.2972P] where P = (Fo^2 + 2Fc^2)/3
3612 reflections	(Δ/σ)max = 0.001
237 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Special details

Experimental. Mass spectrum: MS (70 eV) m/z (%) = 343 (M⁺, 100), 314 (32), 231 (30). HR—MS found 343.1313

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.3564 (3)	0.34566 (13)	0.64534 (19)	0.0311 (6)
C2	0.3717 (4)	0.26808 (16)	0.6605 (2)	0.0333 (7)
N3	0.2991 (3)	0.22236 (13)	0.57325 (19)	0.0327 (6)
C4	0.2240 (4)	0.24889 (16)	0.4732 (2)	0.0338 (7)
C4A	0.2229 (4)	0.33099 (15)	0.4611 (2)	0.0297 (7)
C5	0.1674 (4)	0.36487 (17)	0.3632 (3)	0.0381 (8)
H5	0.1293	0.3348	0.3009	0.046*
C6	0.1674 (4)	0.44308 (16)	0.3561 (2)	0.0361 (7)
H6	0.1311	0.4674	0.2886	0.043*
C7	0.2206 (4)	0.48579 (16)	0.4482 (2)	0.0314 (7)
N8	0.2802 (3)	0.45337 (13)	0.54326 (19)	0.0327 (6)
C8A	0.2842 (3)	0.37789 (15)	0.5478 (2)	0.0290 (7)
C11	0.4261 (4)	0.39266 (17)	0.7378 (2)	0.0408 (8)
H11A	0.3714	0.3755	0.8013	0.061*
H11B	0.3915	0.4458	0.7222	0.061*
H11C	0.5623	0.3883	0.7521	0.061*
O2	0.4440 (3)	0.24105 (11)	0.74449 (17)	0.0406 (6)
C31	0.3064 (4)	0.14025 (16)	0.5885 (3)	0.0396 (8)
H31A	0.1801	0.1192	0.5734	0.059*
H32B	0.3587	0.1286	0.6633	0.059*
H33C	0.3853	0.1177	0.5390	0.059*
O4	0.1638 (3)	0.20493 (11)	0.40182 (17)	0.0417 (6)
C71	0.2139 (3)	0.57038 (16)	0.4453 (2)	0.0296 (7)
C72	0.1204 (4)	0.60843 (15)	0.3571 (2)	0.0346 (7)
H72	0.0560	0.5804	0.2985	0.041*
C73	0.1205 (4)	0.68687 (16)	0.3538 (2)	0.0342 (7)
H73	0.0569	0.7121	0.2922	0.041*
C74	0.2115 (4)	0.72988 (16)	0.4384 (2)	0.0316 (7)
C75	0.3013 (4)	0.69129 (16)	0.5274 (2)	0.0342 (7)
H75	0.3628	0.7192	0.5869	0.041*
C76	0.3025 (4)	0.61227 (16)	0.5308 (2)	0.0326 (7)
H76	0.3650	0.5869	0.5925	0.039*
C81	0.2134 (4)	0.81360 (16)	0.4331 (2)	0.0313 (7)
C82	0.2154 (4)	0.85040 (16)	0.3347 (2)	0.0349 (7)
H82	0.2156	0.8213	0.2707	0.042*
C83	0.2170 (4)	0.92868 (17)	0.3291 (3)	0.0403 (8)
H83	0.2168	0.9531	0.2612	0.048*
C84	0.2188 (4)	0.97151 (17)	0.4210 (3)	0.0428 (8)
H84	0.2207	1.0255	0.4169	0.051*
C85	0.2180 (4)	0.93597 (17)	0.5196 (3)	0.0417 (8)
H85	0.2189	0.9654	0.5835	0.050*
C86	0.2159 (4)	0.85778 (16)	0.5248 (2)	0.0352 (7)
H86	0.2161	0.8337	0.5929	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0337 (13)	0.0273 (13)	0.0326 (14)	0.0034 (10)	0.0059 (11)	−0.0022 (10)
C2	0.0306 (16)	0.0302 (17)	0.0399 (18)	0.0024 (12)	0.0086 (14)	−0.0009 (14)
N3	0.0336 (13)	0.0261 (13)	0.0389 (15)	0.0013 (10)	0.0062 (11)	−0.0007 (11)
C4	0.0307 (15)	0.0320 (17)	0.0399 (18)	−0.0028 (12)	0.0099 (13)	0.0007 (14)
C4A	0.0259 (14)	0.0281 (16)	0.0354 (17)	0.0000 (11)	0.0049 (12)	−0.0005 (12)
C5	0.0356 (16)	0.0392 (18)	0.0388 (19)	−0.0012 (13)	0.0022 (14)	−0.0026 (14)
C6	0.0418 (17)	0.0320 (17)	0.0336 (17)	−0.0015 (13)	0.0013 (14)	−0.0001 (13)
C7	0.0282 (15)	0.0306 (17)	0.0360 (17)	−0.0014 (11)	0.0060 (13)	−0.0010 (13)
N8	0.0288 (13)	0.0319 (14)	0.0372 (15)	0.0013 (10)	0.0042 (11)	0.0026 (11)
C8A	0.0266 (14)	0.0261 (15)	0.0348 (17)	0.0015 (11)	0.0059 (13)	0.0008 (12)
C11	0.0494 (18)	0.0319 (17)	0.0392 (18)	0.0016 (14)	−0.0005 (15)	−0.0070 (13)
O2	0.0463 (13)	0.0354 (12)	0.0390 (13)	0.0064 (9)	0.0019 (10)	0.0044 (10)
C31	0.0409 (17)	0.0275 (17)	0.051 (2)	0.0035 (13)	0.0092 (15)	0.0019 (14)
O4	0.0429 (12)	0.0354 (12)	0.0463 (14)	−0.0044 (9)	0.0041 (10)	−0.0058 (10)
C71	0.0258 (14)	0.0283 (16)	0.0350 (17)	−0.0008 (11)	0.0052 (12)	0.0021 (12)
C72	0.0347 (16)	0.0300 (16)	0.0386 (18)	−0.0017 (12)	0.0036 (13)	−0.0035 (13)
C73	0.0307 (15)	0.0330 (16)	0.0382 (18)	0.0031 (12)	0.0024 (13)	0.0036 (13)
C74	0.0270 (14)	0.0272 (16)	0.0410 (18)	−0.0003 (11)	0.0063 (13)	−0.0013 (13)
C75	0.0317 (16)	0.0341 (18)	0.0374 (18)	−0.0035 (12)	0.0064 (13)	−0.0008 (13)
C76	0.0280 (15)	0.0331 (17)	0.0359 (17)	0.0011 (12)	0.0012 (13)	0.0027 (13)
C81	0.0267 (15)	0.0300 (16)	0.0372 (18)	−0.0006 (11)	0.0046 (13)	−0.0013 (13)
C82	0.0321 (16)	0.0312 (16)	0.0401 (18)	0.0009 (12)	0.0010 (13)	−0.0024 (13)
C83	0.0395 (17)	0.0363 (18)	0.0440 (19)	−0.0003 (13)	0.0020 (14)	0.0011 (14)
C84	0.0478 (19)	0.0269 (16)	0.053 (2)	−0.0016 (14)	0.0032 (15)	0.0021 (15)
C85	0.0478 (19)	0.0349 (18)	0.0422 (19)	−0.0013 (14)	0.0056 (15)	−0.0076 (14)
C86	0.0340 (16)	0.0334 (17)	0.0378 (18)	−0.0037 (13)	0.0038 (13)	0.0039 (13)

Geometric parameters (Å, º)

N1—C2	1.380 (4)	C31—H33C	0.9800
N1—C8A	1.380 (3)	C71—C76	1.381 (4)
N1—C11	1.453 (4)	C71—C72	1.385 (4)
C2—O2	1.204 (3)	C72—C73	1.380 (4)
C2—N3	1.398 (4)	C72—H72	0.9500
N3—C4	1.375 (4)	C73—C74	1.391 (4)
N3—C31	1.456 (4)	C73—H73	0.9500
C4—O4	1.215 (3)	C74—C75	1.386 (4)
C4—C4A	1.451 (4)	C74—C81	1.474 (4)
C4A—C5	1.370 (4)	C75—C76	1.390 (4)
C4A—C8A	1.386 (4)	C75—H75	0.9500
C5—C6	1.378 (4)	C76—H76	0.9500
C5—H5	0.9500	C81—C86	1.382 (4)
C6—C7	1.384 (4)	C81—C82	1.390 (4)
C6—H6	0.9500	C82—C83	1.378 (4)
C7—N8	1.335 (3)	C82—H82	0.9500
C7—C71	1.488 (4)	C83—C84	1.371 (4)
N8—C8A	1.328 (3)	C83—H83	0.9500
C11—H11A	0.9800	C84—C85	1.382 (4)
C11—H11B	0.9800	C84—H84	0.9500
C11—H11C	0.9800	C85—C86	1.377 (4)
C31—H31A	0.9800	C85—H85	0.9500
C31—H32B	0.9800	C86—H86	0.9500
C2—N1—C8A	122.8 (2)	H31A—C31—H33C	109.5
C2—N1—C11	116.1 (2)	H32B—C31—H33C	109.5
C8A—N1—C11	121.1 (2)	C76—C71—C72	118.9 (3)
O2—C2—N1	121.8 (3)	C76—C71—C7	120.3 (3)
O2—C2—N3	121.6 (3)	C72—C71—C7	120.8 (3)
N1—C2—N3	116.5 (3)	C73—C72—C71	120.3 (3)
C4—N3—C2	125.0 (2)	C73—C72—H72	119.8
C4—N3—C31	117.3 (2)	C71—C72—H72	119.8
C2—N3—C31	117.7 (2)	C72—C73—C74	121.5 (3)
O4—C4—N3	120.6 (3)	C72—C73—H73	119.2
O4—C4—C4A	124.0 (3)	C74—C73—H73	119.2
N3—C4—C4A	115.4 (3)	C75—C74—C73	117.7 (3)
C5—C4A—C8A	117.6 (3)	C75—C74—C81	121.2 (3)
C5—C4A—C4	121.5 (3)	C73—C74—C81	121.0 (3)
C8A—C4A—C4	120.9 (3)	C74—C75—C76	121.0 (3)
C4A—C5—C6	119.3 (3)	C74—C75—H75	119.5
C4A—C5—H5	120.4	C76—C75—H75	119.5
C6—C5—H5	120.4	C71—C76—C75	120.6 (3)
C5—C6—C7	119.4 (3)	C71—C76—H76	119.7
C5—C6—H6	120.3	C75—C76—H76	119.7
C7—C6—H6	120.3	C86—C81—C82	118.0 (3)
N8—C7—C6	121.8 (3)	C86—C81—C74	121.6 (3)
N8—C7—C71	117.0 (3)	C82—C81—C74	120.4 (3)
C6—C7—C71	121.2 (3)	C83—C82—C81	120.7 (3)
C8A—N8—C7	117.9 (3)	C83—C82—H82	119.6
N8—C8A—N1	116.9 (2)	C81—C82—H82	119.6
N8—C8A—C4A	123.9 (3)	C84—C83—C82	120.3 (3)
N1—C8A—C4A	119.2 (2)	C84—C83—H83	119.8
N1—C11—H11A	109.5	C82—C83—H83	119.8
N1—C11—H11B	109.5	C83—C84—C85	119.8 (3)
H11A—C11—H11B	109.5	C83—C84—H84	120.1
N1—C11—H11C	109.5	C85—C84—H84	120.1
H11A—C11—H11C	109.5	C86—C85—C84	119.7 (3)
H11B—C11—H11C	109.5	C86—C85—H85	120.2
N3—C31—H31A	109.5	C84—C85—H85	120.2
N3—C31—H32B	109.5	C85—C86—C81	121.4 (3)
H31A—C31—H32B	109.5	C85—C86—H86	119.3
N3—C31—H33C	109.5	C81—C86—H86	119.3
C8A—N1—C2—O2	176.0 (2)	C4—C4A—C8A—N8	−177.3 (2)
C11—N1—C2—O2	−2.3 (4)	C5—C4A—C8A—N1	−174.4 (2)
C8A—N1—C2—N3	−3.8 (4)	C4—C4A—C8A—N1	3.5 (4)
C11—N1—C2—N3	177.9 (2)	N8—C7—C71—C76	13.5 (4)
O2—C2—N3—C4	−176.2 (3)	C6—C7—C71—C76	−166.5 (3)
N1—C2—N3—C4	3.6 (4)	N8—C7—C71—C72	−167.1 (2)
O2—C2—N3—C31	2.6 (4)	C6—C7—C71—C72	12.9 (4)
N1—C2—N3—C31	−177.5 (2)	C76—C71—C72—C73	1.7 (4)
C2—N3—C4—O4	−179.9 (2)	C7—C71—C72—C73	−177.8 (2)
C31—N3—C4—O4	1.2 (4)	C71—C72—C73—C74	−0.7 (4)
C2—N3—C4—C4A	0.0 (4)	C72—C73—C74—C75	−0.7 (4)
C31—N3—C4—C4A	−178.9 (2)	C72—C73—C74—C81	178.9 (2)
O4—C4—C4A—C5	−5.9 (4)	C73—C74—C75—C76	1.1 (4)
N3—C4—C4A—C5	174.2 (2)	C81—C74—C75—C76	−178.5 (2)
O4—C4—C4A—C8A	176.3 (3)	C72—C71—C76—C75	−1.3 (4)
N3—C4—C4A—C8A	−3.6 (4)	C7—C71—C76—C75	178.2 (2)
C8A—C4A—C5—C6	−2.6 (4)	C74—C75—C76—C71	−0.1 (4)
C4—C4A—C5—C6	179.5 (2)	C75—C74—C81—C86	−32.7 (4)
C4A—C5—C6—C7	−1.0 (4)	C73—C74—C81—C86	147.7 (3)
C5—C6—C7—N8	3.0 (4)	C75—C74—C81—C82	146.4 (3)
C5—C6—C7—C71	−177.0 (2)	C73—C74—C81—C82	−33.2 (4)
C6—C7—N8—C8A	−1.1 (4)	C86—C81—C82—C83	−0.9 (4)
C71—C7—N8—C8A	178.9 (2)	C74—C81—C82—C83	179.9 (2)
C7—N8—C8A—N1	176.3 (2)	C81—C82—C83—C84	0.8 (4)
C7—N8—C8A—C4A	−2.8 (4)	C82—C83—C84—C85	−0.4 (4)
C2—N1—C8A—N8	−178.8 (2)	C83—C84—C85—C86	0.2 (4)
C11—N1—C8A—N8	−0.6 (4)	C84—C85—C86—C81	−0.4 (4)
C2—N1—C8A—C4A	0.4 (4)	C82—C81—C86—C85	0.7 (4)
C11—N1—C8A—C4A	178.6 (3)	C74—C81—C86—C85	179.9 (3)
C5—C4A—C8A—N8	4.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C75—H75···O2^i	0.95	2.39	3.294 (3)	158
C76—H76···N8	0.95	2.48	2.805 (4)	100

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

(III) 7-(4-fluorophenyl)-3-methylpyrido[2,3-d]pyrimidine- 2,4(1H,3H)-dione

Crystal data

C14H10FN3O2	F(000) = 560
Mr = 271.25	Dx = 1.559 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2636 reflections
a = 6.7658 (8) Å	θ = 3.4–27.5°
b = 12.978 (2) Å	µ = 0.12 mm^−1
c = 13.162 (2) Å	T = 120 K
V = 1155.7 (3) Å^3	Block, yellow
Z = 4	0.10 × 0.10 × 0.10 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	1538 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	833 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.164
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.4°
ϕ & ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→16
Tmin = 0.968, Tmax = 0.988	l = −16→17
11820 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0734P)^2] where P = (Fo^2 + 2Fc^2)/3
1538 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. Mass spectrum: MS (70 eV) m/z (%) = 271 (M⁺, 100), 242 (19), 214 (22), 187 (19), 158 (18), 69 (27). HRMS found 271.0752

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4355 (5)	0.3063 (3)	0.2496 (3)	0.0293 (10)
H1	0.4473	0.3734	0.2574	0.035*
C2	0.4439 (7)	0.2678 (4)	0.1534 (4)	0.0288 (12)
N3	0.4185 (6)	0.1613 (3)	0.1439 (3)	0.0289 (9)
C4	0.3932 (6)	0.0941 (4)	0.2250 (3)	0.0277 (11)
C4A	0.3878 (6)	0.1408 (3)	0.3250 (3)	0.0239 (10)
C5	0.3664 (6)	0.0822 (4)	0.4131 (4)	0.0288 (11)
H5	0.3537	0.0094	0.4092	0.035*
C6	0.3638 (7)	0.1316 (4)	0.5063 (3)	0.0304 (12)
H6	0.3467	0.0933	0.5672	0.036*
C7	0.3865 (6)	0.2386 (4)	0.5097 (3)	0.0250 (11)
N8	0.4092 (5)	0.2959 (3)	0.4250 (3)	0.0263 (9)
C8A	0.4096 (6)	0.2463 (3)	0.3366 (3)	0.0250 (11)
O2	0.4729 (5)	0.3226 (3)	0.0793 (3)	0.0396 (10)
C31	0.4311 (8)	0.1208 (4)	0.0399 (3)	0.0375 (13)
H31A	0.4326	0.0453	0.0418	0.056*
H31B	0.5526	0.1458	0.0077	0.056*
H31C	0.3165	0.1443	0.0007	0.056*
O4	0.3753 (4)	0.0001 (2)	0.2097 (2)	0.0345 (8)
C71	0.3861 (6)	0.2981 (4)	0.6059 (3)	0.0264 (11)
C72	0.4119 (7)	0.2510 (4)	0.7002 (3)	0.0342 (13)
H72	0.4283	0.1783	0.7034	0.041*
C73	0.4141 (6)	0.3080 (4)	0.7901 (4)	0.0339 (12)
H73	0.4327	0.2755	0.8541	0.041*
C74	0.3887 (7)	0.4122 (4)	0.7827 (4)	0.0338 (12)
C75	0.3643 (7)	0.4628 (4)	0.6932 (4)	0.0333 (12)
H75	0.3487	0.5355	0.6913	0.040*
C76	0.3630 (7)	0.4039 (4)	0.6036 (4)	0.0301 (12)
H76	0.3458	0.4375	0.5401	0.036*
F74	0.3872 (5)	0.4691 (2)	0.86986 (19)	0.0498 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.034 (2)	0.020 (2)	0.034 (2)	0.0022 (17)	−0.0023 (19)	−0.0002 (19)
C2	0.029 (3)	0.028 (3)	0.029 (3)	0.002 (2)	0.001 (2)	0.000 (3)
N3	0.034 (2)	0.025 (2)	0.027 (2)	0.0004 (19)	0.0003 (19)	−0.0028 (18)
C4	0.024 (2)	0.029 (3)	0.031 (3)	0.000 (2)	−0.004 (2)	0.000 (2)
C4A	0.020 (2)	0.024 (3)	0.028 (2)	0.004 (2)	−0.001 (2)	−0.001 (2)
C5	0.028 (2)	0.022 (3)	0.037 (3)	0.001 (2)	−0.002 (2)	0.002 (2)
C6	0.031 (3)	0.024 (3)	0.036 (3)	0.000 (2)	−0.003 (2)	0.007 (2)
C7	0.017 (2)	0.029 (3)	0.029 (3)	−0.001 (2)	0.002 (2)	0.001 (2)
N8	0.026 (2)	0.023 (2)	0.030 (2)	−0.0027 (17)	−0.0020 (19)	−0.0034 (19)
C8A	0.024 (2)	0.019 (3)	0.032 (3)	0.0035 (19)	0.000 (2)	0.005 (2)
O2	0.056 (2)	0.036 (2)	0.0266 (18)	−0.0018 (18)	0.0011 (17)	0.0016 (18)
C31	0.048 (3)	0.031 (3)	0.033 (3)	0.004 (2)	−0.003 (3)	−0.007 (3)
O4	0.0417 (18)	0.0234 (18)	0.0383 (19)	−0.0005 (17)	−0.0011 (16)	−0.0025 (17)
C71	0.020 (2)	0.032 (3)	0.027 (2)	−0.002 (2)	0.003 (2)	0.000 (2)
C72	0.033 (3)	0.031 (3)	0.038 (3)	−0.002 (2)	−0.001 (2)	0.000 (3)
C73	0.028 (3)	0.043 (3)	0.031 (3)	−0.005 (3)	−0.001 (2)	0.003 (3)
C74	0.035 (3)	0.042 (3)	0.024 (3)	−0.008 (3)	0.005 (2)	−0.012 (3)
C75	0.032 (2)	0.025 (3)	0.043 (3)	−0.004 (2)	0.007 (2)	−0.011 (2)
C76	0.027 (2)	0.026 (3)	0.038 (3)	−0.002 (2)	0.010 (2)	−0.001 (2)
F74	0.0562 (18)	0.056 (2)	0.0373 (17)	−0.0062 (17)	0.0028 (15)	−0.0146 (16)

Geometric parameters (Å, º)

N1—C2	1.362 (6)	C7—C71	1.483 (7)
N1—C8A	1.395 (5)	N8—C8A	1.329 (5)
N1—H1	0.8800	C31—H31A	0.9800
C2—O2	1.222 (5)	C31—H31B	0.9800
C2—N3	1.399 (6)	C31—H31C	0.9800
N3—C4	1.389 (6)	C71—C76	1.383 (6)
N3—C31	1.468 (5)	C71—C72	1.394 (6)
C4—O4	1.242 (5)	C72—C73	1.395 (7)
C4—C4A	1.449 (6)	C72—H72	0.9500
C4A—C8A	1.386 (6)	C73—C74	1.367 (7)
C4A—C5	1.395 (6)	C73—H73	0.9500
C5—C6	1.384 (7)	C74—C75	1.359 (6)
C5—H5	0.9500	C74—F74	1.364 (5)
C6—C7	1.398 (6)	C75—C76	1.405 (7)
C6—H6	0.9500	C75—H75	0.9500
C7—N8	1.349 (5)	C76—H76	0.9500
C2—N1—C8A	124.3 (4)	N8—C8A—N1	116.7 (4)
C2—N1—H1	117.9	C4A—C8A—N1	118.3 (4)
C8A—N1—H1	117.9	N3—C31—H31A	109.5
O2—C2—N1	122.3 (4)	N3—C31—H31B	109.5
O2—C2—N3	121.5 (4)	H31A—C31—H31B	109.5
N1—C2—N3	116.2 (4)	N3—C31—H31C	109.5
C4—N3—C2	124.5 (4)	H31A—C31—H31C	109.5
C4—N3—C31	120.0 (4)	H31B—C31—H31C	109.5
C2—N3—C31	115.5 (4)	C76—C71—C72	118.0 (5)
O4—C4—N3	120.2 (4)	C76—C71—C7	119.9 (4)
O4—C4—C4A	123.7 (4)	C72—C71—C7	122.1 (4)
N3—C4—C4A	116.0 (4)	C71—C72—C73	121.6 (5)
C8A—C4A—C5	117.3 (4)	C71—C72—H72	119.2
C8A—C4A—C4	120.7 (4)	C73—C72—H72	119.2
C5—C4A—C4	122.0 (4)	C74—C73—C72	117.6 (5)
C6—C5—C4A	119.1 (4)	C74—C73—H73	121.2
C6—C5—H5	120.5	C72—C73—H73	121.2
C4A—C5—H5	120.5	C75—C74—F74	117.8 (4)
C5—C6—C7	119.1 (5)	C75—C74—C73	123.7 (4)
C5—C6—H6	120.4	F74—C74—C73	118.5 (5)
C7—C6—H6	120.4	C74—C75—C76	117.7 (4)
N8—C7—C6	122.2 (4)	C74—C75—H75	121.1
N8—C7—C71	114.8 (4)	C76—C75—H75	121.1
C6—C7—C71	122.9 (4)	C71—C76—C75	121.4 (5)
C8A—N8—C7	117.2 (4)	C71—C76—H76	119.3
N8—C8A—C4A	125.0 (4)	C75—C76—H76	119.3
C8A—N1—C2—O2	−177.7 (4)	C7—N8—C8A—N1	−179.3 (4)
C8A—N1—C2—N3	1.9 (6)	C5—C4A—C8A—N8	−0.9 (7)
O2—C2—N3—C4	177.2 (4)	C4—C4A—C8A—N8	−179.1 (4)
N1—C2—N3—C4	−2.4 (6)	C5—C4A—C8A—N1	178.6 (4)
O2—C2—N3—C31	0.5 (7)	C4—C4A—C8A—N1	0.4 (6)
N1—C2—N3—C31	−179.1 (4)	C2—N1—C8A—N8	178.5 (4)
C2—N3—C4—O4	−178.7 (4)	C2—N1—C8A—C4A	−1.0 (6)
C31—N3—C4—O4	−2.1 (6)	N8—C7—C71—C76	14.6 (6)
C2—N3—C4—C4A	1.8 (6)	C6—C7—C71—C76	−165.0 (4)
C31—N3—C4—C4A	178.4 (4)	N8—C7—C71—C72	−164.3 (4)
O4—C4—C4A—C8A	179.7 (4)	C6—C7—C71—C72	16.1 (7)
N3—C4—C4A—C8A	−0.8 (6)	C76—C71—C72—C73	0.1 (7)
O4—C4—C4A—C5	1.6 (7)	C7—C71—C72—C73	179.1 (4)
N3—C4—C4A—C5	−178.9 (4)	C71—C72—C73—C74	0.5 (7)
C8A—C4A—C5—C6	1.3 (6)	C72—C73—C74—C75	−1.0 (7)
C4—C4A—C5—C6	179.5 (4)	C72—C73—C74—F74	179.0 (4)
C4A—C5—C6—C7	−1.2 (7)	F74—C74—C75—C76	−179.1 (4)
C5—C6—C7—N8	0.6 (7)	C73—C74—C75—C76	0.8 (7)
C5—C6—C7—C71	−179.8 (4)	C72—C71—C76—C75	−0.3 (7)
C6—C7—N8—C8A	−0.1 (6)	C7—C71—C76—C75	−179.2 (4)
C71—C7—N8—C8A	−179.7 (4)	C74—C75—C76—C71	−0.2 (6)
C7—N8—C8A—C4A	0.2 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.88	2.08	2.874 (4)	149
C76—H76···N8	0.95	2.42	2.755 (7)	100

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

(IV)

Crystal data

C15H13N3O3	F(000) = 592
Mr = 283.28	Dx = 1.506 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c-2ac	Cell parameters from 1439 reflections
a = 6.6312 (11) Å	θ = 3.0–27.5°
b = 6.8121 (15) Å	µ = 0.11 mm^−1
c = 27.653 (7) Å	T = 120 K
V = 1249.2 (5) Å^3	Block, yellow
Z = 4	0.28 × 0.24 × 0.22 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	1439 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1181 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ & ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
Tmin = 0.961, Tmax = 0.977	l = −35→24
8019 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 1.8263P] where P = (Fo^2 + 2Fc^2)/3
1439 reflections	(Δ/σ)max = 0.001
192 parameters	Δρmax = 0.36 e Å^−3
1 restraint	Δρmin = −0.39 e Å^−3

Special details

Experimental. Mass spectrum: MS (70 eV) m/z (%) = 283 (M⁺, 100), 254 (10), 226 (20), 155 (8). HR—MS found 283.0966

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4060 (6)	0.2722 (6)	0.12467 (14)	0.0249 (9)
H1	0.5364	0.2894	0.1287	0.030*
C2	0.3255 (8)	0.2656 (8)	0.07964 (17)	0.0273 (11)
N3	0.1173 (6)	0.2446 (6)	0.07641 (14)	0.0250 (9)
C4	−0.0076 (7)	0.2280 (7)	0.11555 (17)	0.0231 (10)
C4A	0.0882 (7)	0.2336 (7)	0.16283 (18)	0.0226 (9)
C5	−0.0217 (7)	0.2147 (7)	0.20436 (17)	0.0225 (10)
H5	−0.1642	0.2013	0.2032	0.027*
C6	0.0785 (8)	0.2155 (7)	0.24795 (16)	0.0222 (10)
H6	0.0061	0.2011	0.2774	0.027*
C7	0.2882 (7)	0.2380 (7)	0.24835 (15)	0.0176 (9)
N8	0.3962 (6)	0.2585 (6)	0.20775 (14)	0.0216 (8)
C8A	0.2960 (7)	0.2552 (7)	0.16624 (17)	0.0211 (9)
O2	0.4287 (6)	0.2763 (6)	0.04349 (11)	0.0355 (10)
C31	0.0296 (8)	0.2343 (8)	0.02801 (16)	0.0288 (11)
H31A	0.0433	0.1004	0.0154	0.043*
H31B	0.1003	0.3259	0.0066	0.043*
H31C	−0.1135	0.2695	0.0296	0.043*
O4	−0.1875 (5)	0.2024 (7)	0.11046 (13)	0.0358 (10)
C71	0.3976 (8)	0.2384 (7)	0.29459 (15)	0.0204 (11)
C72	0.3115 (7)	0.1589 (7)	0.33615 (15)	0.0211 (10)
H72	0.1820	0.0999	0.3342	0.025*
C73	0.4093 (7)	0.1639 (6)	0.37970 (15)	0.0198 (10)
H73	0.3475	0.1080	0.4075	0.024*
C74	0.5977 (7)	0.2497 (7)	0.38355 (15)	0.0193 (10)
C75	0.6861 (7)	0.3325 (7)	0.34289 (15)	0.0216 (10)
H75	0.8144	0.3940	0.3452	0.026*
C76	0.5862 (7)	0.3248 (7)	0.29893 (15)	0.0194 (10)
H76	0.6482	0.3800	0.2711	0.023*
O7	0.6810 (5)	0.2436 (5)	0.42776 (12)	0.0241 (8)
C77	0.8726 (8)	0.3323 (8)	0.43432 (19)	0.0304 (11)
H77A	0.9709	0.2699	0.4128	0.046*
H77C	0.9157	0.3158	0.4680	0.046*
H77B	0.8636	0.4726	0.4267	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0127 (17)	0.040 (2)	0.0217 (19)	−0.0025 (17)	0.0008 (15)	0.0036 (17)
C2	0.025 (2)	0.041 (3)	0.016 (2)	0.001 (2)	0.000 (2)	0.004 (2)
N3	0.019 (2)	0.035 (2)	0.0209 (19)	0.0017 (17)	−0.0045 (16)	0.0007 (16)
C4	0.021 (2)	0.027 (2)	0.022 (2)	0.0028 (19)	0.0014 (19)	−0.003 (2)
C4A	0.018 (2)	0.025 (2)	0.025 (2)	0.0007 (19)	0.000 (2)	−0.001 (2)
C5	0.015 (2)	0.025 (2)	0.028 (2)	0.0005 (18)	0.0025 (19)	−0.007 (2)
C6	0.020 (2)	0.023 (2)	0.023 (2)	0.001 (2)	0.0042 (18)	−0.0005 (18)
C7	0.019 (2)	0.019 (2)	0.0155 (19)	−0.0004 (18)	0.0006 (16)	0.0004 (16)
N8	0.0171 (17)	0.028 (2)	0.0196 (18)	0.0001 (16)	0.0001 (16)	0.0020 (16)
C8A	0.018 (2)	0.026 (2)	0.019 (2)	0.0005 (18)	0.0021 (19)	−0.0001 (17)
O2	0.0204 (17)	0.069 (3)	0.0172 (17)	−0.0022 (18)	0.0024 (14)	0.0054 (18)
C31	0.025 (2)	0.045 (3)	0.017 (2)	0.000 (2)	−0.0033 (19)	0.002 (2)
O4	0.0154 (16)	0.067 (3)	0.0252 (17)	0.0009 (16)	−0.0007 (13)	−0.0022 (18)
C71	0.018 (2)	0.023 (3)	0.021 (2)	0.0020 (19)	0.0001 (17)	−0.0015 (18)
C72	0.019 (2)	0.021 (2)	0.023 (2)	−0.0018 (18)	0.0024 (18)	0.0000 (17)
C73	0.023 (2)	0.020 (2)	0.016 (2)	0.0000 (19)	0.0063 (17)	0.0010 (16)
C74	0.019 (2)	0.019 (2)	0.019 (2)	0.0024 (18)	0.0016 (18)	−0.0021 (18)
C75	0.018 (2)	0.026 (3)	0.021 (2)	−0.0008 (19)	−0.0009 (18)	0.0007 (18)
C76	0.020 (2)	0.020 (2)	0.018 (2)	0.0031 (19)	0.0027 (17)	−0.0002 (17)
O7	0.0208 (17)	0.033 (2)	0.0180 (14)	−0.0026 (14)	−0.0007 (13)	−0.0001 (14)
C77	0.026 (2)	0.037 (3)	0.028 (2)	−0.008 (2)	−0.0030 (19)	0.002 (2)

Geometric parameters (Å, º)

N1—C2	1.356 (6)	C31—H31A	0.9800
N1—C8A	1.366 (6)	C31—H31B	0.9800
N1—H1	0.8800	C31—H31C	0.9800
C2—O2	1.213 (6)	C71—C76	1.387 (7)
C2—N3	1.391 (6)	C71—C72	1.393 (6)
N3—C4	1.368 (6)	C72—C73	1.368 (6)
N3—C31	1.461 (6)	C72—H72	0.9500
C4—O4	1.214 (6)	C73—C74	1.383 (6)
C4—C4A	1.454 (6)	C73—H73	0.9500
C4A—C5	1.366 (6)	C74—O7	1.342 (5)
C4A—C8A	1.389 (6)	C74—C75	1.388 (6)
C5—C6	1.376 (6)	C75—C76	1.386 (6)
C5—H5	0.9500	C75—H75	0.9500
C6—C7	1.399 (7)	C76—H76	0.9500
C6—H6	0.9500	O7—C77	1.419 (6)
C7—N8	1.339 (6)	C77—H77A	0.9800
C7—C71	1.470 (6)	C77—H77C	0.9800
N8—C8A	1.326 (6)	C77—H77B	0.9800
C2—N1—C8A	124.1 (4)	H31A—C31—H31B	109.5
C2—N1—H1	120.4	N3—C31—H31C	109.5
C8A—N1—H1	115.5	H31A—C31—H31C	109.5
O2—C2—N1	122.2 (4)	H31B—C31—H31C	109.5
O2—C2—N3	120.8 (4)	C76—C71—C72	117.6 (4)
N1—C2—N3	116.9 (4)	C76—C71—C7	121.4 (4)
C4—N3—C2	124.0 (4)	C72—C71—C7	121.0 (4)
C4—N3—C31	118.7 (4)	C73—C72—C71	121.5 (4)
C2—N3—C31	117.3 (4)	C73—C72—H72	119.3
O4—C4—N3	121.0 (4)	C71—C72—H72	119.3
O4—C4—C4A	122.5 (4)	C72—C73—C74	120.4 (4)
N3—C4—C4A	116.4 (4)	C72—C73—H73	119.8
C5—C4A—C8A	118.8 (5)	C74—C73—H73	119.8
C5—C4A—C4	121.4 (4)	O7—C74—C73	115.4 (4)
C8A—C4A—C4	119.8 (4)	O7—C74—C75	125.2 (4)
C4A—C5—C6	118.6 (4)	C73—C74—C75	119.4 (4)
C4A—C5—H5	120.7	C76—C75—C74	119.5 (4)
C6—C5—H5	120.7	C76—C75—H75	120.2
C5—C6—C7	119.1 (4)	C74—C75—H75	120.2
C5—C6—H6	120.4	C75—C76—C71	121.6 (4)
C7—C6—H6	120.4	C75—C76—H76	119.2
N8—C7—C6	122.4 (4)	C71—C76—H76	119.2
N8—C7—C71	117.7 (4)	C74—O7—C77	118.1 (4)
C6—C7—C71	119.8 (4)	O7—C77—H77A	109.5
C8A—N8—C7	117.1 (4)	O7—C77—H77C	109.5
N8—C8A—N1	117.3 (4)	H77A—C77—H77C	109.5
N8—C8A—C4A	123.9 (4)	O7—C77—H77B	109.5
N1—C8A—C4A	118.8 (4)	H77A—C77—H77B	109.5
N3—C31—H31A	109.5	H77C—C77—H77B	109.5
N3—C31—H31B	109.5
C8A—N1—C2—O2	−178.1 (5)	C2—N1—C8A—N8	178.0 (4)
C8A—N1—C2—N3	1.5 (7)	C2—N1—C8A—C4A	−1.3 (7)
O2—C2—N3—C4	178.7 (5)	C5—C4A—C8A—N8	0.1 (8)
N1—C2—N3—C4	−0.9 (7)	C4—C4A—C8A—N8	−178.9 (5)
O2—C2—N3—C31	0.6 (8)	C5—C4A—C8A—N1	179.4 (5)
N1—C2—N3—C31	−179.1 (5)	C4—C4A—C8A—N1	0.4 (7)
C2—N3—C4—O4	−177.1 (5)	N8—C7—C71—C76	22.9 (6)
C31—N3—C4—O4	1.0 (7)	C6—C7—C71—C76	−157.4 (5)
C2—N3—C4—C4A	0.1 (7)	N8—C7—C71—C72	−159.8 (4)
C31—N3—C4—C4A	178.3 (4)	C6—C7—C71—C72	19.9 (7)
O4—C4—C4A—C5	−1.6 (8)	C76—C71—C72—C73	−0.5 (7)
N3—C4—C4A—C5	−178.8 (5)	C7—C71—C72—C73	−178.0 (4)
O4—C4—C4A—C8A	177.3 (5)	C71—C72—C73—C74	0.3 (7)
N3—C4—C4A—C8A	0.1 (6)	C72—C73—C74—O7	−179.0 (4)
C8A—C4A—C5—C6	−0.8 (7)	C72—C73—C74—C75	0.6 (6)
C4—C4A—C5—C6	178.2 (4)	O7—C74—C75—C76	178.4 (4)
C4A—C5—C6—C7	0.8 (7)	C73—C74—C75—C76	−1.2 (7)
C5—C6—C7—N8	−0.1 (8)	C74—C75—C76—C71	0.9 (7)
C5—C6—C7—C71	−179.8 (4)	C72—C71—C76—C75	−0.1 (7)
C6—C7—N8—C8A	−0.6 (7)	C7—C71—C76—C75	177.3 (4)
C71—C7—N8—C8A	179.1 (4)	C73—C74—O7—C77	−178.8 (4)
C7—N8—C8A—N1	−178.7 (4)	C75—C74—O7—C77	1.6 (7)
C7—N8—C8A—C4A	0.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.88	1.99	2.765 (5)	146
C72—H72···Cg^ii	0.95	2.65	3.448 (5)	142
C75—H75···Cg^iii	0.95	2.75	3.548 (5)	142

Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y, z; (iii) x+1/2, −y+1, z.