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Two isomeric pyridine-substituted norbornenedicarboximide derivatives, namely N-(pyridin-2-yl)-exo-norbornene-5,6-di­carboximide, (I), and N-(pyridin-3-yl)-exo-norbornene-5,6-dicarboximide, (II), both C14H12N2O4, have been crystallized and their structures unequivocally determined by single-crystal X-ray diffraction. The mol­ecules consist of norbornene moieties fused to a dicarboximide ring substituted at the N atom by either pyridin-2-yl or pyridin-3-yl in an anti configuration with respect to the double bond, thus affording exo isomers. In both compounds, the asymmetric unit consists of two independent mol­ecules (Z′ = 2). In compound (I), the pyridine rings of the two independent mol­ecules adopt different conformations, i.e. syn and anti, with respect to the methyl­ene bridge. The inter­molecular contacts of (I) are dominated by C—H...O inter­actions. In contrast, in compound (II), the pyridine rings of both mol­ecules have an anti conformation and the two independent mol­ecules are linked by carbon­yl–carbonyl inter­actions, as well as by C—H...O and C—H...N contacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615001886/ky3070sup1.cif
Contains datablocks I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001886/ky3070Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001886/ky3070IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615001886/ky3070Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615001886/ky3070IIsup5.cml
Supplementary material

CCDC references: 1046071; 1046070

Introduction top

Dicarboximides are compounds with a wide variety of properties and applications. For instance, dicarboximides such as vinclozolin, iprodione and procymidone are used as fungicides in greenhouses. Others inhibit DNA and RNA synthesis and cell division in fungi e.g. Botrytis cinerea (Angioni et al., 2012; LaMondia & Douglas, 1997; Vetcher et al., 2007). N-Octylbi­cyclo­heptenedicarboximide (MGK-264) is an active ingredient in insect repellents and in some common pesticides (Katz et al., 2008; Hanif & Singh, 2013; Kayedi et al., 2014). Cantharimide derivatives (bicyclic dicarboximides) exhibit anti­cancer activity, a broad spectrum cytotoxicity, and anti­proliferative and anti­plasmodial activities (Wu et al., 2014; Hill et al., 2007; Bajsa et al., 2010; Puerto et al., 2013; Robertson et al., 2011). Some norbornenedicarboximides also show binding affinity and selectivity towards serotonin receptors (Fiorino et al., 2014).

Due to their high photochemical stability, simple synthetic modification and optical/redox characteristics, other dicarboximide aryl­ene derivatives, have found applications in the design of field-effect transistors, molecular electronics, light-harvesting arrays, solar cells, light-emitting diodes and fluorescent labelling (Grucela-Zajac et al., 2014; Jones et al., 2004; Lukas et al., 2001; Chan et al., 2012; Tomizaki et al., 2002; Nakaya et al., 2001).

In the field of polymers, dicarboximides have been used to test functional group tolerance of ring-opening metathesis polymerization (ROMP) catalysts, and a series of exo- and endo-N-alkyl- and N-aryl­norbornenedicarboximides have been used as starting materials and successfully polymerized using both classical and well-defined initiators in aqueous media (Yu et al., 2013; You et al., 2013; Yoon et al., 2012; Gallivan et al., 2005; Czelusniak et al., 2008).

Two isomeric pyridine-susbstituted norbornenedicarboximide derivatives, namely N-(pyridin-2-yl)-exo-norbornene-5,6-dicarboximide, (I), and N-(pyridin-3-yl)-exo-norbornene-5,6-dicarboximide, (II), have been crystallized and their structures unequivocally determined by single-crystal X-ray diffraction.

Experimental top

Synthesis and crystallization top

Preparation of N-(pyridin-2-yl)-exo-norbornene-5,6-dicarboximide, (I) top

To a solution of exo-norbornene-5,6-di­carb­oxy­lic anhydride (3.12 g, 19.0 mmol) in xylene (29 ml), 2-amino­pyridine (1.79 g, 19.0 mmol) was added. The resulting reaction mixture was refluxed for 3 h. After cooling the mixture to room temperature, the precipitate was removed by filtration under vacuum. The collected filtrate was recrystallized twice from toluene. Compound (I) was obtained as a white crystalline powder in 81% yield (3.70 g, 15.4 mmol). Single crystals suitable for X-ray determination were obtained by slow evaporation of an ethyl acetate solution of (I) (m.p. 405–407 K).

Preparation of N-(pyridin-3-yl)-exo-norbornene-5,6-dicarboximide, (II) top

To a solution of exo-norbornene-5,6-di­carb­oxy­lic anhydride (3.16 g, 19.3 mmol) in xylene (29 ml), 3-amino­pyridine (1.82 g, 19.3 mmol) was added. The resulting reaction mixture was refluxed for 2 h to produce a slurry of amic acid that was filtered and dried to yield 89% (4.43 g, 17.2 mmol). The amic acid was taken up in acetic anhydride (14.61 ml, 0.15 mmol), and anhydrous sodium acetate (0.67 g, 8.11 mmol) was added. The reaction mixture was heated and stirred for 4 h at 358 K and then poured into ice water. The mixture was stirred for 5 min and the precipitate which formed was collected by filtration and washed with cold water. The product was further dried under reduced pressure and recrystallized from toluene twice and the solid removed by filtration under vacuum. Compound (II) was obtained as pale-yellow crystals in 83% yield (3.43 g, 14.3 mmol). Crystals suitable for X-ray diffraction studies were obtained by slow evaporation of a saturated toluene solution (m.p. 455–457 K).

Spectroscopic data top

For (I), 1H NMR (300 MHz, CDCl3, 298 K): δ 8.65, 7.85, 7.36, 7.28 (Harom), 6.34 (H—CC, t, 2H), 3.4 (H—C—CC, s, 2H), 2.8 (H—C—CO, t, 2H), 1.6 (H—CH, m, 2H); 13C NMR (75 MHz, CDCl3): δ 176.3 (CO), 149.6, 145.9, 138.2, 123.8, 121.8 (Carom), 137.8 (CC), 47.9 (Callylic), 45.7 (C a [Cα?]), 42.8 (CH2); IR (KBr): 2992 (ν C—H), 1760 (νas CO), 1698 (νs CO), 1467–1588 (ν CC, CN Ar), 1366 (ν C—N) cm-1; MS (m/z): 240 (M+). Analysis calculated for C14H12N2O2: C 69.99, H 5.03, N 11.66, O 13.32%; found: C 69.85, H 5.13, N 11.64%. [O determined?]

For (II), 1H NMR (200 MHz, CDCl3/DMSO, 298 K): δ 8.58, 8.50, 7.73, 7.49 (Harom), 6.33 (H—CC, t, 2H), 3.23 (H—C—CC, s, 2H), 2.87 (H—C—CO, s, 2H), 1.48 (H—CH, s, 2H); 13C NMR (75 MHz, CDCl3/DMSO): δ 174.5 (CO), 147.2, 145.5, 132.5, 127.1, 121.9 (Carom), 135.9 (CC), 45.9 (Callylic), 43.2 (C a [Cα?]), 41.0 (CH2); IR (KBr): 2967 (ν C—H), 1773 (νas C O), 1691 (νss CO), 1582–1483 (ν CC, CN Ar), 1378 (ν C—N) cm-1; MS (m/z): 240 (M+). Analysis calculated for C14H12N2O2: C 69.99, H 5.03, N 11.66, O 13.32%; found: C 69.945, H 5.120, N 11.625%. [O determined?]

Refinement top

All H atoms were placed in idealized positions and refined in riding modes such that Uiso(H) = 1.2Ueq of the parent atom. C—H distances of 0.93, 0.97 and 0.98 Å were used for sp2, sp3 (CH2) and sp3 (CH) groups, respectively. [better as "methine, methyl­ene and methyl H atoms, respectively"?]

Results and discussion top

N-(Pyridin-2-yl)-exo-norbornene-5,6-dicarboximide, (I) (Fig. 1a), and N-(pyridin-3-yl)-exo-norbornene-5,6-dicarboximide, (II) (Fig. 1b), were crystallized and their structures determined unequivocally by X-ray diffraction techniques.

Compound (I) crystallized in the triclinic centrosymmetric P1 space group, while compound (II) crystallized in the monoclinic noncentrosymmetric Cc space group. In both compounds, the asymmetric unit consists of two independent molecules (A and B) with similar values of bond lengths and angles that are in agreement with those found in similar compounds (Dvorkin et al., 1987; Anbei et al., 1984). The latter literature example is the phenyl analogue N-phenyl-exo-norbornene-5,6-dicarboximide (Anbei et al., 1984), which also presents two molecules per asymmetric unit. The two independent molecules in compound (I) are linked by one hydrogen bond (C6B—H6B···O2A = 2.59 Å; Table 2) through a carbonyl O atom, whilst in compound (II), the two independent molecules are linked by a weak dipole–diplole contact (CO···C) between carbonyl groups [range of O···C distances = 3.034 (9)–3.255 (9) Å]. This type of inter­action is not observed in compound (I); however, it is present in N-phenyl-exo-norbornene-5,6-dicarboximide (CO···C = 3.19 Å).

In compound (I), the mean planes of the pyridine (pyr) and dicarboximide rings form a dihedral angle of 87.83 (6)° for molecule A and of 62.18 (6)° for molecule B. That molecule A has a near perpendicular conformation is also shown by the the C5A—N4A—C12A—C13A torsion angle of 90.67 (19)°; the equivalent torsion angle is only -116.64 (16)° in molecule B. It is noteworthy that molecule A shows a syn configuration of the pyridine N atom with respect to the bridging methyl­ene C atom of the norbornene moiety, while molecule B exhibits an anti configuration. Both independent molecules in (II) have an anti configuration. The angle between the mean planes of pyridine and dicarboximide rings are markedly different from those in (I), with values of 50.4 (2) and 53.01 (9)°, respectively. The C3A—N4A—C13A—C14A and C3B—N4B—C13B—C14B torsion angles are 51.2 (7) and 53.4 (7)°, respectively. Equivalent inter­planar rotation angles have been reported previously in endo-conformed norbornene dicarboximide derivatives (Tian, Hu & Niu, 2007; Tian, Xiong & Dong, 2007), showing that the ring-bonding N—Cpyr [N4A—C12A = 1.4327 (18) Å and N4B—C12B = 1.4324 (17) Å in (I), and N4A—C13A = 1.422 (6) Å and N4B—C13B = 1.422 (6) Å in (II)] constitutes a single longer bond (vide infra) with a high capacity for rotation and thus stabilization by different types of inter­actions. In this sense, supra­molecular inter­actions become important to analyse the spatial arrangement of the crystal structures of compounds such as those reported in this work.

In the dicarboximide ring, the N—C(O) bond lengths are similar to those found in other N-substituted aryl­male­imide structures (Miller et al., 2000). The C3A—N4A and C5A—N4A bond lengths for molecule A [1.3868 (18) and 1.3936 (19) Å, respectively] and the C3B—N4B and C5B—N4B bond lengths bond lengths for molecule B [1.4007 (18) and 1.4015 (18) Å, respectively] are slightly shorter than the value reported for a typical Csp2—Nsp3 imide bond (1.409 Å; Lide, 2010). A similar situation is observed for the two independent molecules of compound (II), with C3A—N4A and N4A—C5A bond lengths of 1.398 (6) and 1.397 (6) Å, respectively, for molecule A, and C3B—N4B and N4B—C5B bond lengths of 1.402 (7) and 1.396 (6) Å, respectively, for molecule B. Analogously, the O1A—C3A and O2A—C5A bond lengths for molecule A [1.2080 (18) and 1.2031 (18) Å, respectively], and the O1B—C3B and O2B—C5B bond lengths for molecule B [1.2057 (17) and 1.2022 (17) Å, respectively], are slightly longer than the typical value reported for amide carbonyl Csp2\dn O bonds (1.198 Å for cyclic amides). This behaviour is also observed in the crystal structure of compound (II) [O1A—C3A = 1.206 (6) Å and O2A—C5A = 1.208 (6) Å for molecule A, and O1B—C3B = 1.200 (6) Å and O2B—C5A = 1.203 (6) Å for molecule B]. As the conformations of these molecules vary widely, it is fair to say that these structural effects are mainly observed due to resonance effects in the dicarboximide group (Lide, 2010; Miller et al., 2000). As a result, the bond lengths of this fragment in both compounds are similar and comparable with values reported for other similar exo-conformed norbornenedicarboximides (Tian, Hu et al., 2007; Tian, Xiong et al., 2007).

The geometry parameters of the N-pyridinylcarboximide molecules in (I) are in agreement with other N-aryl­male­imides derivatives [N4A—C12A = 1.4327 (18) Å for molecule A and N4B—C12B = 1.4324 (17) Å for molecule B]. However, the same data for both molecules of (II) [1.422 (6) Å] are shorter distance between the cyclic groups when compared to those observed in (I). However, these are still longer than the values quoted for a typical Nsp3—Car bond of 1.370 Å (Lide, 2010). Also, the molecules show dicarboximide rings with quasi-planar conformations, described by the C2—C3—N4—C5 torsion angles of 2.74 (17) and -1.78 (16)° for molecules A and B, respectively, of compound (I), and described by the C6—C5—N4—C3 torsion angles of -7.7 (5) and -5.8 (5)° for molecules A and B, respectively, of compound (II). In the same context, the sum of the angles that define the three bonds of the N4A and N4B atoms for both compounds is 360°, indicating the sp2 character of both N atoms. All these observations support conjugated delocalization of the nitro­gen lone pair of the imide group, which contributes to lengthening of the N—Cpyr bond.

On the other hand, in both (I) and (II), the pyride ring exhibits shorter N—C distances than those typically shown by the Nar—Car bonds of aromatic N-heterocycles (Lide, 2010). As a consequence, the inter­nal angles of the pyridine ring are larger for those C atoms that neighbour the N atom and smaller at the N atom itself. Moreover, resonance effects cause shorter N—C(pyridine) bond lengths in (II) than in (I). This is probably due to the position of the N atom in the aromatic ring (Miller et al., 2000). These bond geometries are similar to those previously reported for other pyridine groups in amide derivatives (Velikova et al., 1997).

Analysis of the crystal packing of (I) shows the presence of C—H···O hydrogen bonds, with the carbonyl O atoms functioning as hydrogen-bond acceptors. Four C—H···O inter­actions (C6B—H6B···O2A, C9A—H9A···O2Aii, C9B—H9B···O2Biii and C14B—H14B···O1Ai; see Table 2 for details) give a one-dimensional infinite polymeric arrangement parallel to the [100] axis (Fig. 2). Additionally, molecule A inter­acts with molecule B through hydrogen bonds between carbonyl atom O1A atom and pyridine atom N11A with the H atoms of C14B and C13B, respectively (Table 2). Both contacts define a dimeric unit that forms an R22(9) ring pattern (Fig. 3). Additionally, acceptor atom O1A acts in a bifurcated manner with a short inter­action to atom H14B. When the contacts C13B—H13B···N11Ai and C14B—H14B···O1Ai are extended, a centrosymmetric R22(4) ring is formed by two C14B—H14B···O1Aiv inter­actions (Fig. 3). Inter­molecular ππ inter­actions are observed between the N11A/C12A–C16A pyridine rings of neighbouring molecules, resulting in the formation of dimers (Fig. 4). The distances between centroids is 3.861 Å [symmetry code: -x+1, -y, -z; perpendicular distance = 3.489 (7) Å]. The hydrogen bonds that involved the O and N atoms in combination with the ππ and C—H···π inter­actions of Table 2 generate the three-dimensional arrangement.

In compound (II), the inter­molecular arrangements observed in both molecules are formed by the presence of weak hydrogen bonds, viz. C15A—H15A···N11Ai and C14A—H14A···O2Ai for molecule A and C15B—H15B···N11Bii and C14B—H14B···O2Bii for molecule B (Table 3). These inter­actions form a 10-membered R22(10) ring, and when these contacts are extended, inter­linked zigzagg chains are observed parallel to the [001] direction (Fig. 5). The chains are linked by C—H···π inter­actions, giving rise to a two-dimensional arrangement parallel to the bc plane (Fig. 6). C—H···π inter­actions between molecules A and B involve the N11A/C12A–C16A (Cg1) and N11B/C12B—C16B (Cg2) pyridine rings. These inter­actions are C2A—H2A···Cg1iii [2.88 Å; C2A—Cg1iii = 3.705 (3) Å] and C2B—H2B···Cg2i [2.80 Å; C2B—Cg2i = 3.622 (4) Å] (see Table 3 for details and symmetry codes).

Computing details top

Data collection: APEX2 (Bruker, 2012) for (I); SMART (Bruker, 2012) for (II). Cell refinement: APEX2 (Bruker, 2012) for (I); SMART (Bruker, 2012) for (II). For both compounds, data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008)and PLATON (Spek, 2009) for (I); SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009) for (II).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (a) compound (I) and (b) compound (II), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 30% probability level in each case.
[Figure 2] Fig. 2. C—H···O hydrogen bonds (dashed lines) observed in compound (I), producing an infinite arrangement along the [100] axis.
[Figure 3] Fig. 3. Packing diagram of (I), showing the array of molecules A and B forming four- and nine-membered rings.
[Figure 4] Fig. 4. The dimer generated by ππ stacking in compound (I).
[Figure 5] Fig. 5. The arrangement of molecules in compound (II), forming zigzag chains. The graph-set motif () is indicated. The C—H···N and C—H···O hydrogen-bond interactions are represented as dashed lines.
[Figure 6] Fig. 6. The arrangement of molecules in compound (II) generated by the stacking of zigzag chains through C—H···π interactions parallel to the bc plane.
(I) N-(Pyridin-2-yl)-exo-norbornene-5,6-dicarboximide top
Crystal data top
C14H12N2O2Z = 4
Mr = 240.26F(000) = 504
Triclinic, P1Dx = 1.363 Mg m3
a = 8.4147 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.1827 (3) ÅCell parameters from 5305 reflections
c = 15.2673 (5) Åθ = 2.7–27.4°
α = 87.174 (3)°µ = 0.09 mm1
β = 89.870 (3)°T = 298 K
γ = 83.631 (3)°Prism, colourless
V = 1170.99 (7) Å30.35 × 0.28 × 0.22 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5376 independent reflections
Radiation source: fine-focus sealed tube3946 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 8.333 pixels mm-1θmax = 27.5°, θmin = 2.6°
ω scansh = 109
Absorption correction: multi-scan
(Sheldrick, 2008)
k = 1111
Tmin = 0.964, Tmax = 0.982l = 1919
12024 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045 w = 1/[σ2(Fo2) + (0.0466P)2 + 0.2365P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.114(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.18 e Å3
5376 reflectionsΔρmin = 0.22 e Å3
326 parametersExtinction correction: SHELXL2013 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.025 (2)
Crystal data top
C14H12N2O2γ = 83.631 (3)°
Mr = 240.26V = 1170.99 (7) Å3
Triclinic, P1Z = 4
a = 8.4147 (3) ÅMo Kα radiation
b = 9.1827 (3) ŵ = 0.09 mm1
c = 15.2673 (5) ÅT = 298 K
α = 87.174 (3)°0.35 × 0.28 × 0.22 mm
β = 89.870 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5376 independent reflections
Absorption correction: multi-scan
(Sheldrick, 2008)
3946 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.982Rint = 0.026
12024 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å3
5376 reflectionsΔρmin = 0.22 e Å3
326 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.06977 (14)0.12049 (14)0.39300 (7)0.0566 (3)
O2A0.38087 (13)0.23142 (16)0.16141 (8)0.0647 (4)
C1A0.09795 (19)0.06819 (18)0.21010 (11)0.0470 (4)
H1A0.14570.00690.25510.056*
C2A0.01459 (17)0.19849 (16)0.24340 (10)0.0396 (3)
H2A0.09290.28120.25740.048*
C3A0.10033 (17)0.15639 (16)0.31820 (10)0.0392 (3)
N4A0.25449 (14)0.16395 (13)0.28736 (8)0.0381 (3)
C5A0.25894 (18)0.21340 (17)0.19971 (10)0.0418 (4)
C6A0.09042 (17)0.23835 (16)0.16514 (10)0.0405 (3)
H6A0.06260.34000.14320.049*
C7A0.05316 (19)0.12697 (19)0.09606 (10)0.0471 (4)
H7A0.12930.11380.04770.057*
C8A0.1192 (2)0.1717 (2)0.07065 (12)0.0573 (5)
H8A0.15570.21590.01730.069*
C9A0.2086 (2)0.1366 (2)0.13770 (13)0.0581 (5)
H9A0.31970.15130.14010.070*
C10A0.0353 (2)0.00878 (17)0.15548 (11)0.0486 (4)
H10A0.13100.04170.18950.058*
H10B0.00110.08920.12400.058*
N11A0.46590 (16)0.00306 (14)0.33950 (9)0.0466 (3)
C12A0.39518 (17)0.13269 (16)0.34068 (9)0.0375 (3)
C13A0.4469 (2)0.24153 (18)0.38837 (11)0.0511 (4)
H13A0.39050.33460.38780.061*
C14A0.5850 (2)0.2085 (2)0.43710 (12)0.0599 (5)
H14A0.62480.27940.46970.072*
C15A0.6626 (2)0.0691 (2)0.43654 (11)0.0551 (4)
H15A0.75660.04370.46840.066*
C16A0.5988 (2)0.0321 (2)0.38808 (11)0.0538 (4)
H16A0.65110.12690.38900.065*
O1B0.52441 (13)0.60419 (14)0.37118 (7)0.0542 (3)
O2B0.20684 (12)0.59480 (14)0.13073 (7)0.0522 (3)
C1B0.69711 (19)0.70130 (19)0.19339 (11)0.0488 (4)
H1B0.74760.74660.24130.059*
C2B0.60436 (17)0.56764 (17)0.21968 (10)0.0401 (3)
H2B0.67780.47790.23000.048*
C3B0.49149 (17)0.59216 (16)0.29525 (10)0.0391 (3)
N4B0.33491 (13)0.59765 (13)0.26331 (8)0.0372 (3)
C5B0.32900 (17)0.58359 (16)0.17242 (10)0.0375 (3)
C6B0.49779 (16)0.55705 (17)0.13894 (10)0.0388 (3)
H6B0.51850.46120.11310.047*
C7B0.54489 (19)0.68291 (19)0.07552 (11)0.0484 (4)
H7B0.47090.71360.02690.058*
C8B0.7162 (2)0.6361 (2)0.05091 (12)0.0568 (5)
H8B0.75190.60460.00340.068*
C9B0.8057 (2)0.6480 (2)0.11999 (13)0.0579 (5)
H9B0.91630.62730.12320.070*
C10B0.5696 (2)0.79921 (18)0.14085 (12)0.0546 (4)
H10C0.60970.88550.11350.065*
H10D0.47460.82720.17490.065*
N11B0.10435 (15)0.51136 (14)0.32228 (9)0.0451 (3)
C12B0.19597 (16)0.62048 (16)0.31743 (9)0.0359 (3)
C13B0.16742 (19)0.74792 (17)0.36120 (10)0.0438 (4)
H13B0.23550.82090.35540.053*
C14B0.0340 (2)0.76370 (19)0.41411 (11)0.0501 (4)
H14B0.01060.84800.44520.060*
C15B0.06371 (19)0.65365 (19)0.42029 (10)0.0472 (4)
H15B0.15430.66190.45550.057*
C16B0.02479 (19)0.53100 (19)0.37337 (11)0.0489 (4)
H16B0.09220.45730.37740.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0510 (7)0.0803 (9)0.0399 (6)0.0112 (6)0.0085 (5)0.0078 (6)
O2A0.0389 (6)0.0941 (10)0.0613 (8)0.0219 (6)0.0004 (6)0.0265 (7)
C1A0.0430 (9)0.0525 (9)0.0493 (9)0.0208 (7)0.0046 (7)0.0053 (7)
C2A0.0317 (7)0.0404 (8)0.0474 (9)0.0038 (6)0.0003 (6)0.0090 (7)
C3A0.0376 (8)0.0398 (8)0.0416 (9)0.0063 (6)0.0049 (6)0.0103 (6)
N4A0.0325 (6)0.0428 (7)0.0393 (7)0.0061 (5)0.0020 (5)0.0006 (5)
C5A0.0373 (8)0.0428 (8)0.0462 (9)0.0116 (6)0.0027 (7)0.0066 (7)
C6A0.0366 (8)0.0381 (8)0.0470 (9)0.0083 (6)0.0062 (6)0.0059 (6)
C7A0.0446 (9)0.0599 (10)0.0379 (8)0.0110 (7)0.0011 (7)0.0022 (7)
C8A0.0527 (10)0.0667 (12)0.0543 (11)0.0149 (9)0.0174 (9)0.0015 (9)
C9A0.0383 (9)0.0704 (12)0.0688 (12)0.0153 (8)0.0082 (8)0.0152 (10)
C10A0.0560 (10)0.0416 (9)0.0500 (9)0.0104 (7)0.0004 (8)0.0100 (7)
N11A0.0432 (7)0.0445 (7)0.0514 (8)0.0005 (6)0.0068 (6)0.0071 (6)
C12A0.0345 (7)0.0416 (8)0.0368 (8)0.0066 (6)0.0012 (6)0.0002 (6)
C13A0.0575 (10)0.0401 (9)0.0560 (10)0.0069 (7)0.0113 (8)0.0033 (7)
C14A0.0612 (11)0.0641 (12)0.0578 (11)0.0196 (9)0.0158 (9)0.0083 (9)
C15A0.0381 (9)0.0782 (13)0.0482 (10)0.0038 (8)0.0096 (7)0.0021 (9)
C16A0.0441 (9)0.0594 (10)0.0551 (10)0.0087 (8)0.0053 (8)0.0061 (8)
O1B0.0484 (7)0.0754 (8)0.0395 (7)0.0101 (6)0.0083 (5)0.0025 (6)
O2B0.0336 (6)0.0801 (8)0.0447 (6)0.0113 (5)0.0029 (5)0.0090 (6)
C1B0.0393 (8)0.0591 (10)0.0518 (10)0.0200 (7)0.0007 (7)0.0090 (8)
C2B0.0307 (7)0.0429 (8)0.0464 (9)0.0039 (6)0.0003 (6)0.0017 (7)
C3B0.0348 (8)0.0409 (8)0.0421 (9)0.0067 (6)0.0027 (6)0.0003 (6)
N4B0.0305 (6)0.0459 (7)0.0361 (7)0.0062 (5)0.0023 (5)0.0064 (5)
C5B0.0334 (7)0.0414 (8)0.0394 (8)0.0099 (6)0.0025 (6)0.0066 (6)
C6B0.0321 (7)0.0435 (8)0.0428 (8)0.0093 (6)0.0042 (6)0.0100 (6)
C7B0.0428 (9)0.0632 (11)0.0402 (9)0.0126 (8)0.0019 (7)0.0025 (7)
C8B0.0467 (10)0.0759 (12)0.0514 (10)0.0218 (9)0.0155 (8)0.0065 (9)
C9B0.0351 (9)0.0713 (12)0.0701 (12)0.0180 (8)0.0113 (8)0.0032 (9)
C10B0.0549 (10)0.0441 (9)0.0660 (11)0.0130 (8)0.0088 (9)0.0012 (8)
N11B0.0421 (7)0.0445 (7)0.0504 (8)0.0098 (6)0.0091 (6)0.0096 (6)
C12B0.0326 (7)0.0413 (8)0.0336 (7)0.0027 (6)0.0008 (6)0.0035 (6)
C13B0.0447 (9)0.0421 (8)0.0457 (9)0.0071 (7)0.0011 (7)0.0077 (7)
C14B0.0532 (10)0.0499 (9)0.0464 (9)0.0027 (8)0.0040 (8)0.0133 (7)
C15B0.0399 (8)0.0607 (10)0.0387 (8)0.0036 (7)0.0084 (7)0.0004 (7)
C16B0.0427 (9)0.0539 (10)0.0517 (10)0.0122 (7)0.0103 (7)0.0035 (8)
Geometric parameters (Å, º) top
O1A—C3A1.2080 (18)O1B—C3B1.2057 (17)
O2A—C5A1.2031 (18)O2B—C5B1.2022 (17)
C1A—C9A1.513 (2)C1B—C9B1.510 (2)
C1A—C10A1.527 (2)C1B—C10B1.524 (2)
C1A—C2A1.559 (2)C1B—C2B1.562 (2)
C1A—H1A0.9800C1B—H1B0.9800
C2A—C3A1.506 (2)C2B—C3B1.502 (2)
C2A—C6A1.538 (2)C2B—C6B1.539 (2)
C2A—H2A0.9800C2B—H2B0.9800
C3A—N4A1.3868 (18)C3B—N4B1.4007 (18)
N4A—C5A1.3936 (19)N4B—C5B1.4015 (18)
N4A—C12A1.4327 (18)N4B—C12B1.4324 (17)
C5A—C6A1.504 (2)C5B—C6B1.5067 (19)
C6A—C7A1.561 (2)C6B—C7B1.556 (2)
C6A—H6A0.9800C6B—H6B0.9800
C7A—C8A1.509 (2)C7B—C8B1.510 (2)
C7A—C10A1.526 (2)C7B—C10B1.528 (2)
C7A—H7A0.9800C7B—H7B0.9800
C8A—C9A1.317 (3)C8B—C9B1.313 (3)
C8A—H8A0.9300C8B—H8B0.9300
C9A—H9A0.9300C9B—H9B0.9300
C10A—H10A0.9700C10B—H10C0.9700
C10A—H10B0.9700C10B—H10D0.9700
N11A—C12A1.3213 (19)N11B—C12B1.3295 (19)
N11A—C16A1.338 (2)N11B—C16B1.3373 (19)
C12A—C13A1.374 (2)C12B—C13B1.374 (2)
C13A—C14A1.378 (2)C13B—C14B1.380 (2)
C13A—H13A0.9300C13B—H13B0.9300
C14A—C15A1.372 (3)C14B—C15B1.371 (2)
C14A—H14A0.9300C14B—H14B0.9300
C15A—C16A1.371 (2)C15B—C16B1.373 (2)
C15A—H15A0.9300C15B—H15B0.9300
C16A—H16A0.9300C16B—H16B0.9300
C9A—C1A—C10A100.07 (13)C9B—C1B—C10B100.04 (14)
C9A—C1A—C2A104.50 (13)C9B—C1B—C2B104.32 (13)
C10A—C1A—C2A101.05 (12)C10B—C1B—C2B100.98 (12)
C9A—C1A—H1A116.3C9B—C1B—H1B116.4
C10A—C1A—H1A116.3C10B—C1B—H1B116.4
C2A—C1A—H1A116.3C2B—C1B—H1B116.4
C3A—C2A—C6A105.19 (11)C3B—C2B—C6B105.64 (11)
C3A—C2A—C1A114.02 (13)C3B—C2B—C1B114.41 (13)
C6A—C2A—C1A102.86 (12)C6B—C2B—C1B102.71 (12)
C3A—C2A—H2A111.4C3B—C2B—H2B111.2
C6A—C2A—H2A111.4C6B—C2B—H2B111.2
C1A—C2A—H2A111.4C1B—C2B—H2B111.2
O1A—C3A—N4A123.66 (14)O1B—C3B—N4B123.94 (14)
O1A—C3A—C2A128.00 (14)O1B—C3B—C2B127.87 (13)
N4A—C3A—C2A108.34 (12)N4B—C3B—C2B108.19 (12)
C3A—N4A—C5A113.05 (12)C3B—N4B—C5B112.72 (12)
C3A—N4A—C12A124.00 (12)C3B—N4B—C12B123.48 (12)
C5A—N4A—C12A122.86 (12)C5B—N4B—C12B123.77 (11)
O2A—C5A—N4A123.33 (14)O2B—C5B—N4B123.72 (13)
O2A—C5A—C6A128.20 (14)O2B—C5B—C6B127.86 (13)
N4A—C5A—C6A108.47 (12)N4B—C5B—C6B108.40 (12)
C5A—C6A—C2A104.88 (12)C5B—C6B—C2B104.91 (12)
C5A—C6A—C7A113.57 (13)C5B—C6B—C7B113.28 (13)
C2A—C6A—C7A102.90 (11)C2B—C6B—C7B103.08 (11)
C5A—C6A—H6A111.7C5B—C6B—H6B111.7
C2A—C6A—H6A111.7C2B—C6B—H6B111.7
C7A—C6A—H6A111.7C7B—C6B—H6B111.7
C8A—C7A—C10A100.32 (14)C8B—C7B—C10B100.25 (14)
C8A—C7A—C6A104.67 (13)C8B—C7B—C6B104.81 (13)
C10A—C7A—C6A100.76 (12)C10B—C7B—C6B100.45 (12)
C8A—C7A—H7A116.2C8B—C7B—H7B116.3
C10A—C7A—H7A116.2C10B—C7B—H7B116.3
C6A—C7A—H7A116.2C6B—C7B—H7B116.3
C9A—C8A—C7A107.68 (16)C9B—C8B—C7B107.68 (15)
C9A—C8A—H8A126.2C9B—C8B—H8B126.2
C7A—C8A—H8A126.2C7B—C8B—H8B126.2
C8A—C9A—C1A107.60 (15)C8B—C9B—C1B107.87 (15)
C8A—C9A—H9A126.2C8B—C9B—H9B126.1
C1A—C9A—H9A126.2C1B—C9B—H9B126.1
C7A—C10A—C1A94.06 (12)C1B—C10B—C7B94.20 (13)
C7A—C10A—H10A112.9C1B—C10B—H10C112.9
C1A—C10A—H10A112.9C7B—C10B—H10C112.9
C7A—C10A—H10B112.9C1B—C10B—H10D112.9
C1A—C10A—H10B112.9C7B—C10B—H10D112.9
H10A—C10A—H10B110.3H10C—C10B—H10D110.3
C12A—N11A—C16A115.76 (14)C12B—N11B—C16B116.05 (13)
N11A—C12A—C13A124.89 (14)N11B—C12B—C13B124.75 (14)
N11A—C12A—N4A115.54 (13)N11B—C12B—N4B115.60 (12)
C13A—C12A—N4A119.56 (13)C13B—C12B—N4B119.64 (13)
C12A—C13A—C14A117.94 (16)C12B—C13B—C14B117.60 (15)
C12A—C13A—H13A121.0C12B—C13B—H13B121.2
C14A—C13A—H13A121.0C14B—C13B—H13B121.2
C15A—C14A—C13A118.71 (16)C15B—C14B—C13B119.23 (15)
C15A—C14A—H14A120.6C15B—C14B—H14B120.4
C13A—C14A—H14A120.6C13B—C14B—H14B120.4
C16A—C15A—C14A118.61 (15)C14B—C15B—C16B118.52 (15)
C16A—C15A—H15A120.7C14B—C15B—H15B120.7
C14A—C15A—H15A120.7C16B—C15B—H15B120.7
N11A—C16A—C15A124.07 (16)N11B—C16B—C15B123.85 (15)
N11A—C16A—H16A118.0N11B—C16B—H16B118.1
C15A—C16A—H16A118.0C15B—C16B—H16B118.1
C9A—C1A—C2A—C3A178.71 (13)C9B—C1B—C2B—C3B177.69 (13)
C10A—C1A—C2A—C3A77.73 (15)C10B—C1B—C2B—C3B78.85 (15)
C9A—C1A—C2A—C6A67.96 (15)C9B—C1B—C2B—C6B68.37 (15)
C10A—C1A—C2A—C6A35.60 (15)C10B—C1B—C2B—C6B35.09 (15)
C6A—C2A—C3A—O1A178.14 (15)C6B—C2B—C3B—O1B178.61 (15)
C1A—C2A—C3A—O1A69.9 (2)C1B—C2B—C3B—O1B69.2 (2)
C6A—C2A—C3A—N4A2.32 (15)C6B—C2B—C3B—N4B0.70 (16)
C1A—C2A—C3A—N4A109.61 (14)C1B—C2B—C3B—N4B111.50 (14)
O1A—C3A—N4A—C5A177.70 (14)O1B—C3B—N4B—C5B178.87 (15)
C2A—C3A—N4A—C5A2.74 (17)C2B—C3B—N4B—C5B1.78 (16)
O1A—C3A—N4A—C12A1.1 (2)O1B—C3B—N4B—C12B1.0 (2)
C2A—C3A—N4A—C12A179.31 (12)C2B—C3B—N4B—C12B179.67 (12)
C3A—N4A—C5A—O2A177.92 (15)C3B—N4B—C5B—O2B175.00 (14)
C12A—N4A—C5A—O2A1.3 (2)C12B—N4B—C5B—O2B2.9 (2)
C3A—N4A—C5A—C6A1.96 (17)C3B—N4B—C5B—C6B3.58 (16)
C12A—N4A—C5A—C6A178.58 (12)C12B—N4B—C5B—C6B178.54 (12)
O2A—C5A—C6A—C2A179.50 (17)O2B—C5B—C6B—C2B174.74 (15)
N4A—C5A—C6A—C2A0.36 (16)N4B—C5B—C6B—C2B3.77 (15)
O2A—C5A—C6A—C7A68.9 (2)O2B—C5B—C6B—C7B63.1 (2)
N4A—C5A—C6A—C7A111.22 (14)N4B—C5B—C6B—C7B115.45 (14)
C3A—C2A—C6A—C5A1.16 (15)C3B—C2B—C6B—C5B2.67 (15)
C1A—C2A—C6A—C5A118.48 (13)C1B—C2B—C6B—C5B117.53 (13)
C3A—C2A—C6A—C7A120.19 (12)C3B—C2B—C6B—C7B121.47 (13)
C1A—C2A—C6A—C7A0.54 (15)C1B—C2B—C6B—C7B1.27 (14)
C5A—C6A—C7A—C8A179.94 (13)C5B—C6B—C7B—C8B179.37 (13)
C2A—C6A—C7A—C8A67.27 (15)C2B—C6B—C7B—C8B66.57 (15)
C5A—C6A—C7A—C10A76.28 (15)C5B—C6B—C7B—C10B75.73 (15)
C2A—C6A—C7A—C10A36.51 (14)C2B—C6B—C7B—C10B37.08 (15)
C10A—C7A—C8A—C9A32.89 (18)C10B—C7B—C8B—C9B32.39 (19)
C6A—C7A—C8A—C9A71.22 (17)C6B—C7B—C8B—C9B71.41 (18)
C7A—C8A—C9A—C1A0.3 (2)C7B—C8B—C9B—C1B0.7 (2)
C10A—C1A—C9A—C8A33.39 (17)C10B—C1B—C9B—C8B33.59 (18)
C2A—C1A—C9A—C8A70.91 (17)C2B—C1B—C9B—C8B70.59 (18)
C8A—C7A—C10A—C1A49.82 (14)C9B—C1B—C10B—C7B49.75 (14)
C6A—C7A—C10A—C1A57.44 (13)C2B—C1B—C10B—C7B57.13 (14)
C9A—C1A—C10A—C7A49.88 (14)C8B—C7B—C10B—C1B49.46 (15)
C2A—C1A—C10A—C7A57.21 (14)C6B—C7B—C10B—C1B57.84 (14)
C16A—N11A—C12A—C13A1.0 (2)C16B—N11B—C12B—C13B0.6 (2)
C16A—N11A—C12A—N4A178.96 (14)C16B—N11B—C12B—N4B179.34 (13)
C3A—N4A—C12A—N11A94.41 (17)C3B—N4B—C12B—N11B117.75 (15)
C5A—N4A—C12A—N11A89.34 (17)C5B—N4B—C12B—N11B64.59 (19)
C3A—N4A—C12A—C13A85.58 (19)C3B—N4B—C12B—C13B61.02 (19)
C5A—N4A—C12A—C13A90.67 (19)C5B—N4B—C12B—C13B116.64 (16)
N11A—C12A—C13A—C14A1.7 (3)N11B—C12B—C13B—C14B0.1 (2)
N4A—C12A—C13A—C14A178.34 (15)N4B—C12B—C13B—C14B178.59 (13)
C12A—C13A—C14A—C15A0.8 (3)C12B—C13B—C14B—C15B0.4 (2)
C13A—C14A—C15A—C16A0.6 (3)C13B—C14B—C15B—C16B0.1 (2)
C12A—N11A—C16A—C15A0.5 (3)C12B—N11B—C16B—C15B1.0 (2)
C14A—C15A—C16A—N11A1.2 (3)C14B—C15B—C16B—N11B0.7 (3)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N4A/C3A/C2A/C6A/C5A ring and Cg2 is the centroid of the N4B/C3B/C2B/C6B/C5B ring.
D—H···AD—HH···AD···AD—H···A
C6B—H6B···O2A0.982.593.252 (2)125
C13B—H13B···N11Ai0.932.663.584 (2)171
C9A—H9A···O2Aii0.932.573.490 (2)179
C9B—H9B···O2Biii0.932.433.360 (2)175
C14B—H14B···O1Aiv0.932.583.265 (2)131
C14B—H14B···O1Ai0.932.693.323 (2)126
C10A—H10A···Cg10.972.362.569 (2)91
C10B—H10B···Cg20.972.362.577 (2)91
Symmetry codes: (i) x, y+1, z; (ii) x1, y, z; (iii) x+1, y, z; (iv) x, y+1, z+1.
(II) N-(Pyridin-3-yl)-exo-norbornene-5,6-dicarboximide top
Crystal data top
C14H12N2O2F(000) = 1008
Mr = 240.26Dx = 1.403 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 23.240 (4) ÅCell parameters from 4124 reflections
b = 9.4869 (15) Åθ = 2.3–24.8°
c = 10.7258 (17) ŵ = 0.10 mm1
β = 105.820 (2)°T = 298 K
V = 2275.2 (6) Å3Prism, colourless
Z = 80.38 × 0.16 × 0.04 mm
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
3194 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.073
Graphite monochromatorθmax = 25.4°, θmin = 1.8°
Detector resolution: 0.83 pixels mm-1h = 2727
ω scansk = 1111
9073 measured reflectionsl = 1212
4139 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.060 w = 1/[σ2(Fo2) + (0.0776P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.139(Δ/σ)max < 0.001
S = 0.95Δρmax = 0.17 e Å3
4139 reflectionsΔρmin = 0.22 e Å3
325 parametersAbsolute structure: Flack x determined using 1280 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraintsAbsolute structure parameter: 1.6 (10)
Crystal data top
C14H12N2O2V = 2275.2 (6) Å3
Mr = 240.26Z = 8
Monoclinic, CcMo Kα radiation
a = 23.240 (4) ŵ = 0.10 mm1
b = 9.4869 (15) ÅT = 298 K
c = 10.7258 (17) Å0.38 × 0.16 × 0.04 mm
β = 105.820 (2)°
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
3194 reflections with I > 2σ(I)
9073 measured reflectionsRint = 0.073
4139 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.139Δρmax = 0.17 e Å3
S = 0.95Δρmin = 0.22 e Å3
4139 reflectionsAbsolute structure: Flack x determined using 1280 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
325 parametersAbsolute structure parameter: 1.6 (10)
2 restraints
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.47359 (16)0.8145 (4)0.7921 (4)0.0502 (10)
O2A0.47292 (16)0.4575 (4)1.0747 (3)0.0460 (9)
C1A0.6042 (2)0.6863 (6)0.9166 (5)0.0481 (13)
H1A0.60440.72680.83270.058*
C2A0.5542 (2)0.7397 (5)0.9767 (5)0.0380 (11)
H2A0.56450.83151.01880.046*
C3A0.4923 (2)0.7410 (5)0.8862 (5)0.0374 (11)
N4A0.45784 (17)0.6402 (4)0.9280 (4)0.0349 (10)
C5A0.4915 (2)0.5606 (5)1.0321 (5)0.0352 (11)
C6A0.5527 (2)0.6236 (5)1.0768 (5)0.0385 (12)
H6A0.56020.66271.16440.046*
C7A0.6040 (3)0.5233 (6)1.0658 (5)0.0473 (13)
H7A0.60430.42961.10450.057*
C8A0.6605 (3)0.6078 (7)1.1118 (6)0.0558 (16)
H8A0.69010.59431.18910.067*
C9A0.6610 (2)0.7035 (7)1.0246 (6)0.0522 (14)
H9A0.69080.77001.02830.063*
C10A0.5955 (3)0.5270 (6)0.9197 (6)0.0530 (15)
H10A0.55590.49720.87050.064*
H10B0.62590.47450.89300.064*
N11A0.2988 (2)0.5995 (6)0.9071 (5)0.0533 (13)
C12A0.3578 (2)0.6189 (6)0.9511 (5)0.0431 (13)
H12A0.37420.63181.03960.052*
C13A0.3955 (2)0.6207 (5)0.8713 (5)0.0339 (11)
C14A0.3720 (2)0.6040 (6)0.7404 (5)0.0414 (12)
H14A0.39640.60420.68470.050*
C15A0.3112 (2)0.5869 (7)0.6940 (6)0.0499 (14)
H15A0.29330.57740.60560.060*
C16A0.2773 (3)0.5843 (7)0.7805 (6)0.0564 (16)
H16A0.23630.57100.74780.068*
O1B0.45268 (16)0.6834 (4)0.2792 (4)0.0504 (10)
O2B0.46062 (16)1.0423 (4)0.5648 (3)0.0462 (9)
C1B0.3247 (2)0.8234 (7)0.2505 (5)0.0500 (14)
H1B0.32330.77920.16720.060*
C2B0.3737 (2)0.7676 (5)0.3700 (5)0.0393 (12)
H2B0.36190.67790.40110.047*
C3B0.4357 (2)0.7594 (5)0.3515 (5)0.0383 (11)
N4B0.47189 (17)0.8586 (4)0.4336 (4)0.0351 (10)
C5B0.4401 (2)0.9417 (5)0.4993 (4)0.0342 (11)
C6B0.3773 (2)0.8860 (5)0.4698 (5)0.0365 (12)
H6B0.36810.85090.54810.044*
C7B0.3297 (2)0.9930 (6)0.3965 (5)0.0438 (12)
H7B0.33251.08820.43320.053*
C8B0.2706 (2)0.9193 (7)0.3775 (6)0.0522 (15)
H8B0.24150.94120.41920.063*
C9B0.2673 (3)0.8187 (7)0.2918 (6)0.0560 (15)
H9B0.23570.75630.26190.067*
C10B0.3379 (3)0.9811 (6)0.2607 (5)0.0508 (14)
H10C0.37811.00360.25750.061*
H10D0.30891.03600.19700.061*
N11B0.6322 (2)0.8779 (6)0.5957 (5)0.0574 (13)
C12B0.5727 (2)0.8678 (6)0.5707 (5)0.0467 (13)
H12B0.55650.85700.64030.056*
C13B0.5343 (2)0.8723 (5)0.4488 (4)0.0348 (11)
C14B0.5569 (2)0.8901 (6)0.3441 (5)0.0444 (13)
H14B0.53180.89550.26030.053*
C15B0.6180 (3)0.8995 (6)0.3679 (6)0.0532 (15)
H15B0.63520.91130.29970.064*
C16B0.6533 (3)0.8914 (7)0.4921 (6)0.0574 (16)
H16B0.69450.89560.50570.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.048 (2)0.046 (2)0.055 (2)0.0005 (17)0.0095 (18)0.019 (2)
O2A0.050 (2)0.044 (2)0.048 (2)0.0010 (18)0.0213 (17)0.0101 (18)
C1A0.046 (3)0.056 (3)0.047 (3)0.002 (3)0.019 (3)0.006 (3)
C2A0.038 (3)0.033 (3)0.042 (3)0.001 (2)0.010 (2)0.001 (2)
C3A0.043 (3)0.031 (3)0.042 (3)0.002 (2)0.016 (2)0.002 (2)
N4A0.033 (2)0.033 (2)0.039 (2)0.0002 (17)0.0116 (19)0.0029 (18)
C5A0.044 (3)0.033 (3)0.033 (3)0.004 (2)0.017 (2)0.000 (2)
C6A0.044 (3)0.038 (3)0.034 (3)0.000 (2)0.012 (2)0.000 (2)
C7A0.046 (3)0.041 (3)0.057 (3)0.011 (2)0.017 (3)0.009 (3)
C8A0.040 (3)0.065 (4)0.060 (4)0.012 (3)0.008 (3)0.006 (3)
C9A0.033 (3)0.061 (4)0.063 (4)0.001 (3)0.014 (3)0.002 (3)
C10A0.046 (3)0.056 (4)0.062 (4)0.005 (3)0.023 (3)0.013 (3)
N11A0.040 (3)0.070 (3)0.056 (3)0.007 (2)0.023 (2)0.006 (3)
C12A0.042 (3)0.047 (3)0.043 (3)0.006 (3)0.015 (2)0.001 (2)
C13A0.036 (3)0.028 (2)0.041 (3)0.004 (2)0.015 (2)0.001 (2)
C14A0.042 (3)0.045 (3)0.040 (3)0.005 (2)0.016 (2)0.002 (2)
C15A0.044 (3)0.064 (4)0.042 (3)0.004 (3)0.013 (3)0.003 (3)
C16A0.035 (3)0.073 (4)0.060 (4)0.002 (3)0.011 (3)0.002 (3)
O1B0.050 (2)0.047 (2)0.058 (2)0.0010 (18)0.0193 (18)0.018 (2)
O2B0.051 (2)0.046 (2)0.0413 (19)0.0063 (18)0.0121 (16)0.0115 (18)
C1B0.039 (3)0.065 (4)0.044 (3)0.000 (3)0.008 (2)0.010 (3)
C2B0.039 (3)0.033 (3)0.047 (3)0.006 (2)0.013 (2)0.002 (2)
C3B0.040 (3)0.036 (3)0.039 (3)0.000 (2)0.010 (2)0.000 (2)
N4B0.034 (2)0.035 (2)0.036 (2)0.0016 (18)0.0096 (18)0.0031 (19)
C5B0.041 (3)0.033 (3)0.028 (2)0.003 (2)0.009 (2)0.004 (2)
C6B0.041 (3)0.038 (3)0.034 (3)0.000 (2)0.016 (2)0.001 (2)
C7B0.043 (3)0.036 (3)0.055 (3)0.004 (2)0.018 (2)0.003 (2)
C8B0.039 (3)0.059 (4)0.062 (4)0.009 (3)0.021 (3)0.007 (3)
C9B0.037 (3)0.062 (4)0.066 (4)0.004 (3)0.008 (3)0.001 (3)
C10B0.041 (3)0.059 (4)0.052 (3)0.007 (3)0.014 (3)0.019 (3)
N11B0.046 (3)0.071 (3)0.050 (3)0.010 (2)0.003 (2)0.002 (3)
C12B0.045 (3)0.050 (3)0.043 (3)0.004 (3)0.009 (2)0.005 (3)
C13B0.038 (3)0.030 (3)0.035 (3)0.002 (2)0.007 (2)0.003 (2)
C14B0.043 (3)0.050 (3)0.040 (3)0.003 (2)0.012 (2)0.002 (2)
C15B0.045 (4)0.066 (4)0.052 (3)0.004 (3)0.019 (3)0.001 (3)
C16B0.035 (3)0.064 (4)0.072 (4)0.002 (3)0.012 (3)0.005 (3)
Geometric parameters (Å, º) top
O1A—C3A1.206 (6)O1B—C3B1.200 (6)
O2A—C5A1.208 (6)O2B—C5B1.203 (6)
C1A—C9A1.508 (8)C1B—C9B1.517 (8)
C1A—C10A1.526 (9)C1B—C10B1.525 (9)
C1A—C2A1.560 (7)C1B—C2B1.556 (7)
C1A—H1A0.9800C1B—H1B0.9800
C2A—C3A1.500 (7)C2B—C3B1.510 (7)
C2A—C6A1.545 (7)C2B—C6B1.538 (7)
C2A—H2A0.9800C2B—H2B0.9800
C3A—N4A1.398 (6)C3B—N4B1.402 (7)
N4A—C5A1.397 (6)N4B—C5B1.396 (6)
N4A—C13A1.422 (6)N4B—C13B1.422 (6)
C5A—C6A1.497 (7)C5B—C6B1.501 (7)
C6A—C7A1.555 (7)C6B—C7B1.548 (7)
C6A—H6A0.9800C6B—H6B0.9800
C7A—C8A1.503 (9)C7B—C8B1.505 (8)
C7A—C10A1.525 (8)C7B—C10B1.524 (7)
C7A—H7A0.9800C7B—H7B0.9800
C8A—C9A1.307 (8)C8B—C9B1.313 (9)
C8A—H8A0.9300C8B—H8B0.9300
C9A—H9A0.9300C9B—H9B0.9300
C10A—H10A0.9700C10B—H10C0.9700
C10A—H10B0.9700C10B—H10D0.9700
N11A—C16A1.320 (8)N11B—C12B1.337 (7)
N11A—C12A1.335 (7)N11B—C16B1.337 (8)
C12A—C13A1.383 (7)C12B—C13B1.368 (7)
C12A—H12A0.9300C12B—H12B0.9300
C13A—C14A1.369 (7)C13B—C14B1.372 (7)
C14A—C15A1.374 (7)C14B—C15B1.377 (7)
C14A—H14A0.9300C14B—H14B0.9300
C15A—C16A1.372 (8)C15B—C16B1.362 (8)
C15A—H15A0.9300C15B—H15B0.9300
C16A—H16A0.9300C16B—H16B0.9300
C9A—C1A—C10A100.7 (5)C9B—C1B—C10B100.5 (5)
C9A—C1A—C2A104.0 (4)C9B—C1B—C2B104.8 (5)
C10A—C1A—C2A101.2 (4)C10B—C1B—C2B100.8 (4)
C9A—C1A—H1A116.2C9B—C1B—H1B116.1
C10A—C1A—H1A116.2C10B—C1B—H1B116.1
C2A—C1A—H1A116.2C2B—C1B—H1B116.1
C3A—C2A—C6A104.9 (4)C3B—C2B—C6B104.8 (4)
C3A—C2A—C1A115.2 (4)C3B—C2B—C1B114.8 (4)
C6A—C2A—C1A102.5 (4)C6B—C2B—C1B102.3 (4)
C3A—C2A—H2A111.2C3B—C2B—H2B111.4
C6A—C2A—H2A111.2C6B—C2B—H2B111.4
C1A—C2A—H2A111.2C1B—C2B—H2B111.4
O1A—C3A—N4A123.9 (5)O1B—C3B—N4B124.3 (5)
O1A—C3A—C2A127.6 (5)O1B—C3B—C2B127.5 (5)
N4A—C3A—C2A108.6 (4)N4B—C3B—C2B108.2 (4)
C5A—N4A—C3A112.4 (4)C5B—N4B—C3B112.8 (4)
C5A—N4A—C13A123.7 (4)C5B—N4B—C13B123.7 (4)
C3A—N4A—C13A123.9 (4)C3B—N4B—C13B123.5 (4)
O2A—C5A—N4A124.1 (5)O2B—C5B—N4B124.2 (5)
O2A—C5A—C6A127.5 (5)O2B—C5B—C6B127.6 (4)
N4A—C5A—C6A108.4 (4)N4B—C5B—C6B108.2 (4)
C5A—C6A—C2A105.2 (4)C5B—C6B—C2B105.7 (4)
C5A—C6A—C7A114.4 (4)C5B—C6B—C7B113.3 (4)
C2A—C6A—C7A102.8 (4)C2B—C6B—C7B103.3 (4)
C5A—C6A—H6A111.3C5B—C6B—H6B111.4
C2A—C6A—H6A111.3C2B—C6B—H6B111.4
C7A—C6A—H6A111.3C7B—C6B—H6B111.4
C8A—C7A—C10A100.5 (5)C8B—C7B—C10B100.5 (5)
C8A—C7A—C6A105.5 (5)C8B—C7B—C6B105.3 (4)
C10A—C7A—C6A100.1 (4)C10B—C7B—C6B100.3 (4)
C8A—C7A—H7A116.1C8B—C7B—H7B116.1
C10A—C7A—H7A116.1C10B—C7B—H7B116.1
C6A—C7A—H7A116.1C6B—C7B—H7B116.1
C9A—C8A—C7A108.2 (5)C9B—C8B—C7B108.0 (5)
C9A—C8A—H8A125.9C9B—C8B—H8B126.0
C7A—C8A—H8A125.9C7B—C8B—H8B126.0
C8A—C9A—C1A107.3 (5)C8B—C9B—C1B107.2 (5)
C8A—C9A—H9A126.3C8B—C9B—H9B126.4
C1A—C9A—H9A126.3C1B—C9B—H9B126.4
C7A—C10A—C1A93.7 (4)C7B—C10B—C1B93.8 (4)
C7A—C10A—H10A113.0C7B—C10B—H10C113.0
C1A—C10A—H10A113.0C1B—C10B—H10C113.0
C7A—C10A—H10B113.0C7B—C10B—H10D113.0
C1A—C10A—H10B113.0C1B—C10B—H10D113.0
H10A—C10A—H10B110.4H10C—C10B—H10D110.4
C16A—N11A—C12A116.3 (5)C12B—N11B—C16B115.7 (5)
N11A—C12A—C13A123.1 (5)N11B—C12B—C13B124.0 (5)
N11A—C12A—H12A118.5N11B—C12B—H12B118.0
C13A—C12A—H12A118.5C13B—C12B—H12B118.0
C14A—C13A—C12A119.3 (5)C12B—C13B—C14B119.4 (5)
C14A—C13A—N4A122.0 (4)C12B—C13B—N4B119.1 (5)
C12A—C13A—N4A118.7 (4)C14B—C13B—N4B121.5 (4)
C13A—C14A—C15A118.0 (5)C13B—C14B—C15B117.4 (5)
C13A—C14A—H14A121.0C13B—C14B—H14B121.3
C15A—C14A—H14A121.0C15B—C14B—H14B121.3
C16A—C15A—C14A118.7 (5)C16B—C15B—C14B119.5 (5)
C16A—C15A—H15A120.6C16B—C15B—H15B120.2
C14A—C15A—H15A120.6C14B—C15B—H15B120.2
N11A—C16A—C15A124.5 (5)N11B—C16B—C15B124.0 (5)
N11A—C16A—H16A117.7N11B—C16B—H16B118.0
C15A—C16A—H16A117.7C15B—C16B—H16B118.0
C9A—C1A—C2A—C3A177.0 (5)C9B—C1B—C2B—C3B178.8 (5)
C10A—C1A—C2A—C3A78.9 (5)C10B—C1B—C2B—C3B77.1 (5)
C9A—C1A—C2A—C6A69.7 (5)C9B—C1B—C2B—C6B68.3 (5)
C10A—C1A—C2A—C6A34.4 (5)C10B—C1B—C2B—C6B35.8 (5)
C6A—C2A—C3A—O1A179.0 (5)C6B—C2B—C3B—O1B177.9 (5)
C1A—C2A—C3A—O1A67.1 (7)C1B—C2B—C3B—O1B66.5 (7)
C6A—C2A—C3A—N4A0.9 (5)C6B—C2B—C3B—N4B1.5 (5)
C1A—C2A—C3A—N4A112.8 (5)C1B—C2B—C3B—N4B113.0 (5)
O1A—C3A—N4A—C5A174.5 (5)O1B—C3B—N4B—C5B174.8 (5)
C2A—C3A—N4A—C5A5.4 (5)C2B—C3B—N4B—C5B4.6 (6)
O1A—C3A—N4A—C13A5.6 (7)O1B—C3B—N4B—C13B5.5 (8)
C2A—C3A—N4A—C13A174.6 (4)C2B—C3B—N4B—C13B175.0 (4)
C3A—N4A—C5A—O2A171.2 (5)C3B—N4B—C5B—O2B172.4 (5)
C13A—N4A—C5A—O2A8.8 (7)C13B—N4B—C5B—O2B8.0 (7)
C3A—N4A—C5A—C6A7.7 (5)C3B—N4B—C5B—C6B5.8 (5)
C13A—N4A—C5A—C6A172.3 (4)C13B—N4B—C5B—C6B173.8 (4)
O2A—C5A—C6A—C2A172.2 (5)O2B—C5B—C6B—C2B173.6 (5)
N4A—C5A—C6A—C2A6.6 (5)N4B—C5B—C6B—C2B4.5 (5)
O2A—C5A—C6A—C7A60.3 (7)O2B—C5B—C6B—C7B61.3 (6)
N4A—C5A—C6A—C7A118.6 (4)N4B—C5B—C6B—C7B116.8 (4)
C3A—C2A—C6A—C5A3.4 (5)C3B—C2B—C6B—C5B1.8 (5)
C1A—C2A—C6A—C5A117.3 (4)C1B—C2B—C6B—C5B118.4 (4)
C3A—C2A—C6A—C7A123.4 (4)C3B—C2B—C6B—C7B121.0 (4)
C1A—C2A—C6A—C7A2.7 (5)C1B—C2B—C6B—C7B0.8 (5)
C5A—C6A—C7A—C8A178.6 (5)C5B—C6B—C7B—C8B179.3 (4)
C2A—C6A—C7A—C8A65.2 (5)C2B—C6B—C7B—C8B66.8 (5)
C5A—C6A—C7A—C10A74.6 (5)C5B—C6B—C7B—C10B76.6 (5)
C2A—C6A—C7A—C10A38.8 (5)C2B—C6B—C7B—C10B37.2 (5)
C10A—C7A—C8A—C9A32.8 (6)C10B—C7B—C8B—C9B33.3 (6)
C6A—C7A—C8A—C9A71.0 (6)C6B—C7B—C8B—C9B70.6 (6)
C7A—C8A—C9A—C1A0.2 (7)C7B—C8B—C9B—C1B0.2 (7)
C10A—C1A—C9A—C8A33.1 (6)C10B—C1B—C9B—C8B32.8 (6)
C2A—C1A—C9A—C8A71.4 (6)C2B—C1B—C9B—C8B71.4 (6)
C8A—C7A—C10A—C1A49.1 (5)C8B—C7B—C10B—C1B49.6 (5)
C6A—C7A—C10A—C1A59.0 (5)C6B—C7B—C10B—C1B58.2 (4)
C9A—C1A—C10A—C7A49.3 (5)C9B—C1B—C10B—C7B49.5 (5)
C2A—C1A—C10A—C7A57.5 (5)C2B—C1B—C10B—C7B57.9 (4)
C16A—N11A—C12A—C13A1.3 (8)C16B—N11B—C12B—C13B0.8 (9)
N11A—C12A—C13A—C14A1.0 (8)N11B—C12B—C13B—C14B0.9 (8)
N11A—C12A—C13A—N4A179.1 (5)N11B—C12B—C13B—N4B179.1 (5)
C5A—N4A—C13A—C14A128.9 (5)C5B—N4B—C13B—C12B53.0 (7)
C3A—N4A—C13A—C14A51.2 (7)C3B—N4B—C13B—C12B126.6 (5)
C5A—N4A—C13A—C12A51.2 (6)C5B—N4B—C13B—C14B127.0 (5)
C3A—N4A—C13A—C12A128.7 (5)C3B—N4B—C13B—C14B53.4 (7)
C12A—C13A—C14A—C15A0.4 (7)C12B—C13B—C14B—C15B1.3 (7)
N4A—C13A—C14A—C15A179.5 (5)N4B—C13B—C14B—C15B178.7 (5)
C13A—C14A—C15A—C16A1.4 (9)C13B—C14B—C15B—C16B0.2 (8)
C12A—N11A—C16A—C15A0.2 (9)C12B—N11B—C16B—C15B2.1 (9)
C14A—C15A—C16A—N11A1.2 (10)C14B—C15B—C16B—N11B1.6 (10)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the N11B/C13B–C16B ring and Cg2 is the centroid of the N11A/C13A–C16A ring.
D—H···AD—HH···AD···AD—H···A
C14A—H14A···O2Ai0.932.463.358 (4)163
C15A—H15A···N11Ai0.932.743.493 (6)138
C14B—H14B···02Bii0.932.363.276 (5)167
C15B—H15B···N11Bii0.932.953.690 (6)137
C2A—H2A···Cg1iii0.982.883.705 (3)142
C2B—H2B···Cg2i0.982.803.622 (4)142
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+2, z1/2; (iii) x, y+2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H12N2O2C14H12N2O2
Mr240.26240.26
Crystal system, space groupTriclinic, P1Monoclinic, Cc
Temperature (K)298298
a, b, c (Å)8.4147 (3), 9.1827 (3), 15.2673 (5)23.240 (4), 9.4869 (15), 10.7258 (17)
α, β, γ (°)87.174 (3), 89.870 (3), 83.631 (3)90, 105.820 (2), 90
V3)1170.99 (7)2275.2 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.090.10
Crystal size (mm)0.35 × 0.28 × 0.220.38 × 0.16 × 0.04
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area detector
diffractometer
Absorption correctionMulti-scan
(Sheldrick, 2008)
Tmin, Tmax0.964, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
12024, 5376, 3946 9073, 4139, 3194
Rint0.0260.073
(sin θ/λ)max1)0.6500.603
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.114, 1.02 0.060, 0.139, 0.95
No. of reflections53764139
No. of parameters326325
No. of restraints02
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.220.17, 0.22
Absolute structure?Flack x determined using 1280 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Absolute structure parameter?1.6 (10)

Computer programs: APEX2 (Bruker, 2012), SMART (Bruker, 2012), SAINT (Bruker, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008)and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
Cg1 is the centroid of the N4A/C3A/C2A/C6A/C5A ring and Cg2 is the centroid of the N4B/C3B/C2B/C6B/C5B ring.
D—H···AD—HH···AD···AD—H···A
C6B—H6B···O2A0.982.593.252 (2)124.7
C13B—H13B···N11Ai0.932.663.584 (2)171.4
C9A—H9A···O2Aii0.932.573.490 (2)179
C9B—H9B···O2Biii0.932.433.360 (2)175
C14B—H14B···O1Aiv0.932.583.265 (2)131
C14B—H14B···O1Ai0.932.693.323 (2)126
C10A—H10A···Cg10.972.362.569 (2)91
C10B—H10B···Cg20.972.362.577 (2)91
Symmetry codes: (i) x, y+1, z; (ii) x1, y, z; (iii) x+1, y, z; (iv) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
Cg1 is the centroid of the N11B/C13B–C16B ring and Cg2 is the centroid of the N11A/C13A–C16A ring.
D—H···AD—HH···AD···AD—H···A
C14A—H14A···O2Ai0.932.463.358 (4)163
C15A—H15A···N11Ai0.932.743.493 (6)138
C14B—H14B···02Bii0.932.363.276 (5)167
C15B—H15B···N11Bii0.932.953.690 (6)137
C2A—H2A···Cg1iii0.982.883.705 (3)142
C2B—H2B···Cg2i0.982.803.622 (4)142
Symmetry codes: (i) x, y+1, z1/2; (ii) x, y+2, z1/2; (iii) x, y+2, z+1/2.
 

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