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N-(2-Bromo­ethyl)-4-piperidino-1,8-naphthalimide, C19H19BrN2O2, (I), and N-(3-bromo­propyl)-4-piperidino-1,8-naphthal­imide, C20H21BrN2O2, (II), are an homologous pair of 1,8-naphthalimide derivatives. The naphthalimide units are planar and each piperidine substituent adopts a chair conformation. This study emphasizes the importance of [pi]-stacking interactions, often augmented by other contacts, in determining the crystal structures of 1,8-naphthalimide derivatives.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108016120/su3024sup1.cif
Contains datablocks II, global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108016120/su3024Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108016120/su3024IIsup3.hkl
Contains datablock II

CCDC references: 697584; 697585

Comment top

1,8-Napthlimides find widespread use in materials science, including use as dyes (Hirahara et al., 1993), as markers in biomedical science (Stewart, 1981a,b) and as optical brighteners (Dorlars et al., 1975). Our interest in these compounds centres on the incorporation of fluorescent naphthalimide units into molecular assemblies that contain both redox-active and fluorescent functionalities joined by conductive alkene or alkyne linkages (McAdam et al., 2000, 2003, 2005), enamines (McAdam et al., 2004) or sugar derivatives of the naphthalimides (Cavigiolo et al., 2004), and the incorporation of fluorescent naphthalimides into polymeric systems (Dana et al., 2007). Of particular recent interest is the use of fluorescent naphthalimides or polyaromatic hydrocarbons in the redox-triggered absorption of radiation in the near-IR region of the electromagnetic spectrum (McAdam et al., 2003; Cuffe et al., 2005). We report here the syntheses and crystal structures of an homologous pair of 1,8-naphthalimide derivatives, N-(2-bromoethyl)-4-piperidino-1,8-naphthalimide, (I), and N-(3-bromopropyl)-4-piperidino-1,8-naphthalimide, (II), prepared as precursors to the syntheses of ferrocene–naphthalimide and related poly ad systems (Tagg, 2008).

Each molecule comprises a 1,8-naphthlimide ring system, with a piperidine substituent at the 4-position of the naphthalene ring and with the N atom of the dicarboximide ring carrying a bromoethyl substituent in (I) (Fig. 1) and a bromopropyl substituent in (II) (Fig. 2). Intramolecular C13—H···O interactions generate two S(5) ring motifs (Bernstein et al., 1995) involving both of the dicarboximide O atoms in each compound. These serve to orient the N1—C13—C14 segments of the molecules approximately at right angles to the planes of the naphthalimides, with dihedral angles of 83.48 (10)° for (I) and 82.35 (13)° for (II). The naphthalimide units are essentially planar in each compound, with r.m.s. deviations from the mean planes through all 15 atoms, including the dicarboximide O atoms, of 0.048 Å for (I) and 0.019 Å for (II). The C13 and N2 substituents are displaced only slightly from these planes, by 0.0278 (19) and -0.0807 (17) Å in opposite directions for (I) and somewhat more extensively, by 0.1108 (15) and 0.1224 (14), but both in the same direction, for (II). The piperidine rings each adopt classical chair conformations, with Cremer & Pople (1975) puckering parameters of Q2 = 0.0447 (15) Å, ϕ2 = 178 (2)° and Q3 = -0.5847 (15) Å for the N2/C15–C19 ring in (I), and Q2 = 0.0186 (17) Å, ϕ2 = 324 (5)° and Q3 = 0.5808 (17) Å for the N2/C16–C20 ring in (II).

A search of the Cambridge Structural Database (Version 5.29, updated to January 2008; Allen, 2002) reveals 12 other naphthalimide derivatives with amine substituents in the 4-position and an alkyl chain with two or more C atoms on the dicarboximide N atom (Banthia & Samanta, 2005, 2006; Banthia & Paul, 2005; Bardajee et al., 2006; Baughman et al., 1995; Shi et al., 2005; Gunnlaugsson et al., 2003, 2005; Qin et al., 2007). In contrast, the structures of only two other 4-piperidinonapthalimide derivatives have been reported previously (McAdam et al., 2003, 2005). Bond-length variations within the dicarboximide ring are consistent with significant delocalization over the naphthalimide unit. However, predictably (Easton et al., 1992; Batchelor et al., 1997), delocalization does not extend to the alkyl substituent, as evidenced by N1—C13 bond distances of 1.4667 (17) Å for (I) and 1.472 (2) Å for (II). These values compare with the corresponding average distance of 1.482 Å found for the 12 related naphthalimide derivatives using VISTA (CCDC, 1994). In contrast, the C4—N2 bonds from the naphthalene ring to the piperidine N atom are relatively short [1.4005 (17) Å for (I) and 1.411 (2) Å for (II)], suggesting some delocalization between the naphthalene and piperidine units. However, these distances are somewhat longer than the average value of 1.365 Å in the related N-alkyl-4-amidonaphthalimide derivatives, but compare somewhat more closely with the values of 1.4088 (19) and 1.376 (4) Å found for the two other reported 4-piperidinonaphthalimides (McAdam et al., 2003, 2005).

Naphthalimide compounds are well known to aggregate through π-stacking interactions in the solid state (McAdam et al., 2000; Sarma et al., 2007; Reger et al., 2005) and this often results in poor solubility and difficulty in obtaining crystalline materials (Keeling et al., 2003; Figueiredo et al., 2005). Offset ππ interactions are major contributors to the packing in both (I) and (II). However, such interactions are supported differently, despite the close relationship between these structures.

For (I), offset ππ interactions form head-to-tail dimers via inversion-related Cg1···Cg3i [3.6442 (8) Å] and Cg3···Cg3i [3.6923 (8) Å] contacts [symmetry code: (i) -x, 1-y, 1-z; Cg1 and Cg3 are the centroids of the N1/C1/C8/C11/C12 and C5–C10 rings, respectively]. Pairs of dimers are further aggregated through weaker Cg3···Cg1ii [3.9078 (8) Å] contacts [symmetry code: (ii) 1-x, 1-y, 1-z], forming columns down a (Fig. 3). The crystal packing in (I) is further stabilized by non-classical C—H···Br and C—H···O interactions that result in the formation of two sets of inversion-related dimers. C14—H14A···Br1 hydrogen bonds generate an R22(6) graph-set motif, while a pair of C15—H15A···O11 contacts forms an R22(18) ring (Fig. 4). These dimers combine to form shallow steps along the diagonal of the ac plane (Fig. 5). In the general packing, adjacent molecules in each of the π-stacked columns down a forms rows along c through the C14—H14A···Br1 dimers. The C—H···O dimers link adjacent rows into a three-dimensional network (Fig. 6).

In the crystal packing of (II), pairs of molecules are arranged in an obverse fashion through head-to-head offset π-stacking interactions that involve all three rings of the naphthalimide unit [Cg4···Cg5iii = 3.4956 (9), Cg4···Cg6iii = 3.8629 (9), Cg5···Cg6iii = 3.4896 (9) Å; symmetry code: (iii) x, 1/2-y, 1/2+z; Cg5, Cg6 and Cg7 are the centroids of the N1/C1/C8/C11/C12, C1–C4/C9/C10 and C5–C10 rings, respectively]. These contacts form extended columns down c and are augmented by C15—H15B···O11 interactions (Fig. 7). Pairs of molecules also form centrosymmetric dimers, with an R22(10) graph-set motif, through C7—H7···O12 hydrogen bonds (Fig. 8). These link adjacent molecules in each π-stacked column to form zigzag chains along b (Fig. 9). Weak C20—H20A···Br1iv hydrogen bonds [C20···Br1iv = 3.6506 (16) Å; symmetry code: (iv) 1 + x, 1/2 - y, 1/2 + z], not shown, appear to be the only links between adjacent chains and may contribute to the overall packing network.

Experimental top

N-(2-hydroxyethyl)-4-piperidino-1,8-naphthalimide (Lei et al., 2005) and 4-piperidinonaphthalic anhydride (Kupriyan et al., 2004) were prepared by published or modified literature methods.

PBr3 (0.87 ml, 9.24 mmol) in tetrahydrofuran (THF, 10 ml) was added to a mixture of N-(2-hydroxyethyl)-4-piperidino-1,8-naphthalimide (1.00 g, 3.08 mmol) and pyridine (0.75 ml, 9.24 mmol) in THF (20 ml) and heated at 323 K for 16 h. The mixture was poured into ice–water, extracted with chloroform and dried over magnesium sulfate. Column chromatography (SiO2, CH2Cl2) yielded 0.71 g (60%) of (I) and recrystallization from CH2Cl2–EtOH (1:1, v/v) gave yellow crystals suitable for X-ray analysis. Analysis, calculated for C19H19N2O2Br: C 58.93, H 4.95, N 7.23%; found: C 58.94, H 4.98, N 7.12%; ESI-MS: 409.05 [calculated (M+Na)+ 409.05]; 1H NMR (Frequency?, Solvent?, δ, p.p.m.): 1.75 (m, 2H, pip. H), 1.89 (m, 4H, pip. H), 3.24 [t (J = 5 Hz), 4H, pip. H], 3.66 [t (J = 7 Hz), 2H, –CH2—Br], 4.60 [t (J = 7 Hz), 2H, N—CH2–], 7.18 [d (J = 8 Hz), naphth. H3], 7.68 [dd (J = 8, 7 Hz), naphth. H6], 8.41 [dd (J = 8, 1 Hz), naphth. H5], 8.51 [d (J = 8 Hz), naphth. H2], 8.58 [dd (J = 7, 1 Hz), naphth. H7]; IR (KBr): νCO 1693, 1654 cm-1; UV–vis (CH2Cl2): λmax (ε) 414 (11400); emission (CH2Cl2): λflu 519 nm, ϕf 0.46.

4-Piperidinonaphthalic anhydride (1.00 g, 3.55 mmol) and 3-bromopropylamine hydrobromide (1.55 g, 7.10 mmol) were refluxed in propan-2-ol (50 ml) in the presence of Et3N (2 ml) for 10 h. The mixture was washed with saturated aqueous NaCl and extracted with chloroform. Column chromatography (SiO2, CH2Cl2) yielded 0.42 g (30%) of (II) and recrystallization from CH2Cl2–MeOH (1:1 v/v) gave yellow crystals suitable for X-ray analysis. Analysis, calculated for C20H21N2O2Br: C 59.86, H 5.28, N 6.98%; found: C 60.09, H 5.32, N 6.99%; ESI-MS: 423.07 [calculated (M+Na)+ 423.07]; 1H NMR (Frequency?, Solvent?, δ, p.p.m.): 1.73 (m, 2H, pip. H), 1.89 (m, 4H, pip. H), 2.32 [qt (J = 7 Hz), 2H, N—CH2—CH2–], 3.24 [t (J = 5 Hz), 4H, pip. H], 3.49 [t (J = 7 Hz), 2H, –CH2—Br], 4.31 [t (J = 7 Hz), 2H, N—CH2–], 7.18 [d (J = 8 Hz), naphth. H3], 7.68 [dd (J = 9, 8 Hz), naphth. H6], 8.39 [dd (J = 8, 1 Hz), naphth. H5], 8.50 [d (J = 8 Hz), naphth. H2], 8.57 [dd (J = 7, 1 Hz), naphth. H7]; IR (KBr): νCO 1686, 1648 cm-1; UV–vis (CH2Cl2): λmax (ε) 412 (11400); emission (CH2Cl2): λflu 518 nm, ϕf 0.51.

Refinement top

All H atoms for both structures were positioned geometrically and refined using a riding model, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

For both compounds, data collection: APEX2 (Bruker 2005); cell refinement: APEX2 (Bruker 2005) and SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed lines.

Fig. 2. The structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are shown as dashed lines.

Fig. 3. The π-stacking along a for (I). Spheres represent ring centroids and centroid-to-centroid interactions are shown as dotted lines.

Fig. 4. Dimer formation in the structure of (II), with hydrogen bonds shown as dashed lines.

Fig 5. Part of the structure of (I), showing the formation of shallow steps along the bc diagonal. Hydrogen bonds are shown as dashed lines.

Fig. 6. The crystal packing of (I), viewed down a, showing the three-dimensional network structure generated by ππ stacking interactions and C—H···O(Br) hydrogen bonds (dashed lines).

Fig. 7. The ππ stacking of (II), augmented by C—H···O hydrogen bonds (dashed lines). Spheres represent ring centroids and centroid-to-centroid interactions are shown as dotted lines.

Fig. 8. Centrosymmetric dimers of (II) formed by C—H···O hydrogen bonds (dashed lines).

Fig. 9. Columns of π-stacked molecules of (II), viewed down the c axis, with hydrogen bonds shown as dashed lines.
(I) N-(2-bromoethyl)-4-piperidino-1,8-naphthalimide top
Crystal data top
C19H19BrN2O2Z = 2
Mr = 387.27F(000) = 396
Triclinic, P1Dx = 1.601 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3476 (4) ÅCell parameters from 5259 reflections
b = 9.3218 (5) Åθ = 5.3–65.7°
c = 12.2905 (6) ŵ = 2.57 mm1
α = 82.039 (3)°T = 90 K
β = 84.205 (2)°Plate, yellow
γ = 74.937 (3)°0.56 × 0.46 × 0.12 mm
V = 803.19 (7) Å3
Data collection top
Bruker Nonius APEXII CCD
diffractometer
4650 independent reflections
Radiation source: fine-focus sealed tube4402 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker 2005)
h = 1010
Tmin = 0.326, Tmax = 0.734k = 1013
13527 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0325P)2 + 0.3733P]
where P = (Fo2 + 2Fc2)/3
4650 reflections(Δ/σ)max = 0.002
217 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.71 e Å3
Crystal data top
C19H19BrN2O2γ = 74.937 (3)°
Mr = 387.27V = 803.19 (7) Å3
Triclinic, P1Z = 2
a = 7.3476 (4) ÅMo Kα radiation
b = 9.3218 (5) ŵ = 2.57 mm1
c = 12.2905 (6) ÅT = 90 K
α = 82.039 (3)°0.56 × 0.46 × 0.12 mm
β = 84.205 (2)°
Data collection top
Bruker Nonius APEXII CCD
diffractometer
4650 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker 2005)
4402 reflections with I > 2σ(I)
Tmin = 0.326, Tmax = 0.734Rint = 0.034
13527 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.067H-atom parameters constrained
S = 1.07Δρmax = 0.54 e Å3
4650 reflectionsΔρmin = 0.71 e Å3
217 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.229787 (18)0.629162 (15)1.007839 (10)0.01702 (5)
O110.32682 (17)0.21282 (12)0.78655 (9)0.0227 (2)
O120.29384 (16)0.69204 (12)0.63628 (9)0.0201 (2)
N10.32272 (16)0.44977 (13)0.70847 (9)0.0130 (2)
N20.20463 (16)0.15410 (12)0.28282 (9)0.0126 (2)
C10.28358 (17)0.26533 (14)0.59499 (10)0.0118 (2)
C20.27453 (19)0.12217 (15)0.58289 (11)0.0139 (2)
H20.28690.04840.64510.017*
C30.24740 (19)0.08385 (14)0.48035 (11)0.0139 (2)
H30.24160.01540.47450.017*
C40.22886 (17)0.18830 (14)0.38699 (10)0.0115 (2)
C50.18684 (17)0.45735 (14)0.31113 (11)0.0120 (2)
H50.16130.43570.24180.014*
C60.18378 (19)0.60254 (15)0.32538 (11)0.0142 (2)
H60.15660.67960.26570.017*
C70.22051 (19)0.63675 (14)0.42711 (11)0.0139 (2)
H70.22050.73640.43580.017*
C80.25680 (17)0.52573 (14)0.51481 (11)0.0114 (2)
C90.25821 (16)0.37629 (13)0.50255 (10)0.0103 (2)
C100.22759 (17)0.34038 (14)0.39879 (10)0.0104 (2)
C110.31183 (18)0.30231 (15)0.70320 (11)0.0138 (2)
C120.29129 (18)0.56542 (15)0.62160 (11)0.0136 (2)
C130.36250 (18)0.48749 (16)0.81410 (11)0.0153 (2)
H13A0.44090.56080.80120.018*
H13B0.43340.39650.85780.018*
C140.17800 (18)0.55310 (15)0.87669 (11)0.0136 (2)
H14A0.10750.47530.89860.016*
H14B0.09930.63540.82900.016*
C150.36388 (18)0.15987 (15)0.19907 (11)0.0144 (2)
H15A0.46940.07040.21380.017*
H15B0.40980.24960.20370.017*
C160.3002 (2)0.16551 (16)0.08421 (11)0.0176 (3)
H16A0.40850.16560.02930.021*
H16B0.20160.25900.06730.021*
C170.2214 (2)0.03070 (17)0.07635 (12)0.0208 (3)
H17A0.16780.04170.00400.025*
H17B0.32480.06190.08200.025*
C180.0684 (2)0.01861 (15)0.16836 (12)0.0180 (3)
H18A0.04300.10420.15620.022*
H18B0.02830.07460.16680.022*
C190.1405 (2)0.01786 (15)0.28051 (12)0.0164 (2)
H19A0.03830.01280.33880.020*
H19B0.24650.07130.29510.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01930 (7)0.02308 (8)0.01071 (7)0.00550 (5)0.00212 (5)0.00766 (5)
O110.0362 (6)0.0187 (5)0.0122 (5)0.0031 (4)0.0076 (4)0.0012 (4)
O120.0311 (5)0.0184 (5)0.0158 (5)0.0136 (4)0.0017 (4)0.0077 (4)
N10.0137 (5)0.0170 (5)0.0101 (5)0.0044 (4)0.0014 (4)0.0057 (4)
N20.0185 (5)0.0128 (5)0.0095 (5)0.0086 (4)0.0000 (4)0.0037 (4)
C10.0128 (5)0.0135 (5)0.0091 (5)0.0025 (4)0.0014 (4)0.0026 (4)
C20.0176 (6)0.0133 (5)0.0106 (6)0.0035 (4)0.0025 (4)0.0005 (4)
C30.0199 (6)0.0109 (5)0.0122 (6)0.0052 (4)0.0023 (4)0.0023 (4)
C40.0132 (5)0.0129 (5)0.0098 (5)0.0050 (4)0.0008 (4)0.0034 (4)
C50.0129 (5)0.0141 (5)0.0096 (5)0.0045 (4)0.0004 (4)0.0020 (4)
C60.0179 (6)0.0126 (5)0.0119 (6)0.0042 (4)0.0001 (4)0.0004 (4)
C70.0184 (6)0.0112 (5)0.0133 (6)0.0056 (4)0.0018 (4)0.0037 (4)
C80.0123 (5)0.0132 (5)0.0102 (5)0.0048 (4)0.0008 (4)0.0044 (4)
C90.0099 (5)0.0120 (5)0.0099 (5)0.0035 (4)0.0004 (4)0.0033 (4)
C100.0109 (5)0.0116 (5)0.0098 (5)0.0039 (4)0.0000 (4)0.0031 (4)
C110.0141 (5)0.0156 (6)0.0113 (6)0.0011 (4)0.0022 (4)0.0044 (4)
C120.0141 (5)0.0171 (6)0.0117 (6)0.0066 (4)0.0014 (4)0.0050 (5)
C130.0139 (5)0.0220 (6)0.0118 (6)0.0043 (5)0.0022 (4)0.0079 (5)
C140.0150 (5)0.0182 (6)0.0098 (5)0.0055 (4)0.0013 (4)0.0060 (4)
C150.0158 (5)0.0159 (6)0.0123 (6)0.0043 (4)0.0007 (4)0.0047 (5)
C160.0214 (6)0.0211 (6)0.0100 (6)0.0041 (5)0.0012 (5)0.0047 (5)
C170.0284 (7)0.0207 (7)0.0148 (6)0.0040 (5)0.0043 (5)0.0092 (5)
C180.0264 (7)0.0142 (6)0.0171 (6)0.0083 (5)0.0076 (5)0.0033 (5)
C190.0265 (6)0.0130 (6)0.0137 (6)0.0109 (5)0.0044 (5)0.0014 (5)
Geometric parameters (Å, º) top
Br1—C141.9561 (13)C7—H70.9500
O11—C111.2230 (17)C8—C91.4191 (17)
O12—C121.2236 (17)C8—C121.4745 (18)
N1—C121.3990 (17)C9—C101.4157 (17)
N1—C111.4082 (17)C13—C141.5140 (18)
N1—C131.4667 (17)C13—H13A0.9900
N2—C41.4004 (17)C13—H13B0.9900
N2—C191.4694 (16)C14—H14A0.9900
N2—C151.4852 (17)C14—H14B0.9900
C1—C21.3822 (18)C15—C161.5216 (19)
C1—C91.4186 (17)C15—H15A0.9900
C1—C111.4666 (18)C15—H15B0.9900
C2—C31.4028 (19)C16—C171.532 (2)
C2—H20.9500C16—H16A0.9900
C3—C41.3916 (17)C16—H16B0.9900
C3—H30.9500C17—C181.526 (2)
C4—C101.4425 (17)C17—H17A0.9900
C5—C61.3828 (18)C17—H17B0.9900
C5—C101.4174 (17)C18—C191.524 (2)
C5—H50.9500C18—H18A0.9900
C6—C71.4003 (19)C18—H18B0.9900
C6—H60.9500C19—H19A0.9900
C7—C81.3819 (18)C19—H19B0.9900
C12—N1—C11125.02 (11)N1—C13—C14109.26 (10)
C12—N1—C13117.07 (11)N1—C13—H13A109.8
C11—N1—C13117.86 (11)C14—C13—H13A109.8
C4—N2—C19116.27 (10)N1—C13—H13B109.8
C4—N2—C15115.52 (10)C14—C13—H13B109.8
C19—N2—C15110.29 (11)H13A—C13—H13B108.3
C2—C1—C9119.08 (12)C13—C14—Br1109.52 (9)
C2—C1—C11120.03 (11)C13—C14—H14A109.8
C9—C1—C11120.84 (12)Br1—C14—H14A109.8
C1—C2—C3121.20 (11)C13—C14—H14B109.8
C1—C2—H2119.4Br1—C14—H14B109.8
C3—C2—H2119.4H14A—C14—H14B108.2
C4—C3—C2121.32 (12)N2—C15—C16110.23 (11)
C4—C3—H3119.3N2—C15—H15A109.6
C2—C3—H3119.3C16—C15—H15A109.6
C3—C4—N2123.14 (12)N2—C15—H15B109.6
C3—C4—C10118.44 (12)C16—C15—H15B109.6
N2—C4—C10118.38 (11)H15A—C15—H15B108.1
C6—C5—C10120.80 (12)C15—C16—C17110.55 (11)
C6—C5—H5119.6C15—C16—H16A109.5
C10—C5—H5119.6C17—C16—H16A109.5
C5—C6—C7120.46 (12)C15—C16—H16B109.5
C5—C6—H6119.8C17—C16—H16B109.5
C7—C6—H6119.8H16A—C16—H16B108.1
C8—C7—C6120.11 (12)C18—C17—C16110.45 (12)
C8—C7—H7119.9C18—C17—H17A109.6
C6—C7—H7119.9C16—C17—H17A109.6
C7—C8—C9120.43 (12)C18—C17—H17B109.6
C7—C8—C12118.97 (12)C16—C17—H17B109.6
C9—C8—C12120.59 (11)H17A—C17—H17B108.1
C10—C9—C1120.53 (11)C19—C18—C17110.93 (12)
C10—C9—C8119.58 (11)C19—C18—H18A109.5
C1—C9—C8119.85 (12)C17—C18—H18A109.5
C9—C10—C5118.55 (11)C19—C18—H18B109.5
C9—C10—C4119.28 (11)C17—C18—H18B109.5
C5—C10—C4122.09 (12)H18A—C18—H18B108.0
O11—C11—N1119.69 (13)N2—C19—C18109.93 (11)
O11—C11—C1123.66 (13)N2—C19—H19A109.7
N1—C11—C1116.65 (11)C18—C19—H19A109.7
O12—C12—N1120.01 (13)N2—C19—H19B109.7
O12—C12—C8123.23 (12)C18—C19—H19B109.7
N1—C12—C8116.76 (11)H19A—C19—H19B108.2
(II) N-(3-bromopropyl)-4-piperidino-1,8-naphthalimide top
Crystal data top
C20H21BrN2O2F(000) = 824
Mr = 401.30Dx = 1.522 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9183 reflections
a = 12.4165 (3) Åθ = 2.3–31.9°
b = 17.7709 (5) ŵ = 2.36 mm1
c = 7.9618 (2) ÅT = 90 K
β = 94.569 (1)°Plate, yellow
V = 1751.21 (8) Å30.62 × 0.14 × 0.04 mm
Z = 4
Data collection top
Bruker Nonius APEXII CCD
diffractometer
5571 independent reflections
Radiation source: fine-focus sealed tube4434 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scansθmax = 31.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker 2005)
h = 1717
Tmin = 0.201, Tmax = 0.911k = 2525
30759 measured reflectionsl = 1111
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0407P)2 + 1.4674P]
where P = (Fo2 + 2Fc2)/3
5571 reflections(Δ/σ)max < 0.001
226 parametersΔρmax = 1.12 e Å3
0 restraintsΔρmin = 0.99 e Å3
Crystal data top
C20H21BrN2O2V = 1751.21 (8) Å3
Mr = 401.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.4165 (3) ŵ = 2.36 mm1
b = 17.7709 (5) ÅT = 90 K
c = 7.9618 (2) Å0.62 × 0.14 × 0.04 mm
β = 94.569 (1)°
Data collection top
Bruker Nonius APEXII CCD
diffractometer
5571 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker 2005)
4434 reflections with I > 2σ(I)
Tmin = 0.201, Tmax = 0.911Rint = 0.052
30759 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.02Δρmax = 1.12 e Å3
5571 reflectionsΔρmin = 0.99 e Å3
226 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.527590 (16)0.344479 (14)0.08936 (3)0.03387 (8)
C10.07010 (12)0.21710 (9)0.13372 (19)0.0101 (3)
C20.05950 (13)0.13995 (9)0.1262 (2)0.0117 (3)
H20.11270.10870.16990.014*
C30.02862 (12)0.10695 (9)0.0549 (2)0.0119 (3)
H30.03390.05370.05080.014*
C40.10850 (12)0.15060 (9)0.00995 (19)0.0106 (3)
C50.17083 (13)0.28019 (9)0.0824 (2)0.0123 (3)
H50.22950.25970.13710.015*
C60.15774 (13)0.35695 (9)0.0764 (2)0.0139 (3)
H60.20830.38880.12480.017*
C70.07062 (13)0.38882 (9)0.0005 (2)0.0128 (3)
H70.06280.44200.00470.015*
C80.00351 (13)0.34286 (9)0.07011 (19)0.0107 (3)
C90.00834 (12)0.26353 (9)0.06657 (18)0.0095 (3)
C100.09767 (12)0.23118 (9)0.00795 (19)0.0101 (3)
C110.16305 (12)0.24960 (9)0.21211 (19)0.0112 (3)
O110.23120 (10)0.21141 (7)0.27405 (16)0.0172 (2)
C120.09637 (13)0.37712 (9)0.1471 (2)0.0125 (3)
O120.10989 (10)0.44520 (7)0.15472 (17)0.0187 (3)
N10.17076 (11)0.32831 (7)0.21262 (17)0.0112 (2)
C130.26345 (13)0.36280 (9)0.2877 (2)0.0143 (3)
H13A0.23890.40870.35010.017*
H13B0.29140.32720.36940.017*
C140.35487 (14)0.38371 (10)0.1556 (2)0.0178 (3)
H14A0.41060.41260.21040.021*
H14B0.32580.41650.06930.021*
C150.40682 (15)0.31494 (11)0.0701 (2)0.0203 (3)
H15A0.43320.28090.15620.024*
H15B0.35240.28740.00970.024*
N20.19869 (11)0.11816 (8)0.07946 (17)0.0114 (2)
C160.18654 (13)0.03899 (9)0.1283 (2)0.0133 (3)
H16A0.11580.03160.19280.016*
H16B0.18810.00730.02590.016*
C170.27673 (13)0.01469 (9)0.2355 (2)0.0156 (3)
H17A0.27110.04320.34260.019*
H17B0.26880.03950.26270.019*
C180.38716 (14)0.02853 (10)0.1428 (2)0.0188 (3)
H18A0.44460.01660.21790.023*
H18B0.39660.00480.04300.023*
C190.39682 (13)0.11066 (10)0.0871 (2)0.0179 (3)
H19A0.46640.11850.01950.022*
H19B0.39560.14370.18740.022*
C200.30362 (13)0.13121 (10)0.0176 (2)0.0148 (3)
H20A0.30770.10040.12150.018*
H20B0.30950.18480.05100.018*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01854 (10)0.05145 (16)0.03016 (12)0.00572 (9)0.00723 (8)0.00056 (9)
C10.0093 (6)0.0119 (7)0.0089 (6)0.0008 (5)0.0000 (5)0.0002 (5)
C20.0116 (7)0.0118 (7)0.0120 (7)0.0018 (5)0.0017 (5)0.0007 (5)
C30.0127 (7)0.0093 (6)0.0137 (7)0.0003 (5)0.0016 (5)0.0012 (5)
C40.0102 (6)0.0124 (7)0.0088 (6)0.0006 (5)0.0011 (5)0.0007 (5)
C50.0111 (6)0.0151 (7)0.0109 (7)0.0011 (5)0.0018 (5)0.0002 (5)
C60.0127 (7)0.0158 (7)0.0132 (7)0.0039 (6)0.0021 (5)0.0023 (6)
C70.0143 (7)0.0118 (7)0.0122 (7)0.0016 (5)0.0006 (5)0.0010 (5)
C80.0109 (6)0.0116 (7)0.0096 (6)0.0004 (5)0.0003 (5)0.0003 (5)
C90.0096 (6)0.0115 (7)0.0071 (6)0.0008 (5)0.0007 (5)0.0001 (5)
C100.0098 (6)0.0118 (7)0.0085 (6)0.0013 (5)0.0001 (5)0.0001 (5)
C110.0111 (6)0.0114 (7)0.0109 (7)0.0001 (5)0.0003 (5)0.0003 (5)
O110.0151 (6)0.0147 (6)0.0228 (6)0.0012 (4)0.0079 (5)0.0004 (5)
C120.0129 (7)0.0127 (7)0.0120 (7)0.0001 (5)0.0010 (5)0.0011 (5)
O120.0200 (6)0.0111 (5)0.0260 (7)0.0010 (4)0.0070 (5)0.0012 (5)
N10.0107 (6)0.0106 (6)0.0124 (6)0.0004 (5)0.0023 (5)0.0006 (5)
C130.0142 (7)0.0144 (7)0.0148 (7)0.0013 (6)0.0044 (6)0.0029 (6)
C140.0138 (7)0.0171 (8)0.0226 (8)0.0039 (6)0.0033 (6)0.0012 (6)
C150.0156 (8)0.0259 (9)0.0189 (8)0.0014 (7)0.0019 (6)0.0012 (7)
N20.0090 (6)0.0118 (6)0.0135 (6)0.0010 (5)0.0010 (5)0.0017 (5)
C160.0128 (7)0.0111 (7)0.0161 (7)0.0007 (5)0.0023 (6)0.0002 (6)
C170.0147 (7)0.0140 (7)0.0184 (8)0.0027 (6)0.0040 (6)0.0015 (6)
C180.0118 (7)0.0202 (8)0.0249 (9)0.0034 (6)0.0047 (6)0.0003 (7)
C190.0106 (7)0.0206 (8)0.0229 (8)0.0011 (6)0.0031 (6)0.0010 (7)
C200.0102 (7)0.0193 (8)0.0146 (7)0.0007 (6)0.0007 (5)0.0015 (6)
Geometric parameters (Å, º) top
Br1—C151.9579 (18)C13—C141.531 (2)
C1—C21.379 (2)C13—H13A0.9900
C1—C91.414 (2)C13—H13B0.9900
C1—C111.473 (2)C14—C151.517 (3)
C2—C31.401 (2)C14—H14A0.9900
C2—H20.9500C14—H14B0.9900
C3—C41.391 (2)C15—H15A0.9900
C3—H30.9500C15—H15B0.9900
C4—N21.411 (2)N2—C161.464 (2)
C4—C101.438 (2)N2—C201.479 (2)
C5—C61.375 (2)C16—C171.524 (2)
C5—C101.422 (2)C16—H16A0.9900
C5—H50.9500C16—H16B0.9900
C6—C71.404 (2)C17—C181.525 (2)
C6—H60.9500C17—H17A0.9900
C7—C81.379 (2)C17—H17B0.9900
C7—H70.9500C18—C191.527 (3)
C8—C91.418 (2)C18—H18A0.9900
C8—C121.479 (2)C18—H18B0.9900
C9—C101.420 (2)C19—C201.524 (2)
C11—O111.2192 (19)C19—H19A0.9900
C11—N11.402 (2)C19—H19B0.9900
C12—O121.224 (2)C20—H20A0.9900
C12—N11.398 (2)C20—H20B0.9900
N1—C131.472 (2)
C2—C1—C9119.53 (14)C15—C14—C13112.21 (14)
C2—C1—C11119.27 (14)C15—C14—H14A109.2
C9—C1—C11121.20 (14)C13—C14—H14A109.2
C1—C2—C3120.95 (14)C15—C14—H14B109.2
C1—C2—H2119.5C13—C14—H14B109.2
C3—C2—H2119.5H14A—C14—H14B107.9
C4—C3—C2121.34 (14)C14—C15—Br1110.55 (13)
C4—C3—H3119.3C14—C15—H15A109.5
C2—C3—H3119.3Br1—C15—H15A109.5
C3—C4—N2121.97 (14)C14—C15—H15B109.5
C3—C4—C10118.76 (14)Br1—C15—H15B109.5
N2—C4—C10119.27 (13)H15A—C15—H15B108.1
C6—C5—C10120.79 (14)C4—N2—C16115.37 (13)
C6—C5—H5119.6C4—N2—C20115.11 (13)
C10—C5—H5119.6C16—N2—C20110.93 (13)
C5—C6—C7120.86 (15)N2—C16—C17110.87 (13)
C5—C6—H6119.6N2—C16—H16A109.5
C7—C6—H6119.6C17—C16—H16A109.5
C8—C7—C6119.87 (15)N2—C16—H16B109.5
C8—C7—H7120.1C17—C16—H16B109.5
C6—C7—H7120.1H16A—C16—H16B108.1
C7—C8—C9120.48 (14)C16—C17—C18110.85 (14)
C7—C8—C12119.32 (14)C16—C17—H17A109.5
C9—C8—C12120.20 (13)C18—C17—H17A109.5
C1—C9—C8119.81 (14)C16—C17—H17B109.5
C1—C9—C10120.41 (14)C18—C17—H17B109.5
C8—C9—C10119.77 (13)H17A—C17—H17B108.1
C9—C10—C5118.19 (14)C17—C18—C19109.97 (14)
C9—C10—C4118.97 (13)C17—C18—H18A109.7
C5—C10—C4122.81 (14)C19—C18—H18A109.7
O11—C11—N1120.30 (14)C17—C18—H18B109.7
O11—C11—C1123.06 (14)C19—C18—H18B109.7
N1—C11—C1116.64 (13)H18A—C18—H18B108.2
O12—C12—N1119.83 (14)C20—C19—C18110.02 (14)
O12—C12—C8122.83 (14)C20—C19—H19A109.7
N1—C12—C8117.34 (14)C18—C19—H19A109.7
C12—N1—C11124.79 (13)C20—C19—H19B109.7
C12—N1—C13117.03 (13)C18—C19—H19B109.7
C11—N1—C13118.18 (13)H19A—C19—H19B108.2
N1—C13—C14112.53 (13)N2—C20—C19110.61 (14)
N1—C13—H13A109.1N2—C20—H20A109.5
C14—C13—H13A109.1C19—C20—H20A109.5
N1—C13—H13B109.1N2—C20—H20B109.5
C14—C13—H13B109.1C19—C20—H20B109.5
H13A—C13—H13B107.8H20A—C20—H20B108.1
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O12i0.952.473.250 (2)140
C15—H15B···O11ii0.992.503.369 (2)147
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H19BrN2O2C20H21BrN2O2
Mr387.27401.30
Crystal system, space groupTriclinic, P1Monoclinic, P21/c
Temperature (K)9090
a, b, c (Å)7.3476 (4), 9.3218 (5), 12.2905 (6)12.4165 (3), 17.7709 (5), 7.9618 (2)
α, β, γ (°)82.039 (3), 84.205 (2), 74.937 (3)90, 94.569 (1), 90
V3)803.19 (7)1751.21 (8)
Z24
Radiation typeMo KαMo Kα
µ (mm1)2.572.36
Crystal size (mm)0.56 × 0.46 × 0.120.62 × 0.14 × 0.04
Data collection
DiffractometerBruker Nonius APEXII CCD
diffractometer
Bruker Nonius APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker 2005)
Multi-scan
(SADABS; Bruker 2005)
Tmin, Tmax0.326, 0.7340.201, 0.911
No. of measured, independent and
observed [I > 2σ(I)] reflections
13527, 4650, 4402 30759, 5571, 4434
Rint0.0340.052
(sin θ/λ)max1)0.7030.725
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.067, 1.07 0.037, 0.098, 1.02
No. of reflections46505571
No. of parameters217226
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.711.12, 0.99

Computer programs: , APEX2 (Bruker 2005) and SAINT (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O12i0.952.473.250 (2)139.5
C15—H15B···O11ii0.992.503.369 (2)146.8
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z1/2.
 

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