N-(5-Phenyl­seleno)­pentyl­phthal­imide

Molecules of the title compound, C₁₉H₁₉NO₂Se, are linked into centrosymmetric dimers via hydrogen bonds of the C—H...O type. There is also a weak π–π stacking interaction between parallel phthal­imide groups belonging to neighbouring dimers in the crystal. The seleno­pentyl group has a planar zigzag conformation and is approximately coplanar with the phenyl ring. The phthal­imide plane forms a dihedral angle of 80.46 (7)° with the least-squares plane of the phenyl­seleno­pentyl moiety.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.098
• Data-to-parameter ratio = 14.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Oxidation–fragmentation of organoselenides is a useful reaction in organic synthesis (Reich et al., 1978). In order to further investigate the effect of substituents on the course of the reaction, compound (I) was prepared. Its crystal and molecular structures are reported in the present paper (Fig. 1).

The selenopentyl chain in molecule (I) has a typical planar (within 0.06 Å) zigzag conformation. It is in fact coplanar with the Ph ring bonded to the Se atom, so that the deviations of atoms from the least-squares plane passing through atoms Se1 and C9–C19 do not exceed 0.06 Å. The dihedral angle formed by this plane and the plane of the phthalimide group is 80.46 (7)°

The crystal packing of (I) features centrosymmetric dimers held together by hydrogen bonds of the C—H···O type [C6—H6A···O2ⁱ: H6A···O2ⁱ 2.56 Å, C6···O2ⁱ 3.410 (4) Å and C6—H6A···O2ⁱ 152.2°; symmetry code: (i) -x, 1 - y, 1 - z]. No interactions of such type, however, were found in the structure of the similar tellurium derivative N-[2-(4-methoxyphenyl)telluro]ethylphthalimide (Singh et al., 2000). A weak π–π-stacking interaction between two parallel phthalimide groups belonging to the neighbouring hydrogen-bonded dimers is also observed in the crystal of (I). The phthalimide moieties are stacked in a head-to-tail fashion with a small offset relative to each other. The distance between the parallel phthalimide planes is 3.728 (4) Å.

S2. Experimental

5-Bromopentylphthalimide (1.0 g, 3.2 mmol) and potassium phthalimide (6.1 g, 3.6 mmol) were mixed in DMF (20 ml). The mixture was heated to 368–373 K under nitrogen and stirred for 8 h. It was then cooled to room temperature, diluted with water (20 ml) and extracted with chloroform. The chloroform layer was washed in turn with water, solution of 10% NaOH and again water, dried over anhydrous magnesium sulfate, filtered and evaporated. The light-yellow residue was recrystallized from a 1:1 mixture of dichloromethane and petroleum ether (303–333 K). Colorless crystals of (I) were obtained (0.96 g, 2.6 mmol, 82%).

S3. Refinement

All H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation with their displacement parameters equal to 1.2U_eq of the carrier atom.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Atom-labeling scheme in structure (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

N-(5-Phenylseleno)pentylphthalimide

Crystal data

C19H19NO2Se	F(000) = 760
Mr = 372.31	Dx = 1.442 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.481 (2) Å	Cell parameters from 60 reflections
b = 18.196 (5) Å	θ = 2.4–30.2°
c = 11.265 (3) Å	µ = 2.20 mm^−1
β = 99.361 (5)°	T = 293 K
V = 1715.3 (8) Å^3	Prism, colorless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection

Bruker CCD area-detector diffractometer	3033 independent reflections
Radiation source: fine-focus sealed tube	1819 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.558, Tmax = 0.668	k = −21→21
7064 measured reflections	l = −7→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
3033 reflections	(Δ/σ)max = 0.027
208 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

Geometry. Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

4.5620 (0.0081) x + 4.0506 (0.0149) y + 8.0519 (0.0091) z = 6.5395 (0.0068)

* 0.0061 (0.0022) C1 * -0.0048 (0.0027) C2 * -0.0026 (0.0026) C3 * 0.0011 (0.0027) C4 * -0.0012 (0.0027) C5 * 0.0042 (0.0025) C6 * 0.0024 (0.0028) C7 * -0.0050 (0.0022) C8 0.0093 (0.0036) N1

Rms deviation of fitted atoms = 0.0039

7.3148 (0.0048) x + 4.6538 (0.0072) y - 6.4347 (0.0087) z = 3.1766 (0.0058)

Angle to previous plane (with approximate e.s.d.) = 80.46 (0.07)

* -0.0378 (0.0028) C9 * 0.0093 (0.0030) C10 * 0.0486 (0.0031) C11 * 0.0296 (0.0032) C12 * -0.0594 (0.0034) C13 * -0.0036 (0.0016) Se1 * 0.0127 (0.0029) C14 * 0.0123 (0.0030) C15 * 0.0078 (0.0027) C16 * -0.0050 (0.0030) C17 * -0.0062 (0.0030) C18 * -0.0081 (0.0028) C19

Rms deviation of fitted atoms = 0.0271

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 (Ų)

	x	y	z	Uiso*/Ueq
Se1	0.39622 (5)	1.00459 (2)	0.68386 (4)	0.07076 (18)
O1	0.4897 (3)	0.62297 (13)	0.2221 (2)	0.0784 (8)
O2	0.0951 (3)	0.60872 (13)	0.4509 (2)	0.0781 (8)
N1	0.2850 (3)	0.63466 (14)	0.3326 (2)	0.0564 (7)
C1	0.4028 (4)	0.59636 (19)	0.2847 (3)	0.0556 (9)
C2	0.3935 (4)	0.51971 (16)	0.3272 (3)	0.0479 (8)
C3	0.4845 (4)	0.4592 (2)	0.3063 (3)	0.0599 (9)
H3A	0.5645	0.4626	0.2592	0.072*
C4	0.4506 (5)	0.3940 (2)	0.3588 (3)	0.0686 (10)
H4A	0.5094	0.3522	0.3470	0.082*
C5	0.3313 (5)	0.3891 (2)	0.4285 (3)	0.0701 (11)
H5A	0.3107	0.3441	0.4622	0.084*
C6	0.2422 (4)	0.4498 (2)	0.4492 (3)	0.0618 (9)
H6A	0.1623	0.4467	0.4966	0.074*
C7	0.2761 (4)	0.51509 (17)	0.3969 (3)	0.0489 (8)
C8	0.2026 (4)	0.58839 (19)	0.4007 (3)	0.0576 (9)
C9	0.2561 (4)	0.71347 (17)	0.3193 (3)	0.0663 (10)
H9A	0.1418	0.7224	0.3054	0.080*
H9B	0.2986	0.7311	0.2496	0.080*
C10	0.3326 (4)	0.75602 (17)	0.4297 (3)	0.0625 (9)
H10A	0.3028	0.7334	0.5008	0.075*
H10B	0.4478	0.7530	0.4364	0.075*
C11	0.2839 (4)	0.83565 (18)	0.4258 (3)	0.0623 (9)
H11A	0.1682	0.8386	0.4151	0.075*
H11B	0.3182	0.8588	0.3568	0.075*
C12	0.3536 (4)	0.87762 (18)	0.5385 (3)	0.0656 (10)
H12A	0.4691	0.8786	0.5451	0.079*
H12B	0.3277	0.8519	0.6082	0.079*
C13	0.2921 (4)	0.95597 (19)	0.5390 (3)	0.0649 (10)
H13A	0.1773	0.9558	0.5368	0.078*
H13B	0.3150	0.9820	0.4686	0.078*
C14	0.3168 (4)	1.10262 (18)	0.6620 (3)	0.0544 (9)
C15	0.2142 (4)	1.1264 (2)	0.5625 (3)	0.0641 (10)
H15A	0.1801	1.0939	0.4998	0.077*
C16	0.1609 (4)	1.1988 (2)	0.5550 (4)	0.0743 (11)
H16A	0.0919	1.2148	0.4873	0.089*
C17	0.2100 (5)	1.2462 (2)	0.6471 (4)	0.0757 (11)
H17A	0.1742	1.2945	0.6427	0.091*
C18	0.3119 (5)	1.2224 (2)	0.7460 (4)	0.0723 (11)
H18A	0.3460	1.2551	0.8083	0.087*
C19	0.3645 (4)	1.1516 (2)	0.7548 (3)	0.0645 (10)
H19A	0.4326	1.1362	0.8234	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Se1	0.0741 (3)	0.0623 (3)	0.0722 (3)	0.0070 (2)	0.0007 (2)	0.0016 (2)
O1	0.0886 (19)	0.0720 (18)	0.0830 (19)	−0.0023 (14)	0.0392 (17)	0.0098 (14)
O2	0.0691 (17)	0.0781 (18)	0.0942 (19)	0.0041 (13)	0.0347 (16)	−0.0103 (15)
N1	0.0610 (18)	0.0493 (17)	0.0612 (18)	0.0040 (14)	0.0173 (15)	−0.0005 (14)
C1	0.058 (2)	0.059 (2)	0.050 (2)	−0.0065 (18)	0.0071 (19)	−0.0040 (18)
C2	0.0435 (18)	0.050 (2)	0.0491 (19)	−0.0052 (14)	0.0038 (16)	−0.0053 (15)
C3	0.056 (2)	0.058 (2)	0.066 (2)	−0.0002 (18)	0.0138 (19)	−0.0075 (19)
C4	0.069 (3)	0.058 (3)	0.074 (3)	0.0095 (19)	−0.003 (2)	−0.009 (2)
C5	0.081 (3)	0.051 (2)	0.075 (3)	−0.010 (2)	0.001 (2)	0.0040 (19)
C6	0.059 (2)	0.064 (2)	0.063 (2)	−0.0154 (19)	0.0123 (19)	0.0013 (19)
C7	0.0453 (18)	0.053 (2)	0.0481 (18)	−0.0081 (15)	0.0066 (16)	−0.0022 (16)
C8	0.052 (2)	0.060 (2)	0.061 (2)	−0.0021 (18)	0.0085 (19)	−0.0076 (19)
C9	0.071 (2)	0.054 (2)	0.073 (3)	0.0105 (18)	0.011 (2)	0.003 (2)
C10	0.068 (2)	0.051 (2)	0.069 (3)	0.0049 (17)	0.013 (2)	0.0056 (18)
C11	0.059 (2)	0.056 (2)	0.072 (3)	0.0043 (17)	0.013 (2)	0.0021 (19)
C12	0.068 (2)	0.057 (2)	0.072 (3)	0.0017 (18)	0.015 (2)	0.007 (2)
C13	0.064 (2)	0.056 (2)	0.075 (3)	0.0018 (18)	0.011 (2)	−0.0009 (19)
C14	0.051 (2)	0.055 (2)	0.061 (2)	−0.0036 (16)	0.0197 (19)	0.0025 (18)
C15	0.061 (2)	0.069 (3)	0.062 (2)	−0.0048 (19)	0.009 (2)	0.003 (2)
C16	0.067 (3)	0.071 (3)	0.085 (3)	0.007 (2)	0.013 (2)	0.017 (2)
C17	0.077 (3)	0.058 (2)	0.102 (3)	0.008 (2)	0.041 (3)	0.007 (3)
C18	0.079 (3)	0.066 (3)	0.079 (3)	−0.005 (2)	0.033 (2)	−0.010 (2)
C19	0.061 (2)	0.070 (3)	0.063 (2)	−0.0013 (19)	0.012 (2)	−0.002 (2)

Geometric parameters (Å, º)

Se1—C13	1.938 (3)	C10—C11	1.505 (4)
Se1—C14	1.908 (3)	C10—H10A	0.9700
O1—C1	1.202 (4)	C10—H10B	0.9700
O2—C8	1.207 (4)	C11—C12	1.516 (5)
N1—C1	1.396 (4)	C11—H11A	0.9700
N1—C8	1.401 (4)	C11—H11B	0.9700
N1—C9	1.459 (4)	C12—C13	1.519 (4)
C1—C2	1.481 (4)	C12—H12A	0.9700
C2—C7	1.367 (4)	C12—H12B	0.9700
C2—C3	1.386 (4)	C13—H13A	0.9700
C3—C4	1.378 (5)	C13—H13B	0.9700
C3—H3A	0.9300	C14—C15	1.372 (4)
C4—C5	1.380 (5)	C14—C19	1.384 (5)
C4—H4A	0.9300	C15—C16	1.392 (5)
C5—C6	1.378 (5)	C15—H15A	0.9300
C5—H5A	0.9300	C16—C17	1.360 (5)
C6—C7	1.378 (4)	C16—H16A	0.9300
C6—H6A	0.9300	C17—C18	1.364 (5)
C7—C8	1.476 (4)	C17—H17A	0.9300
C9—C10	1.518 (4)	C18—C19	1.361 (5)
C9—H9A	0.9700	C18—H18A	0.9300
C9—H9B	0.9700	C19—H19A	0.9300
C14—Se1—C13	102.42 (15)	C9—C10—H10B	109.0
C1—N1—C8	111.3 (3)	H10A—C10—H10B	107.8
C1—N1—C9	124.8 (3)	C10—C11—C12	113.1 (3)
C8—N1—C9	123.8 (3)	C10—C11—H11A	109.0
O1—C1—N1	124.8 (3)	C12—C11—H11A	109.0
O1—C1—C2	129.7 (3)	C10—C11—H11B	109.0
N1—C1—C2	105.5 (3)	C12—C11—H11B	109.0
C7—C2—C3	121.7 (3)	H11A—C11—H11B	107.8
C7—C2—C1	109.0 (3)	C11—C12—C13	112.9 (3)
C3—C2—C1	129.2 (3)	C11—C12—H12A	109.0
C2—C3—C4	116.8 (3)	C13—C12—H12A	109.0
C2—C3—H3A	121.6	C11—C12—H12B	109.0
C4—C3—H3A	121.6	C13—C12—H12B	109.0
C5—C4—C3	121.5 (3)	H12A—C12—H12B	107.8
C5—C4—H4A	119.2	C12—C13—Se1	108.8 (2)
C3—C4—H4A	119.2	C12—C13—H13A	109.9
C4—C5—C6	121.2 (3)	Se1—C13—H13A	109.9
C4—C5—H5A	119.4	C12—C13—H13B	109.9
C6—C5—H5A	119.4	Se1—C13—H13B	109.9
C7—C6—C5	117.4 (3)	H13A—C13—H13B	108.3
C7—C6—H6A	121.3	C15—C14—C19	118.9 (3)
C5—C6—H6A	121.3	C15—C14—Se1	124.3 (3)
C2—C7—C6	121.4 (3)	C19—C14—Se1	116.8 (3)
C2—C7—C8	108.1 (3)	C14—C15—C16	120.3 (4)
C6—C7—C8	130.5 (3)	C14—C15—H15A	119.9
O2—C8—N1	123.7 (3)	C16—C15—H15A	119.9
O2—C8—C7	130.2 (3)	C17—C16—C15	119.8 (4)
N1—C8—C7	106.1 (3)	C17—C16—H16A	120.1
N1—C9—C10	112.0 (3)	C15—C16—H16A	120.1
N1—C9—H9A	109.2	C16—C17—C18	119.8 (4)
C10—C9—H9A	109.2	C16—C17—H17A	120.1
N1—C9—H9B	109.2	C18—C17—H17A	120.1
C10—C9—H9B	109.2	C17—C18—C19	121.0 (4)
H9A—C9—H9B	107.9	C17—C18—H18A	119.5
C11—C10—C9	112.9 (3)	C19—C18—H18A	119.5
C11—C10—H10A	109.0	C18—C19—C14	120.2 (4)
C9—C10—H10A	109.0	C18—C19—H19A	119.9
C11—C10—H10B	109.0	C14—C19—H19A	119.9
C8—N1—C1—O1	179.4 (3)	C9—N1—C8—C7	−176.1 (3)
C9—N1—C1—O1	−3.7 (5)	C2—C7—C8—O2	179.5 (4)
C8—N1—C1—C2	−0.3 (4)	C6—C7—C8—O2	0.1 (6)
C9—N1—C1—C2	176.7 (3)	C2—C7—C8—N1	−1.1 (3)
O1—C1—C2—C7	179.9 (4)	C6—C7—C8—N1	179.5 (3)
N1—C1—C2—C7	−0.4 (3)	C1—N1—C9—C10	−99.0 (4)
O1—C1—C2—C3	0.8 (6)	C8—N1—C9—C10	77.5 (4)
N1—C1—C2—C3	−179.5 (3)	N1—C9—C10—C11	−171.4 (3)
C7—C2—C3—C4	0.3 (5)	C9—C10—C11—C12	177.3 (3)
C1—C2—C3—C4	179.2 (3)	C10—C11—C12—C13	−174.7 (3)
C2—C3—C4—C5	0.2 (5)	C11—C12—C13—Se1	−177.7 (2)
C3—C4—C5—C6	−0.6 (5)	C14—Se1—C13—C12	175.7 (2)
C4—C5—C6—C7	0.5 (5)	C13—Se1—C14—C15	−1.2 (3)
C3—C2—C7—C6	−0.4 (5)	C13—Se1—C14—C19	177.2 (3)
C1—C2—C7—C6	−179.5 (3)	C19—C14—C15—C16	0.8 (5)
C3—C2—C7—C8	−179.9 (3)	Se1—C14—C15—C16	179.2 (3)
C1—C2—C7—C8	1.0 (3)	C14—C15—C16—C17	−0.4 (5)
C5—C6—C7—C2	0.0 (5)	C15—C16—C17—C18	0.4 (6)
C5—C6—C7—C8	179.4 (3)	C16—C17—C18—C19	−0.7 (6)
C1—N1—C8—O2	−179.8 (3)	C17—C18—C19—C14	1.0 (5)
C9—N1—C8—O2	3.3 (5)	C15—C14—C19—C18	−1.1 (5)
C1—N1—C8—C7	0.8 (4)	Se1—C14—C19—C18	−179.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2^i	0.93	2.56	3.410 (4)	152

Symmetry code: (i) −x, −y+1, −z+1.