organic compounds
2-[2-(4-Methylpiperazin-1-yl)ethyl]isoindoline-1,3-dione
aKey Laboratory of Fine Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China
*Correspondence e-mail: shaoying810724@163.com
In the title compound, C15H19N3O2, the piperazine ring adopts a chair conformation, with its N—C bonds in pseudo-equatorial orientations. The dihedral angle between the C atoms of the piperazine ring and the phthalamide ring system (r.m.s. deviaiton = 0.008 Å) is 89.30 (8)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, generating a three-dimensional network and aromatic π–π interactions also occur [centroid–centroid distances = 3.556 (1)–3.716 (1) Å].
CCDC reference: 984236
Related literature
For background to piperazine derivatives, see: Tian et al. (2011); Stauffer (2011). For the preparation, see: Ghosh et al. (2010). For a similar structure, see: Shao et al. (2012).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 984236
10.1107/S1600536814002232/hb7071sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002232/hb7071Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002232/hb7071Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536814002232/hb7071Isup4.cml
A suspension of N-(2-bromoethyl)phthalimide (2.54 g, 10.0 mmol), N-methylpiperazine (1.10 g, 11.1 mmol) and K2CO3 (2.70 g, 19.6 mmol) in 20 ml CH3CN was stirred at room temperature for 0.5 h, and then heated to reflux for over 20 h. After cooling and filtration, the filter residue was washed with CH3CN. And the filtrate and washing were combined prior to removing the solvent under vacuum. The title compound (2.15 g, 7.9 mmol) was obtained as colorless needles with m.p. 102.2–103.0 °C, after recrystallization from n-hexane. Colourless blocks were obtained by slow evaporation of CH3OH.
All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. View of the title compound, showing 50% probability ellipsoids. | |
Fig. 2. Perspective view of the title compound along a direction. Labels of atoms have been omitted for clarity. |
C15H19N3O2 | Z = 2 |
Mr = 273.33 | F(000) = 292 |
Triclinic, P1 | Dx = 1.254 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9537 (12) Å | Cell parameters from 2417 reflections |
b = 8.4410 (15) Å | θ = 2.8–29.0° |
c = 12.563 (2) Å | µ = 0.09 mm−1 |
α = 96.260 (4)° | T = 296 K |
β = 98.381 (4)° | Block, colorless |
γ = 92.647 (3)° | 0.30 × 0.28 × 0.25 mm |
V = 723.7 (2) Å3 |
Bruker APEXII CCD diffractometer | 2654 independent reflections |
Radiation source: fine-focus sealed tube | 2206 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 25.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→8 |
Tmin = 0.975, Tmax = 0.979 | k = −10→9 |
4194 measured reflections | l = −7→15 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.154 | w = 1/[σ2(Fo2) + (0.0987P)2 + 0.097P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2654 reflections | Δρmax = 0.17 e Å−3 |
183 parameters | Δρmin = −0.18 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.074 (13) |
C15H19N3O2 | γ = 92.647 (3)° |
Mr = 273.33 | V = 723.7 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9537 (12) Å | Mo Kα radiation |
b = 8.4410 (15) Å | µ = 0.09 mm−1 |
c = 12.563 (2) Å | T = 296 K |
α = 96.260 (4)° | 0.30 × 0.28 × 0.25 mm |
β = 98.381 (4)° |
Bruker APEXII CCD diffractometer | 2654 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2206 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.979 | Rint = 0.022 |
4194 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.17 e Å−3 |
2654 reflections | Δρmin = −0.18 e Å−3 |
183 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7472 (2) | 0.1040 (2) | 0.64462 (16) | 0.0663 (5) | |
H1 | 0.7495 | 0.1864 | 0.7004 | 0.080* | |
C2 | 0.7384 (3) | −0.0535 (3) | 0.6639 (2) | 0.0853 (7) | |
H2 | 0.7335 | −0.0780 | 0.7339 | 0.102* | |
C3 | 0.7366 (3) | −0.1743 (3) | 0.5820 (3) | 0.0952 (9) | |
H3 | 0.7321 | −0.2795 | 0.5976 | 0.114* | |
C4 | 0.7415 (3) | −0.1437 (2) | 0.4756 (2) | 0.0866 (8) | |
H4 | 0.7398 | −0.2263 | 0.4200 | 0.104* | |
C5 | 0.7489 (2) | 0.0147 (2) | 0.45574 (15) | 0.0583 (5) | |
C6 | 0.75250 (19) | 0.13529 (18) | 0.53922 (13) | 0.0490 (4) | |
C7 | 0.7637 (2) | 0.28929 (18) | 0.49368 (12) | 0.0470 (4) | |
C8 | 0.7547 (2) | 0.0895 (2) | 0.35403 (15) | 0.0623 (5) | |
C9 | 0.7949 (2) | 0.3733 (3) | 0.31185 (14) | 0.0682 (5) | |
H9A | 0.8471 | 0.3229 | 0.2500 | 0.082* | |
H9B | 0.8920 | 0.4539 | 0.3501 | 0.082* | |
C10 | 0.6130 (3) | 0.4551 (2) | 0.27092 (14) | 0.0618 (5) | |
H10A | 0.5547 | 0.4975 | 0.3328 | 0.074* | |
H10B | 0.6512 | 0.5447 | 0.2348 | 0.074* | |
C11 | 0.5329 (2) | 0.3035 (2) | 0.09326 (13) | 0.0585 (4) | |
H11A | 0.6436 | 0.2385 | 0.1059 | 0.070* | |
H11B | 0.5750 | 0.3973 | 0.0624 | 0.070* | |
C12 | 0.3737 (3) | 0.2097 (2) | 0.01439 (13) | 0.0613 (5) | |
H12A | 0.4212 | 0.1801 | −0.0534 | 0.074* | |
H12B | 0.3373 | 0.1124 | 0.0431 | 0.074* | |
C13 | 0.1346 (2) | 0.3462 (2) | 0.09674 (13) | 0.0534 (4) | |
H13A | 0.0968 | 0.2504 | 0.1267 | 0.064* | |
H13B | 0.0211 | 0.4083 | 0.0848 | 0.064* | |
C14 | 0.2917 (2) | 0.44238 (19) | 0.17559 (12) | 0.0532 (4) | |
H14A | 0.3254 | 0.5402 | 0.1467 | 0.064* | |
H14B | 0.2430 | 0.4712 | 0.2432 | 0.064* | |
C15 | 0.0515 (3) | 0.2147 (3) | −0.08443 (17) | 0.0777 (6) | |
H15A | 0.0143 | 0.1167 | −0.0585 | 0.117* | |
H15B | 0.0996 | 0.1915 | −0.1519 | 0.117* | |
H15C | −0.0595 | 0.2779 | −0.0951 | 0.117* | |
N1 | 0.46613 (18) | 0.35309 (15) | 0.19655 (9) | 0.0484 (3) | |
N2 | 0.20302 (19) | 0.30264 (16) | −0.00548 (10) | 0.0541 (4) | |
N3 | 0.76325 (17) | 0.25325 (17) | 0.38367 (10) | 0.0521 (4) | |
O1 | 0.77364 (19) | 0.42351 (14) | 0.54040 (10) | 0.0671 (4) | |
O2 | 0.7541 (2) | 0.0268 (2) | 0.26330 (12) | 0.0968 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0513 (9) | 0.0830 (13) | 0.0639 (11) | 0.0043 (8) | −0.0028 (8) | 0.0210 (9) |
C2 | 0.0537 (11) | 0.0913 (16) | 0.1136 (18) | 0.0011 (10) | −0.0070 (11) | 0.0526 (15) |
C3 | 0.0492 (11) | 0.0704 (14) | 0.164 (3) | 0.0016 (9) | −0.0154 (13) | 0.0502 (17) |
C4 | 0.0445 (9) | 0.0536 (11) | 0.149 (2) | 0.0062 (7) | −0.0133 (11) | −0.0109 (12) |
C5 | 0.0338 (7) | 0.0555 (9) | 0.0795 (12) | 0.0077 (6) | −0.0046 (7) | −0.0040 (8) |
C6 | 0.0329 (7) | 0.0546 (9) | 0.0564 (9) | 0.0042 (6) | −0.0025 (6) | 0.0048 (7) |
C7 | 0.0382 (7) | 0.0555 (9) | 0.0436 (8) | 0.0009 (6) | −0.0003 (6) | −0.0014 (6) |
C8 | 0.0384 (8) | 0.0796 (12) | 0.0612 (10) | 0.0113 (7) | 0.0005 (7) | −0.0197 (8) |
C9 | 0.0503 (9) | 0.1015 (14) | 0.0504 (9) | −0.0138 (9) | 0.0030 (7) | 0.0131 (9) |
C10 | 0.0672 (10) | 0.0666 (10) | 0.0485 (9) | −0.0100 (8) | 0.0004 (7) | 0.0109 (7) |
C11 | 0.0535 (9) | 0.0802 (11) | 0.0439 (8) | 0.0120 (8) | 0.0104 (7) | 0.0087 (8) |
C12 | 0.0636 (10) | 0.0726 (11) | 0.0466 (9) | 0.0210 (8) | 0.0065 (7) | −0.0027 (8) |
C13 | 0.0515 (9) | 0.0584 (9) | 0.0511 (9) | 0.0121 (7) | 0.0080 (7) | 0.0067 (7) |
C14 | 0.0598 (9) | 0.0564 (9) | 0.0442 (8) | 0.0118 (7) | 0.0090 (7) | 0.0040 (7) |
C15 | 0.0771 (13) | 0.0777 (13) | 0.0673 (12) | 0.0170 (10) | −0.0150 (10) | −0.0104 (10) |
N1 | 0.0503 (7) | 0.0565 (8) | 0.0385 (7) | 0.0033 (5) | 0.0062 (5) | 0.0066 (5) |
N2 | 0.0588 (8) | 0.0588 (8) | 0.0423 (7) | 0.0119 (6) | 0.0009 (6) | 0.0015 (6) |
N3 | 0.0424 (7) | 0.0677 (9) | 0.0434 (7) | 0.0035 (5) | 0.0020 (5) | −0.0005 (6) |
O1 | 0.0850 (9) | 0.0542 (7) | 0.0564 (7) | 0.0002 (6) | 0.0027 (6) | −0.0058 (5) |
O2 | 0.0825 (10) | 0.1228 (13) | 0.0717 (9) | 0.0219 (9) | 0.0034 (7) | −0.0439 (9) |
C1—C2 | 1.377 (3) | C10—H10A | 0.9700 |
C1—C6 | 1.384 (3) | C10—H10B | 0.9700 |
C1—H1 | 0.9300 | C11—N1 | 1.466 (2) |
C2—C3 | 1.366 (4) | C11—C12 | 1.504 (2) |
C2—H2 | 0.9300 | C11—H11A | 0.9700 |
C3—C4 | 1.394 (4) | C11—H11B | 0.9700 |
C3—H3 | 0.9300 | C12—N2 | 1.459 (2) |
C4—C5 | 1.386 (3) | C12—H12A | 0.9700 |
C4—H4 | 0.9300 | C12—H12B | 0.9700 |
C5—C6 | 1.376 (2) | C13—N2 | 1.450 (2) |
C5—C8 | 1.490 (3) | C13—C14 | 1.503 (2) |
C6—C7 | 1.480 (2) | C13—H13A | 0.9700 |
C7—O1 | 1.2120 (19) | C13—H13B | 0.9700 |
C7—N3 | 1.382 (2) | C14—N1 | 1.464 (2) |
C8—O2 | 1.202 (2) | C14—H14A | 0.9700 |
C8—N3 | 1.388 (2) | C14—H14B | 0.9700 |
C9—N3 | 1.458 (2) | C15—N2 | 1.451 (2) |
C9—C10 | 1.519 (3) | C15—H15A | 0.9600 |
C9—H9A | 0.9700 | C15—H15B | 0.9600 |
C9—H9B | 0.9700 | C15—H15C | 0.9600 |
C10—N1 | 1.457 (2) | ||
C2—C1—C6 | 117.6 (2) | C12—C11—H11A | 109.4 |
C2—C1—H1 | 121.2 | N1—C11—H11B | 109.4 |
C6—C1—H1 | 121.2 | C12—C11—H11B | 109.4 |
C3—C2—C1 | 121.1 (2) | H11A—C11—H11B | 108.0 |
C3—C2—H2 | 119.4 | N2—C12—C11 | 111.05 (14) |
C1—C2—H2 | 119.4 | N2—C12—H12A | 109.4 |
C2—C3—C4 | 121.6 (2) | C11—C12—H12A | 109.4 |
C2—C3—H3 | 119.2 | N2—C12—H12B | 109.4 |
C4—C3—H3 | 119.2 | C11—C12—H12B | 109.4 |
C5—C4—C3 | 117.5 (2) | H12A—C12—H12B | 108.0 |
C5—C4—H4 | 121.3 | N2—C13—C14 | 110.46 (13) |
C3—C4—H4 | 121.3 | N2—C13—H13A | 109.6 |
C6—C5—C4 | 120.36 (19) | C14—C13—H13A | 109.6 |
C6—C5—C8 | 107.93 (15) | N2—C13—H13B | 109.6 |
C4—C5—C8 | 131.71 (19) | C14—C13—H13B | 109.6 |
C5—C6—C1 | 121.86 (17) | H13A—C13—H13B | 108.1 |
C5—C6—C7 | 107.87 (15) | N1—C14—C13 | 111.53 (13) |
C1—C6—C7 | 130.27 (15) | N1—C14—H14A | 109.3 |
O1—C7—N3 | 124.58 (15) | C13—C14—H14A | 109.3 |
O1—C7—C6 | 128.68 (14) | N1—C14—H14B | 109.3 |
N3—C7—C6 | 106.73 (13) | C13—C14—H14B | 109.3 |
O2—C8—N3 | 124.7 (2) | H14A—C14—H14B | 108.0 |
O2—C8—C5 | 129.28 (19) | N2—C15—H15A | 109.5 |
N3—C8—C5 | 106.01 (14) | N2—C15—H15B | 109.5 |
N3—C9—C10 | 114.32 (13) | H15A—C15—H15B | 109.5 |
N3—C9—H9A | 108.7 | N2—C15—H15C | 109.5 |
C10—C9—H9A | 108.7 | H15A—C15—H15C | 109.5 |
N3—C9—H9B | 108.7 | H15B—C15—H15C | 109.5 |
C10—C9—H9B | 108.7 | C10—N1—C14 | 108.35 (13) |
H9A—C9—H9B | 107.6 | C10—N1—C11 | 112.08 (13) |
N1—C10—C9 | 114.94 (15) | C14—N1—C11 | 108.84 (12) |
N1—C10—H10A | 108.5 | C13—N2—C15 | 111.53 (14) |
C9—C10—H10A | 108.5 | C13—N2—C12 | 108.61 (12) |
N1—C10—H10B | 108.5 | C15—N2—C12 | 111.25 (13) |
C9—C10—H10B | 108.5 | C7—N3—C8 | 111.45 (15) |
H10A—C10—H10B | 107.5 | C7—N3—C9 | 123.36 (15) |
N1—C11—C12 | 111.26 (13) | C8—N3—C9 | 124.69 (15) |
N1—C11—H11A | 109.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.93 | 2.57 | 3.406 (3) | 149 |
C15—H15B···O2ii | 0.96 | 2.53 | 3.343 (3) | 142 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.93 | 2.57 | 3.406 (3) | 149 |
C15—H15B···O2ii | 0.96 | 2.53 | 3.343 (3) | 142 |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z. |
CgI | CgJ | CgI···CgJ |
Cg1 | Cg3i | 3.607 (1) |
Cg1 | Cg3ii | 3.716 (1) |
Cg1 | Cg3i | 3.556 (1) |
Symmetry codes: (i) 1-x, -y, 1-z; (ii) 2-x, -y, 1-z; Cg1 and Cg3 are the centroids of the N3–C7–C6–C5–C8 and C1–C6 rings. |
Acknowledgements
We gratefully acknowledge the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD) and the Natural Science Foundation of Jiangsu Education Department (No. SCZ1212400004) for financial support.
References
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Piperazine derivatives have received much attention for their pharmaceutical activities (Tian, et al., 2011; Stauffer, 2011). The title compound was synthesized from N-(2-bromoethyl)phthalimide and N-methylpiperazine (Ghosh, et al., 2010), as a drug intermediate. In the molecule, Fig. 1, the six-membered piperazine ring adopts the chair conformation. The phthalimide ring is coplanar [r.m.s. deviations = 0.01 Å]. In the crystal, Fig. 2, molecules are linked via intermolecular C–H···O hydrogen bonding interactions (Table 1) and π···π stacking interactions involving the benzene and maleinimide rings (Table 2), which is different form the similar compound (Shao, et al., 2012).