2-{4-[(1,3-Benzodioxol-5-yl)meth-yl]piperazin-1-yl}pyrimidine.

In the title compound, C16H18N4O2, known also as peribedil, the dihedral angle between the mean planes of the pyrimidine and benzene rings is 56.5 (8)°. The 1,3-dioxole fragment adopts an envelope conformation with the methyl-ene C atom forming the flap; this atom deviates by 0.232 (3) Å from the plane defined by the remaining atoms of the 1,3-benzodioxole unit. In the crystal, C-H⋯π inter-actions between c-glide-related mol-ecules arrange them into columns extending along the c-axis direction. The columns related by a unit translation along the b axis are packed into (100) layers via another C-H⋯π inter-action involving the pyrimidine ring as an acceptor.

Related literature

For details of the synthesis of piribedil, see: Duncton et al. (2006 ▶); Conroy & Denton (1953 ▶); Hamid et al. (2007 ▶). For the pharmacological activity of the title compound, see: Rondot et al. (1992 ▶).

Experimental

Crystal data

C16H18N4O2

M = 298.34

Orthorhombic,

a = 21.3085 (6) Å

b = 18.6249 (4) Å

c = 7.48851 (19) Å

V = 2971.95 (12) Å3

Z = 8

Cu Kα radiation

μ = 0.74 mm−1

T = 291 K

0.25 × 0.2 × 0.2 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶)’ T min = 0.910, T max = 1.000

6334 measured reflections

2635 independent reflections

2186 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.112

S = 1.03

2635 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.14 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813016851/gk2582sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813016851/gk2582Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813016851/gk2582Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H18N4O2	Dx = 1.334 Mg m−3
Mr = 298.34	Melting point = 370–372 K
Orthorhombic, Pccn	Cu Kα radiation, λ = 1.5418 Å
a = 21.3085 (6) Å	Cell parameters from 2402 reflections
b = 18.6249 (4) Å	θ = 3.2–67.0°
c = 7.48851 (19) Å	µ = 0.74 mm−1
V = 2971.95 (12) Å3	T = 291 K
Z = 8	Block, colorless
F(000) = 1264	0.25 × 0.2 × 0.2 mm

Agilent Xcalibur (Eos, Gemini) diffractometer	2635 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2186 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 16.2312 pixels mm-1	θmax = 67.1°, θmin = 3.2°
ω scans	h = −25→24
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)'	k = −22→19
Tmin = 0.910, Tmax = 1.000	l = −7→8
6334 measured reflections

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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.112	w = 1/[σ2(Fo2) + (0.0574P)2 + 0.4246P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2635 reflections	Δρmax = 0.13 e Å−3
200 parameters	Δρmin = −0.14 e Å−3
0 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00143 (18)

Experimental. 1H NMR (400 MHz, CDCl3, p.p.m.): 8.30 (d, J = 4.7 Hz, 1H), 6.90 (s, 1H), 6.76 (s, 1H), 6.47 (s, J = 4.7 Hz, 1H), 6.20 (dt, J = 10.6, 2.2 Hz, 1H), 5.95 (s, 1H), 3.89–3.66 (m, 2H), 3.46 (s, 1H), 2.58–2.27 (m, 2H); 13C NMR (101 MHz, CDCl3, p.p.m.): 161.67, 157.70, 147.68, 146.66, 131.91, 122.23 ,109.72, 109.50, 107.90, 100.91, 62.89, 52.85, 43.69; ESI–HRMS m/z: 299.1506 (calculated for C16H19N4O2 [M + 1]+: 299.1508).

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
O1	0.65086 (6)	0.79907 (7)	0.4624 (2)	0.0734 (4)
O2	0.55046 (6)	0.77275 (6)	0.55466 (19)	0.0663 (4)
N1	0.59429 (6)	0.33262 (7)	1.31759 (19)	0.0498 (3)
N2	0.69678 (6)	0.38529 (7)	1.31927 (17)	0.0476 (3)
N3	0.62385 (6)	0.41598 (6)	1.10454 (18)	0.0457 (3)
N4	0.59232 (6)	0.49704 (6)	0.79397 (17)	0.0440 (3)
C1	0.61119 (9)	0.29307 (9)	1.4583 (2)	0.0557 (4)
H1	0.5819	0.2616	1.5070	0.067*
C2	0.66955 (9)	0.29663 (9)	1.5342 (2)	0.0575 (4)
H2	0.6805	0.2685	1.6318	0.069*
C3	0.71099 (9)	0.34407 (9)	1.4582 (2)	0.0545 (4)
H3	0.7511	0.3475	1.5066	0.065*
C4	0.63848 (7)	0.37709 (7)	1.2534 (2)	0.0404 (3)
C5	0.65864 (8)	0.48112 (8)	1.0596 (2)	0.0508 (4)
H5A	0.7019	0.4762	1.0982	0.061*
H5B	0.6404	0.5218	1.1219	0.061*
C6	0.65682 (7)	0.49460 (8)	0.8609 (2)	0.0489 (4)
H6A	0.6775	0.5398	0.8348	0.059*
H6B	0.6796	0.4568	0.7998	0.059*
C7	0.56029 (8)	0.41465 (9)	1.0326 (2)	0.0503 (4)
H7A	0.5350	0.4509	1.0914	0.060*
H7B	0.5414	0.3682	1.0552	0.060*
C8	0.56174 (8)	0.42877 (8)	0.8347 (2)	0.0512 (4)
H8A	0.5841	0.3902	0.7755	0.061*
H8B	0.5192	0.4295	0.7890	0.061*
C9	0.59173 (9)	0.51044 (9)	0.6002 (2)	0.0545 (4)
H9A	0.5501	0.5006	0.5541	0.065*
H9B	0.6208	0.4777	0.5426	0.065*
C10	0.56549 (8)	0.64162 (9)	0.5773 (2)	0.0495 (4)
H10	0.5247	0.6319	0.6144	0.059*
C11	0.60958 (8)	0.58649 (9)	0.5536 (2)	0.0491 (4)
C12	0.66915 (9)	0.60274 (11)	0.4929 (3)	0.0619 (5)
H12	0.6975	0.5655	0.4746	0.074*
C13	0.68819 (9)	0.67322 (11)	0.4582 (3)	0.0691 (5)
H13	0.7284	0.6837	0.4175	0.083*
C14	0.64478 (8)	0.72593 (10)	0.4871 (2)	0.0567 (4)
C15	0.58497 (8)	0.71057 (9)	0.5435 (2)	0.0494 (4)
C16	0.59495 (9)	0.82922 (10)	0.5360 (3)	0.0644 (5)
H16A	0.6037	0.8507	0.6513	0.077*
H16B	0.5786	0.8662	0.4574	0.077*

	U11	U22	U33	U12	U13	U23
O1	0.0539 (8)	0.0690 (8)	0.0972 (11)	−0.0100 (7)	−0.0008 (7)	0.0219 (8)
O2	0.0523 (7)	0.0565 (7)	0.0901 (9)	0.0039 (6)	0.0045 (7)	0.0059 (6)
N1	0.0442 (7)	0.0486 (7)	0.0564 (8)	−0.0013 (6)	0.0050 (6)	0.0033 (6)
N2	0.0433 (7)	0.0517 (7)	0.0477 (7)	−0.0018 (6)	−0.0037 (6)	0.0038 (6)
N3	0.0380 (7)	0.0450 (6)	0.0542 (7)	−0.0030 (5)	−0.0059 (6)	0.0058 (6)
N4	0.0415 (7)	0.0422 (6)	0.0484 (7)	0.0022 (5)	−0.0063 (5)	−0.0005 (5)
C1	0.0596 (11)	0.0488 (8)	0.0588 (10)	−0.0012 (8)	0.0133 (8)	0.0074 (8)
C2	0.0655 (11)	0.0567 (9)	0.0502 (9)	0.0051 (9)	0.0014 (8)	0.0102 (8)
C3	0.0535 (10)	0.0591 (9)	0.0510 (9)	0.0018 (8)	−0.0078 (8)	0.0040 (8)
C4	0.0403 (7)	0.0372 (7)	0.0439 (8)	0.0042 (6)	0.0034 (6)	−0.0050 (6)
C5	0.0496 (9)	0.0459 (8)	0.0569 (9)	−0.0080 (7)	−0.0131 (7)	0.0060 (7)
C6	0.0406 (8)	0.0501 (8)	0.0560 (9)	−0.0019 (7)	−0.0057 (7)	0.0064 (7)
C7	0.0366 (8)	0.0486 (8)	0.0656 (10)	−0.0008 (7)	−0.0031 (7)	0.0062 (8)
C8	0.0418 (8)	0.0476 (8)	0.0642 (10)	−0.0012 (7)	−0.0128 (7)	−0.0025 (8)
C9	0.0568 (10)	0.0563 (9)	0.0505 (9)	0.0028 (8)	−0.0106 (8)	−0.0043 (8)
C10	0.0375 (8)	0.0616 (9)	0.0495 (9)	−0.0008 (7)	−0.0004 (7)	0.0046 (7)
C11	0.0461 (9)	0.0599 (9)	0.0412 (8)	0.0034 (7)	−0.0069 (6)	0.0020 (7)
C12	0.0467 (10)	0.0742 (11)	0.0649 (11)	0.0142 (9)	0.0008 (8)	0.0053 (9)
C13	0.0371 (9)	0.0875 (13)	0.0827 (13)	0.0006 (9)	0.0073 (9)	0.0176 (11)
C14	0.0433 (9)	0.0685 (10)	0.0582 (9)	−0.0046 (8)	−0.0038 (7)	0.0129 (8)
C15	0.0411 (8)	0.0580 (9)	0.0490 (8)	0.0055 (7)	−0.0030 (7)	0.0055 (7)
C16	0.0618 (12)	0.0592 (10)	0.0723 (12)	−0.0022 (9)	−0.0057 (9)	0.0125 (9)

O1—C14	1.381 (2)	C6—H6A	0.9700
O1—C16	1.428 (2)	C6—H6B	0.9700
O2—C15	1.374 (2)	C7—H7A	0.9700
O2—C16	1.423 (2)	C7—H7B	0.9700
N1—C1	1.335 (2)	C7—C8	1.505 (2)
N1—C4	1.343 (2)	C8—H8A	0.9700
N2—C3	1.328 (2)	C8—H8B	0.9700
N2—C4	1.345 (2)	C9—H9A	0.9700
N3—C4	1.365 (2)	C9—H9B	0.9700
N3—C5	1.4611 (19)	C9—C11	1.508 (2)
N3—C7	1.458 (2)	C10—H10	0.9300
N4—C6	1.4636 (19)	C10—C11	1.403 (2)
N4—C8	1.4610 (19)	C10—C15	1.373 (2)
N4—C9	1.472 (2)	C11—C12	1.382 (3)
C1—H1	0.9300	C12—H12	0.9300
C1—C2	1.369 (3)	C12—C13	1.398 (3)
C2—H2	0.9300	C13—H13	0.9300
C2—C3	1.373 (3)	C13—C14	1.366 (3)
C3—H3	0.9300	C14—C15	1.373 (2)
C5—H5A	0.9700	C16—H16A	0.9700
C5—H5B	0.9700	C16—H16B	0.9700
C5—C6	1.510 (2)
C14—O1—C16	104.96 (14)	C8—C7—H7A	109.7
C15—O2—C16	105.09 (14)	C8—C7—H7B	109.7
C1—N1—C4	115.70 (15)	N4—C8—C7	111.53 (13)
C3—N2—C4	115.61 (14)	N4—C8—H8A	109.3
C4—N3—C5	120.85 (13)	N4—C8—H8B	109.3
C4—N3—C7	120.32 (13)	C7—C8—H8A	109.3
C7—N3—C5	113.60 (12)	C7—C8—H8B	109.3
C6—N4—C9	110.51 (13)	H8A—C8—H8B	108.0
C8—N4—C6	108.67 (11)	N4—C9—H9A	109.1
C8—N4—C9	110.47 (13)	N4—C9—H9B	109.1
N1—C1—H1	118.5	N4—C9—C11	112.68 (13)
N1—C1—C2	123.09 (16)	H9A—C9—H9B	107.8
C2—C1—H1	118.5	C11—C9—H9A	109.1
C1—C2—H2	121.8	C11—C9—H9B	109.1
C1—C2—C3	116.33 (16)	C11—C10—H10	121.3
C3—C2—H2	121.8	C15—C10—H10	121.3
N2—C3—C2	123.37 (17)	C15—C10—C11	117.31 (15)
N2—C3—H3	118.3	C10—C11—C9	119.30 (15)
C2—C3—H3	118.3	C12—C11—C9	120.90 (16)
N1—C4—N2	125.88 (14)	C12—C11—C10	119.77 (16)
N1—C4—N3	117.34 (14)	C11—C12—H12	118.9
N2—C4—N3	116.75 (13)	C11—C12—C13	122.22 (17)
N3—C5—H5A	109.5	C13—C12—H12	118.9
N3—C5—H5B	109.5	C12—C13—H13	121.7
N3—C5—C6	110.62 (13)	C14—C13—C12	116.67 (17)
H5A—C5—H5B	108.1	C14—C13—H13	121.7
C6—C5—H5A	109.5	C13—C14—O1	128.63 (17)
C6—C5—H5B	109.5	C13—C14—C15	121.84 (17)
N4—C6—C5	111.51 (13)	C15—C14—O1	109.50 (16)
N4—C6—H6A	109.3	C10—C15—O2	127.97 (15)
N4—C6—H6B	109.3	C14—C15—O2	109.87 (15)
C5—C6—H6A	109.3	C14—C15—C10	122.15 (16)
C5—C6—H6B	109.3	O1—C16—H16A	110.2
H6A—C6—H6B	108.0	O1—C16—H16B	110.2
N3—C7—H7A	109.7	O2—C16—O1	107.65 (15)
N3—C7—H7B	109.7	O2—C16—H16A	110.2
N3—C7—C8	109.99 (14)	O2—C16—H16B	110.2
H7A—C7—H7B	108.2	H16A—C16—H16B	108.5
O1—C14—C15—O2	0.8 (2)	C7—N3—C5—C6	−52.15 (18)
O1—C14—C15—C10	179.46 (16)	C8—N4—C6—C5	−58.80 (17)
N1—C1—C2—C3	0.3 (3)	C8—N4—C9—C11	167.44 (13)
N3—C5—C6—N4	54.89 (18)	C9—N4—C6—C5	179.83 (13)
N3—C7—C8—N4	−56.91 (17)	C9—N4—C8—C7	−178.59 (14)
N4—C9—C11—C10	−76.79 (19)	C9—C11—C12—C13	−176.31 (18)
N4—C9—C11—C12	101.32 (19)	C10—C11—C12—C13	1.8 (3)
C1—N1—C4—N2	−0.8 (2)	C11—C10—C15—O2	178.97 (16)
C1—N1—C4—N3	177.08 (13)	C11—C10—C15—C14	0.6 (3)
C1—C2—C3—N2	0.3 (3)	C11—C12—C13—C14	0.0 (3)
C3—N2—C4—N1	1.3 (2)	C12—C13—C14—O1	−179.37 (19)
C3—N2—C4—N3	−176.54 (14)	C12—C13—C14—C15	−1.4 (3)
C4—N1—C1—C2	−0.1 (2)	C13—C14—C15—O2	−177.46 (18)
C4—N2—C3—C2	−1.0 (2)	C13—C14—C15—C10	1.2 (3)
C4—N3—C5—C6	153.35 (14)	C14—O1—C16—O2	−16.4 (2)
C4—N3—C7—C8	−152.42 (14)	C15—O2—C16—O1	16.9 (2)
C5—N3—C4—N1	159.58 (14)	C15—C10—C11—C9	176.11 (14)
C5—N3—C4—N2	−22.4 (2)	C15—C10—C11—C12	−2.0 (2)
C5—N3—C7—C8	52.93 (18)	C16—O1—C14—C13	−172.2 (2)
C6—N4—C8—C7	60.01 (17)	C16—O1—C14—C15	9.7 (2)
C6—N4—C9—C11	−72.26 (17)	C16—O2—C15—C10	170.46 (18)
C7—N3—C4—N1	6.8 (2)	C16—O2—C15—C14	−11.0 (2)
C7—N3—C4—N2	−175.17 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg1i	0.93	2.83	3.6771 (17)	152
C9—H9B···Cg1ii	0.97	2.92	3.8090 (18)	152
C16—H16A···Cg2iii	0.97	2.80	3.689 (2)	153

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the pyrimidine ring and Cg2 is the centroid of the benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg1i	0.93	2.83	3.6771 (17)	152
C9—H9B⋯Cg1ii	0.97	2.92	3.8090 (18)	152
C16—H16A⋯Cg2iii	0.97	2.80	3.689 (2)	153

Symmetry codes: (i) ; (ii) ; (iii) .