4-(2-Meth-oxy-phen-yl)piperazin-1-ium 6-chloro-5-isopropyl-2,4-dioxopyrimidin-1-ide.

In the cation of the title salt, C11H17N2O(+)·C7H8ClN2O2 (-), the piperazine ring adopts a distorted chair conformation and contains a positively charged N atom with quaternary character. Its mean plane makes a dihedral angle of 42.36 (8)° with the phenyl ring of its 2-meth-oxy-phenyl substituent. The 2,4-dioxopyrimidin-1-ide anion is generated by deprotonation of the N atom at the 1-position of the pyrimidine-dione ring. Intra-molecular C-H⋯O hydrogen bonds generate S(6) ring motifs in both the cation and the anion. In the crystal, N-H⋯O, N-H⋯N and C-H⋯O hydrogen bonds are also observed, resulting in a two-dimensional network parallel to the ab plane. The crystal stability is further consolidated by weak C-H⋯π inter-actions.

Related literature

For the chemotherapeutic activity of pyrimidine-2,4-dione derivatives, see: Ghoshal & Jacob (1997 ▶); Spacilova et al. (2007 ▶); Blokhina et al. (1972 ▶); Tanaka et al. (1995 ▶); El-Emam et al. (2004 ▶); Al-Turkistani et al. (2011 ▶). For the acidity of pyrim­idine-2,4-dione derivatives, see: Kurinovich & Lee (2002 ▶); Jang et al. (2001 ▶); Nguyen et al. (1998 ▶). For the structures of other piperazinium salts, see: Craig et al. (2012 ▶); Dayananda et al. (2012 ▶); Fun et al. (2010 ▶). For reference bond lengths, see: Allen et al. (1987 ▶) and for hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C11H17N2O+·C7H8ClN2O2 −

M = 380.87

Monoclinic,

a = 8.9416 (2) Å

b = 10.5152 (3) Å

c = 20.5626 (5) Å

β = 98.832 (1)°

V = 1910.43 (8) Å3

Z = 4

Cu Kα radiation

μ = 1.99 mm−1

T = 296 K

0.81 × 0.13 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.296, T max = 0.907

11481 measured reflections

3531 independent reflections

3204 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.118

S = 1.06

3531 reflections

251 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814002256/sj5388sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002256/sj5388Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002256/sj5388Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H17N2O+·C7H8ClN2O2−	F(000) = 808
Mr = 380.87	Dx = 1.324 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 3769 reflections
a = 8.9416 (2) Å	θ = 4.2–69.6°
b = 10.5152 (3) Å	µ = 1.99 mm−1
c = 20.5626 (5) Å	T = 296 K
β = 98.832 (1)°	Plate, colourless
V = 1910.43 (8) Å3	0.81 × 0.13 × 0.05 mm
Z = 4

Bruker APEXII CCD diffractometer	3531 independent reflections
Radiation source: fine-focus sealed tube	3204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 69.8°, θmin = 4.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.296, Tmax = 0.907	k = −12→9
11481 measured reflections	l = −24→24

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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.0615P)2 + 0.5789P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
3531 reflections	Δρmax = 0.33 e Å−3
251 parameters	Δρmin = −0.32 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (5)

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
Cl1	0.50958 (5)	0.52933 (5)	0.21770 (2)	0.05543 (19)
O2	0.20219 (13)	0.51968 (11)	0.00176 (5)	0.0368 (3)
N4	0.34035 (14)	0.51859 (13)	0.10447 (7)	0.0340 (3)
C14	0.20877 (17)	0.51323 (14)	0.06313 (7)	0.0300 (3)
N3	0.07667 (15)	0.50064 (14)	0.08862 (7)	0.0347 (3)
C15	0.0644 (2)	0.49113 (17)	0.15482 (8)	0.0387 (4)
O3	−0.06114 (16)	0.47528 (17)	0.17059 (7)	0.0623 (4)
C12	0.33057 (18)	0.51541 (15)	0.16938 (8)	0.0347 (3)
C13	0.2058 (2)	0.50286 (16)	0.19945 (8)	0.0370 (4)
C16	0.2061 (2)	0.49421 (19)	0.27315 (9)	0.0478 (4)
H16A	0.3083	0.5163	0.2947	0.057*
C17	0.0969 (3)	0.5878 (2)	0.29765 (10)	0.0591 (5)
H17A	0.1235	0.6729	0.2871	0.089*
H17B	0.1029	0.5796	0.3445	0.089*
H17C	−0.0044	0.5697	0.2768	0.089*
C18	0.1753 (4)	0.3582 (2)	0.29280 (12)	0.0783 (8)
H18A	0.2574	0.3045	0.2849	0.118*
H18B	0.0829	0.3287	0.2672	0.118*
H18C	0.1661	0.3556	0.3387	0.118*
O1	0.73479 (17)	0.92628 (13)	0.14090 (7)	0.0524 (3)
N2	0.57634 (15)	1.36876 (13)	0.05996 (7)	0.0347 (3)
N1	0.66629 (14)	1.10889 (13)	0.04804 (6)	0.0343 (3)
C11	0.59845 (18)	1.18107 (15)	−0.00956 (8)	0.0359 (3)
H11A	0.5429	1.1240	−0.0416	0.043*
H11B	0.6774	1.2216	−0.0297	0.043*
C5	0.79466 (19)	0.97928 (16)	−0.02689 (9)	0.0393 (4)
H5A	0.7690	1.0388	−0.0602	0.047*
C10	0.49247 (17)	1.28106 (16)	0.01019 (9)	0.0384 (4)
H10A	0.4484	1.3291	−0.0283	0.046*
H10B	0.4109	1.2403	0.0285	0.046*
C8	0.75164 (18)	1.19407 (16)	0.09704 (8)	0.0375 (4)
H8A	0.8336	1.2332	0.0784	0.045*
H8B	0.7956	1.1449	0.1351	0.045*
C3	0.9169 (2)	0.78466 (17)	0.00959 (10)	0.0485 (5)
H3A	0.9744	0.7141	0.0018	0.058*
C1	0.78835 (18)	0.90656 (16)	0.08317 (9)	0.0395 (4)
C9	0.65130 (19)	1.29640 (16)	0.11833 (8)	0.0374 (4)
H9A	0.5750	1.2581	0.1409	0.045*
H9B	0.7114	1.3539	0.1487	0.045*
C4	0.87617 (19)	0.87161 (18)	−0.03948 (10)	0.0457 (4)
H4A	0.9028	0.8588	−0.0810	0.055*
C6	0.75084 (17)	0.99994 (15)	0.03383 (8)	0.0344 (3)
C2	0.8731 (2)	0.80127 (17)	0.07064 (10)	0.0473 (4)
H2A	0.9005	0.7414	0.1036	0.057*
C7	0.7453 (3)	0.8242 (2)	0.18654 (11)	0.0666 (6)
H7A	0.6991	0.8485	0.2238	0.100*
H7B	0.8499	0.8039	0.2008	0.100*
H7C	0.6942	0.7511	0.1658	0.100*
H2N2	0.646 (2)	1.408 (2)	0.0405 (10)	0.040 (5)*
H1N2	0.511 (2)	1.428 (2)	0.0733 (10)	0.043 (5)*
H1N3	−0.006 (3)	0.4964 (19)	0.0606 (11)	0.042 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0362 (3)	0.0756 (4)	0.0511 (3)	0.0075 (2)	−0.00393 (18)	−0.0107 (2)
O2	0.0322 (5)	0.0468 (7)	0.0329 (6)	−0.0035 (5)	0.0101 (4)	0.0021 (4)
N4	0.0269 (6)	0.0386 (7)	0.0378 (7)	0.0026 (5)	0.0087 (5)	−0.0008 (5)
C14	0.0288 (7)	0.0278 (7)	0.0351 (8)	0.0002 (5)	0.0105 (6)	0.0000 (5)
N3	0.0263 (7)	0.0453 (8)	0.0335 (7)	−0.0026 (5)	0.0077 (6)	−0.0013 (5)
C15	0.0376 (8)	0.0440 (9)	0.0371 (9)	−0.0034 (7)	0.0142 (7)	−0.0024 (7)
O3	0.0402 (7)	0.1034 (12)	0.0476 (8)	−0.0184 (7)	0.0209 (6)	−0.0075 (7)
C12	0.0319 (8)	0.0338 (8)	0.0379 (8)	0.0042 (6)	0.0038 (6)	−0.0034 (6)
C13	0.0396 (9)	0.0373 (8)	0.0353 (8)	0.0021 (6)	0.0098 (7)	−0.0021 (6)
C16	0.0551 (11)	0.0542 (11)	0.0350 (9)	0.0060 (9)	0.0101 (8)	−0.0027 (7)
C17	0.0753 (14)	0.0635 (13)	0.0417 (10)	0.0122 (11)	0.0194 (9)	−0.0062 (9)
C18	0.130 (2)	0.0601 (14)	0.0516 (12)	0.0141 (15)	0.0340 (14)	0.0112 (10)
O1	0.0662 (8)	0.0449 (7)	0.0478 (7)	0.0088 (6)	0.0147 (6)	0.0087 (6)
N2	0.0304 (6)	0.0304 (7)	0.0467 (8)	0.0003 (5)	0.0164 (6)	0.0005 (5)
N1	0.0326 (6)	0.0310 (7)	0.0383 (7)	0.0024 (5)	0.0029 (5)	−0.0018 (5)
C11	0.0347 (7)	0.0346 (8)	0.0379 (8)	0.0010 (6)	0.0037 (6)	−0.0005 (6)
C5	0.0348 (8)	0.0388 (9)	0.0442 (9)	−0.0001 (6)	0.0054 (7)	−0.0022 (7)
C10	0.0315 (8)	0.0360 (8)	0.0472 (9)	0.0024 (6)	0.0044 (7)	0.0029 (7)
C8	0.0348 (8)	0.0355 (8)	0.0410 (8)	0.0023 (6)	0.0019 (6)	−0.0025 (6)
C3	0.0374 (8)	0.0347 (9)	0.0734 (13)	0.0048 (7)	0.0090 (8)	−0.0090 (8)
C1	0.0364 (8)	0.0345 (8)	0.0464 (9)	−0.0008 (7)	0.0025 (7)	−0.0001 (7)
C9	0.0387 (8)	0.0359 (8)	0.0391 (8)	−0.0022 (7)	0.0107 (7)	−0.0021 (6)
C4	0.0378 (8)	0.0449 (10)	0.0558 (11)	0.0000 (7)	0.0112 (8)	−0.0123 (8)
C6	0.0278 (7)	0.0297 (8)	0.0449 (9)	−0.0005 (6)	0.0034 (6)	−0.0025 (6)
C2	0.0440 (9)	0.0333 (9)	0.0627 (11)	0.0052 (7)	0.0020 (8)	0.0044 (8)
C7	0.0879 (16)	0.0568 (13)	0.0546 (12)	−0.0033 (12)	0.0087 (11)	0.0155 (10)

Cl1—C12	1.7557 (17)	N1—C6	1.427 (2)
O2—C14	1.2561 (19)	N1—C11	1.458 (2)
N4—C14	1.343 (2)	N1—C8	1.471 (2)
N4—C12	1.351 (2)	C11—C10	1.512 (2)
C14—N3	1.3702 (19)	C11—H11A	0.9700
N3—C15	1.386 (2)	C11—H11B	0.9700
N3—H1N3	0.86 (3)	C5—C6	1.382 (2)
C15—O3	1.226 (2)	C5—C4	1.392 (2)
C15—C13	1.449 (3)	C5—H5A	0.9300
C12—C13	1.362 (2)	C10—H10A	0.9700
C13—C16	1.518 (2)	C10—H10B	0.9700
C16—C18	1.523 (3)	C8—C9	1.508 (2)
C16—C17	1.526 (3)	C8—H8A	0.9700
C16—H16A	0.9800	C8—H8B	0.9700
C17—H17A	0.9600	C3—C4	1.369 (3)
C17—H17B	0.9600	C3—C2	1.383 (3)
C17—H17C	0.9600	C3—H3A	0.9300
C18—H18A	0.9600	C1—C2	1.388 (2)
C18—H18B	0.9600	C1—C6	1.415 (2)
C18—H18C	0.9600	C9—H9A	0.9700
O1—C1	1.362 (2)	C9—H9B	0.9700
O1—C7	1.419 (2)	C4—H4A	0.9300
N2—C9	1.491 (2)	C2—H2A	0.9300
N2—C10	1.491 (2)	C7—H7A	0.9600
N2—H2N2	0.89 (2)	C7—H7B	0.9600
N2—H1N2	0.93 (2)	C7—H7C	0.9600
C14—N4—C12	116.17 (13)	C10—C11—H11A	109.6
O2—C14—N4	122.35 (13)	N1—C11—H11B	109.6
O2—C14—N3	118.64 (14)	C10—C11—H11B	109.6
N4—C14—N3	119.00 (14)	H11A—C11—H11B	108.2
C14—N3—C15	125.85 (15)	C6—C5—C4	121.67 (17)
C14—N3—H1N3	116.7 (14)	C6—C5—H5A	119.2
C15—N3—H1N3	117.5 (14)	C4—C5—H5A	119.2
O3—C15—N3	118.90 (17)	N2—C10—C11	110.14 (13)
O3—C15—C13	126.11 (16)	N2—C10—H10A	109.6
N3—C15—C13	114.99 (14)	C11—C10—H10A	109.6
N4—C12—C13	129.23 (16)	N2—C10—H10B	109.6
N4—C12—Cl1	111.43 (12)	C11—C10—H10B	109.6
C13—C12—Cl1	119.34 (13)	H10A—C10—H10B	108.1
C12—C13—C15	114.63 (15)	N1—C8—C9	111.34 (13)
C12—C13—C16	125.66 (17)	N1—C8—H8A	109.4
C15—C13—C16	119.64 (15)	C9—C8—H8A	109.4
C13—C16—C18	110.40 (16)	N1—C8—H8B	109.4
C13—C16—C17	112.83 (16)	C9—C8—H8B	109.4
C18—C16—C17	111.53 (18)	H8A—C8—H8B	108.0
C13—C16—H16A	107.3	C4—C3—C2	120.27 (16)
C18—C16—H16A	107.3	C4—C3—H3A	119.9
C17—C16—H16A	107.3	C2—C3—H3A	119.9
C16—C17—H17A	109.5	O1—C1—C2	123.92 (16)
C16—C17—H17B	109.5	O1—C1—C6	116.29 (15)
H17A—C17—H17B	109.5	C2—C1—C6	119.78 (16)
C16—C17—H17C	109.5	N2—C9—C8	110.15 (13)
H17A—C17—H17C	109.5	N2—C9—H9A	109.6
H17B—C17—H17C	109.5	C8—C9—H9A	109.6
C16—C18—H18A	109.5	N2—C9—H9B	109.6
C16—C18—H18B	109.5	C8—C9—H9B	109.6
H18A—C18—H18B	109.5	H9A—C9—H9B	108.1
C16—C18—H18C	109.5	C3—C4—C5	119.60 (17)
H18A—C18—H18C	109.5	C3—C4—H4A	120.2
H18B—C18—H18C	109.5	C5—C4—H4A	120.2
C1—O1—C7	117.67 (16)	C5—C6—C1	118.03 (15)
C9—N2—C10	110.69 (13)	C5—C6—N1	122.93 (15)
C9—N2—H2N2	109.9 (13)	C1—C6—N1	119.01 (15)
C10—N2—H2N2	106.8 (13)	C3—C2—C1	120.56 (18)
C9—N2—H1N2	109.4 (13)	C3—C2—H2A	119.7
C10—N2—H1N2	110.2 (13)	C1—C2—H2A	119.7
H2N2—N2—H1N2	109.8 (18)	O1—C7—H7A	109.5
C6—N1—C11	114.77 (13)	O1—C7—H7B	109.5
C6—N1—C8	113.17 (12)	H7A—C7—H7B	109.5
C11—N1—C8	110.29 (13)	O1—C7—H7C	109.5
N1—C11—C10	110.09 (13)	H7A—C7—H7C	109.5
N1—C11—H11A	109.6	H7B—C7—H7C	109.5
C12—N4—C14—O2	177.57 (14)	N1—C11—C10—N2	58.83 (17)
C12—N4—C14—N3	−2.2 (2)	C6—N1—C8—C9	−171.18 (13)
O2—C14—N3—C15	179.40 (15)	C11—N1—C8—C9	58.72 (17)
N4—C14—N3—C15	−0.8 (2)	C7—O1—C1—C2	−10.5 (3)
C14—N3—C15—O3	−177.21 (17)	C7—O1—C1—C6	168.37 (18)
C14—N3—C15—C13	3.5 (2)	C10—N2—C9—C8	55.06 (16)
C14—N4—C12—C13	2.6 (2)	N1—C8—C9—N2	−56.08 (18)
C14—N4—C12—Cl1	−177.68 (11)	C2—C3—C4—C5	2.2 (3)
N4—C12—C13—C15	0.1 (3)	C6—C5—C4—C3	−1.3 (3)
Cl1—C12—C13—C15	−179.54 (12)	C4—C5—C6—C1	−1.4 (2)
N4—C12—C13—C16	177.04 (17)	C4—C5—C6—N1	−179.53 (15)
Cl1—C12—C13—C16	−2.6 (2)	O1—C1—C6—C5	−175.88 (15)
O3—C15—C13—C12	177.77 (18)	C2—C1—C6—C5	3.0 (2)
N3—C15—C13—C12	−3.0 (2)	O1—C1—C6—N1	2.4 (2)
O3—C15—C13—C16	0.7 (3)	C2—C1—C6—N1	−178.73 (15)
N3—C15—C13—C16	179.89 (15)	C11—N1—C6—C5	14.0 (2)
C12—C13—C16—C18	−105.4 (2)	C8—N1—C6—C5	−113.80 (17)
C15—C13—C16—C18	71.4 (2)	C11—N1—C6—C1	−164.14 (14)
C12—C13—C16—C17	129.0 (2)	C8—N1—C6—C1	68.06 (18)
C15—C13—C16—C17	−54.2 (2)	C4—C3—C2—C1	−0.5 (3)
C6—N1—C11—C10	171.16 (13)	O1—C1—C2—C3	176.69 (17)
C8—N1—C11—C10	−59.59 (16)	C6—C1—C2—C3	−2.1 (3)
C9—N2—C10—C11	−56.62 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···O2i	0.892 (19)	1.881 (19)	2.7713 (18)	176 (2)
N2—H1N2···N4ii	0.92 (2)	1.987 (19)	2.8923 (19)	166.2 (18)
N3—H1N3···O2iii	0.87 (2)	2.02 (3)	2.8799 (18)	177 (2)
C8—H8B···O1	0.97	2.37	2.968 (2)	119
C9—H9B···O3iv	0.97	2.38	3.234 (2)	146
C17—H17C···O3	0.96	2.38	3.015 (3)	123
C10—H10B···Cg2i	0.97	2.65	3.4041 (17)	134

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is centroid of the C1—C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯O2i	0.892 (19)	1.881 (19)	2.7713 (18)	176 (2)
N2—H1N2⋯N4ii	0.92 (2)	1.987 (19)	2.8923 (19)	166.2 (18)
N3—H1N3⋯O2iii	0.87 (2)	2.02 (3)	2.8799 (18)	177 (2)
C8—H8B⋯O1	0.97	2.37	2.968 (2)	119
C9—H9B⋯O3iv	0.97	2.38	3.234 (2)	146
C17—H17C⋯O3	0.96	2.38	3.015 (3)	123
C10—H10B⋯Cg2i	0.97	2.65	3.4041 (17)	134

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