1-Piperonylpiperazinium 4-nitro-benzoate monohydrate.

IN THE TITLE HYDRATED SALT [SYSTEMATIC NAME: 1-(1,3-benzodioxol-5-ylmeth-yl)piperazin-1-ium 4-nitro-benzoate monohydrate], C12H17N2O2 (+)·C7H4NO4 (-)·H2O, the piperazinium ring of the cation adopts a slightly distorted chair conformation. The piperonyl and piperazine rings are rotated with respect to each other with an N-C-C-C torsion angle of 45.6 (2)°. In the anion, the nitro group is almost coplanar with the adjacent benzene ring, forming a dihedral angle of only 3.9 (4)°. In the crystal, the cations, anions and water mol-ecules are linked through N-H⋯O and O-H⋯O hydrogen bonds into chains along the a axis. In addition, weaker inter-molecular C-H⋯O inter-actions are also observed within the chains. The anions form centrosymmetric couples through π-stacking inter-actions, with an inter-centroid distance of 3.681 (4) Å between the benzene rings.

Related literature

For the drug, piribedil {systematic name: 2-[4-(benzo[1,3]dioxol-5-ylmeth­yl)piperazin-1-yl]pyrimidine}, an anti­parkin­sonian agent, see: Millan et al. (2001 ▶). For piperonylpiperazine derivatives with α-adrenergic antagonist and vasodilator properties, see: Gobert et al. (2003 ▶); Gilbert et al. (1968 ▶). For the use of piperazine in the construction of various bioactive mol­ecules, see: Choudhary et al. (2006 ▶). For the anti­microbial activity of piperazine derivatives, see: Kharb et al. (2012 ▶). For related biologically active compounds, see: Brockunier et al. (2004 ▶); Bogatcheva et al. (2006 ▶). For a review on the current pharmacological and toxicological information for piperazine derivatives, see: Elliott (2011 ▶). For a related structure, see: Capuano et al. (2000 ▶). For puckering parameters, see Cremer & Pople (1975 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C12H17N2O2 +·C7H4NO4 −·H2O

M = 405.40

Triclinic,

a = 6.0745 (5) Å

b = 12.0617 (11) Å

c = 13.4817 (10) Å

α = 92.561 (7)°

β = 98.753 (7)°

γ = 93.326 (7)°

V = 973.20 (14) Å3

Z = 2

Cu Kα radiation

μ = 0.90 mm−1

T = 173 K

0.42 × 0.36 × 0.24 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.882, T max = 1.000

6403 measured reflections

3761 independent reflections

3196 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.120

S = 1.03

3761 reflections

263 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶; Palatinus & van der Lee, 2008 ▶; Palatinus et al., 2012 ▶); 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. DOI: 10.1107/S160053681400261X/ld2118sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400261X/ld2118Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681400261X/ld2118Isup3.cml

CCDC reference:

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

C12H17N2O2+·C7H4NO4−·H2O	Z = 2
Mr = 405.40	F(000) = 428
Triclinic, P1	Dx = 1.383 Mg m−3
a = 6.0745 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.0617 (11) Å	Cell parameters from 2866 reflections
c = 13.4817 (10) Å	θ = 3.3–72.4°
α = 92.561 (7)°	µ = 0.90 mm−1
β = 98.753 (7)°	T = 173 K
γ = 93.326 (7)°	Irregular, colourless
V = 973.20 (14) Å3	0.42 × 0.36 × 0.24 mm

Agilent Xcalibur (Eos, Gemini) diffractometer	3761 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3196 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.021
ω scans	θmax = 72.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −7→7
Tmin = 0.882, Tmax = 1.000	k = −14→13
6403 measured reflections	l = −16→15

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043	w = 1/[σ2(Fo2) + (0.0563P)2 + 0.0984P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.27 e Å−3
3761 reflections	Δρmin = −0.20 e Å−3
263 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0049 (6)
Primary atom site location: structure-invariant direct methods

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

	x	y	z	Uiso*/Ueq
O1A	0.5807 (2)	0.15502 (11)	0.58196 (11)	0.0590 (4)
O2A	0.5429 (2)	0.34467 (10)	0.59022 (10)	0.0501 (3)
N1A	−0.1474 (2)	0.41016 (10)	0.31368 (9)	0.0318 (3)
N2A	−0.1698 (2)	0.54167 (10)	0.14110 (9)	0.0332 (3)
H2AA	−0.2433	0.4918	0.0891	0.040*
H2AB	−0.1248	0.6053	0.1115	0.040*
C1A	−0.1964 (3)	0.31162 (14)	0.36785 (13)	0.0403 (4)
H1AA	−0.2762	0.2532	0.3195	0.048*
H1AB	−0.2965	0.3308	0.4166	0.048*
C2A	0.0109 (3)	0.26602 (13)	0.42328 (11)	0.0369 (3)
C3A	0.0366 (3)	0.15269 (14)	0.41979 (13)	0.0446 (4)
H3A	−0.0772	0.1047	0.3811	0.054*
C4A	0.2234 (3)	0.10638 (14)	0.47100 (14)	0.0500 (4)
H4A	0.2393	0.0285	0.4678	0.060*
C5A	0.3822 (3)	0.17849 (14)	0.52603 (12)	0.0426 (4)
C6A	0.6796 (3)	0.25825 (15)	0.62731 (13)	0.0466 (4)
H6AA	0.8318	0.2712	0.6106	0.056*
H6AB	0.6907	0.2575	0.7013	0.056*
C7A	0.3587 (3)	0.29153 (13)	0.53067 (11)	0.0375 (3)
C8A	0.1769 (3)	0.33840 (13)	0.48093 (12)	0.0378 (3)
H8A	0.1632	0.4165	0.4851	0.045*
C9A	−0.3555 (2)	0.45704 (13)	0.27135 (11)	0.0337 (3)
H9AA	−0.4451	0.4722	0.3254	0.040*
H9AB	−0.4436	0.4028	0.2212	0.040*
C10A	−0.3064 (3)	0.56353 (13)	0.22182 (12)	0.0353 (3)
H10A	−0.4481	0.5943	0.1927	0.042*
H10B	−0.2245	0.6190	0.2726	0.042*
C11A	0.0375 (2)	0.48756 (13)	0.18124 (12)	0.0349 (3)
H11A	0.1350	0.5397	0.2300	0.042*
H11B	0.1200	0.4685	0.1256	0.042*
C12A	−0.0217 (3)	0.38327 (12)	0.23225 (11)	0.0336 (3)
H12A	−0.1124	0.3295	0.1826	0.040*
H12B	0.1165	0.3483	0.2598	0.040*
O1B	1.02663 (19)	0.27812 (9)	−0.04752 (9)	0.0437 (3)
O2B	1.3475 (2)	0.26959 (12)	0.05605 (11)	0.0591 (4)
O3B	0.8956 (2)	−0.16582 (12)	0.28622 (10)	0.0616 (4)
O4B	0.5845 (2)	−0.15818 (12)	0.18715 (11)	0.0595 (4)
N1B	0.7773 (2)	−0.12428 (11)	0.21838 (10)	0.0409 (3)
C1B	1.0487 (2)	0.14427 (11)	0.07692 (11)	0.0301 (3)
C2B	1.1819 (2)	0.09318 (13)	0.15270 (12)	0.0357 (3)
H2B	1.3335	0.1195	0.1723	0.043*
C3B	1.0959 (3)	0.00431 (13)	0.19982 (12)	0.0369 (3)
H3B	1.1868	−0.0319	0.2505	0.044*
C4B	0.8739 (2)	−0.02983 (12)	0.17066 (11)	0.0319 (3)
C5B	0.7362 (2)	0.02062 (12)	0.09760 (11)	0.0329 (3)
H5B	0.5832	−0.0040	0.0803	0.039*
C6B	0.8256 (2)	0.10799 (12)	0.04996 (11)	0.0329 (3)
H6B	0.7341	0.1431	−0.0013	0.039*
C7B	1.1503 (3)	0.23837 (12)	0.02427 (12)	0.0355 (3)
O1W	0.34602 (17)	0.60766 (9)	0.01811 (8)	0.0378 (3)
H1WA	0.4609	0.6478	−0.0004	0.057*
H1WB	0.2443	0.6571	0.0317	0.057*

	U11	U22	U33	U12	U13	U23
O1A	0.0637 (8)	0.0486 (8)	0.0625 (8)	0.0261 (6)	−0.0051 (7)	−0.0006 (6)
O2A	0.0471 (7)	0.0435 (7)	0.0574 (8)	0.0115 (5)	−0.0010 (6)	−0.0032 (6)
N1A	0.0333 (6)	0.0342 (6)	0.0301 (6)	0.0046 (5)	0.0096 (5)	0.0081 (5)
N2A	0.0372 (7)	0.0298 (6)	0.0332 (6)	−0.0004 (5)	0.0060 (5)	0.0086 (5)
C1A	0.0417 (8)	0.0422 (9)	0.0399 (8)	0.0020 (7)	0.0123 (7)	0.0149 (7)
C2A	0.0452 (9)	0.0383 (8)	0.0305 (7)	0.0060 (7)	0.0124 (6)	0.0105 (6)
C3A	0.0591 (10)	0.0377 (9)	0.0374 (8)	0.0035 (7)	0.0081 (7)	0.0026 (7)
C4A	0.0716 (12)	0.0331 (8)	0.0468 (10)	0.0140 (8)	0.0095 (9)	0.0039 (7)
C5A	0.0532 (10)	0.0405 (9)	0.0366 (8)	0.0172 (7)	0.0085 (7)	0.0059 (7)
C6A	0.0491 (10)	0.0522 (10)	0.0404 (9)	0.0139 (8)	0.0073 (7)	0.0065 (8)
C7A	0.0456 (9)	0.0368 (8)	0.0326 (8)	0.0072 (7)	0.0123 (6)	0.0029 (6)
C8A	0.0468 (9)	0.0317 (8)	0.0384 (8)	0.0078 (6)	0.0138 (7)	0.0081 (6)
C9A	0.0312 (7)	0.0382 (8)	0.0332 (7)	0.0041 (6)	0.0081 (6)	0.0055 (6)
C10A	0.0354 (7)	0.0349 (8)	0.0368 (8)	0.0078 (6)	0.0065 (6)	0.0053 (6)
C11A	0.0315 (7)	0.0378 (8)	0.0375 (8)	0.0017 (6)	0.0105 (6)	0.0094 (6)
C12A	0.0374 (8)	0.0328 (7)	0.0335 (7)	0.0074 (6)	0.0114 (6)	0.0067 (6)
O1B	0.0434 (6)	0.0370 (6)	0.0553 (7)	0.0035 (5)	0.0167 (5)	0.0182 (5)
O2B	0.0420 (7)	0.0654 (9)	0.0692 (9)	−0.0174 (6)	0.0100 (6)	0.0172 (7)
O3B	0.0658 (9)	0.0635 (9)	0.0555 (8)	0.0021 (7)	0.0009 (7)	0.0353 (7)
O4B	0.0504 (7)	0.0568 (8)	0.0712 (9)	−0.0115 (6)	0.0075 (7)	0.0281 (7)
N1B	0.0471 (8)	0.0380 (7)	0.0393 (7)	0.0017 (6)	0.0096 (6)	0.0128 (6)
C1B	0.0330 (7)	0.0255 (7)	0.0334 (7)	0.0031 (5)	0.0107 (6)	−0.0002 (6)
C2B	0.0300 (7)	0.0373 (8)	0.0395 (8)	0.0008 (6)	0.0050 (6)	0.0015 (6)
C3B	0.0381 (8)	0.0400 (8)	0.0327 (8)	0.0077 (6)	0.0022 (6)	0.0080 (6)
C4B	0.0390 (8)	0.0286 (7)	0.0299 (7)	0.0032 (6)	0.0092 (6)	0.0056 (6)
C5B	0.0302 (7)	0.0327 (7)	0.0350 (8)	−0.0017 (6)	0.0032 (6)	0.0062 (6)
C6B	0.0338 (7)	0.0309 (7)	0.0338 (7)	0.0033 (6)	0.0027 (6)	0.0068 (6)
C7B	0.0367 (8)	0.0295 (7)	0.0436 (9)	0.0019 (6)	0.0170 (7)	0.0028 (6)
O1W	0.0347 (5)	0.0365 (6)	0.0422 (6)	−0.0020 (4)	0.0061 (5)	0.0073 (5)

O1A—C5A	1.373 (2)	C9A—C10A	1.509 (2)
O1A—C6A	1.421 (2)	C10A—H10A	0.9900
O2A—C6A	1.431 (2)	C10A—H10B	0.9900
O2A—C7A	1.3802 (19)	C11A—H11A	0.9900
N1A—C1A	1.4619 (19)	C11A—H11B	0.9900
N1A—C9A	1.4617 (18)	C11A—C12A	1.511 (2)
N1A—C12A	1.4648 (18)	C12A—H12A	0.9900
N2A—H2AA	0.9422	C12A—H12B	0.9900
N2A—H2AB	0.9268	O1B—C7B	1.2622 (19)
N2A—C10A	1.4888 (19)	O2B—C7B	1.2400 (19)
N2A—C11A	1.4913 (18)	O3B—N1B	1.2192 (18)
C1A—H1AA	0.9900	O4B—N1B	1.2231 (18)
C1A—H1AB	0.9900	N1B—C4B	1.4693 (19)
C1A—C2A	1.509 (2)	C1B—C2B	1.393 (2)
C2A—C3A	1.384 (2)	C1B—C6B	1.388 (2)
C2A—C8A	1.408 (2)	C1B—C7B	1.516 (2)
C3A—H3A	0.9500	C2B—H2B	0.9500
C3A—C4A	1.395 (2)	C2B—C3B	1.387 (2)
C4A—H4A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.366 (3)	C3B—C4B	1.379 (2)
C5A—C7A	1.379 (2)	C4B—C5B	1.379 (2)
C6A—H6AA	0.9900	C5B—H5B	0.9500
C6A—H6AB	0.9900	C5B—C6B	1.385 (2)
C7A—C8A	1.367 (2)	C6B—H6B	0.9500
C8A—H8A	0.9500	O1W—H1WA	0.8987
C9A—H9AA	0.9900	O1W—H1WB	0.9158
C9A—H9AB	0.9900
C5A—O1A—C6A	106.07 (13)	C10A—C9A—H9AA	109.6
C7A—O2A—C6A	105.74 (13)	C10A—C9A—H9AB	109.6
C1A—N1A—C12A	111.33 (12)	N2A—C10A—C9A	109.95 (12)
C9A—N1A—C1A	109.81 (12)	N2A—C10A—H10A	109.7
C9A—N1A—C12A	108.99 (11)	N2A—C10A—H10B	109.7
H2AA—N2A—H2AB	107.3	C9A—C10A—H10A	109.7
C10A—N2A—H2AA	113.1	C9A—C10A—H10B	109.7
C10A—N2A—H2AB	113.7	H10A—C10A—H10B	108.2
C10A—N2A—C11A	110.93 (11)	N2A—C11A—H11A	109.7
C11A—N2A—H2AA	104.7	N2A—C11A—H11B	109.7
C11A—N2A—H2AB	106.6	N2A—C11A—C12A	109.91 (12)
N1A—C1A—H1AA	109.0	H11A—C11A—H11B	108.2
N1A—C1A—H1AB	109.0	C12A—C11A—H11A	109.7
N1A—C1A—C2A	112.76 (13)	C12A—C11A—H11B	109.7
H1AA—C1A—H1AB	107.8	N1A—C12A—C11A	110.19 (12)
C2A—C1A—H1AA	109.0	N1A—C12A—H12A	109.6
C2A—C1A—H1AB	109.0	N1A—C12A—H12B	109.6
C3A—C2A—C1A	120.29 (15)	C11A—C12A—H12A	109.6
C3A—C2A—C8A	119.60 (15)	C11A—C12A—H12B	109.6
C8A—C2A—C1A	120.09 (14)	H12A—C12A—H12B	108.1
C2A—C3A—H3A	118.8	O3B—N1B—O4B	123.48 (14)
C2A—C3A—C4A	122.45 (17)	O3B—N1B—C4B	117.98 (14)
C4A—C3A—H3A	118.8	O4B—N1B—C4B	118.52 (13)
C3A—C4A—H4A	121.6	C2B—C1B—C7B	119.39 (13)
C5A—C4A—C3A	116.74 (16)	C6B—C1B—C2B	119.79 (14)
C5A—C4A—H4A	121.6	C6B—C1B—C7B	120.82 (13)
O1A—C5A—C7A	110.07 (15)	C1B—C2B—H2B	119.6
C4A—C5A—O1A	128.41 (16)	C3B—C2B—C1B	120.75 (14)
C4A—C5A—C7A	121.52 (16)	C3B—C2B—H2B	119.6
O1A—C6A—O2A	108.35 (14)	C2B—C3B—H3B	121.1
O1A—C6A—H6AA	110.0	C4B—C3B—C2B	117.81 (14)
O1A—C6A—H6AB	110.0	C4B—C3B—H3B	121.1
O2A—C6A—H6AA	110.0	C3B—C4B—N1B	119.33 (13)
O2A—C6A—H6AB	110.0	C3B—C4B—C5B	122.89 (14)
H6AA—C6A—H6AB	108.4	C5B—C4B—N1B	117.78 (13)
C5A—C7A—O2A	109.55 (14)	C4B—C5B—H5B	120.7
C8A—C7A—O2A	127.90 (14)	C4B—C5B—C6B	118.61 (13)
C8A—C7A—C5A	122.54 (15)	C6B—C5B—H5B	120.7
C2A—C8A—H8A	121.4	C1B—C6B—H6B	119.9
C7A—C8A—C2A	117.14 (14)	C5B—C6B—C1B	120.13 (13)
C7A—C8A—H8A	121.4	C5B—C6B—H6B	119.9
N1A—C9A—H9AA	109.6	O1B—C7B—C1B	117.18 (13)
N1A—C9A—H9AB	109.6	O2B—C7B—O1B	125.94 (15)
N1A—C9A—C10A	110.19 (12)	O2B—C7B—C1B	116.88 (14)
H9AA—C9A—H9AB	108.1	H1WA—O1W—H1WB	106.6
O1A—C5A—C7A—O2A	0.01 (19)	C9A—N1A—C1A—C2A	−173.67 (12)
O1A—C5A—C7A—C8A	179.33 (15)	C9A—N1A—C12A—C11A	61.80 (15)
O2A—C7A—C8A—C2A	179.03 (14)	C10A—N2A—C11A—C12A	55.02 (16)
N1A—C1A—C2A—C3A	−135.98 (16)	C11A—N2A—C10A—C9A	−55.19 (16)
N1A—C1A—C2A—C8A	45.6 (2)	C12A—N1A—C1A—C2A	65.54 (16)
N1A—C9A—C10A—N2A	58.74 (16)	C12A—N1A—C9A—C10A	−61.96 (15)
N2A—C11A—C12A—N1A	−58.34 (16)	O3B—N1B—C4B—C3B	3.6 (2)
C1A—N1A—C9A—C10A	175.85 (12)	O3B—N1B—C4B—C5B	−176.66 (15)
C1A—N1A—C12A—C11A	−176.93 (12)	O4B—N1B—C4B—C3B	−175.27 (15)
C1A—C2A—C3A—C4A	−178.95 (15)	O4B—N1B—C4B—C5B	4.5 (2)
C1A—C2A—C8A—C7A	178.88 (13)	N1B—C4B—C5B—C6B	−178.38 (13)
C2A—C3A—C4A—C5A	0.3 (3)	C1B—C2B—C3B—C4B	−1.4 (2)
C3A—C2A—C8A—C7A	0.5 (2)	C2B—C1B—C6B—C5B	−0.6 (2)
C3A—C4A—C5A—O1A	−179.27 (16)	C2B—C1B—C7B—O1B	176.26 (13)
C3A—C4A—C5A—C7A	0.0 (3)	C2B—C1B—C7B—O2B	−4.0 (2)
C4A—C5A—C7A—O2A	−179.42 (16)	C2B—C3B—C4B—N1B	179.53 (13)
C4A—C5A—C7A—C8A	−0.1 (3)	C2B—C3B—C4B—C5B	−0.2 (2)
C5A—O1A—C6A—O2A	−4.64 (19)	C3B—C4B—C5B—C6B	1.3 (2)
C5A—C7A—C8A—C2A	−0.2 (2)	C4B—C5B—C6B—C1B	−0.9 (2)
C6A—O1A—C5A—C4A	−177.74 (18)	C6B—C1B—C2B—C3B	1.8 (2)
C6A—O1A—C5A—C7A	2.89 (19)	C6B—C1B—C7B—O1B	−3.2 (2)
C6A—O2A—C7A—C5A	−2.88 (18)	C6B—C1B—C7B—O2B	176.51 (14)
C6A—O2A—C7A—C8A	177.85 (16)	C7B—C1B—C2B—C3B	−177.71 (13)
C7A—O2A—C6A—O1A	4.63 (19)	C7B—C1B—C6B—C5B	178.89 (13)
C8A—C2A—C3A—C4A	−0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O1Wi	0.94	1.84	2.7800 (16)	172
N2A—H2AB···O1Bii	0.93	1.80	2.7262 (16)	175
C9A—H9AA···O2Aiii	0.99	2.58	3.3260 (19)	132
C10A—H10A···O1Wiv	0.99	2.51	3.2833 (19)	135
O1W—H1WA···O2Bv	0.90	1.76	2.6526 (16)	170
O1W—H1WB···O1Bii	0.92	1.90	2.7867 (16)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O1W i	0.94	1.84	2.7800 (16)	172
N2A—H2AB⋯O1B ii	0.93	1.80	2.7262 (16)	175
C9A—H9AA⋯O2A iii	0.99	2.58	3.3260 (19)	132
C10A—H10A⋯O1W iv	0.99	2.51	3.2833 (19)	135
O1W—H1WA⋯O2B v	0.90	1.76	2.6526 (16)	170
O1W—H1WB⋯O1B ii	0.92	1.90	2.7867 (16)	163

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