1-Piperonylpiperazinium 4-chloro-benzoate.

In the title salt {systematic name: 1-[(1,3-benzodioxol-5-yl)meth-yl]piperazin-1-ium 4-chloro-benzoate}, C12H17N2O2 (+)·C7H4ClO2 (-), the piperazine ring adopts a slightly disordered chair conformation. The dioxole ring is in a flattened envelope conformation with the methyl-ene C atom forming the flap. The relative orientation of the piperonyl ring system and the piperazine rings is reflected in the N-C-C C torsion angle of 132.3 (1)°. In the anion, the mean plane of the carboxyl-ate group is twisted from that of the benzene ring by 14.8 (9)°. In the crystal, the components are linked by N-H⋯O and weak C-H⋯O hydrogen bonds, forming chains along [010].

Related literature

For the biological activity of related compounds, see: Brockunier et al. (2004 ▶); Bogatcheva et al. (2006 ▶); Elliott (2011 ▶); Gilbert et al. (1968 ▶); Gobert et al. (2003 ▶); Millan et al. (2001 ▶). 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 +·C7H4ClO2 −

M = 376.83

Monoclinic,

a = 16.9967 (6) Å

b = 8.5990 (3) Å

c = 12.4150 (5) Å

β = 90.923 (3)°

V = 1814.27 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 173 K

0.48 × 0.26 × 0.18 mm

Data collection

Agilent Gemini EOS diffractometer

Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T min = 0.787, T max = 1.000

22917 measured reflections

6302 independent reflections

4472 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.120

S = 1.04

6302 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.32 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 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) in OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814002037/lh5687sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002037/lh5687Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002037/lh5687Isup3.cml

CCDC reference:

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

C12H17N2O2+·C7H4ClO2−	F(000) = 792
Mr = 376.83	Dx = 1.380 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.9967 (6) Å	Cell parameters from 5056 reflections
b = 8.5990 (3) Å	θ = 3.1–32.8°
c = 12.4150 (5) Å	µ = 0.24 mm−1
β = 90.923 (3)°	T = 173 K
V = 1814.27 (12) Å3	Irregular, light yellow
Z = 4	0.48 × 0.26 × 0.18 mm

Agilent Gemini EOS diffractometer	6302 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4472 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm-1	Rint = 0.033
ω scans	θmax = 32.8°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −21→25
Tmin = 0.787, Tmax = 1.000	k = −12→12
22917 measured reflections	l = −17→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.120	w = 1/[σ2(Fo2) + (0.0455P)2 + 0.5274P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
6302 reflections	Δρmax = 0.30 e Å−3
235 parameters	Δρmin = −0.32 e Å−3
0 restraints

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	0.46343 (6)	0.65641 (14)	0.06488 (9)	0.0439 (3)
O2A	0.55838 (7)	0.84302 (13)	0.03707 (9)	0.0452 (3)
N1A	0.79257 (6)	0.70236 (13)	0.30762 (9)	0.0280 (2)
N2A	0.95243 (6)	0.60800 (13)	0.27472 (10)	0.0298 (2)
H2AA	0.9590	0.5293	0.3218	0.036*
H2AB	0.9978	0.6209	0.2395	0.036*
C1A	0.71612 (8)	0.69075 (19)	0.35969 (12)	0.0360 (3)
H1AA	0.7072	0.7843	0.4014	0.043*
H1AB	0.7170	0.6033	0.4090	0.043*
C2A	0.64927 (8)	0.66996 (16)	0.27979 (11)	0.0301 (3)
C3A	0.64318 (8)	0.77080 (16)	0.19132 (11)	0.0321 (3)
H3A	0.6810	0.8466	0.1789	0.039*
C4A	0.57955 (8)	0.75298 (16)	0.12438 (11)	0.0304 (3)
C5A	0.49379 (11)	0.7623 (2)	−0.01222 (14)	0.0474 (4)
H5AA	0.4533	0.8355	−0.0346	0.057*
H5AB	0.5113	0.7063	−0.0753	0.057*
C6A	0.52267 (8)	0.64112 (17)	0.14120 (11)	0.0312 (3)
C7A	0.52767 (9)	0.54095 (18)	0.22546 (12)	0.0373 (3)
H7A	0.4895	0.4654	0.2367	0.045*
C8A	0.59275 (9)	0.55669 (18)	0.29434 (12)	0.0352 (3)
H8A	0.5983	0.4885	0.3521	0.042*
C9A	0.85456 (8)	0.73757 (16)	0.38737 (11)	0.0305 (3)
H9AA	0.8570	0.6553	0.4408	0.037*
H9AB	0.8422	0.8340	0.4239	0.037*
C10A	0.93326 (8)	0.75244 (15)	0.33388 (12)	0.0313 (3)
H10A	0.9320	0.8395	0.2842	0.038*
H10B	0.9738	0.7727	0.3880	0.038*
C11A	0.88861 (8)	0.56853 (18)	0.19658 (12)	0.0349 (3)
H11A	0.9003	0.4701	0.1621	0.042*
H11B	0.8854	0.6479	0.1412	0.042*
C12A	0.81076 (8)	0.55708 (16)	0.25287 (12)	0.0316 (3)
H12A	0.7695	0.5336	0.2005	0.038*
H12B	0.8129	0.4730	0.3049	0.038*
Cl1B	0.33436 (2)	0.68123 (5)	0.27279 (3)	0.04524 (12)
O1B	0.02434 (6)	0.65334 (11)	0.59960 (8)	0.0335 (2)
O2B	0.07906 (6)	0.87721 (13)	0.65085 (9)	0.0411 (3)
C1B	0.14214 (7)	0.73384 (14)	0.51518 (10)	0.0255 (2)
C2B	0.21013 (8)	0.82354 (16)	0.52310 (12)	0.0308 (3)
H2B	0.2152	0.8966	0.5780	0.037*
C3B	0.27034 (8)	0.80532 (16)	0.45013 (12)	0.0339 (3)
H3B	0.3161	0.8642	0.4562	0.041*
C4B	0.26105 (8)	0.69800 (16)	0.36822 (11)	0.0310 (3)
C5B	0.19465 (8)	0.60586 (16)	0.35906 (11)	0.0311 (3)
H5B	0.1897	0.5333	0.3038	0.037*
C6B	0.13543 (8)	0.62363 (15)	0.43395 (11)	0.0284 (3)
H6B	0.0909	0.5610	0.4296	0.034*
C7B	0.07682 (8)	0.75601 (15)	0.59450 (11)	0.0275 (3)

	U11	U22	U33	U12	U13	U23
O1A	0.0290 (5)	0.0598 (7)	0.0426 (6)	−0.0056 (5)	−0.0065 (4)	0.0000 (5)
O2A	0.0446 (6)	0.0445 (6)	0.0461 (6)	−0.0058 (5)	−0.0140 (5)	0.0112 (5)
N1A	0.0247 (5)	0.0295 (5)	0.0297 (6)	0.0009 (4)	−0.0029 (4)	−0.0040 (4)
N2A	0.0248 (5)	0.0248 (5)	0.0398 (6)	0.0004 (4)	−0.0013 (4)	0.0035 (5)
C1A	0.0289 (7)	0.0482 (9)	0.0310 (7)	0.0017 (6)	0.0001 (5)	−0.0022 (6)
C2A	0.0243 (6)	0.0350 (7)	0.0311 (6)	0.0031 (5)	0.0028 (5)	−0.0031 (5)
C3A	0.0278 (6)	0.0295 (7)	0.0391 (7)	−0.0028 (5)	0.0005 (5)	−0.0004 (5)
C4A	0.0292 (6)	0.0292 (6)	0.0328 (7)	0.0029 (5)	0.0012 (5)	−0.0007 (5)
C5A	0.0497 (10)	0.0517 (10)	0.0403 (8)	−0.0057 (8)	−0.0118 (7)	−0.0001 (7)
C6A	0.0226 (6)	0.0374 (7)	0.0337 (7)	0.0002 (5)	0.0022 (5)	−0.0067 (6)
C7A	0.0312 (7)	0.0422 (8)	0.0387 (8)	−0.0097 (6)	0.0072 (6)	−0.0005 (6)
C8A	0.0341 (7)	0.0399 (8)	0.0317 (7)	−0.0015 (6)	0.0058 (5)	0.0035 (6)
C9A	0.0309 (7)	0.0293 (6)	0.0310 (6)	0.0010 (5)	−0.0055 (5)	−0.0025 (5)
C10A	0.0287 (6)	0.0239 (6)	0.0411 (7)	−0.0019 (5)	−0.0072 (5)	−0.0013 (5)
C11A	0.0304 (7)	0.0355 (7)	0.0385 (7)	0.0033 (5)	−0.0030 (6)	−0.0084 (6)
C12A	0.0276 (6)	0.0276 (6)	0.0393 (7)	−0.0002 (5)	−0.0049 (5)	−0.0056 (5)
Cl1B	0.0359 (2)	0.0490 (2)	0.0512 (2)	−0.00034 (16)	0.01216 (16)	0.00508 (18)
O1B	0.0296 (5)	0.0288 (5)	0.0421 (6)	−0.0036 (4)	0.0024 (4)	0.0014 (4)
O2B	0.0365 (6)	0.0362 (5)	0.0509 (6)	−0.0063 (4)	0.0073 (5)	−0.0127 (5)
C1B	0.0249 (6)	0.0224 (6)	0.0289 (6)	0.0012 (4)	−0.0045 (5)	0.0052 (5)
C2B	0.0282 (6)	0.0271 (6)	0.0369 (7)	−0.0019 (5)	−0.0059 (5)	−0.0003 (5)
C3B	0.0250 (6)	0.0303 (7)	0.0463 (8)	−0.0035 (5)	−0.0036 (5)	0.0042 (6)
C4B	0.0248 (6)	0.0321 (7)	0.0362 (7)	0.0033 (5)	0.0005 (5)	0.0084 (5)
C5B	0.0299 (6)	0.0313 (7)	0.0322 (7)	0.0020 (5)	−0.0043 (5)	−0.0003 (5)
C6B	0.0240 (6)	0.0281 (6)	0.0330 (7)	−0.0018 (5)	−0.0052 (5)	0.0030 (5)
C7B	0.0261 (6)	0.0253 (6)	0.0309 (6)	0.0024 (5)	−0.0046 (5)	0.0031 (5)

O1A—C5A	1.424 (2)	C9A—H9AA	0.9700
O1A—C6A	1.3777 (17)	C9A—H9AB	0.9700
O2A—C4A	1.3753 (17)	C9A—C10A	1.508 (2)
O2A—C5A	1.4281 (19)	C10A—H10A	0.9700
N1A—C1A	1.4640 (17)	C10A—H10B	0.9700
N1A—C9A	1.4658 (16)	C11A—H11A	0.9700
N1A—C12A	1.4578 (17)	C11A—H11B	0.9700
N2A—H2AA	0.9000	C11A—C12A	1.510 (2)
N2A—H2AB	0.9000	C12A—H12A	0.9700
N2A—C10A	1.4818 (17)	C12A—H12B	0.9700
N2A—C11A	1.4829 (18)	Cl1B—C4B	1.7391 (14)
C1A—H1AA	0.9700	O1B—C7B	1.2573 (16)
C1A—H1AB	0.9700	O2B—C7B	1.2554 (16)
C1A—C2A	1.5069 (19)	C1B—C2B	1.3916 (18)
C2A—C3A	1.4019 (19)	C1B—C6B	1.3873 (18)
C2A—C8A	1.382 (2)	C1B—C7B	1.5079 (18)
C3A—H3A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.3619 (19)	C2B—C3B	1.386 (2)
C4A—C6A	1.3820 (19)	C3B—H3B	0.9300
C5A—H5AA	0.9700	C3B—C4B	1.380 (2)
C5A—H5AB	0.9700	C4B—C5B	1.382 (2)
C6A—C7A	1.357 (2)	C5B—H5B	0.9300
C7A—H7A	0.9300	C5B—C6B	1.3896 (19)
C7A—C8A	1.394 (2)	C6B—H6B	0.9300
C8A—H8A	0.9300
C6A—O1A—C5A	104.75 (11)	N1A—C9A—C10A	110.67 (11)
C4A—O2A—C5A	104.70 (12)	H9AA—C9A—H9AB	108.1
C1A—N1A—C9A	110.44 (11)	C10A—C9A—H9AA	109.5
C12A—N1A—C1A	110.11 (11)	C10A—C9A—H9AB	109.5
C12A—N1A—C9A	109.66 (10)	N2A—C10A—C9A	110.53 (11)
H2AA—N2A—H2AB	108.1	N2A—C10A—H10A	109.5
C10A—N2A—H2AA	109.5	N2A—C10A—H10B	109.5
C10A—N2A—H2AB	109.5	C9A—C10A—H10A	109.5
C10A—N2A—C11A	110.60 (10)	C9A—C10A—H10B	109.5
C11A—N2A—H2AA	109.5	H10A—C10A—H10B	108.1
C11A—N2A—H2AB	109.5	N2A—C11A—H11A	109.6
N1A—C1A—H1AA	109.1	N2A—C11A—H11B	109.6
N1A—C1A—H1AB	109.1	N2A—C11A—C12A	110.45 (12)
N1A—C1A—C2A	112.49 (11)	H11A—C11A—H11B	108.1
H1AA—C1A—H1AB	107.8	C12A—C11A—H11A	109.6
C2A—C1A—H1AA	109.1	C12A—C11A—H11B	109.6
C2A—C1A—H1AB	109.1	N1A—C12A—C11A	110.74 (11)
C3A—C2A—C1A	119.20 (13)	N1A—C12A—H12A	109.5
C8A—C2A—C1A	121.06 (13)	N1A—C12A—H12B	109.5
C8A—C2A—C3A	119.71 (13)	C11A—C12A—H12A	109.5
C2A—C3A—H3A	121.4	C11A—C12A—H12B	109.5
C4A—C3A—C2A	117.16 (13)	H12A—C12A—H12B	108.1
C4A—C3A—H3A	121.4	C2B—C1B—C7B	120.21 (12)
O2A—C4A—C6A	109.64 (12)	C6B—C1B—C2B	119.24 (12)
C3A—C4A—O2A	127.79 (13)	C6B—C1B—C7B	120.56 (11)
C3A—C4A—C6A	122.46 (13)	C1B—C2B—H2B	119.6
O1A—C5A—O2A	107.89 (12)	C3B—C2B—C1B	120.80 (13)
O1A—C5A—H5AA	110.1	C3B—C2B—H2B	119.6
O1A—C5A—H5AB	110.1	C2B—C3B—H3B	120.7
O2A—C5A—H5AA	110.1	C4B—C3B—C2B	118.69 (13)
O2A—C5A—H5AB	110.1	C4B—C3B—H3B	120.7
H5AA—C5A—H5AB	108.4	C3B—C4B—Cl1B	118.85 (11)
O1A—C6A—C4A	109.57 (13)	C3B—C4B—C5B	121.83 (13)
C7A—C6A—O1A	128.82 (13)	C5B—C4B—Cl1B	119.31 (11)
C7A—C6A—C4A	121.54 (13)	C4B—C5B—H5B	120.6
C6A—C7A—H7A	121.6	C4B—C5B—C6B	118.77 (13)
C6A—C7A—C8A	116.78 (13)	C6B—C5B—H5B	120.6
C8A—C7A—H7A	121.6	C1B—C6B—C5B	120.64 (12)
C2A—C8A—C7A	122.33 (14)	C1B—C6B—H6B	119.7
C2A—C8A—H8A	118.8	C5B—C6B—H6B	119.7
C7A—C8A—H8A	118.8	O1B—C7B—C1B	118.33 (12)
N1A—C9A—H9AA	109.5	O2B—C7B—O1B	124.75 (13)
N1A—C9A—H9AB	109.5	O2B—C7B—C1B	116.92 (12)
O1A—C6A—C7A—C8A	−176.43 (14)	C6A—C7A—C8A—C2A	1.1 (2)
O2A—C4A—C6A—O1A	0.07 (16)	C8A—C2A—C3A—C4A	1.3 (2)
O2A—C4A—C6A—C7A	−177.15 (13)	C9A—N1A—C1A—C2A	174.49 (12)
N1A—C1A—C2A—C3A	−49.87 (18)	C9A—N1A—C12A—C11A	−59.59 (14)
N1A—C1A—C2A—C8A	132.26 (14)	C10A—N2A—C11A—C12A	−55.32 (15)
N1A—C9A—C10A—N2A	−57.53 (14)	C11A—N2A—C10A—C9A	55.29 (14)
N2A—C11A—C12A—N1A	57.83 (15)	C12A—N1A—C1A—C2A	−64.26 (15)
C1A—N1A—C9A—C10A	−179.02 (11)	C12A—N1A—C9A—C10A	59.46 (14)
C1A—N1A—C12A—C11A	178.69 (11)	Cl1B—C4B—C5B—C6B	−178.09 (10)
C1A—C2A—C3A—C4A	−176.59 (13)	C1B—C2B—C3B—C4B	1.0 (2)
C1A—C2A—C8A—C7A	175.95 (13)	C2B—C1B—C6B—C5B	−2.03 (19)
C2A—C3A—C4A—O2A	175.68 (13)	C2B—C1B—C7B—O1B	−165.32 (12)
C2A—C3A—C4A—C6A	0.0 (2)	C2B—C1B—C7B—O2B	14.80 (18)
C3A—C2A—C8A—C7A	−1.9 (2)	C2B—C3B—C4B—Cl1B	177.00 (10)
C3A—C4A—C6A—O1A	176.46 (13)	C2B—C3B—C4B—C5B	−1.9 (2)
C3A—C4A—C6A—C7A	−0.8 (2)	C3B—C4B—C5B—C6B	0.8 (2)
C4A—O2A—C5A—O1A	18.16 (18)	C4B—C5B—C6B—C1B	1.22 (19)
C4A—C6A—C7A—C8A	0.2 (2)	C6B—C1B—C2B—C3B	0.89 (19)
C5A—O1A—C6A—C4A	11.18 (16)	C6B—C1B—C7B—O1B	14.36 (18)
C5A—O1A—C6A—C7A	−171.86 (16)	C6B—C1B—C7B—O2B	−165.52 (12)
C5A—O2A—C4A—C3A	172.60 (15)	C7B—C1B—C2B—C3B	−179.42 (12)
C5A—O2A—C4A—C6A	−11.25 (16)	C7B—C1B—C6B—C5B	178.29 (11)
C6A—O1A—C5A—O2A	−18.11 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O1Bi	0.90	1.87	2.7606 (15)	171
N2A—H2AB···O2Bii	0.90	1.78	2.6684 (16)	169
C10A—H10A···O2Biii	0.97	2.57	3.1974 (17)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O1B i	0.90	1.87	2.7606 (15)	171
N2A—H2AB⋯O2B ii	0.90	1.78	2.6684 (16)	169
C10A—H10A⋯O2B iii	0.97	2.57	3.1974 (17)	122

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