2-{[2-(Piperazin-4-ium-1-yl)ethyl-iminio]meth-yl}phenolate 0.06-chloride 0.94-perchlorate.

The structure of the title salt, C(13)H(20)N(3)O(+)·0.94ClO(4) (-)·0.06Cl(-), contains a zwitterionic Schiff base with a net positive charge and a perchlorate anion having substitutional disorder with Cl. In the cation, the azomethine N atom is protonated and donates hydrogen bonds to the phenolate O atom and to the tertiary N atom of the piperazine ring. In the crystal, two Schiff base mol-ecules are linked about a center of inversion by a pair of N-H⋯O hydrogen bonds. The resulting dimers are N-H⋯O and C-H⋯O hydrogen bonded to the perchlorate anions, forming a three-dimensional structure. The network is further consolidated by C-H⋯π inter-actions.

Related literature

For the structure of a nickel(II) complex of the ligand, see: Mukhopadhyay et al. (2003 ▶). For the structure of a cadmium(II) complex of the ligand, see: Saleh Salga et al. (2010 ▶).

Experimental

Crystal data

C13H20N3O+·0.94ClO4 −·0.06Cl−

M = 329.74

Monoclinic,

a = 11.2322 (2) Å

b = 6.5240 (1) Å

c = 21.0087 (4) Å

β = 90.597 (1)°

V = 1539.41 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 100 K

0.28 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.927, T max = 0.952

11909 measured reflections

2860 independent reflections

2393 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.127

S = 1.04

2860 reflections

213 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: ’SHELXL97 (Sheldrick, 2008 ▶) and publCIF (Westrip, 2010 ▶)’.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811042255/pv2459sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042255/pv2459Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811042255/pv2459Isup3.cml

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

C13H20N3O+·0.94ClO4−·0.06Cl−	F(000) = 696
Mr = 329.74	Dx = 1.423 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3417 reflections
a = 11.2322 (2) Å	θ = 2.7–29.0°
b = 6.5240 (1) Å	µ = 0.27 mm−1
c = 21.0087 (4) Å	T = 100 K
β = 90.597 (1)°	Block, brown
V = 1539.41 (5) Å3	0.28 × 0.22 × 0.18 mm
Z = 4

Bruker APEXII CCD diffractometer	2860 independent reflections
Radiation source: fine-focus sealed tube	2393 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.927, Tmax = 0.952	k = −7→7
11909 measured reflections	l = −24→25

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0613P)2 + 1.4958P] where P = (Fo2 + 2Fc2)/3
2860 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.58 e Å−3
6 restraints	Δρmin = −0.27 e Å−3

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	Occ. (<1)
O1	0.92876 (14)	0.3289 (3)	0.88619 (8)	0.0288 (4)
N1	0.72796 (16)	0.1530 (3)	0.85235 (9)	0.0241 (4)
H1	0.793 (2)	0.153 (4)	0.8761 (12)	0.029*
N2	0.72451 (16)	−0.0667 (3)	0.97192 (9)	0.0227 (4)
N3	0.85668 (19)	−0.2651 (3)	1.07210 (10)	0.0279 (5)
H3A	0.802 (3)	−0.323 (4)	1.0941 (13)	0.033*
H3B	0.934 (2)	−0.290 (4)	1.0894 (12)	0.033*
C1	0.90467 (19)	0.4724 (4)	0.84465 (10)	0.0232 (5)
C2	0.9791 (2)	0.6457 (4)	0.83660 (11)	0.0258 (5)
H2	1.0491	0.6584	0.8620	0.031*
C3	0.9523 (2)	0.7957 (4)	0.79292 (11)	0.0265 (5)
H3	1.0041	0.9099	0.7888	0.032*
C4	0.8498 (2)	0.7835 (4)	0.75421 (11)	0.0285 (5)
H4	0.8325	0.8877	0.7239	0.034*
C5	0.7754 (2)	0.6190 (4)	0.76094 (11)	0.0258 (5)
H5	0.7057	0.6100	0.7351	0.031*
C6	0.80000 (19)	0.4627 (3)	0.80549 (10)	0.0224 (5)
C7	0.71557 (19)	0.3007 (4)	0.81201 (10)	0.0233 (5)
H7	0.6468	0.3017	0.7853	0.028*
C8	0.6394 (2)	−0.0046 (4)	0.86529 (11)	0.0267 (5)
H8A	0.6691	−0.1401	0.8514	0.032*
H8B	0.5648	0.0255	0.8416	0.032*
C9	0.61617 (19)	−0.0068 (4)	0.93633 (11)	0.0253 (5)
H9A	0.5904	0.1311	0.9502	0.030*
H9B	0.5513	−0.1047	0.9456	0.030*
C10	0.7358 (2)	−0.2908 (4)	0.97354 (12)	0.0279 (5)
H10A	0.7346	−0.3456	0.9296	0.034*
H10B	0.6678	−0.3507	0.9967	0.034*
C11	0.8518 (2)	−0.3499 (4)	1.00654 (12)	0.0317 (6)
H11A	0.8584	−0.5011	1.0083	0.038*
H11B	0.9197	−0.2968	0.9818	0.038*
C12	0.8353 (2)	−0.0404 (4)	1.07244 (12)	0.0284 (5)
H12A	0.9028	0.0304	1.0520	0.034*
H12B	0.8303	0.0085	1.1169	0.034*
C13	0.7209 (2)	0.0115 (4)	1.03721 (11)	0.0274 (5)
H13A	0.6525	−0.0499	1.0597	0.033*
H13B	0.7099	0.1620	1.0365	0.033*
Cl1	0.40865 (5)	0.51801 (10)	0.85512 (4)	0.0300 (2)	0.937 (3)
O2	0.4847 (3)	0.5543 (5)	0.90856 (15)	0.0754 (9)	0.937 (3)
O3	0.4569 (2)	0.6021 (6)	0.79982 (15)	0.0915 (11)	0.937 (3)
O4	0.29220 (18)	0.5955 (4)	0.86711 (11)	0.0508 (6)	0.937 (3)
O5	0.3970 (2)	0.3003 (3)	0.84855 (11)	0.0556 (7)	0.937 (3)
Cl2	0.4427 (11)	0.4812 (19)	0.8918 (7)	0.035 (4)*	0.063 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0230 (8)	0.0290 (9)	0.0341 (9)	−0.0034 (7)	−0.0090 (7)	0.0078 (7)
N1	0.0182 (9)	0.0287 (11)	0.0252 (10)	−0.0029 (8)	−0.0033 (8)	0.0015 (8)
N2	0.0191 (9)	0.0236 (10)	0.0254 (10)	0.0013 (8)	−0.0021 (7)	−0.0009 (8)
N3	0.0203 (10)	0.0295 (11)	0.0337 (11)	−0.0054 (8)	−0.0065 (8)	0.0061 (9)
C1	0.0221 (11)	0.0261 (12)	0.0214 (11)	0.0016 (9)	0.0008 (9)	−0.0008 (9)
C2	0.0220 (11)	0.0283 (12)	0.0272 (12)	−0.0016 (9)	−0.0020 (9)	−0.0022 (10)
C3	0.0262 (12)	0.0237 (12)	0.0298 (12)	−0.0021 (9)	0.0064 (9)	−0.0006 (10)
C4	0.0308 (12)	0.0282 (13)	0.0266 (12)	0.0055 (10)	0.0044 (10)	0.0048 (10)
C5	0.0215 (11)	0.0314 (13)	0.0244 (12)	0.0042 (9)	−0.0012 (9)	0.0009 (10)
C6	0.0205 (11)	0.0247 (12)	0.0222 (11)	0.0018 (9)	0.0008 (9)	−0.0022 (9)
C7	0.0184 (10)	0.0292 (12)	0.0223 (11)	0.0021 (9)	−0.0021 (8)	−0.0012 (9)
C8	0.0220 (11)	0.0292 (13)	0.0289 (12)	−0.0053 (9)	−0.0034 (9)	0.0027 (10)
C9	0.0187 (11)	0.0267 (12)	0.0305 (13)	0.0009 (9)	0.0003 (9)	0.0025 (10)
C10	0.0253 (12)	0.0249 (12)	0.0334 (13)	0.0015 (9)	−0.0079 (10)	−0.0040 (10)
C11	0.0291 (12)	0.0253 (13)	0.0406 (14)	0.0053 (10)	−0.0108 (11)	−0.0044 (11)
C12	0.0259 (12)	0.0278 (13)	0.0315 (13)	−0.0027 (10)	−0.0035 (10)	−0.0037 (10)
C13	0.0260 (12)	0.0270 (12)	0.0293 (13)	0.0024 (9)	−0.0014 (10)	−0.0039 (10)
Cl1	0.0209 (3)	0.0334 (4)	0.0357 (5)	−0.0080 (2)	−0.0022 (3)	−0.0010 (3)
O2	0.0628 (17)	0.0668 (17)	0.095 (2)	−0.0180 (14)	−0.0517 (16)	−0.0201 (16)
O3	0.0471 (15)	0.134 (3)	0.094 (2)	0.0135 (16)	0.0184 (14)	0.080 (2)
O4	0.0304 (11)	0.0582 (14)	0.0639 (15)	0.0050 (10)	0.0055 (10)	−0.0243 (12)
O5	0.0702 (16)	0.0310 (12)	0.0651 (15)	−0.0043 (11)	−0.0238 (12)	−0.0091 (10)

O1—C1	1.306 (3)	C6—C7	1.427 (3)
N1—C7	1.290 (3)	C7—H7	0.9500
N1—C8	1.458 (3)	C8—C9	1.518 (3)
N1—H1	0.88 (3)	C8—H8A	0.9900
N2—C13	1.464 (3)	C8—H8B	0.9900
N2—C10	1.468 (3)	C9—H9A	0.9900
N2—C9	1.474 (3)	C9—H9B	0.9900
N3—C11	1.485 (3)	C10—C11	1.519 (3)
N3—C12	1.485 (3)	C10—H10A	0.9900
N3—H3A	0.86 (3)	C10—H10B	0.9900
N3—H3B	0.96 (3)	C11—H11A	0.9900
C1—C2	1.417 (3)	C11—H11B	0.9900
C1—C6	1.429 (3)	C12—C13	1.514 (3)
C2—C3	1.373 (3)	C12—H12A	0.9900
C2—H2	0.9500	C12—H12B	0.9900
C3—C4	1.405 (3)	C13—H13A	0.9900
C3—H3	0.9500	C13—H13B	0.9900
C4—C5	1.369 (3)	Cl1—O3	1.399 (3)
C4—H4	0.9500	Cl1—O2	1.424 (3)
C5—C6	1.410 (3)	Cl1—O4	1.427 (2)
C5—H5	0.9500	Cl1—O5	1.433 (2)
C7—N1—C8	125.5 (2)	H8A—C8—H8B	108.4
C7—N1—H1	117.1 (17)	N2—C9—C8	110.59 (18)
C8—N1—H1	117.3 (17)	N2—C9—H9A	109.5
C13—N2—C10	109.16 (18)	C8—C9—H9A	109.5
C13—N2—C9	110.63 (17)	N2—C9—H9B	109.5
C10—N2—C9	110.26 (17)	C8—C9—H9B	109.5
C11—N3—C12	111.59 (19)	H9A—C9—H9B	108.1
C11—N3—H3A	108.3 (19)	N2—C10—C11	109.68 (19)
C12—N3—H3A	108.3 (18)	N2—C10—H10A	109.7
C11—N3—H3B	108.3 (16)	C11—C10—H10A	109.7
C12—N3—H3B	108.3 (16)	N2—C10—H10B	109.7
H3A—N3—H3B	112 (2)	C11—C10—H10B	109.7
O1—C1—C2	122.2 (2)	H10A—C10—H10B	108.2
O1—C1—C6	121.1 (2)	N3—C11—C10	110.6 (2)
C2—C1—C6	116.7 (2)	N3—C11—H11A	109.5
C3—C2—C1	121.5 (2)	C10—C11—H11A	109.5
C3—C2—H2	119.2	N3—C11—H11B	109.5
C1—C2—H2	119.2	C10—C11—H11B	109.5
C2—C3—C4	121.3 (2)	H11A—C11—H11B	108.1
C2—C3—H3	119.3	N3—C12—C13	110.77 (19)
C4—C3—H3	119.3	N3—C12—H12A	109.5
C5—C4—C3	118.8 (2)	C13—C12—H12A	109.5
C5—C4—H4	120.6	N3—C12—H12B	109.5
C3—C4—H4	120.6	C13—C12—H12B	109.5
C4—C5—C6	121.3 (2)	H12A—C12—H12B	108.1
C4—C5—H5	119.3	N2—C13—C12	110.40 (19)
C6—C5—H5	119.3	N2—C13—H13A	109.6
C5—C6—C7	118.2 (2)	C12—C13—H13A	109.6
C5—C6—C1	120.3 (2)	N2—C13—H13B	109.6
C7—C6—C1	121.4 (2)	C12—C13—H13B	109.6
N1—C7—C6	123.3 (2)	H13A—C13—H13B	108.1
N1—C7—H7	118.4	O3—Cl1—O2	110.8 (2)
C6—C7—H7	118.4	O3—Cl1—O4	111.81 (16)
N1—C8—C9	108.35 (19)	O2—Cl1—O4	110.21 (16)
N1—C8—H8A	110.0	O3—Cl1—O5	110.2 (2)
C9—C8—H8A	110.0	O2—Cl1—O5	107.10 (16)
N1—C8—H8B	110.0	O4—Cl1—O5	106.59 (15)
C9—C8—H8B	110.0

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88 (3)	1.92 (3)	2.622 (2)	136 (2)
N1—H1···N2	0.88 (3)	2.59 (3)	2.893 (3)	100.9 (19)
N3—H3A···O4i	0.86 (3)	2.23 (3)	3.020 (3)	153 (2)
N3—H3A···O5i	0.86 (3)	2.55 (3)	3.325 (3)	149 (2)
N3—H3B···O1ii	0.96 (3)	1.64 (3)	2.589 (2)	176 (2)
C5—H5···O5iii	0.95	2.43	3.217 (3)	140.
C7—H7···O3iv	0.95	2.49	3.295 (3)	142.
C9—H9B···O2v	0.99	2.47	3.271 (4)	138.
C13—H13A···O5i	0.99	2.59	3.423 (4)	142.
C13—H13B···O4vi	0.99	2.57	3.263 (3)	127.
C3—H3···Cg1vii	0.95	2.70	3.500 (3)	142
C8—H8A···Cg1v	0.99	2.99	3.849 (3)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.88 (3)	1.92 (3)	2.622 (2)	136 (2)
N1—H1⋯N2	0.88 (3)	2.59 (3)	2.893 (3)	100.9 (19)
N3—H3A⋯O4i	0.86 (3)	2.23 (3)	3.020 (3)	153 (2)
N3—H3A⋯O5i	0.86 (3)	2.55 (3)	3.325 (3)	149 (2)
N3—H3B⋯O1ii	0.96 (3)	1.64 (3)	2.589 (2)	176 (2)
C5—H5⋯O5iii	0.95	2.43	3.217 (3)	140
C7—H7⋯O3iv	0.95	2.49	3.295 (3)	142
C9—H9B⋯O2v	0.99	2.47	3.271 (4)	138
C13—H13A⋯O5i	0.99	2.59	3.423 (4)	142
C13—H13B⋯O4vi	0.99	2.57	3.263 (3)	127
C3—H3⋯Cg1vii	0.95	2.70	3.500 (3)	142
C8—H8A⋯Cg1v	0.99	2.99	3.849 (3)	145

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