1,4-Dimethyl-piperazin-1-ium 3-hy-droxy-2-naphtho-ate.

The reaction of 1,4-dimethyl-piperazine and 3-hy-droxy-2-naphthoic acid gives the title 1:1 salt, C(6)H(15)N(2) (+)·C(11)H(7)O(3) (-), with a singly protonated piperazinium cation. In the crystal, a single N-H⋯O hydrogen bond links the cations and anions into discrete pairs and the aromatic anions stack along the crystallographic a-axis direction. This results in layers of cations and anions alternating along the crystallographic c-axis direction. An intra-molecular O-H⋯O hydrogen bond is also present.

Related literature

For general descriptions of the salt selection process in the pharmacy industry, see: Stahl & Wermuth (2002 ▶); Gould (1986 ▶); Serajuddin (2007 ▶). For structures of monoprotonated 1,4-dimethyl­piperazinium, see: Clemente et al. (1999 ▶); Marzotto et al. (2001 ▶). For systematic structural studies of structure–property relationships of salts in a pharmaceutical context, see: Arlin et al. (2011 ▶); Kennedy et al. (2011 ▶). For the Cambridge Structural Database, see: Allen (2002 ▶). For a related aryl carboxyl­ate structure, see: Burchell et al. (2001 ▶).

Experimental

Crystal data

C6H15N2 +·C11H7O3 −

M = 302.37

Monoclinic,

a = 5.8772 (16) Å

b = 10.892 (2) Å

c = 12.562 (2) Å

β = 100.29 (2)°

V = 791.2 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.20 × 0.15 × 0.08 mm

Data collection

Oxford Diffraction Xcaliber S diffractometer

7855 measured reflections

2996 independent reflections

1608 reflections with I > 2σ(I)

R int = 0.119

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.121

S = 0.83

2996 reflections

203 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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: ORTEP-3 (Farrugia, 1997 ▶) and X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005375/lh5414sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005375/lh5414Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812005375/lh5414Isup3.cml

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

C6H15N2+·C11H7O3−	F(000) = 324
Mr = 302.37	Dx = 1.269 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1466 reflections
a = 5.8772 (16) Å	θ = 2.5–31.3°
b = 10.892 (2) Å	µ = 0.09 mm−1
c = 12.562 (2) Å	T = 293 K
β = 100.29 (2)°	Fragment, colourless
V = 791.2 (3) Å3	0.20 × 0.15 × 0.08 mm
Z = 2

Oxford Diffraction Xcaliber S diffractometer	1608 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.119
Graphite monochromator	θmax = 26.0°, θmin = 2.5°
Detector resolution: 16.0268 pixels mm-1	h = −7→7
ω scans	k = −13→13
7855 measured reflections	l = −15→15
2996 independent 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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3
S = 0.83	(Δ/σ)max < 0.001
2996 reflections	Δρmax = 0.14 e Å−3
203 parameters	Δρmin = −0.16 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (5)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.4807 (4)	0.4173 (2)	0.83756 (18)	0.0698 (7)
O2	0.7191 (4)	0.2587 (2)	0.86723 (18)	0.0693 (7)
O3	0.6220 (4)	0.0581 (2)	0.7662 (2)	0.0713 (7)
H3	0.6909	0.1050	0.8120	0.107*
N1	0.0615 (5)	0.2188 (2)	0.18076 (18)	0.0540 (7)
N2	0.2028 (4)	0.0436 (2)	0.03575 (18)	0.0485 (6)
H2	0.3079	0.0004	0.0834	0.058*
C1	0.5324 (6)	0.3081 (3)	0.8212 (2)	0.0499 (8)
C2	0.3691 (5)	0.2334 (2)	0.7444 (2)	0.0421 (7)
C3	0.4223 (5)	0.1106 (3)	0.7177 (2)	0.0492 (8)
C4	0.2712 (6)	0.0446 (3)	0.6450 (2)	0.0577 (8)
H4	0.3089	−0.0353	0.6286	0.069*
C5	0.0600 (6)	0.0946 (3)	0.5943 (2)	0.0511 (8)
C6	0.0011 (5)	0.2159 (3)	0.6212 (2)	0.0481 (8)
C7	0.1630 (5)	0.2818 (2)	0.6959 (2)	0.0460 (7)
H7	0.1275	0.3618	0.7128	0.055*
C8	−0.1018 (7)	0.0297 (3)	0.5177 (3)	0.0691 (10)
H8	−0.0694	−0.0504	0.4995	0.083*
C9	−0.3021 (7)	0.0825 (4)	0.4708 (3)	0.0819 (12)
H9	−0.4035	0.0387	0.4192	0.098*
C10	−0.3613 (7)	0.2015 (4)	0.4978 (3)	0.0815 (12)
H10	−0.5014	0.2359	0.4653	0.098*
C11	−0.2116 (6)	0.2662 (3)	0.5721 (3)	0.0642 (9)
H11	−0.2509	0.3450	0.5907	0.077*
C12	0.2864 (6)	0.2257 (3)	0.1499 (3)	0.0621 (9)
H12A	0.3974	0.1803	0.2017	0.074*
H12B	0.3362	0.3107	0.1514	0.074*
C13	0.2821 (6)	0.1748 (3)	0.0404 (3)	0.0582 (9)
H13A	0.4357	0.1793	0.0224	0.070*
H13B	0.1784	0.2230	−0.0123	0.070*
C14	−0.0210 (5)	0.0334 (3)	0.0721 (2)	0.0559 (8)
H14A	−0.0635	−0.0524	0.0751	0.067*
H14B	−0.1396	0.0745	0.0208	0.067*
C15	−0.0076 (6)	0.0901 (3)	0.1817 (2)	0.0572 (9)
H15A	−0.1573	0.0843	0.2036	0.069*
H15B	0.1034	0.0454	0.2339	0.069*
C16	0.0568 (7)	0.2757 (3)	0.2852 (3)	0.0778 (11)
H16A	0.1569	0.2313	0.3408	0.117*
H16B	−0.0983	0.2742	0.2995	0.117*
H16C	0.1086	0.3592	0.2841	0.117*
C17	0.1976 (6)	−0.0108 (3)	−0.0721 (2)	0.0694 (10)
H17A	0.1472	−0.0946	−0.0717	0.104*
H17B	0.3498	−0.0079	−0.0898	0.104*
H17C	0.0926	0.0347	−0.1249	0.104*

	U11	U22	U33	U12	U13	U23
O1	0.0622 (15)	0.0473 (14)	0.0920 (16)	0.0018 (12)	−0.0080 (11)	−0.0174 (12)
O2	0.0633 (17)	0.0680 (15)	0.0704 (14)	0.0035 (13)	−0.0053 (12)	−0.0016 (12)
O3	0.0711 (16)	0.0539 (14)	0.0857 (16)	0.0150 (13)	0.0058 (12)	0.0047 (12)
N1	0.0617 (18)	0.0417 (15)	0.0584 (15)	0.0002 (14)	0.0099 (12)	0.0000 (12)
N2	0.0493 (15)	0.0434 (14)	0.0510 (14)	0.0044 (12)	0.0042 (10)	0.0066 (12)
C1	0.049 (2)	0.047 (2)	0.0516 (18)	−0.0045 (16)	0.0016 (15)	0.0030 (15)
C2	0.0478 (18)	0.0365 (15)	0.0419 (15)	−0.0003 (14)	0.0074 (13)	0.0016 (13)
C3	0.055 (2)	0.0392 (17)	0.0534 (17)	0.0029 (15)	0.0085 (15)	0.0040 (15)
C4	0.079 (2)	0.0358 (16)	0.062 (2)	0.0007 (18)	0.0225 (17)	−0.0012 (15)
C5	0.066 (2)	0.0445 (19)	0.0440 (16)	−0.0126 (16)	0.0121 (15)	−0.0028 (14)
C6	0.0483 (19)	0.0502 (19)	0.0452 (15)	−0.0061 (15)	0.0069 (14)	0.0008 (15)
C7	0.057 (2)	0.0347 (15)	0.0462 (15)	0.0011 (15)	0.0089 (14)	−0.0039 (12)
C8	0.086 (3)	0.062 (2)	0.059 (2)	−0.021 (2)	0.0122 (19)	−0.0126 (18)
C9	0.078 (3)	0.101 (3)	0.061 (2)	−0.034 (3)	−0.0001 (19)	−0.008 (2)
C10	0.068 (3)	0.105 (3)	0.065 (2)	−0.015 (2)	−0.0048 (19)	0.013 (2)
C11	0.061 (2)	0.065 (2)	0.0631 (19)	0.0012 (19)	0.0015 (16)	0.0026 (17)
C12	0.065 (2)	0.0412 (18)	0.078 (2)	−0.0092 (17)	0.0058 (17)	0.0020 (17)
C13	0.063 (2)	0.0390 (17)	0.074 (2)	−0.0047 (16)	0.0165 (16)	0.0120 (15)
C14	0.0497 (19)	0.0503 (18)	0.067 (2)	−0.0031 (15)	0.0078 (15)	0.0032 (16)
C15	0.064 (2)	0.050 (2)	0.0585 (19)	−0.0035 (16)	0.0110 (16)	0.0051 (15)
C16	0.098 (3)	0.067 (2)	0.067 (2)	0.004 (2)	0.0124 (19)	−0.0089 (18)
C17	0.082 (3)	0.068 (2)	0.058 (2)	0.013 (2)	0.0097 (17)	0.0025 (18)

O1—C1	1.253 (4)	C8—H8	0.9300
O2—C1	1.265 (4)	C9—C10	1.399 (6)
O3—C3	1.349 (4)	C9—H9	0.9300
O3—H3	0.8200	C10—C11	1.360 (5)
N1—C12	1.445 (4)	C10—H10	0.9300
N1—C16	1.455 (4)	C11—H11	0.9300
N1—C15	1.460 (4)	C12—C13	1.479 (5)
N2—C14	1.472 (4)	C12—H12A	0.9700
N2—C17	1.474 (4)	C12—H12B	0.9700
N2—C13	1.501 (4)	C13—H13A	0.9700
N2—H2	0.9100	C13—H13B	0.9700
C1—C2	1.479 (4)	C14—C15	1.497 (4)
C2—C7	1.361 (4)	C14—H14A	0.9700
C2—C3	1.427 (4)	C14—H14B	0.9700
C3—C4	1.360 (4)	C15—H15A	0.9700
C4—C5	1.400 (4)	C15—H15B	0.9700
C4—H4	0.9300	C16—H16A	0.9600
C5—C8	1.416 (4)	C16—H16B	0.9600
C5—C6	1.421 (4)	C16—H16C	0.9600
C6—C11	1.403 (4)	C17—H17A	0.9600
C6—C7	1.408 (4)	C17—H17B	0.9600
C7—H7	0.9300	C17—H17C	0.9600
C8—C9	1.348 (5)
C3—O3—H3	109.5	C10—C11—C6	121.1 (4)
C12—N1—C16	112.7 (3)	C10—C11—H11	119.5
C12—N1—C15	108.7 (2)	C6—C11—H11	119.5
C16—N1—C15	110.6 (3)	N1—C12—C13	111.5 (3)
C14—N2—C17	112.5 (2)	N1—C12—H12A	109.3
C14—N2—C13	110.4 (2)	C13—C12—H12A	109.3
C17—N2—C13	111.9 (2)	N1—C12—H12B	109.3
C14—N2—H2	107.2	C13—C12—H12B	109.3
C17—N2—H2	107.2	H12A—C12—H12B	108.0
C13—N2—H2	107.2	C12—C13—N2	110.3 (3)
O1—C1—O2	123.0 (3)	C12—C13—H13A	109.6
O1—C1—C2	118.8 (3)	N2—C13—H13A	109.6
O2—C1—C2	118.2 (3)	C12—C13—H13B	109.6
C7—C2—C3	118.2 (3)	N2—C13—H13B	109.6
C7—C2—C1	120.1 (3)	H13A—C13—H13B	108.1
C3—C2—C1	121.7 (3)	N2—C14—C15	110.6 (2)
O3—C3—C4	119.4 (3)	N2—C14—H14A	109.5
O3—C3—C2	120.1 (3)	C15—C14—H14A	109.5
C4—C3—C2	120.6 (3)	N2—C14—H14B	109.5
C3—C4—C5	121.3 (3)	C15—C14—H14B	109.5
C3—C4—H4	119.4	H14A—C14—H14B	108.1
C5—C4—H4	119.4	N1—C15—C14	111.0 (2)
C4—C5—C8	123.2 (3)	N1—C15—H15A	109.4
C4—C5—C6	119.2 (3)	C14—C15—H15A	109.4
C8—C5—C6	117.6 (3)	N1—C15—H15B	109.4
C11—C6—C7	122.5 (3)	C14—C15—H15B	109.4
C11—C6—C5	119.6 (3)	H15A—C15—H15B	108.0
C7—C6—C5	117.9 (3)	N1—C16—H16A	109.5
C2—C7—C6	122.8 (3)	N1—C16—H16B	109.5
C2—C7—H7	118.6	H16A—C16—H16B	109.5
C6—C7—H7	118.6	N1—C16—H16C	109.5
C9—C8—C5	120.8 (4)	H16A—C16—H16C	109.5
C9—C8—H8	119.6	H16B—C16—H16C	109.5
C5—C8—H8	119.6	N2—C17—H17A	109.5
C8—C9—C10	121.7 (3)	N2—C17—H17B	109.5
C8—C9—H9	119.2	H17A—C17—H17B	109.5
C10—C9—H9	119.2	N2—C17—H17C	109.5
C11—C10—C9	119.2 (4)	H17A—C17—H17C	109.5
C11—C10—H10	120.4	H17B—C17—H17C	109.5
C9—C10—H10	120.4
O1—C1—C2—C7	−2.5 (5)	C5—C6—C7—C2	−1.4 (4)
O2—C1—C2—C7	177.8 (3)	C4—C5—C8—C9	−179.6 (3)
O1—C1—C2—C3	176.7 (3)	C6—C5—C8—C9	1.2 (5)
O2—C1—C2—C3	−3.0 (4)	C5—C8—C9—C10	−1.8 (6)
C7—C2—C3—O3	−178.2 (3)	C8—C9—C10—C11	0.9 (6)
C1—C2—C3—O3	2.6 (4)	C9—C10—C11—C6	0.5 (6)
C7—C2—C3—C4	0.6 (4)	C7—C6—C11—C10	178.0 (3)
C1—C2—C3—C4	−178.6 (3)	C5—C6—C11—C10	−1.0 (5)
O3—C3—C4—C5	178.8 (3)	C16—N1—C12—C13	−176.1 (3)
C2—C3—C4—C5	−0.1 (4)	C15—N1—C12—C13	60.9 (3)
C3—C4—C5—C8	179.6 (3)	N1—C12—C13—N2	−58.3 (4)
C3—C4—C5—C6	−1.2 (4)	C14—N2—C13—C12	54.3 (3)
C4—C5—C6—C11	−179.0 (3)	C17—N2—C13—C12	−179.6 (3)
C8—C5—C6—C11	0.2 (4)	C17—N2—C14—C15	−179.8 (3)
C4—C5—C6—C7	1.9 (4)	C13—N2—C14—C15	−54.0 (3)
C8—C5—C6—C7	−178.9 (3)	C12—N1—C15—C14	−60.2 (3)
C3—C2—C7—C6	0.1 (4)	C16—N1—C15—C14	175.6 (3)
C1—C2—C7—C6	179.3 (3)	N2—C14—C15—N1	57.8 (3)
C11—C6—C7—C2	179.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.81	2.541 (3)	148
N2—H2···O1i	0.91	1.71	2.613 (3)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.81	2.541 (3)	148
N2—H2⋯O1i	0.91	1.71	2.613 (3)	174

Symmetry code: (i) .