2,2'-(Piperazine-1,4-di-yl)diethanaminium bis-(2-hy-droxy-benzoate).

The asymmetric unit of the title salt, C(8)H(22)N(4) (2+)·2C(7)H(5)O(3) (-), comprises half a 2,2'-(piperazine-1,4-di-yl)diethan-aminium dication plus a 2-hy-droxy-benzoate anion. In the crystal, the anions and cations are linked by N-H⋯O and O-H⋯O hydrogen bonds to form infinite two-dimensional networks parallel with the a unit-cell face. The conformation adopted by the cation in the crystal is very similar to that adopted by the same cation in the structures of the nitrate and tetra-hydrogen penta-borate salts.

Related literature

For the structures of the nitrate and tetra­hydrogen penta­borate salts of the 1,4-di(2-ammonio­eth­yl)piperazine cation, see: Junk & Smith (2005 ▶); Jiang et al. (2009 ▶); Yang et al. (2011 ▶).

Experimental

Crystal data

C8H22N4 2+·2C7H5O3 −

M = 448.52

Monoclinic,

a = 11.5374 (4) Å

b = 6.4759 (2) Å

c = 15.5264 (6) Å

β = 104.207 (2)°

V = 1124.58 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 180 K

0.37 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.852, T max = 0.995

19655 measured reflections

3261 independent reflections

2013 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.147

S = 1.08

3261 reflections

157 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.28 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶), SCALEPACK and SORTAV (Blessing, 1995 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶), POV-RAY (Cason, 2004 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030103/jj2133sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030103/jj2133Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812030103/jj2133Isup3.cml

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

C8H22N42+·2C7H5O3−	F(000) = 480
Mr = 448.52	Dx = 1.325 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26933 reflections
a = 11.5374 (4) Å	θ = 1.0–30.0°
b = 6.4759 (2) Å	µ = 0.10 mm−1
c = 15.5264 (6) Å	T = 180 K
β = 104.207 (2)°	Block, yellow
V = 1124.58 (7) Å3	0.37 × 0.10 × 0.05 mm
Z = 2

Nonius KappaCCD diffractometer	3261 independent reflections
Radiation source: fine-focus sealed tube	2013 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Thin slice ω and φ scans	θmax = 30.0°, θmin = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −16→16
Tmin = 0.852, Tmax = 0.995	k = −8→9
19655 measured reflections	l = −21→21

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F2) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0714P)2 + 0.0149P] where P = (Fo2 + 2Fc2)/3
3261 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Experimental. The –OH and –NH3 hydrogen atoms were located and their positions were refined satisfactorily.

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
N1	0.39360 (12)	0.1995 (2)	0.71495 (9)	0.0296 (3)
H1A	0.4724 (16)	0.215 (2)	0.7117 (11)	0.036*
H1B	0.3890 (14)	0.076 (3)	0.7403 (10)	0.036*
H1C	0.3822 (14)	0.299 (3)	0.7516 (11)	0.036*
C2	0.30579 (14)	0.2076 (2)	0.62703 (10)	0.0355 (4)
H2A	0.2242	0.1866	0.6352	0.043*
H2B	0.3228	0.0945	0.5890	0.043*
C3	0.31138 (13)	0.4123 (2)	0.58149 (11)	0.0328 (4)
H3A	0.2467	0.4186	0.5262	0.039*
H3B	0.2985	0.5257	0.6209	0.039*
N4	0.42749 (11)	0.44057 (19)	0.55982 (8)	0.0321 (3)
C5	0.43393 (14)	0.3166 (2)	0.48157 (11)	0.0350 (4)
H5A	0.3691	0.3593	0.4302	0.042*
H5B	0.4219	0.1691	0.4937	0.042*
C6	0.44661 (14)	0.6567 (2)	0.54111 (10)	0.0332 (4)
H6A	0.4446	0.7419	0.5937	0.040*
H6B	0.3817	0.7044	0.4907	0.040*
C7	0.80219 (12)	0.2749 (2)	0.66915 (9)	0.0261 (3)
C8	0.84808 (13)	0.4670 (2)	0.70044 (10)	0.0307 (3)
H8	0.8129	0.5394	0.7408	0.037*
C9	0.94297 (13)	0.5555 (2)	0.67466 (11)	0.0356 (4)
H9	0.9731	0.6863	0.6973	0.043*
C10	0.99343 (14)	0.4510 (3)	0.61536 (11)	0.0390 (4)
H10	1.0584	0.5111	0.5968	0.047*
C11	0.95065 (15)	0.2608 (3)	0.58287 (11)	0.0381 (4)
H11	0.9861	0.1908	0.5420	0.046*
C12	0.85550 (13)	0.1702 (2)	0.60957 (10)	0.0306 (3)
C13	0.69936 (13)	0.1830 (2)	0.69894 (9)	0.0273 (3)
O14	0.64524 (9)	0.28943 (15)	0.74448 (7)	0.0321 (3)
O15	0.67079 (11)	−0.00229 (16)	0.67621 (7)	0.0393 (3)
O16	0.81677 (11)	−0.01682 (18)	0.57563 (8)	0.0418 (3)
H16	0.7652 (17)	−0.055 (3)	0.5996 (14)	0.050*

	U11	U22	U33	U12	U13	U23
N1	0.0299 (7)	0.0264 (7)	0.0360 (7)	−0.0006 (6)	0.0145 (6)	0.0013 (6)
C2	0.0369 (8)	0.0391 (9)	0.0326 (8)	−0.0098 (7)	0.0124 (7)	−0.0004 (7)
C3	0.0312 (8)	0.0365 (9)	0.0327 (8)	0.0006 (7)	0.0115 (6)	0.0030 (7)
N4	0.0301 (7)	0.0310 (7)	0.0359 (7)	−0.0020 (5)	0.0091 (5)	0.0064 (6)
C5	0.0381 (8)	0.0336 (8)	0.0345 (9)	−0.0029 (7)	0.0111 (7)	0.0020 (7)
C6	0.0362 (8)	0.0299 (8)	0.0339 (8)	0.0013 (7)	0.0094 (7)	0.0017 (7)
C7	0.0249 (7)	0.0260 (7)	0.0270 (7)	0.0011 (6)	0.0057 (6)	0.0028 (6)
C8	0.0265 (7)	0.0302 (8)	0.0359 (8)	0.0007 (6)	0.0084 (6)	−0.0030 (7)
C9	0.0298 (8)	0.0322 (8)	0.0435 (9)	−0.0052 (7)	0.0068 (7)	0.0011 (7)
C10	0.0289 (8)	0.0464 (10)	0.0434 (9)	−0.0028 (7)	0.0123 (7)	0.0066 (8)
C11	0.0355 (8)	0.0446 (10)	0.0387 (9)	0.0066 (7)	0.0180 (7)	0.0010 (7)
C12	0.0332 (8)	0.0278 (7)	0.0309 (8)	0.0021 (6)	0.0076 (6)	0.0013 (6)
C13	0.0294 (7)	0.0254 (7)	0.0266 (7)	−0.0011 (6)	0.0061 (6)	0.0025 (6)
O14	0.0321 (6)	0.0299 (6)	0.0379 (6)	0.0002 (4)	0.0154 (5)	−0.0010 (5)
O15	0.0528 (7)	0.0291 (6)	0.0409 (6)	−0.0125 (5)	0.0210 (5)	−0.0062 (5)
O16	0.0532 (8)	0.0314 (6)	0.0466 (7)	−0.0046 (5)	0.0234 (6)	−0.0111 (5)

N1—C2	1.488 (2)	C6—H6B	0.9900
N1—H1A	0.929 (17)	C7—C8	1.392 (2)
N1—H1B	0.900 (18)	C7—C12	1.404 (2)
N1—H1C	0.892 (18)	C7—C13	1.498 (2)
C2—C3	1.511 (2)	C8—C9	1.379 (2)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C9—C10	1.381 (2)
C3—N4	1.4706 (19)	C9—H9	0.9500
C3—H3A	0.9900	C10—C11	1.376 (2)
C3—H3B	0.9900	C10—H10	0.9500
N4—C6	1.4572 (19)	C11—C12	1.394 (2)
N4—C5	1.473 (2)	C11—H11	0.9500
C5—C6i	1.514 (2)	C12—O16	1.3524 (18)
C5—H5A	0.9900	C13—O14	1.2575 (17)
C5—H5B	0.9900	C13—O15	1.2714 (17)
C6—C5i	1.514 (2)	O16—H16	0.81 (2)
C6—H6A	0.9900
C2—N1—H1A	113.7 (10)	N4—C6—H6A	109.6
C2—N1—H1B	109.4 (10)	C5i—C6—H6A	109.6
H1A—N1—H1B	106.6 (14)	N4—C6—H6B	109.6
C2—N1—H1C	112.7 (10)	C5i—C6—H6B	109.6
H1A—N1—H1C	104.7 (15)	H6A—C6—H6B	108.1
H1B—N1—H1C	109.4 (15)	C8—C7—C12	118.06 (14)
N1—C2—C3	111.24 (13)	C8—C7—C13	120.61 (13)
N1—C2—H2A	109.4	C12—C7—C13	121.33 (13)
C3—C2—H2A	109.4	C9—C8—C7	122.09 (14)
N1—C2—H2B	109.4	C9—C8—H8	119.0
C3—C2—H2B	109.4	C7—C8—H8	119.0
H2A—C2—H2B	108.0	C8—C9—C10	118.95 (15)
N4—C3—C2	111.24 (12)	C8—C9—H9	120.5
N4—C3—H3A	109.4	C10—C9—H9	120.5
C2—C3—H3A	109.4	C11—C10—C9	120.74 (15)
N4—C3—H3B	109.4	C11—C10—H10	119.6
C2—C3—H3B	109.4	C9—C10—H10	119.6
H3A—C3—H3B	108.0	C10—C11—C12	120.36 (15)
C6—N4—C3	110.87 (12)	C10—C11—H11	119.8
C6—N4—C5	108.55 (12)	C12—C11—H11	119.8
C3—N4—C5	110.73 (11)	O16—C12—C11	118.04 (14)
N4—C5—C6i	111.26 (12)	O16—C12—C7	122.17 (13)
N4—C5—H5A	109.4	C11—C12—C7	119.79 (14)
C6i—C5—H5A	109.4	O14—C13—O15	122.86 (13)
N4—C5—H5B	109.4	O14—C13—C7	119.76 (13)
C6i—C5—H5B	109.4	O15—C13—C7	117.39 (13)
H5A—C5—H5B	108.0	C12—O16—H16	107.4 (14)
N4—C6—C5i	110.31 (13)
N1—C2—C3—N4	64.77 (17)	C9—C10—C11—C12	−0.1 (2)
C2—C3—N4—C6	−162.96 (13)	C10—C11—C12—O16	179.96 (14)
C2—C3—N4—C5	76.48 (16)	C10—C11—C12—C7	0.7 (2)
C6—N4—C5—C6i	58.44 (17)	C8—C7—C12—O16	−179.88 (13)
C3—N4—C5—C6i	−179.64 (12)	C13—C7—C12—O16	0.5 (2)
C3—N4—C6—C5i	−179.69 (12)	C8—C7—C12—C11	−0.7 (2)
C5—N4—C6—C5i	−57.85 (17)	C13—C7—C12—C11	179.64 (13)
C12—C7—C8—C9	0.1 (2)	C8—C7—C13—O14	8.1 (2)
C13—C7—C8—C9	179.72 (13)	C12—C7—C13—O14	−172.27 (13)
C7—C8—C9—C10	0.5 (2)	C8—C7—C13—O15	−172.00 (13)
C8—C9—C10—C11	−0.5 (2)	C12—C7—C13—O15	7.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O14	0.929 (17)	1.992 (18)	2.8853 (17)	160.9 (14)
N1—H1B···O14ii	0.900 (18)	1.923 (19)	2.7909 (17)	161.5 (14)
N1—H1C···O15iii	0.892 (18)	1.902 (19)	2.7843 (17)	169.9 (15)
O16—H16···O15	0.81 (2)	1.83 (2)	2.5641 (16)	149.4 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O14	0.929 (17)	1.992 (18)	2.8853 (17)	160.9 (14)
N1—H1B⋯O14i	0.900 (18)	1.923 (19)	2.7909 (17)	161.5 (14)
N1—H1C⋯O15ii	0.892 (18)	1.902 (19)	2.7843 (17)	169.9 (15)
O16—H16⋯O15	0.81 (2)	1.83 (2)	2.5641 (16)	149.4 (19)

Symmetry codes: (i) ; (ii) .