Piperazinediium bis-(2-carboxy-pyridine-3-carboxyl-ate).

The asymmetric unit of the title salt, C(4)H(12)N(2) (2+)·2C(7)H(4)NO(4) (-) or pipzH(2) (2+)·2(py-2,3-dcH(-)), prepared by a reaction between pyridine-2,3-dicarboxylic acid (py-2,3-dcH(2)) and piperazine (pipz), contains a monoanion and half of a centrosymmetric dication. The anionic fragment individually has two intra-molecular hydrogen bonds, an almost linear O-H⋯O bond between two carboxyl-ate groups and a C-H⋯O bond between the aromatic ring and carboxyl-ate group. Other O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds are responsible for three-dimensional expansion of the structure.

Related literature

For related literature, see: Aghabozorg et al. (2006 ▶); Aghabozorg, Daneshvar et al. (2007 ▶); Aghabozorg, Sadr-khanlou et al. (2007 ▶); Khalil & Attia (1999 ▶); Manteghi et al. (2007 ▶).

Experimental

Crystal data

C4H12N2 2+·2C7H4NO4 −

M = 420.38

Monoclinic,

a = 8.0116 (6) Å

b = 11.0588 (9) Å

c = 10.4621 (7) Å

β = 106.574 (2)°

V = 888.42 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 100 (2) K

0.20 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: none

6962 measured reflections

2341 independent reflections

2104 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.03

2341 reflections

136 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 1998 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Version 1.4.2; Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065002/om2187sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065002/om2187Isup2.hkl

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

C4H12N22+·2C7H4NO4−	F(000) = 440
Mr = 420.38	Dx = 1.571 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2095 reflections
a = 8.0116 (6) Å	θ = 2.7–28.6°
b = 11.0588 (9) Å	µ = 0.13 mm−1
c = 10.4621 (7) Å	T = 100 K
β = 106.574 (2)°	Prism, colourless
V = 888.42 (11) Å3	0.20 × 0.15 × 0.15 mm
Z = 2

Bruker SMART APEXII diffractometer	2104 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
graphite	θmax = 29.0°, θmin = 2.7°
φ and ω scans	h = −10→10
6962 measured reflections	k = −15→15
2341 independent reflections	l = −14→12

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)] = 0.034	Hydrogen site location: mixed
wR(F2) = 0.084	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.035P)2 + 0.450P] where P = (Fo2 + 2Fc2)/3
2341 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.22 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
O1	0.88615 (11)	0.17340 (7)	0.51531 (8)	0.02036 (18)
O2	0.98274 (10)	0.08122 (7)	0.70930 (8)	0.02041 (18)
O3	0.72179 (11)	0.13267 (7)	0.28657 (8)	0.02033 (18)
H3O	0.7842	0.1467	0.3657	0.030*
O4	0.54664 (10)	−0.00934 (8)	0.17740 (8)	0.02126 (18)
N1	0.77161 (11)	−0.10247 (8)	0.63974 (9)	0.01409 (18)
N2	0.98062 (11)	0.40793 (8)	0.59237 (8)	0.01352 (17)
H2A	1.0047	0.4441	0.6726	0.016*
H2B	0.9555	0.3300	0.6036	0.016*
C1	0.76624 (12)	−0.02324 (8)	0.54104 (10)	0.01174 (18)
C2	0.65530 (12)	−0.04141 (9)	0.41030 (10)	0.01209 (19)
C3	0.54476 (13)	−0.14260 (9)	0.39063 (10)	0.0147 (2)
H3A	0.4655	−0.1565	0.3052	0.018*
C4	0.54919 (13)	−0.22223 (9)	0.49329 (11)	0.0161 (2)
H4A	0.4736	−0.2902	0.4802	0.019*
C5	0.66802 (14)	−0.19939 (9)	0.61616 (10)	0.0160 (2)
H5A	0.6760	−0.2552	0.6867	0.019*
C6	0.88903 (13)	0.08412 (9)	0.59330 (10)	0.01317 (19)
C7	0.63871 (13)	0.03075 (9)	0.28268 (10)	0.01448 (19)
C8	1.13286 (13)	0.40868 (9)	0.53727 (10)	0.0146 (2)
H8A	1.1067	0.3580	0.4560	0.018*
H8B	1.2353	0.3736	0.6036	0.018*
C9	0.82508 (13)	0.46401 (9)	0.49653 (10)	0.0147 (2)
H9A	0.7270	0.4659	0.5365	0.018*
H9B	0.7892	0.4149	0.4141	0.018*

	U11	U22	U33	U12	U13	U23
O1	0.0283 (4)	0.0139 (3)	0.0167 (4)	−0.0056 (3)	0.0029 (3)	0.0024 (3)
O2	0.0234 (4)	0.0200 (4)	0.0146 (4)	−0.0074 (3)	0.0003 (3)	0.0013 (3)
O3	0.0268 (4)	0.0184 (4)	0.0135 (3)	−0.0025 (3)	0.0021 (3)	0.0034 (3)
O4	0.0197 (4)	0.0294 (4)	0.0129 (4)	−0.0027 (3)	0.0019 (3)	0.0005 (3)
N1	0.0165 (4)	0.0130 (4)	0.0133 (4)	0.0001 (3)	0.0051 (3)	0.0006 (3)
N2	0.0147 (4)	0.0136 (4)	0.0120 (4)	−0.0018 (3)	0.0033 (3)	0.0006 (3)
C1	0.0120 (4)	0.0110 (4)	0.0129 (4)	0.0007 (3)	0.0047 (3)	−0.0008 (3)
C2	0.0119 (4)	0.0128 (4)	0.0123 (4)	0.0023 (3)	0.0047 (3)	−0.0005 (3)
C3	0.0124 (4)	0.0162 (4)	0.0158 (5)	0.0002 (3)	0.0044 (4)	−0.0040 (4)
C4	0.0160 (4)	0.0131 (4)	0.0209 (5)	−0.0022 (3)	0.0082 (4)	−0.0034 (4)
C5	0.0202 (5)	0.0125 (4)	0.0171 (5)	−0.0004 (4)	0.0084 (4)	0.0011 (4)
C6	0.0136 (4)	0.0123 (4)	0.0145 (4)	−0.0005 (3)	0.0054 (3)	−0.0009 (3)
C7	0.0130 (4)	0.0181 (5)	0.0128 (4)	0.0035 (3)	0.0044 (3)	0.0017 (4)
C8	0.0143 (4)	0.0156 (4)	0.0143 (4)	0.0032 (3)	0.0046 (4)	0.0000 (3)
C9	0.0113 (4)	0.0181 (5)	0.0138 (4)	−0.0013 (3)	0.0023 (3)	0.0003 (4)

O1—C6	1.2769 (12)	C2—C3	1.4053 (14)
O2—C6	1.2319 (12)	C2—C7	1.5284 (14)
O3—C7	1.3036 (13)	C3—C4	1.3815 (15)
O3—H3O	0.8501	C3—H3A	0.9500
O4—C7	1.2209 (13)	C4—C5	1.3872 (15)
N1—C5	1.3348 (13)	C4—H4A	0.9500
N1—C1	1.3456 (12)	C5—H5A	0.9500
N2—C8	1.4903 (13)	C8—C9i	1.5129 (14)
N2—C9	1.4933 (13)	C8—H8A	0.9900
N2—H2A	0.9000	C8—H8B	0.9900
N2—H2B	0.9000	C9—C8i	1.5129 (14)
C1—C2	1.4169 (13)	C9—H9A	0.9900
C1—C6	1.5394 (13)	C9—H9B	0.9900
C7—O3—H3O	110.0	N1—C5—H5A	118.5
C5—N1—C1	119.93 (9)	C4—C5—H5A	118.5
C8—N2—C9	110.87 (7)	O2—C6—O1	122.99 (9)
C8—N2—H2A	112.1	O2—C6—C1	118.55 (9)
C9—N2—H2A	110.9	O1—C6—C1	118.44 (9)
C8—N2—H2B	107.1	O4—C7—O3	120.92 (9)
C9—N2—H2B	108.1	O4—C7—C2	118.56 (9)
H2A—N2—H2B	107.5	O3—C7—C2	120.51 (9)
N1—C1—C2	121.50 (9)	N2—C8—C9i	110.92 (8)
N1—C1—C6	110.63 (8)	N2—C8—H8A	109.5
C2—C1—C6	127.85 (9)	C9i—C8—H8A	109.5
C3—C2—C1	116.74 (9)	N2—C8—H8B	109.5
C3—C2—C7	113.19 (8)	C9i—C8—H8B	109.5
C1—C2—C7	130.06 (9)	H8A—C8—H8B	108.0
C4—C3—C2	121.22 (9)	N2—C9—C8i	110.15 (8)
C4—C3—H3A	119.4	N2—C9—H9A	109.6
C2—C3—H3A	119.4	C8i—C9—H9A	109.6
C3—C4—C5	117.58 (9)	N2—C9—H9B	109.6
C3—C4—H4A	121.2	C8i—C9—H9B	109.6
C5—C4—H4A	121.2	H9A—C9—H9B	108.1
N1—C5—C4	122.94 (9)
C5—N1—C1—C2	−1.52 (14)	N1—C1—C6—O2	5.34 (13)
C5—N1—C1—C6	176.91 (9)	C2—C1—C6—O2	−176.36 (10)
N1—C1—C2—C3	3.28 (14)	N1—C1—C6—O1	−173.07 (9)
C6—C1—C2—C3	−174.85 (9)	C2—C1—C6—O1	5.23 (15)
N1—C1—C2—C7	−174.82 (9)	C3—C2—C7—O4	−6.01 (13)
C6—C1—C2—C7	7.04 (16)	C1—C2—C7—O4	172.15 (10)
C1—C2—C3—C4	−2.13 (14)	C3—C2—C7—O3	174.22 (9)
C7—C2—C3—C4	176.30 (9)	C1—C2—C7—O3	−7.62 (16)
C2—C3—C4—C5	−0.66 (15)	C9—N2—C8—C9i	57.28 (11)
C1—N1—C5—C4	−1.56 (15)	C8—N2—C9—C8i	−56.84 (11)
C3—C4—C5—N1	2.64 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.85	1.57	2.4219 (11)	175
N2—H2A···O2ii	0.90	1.94	2.7778 (12)	154
N2—H2B···O1	0.90	1.97	2.7571 (11)	146
C3—H3A···O4	0.95	2.31	2.6773 (13)	102
C8—H8A···O2iii	0.99	2.58	3.2982 (13)	130
C9—H9A···O4iv	0.99	2.39	3.3491 (14)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1	0.85	1.57	2.4219 (11)	175
N2—H2A⋯O2i	0.90	1.94	2.7778 (12)	154
N2—H2B⋯O1	0.90	1.97	2.7571 (11)	146
C3—H3A⋯O4	0.95	2.31	2.6773 (13)	102
C8—H8A⋯O2ii	0.99	2.58	3.2982 (13)	130
C9—H9A⋯O4iii	0.99	2.39	3.3491 (14)	163

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