Piperazine-1,4-diium pyridine-2,3-dicarboxyl-ate methanol monosolvate.

The title solvated molecular salt, C(4)H(12)N(2) (2+)·C(7)H(3)NO(4) (2-)·CH(3)OH or (pipzH(2))(py-2,3-dc)·MeOH, was prepared by the reaction of pyridine-2,3-dicarb-oxy-lic acid (py-2,3-dcH(2)) and piperazine (pipz) in methanol (MeOH) as solvent. One of the two carboxylate groups of the acid fragment is nearly perpendicular to the pyridine ring and the other is almost in its plane [C-C-C-O torsion angles = -85.50 (11) and 88.07 (11)° and N-C-C-O torsion angles = -176.31 (8) and 5.41 (13)°]. In the crystal, the components are linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For similar ion pairs, see: Aghabozorg, Manteghi & Ghadermazi (2008 ▶); Aghabozorg, Manteghi & Sheshmani (2008 ▶). For related metal complexes, see: Barszcz et al. (2010 ▶); Li & Li (2004 ▶).

Experimental

Crystal data

C4H12N2 2+·C7H3NO4 2−·CH4O

M = 285.30

Monoclinic,

a = 8.2541 (6) Å

b = 11.8988 (8) Å

c = 13.8197 (9) Å

β = 90.288 (2)°

V = 1357.27 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.25 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEXII diffractometer

16044 measured reflections

3579 independent reflections

3189 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.085

S = 1.03

3579 reflections

182 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012384/om2416sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012384/om2416Isup2.hkl

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

C4H12N22+·C7H3NO42−·CH4O	F(000) = 608
Mr = 285.30	Dx = 1.396 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7483 reflections
a = 8.2541 (6) Å	θ = 2.3–28.1°
b = 11.8988 (8) Å	µ = 0.11 mm−1
c = 13.8197 (9) Å	T = 100 K
β = 90.288 (2)°	Prism, colourless
V = 1357.27 (16) Å3	0.25 × 0.20 × 0.10 mm
Z = 4

Bruker SMART APEXII diffractometer	3189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
graphite	θmax = 29.0°, θmin = 2.3°
Detector resolution: 8.3 pixels mm-1	h = −11→11
φ and ω scans	k = −16→16
16044 measured reflections	l = −18→18
3579 independent reflections

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: difference Fourier map
wR(F2) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.035P)2 + 0.650P] where P = (Fo2 + 2Fc2)/3
3579 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.21 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	0.16285 (8)	0.76486 (6)	0.03344 (5)	0.01401 (15)
O2	0.21626 (9)	0.91599 (6)	0.12414 (6)	0.01918 (16)
O3	−0.13943 (9)	0.61040 (6)	0.03291 (5)	0.01666 (16)
O4	−0.11791 (9)	0.70279 (6)	−0.10648 (5)	0.01627 (15)
N1	−0.09833 (10)	0.97903 (7)	0.11968 (6)	0.01339 (17)
N2	0.17152 (10)	1.11819 (7)	0.21302 (6)	0.01264 (16)
H2A	0.1410	1.1746	0.1735	0.015*
H2B	0.1538	1.0523	0.1828	0.015*
N3	0.31476 (10)	1.05117 (7)	0.39424 (6)	0.01304 (16)
H3A	0.3349	1.1189	0.4206	0.016*
H3B	0.3473	0.9987	0.4371	0.016*
C1	−0.05754 (11)	0.88142 (8)	0.07675 (6)	0.01078 (17)
C2	−0.17210 (11)	0.80866 (8)	0.03586 (7)	0.01165 (18)
C3	−0.33567 (12)	0.83780 (9)	0.04316 (7)	0.01506 (19)
H3	−0.4169	0.7896	0.0175	0.018*
C4	−0.37860 (12)	0.93756 (9)	0.08809 (7)	0.0166 (2)
H4	−0.4891	0.9585	0.0943	0.020*
C5	−0.25545 (12)	1.00615 (9)	0.12379 (7)	0.01563 (19)
H5	−0.2845	1.0758	0.1525	0.019*
C6	0.12243 (11)	0.85332 (8)	0.07816 (7)	0.01183 (18)
C7	−0.13540 (11)	0.69936 (8)	−0.01603 (7)	0.01243 (18)
C8	0.07828 (12)	1.12692 (9)	0.30451 (7)	0.01538 (19)
H8A	−0.0383	1.1149	0.2908	0.018*
H8B	0.0914	1.2032	0.3320	0.018*
C9	0.34843 (12)	1.13038 (8)	0.23146 (7)	0.01367 (18)
H9A	0.3709	1.2059	0.2584	0.016*
H9B	0.4080	1.1231	0.1698	0.016*
C10	0.40670 (12)	1.04139 (8)	0.30194 (7)	0.01438 (19)
H10A	0.3901	0.9658	0.2737	0.017*
H10B	0.5239	1.0513	0.3148	0.017*
C11	0.13684 (12)	1.04015 (9)	0.37760 (7)	0.0162 (2)
H11A	0.0790	1.0508	0.4395	0.019*
H11B	0.1121	0.9637	0.3533	0.019*
O5	0.39165 (9)	0.71135 (8)	−0.09625 (6)	0.02485 (19)
H5A	0.3255	0.7344	−0.0537	0.037*
C12	0.29401 (15)	0.65794 (12)	−0.16692 (9)	0.0302 (3)
H1A	0.3427	0.6679	−0.2309	0.045*
H1B	0.1855	0.6913	−0.1667	0.045*
H1C	0.2861	0.5776	−0.1522	0.045*

	U11	U22	U33	U12	U13	U23
O1	0.0156 (3)	0.0103 (3)	0.0162 (3)	0.0017 (2)	0.0019 (3)	−0.0011 (3)
O2	0.0139 (3)	0.0188 (4)	0.0248 (4)	0.0001 (3)	−0.0031 (3)	−0.0083 (3)
O3	0.0236 (4)	0.0110 (3)	0.0153 (3)	−0.0009 (3)	−0.0041 (3)	0.0011 (3)
O4	0.0233 (4)	0.0130 (3)	0.0124 (3)	0.0028 (3)	−0.0019 (3)	−0.0007 (3)
N1	0.0154 (4)	0.0117 (4)	0.0130 (4)	0.0005 (3)	0.0011 (3)	−0.0010 (3)
N2	0.0152 (4)	0.0111 (4)	0.0116 (4)	0.0003 (3)	−0.0022 (3)	0.0000 (3)
N3	0.0168 (4)	0.0105 (4)	0.0118 (4)	−0.0007 (3)	−0.0025 (3)	0.0007 (3)
C1	0.0128 (4)	0.0103 (4)	0.0093 (4)	0.0003 (3)	0.0007 (3)	0.0009 (3)
C2	0.0143 (4)	0.0109 (4)	0.0097 (4)	0.0003 (3)	−0.0006 (3)	0.0008 (3)
C3	0.0135 (4)	0.0173 (5)	0.0144 (4)	−0.0005 (3)	−0.0013 (3)	−0.0005 (4)
C4	0.0134 (4)	0.0201 (5)	0.0163 (4)	0.0037 (4)	0.0002 (3)	0.0002 (4)
C5	0.0181 (5)	0.0136 (4)	0.0152 (4)	0.0032 (4)	0.0023 (3)	−0.0016 (3)
C6	0.0132 (4)	0.0111 (4)	0.0112 (4)	0.0005 (3)	0.0006 (3)	0.0015 (3)
C7	0.0117 (4)	0.0115 (4)	0.0141 (4)	0.0001 (3)	−0.0035 (3)	−0.0015 (3)
C8	0.0142 (4)	0.0172 (5)	0.0148 (4)	0.0009 (4)	0.0003 (3)	0.0002 (4)
C9	0.0142 (4)	0.0137 (4)	0.0132 (4)	−0.0004 (3)	−0.0002 (3)	0.0007 (3)
C10	0.0154 (4)	0.0146 (4)	0.0130 (4)	0.0021 (3)	−0.0011 (3)	−0.0002 (3)
C11	0.0160 (5)	0.0168 (5)	0.0159 (4)	−0.0040 (4)	−0.0006 (3)	0.0028 (4)
O5	0.0159 (4)	0.0345 (5)	0.0242 (4)	−0.0027 (3)	0.0035 (3)	−0.0117 (3)
C12	0.0239 (6)	0.0398 (7)	0.0269 (6)	−0.0016 (5)	0.0002 (5)	−0.0160 (5)

O1—C6	1.2662 (12)	C3—H3	0.9500
O2—C6	1.2469 (12)	C4—C5	1.3920 (14)
O3—C7	1.2566 (12)	C4—H4	0.9500
O4—C7	1.2597 (12)	C5—H5	0.9500
N1—C5	1.3379 (13)	C8—C11	1.5215 (14)
N1—C1	1.3477 (12)	C8—H8A	0.9900
N2—C8	1.4871 (12)	C8—H8B	0.9900
N2—C9	1.4881 (12)	C9—C10	1.5155 (13)
N2—H2A	0.9001	C9—H9A	0.9900
N2—H2B	0.9001	C9—H9B	0.9900
N3—C11	1.4911 (13)	C10—H10A	0.9900
N3—C10	1.4920 (12)	C10—H10B	0.9900
N3—H3A	0.9000	C11—H11A	0.9900
N3—H3B	0.9001	C11—H11B	0.9900
C1—C2	1.3992 (13)	O5—C12	1.4139 (14)
C1—C6	1.5227 (13)	O5—H5A	0.8500
C2—C3	1.3981 (13)	C12—H1A	0.9800
C2—C7	1.5164 (13)	C12—H1B	0.9800
C3—C4	1.3864 (14)	C12—H1C	0.9800
C5—N1—C1	118.09 (8)	O4—C7—C2	117.75 (8)
C8—N2—C9	111.05 (7)	N2—C8—C11	110.67 (8)
C8—N2—H2A	108.6	N2—C8—H8A	109.5
C9—N2—H2A	107.6	C11—C8—H8A	109.5
C8—N2—H2B	111.9	N2—C8—H8B	109.5
C9—N2—H2B	108.8	C11—C8—H8B	109.5
H2A—N2—H2B	108.9	H8A—C8—H8B	108.1
C11—N3—C10	111.47 (7)	N2—C9—C10	110.48 (8)
C11—N3—H3A	108.7	N2—C9—H9A	109.6
C10—N3—H3A	108.9	C10—C9—H9A	109.6
C11—N3—H3B	109.3	N2—C9—H9B	109.6
C10—N3—H3B	110.9	C10—C9—H9B	109.6
H3A—N3—H3B	107.5	H9A—C9—H9B	108.1
N1—C1—C2	122.77 (9)	N3—C10—C9	109.50 (8)
N1—C1—C6	115.44 (8)	N3—C10—H10A	109.8
C2—C1—C6	121.77 (8)	C9—C10—H10A	109.8
C3—C2—C1	117.92 (9)	N3—C10—H10B	109.8
C3—C2—C7	116.24 (8)	C9—C10—H10B	109.8
C1—C2—C7	125.84 (8)	H10A—C10—H10B	108.2
C4—C3—C2	119.59 (9)	N3—C11—C8	110.61 (8)
C4—C3—H3	120.2	N3—C11—H11A	109.5
C2—C3—H3	120.2	C8—C11—H11A	109.5
C3—C4—C5	118.22 (9)	N3—C11—H11B	109.5
C3—C4—H4	120.9	C8—C11—H11B	109.5
C5—C4—H4	120.9	H11A—C11—H11B	108.1
N1—C5—C4	123.36 (9)	C12—O5—H5A	104.9
N1—C5—H5	118.3	O5—C12—H1A	109.5
C4—C5—H5	118.3	O5—C12—H1B	109.5
O2—C6—O1	125.55 (9)	H1A—C12—H1B	109.5
O2—C6—C1	118.59 (8)	O5—C12—H1C	109.5
O1—C6—C1	115.84 (8)	H1A—C12—H1C	109.5
O3—C7—O4	124.39 (9)	H1B—C12—H1C	109.5
O3—C7—C2	117.52 (8)
C5—N1—C1—C2	0.66 (14)	N1—C1—C6—O1	−176.31 (8)
C5—N1—C1—C6	−177.60 (8)	C2—C1—C6—O1	5.41 (13)
N1—C1—C2—C3	−2.12 (14)	C3—C2—C7—O3	−85.50 (11)
C6—C1—C2—C3	176.03 (8)	C1—C2—C7—O3	94.23 (12)
N1—C1—C2—C7	178.16 (9)	C3—C2—C7—O4	88.07 (11)
C6—C1—C2—C7	−3.69 (14)	C1—C2—C7—O4	−92.20 (12)
C1—C2—C3—C4	1.40 (14)	C9—N2—C8—C11	−56.46 (10)
C7—C2—C3—C4	−178.84 (9)	C8—N2—C9—C10	58.30 (10)
C2—C3—C4—C5	0.61 (15)	C11—N3—C10—C9	57.68 (10)
C1—N1—C5—C4	1.56 (15)	N2—C9—C10—N3	−58.17 (10)
C3—C4—C5—N1	−2.20 (15)	C10—N3—C11—C8	−56.39 (11)
N1—C1—C6—O2	5.41 (13)	N2—C8—C11—N3	55.14 (11)
C2—C1—C6—O2	−172.86 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4i	0.90	1.74	2.6257 (11)	168
N2—H2B···O2	0.90	1.89	2.7274 (11)	155
N3—H3A···O1ii	0.90	1.85	2.7379 (11)	169
N3—H3B···O3iii	0.90	1.86	2.7393 (11)	166
O5—H5A···O1	0.85	1.84	2.6867 (10)	171
C3—H3···O5iv	0.95	2.41	3.3163 (13)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4i	0.90	1.74	2.6257 (11)	168
N2—H2B⋯O2	0.90	1.89	2.7274 (11)	155
N3—H3A⋯O1ii	0.90	1.85	2.7379 (11)	169
N3—H3B⋯O3iii	0.90	1.86	2.7393 (11)	166
O5—H5A⋯O1	0.85	1.84	2.6867 (10)	171
C3—H3⋯O5iv	0.95	2.41	3.3163 (13)	159

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