catena-Poly[bis-(4-amino-pyridinium) [[tetra-aqua-nickel(II)]-μ-benzene-1,2,4,5-tetra-carboxyl-ato] dihydrate].

The asymmetric unit of the title compound, {(C(5)H(7)N(2))(2)[Ni(C(10)H(2)O(8))(H(2)O)(4)]·2H(2)O}(n), contains an Ni(II) atom, two water mol-ecules of coordination, one half of a benzene-1,2,4,5-tetra-carboxyl-ate (btec) anionic ligand, one 4-amino-pyridinium cation (papy) and an uncoordinated water mol-ecule. The metal center lies on an inversion center and adopts an octa-hedral geometry with the carboxyl-ate groups tilted out of the mean plane formed by the btec. In the crystal, mol-ecules are linked into one-dimensional coordination polymers running along the ac diagonal. The crystal structure is consolidated by N-H⋯O and O-H⋯O hydrogen bonds.

Related literature

For background to 1,2,4,5-benzene-tetra­carboxyl­ate, see: Du et al. (2007 ▶); Fang et al. (2008 ▶); Loiseau et al. (2005 ▶); Ruiz-Pérez et al. (2004 ▶); Stephenson & Hardie (2006 ▶); Wang et al. (2005 ▶). For related structures, see: Majumder et al. (2006 ▶).

Experimental

Crystal data

(C5H7N2)2[Ni(C10H2O8)(H2O)4]·2H2O

M = 607.17

Triclinic,

a = 7.2115 (1) Å

b = 9.3470 (1) Å

c = 10.6322 (2) Å

α = 112.720 (1)°

β = 108.830 (1)°

γ = 95.582 (1)°

V = 605.13 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.88 mm−1

T = 296 K

0.50 × 0.34 × 0.27 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.729, T max = 0.785

14068 measured reflections

2219 independent reflections

2203 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.055

S = 1.07

2219 reflections

187 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034746/pv2183sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034746/pv2183Isup2.hkl

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

(C5H7N2)2[Ni(C10H2O8)(H2O)4]·2H2O	Z = 1
Mr = 607.17	F(000) = 316
Triclinic, P1	Dx = 1.666 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2115 (1) Å	Cell parameters from 9901 reflections
b = 9.3470 (1) Å	θ = 2.4–31.7°
c = 10.6322 (2) Å	µ = 0.88 mm−1
α = 112.720 (1)°	T = 296 K
β = 108.830 (1)°	Block, green
γ = 95.582 (1)°	0.5 × 0.34 × 0.27 mm
V = 605.13 (2) Å3

Bruker APEXII CCD diffractometer	2219 independent reflections
graphite	2203 reflections with I > 2σ(I)
Detector resolution: 9 pixels mm-1	Rint = 0.023
φ and ω scans	θmax = 25.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
Tmin = 0.729, Tmax = 0.785	k = −11→11
14068 measured reflections	l = −12→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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0286P)2 + 0.2508P] where P = (Fo2 + 2Fc2)/3
2219 reflections	(Δ/σ)max = 0.001
187 parameters	Δρmax = 0.3 e Å−3
0 restraints	Δρmin = −0.26 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
Ni1	0	0	1	0.01722 (8)
C1	0.42401 (18)	0.39111 (14)	1.04216 (14)	0.0178 (2)
C2	0.43069 (18)	0.33541 (15)	0.90138 (14)	0.0180 (2)
C3	0.50542 (18)	0.44605 (15)	0.86090 (14)	0.0188 (3)
H3	0.5083	0.4106	0.7671	0.023*
C4	0.32515 (19)	0.28168 (14)	1.08810 (14)	0.0186 (3)
C5	0.36527 (19)	0.15800 (15)	0.79578 (14)	0.0210 (3)
O1	0.14545 (13)	0.20052 (10)	1.00054 (10)	0.02033 (19)
O2	0.42075 (15)	0.28245 (12)	1.20874 (11)	0.0319 (2)
O3	0.2586 (2)	0.11600 (13)	0.66391 (12)	0.0458 (3)
O4	0.42488 (15)	0.06463 (11)	0.84885 (11)	0.0282 (2)
N6	0.9034 (2)	0.28646 (18)	1.77371 (15)	0.0397 (3)
H6	0.9397	0.244	1.8336	0.048*
C7	0.9976 (2)	0.4382 (2)	1.81496 (17)	0.0379 (4)
H7	1.1004	0.4962	1.9087	0.046*
C8	0.9467 (2)	0.50850 (18)	1.72376 (16)	0.0318 (3)
H8	1.0126	0.6143	1.7554	0.038*
C9	0.7933 (2)	0.42135 (17)	1.58003 (15)	0.0263 (3)
C10	0.6936 (2)	0.26379 (18)	1.54195 (17)	0.0323 (3)
H10	0.5874	0.2034	1.4502	0.039*
C11	0.7530 (3)	0.2008 (2)	1.6396 (2)	0.0385 (4)
H11	0.6883	0.0963	1.6131	0.046*
N12	0.7487 (2)	0.48454 (16)	1.48525 (14)	0.0366 (3)
H12A	0.8135	0.5801	1.5109	0.044*
H12B	0.6549	0.43	1.3981	0.044*
O1W	0.18379 (14)	0.05465 (11)	1.21508 (10)	0.0249 (2)
H1WA	0.2767	0.1294	1.2294	0.037*
H1WB	0.1353	0.0931	1.2806	0.037*
O2W	−0.21078 (14)	0.11312 (11)	1.06521 (11)	0.0250 (2)
H2WA	−0.2557	0.0702	1.1104	0.038*
H2WB	−0.3121	0.1088	0.9937	0.038*
O3W	0.05029 (18)	0.17265 (13)	0.43489 (12)	0.0358 (3)
H3WA	0.1248	0.1693	0.5134	0.054*
H3WB	−0.0649	0.1083	0.4016	0.054*

	U11	U22	U33	U12	U13	U23
Ni1	0.01682 (13)	0.01646 (12)	0.01797 (13)	−0.00033 (9)	0.00487 (9)	0.00990 (9)
C1	0.0150 (6)	0.0182 (6)	0.0194 (6)	0.0003 (5)	0.0045 (5)	0.0102 (5)
C2	0.0159 (6)	0.0171 (6)	0.0190 (6)	0.0011 (5)	0.0046 (5)	0.0085 (5)
C3	0.0188 (6)	0.0199 (6)	0.0172 (6)	0.0013 (5)	0.0067 (5)	0.0088 (5)
C4	0.0212 (6)	0.0155 (6)	0.0190 (6)	0.0018 (5)	0.0079 (5)	0.0082 (5)
C5	0.0220 (6)	0.0179 (6)	0.0217 (6)	0.0010 (5)	0.0090 (5)	0.0079 (5)
O1	0.0182 (4)	0.0195 (4)	0.0217 (4)	−0.0017 (3)	0.0049 (4)	0.0115 (4)
O2	0.0300 (5)	0.0348 (6)	0.0243 (5)	−0.0091 (4)	−0.0002 (4)	0.0193 (4)
O3	0.0665 (8)	0.0240 (5)	0.0223 (5)	0.0006 (5)	−0.0037 (5)	0.0059 (4)
O4	0.0328 (5)	0.0210 (5)	0.0337 (5)	0.0077 (4)	0.0129 (4)	0.0150 (4)
N6	0.0492 (8)	0.0541 (9)	0.0376 (8)	0.0307 (7)	0.0234 (7)	0.0323 (7)
C7	0.0351 (8)	0.0506 (10)	0.0244 (7)	0.0195 (7)	0.0084 (6)	0.0136 (7)
C8	0.0294 (8)	0.0299 (7)	0.0264 (7)	0.0065 (6)	0.0061 (6)	0.0073 (6)
C9	0.0253 (7)	0.0269 (7)	0.0251 (7)	0.0072 (6)	0.0084 (6)	0.0111 (6)
C10	0.0324 (8)	0.0284 (7)	0.0303 (8)	0.0030 (6)	0.0082 (6)	0.0120 (6)
C11	0.0470 (10)	0.0332 (8)	0.0481 (10)	0.0153 (7)	0.0256 (8)	0.0239 (7)
N12	0.0378 (7)	0.0321 (7)	0.0301 (7)	−0.0024 (6)	−0.0001 (6)	0.0176 (6)
O1W	0.0239 (5)	0.0274 (5)	0.0216 (5)	−0.0017 (4)	0.0062 (4)	0.0132 (4)
O2W	0.0231 (5)	0.0244 (5)	0.0301 (5)	0.0040 (4)	0.0106 (4)	0.0149 (4)
O3W	0.0413 (6)	0.0364 (6)	0.0328 (6)	0.0062 (5)	0.0154 (5)	0.0185 (5)

Ni1—O1	2.054 (1)	N6—H6	0.86
Ni1—O1i	2.054 (1)	C7—C8	1.347 (2)
Ni1—O1W	2.063 (1)	C7—H7	0.93
Ni1—O1Wi	2.063 (1)	C8—C9	1.412 (2)
Ni1—O2Wi	2.082 (1)	C8—H8	0.93
Ni1—O2W	2.082 (1)	C9—N12	1.3249 (19)
C1—C3ii	1.3917 (18)	C9—C10	1.413 (2)
C1—C2	1.4012 (18)	C10—C11	1.357 (2)
C1—C4	1.5040 (16)	C10—H10	0.93
C2—C3	1.3894 (17)	C11—H11	0.93
C2—C5	1.5168 (17)	N12—H12A	0.86
C3—C1ii	1.3917 (18)	N12—H12B	0.86
C3—H3	0.93	O1W—H1WA	0.8491
C4—O2	1.2416 (16)	O1W—H1WB	0.8517
C4—O1	1.2673 (16)	O2W—H2WA	0.8491
C5—O3	1.2376 (17)	O2W—H2WB	0.8517
C5—O4	1.2496 (17)	O3W—H3WA	0.8491
N6—C11	1.342 (2)	O3W—H3WB	0.8517
N6—C7	1.344 (2)
O1—Ni1—O1i	180	C4—O1—Ni1	124.64 (8)
O1—Ni1—O1W	94.96 (4)	C11—N6—C7	120.39 (14)
O1i—Ni1—O1W	85.04 (4)	C11—N6—H6	119.8
O1—Ni1—O1Wi	85.04 (4)	C7—N6—H6	119.8
O1i—Ni1—O1Wi	94.96 (4)	N6—C7—C8	121.61 (15)
O1W—Ni1—O1Wi	180	N6—C7—H7	119.2
O1—Ni1—O2Wi	87.65 (4)	C8—C7—H7	119.2
O1i—Ni1—O2Wi	92.35 (4)	C7—C8—C9	119.94 (15)
O1W—Ni1—O2Wi	87.40 (4)	C7—C8—H8	120
O1Wi—Ni1—O2Wi	92.60 (4)	C9—C8—H8	120
O1—Ni1—O2W	92.35 (4)	N12—C9—C8	121.08 (14)
O1i—Ni1—O2W	87.65 (4)	N12—C9—C10	122.01 (13)
O1W—Ni1—O2W	92.60 (4)	C8—C9—C10	116.90 (13)
O1Wi—Ni1—O2W	87.40 (4)	C11—C10—C9	119.85 (15)
O2Wi—Ni1—O2W	180	C11—C10—H10	120.1
C3ii—C1—C2	120.00 (11)	C9—C10—H10	120.1
C3ii—C1—C4	118.01 (11)	N6—C11—C10	121.24 (15)
C2—C1—C4	121.77 (11)	N6—C11—H11	119.4
C3—C2—C1	118.62 (11)	C10—C11—H11	119.4
C3—C2—C5	119.85 (11)	C9—N12—H12A	120
C1—C2—C5	121.49 (11)	C9—N12—H12B	120
C2—C3—C1ii	121.37 (12)	H12A—N12—H12B	120
C2—C3—H3	119.3	Ni1—O1W—H1WA	98.6
C1ii—C3—H3	119.3	Ni1—O1W—H1WB	116.7
O2—C4—O1	125.75 (11)	H1WA—O1W—H1WB	107.6
O2—C4—C1	118.41 (11)	Ni1—O2W—H2WA	109.6
O1—C4—C1	115.78 (11)	Ni1—O2W—H2WB	114
O3—C5—O4	124.70 (12)	H2WA—O2W—H2WB	107.6
O3—C5—C2	118.15 (12)	H3WA—O3W—H3WB	107.6
O4—C5—C2	117.15 (11)
C3ii—C1—C2—C3	−1.1 (2)	O2—C4—O1—Ni1	−20.66 (18)
C4—C1—C2—C3	173.38 (11)	C1—C4—O1—Ni1	162.24 (8)
C3ii—C1—C2—C5	176.81 (11)	O1W—Ni1—O1—C4	21.65 (10)
C4—C1—C2—C5	−8.73 (18)	O1Wi—Ni1—O1—C4	−158.35 (10)
C1—C2—C3—C1ii	1.1 (2)	O2Wi—Ni1—O1—C4	−65.53 (10)
C5—C2—C3—C1ii	−176.83 (11)	O2W—Ni1—O1—C4	114.47 (10)
C3ii—C1—C4—O2	−54.95 (17)	C11—N6—C7—C8	−0.7 (2)
C2—C1—C4—O2	130.48 (13)	N6—C7—C8—C9	−1.1 (2)
C3ii—C1—C4—O1	122.37 (13)	C7—C8—C9—N12	−176.02 (14)
C2—C1—C4—O1	−52.20 (16)	C7—C8—C9—C10	2.8 (2)
C3—C2—C5—O3	−45.83 (18)	N12—C9—C10—C11	175.97 (15)
C1—C2—C5—O3	136.30 (14)	C8—C9—C10—C11	−2.9 (2)
C3—C2—C5—O4	133.70 (13)	C7—N6—C11—C10	0.7 (2)
C1—C2—C5—O4	−44.16 (17)	C9—C10—C11—N6	1.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6···O1iii	0.86	2.12	2.926 (1)	156
N12—H12B···O2	0.86	2.00	2.856 (2)	171
N12—H12A···O3Wii	0.86	2.19	3.048 (2)	174
O1W—H1WA···O2	0.85	1.81	2.634 (1)	163
O1W—H1WB···O3Wiv	0.85	1.85	2.697 (1)	175
O2W—H2WA···O4i	0.85	1.93	2.750 (1)	162
O2W—H2WB···O4v	0.85	1.90	2.732 (1)	165
O3W—H3WA···O3	0.85	1.86	2.694 (2)	168
O3W—H3WB···O3vi	0.85	2.12	2.911 (2)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6⋯O1i	0.86	2.12	2.926 (1)	156
N12—H12B⋯O2	0.86	2.00	2.856 (2)	171
N12—H12A⋯O3Wii	0.86	2.19	3.048 (2)	174
O1W—H1WA⋯O2	0.85	1.81	2.634 (1)	163
O1W—H1WB⋯O3Wiii	0.85	1.85	2.697 (1)	175
O2W—H2WA⋯O4iv	0.85	1.93	2.750 (1)	162
O2W—H2WB⋯O4v	0.85	1.90	2.732 (1)	165
O3W—H3WA⋯O3	0.85	1.86	2.694 (2)	168
O3W—H3WB⋯O3vi	0.85	2.12	2.911 (2)	154

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