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In the title compound, {[Ni(H2O)2(C10H8N2)(C5H5O4)2]·2H2O}n, (I), the NiII atom is located at a center of inversion, and the bridging 4,4′-bi­pyridine has a center of symmetry. Each NiII is in an octahedral environment, coordinated by two H2O, two cis-2-methyl-but-2-enedioate (citraconate) and two bridging 4,4′-bi­pyridine ligands to generate linear chains which interact with the water molecules of crystallization to form a hydrogen-bonding network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015835/ob6074sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015835/ob6074Isup2.hkl
Contains datablock I

CCDC reference: 175970

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.029
  • wR factor = 0.058
  • Data-to-parameter ratio = 12.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C20 H26 N2 Ni1 O12 Atom count from _chemical_formula_moiety:

Comment top

The design of extended frameworks by linking metal centers with multidentate ligands has drawn great attention. Polycarboxylates have been widely used as building blocks to construct many coordination polymers with interesting crystal structures (Eddaoudi et al., 2001). The reaction of a dicarboxylic acid, citraconic acid, a dipyridyl spacer, 4,4'-bipyridine, and Ni2+ resulted in the formation of the title compound, [Ni(H2O)2(4,4'-bipyridine)(citraconate)2.2H2O]n, (I) (Fig. 1).

The structure of (I) is composed of parallel straight chains running in the [0 0 1] direction and crystallization water molecules (Fig. 2). Each Ni2+ ion is located at a crystallographic center of inversion, coordinated by two H2O molecules, two bridging 4,4'-bipyridine ligands and two dangling citraconates, each of which binds to Ni2+ with one oxygen atom of a carboxylate at C6, while the other carboxylic acid at C9 remains protonated. The conformation of the citraconate ligand is similar to that of a free citraconic acid (Batchelor & Jones, 1998), with C6, C7, C8, C9, C10, O3 and O4 nearly in the same plane (r.m.s. deviation = 0.027 Å). The plane formed by the coordinated carboxylate (C6, C7, O1 and O2) is nearly perpendicular to the formal plane at 88.06 (8)° owing to steric hindrance. The linkage of the Ni2+ ions and 4,4'-bipyridines is similar to that of the straight [Ni(4,4'-bipyridine)]2+ chains observed in Ni(oxalate)(4,4'-bipyridine) (Lu et al., 1999), where the pyridine rings are coplanar in one chain. The Ni—O1(carboxylate) distance, 2.2933 (16) Å, is significantly longer than that of Ni—O5(water), 2.0767 (17) Å. Hydrogen bondings are observed among the water molecules and the nearby carboxylic groups, forming a three-dimensional hydrogen-bonding network (Table 2).

Experimental top

Ni(NO3)2.6H2O (0.145 g, 0.5 mmol), 4,4'-bipyridine (0.078 g, 0.5 mmol) and citraconic acid (0.065 g, 0.5 mmol) were dissolved in 5 ml and 15 ml distilled water respectively at 353 K. The two solutions were mixed slowly and sealed in a 30 ml test tube, forming a green solution with pH = 3.6. Then the solution was kept at 298 K for 5 days until many crystals of (I) were observed (yield 95.0%).

Refinement top

All the H atoms were observed in difference electron density maps. During refinement, the coordinates of all hydrogen atoms were fixed, except for H3, H5A-5B, where O—H bonds were allowed to vary and rotate about the C—O or Ni—O bonds; and except for H6A-6B, where the O—H bonds were allowed to vary.

Computing details top

Data collection: XSCANS (Siemens, 1992); cell refinement: XSCANS; data reduction: SHELXTL XPREP (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL XP; software used to prepare material for publication: SHELXTL XCIF.

Figures top
[Figure 1] Fig. 1. The structure and labeling scheme of (I) showing 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing diagram and H-bonding network of (I).
(I) top
Crystal data top
[Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2OF(000) = 568
Mr = 545.12Dx = 1.538 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.065 (1) ÅCell parameters from 25 reflections
b = 15.148 (3) Åθ = 12.2–12.5°
c = 11.113 (2) ŵ = 0.89 mm1
β = 98.09 (1)°T = 293 K
V = 1177.5 (4) Å3Parallelepiped, green
Z = 20.25 × 0.20 × 0.20 mm
Data collection top
Bruker P4
diffractometer
1627 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.016
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
θ/2θ scansh = 18
Absorption correction: ψ scan
(North et al., 1968)
k = 118
Tmin = 0.808, Tmax = 0.842l = 1313
2831 measured reflections3 standard reflections every 97 reflections
2077 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.058 w = 1/[σ2(Fo2) + (0.020P)2 + 0.420P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2077 reflectionsΔρmax = 0.26 e Å3
167 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0067 (3)
Crystal data top
[Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2OV = 1177.5 (4) Å3
Mr = 545.12Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.065 (1) ŵ = 0.89 mm1
b = 15.148 (3) ÅT = 293 K
c = 11.113 (2) Å0.25 × 0.20 × 0.20 mm
β = 98.09 (1)°
Data collection top
Bruker P4
diffractometer
1627 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.016
Tmin = 0.808, Tmax = 0.8423 standard reflections every 97 reflections
2831 measured reflections intensity decay: none
2077 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.058H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.26 e Å3
2077 reflectionsΔρmin = 0.19 e Å3
167 parameters
Special details top

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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni0.50000.50000.50000.02209 (13)
N0.4851 (2)0.50437 (13)0.67944 (14)0.0295 (4)
O10.4832 (2)0.34882 (10)0.50156 (14)0.0343 (4)
O20.1675 (2)0.33124 (11)0.47685 (15)0.0415 (4)
O30.3538 (3)0.22503 (12)0.27811 (17)0.0578 (6)
H30.358 (4)0.2225 (4)0.198 (3)0.069*
O40.4192 (3)0.08158 (13)0.26680 (19)0.0614 (6)
O50.7956 (2)0.48891 (12)0.53474 (14)0.0417 (4)
H5A0.8282 (7)0.4643 (12)0.6055 (15)0.050*
H5B0.8479 (10)0.5478 (11)0.5420 (17)0.050*
O60.3337 (2)0.23348 (11)0.04391 (15)0.0447 (5)
H6A0.4212 (18)0.2119 (5)0.0106 (7)0.054*
H6B0.232 (2)0.2030 (6)0.0199 (5)0.054*
C10.5920 (4)0.56122 (15)0.75117 (19)0.0379 (6)
H10.66480.60220.71550.046*
C20.5996 (4)0.56194 (16)0.87591 (19)0.0376 (6)
H20.67490.60340.92210.045*
C30.4956 (3)0.50120 (16)0.93260 (16)0.0271 (4)
C40.3825 (4)0.44350 (19)0.8575 (2)0.0451 (7)
H40.30830.40190.89080.054*
C50.3793 (4)0.44752 (18)0.7332 (2)0.0442 (7)
H50.29980.40880.68460.053*
C60.3354 (3)0.30207 (16)0.49840 (19)0.0314 (5)
C70.3643 (4)0.20650 (17)0.5349 (2)0.0387 (6)
C80.3890 (4)0.14097 (17)0.4584 (2)0.0438 (6)
H80.40890.08520.49290.053*
C90.3886 (4)0.14621 (18)0.3262 (2)0.0447 (7)
C100.3674 (5)0.19101 (19)0.6692 (2)0.0575 (8)
H10A0.39870.13040.68790.069*
H10B0.24390.20420.69130.069*
H10C0.46160.22860.71400.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0256 (2)0.0306 (2)0.01065 (17)0.0029 (2)0.00432 (13)0.00086 (18)
N0.0343 (10)0.0350 (10)0.0194 (8)0.0027 (11)0.0046 (7)0.0022 (9)
O10.0298 (9)0.0413 (9)0.0319 (8)0.0072 (8)0.0047 (7)0.0024 (8)
O20.0316 (10)0.0450 (11)0.0482 (10)0.0024 (8)0.0066 (8)0.0025 (8)
O30.0870 (16)0.0479 (12)0.0398 (10)0.0035 (11)0.0136 (11)0.0074 (9)
O40.0619 (13)0.0530 (12)0.0677 (13)0.0081 (11)0.0035 (11)0.0241 (11)
O50.0434 (10)0.0487 (11)0.0331 (8)0.0123 (9)0.0057 (7)0.0043 (8)
O60.0374 (10)0.0461 (11)0.0526 (11)0.0049 (9)0.0132 (9)0.0159 (9)
C10.0579 (17)0.0327 (13)0.0236 (11)0.0132 (12)0.0069 (11)0.0015 (10)
C20.0575 (16)0.0349 (13)0.0197 (11)0.0145 (12)0.0027 (11)0.0043 (10)
C30.0309 (11)0.0321 (11)0.0190 (10)0.0027 (12)0.0055 (8)0.0028 (11)
C40.0515 (17)0.0622 (18)0.0238 (12)0.0267 (14)0.0128 (12)0.0042 (12)
C50.0495 (16)0.0604 (18)0.0233 (11)0.0254 (14)0.0076 (11)0.0087 (12)
C60.0321 (14)0.0424 (14)0.0201 (11)0.0032 (12)0.0050 (10)0.0012 (10)
C70.0342 (14)0.0429 (15)0.0380 (13)0.0083 (12)0.0016 (11)0.0039 (12)
C80.0411 (15)0.0370 (14)0.0510 (15)0.0032 (12)0.0011 (13)0.0005 (13)
C90.0349 (14)0.0450 (16)0.0531 (16)0.0014 (13)0.0025 (12)0.0133 (14)
C100.070 (2)0.0547 (18)0.0455 (16)0.0108 (16)0.0002 (15)0.0144 (14)
Geometric parameters (Å, º) top
Ni—Ni2.0128 (16)C1—C21.380 (3)
Ni—N2.0128 (16)C1—H10.9300
Ni—O52.0767 (17)C2—C31.383 (3)
Ni—O5i2.0767 (17)C2—H20.9300
Ni—O12.2933 (16)C3—C41.383 (3)
Ni—O1i2.2933 (16)C3—C3ii1.491 (3)
N—C11.333 (3)C4—C51.379 (3)
N—C51.335 (3)C4—H40.9300
O1—C61.258 (3)C5—H50.9300
O2—C61.257 (3)C6—C71.510 (3)
O3—C91.317 (3)C7—C81.334 (3)
O3—H30.8907C7—C101.509 (3)
O4—C91.217 (3)C8—C91.471 (4)
O5—H5A0.8716C8—H80.9300
O5—H5B0.9643C10—H10A0.9600
O6—H6A0.8310C10—H10B0.9600
O6—H6B0.8646C10—H10C0.9600
Ni—Ni—N180.0C1—C2—H2119.9
Ni—Ni—O589.43 (7)C2—C3—C4116.38 (19)
N—Ni—O590.57 (7)C2—C3—C3ii121.6 (3)
Ni—Ni—O5i90.57 (7)C4—C3—C3ii122.0 (3)
N—Ni—O5i89.43 (7)C3—C4—C5120.2 (2)
O5—Ni—O5i180.0C3—C4—H4119.9
Ni—Ni—O189.12 (7)C5—C4—H4119.9
N—Ni—O190.88 (7)N—C5—C4123.0 (2)
O5—Ni—O188.26 (6)N—C5—H5118.5
O5i—Ni—O191.74 (6)C4—C5—H5118.5
Ni—Ni—O1i90.88 (7)O1—C6—O2124.4 (2)
N—Ni—O1i89.12 (7)O1—C6—C7116.9 (2)
O5—Ni—O1i91.74 (6)O2—C6—C7118.5 (2)
O5i—Ni—O1i88.26 (6)C8—C7—C6124.6 (2)
O1—Ni—O1i180.0C8—C7—C10122.0 (2)
C1—N—C5117.04 (18)C6—C7—C10113.4 (2)
C1—N—Ni120.61 (15)C7—C8—C9127.9 (3)
C5—N—Ni122.20 (15)C7—C8—H8116.1
C6—O1—Ni127.27 (16)C9—C8—H8116.1
C9—O3—H3109.5O4—C9—O3123.1 (3)
Ni—O5—H5A109.5O4—C9—C8121.5 (3)
Ni—O5—H5B107.7O3—C9—C8115.4 (2)
H5A—O5—H5B105.7C7—C10—H10A109.5
H6A—O6—H6B106.9C7—C10—H10B109.5
N—C1—C2123.0 (2)H10A—C10—H10B109.5
N—C1—H1118.5C7—C10—H10C109.5
C2—C1—H1118.5H10A—C10—H10C109.5
C3—C2—C1120.3 (2)H10B—C10—H10C109.5
C3—C2—H2119.9
O5—Ni—N—C151.62 (19)C1—C2—C3—C3ii178.5 (3)
O5i—Ni—N—C1128.38 (19)C2—C3—C4—C50.9 (4)
O1—Ni—N—C1139.88 (19)C3ii—C3—C4—C5179.6 (3)
O1i—Ni—N—C140.12 (19)C1—N—C5—C42.5 (4)
O5—Ni—N—C5123.8 (2)Ni—N—C5—C4173.1 (2)
O5i—Ni—N—C556.2 (2)C3—C4—C5—N1.4 (4)
O1—Ni—N—C535.6 (2)Ni—O1—C6—O210.4 (3)
O1i—Ni—N—C5144.4 (2)Ni—O1—C6—C7163.55 (15)
Ni—Ni—O1—C698.83 (18)O1—C6—C7—C889.8 (3)
N—Ni—O1—C681.17 (18)O2—C6—C7—C895.9 (3)
O5—Ni—O1—C6171.72 (18)O1—C6—C7—C1088.9 (3)
O5i—Ni—O1—C68.28 (18)O2—C6—C7—C1085.4 (3)
C5—N—C1—C21.3 (4)C6—C7—C8—C91.7 (4)
Ni—N—C1—C2174.3 (2)C10—C7—C8—C9179.7 (2)
N—C1—C2—C30.9 (4)C7—C8—C9—O4177.5 (3)
C1—C2—C3—C42.0 (4)C7—C8—C9—O32.2 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O60.891.712.590 (2)169
O5—H5A···O4iii0.871.952.814 (3)175
O5—H5B···O2i0.961.852.741 (3)153
O6—H6A···O2iv0.831.942.752 (2)164
O6—H6B···O1v0.861.912.753 (2)165
Symmetry codes: (i) x+1, y+1, z+1; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y+1/2, z1/2; (v) x1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2O
Mr545.12
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.065 (1), 15.148 (3), 11.113 (2)
β (°) 98.09 (1)
V3)1177.5 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.89
Crystal size (mm)0.25 × 0.20 × 0.20
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.808, 0.842
No. of measured, independent and
observed [I > 2σ(I)] reflections
2831, 2077, 1627
Rint0.016
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.058, 1.04
No. of reflections2077
No. of parameters167
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.19

Computer programs: XSCANS (Siemens, 1992), XSCANS, SHELXTL XPREP (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL XP, SHELXTL XCIF.

Selected geometric parameters (Å, º) top
Ni—N2.0128 (16)Ni—O12.2933 (16)
Ni—O52.0767 (17)C3—C3i1.491 (3)
Nii—Ni—O589.43 (7)N—Ni—O190.88 (7)
N—Ni—O590.57 (7)O5—Ni—O188.26 (6)
Nii—Ni—O189.12 (7)O5ii—Ni—O191.74 (6)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O60.891.712.590 (2)168.7
O5—H5A···O4iii0.871.952.814 (3)174.5
O5—H5B···O2ii0.961.852.741 (3)153.3
O6—H6A···O2iv0.831.942.752 (2)163.9
O6—H6B···O1v0.861.912.753 (2)165.0
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x+1/2, y+1/2, z+1/2; (iv) x+1/2, y+1/2, z1/2; (v) x1/2, y+1/2, z1/2.
 

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