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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
CCDC reference: 175970
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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:
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%).
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.
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.
Crystal data top
[Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2O | F(000) = 568 |
Mr = 545.12 | Dx = 1.538 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.065 (1) Å | Cell parameters from 25 reflections |
b = 15.148 (3) Å | θ = 12.2–12.5° |
c = 11.113 (2) Å | µ = 0.89 mm−1 |
β = 98.09 (1)° | T = 293 K |
V = 1177.5 (4) Å3 | Parallelepiped, green |
Z = 2 | 0.25 × 0.20 × 0.20 mm |
Data collection top
Bruker P4 diffractometer | 1627 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
θ/2θ scans | h = −1→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→18 |
Tmin = 0.808, Tmax = 0.842 | l = −13→13 |
2831 measured reflections | 3 standard reflections every 97 reflections |
2077 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.029 | H 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 reflections | Δρmax = 0.26 e Å−3 |
167 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0067 (3) |
Crystal data top
[Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2O | V = 1177.5 (4) Å3 |
Mr = 545.12 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.065 (1) Å | µ = 0.89 mm−1 |
b = 15.148 (3) Å | T = 293 K |
c = 11.113 (2) Å | 0.25 × 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 = 0.842 | 3 standard reflections every 97 reflections |
2831 measured reflections | intensity decay: none |
2077 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.26 e Å−3 |
2077 reflections | Δρmin = −0.19 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Ni | 0.5000 | 0.5000 | 0.5000 | 0.02209 (13) | |
N | 0.4851 (2) | 0.50437 (13) | 0.67944 (14) | 0.0295 (4) | |
O1 | 0.4832 (2) | 0.34882 (10) | 0.50156 (14) | 0.0343 (4) | |
O2 | 0.1675 (2) | 0.33124 (11) | 0.47685 (15) | 0.0415 (4) | |
O3 | 0.3538 (3) | 0.22503 (12) | 0.27811 (17) | 0.0578 (6) | |
H3 | 0.358 (4) | 0.2225 (4) | 0.198 (3) | 0.069* | |
O4 | 0.4192 (3) | 0.08158 (13) | 0.26680 (19) | 0.0614 (6) | |
O5 | 0.7956 (2) | 0.48891 (12) | 0.53474 (14) | 0.0417 (4) | |
H5A | 0.8282 (7) | 0.4643 (12) | 0.6055 (15) | 0.050* | |
H5B | 0.8479 (10) | 0.5478 (11) | 0.5420 (17) | 0.050* | |
O6 | 0.3337 (2) | 0.23348 (11) | 0.04391 (15) | 0.0447 (5) | |
H6A | 0.4212 (18) | 0.2119 (5) | 0.0106 (7) | 0.054* | |
H6B | 0.232 (2) | 0.2030 (6) | 0.0199 (5) | 0.054* | |
C1 | 0.5920 (4) | 0.56122 (15) | 0.75117 (19) | 0.0379 (6) | |
H1 | 0.6648 | 0.6022 | 0.7155 | 0.046* | |
C2 | 0.5996 (4) | 0.56194 (16) | 0.87591 (19) | 0.0376 (6) | |
H2 | 0.6749 | 0.6034 | 0.9221 | 0.045* | |
C3 | 0.4956 (3) | 0.50120 (16) | 0.93260 (16) | 0.0271 (4) | |
C4 | 0.3825 (4) | 0.44350 (19) | 0.8575 (2) | 0.0451 (7) | |
H4 | 0.3083 | 0.4019 | 0.8908 | 0.054* | |
C5 | 0.3793 (4) | 0.44752 (18) | 0.7332 (2) | 0.0442 (7) | |
H5 | 0.2998 | 0.4088 | 0.6846 | 0.053* | |
C6 | 0.3354 (3) | 0.30207 (16) | 0.49840 (19) | 0.0314 (5) | |
C7 | 0.3643 (4) | 0.20650 (17) | 0.5349 (2) | 0.0387 (6) | |
C8 | 0.3890 (4) | 0.14097 (17) | 0.4584 (2) | 0.0438 (6) | |
H8 | 0.4089 | 0.0852 | 0.4929 | 0.053* | |
C9 | 0.3886 (4) | 0.14621 (18) | 0.3262 (2) | 0.0447 (7) | |
C10 | 0.3674 (5) | 0.19101 (19) | 0.6692 (2) | 0.0575 (8) | |
H10A | 0.3987 | 0.1304 | 0.6879 | 0.069* | |
H10B | 0.2439 | 0.2042 | 0.6913 | 0.069* | |
H10C | 0.4616 | 0.2286 | 0.7140 | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0256 (2) | 0.0306 (2) | 0.01065 (17) | −0.0029 (2) | 0.00432 (13) | −0.00086 (18) |
N | 0.0343 (10) | 0.0350 (10) | 0.0194 (8) | −0.0027 (11) | 0.0046 (7) | −0.0022 (9) |
O1 | 0.0298 (9) | 0.0413 (9) | 0.0319 (8) | −0.0072 (8) | 0.0047 (7) | 0.0024 (8) |
O2 | 0.0316 (10) | 0.0450 (11) | 0.0482 (10) | −0.0024 (8) | 0.0066 (8) | 0.0025 (8) |
O3 | 0.0870 (16) | 0.0479 (12) | 0.0398 (10) | 0.0035 (11) | 0.0136 (11) | −0.0074 (9) |
O4 | 0.0619 (13) | 0.0530 (12) | 0.0677 (13) | 0.0081 (11) | 0.0035 (11) | −0.0241 (11) |
O5 | 0.0434 (10) | 0.0487 (11) | 0.0331 (8) | −0.0123 (9) | 0.0057 (7) | 0.0043 (8) |
O6 | 0.0374 (10) | 0.0461 (11) | 0.0526 (11) | −0.0049 (9) | 0.0132 (9) | −0.0159 (9) |
C1 | 0.0579 (17) | 0.0327 (13) | 0.0236 (11) | −0.0132 (12) | 0.0069 (11) | 0.0015 (10) |
C2 | 0.0575 (16) | 0.0349 (13) | 0.0197 (11) | −0.0145 (12) | 0.0027 (11) | −0.0043 (10) |
C3 | 0.0309 (11) | 0.0321 (11) | 0.0190 (10) | 0.0027 (12) | 0.0055 (8) | −0.0028 (11) |
C4 | 0.0515 (17) | 0.0622 (18) | 0.0238 (12) | −0.0267 (14) | 0.0128 (12) | −0.0042 (12) |
C5 | 0.0495 (16) | 0.0604 (18) | 0.0233 (11) | −0.0254 (14) | 0.0076 (11) | −0.0087 (12) |
C6 | 0.0321 (14) | 0.0424 (14) | 0.0201 (11) | −0.0032 (12) | 0.0050 (10) | −0.0012 (10) |
C7 | 0.0342 (14) | 0.0429 (15) | 0.0380 (13) | −0.0083 (12) | 0.0016 (11) | 0.0039 (12) |
C8 | 0.0411 (15) | 0.0370 (14) | 0.0510 (15) | −0.0032 (12) | −0.0011 (13) | −0.0005 (13) |
C9 | 0.0349 (14) | 0.0450 (16) | 0.0531 (16) | −0.0014 (13) | 0.0025 (12) | −0.0133 (14) |
C10 | 0.070 (2) | 0.0547 (18) | 0.0455 (16) | −0.0108 (16) | 0.0002 (15) | 0.0144 (14) |
Geometric parameters (Å, º) top
Ni—Ni | 2.0128 (16) | C1—C2 | 1.380 (3) |
Ni—N | 2.0128 (16) | C1—H1 | 0.9300 |
Ni—O5 | 2.0767 (17) | C2—C3 | 1.383 (3) |
Ni—O5i | 2.0767 (17) | C2—H2 | 0.9300 |
Ni—O1 | 2.2933 (16) | C3—C4 | 1.383 (3) |
Ni—O1i | 2.2933 (16) | C3—C3ii | 1.491 (3) |
N—C1 | 1.333 (3) | C4—C5 | 1.379 (3) |
N—C5 | 1.335 (3) | C4—H4 | 0.9300 |
O1—C6 | 1.258 (3) | C5—H5 | 0.9300 |
O2—C6 | 1.257 (3) | C6—C7 | 1.510 (3) |
O3—C9 | 1.317 (3) | C7—C8 | 1.334 (3) |
O3—H3 | 0.8907 | C7—C10 | 1.509 (3) |
O4—C9 | 1.217 (3) | C8—C9 | 1.471 (4) |
O5—H5A | 0.8716 | C8—H8 | 0.9300 |
O5—H5B | 0.9643 | C10—H10A | 0.9600 |
O6—H6A | 0.8310 | C10—H10B | 0.9600 |
O6—H6B | 0.8646 | C10—H10C | 0.9600 |
| | | |
Ni—Ni—N | 180.0 | C1—C2—H2 | 119.9 |
Ni—Ni—O5 | 89.43 (7) | C2—C3—C4 | 116.38 (19) |
N—Ni—O5 | 90.57 (7) | C2—C3—C3ii | 121.6 (3) |
Ni—Ni—O5i | 90.57 (7) | C4—C3—C3ii | 122.0 (3) |
N—Ni—O5i | 89.43 (7) | C3—C4—C5 | 120.2 (2) |
O5—Ni—O5i | 180.0 | C3—C4—H4 | 119.9 |
Ni—Ni—O1 | 89.12 (7) | C5—C4—H4 | 119.9 |
N—Ni—O1 | 90.88 (7) | N—C5—C4 | 123.0 (2) |
O5—Ni—O1 | 88.26 (6) | N—C5—H5 | 118.5 |
O5i—Ni—O1 | 91.74 (6) | C4—C5—H5 | 118.5 |
Ni—Ni—O1i | 90.88 (7) | O1—C6—O2 | 124.4 (2) |
N—Ni—O1i | 89.12 (7) | O1—C6—C7 | 116.9 (2) |
O5—Ni—O1i | 91.74 (6) | O2—C6—C7 | 118.5 (2) |
O5i—Ni—O1i | 88.26 (6) | C8—C7—C6 | 124.6 (2) |
O1—Ni—O1i | 180.0 | C8—C7—C10 | 122.0 (2) |
C1—N—C5 | 117.04 (18) | C6—C7—C10 | 113.4 (2) |
C1—N—Ni | 120.61 (15) | C7—C8—C9 | 127.9 (3) |
C5—N—Ni | 122.20 (15) | C7—C8—H8 | 116.1 |
C6—O1—Ni | 127.27 (16) | C9—C8—H8 | 116.1 |
C9—O3—H3 | 109.5 | O4—C9—O3 | 123.1 (3) |
Ni—O5—H5A | 109.5 | O4—C9—C8 | 121.5 (3) |
Ni—O5—H5B | 107.7 | O3—C9—C8 | 115.4 (2) |
H5A—O5—H5B | 105.7 | C7—C10—H10A | 109.5 |
H6A—O6—H6B | 106.9 | C7—C10—H10B | 109.5 |
N—C1—C2 | 123.0 (2) | H10A—C10—H10B | 109.5 |
N—C1—H1 | 118.5 | C7—C10—H10C | 109.5 |
C2—C1—H1 | 118.5 | H10A—C10—H10C | 109.5 |
C3—C2—C1 | 120.3 (2) | H10B—C10—H10C | 109.5 |
C3—C2—H2 | 119.9 | | |
| | | |
O5—Ni—N—C1 | 51.62 (19) | C1—C2—C3—C3ii | 178.5 (3) |
O5i—Ni—N—C1 | −128.38 (19) | C2—C3—C4—C5 | 0.9 (4) |
O1—Ni—N—C1 | 139.88 (19) | C3ii—C3—C4—C5 | −179.6 (3) |
O1i—Ni—N—C1 | −40.12 (19) | C1—N—C5—C4 | −2.5 (4) |
O5—Ni—N—C5 | −123.8 (2) | Ni—N—C5—C4 | 173.1 (2) |
O5i—Ni—N—C5 | 56.2 (2) | C3—C4—C5—N | 1.4 (4) |
O1—Ni—N—C5 | −35.6 (2) | Ni—O1—C6—O2 | 10.4 (3) |
O1i—Ni—N—C5 | 144.4 (2) | Ni—O1—C6—C7 | −163.55 (15) |
Ni—Ni—O1—C6 | −98.83 (18) | O1—C6—C7—C8 | −89.8 (3) |
N—Ni—O1—C6 | 81.17 (18) | O2—C6—C7—C8 | 95.9 (3) |
O5—Ni—O1—C6 | 171.72 (18) | O1—C6—C7—C10 | 88.9 (3) |
O5i—Ni—O1—C6 | −8.28 (18) | O2—C6—C7—C10 | −85.4 (3) |
C5—N—C1—C2 | 1.3 (4) | C6—C7—C8—C9 | −1.7 (4) |
Ni—N—C1—C2 | −174.3 (2) | C10—C7—C8—C9 | 179.7 (2) |
N—C1—C2—C3 | 0.9 (4) | C7—C8—C9—O4 | 177.5 (3) |
C1—C2—C3—C4 | −2.0 (4) | C7—C8—C9—O3 | −2.2 (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···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6 | 0.89 | 1.71 | 2.590 (2) | 169 |
O5—H5A···O4iii | 0.87 | 1.95 | 2.814 (3) | 175 |
O5—H5B···O2i | 0.96 | 1.85 | 2.741 (3) | 153 |
O6—H6A···O2iv | 0.83 | 1.94 | 2.752 (2) | 164 |
O6—H6B···O1v | 0.86 | 1.91 | 2.753 (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, z−1/2; (v) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data |
Chemical formula | [Ni(C10H8N2)(C5H5O4)2(H2O)2]·2H2O |
Mr | 545.12 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.065 (1), 15.148 (3), 11.113 (2) |
β (°) | 98.09 (1) |
V (Å3) | 1177.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.89 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.808, 0.842 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2831, 2077, 1627 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.058, 1.04 |
No. of reflections | 2077 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.19 |
Selected geometric parameters (Å, º) topNi—N | 2.0128 (16) | Ni—O1 | 2.2933 (16) |
Ni—O5 | 2.0767 (17) | C3—C3i | 1.491 (3) |
| | | |
Nii—Ni—O5 | 89.43 (7) | N—Ni—O1 | 90.88 (7) |
N—Ni—O5 | 90.57 (7) | O5—Ni—O1 | 88.26 (6) |
Nii—Ni—O1 | 89.12 (7) | O5ii—Ni—O1 | 91.74 (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···A | D—H | H···A | D···A | D—H···A |
O3—H3···O6 | 0.89 | 1.71 | 2.590 (2) | 168.7 |
O5—H5A···O4iii | 0.87 | 1.95 | 2.814 (3) | 174.5 |
O5—H5B···O2ii | 0.96 | 1.85 | 2.741 (3) | 153.3 |
O6—H6A···O2iv | 0.83 | 1.94 | 2.752 (2) | 163.9 |
O6—H6B···O1v | 0.86 | 1.91 | 2.753 (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, z−1/2; (v) x−1/2, −y+1/2, z−1/2. |
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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).