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The metal atom of the title compound, [Ni(C10H13NO2)2(H2O)2]·2H2O, lies on an inversion center; it is N,O-chelated by the alkyl-substituted 2-pyridylcarboxyl­ate group, and two water mol­ecules complete the octa­hedral environment. The coordinated and solvent water mol­ecules engage in hydrogen bonding with the acceptor O atom of the carboxylate group to furnish a two-dimensional network motif. Three atoms of the butyl group are disordered, with refined site occupancies of 0.681 (8):0.319 (8).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053603/bg2115sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053603/bg2115Isup2.hkl
Contains datablock I

CCDC reference: 667245

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.041
  • wR factor = 0.105
  • Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT301_ALERT_3_C Main Residue Disorder ......................... 17.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 8
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 48
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

5-Butyl-pyridyl-2-carboxylic acid (fusaric acid), unlike the parent unsubstituted carboxylic acid that affords a large number of N,O-chelated metal derivates, forms only three metal carboxylates that have been characterized by crystallography (Fan et al., 2007; He et al., 2007). The aquacadmium derivative (Okabe, Wada & Muranishi, 2002) has two chelating carboxylate groups. The sixth coordination site is taken up by a carboxyl oxygen atom from an adjacent molecule; the water and carboxyl oxygen atoms are cis to each other. The copper derivative has two coordinated methanol molecules whereas the iron(III) derivative is a tris-chelated compound; (Okabe, Muranishi & Wada, 2002). The metal atom in the title nickel(II) derivative (I) (Fig. 1) lies on an inversion center, and presents two coordinated water molecules in the octahedral environment, the remaining sites being occupied by two chelating alky-substituted 2-pyridylcarboxylate groups (Table 1); the coordinated water and the lattice water molecules engage in hydrogen bonding (Table 2) with the carboxyl group to furnish a two-dimensional network motif parallel to (001) (Fig. 2).

Related literature top

See Fan et al. (2007); He et al. (2007); Okabe, Muranishi & Wada (2002) for the copper(II), cobalt(II) and iron(III) derivatives, respectively, and Okabe, Wada & Muranishi (2002) for the cadmium derivative.

Experimental top

Nickel chloride (0.26 g, 20 mmol) and fusaric acid (0.36 g, 20 mmol) were dissolved in a small volume of hot water; aqueous sodium hydroxide (30 mmol) was added to a pH of 7. Crystals suitable for x-ray diffraction appeared from the solution after a few days.

Refinement top

The butyl group is disordered over two positions in the β-, γ- and δ-carbon atoms, and was refined with a distance restraint of C—C 1.54 (1) Å; the vibration of the disordered atoms was restrained to be nearly isotropic. The occupation refined to a 681 (8):319 (8) ratio. The water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O—H 0.85 (3) and H···H 1.39 (3) Å. The carbon-bound H atoms were treated as riding, (C—H: 0.93–0.97 Å). The displacement factors of all H atoms were tied to those of their hosts through a factor of 1.2–1.5

Structure description top

5-Butyl-pyridyl-2-carboxylic acid (fusaric acid), unlike the parent unsubstituted carboxylic acid that affords a large number of N,O-chelated metal derivates, forms only three metal carboxylates that have been characterized by crystallography (Fan et al., 2007; He et al., 2007). The aquacadmium derivative (Okabe, Wada & Muranishi, 2002) has two chelating carboxylate groups. The sixth coordination site is taken up by a carboxyl oxygen atom from an adjacent molecule; the water and carboxyl oxygen atoms are cis to each other. The copper derivative has two coordinated methanol molecules whereas the iron(III) derivative is a tris-chelated compound; (Okabe, Muranishi & Wada, 2002). The metal atom in the title nickel(II) derivative (I) (Fig. 1) lies on an inversion center, and presents two coordinated water molecules in the octahedral environment, the remaining sites being occupied by two chelating alky-substituted 2-pyridylcarboxylate groups (Table 1); the coordinated water and the lattice water molecules engage in hydrogen bonding (Table 2) with the carboxyl group to furnish a two-dimensional network motif parallel to (001) (Fig. 2).

See Fan et al. (2007); He et al. (2007); Okabe, Muranishi & Wada (2002) for the copper(II), cobalt(II) and iron(III) derivatives, respectively, and Okabe, Wada & Muranishi (2002) for the cadmium derivative.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Unit-cell contents of (I). Thermal ellipsoids are shown at the 50% probability level. Symmetry code (i): 1 - x, 1 - y, 1 - z. The minor disorder component of the butyl chain is not shown.
[Figure 2] Fig. 2. Packing view of the two-dimensional structure generated by H-bonding, projected down [001].
Diaquabis(5-n-butylpyridine-2-carboxylato-\k2N,O)nickel(II) dihydrate top
Crystal data top
[Ni(C10H13NO2)2(H2O)2]·2H2OZ = 1
Mr = 487.19F(000) = 258
Triclinic, P1Dx = 1.414 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.2217 (10) ÅCell parameters from 1053 reflections
b = 9.9614 (17) Åθ = 3.6–24.8°
c = 11.5070 (19) ŵ = 0.90 mm1
α = 79.378 (3)°T = 293 K
β = 79.191 (3)°Block, green
γ = 80.152 (3)°0.16 × 0.15 × 0.09 mm
V = 572.05 (17) Å3
Data collection top
Bruker APEX area-detector
diffractometer
2022 independent reflections
Radiation source: fine-focus sealed tube1747 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
φ and ω scansθmax = 25.2°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 66
Tmin = 0.870, Tmax = 0.924k = 1111
3673 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0598P)2 + 0.0105P]
where P = (Fo2 + 2Fc2)/3
2022 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.43 e Å3
48 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Ni(C10H13NO2)2(H2O)2]·2H2Oγ = 80.152 (3)°
Mr = 487.19V = 572.05 (17) Å3
Triclinic, P1Z = 1
a = 5.2217 (10) ÅMo Kα radiation
b = 9.9614 (17) ŵ = 0.90 mm1
c = 11.5070 (19) ÅT = 293 K
α = 79.378 (3)°0.16 × 0.15 × 0.09 mm
β = 79.191 (3)°
Data collection top
Bruker APEX area-detector
diffractometer
2022 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1747 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.924Rint = 0.027
3673 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04148 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.43 e Å3
2022 reflectionsΔρmin = 0.45 e Å3
176 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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.50000.50000.50000.02811 (19)
O20.2417 (4)0.1359 (2)0.5223 (2)0.0458 (6)
O10.2861 (4)0.35853 (18)0.47295 (17)0.0322 (5)
O1W0.8216 (4)0.41784 (19)0.38023 (19)0.0356 (5)
N10.5972 (4)0.3419 (2)0.6331 (2)0.0294 (5)
C20.5090 (5)0.2248 (3)0.6261 (2)0.0299 (6)
C30.5740 (6)0.1037 (3)0.6988 (3)0.0392 (7)
H30.51540.02330.69090.047*
C40.7286 (7)0.1028 (3)0.7844 (3)0.0441 (8)
H40.77440.02100.83460.053*
C50.8152 (5)0.2221 (3)0.7959 (3)0.0358 (7)
C60.7457 (6)0.3387 (3)0.7170 (3)0.0355 (7)
H60.80520.41990.72220.043*
C10.3318 (5)0.2391 (3)0.5330 (3)0.0303 (6)
C70.9731 (6)0.2290 (4)0.8915 (3)0.0506 (9)
H7A1.12020.27860.85530.061*
H7B1.04450.13610.92370.061*
O2W0.8816 (5)0.1367 (2)0.3708 (2)0.0498 (6)
H1W10.785 (7)0.345 (2)0.363 (3)0.075*
H2W10.814 (7)0.063 (2)0.392 (3)0.075*
H1W20.963 (5)0.400 (3)0.410 (3)0.075*
H2W20.995 (6)0.137 (3)0.415 (3)0.075*
C80.8110 (11)0.3002 (6)0.9948 (4)0.0532 (17)0.681 (8)
H8A0.92810.31421.04630.064*0.681 (8)
H8B0.72600.39000.96220.064*0.681 (8)
C90.6039 (12)0.2166 (7)1.0683 (5)0.0642 (19)0.681 (8)
H9A0.68810.12771.10320.077*0.681 (8)
H9B0.48810.20071.01700.077*0.681 (8)
C100.442 (3)0.2930 (18)1.1683 (11)0.070 (3)0.681 (8)
H10A0.31200.23861.21440.105*0.681 (8)
H10B0.35640.38021.13360.105*0.681 (8)
H10C0.55680.30791.21940.105*0.681 (8)
C8'0.8037 (19)0.2008 (11)1.0182 (8)0.048 (3)0.319 (8)
H8'10.72640.11731.02500.058*0.319 (8)
H8'20.91660.18611.07870.058*0.319 (8)
C9'0.584 (2)0.3203 (12)1.0417 (10)0.053 (4)0.319 (8)
H9'10.48320.34130.97640.064*0.319 (8)
H9'20.66280.40141.04300.064*0.319 (8)
C10'0.397 (8)0.289 (4)1.161 (2)0.070 (3)0.319 (8)
H10D0.26590.36761.17160.105*0.319 (8)
H10E0.49560.26801.22580.105*0.319 (8)
H10F0.31250.21101.15870.105*0.319 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0258 (3)0.0260 (3)0.0334 (3)0.00582 (19)0.0074 (2)0.0022 (2)
O20.0487 (14)0.0328 (11)0.0626 (15)0.0153 (10)0.0209 (12)0.0037 (10)
O10.0299 (11)0.0282 (10)0.0399 (12)0.0061 (8)0.0122 (9)0.0003 (9)
O1W0.0306 (11)0.0353 (11)0.0419 (12)0.0047 (9)0.0078 (9)0.0070 (10)
N10.0265 (12)0.0287 (12)0.0334 (13)0.0058 (9)0.0047 (10)0.0048 (10)
C20.0242 (14)0.0299 (15)0.0334 (16)0.0036 (11)0.0003 (12)0.0047 (12)
C30.0421 (18)0.0279 (15)0.0462 (19)0.0066 (13)0.0093 (15)0.0010 (13)
C40.049 (2)0.0360 (17)0.0428 (19)0.0013 (14)0.0125 (15)0.0050 (14)
C50.0256 (15)0.0441 (17)0.0349 (16)0.0004 (12)0.0045 (12)0.0044 (13)
C60.0331 (16)0.0393 (17)0.0353 (17)0.0086 (13)0.0044 (13)0.0068 (13)
C10.0234 (14)0.0321 (15)0.0366 (16)0.0063 (11)0.0027 (12)0.0084 (13)
C70.041 (2)0.069 (2)0.0423 (19)0.0061 (16)0.0145 (16)0.0036 (17)
O2W0.0513 (15)0.0373 (13)0.0634 (16)0.0082 (10)0.0165 (12)0.0059 (11)
C80.060 (4)0.062 (4)0.044 (3)0.012 (3)0.021 (3)0.010 (3)
C90.072 (4)0.059 (4)0.057 (4)0.005 (3)0.005 (3)0.009 (3)
C100.074 (6)0.080 (3)0.056 (3)0.006 (3)0.008 (3)0.015 (2)
C8'0.048 (6)0.051 (6)0.044 (6)0.003 (5)0.016 (5)0.007 (5)
C9'0.058 (7)0.050 (7)0.046 (6)0.008 (5)0.009 (5)0.005 (5)
C10'0.074 (6)0.080 (3)0.056 (3)0.006 (3)0.008 (3)0.015 (2)
Geometric parameters (Å, º) top
Ni1—O12.0398 (18)C7—H7A0.9700
Ni1—O1i2.0398 (18)C7—H7B0.9700
Ni1—N1i2.053 (2)O2W—H2W10.85 (3)
Ni1—N12.053 (2)O2W—H2W20.85 (3)
Ni1—O1W2.113 (2)C8—C91.511 (7)
Ni1—O1Wi2.113 (2)C8—H8A0.9700
O2—C11.236 (3)C8—H8B0.9700
O1—C11.269 (3)C9—C101.534 (9)
O1W—H1W10.85 (3)C9—H9A0.9700
O1W—H1W20.85 (3)C9—H9B0.9700
N1—C61.339 (4)C10—H10A0.9600
N1—C21.347 (3)C10—H10B0.9600
C2—C31.365 (4)C10—H10C0.9600
C2—C11.515 (4)C8'—C9'1.528 (9)
C3—C41.383 (4)C8'—H8'10.9700
C3—H30.9300C8'—H8'20.9700
C4—C51.378 (4)C9'—C10'1.541 (10)
C4—H40.9300C9'—H9'10.9700
C5—C61.377 (4)C9'—H9'20.9700
C5—C71.512 (4)C10'—H10D0.9600
C6—H60.9300C10'—H10E0.9600
C7—C81.536 (5)C10'—H10F0.9600
O1—Ni1—O1i180.00 (10)C8—C7—H7A108.9
O1—Ni1—N1i99.56 (8)C8'—C7—H7A136.8
O1i—Ni1—N1i80.44 (8)C5—C7—H7B108.9
O1—Ni1—N180.44 (8)C8—C7—H7B108.9
O1i—Ni1—N199.56 (8)H7A—C7—H7B107.7
N1i—Ni1—N1180.000 (1)H2W1—O2W—H2W2109.2 (17)
O1—Ni1—O1W89.28 (8)C9—C8—C7112.1 (5)
O1i—Ni1—O1W90.72 (8)C9—C8—H8A109.2
N1i—Ni1—O1W90.35 (8)C7—C8—H8A109.2
N1—Ni1—O1W89.65 (8)C9—C8—H8B109.2
O1—Ni1—O1Wi90.72 (8)C7—C8—H8B109.2
O1i—Ni1—O1Wi89.28 (8)H8A—C8—H8B107.9
N1i—Ni1—O1Wi89.65 (8)C8—C9—C10110.4 (7)
N1—Ni1—O1Wi90.35 (8)C8—C9—H9A109.6
O1W—Ni1—O1Wi180.000 (1)C10—C9—H9A109.6
C1—O1—Ni1115.02 (17)C8—C9—H9B109.6
Ni1—O1W—H1W1108 (3)C10—C9—H9B109.6
Ni1—O1W—H1W2112 (3)H9A—C9—H9B108.1
H1W1—O1W—H1W2110.0 (17)C9—C10—H10A109.5
C6—N1—C2118.2 (2)C9—C10—H10B109.5
C6—N1—Ni1129.16 (19)H10A—C10—H10B109.5
C2—N1—Ni1112.47 (18)C9—C10—H10C109.5
N1—C2—C3121.9 (3)H10A—C10—H10C109.5
N1—C2—C1114.8 (2)H10B—C10—H10C109.5
C3—C2—C1123.3 (3)C9'—C8'—C7112.1 (8)
C2—C3—C4118.9 (3)C9'—C8'—H8'1109.2
C2—C3—H3120.6C7—C8'—H8'1109.2
C4—C3—H3120.6C9'—C8'—H8'2109.2
C5—C4—C3120.4 (3)C7—C8'—H8'2109.2
C5—C4—H4119.8H8'1—C8'—H8'2107.9
C3—C4—H4119.8C8'—C9'—C10'113.0 (18)
C6—C5—C4116.8 (3)C8'—C9'—H9'1109.0
C6—C5—C7120.3 (3)C10'—C9'—H9'1109.0
C4—C5—C7122.8 (3)C8'—C9'—H9'2109.0
N1—C6—C5123.7 (3)C10'—C9'—H9'2109.0
N1—C6—H6118.1H9'1—C9'—H9'2107.8
C5—C6—H6118.1C9'—C10'—H10D109.5
O2—C1—O1125.4 (3)C9'—C10'—H10E109.5
O2—C1—C2118.3 (2)H10D—C10'—H10E109.5
O1—C1—C2116.3 (2)C9'—C10'—H10F109.5
C5—C7—C8113.2 (3)H10D—C10'—H10F109.5
C5—C7—C8'110.1 (5)H10E—C10'—H10F109.5
C5—C7—H7A108.9
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.85 (3)2.04 (2)2.784 (3)147 (3)
O1W—H1W2···O1ii0.85 (3)1.92 (2)2.760 (3)179 (4)
O2W—H2W2···O2ii0.85 (3)1.94 (2)2.792 (3)177 (4)
O2W—H2W1···O2iii0.85 (3)2.08 (2)2.893 (3)160 (3)
Symmetry codes: (ii) x+1, y, z; (iii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C10H13NO2)2(H2O)2]·2H2O
Mr487.19
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.2217 (10), 9.9614 (17), 11.5070 (19)
α, β, γ (°)79.378 (3), 79.191 (3), 80.152 (3)
V3)572.05 (17)
Z1
Radiation typeMo Kα
µ (mm1)0.90
Crystal size (mm)0.16 × 0.15 × 0.09
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.870, 0.924
No. of measured, independent and
observed [I > 2σ(I)] reflections
3673, 2022, 1747
Rint0.027
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.105, 1.06
No. of reflections2022
No. of parameters176
No. of restraints48
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.45

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected bond lengths (Å) top
Ni1—O12.0398 (18)Ni1—O1W2.113 (2)
Ni1—N12.053 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.85 (3)2.04 (2)2.784 (3)147 (3)
O1W—H1W2···O1i0.85 (3)1.92 (2)2.760 (3)179 (4)
O2W—H2W2···O2i0.85 (3)1.94 (2)2.792 (3)177 (4)
O2W—H2W1···O2ii0.85 (3)2.08 (2)2.893 (3)160 (3)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1.
 

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