Hydrothermal synthesis and crystal structure of novel bis(6-carboxypyridine-2-carboxylato-κ³O²,N,O⁶)nickel(II) trihydrate, Ni(Hpydc)₂·3H₂O

The synthesis and crystal structure of the compound bis(6-carboxypyridine-2-carboxylato-κ³O²,N,O⁶)nickel(II) trihydrate, Ni(Hpydc)₂·3H₂O, with a supramolecular network is reported (H₂pydc is pyridine-2,6-dicarboxylic acid). The compound has been prepared by hydrothermal methods. The crystal structure has been solved by direct methods using single-crystal X-ray diffraction data collected at 293 K and refined by full-matrix least-squares procedures to a final R value of 0.0323 for 2779 observed reflections. The compound has distorted octahedral geometry around the metal centre. The complex contains two identical singly ionized ligand molecules. The nickel(II) is bonded to four O atoms and two N atoms from the tridentate ligand molecules, which are nearly perpendicular to each other. Hydrogen-bonded interactions create a three-dimensional supramolecular porous network. The supramolecular structure accounts for the porous structure of the compound as is evident from the Brunauer, Emmett & Teller (BET) surface area of 80 m² g⁻¹. Thermal degradation of the compound shows that lattice water molecules give stability to the crystal structure.

Computing details

Data collection: CrysAlis PRO,Diff.Ltd,Ver 1.171.34.40; cell refinement: CrysAlis PRO, Diff.Ltd,Ver 1.171.34.40; data reduction: CrysAlis PRO, Diff.Ltd,Ver 1.171.34.40; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON(Spek,1999)& PARST(1995).

Figures

bis (2,6-pyridinedicarboxylato)nickelate(II) trihydrate

Crystal data

C14H8N2NiO8·3(H2O)	F(000) = 912
Mr = 444.98	Dx = 1.724 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12492 reflections
a = 13.6825 (3) Å	θ = 3.4–29.0°
b = 10.0465 (2) Å	µ = 1.20 mm^−1
c = 13.7770 (4) Å	T = 293 K
β = 115.166 (3)°	Block-shaped, blue
V = 1714.04 (7) Å^3	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection

CCD area detector diffractometer	3353 independent reflections
Radiation source: fine-focus sealed tube	2779 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan Crys Alis RED	h = −16→16
Tmin = 0.827, Tmax = 1.000	k = −12→12
24855 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0475P)^2 + 0.7877P] where P = (Fo^2 + 2Fc^2)/3
3353 reflections	(Δ/σ)max = 0.001
317 parameters	Δρmax = 0.24 e Å^−3
6 restraints	Δρmin = −0.67 e Å^−3

Special details

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.249899 (18)	−0.00644 (3)	0.247854 (19)	0.02873 (11)
N1	0.10567 (13)	−0.08566 (16)	0.17538 (13)	0.0276 (4)
N2	0.39690 (13)	0.06843 (18)	0.31351 (13)	0.0296 (4)
O1	0.04763 (13)	−0.03015 (17)	0.39594 (13)	0.0426 (4)
O2	0.19331 (12)	0.01026 (15)	0.36673 (12)	0.0362 (4)
O3	0.12844 (14)	−0.15378 (17)	−0.06314 (13)	0.0469 (4)
H3	0.1775	−0.1371	−0.0805	0.070*
O4	0.24035 (12)	−0.05553 (16)	0.09061 (12)	0.0381 (4)
O5	0.51290 (16)	−0.2384 (2)	0.41799 (17)	0.0705 (6)
O6	0.34216 (13)	−0.17635 (15)	0.31878 (13)	0.0421 (4)
O7	0.31933 (13)	0.39304 (16)	0.22385 (14)	0.0470 (4)
H7	0.2594	0.4248	0.1884	0.070*
O8	0.22443 (11)	0.20558 (15)	0.20625 (12)	0.0377 (4)
O1W	0.15290 (17)	0.5154 (2)	0.10971 (17)	0.0491 (5)
O2W	0.2536 (2)	−0.1106 (2)	−0.14525 (19)	0.0576 (5)
O31W	0.4208 (15)	0.0227 (7)	0.0042 (9)	0.163 (6)	0.504 (15)
O32W	0.3421 (8)	0.0807 (11)	−0.0193 (7)	0.094 (4)	0.496 (15)
C1	0.09883 (17)	−0.0341 (2)	0.33990 (17)	0.0316 (5)
C2	0.04520 (16)	−0.0959 (2)	0.22937 (16)	0.0290 (4)
C3	−0.05387 (18)	−0.1593 (2)	0.18443 (19)	0.0375 (5)
C4	−0.08908 (19)	−0.2105 (2)	0.08180 (19)	0.0415 (6)
C5	−0.02516 (17)	−0.1988 (2)	0.02649 (18)	0.0355 (5)
C6	0.07292 (16)	−0.13545 (19)	0.07657 (16)	0.0296 (4)
C7	0.15409 (17)	−0.1128 (2)	0.03198 (16)	0.0324 (5)
C8	0.44417 (19)	−0.1551 (2)	0.36927 (18)	0.0420 (6)
C9	0.47874 (18)	−0.0135 (2)	0.36699 (17)	0.0348 (5)
C10	0.58406 (19)	0.0342 (3)	0.41447 (19)	0.0457 (6)
C11	0.60224 (19)	0.1665 (3)	0.4043 (2)	0.0506 (7)
C12	0.51655 (19)	0.2513 (3)	0.34765 (19)	0.0432 (6)
C13	0.41377 (16)	0.1972 (2)	0.30348 (16)	0.0319 (5)
C14	0.31005 (17)	0.2686 (2)	0.23952 (16)	0.0331 (5)
H31B	0.384 (10)	0.043 (9)	−0.062 (3)	0.13 (3)*	0.504 (15)
H31A	0.446 (7)	0.094 (5)	0.040 (6)	0.13 (3)*	0.504 (15)
H32A	0.393 (6)	0.136 (9)	0.010 (7)	0.13 (3)*	0.496 (15)
H32B	0.301 (6)	0.081 (10)	0.013 (7)	0.13 (3)*	0.496 (15)
H1	0.103 (3)	0.499 (3)	0.125 (3)	0.061 (10)*
H2	0.134 (3)	0.508 (3)	0.051 (3)	0.057 (11)*
H31	−0.0931 (19)	−0.168 (2)	0.2218 (19)	0.041 (7)*
H4	−0.152 (2)	−0.252 (3)	0.049 (2)	0.057 (8)*
H5	−0.048 (2)	−0.233 (3)	−0.044 (2)	0.051 (7)*
H6	0.298 (3)	−0.070 (4)	−0.106 (3)	0.056 (11)*
H71	0.285 (3)	−0.189 (4)	−0.156 (3)	0.102 (14)*
H10	0.637 (2)	−0.021 (3)	0.452 (2)	0.051 (8)*
H11	0.677 (2)	0.192 (3)	0.437 (2)	0.058 (8)*
H12	0.528 (2)	0.348 (3)	0.340 (2)	0.062 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02401 (17)	0.03289 (18)	0.02852 (18)	−0.00146 (10)	0.01043 (13)	−0.00113 (10)
N1	0.0274 (8)	0.0274 (9)	0.0276 (9)	−0.0009 (7)	0.0113 (7)	0.0000 (7)
N2	0.0239 (8)	0.0405 (10)	0.0250 (9)	0.0024 (7)	0.0109 (7)	0.0013 (7)
O1	0.0418 (9)	0.0572 (10)	0.0363 (9)	−0.0044 (8)	0.0238 (8)	−0.0078 (7)
O2	0.0292 (8)	0.0484 (10)	0.0305 (8)	−0.0044 (6)	0.0124 (7)	−0.0081 (6)
O3	0.0602 (10)	0.0516 (10)	0.0370 (9)	−0.0094 (8)	0.0284 (8)	−0.0101 (8)
O4	0.0384 (9)	0.0443 (9)	0.0366 (8)	−0.0030 (7)	0.0207 (7)	−0.0028 (7)
O5	0.0671 (13)	0.0673 (13)	0.0783 (14)	0.0344 (11)	0.0321 (11)	0.0310 (11)
O6	0.0460 (9)	0.0364 (9)	0.0478 (9)	0.0043 (7)	0.0236 (8)	0.0062 (7)
O7	0.0463 (9)	0.0369 (9)	0.0553 (10)	−0.0015 (7)	0.0193 (8)	0.0070 (8)
O8	0.0282 (7)	0.0375 (8)	0.0409 (9)	−0.0004 (6)	0.0084 (7)	0.0016 (7)
O1W	0.0476 (12)	0.0632 (13)	0.0371 (11)	0.0080 (9)	0.0185 (10)	0.0101 (9)
O2W	0.0780 (15)	0.0484 (12)	0.0581 (13)	−0.0036 (12)	0.0402 (12)	−0.0030 (10)
O31W	0.176 (12)	0.049 (4)	0.169 (9)	−0.034 (5)	−0.018 (8)	−0.019 (4)
O32W	0.104 (6)	0.119 (7)	0.091 (5)	−0.077 (5)	0.071 (5)	−0.061 (5)
C1	0.0324 (11)	0.0344 (11)	0.0289 (11)	0.0012 (9)	0.0139 (9)	0.0003 (9)
C2	0.0293 (10)	0.0297 (10)	0.0300 (10)	−0.0001 (8)	0.0144 (9)	0.0017 (8)
C3	0.0352 (12)	0.0382 (12)	0.0426 (13)	−0.0057 (9)	0.0199 (11)	−0.0003 (10)
C4	0.0351 (12)	0.0374 (13)	0.0446 (13)	−0.0108 (10)	0.0101 (11)	−0.0049 (10)
C5	0.0396 (12)	0.0306 (11)	0.0305 (11)	−0.0035 (9)	0.0094 (10)	−0.0033 (9)
C6	0.0350 (11)	0.0244 (10)	0.0273 (10)	0.0015 (8)	0.0112 (9)	−0.0001 (8)
C7	0.0403 (12)	0.0276 (10)	0.0310 (11)	0.0019 (9)	0.0168 (9)	0.0006 (9)
C8	0.0472 (14)	0.0485 (14)	0.0370 (12)	0.0186 (11)	0.0245 (11)	0.0122 (10)
C9	0.0299 (11)	0.0512 (14)	0.0258 (11)	0.0085 (9)	0.0143 (9)	0.0040 (9)
C10	0.0272 (12)	0.0757 (19)	0.0320 (12)	0.0113 (12)	0.0103 (10)	0.0020 (12)
C11	0.0268 (12)	0.078 (2)	0.0440 (14)	−0.0109 (12)	0.0125 (11)	−0.0079 (13)
C12	0.0360 (12)	0.0543 (15)	0.0397 (13)	−0.0106 (11)	0.0165 (10)	−0.0044 (11)
C13	0.0292 (10)	0.0409 (12)	0.0270 (10)	−0.0039 (9)	0.0132 (9)	−0.0016 (9)
C14	0.0362 (11)	0.0367 (12)	0.0282 (10)	−0.0009 (9)	0.0155 (9)	−0.0010 (9)

Geometric parameters (Å, º)

Ni1—N1	1.9619 (16)	O31W—H31A	0.85 (2)
Ni1—N2	1.9703 (17)	O31W—H32A	1.22 (10)
Ni1—O2	2.0947 (15)	O32W—H31B	1.05 (13)
Ni1—O6	2.1008 (15)	O32W—H31A	1.31 (8)
Ni1—O4	2.1709 (15)	O32W—H32A	0.85 (2)
Ni1—O8	2.1948 (15)	O32W—H32B	0.85 (2)
N1—C2	1.331 (3)	C1—C2	1.514 (3)
N1—C6	1.336 (3)	C2—C3	1.383 (3)
N2—C13	1.331 (3)	C3—C4	1.384 (3)
N2—C9	1.332 (3)	C3—H31	0.89 (2)
O1—C1	1.244 (3)	C4—C5	1.388 (3)
O2—C1	1.265 (3)	C4—H4	0.89 (3)
O3—C7	1.272 (3)	C5—C6	1.376 (3)
O3—H3	0.8200	C5—H5	0.95 (3)
O4—C7	1.251 (3)	C6—C7	1.498 (3)
O5—C8	1.224 (3)	C8—C9	1.503 (3)
O6—C8	1.285 (3)	C9—C10	1.390 (3)
O7—C14	1.284 (3)	C10—C11	1.371 (4)
O7—H7	0.8200	C10—H10	0.89 (3)
O8—C14	1.236 (2)	C11—C12	1.390 (4)
O1W—H1	0.81 (3)	C11—H11	0.96 (3)
O1W—H2	0.75 (4)	C12—C13	1.384 (3)
O2W—H6	0.74 (3)	C12—H12	1.00 (3)
O2W—H71	0.94 (4)	C13—C14	1.497 (3)
O31W—H31B	0.86 (2)
N1—Ni1—N2	176.42 (7)	O2—C1—C2	115.87 (18)
N1—Ni1—O2	78.71 (6)	N1—C2—C3	120.62 (19)
N2—Ni1—O2	104.77 (6)	N1—C2—C1	112.32 (17)
N1—Ni1—O6	100.51 (6)	C3—C2—C1	127.05 (19)
N2—Ni1—O6	78.61 (7)	C2—C3—C4	118.5 (2)
O2—Ni1—O6	92.87 (6)	C2—C3—H31	120.0 (16)
N1—Ni1—O4	77.25 (6)	C4—C3—H31	121.4 (16)
N2—Ni1—O4	99.29 (6)	C3—C4—C5	120.2 (2)
O2—Ni1—O4	155.92 (6)	C3—C4—H4	122.3 (18)
O6—Ni1—O4	92.80 (6)	C5—C4—H4	117.6 (18)
N1—Ni1—O8	104.31 (6)	C6—C5—C4	118.1 (2)
N2—Ni1—O8	76.53 (6)	C6—C5—H5	120.6 (16)
O2—Ni1—O8	93.21 (6)	C4—C5—H5	121.2 (16)
O6—Ni1—O8	155.14 (6)	N1—C6—C5	121.13 (19)
O4—Ni1—O8	91.40 (6)	N1—C6—C7	112.04 (17)
C2—N1—C6	121.43 (17)	C5—C6—C7	126.84 (19)
C2—N1—Ni1	118.48 (13)	O4—C7—O3	125.8 (2)
C6—N1—Ni1	119.96 (14)	O4—C7—C6	117.74 (18)
C13—N2—C9	121.08 (18)	O3—C7—C6	116.46 (19)
C13—N2—Ni1	120.76 (14)	O5—C8—O6	126.0 (3)
C9—N2—Ni1	118.16 (15)	O5—C8—C9	118.9 (2)
C1—O2—Ni1	114.51 (13)	O6—C8—C9	115.13 (19)
C7—O3—H3	109.5	N2—C9—C10	120.4 (2)
C7—O4—Ni1	112.86 (13)	N2—C9—C8	113.49 (19)
C8—O6—Ni1	114.60 (15)	C10—C9—C8	126.1 (2)
C14—O7—H7	109.5	C11—C10—C9	118.9 (2)
C14—O8—Ni1	112.36 (13)	C11—C10—H10	122.2 (18)
H1—O1W—H2	109 (4)	C9—C10—H10	118.9 (18)
H6—O2W—H71	107 (3)	C10—C11—C12	120.4 (2)
H31B—O31W—H31A	109 (3)	C10—C11—H11	114.2 (17)
H31B—O31W—H32A	77 (8)	C12—C11—H11	125.4 (17)
H31A—O31W—H32A	41 (6)	C13—C12—C11	117.6 (2)
H31B—O32W—H31A	71 (4)	C13—C12—H12	120.9 (16)
H31B—O32W—H32A	88 (8)	C11—C12—H12	121.5 (16)
H31A—O32W—H32A	36 (8)	N2—C13—C12	121.6 (2)
H31B—O32W—H32B	159 (8)	N2—C13—C14	111.36 (17)
H31A—O32W—H32B	117 (7)	C12—C13—C14	127.0 (2)
H32A—O32W—H32B	110 (3)	O8—C14—O7	125.6 (2)
O1—C1—O2	125.6 (2)	O8—C14—C13	118.95 (19)
O1—C1—C2	118.52 (18)	O7—C14—C13	115.41 (19)
O2—Ni1—N1—C2	−1.96 (14)	O1—C1—C2—C3	−5.3 (3)
O6—Ni1—N1—C2	88.90 (15)	O2—C1—C2—C3	175.2 (2)
O4—Ni1—N1—C2	179.41 (16)	N1—C2—C3—C4	−0.6 (3)
O8—Ni1—N1—C2	−92.42 (15)	C1—C2—C3—C4	−179.6 (2)
O2—Ni1—N1—C6	−177.72 (16)	C2—C3—C4—C5	0.5 (3)
O6—Ni1—N1—C6	−86.86 (15)	C3—C4—C5—C6	0.0 (3)
O4—Ni1—N1—C6	3.65 (15)	C2—N1—C6—C5	0.4 (3)
O8—Ni1—N1—C6	91.82 (15)	Ni1—N1—C6—C5	176.00 (15)
O2—Ni1—N2—C13	−90.76 (16)	C2—N1—C6—C7	−179.71 (17)
O6—Ni1—N2—C13	179.25 (16)	Ni1—N1—C6—C7	−4.1 (2)
O4—Ni1—N2—C13	88.25 (16)	C4—C5—C6—N1	−0.4 (3)
O8—Ni1—N2—C13	−0.97 (15)	C4—C5—C6—C7	179.6 (2)
O2—Ni1—N2—C9	90.00 (15)	Ni1—O4—C7—O3	−179.06 (18)
O6—Ni1—N2—C9	0.01 (15)	Ni1—O4—C7—C6	1.1 (2)
O4—Ni1—N2—C9	−90.99 (15)	N1—C6—C7—O4	1.7 (3)
O8—Ni1—N2—C9	179.80 (16)	C5—C6—C7—O4	−178.4 (2)
N1—Ni1—O2—C1	−0.36 (15)	N1—C6—C7—O3	−178.14 (18)
N2—Ni1—O2—C1	−179.48 (15)	C5—C6—C7—O3	1.8 (3)
O6—Ni1—O2—C1	−100.51 (15)	Ni1—O6—C8—O5	178.7 (2)
O4—Ni1—O2—C1	2.9 (2)	Ni1—O6—C8—C9	−0.8 (2)
O8—Ni1—O2—C1	103.60 (15)	C13—N2—C9—C10	0.5 (3)
N1—Ni1—O4—C7	−2.49 (15)	Ni1—N2—C9—C10	179.75 (16)
N2—Ni1—O4—C7	176.57 (15)	C13—N2—C9—C8	−179.66 (18)
O2—Ni1—O4—C7	−5.8 (2)	Ni1—N2—C9—C8	−0.4 (2)
O6—Ni1—O4—C7	97.67 (15)	O5—C8—C9—N2	−178.7 (2)
O8—Ni1—O4—C7	−106.84 (15)	O6—C8—C9—N2	0.8 (3)
N1—Ni1—O6—C8	176.93 (15)	O5—C8—C9—C10	1.1 (4)
N2—Ni1—O6—C8	0.47 (15)	O6—C8—C9—C10	−179.4 (2)
O2—Ni1—O6—C8	−104.03 (15)	N2—C9—C10—C11	−0.7 (3)
O4—Ni1—O6—C8	99.38 (15)	C8—C9—C10—C11	179.5 (2)
O8—Ni1—O6—C8	0.0 (2)	C9—C10—C11—C12	0.1 (4)
N1—Ni1—O8—C14	−174.82 (14)	C10—C11—C12—C13	0.5 (4)
N2—Ni1—O8—C14	1.59 (14)	C9—N2—C13—C12	0.2 (3)
O2—Ni1—O8—C14	106.03 (14)	Ni1—N2—C13—C12	−179.04 (16)
O6—Ni1—O8—C14	2.1 (2)	C9—N2—C13—C14	179.52 (18)
O4—Ni1—O8—C14	−97.62 (14)	Ni1—N2—C13—C14	0.3 (2)
Ni1—O2—C1—O1	−177.22 (18)	C11—C12—C13—N2	−0.7 (3)
Ni1—O2—C1—C2	2.3 (2)	C11—C12—C13—C14	−179.9 (2)
C6—N1—C2—C3	0.2 (3)	Ni1—O8—C14—O7	177.68 (17)
Ni1—N1—C2—C3	−175.51 (16)	Ni1—O8—C14—C13	−2.0 (2)
C6—N1—C2—C1	179.27 (17)	N2—C13—C14—O8	1.2 (3)
Ni1—N1—C2—C1	3.6 (2)	C12—C13—C14—O8	−179.5 (2)
O1—C1—C2—N1	175.72 (19)	N2—C13—C14—O7	−178.44 (18)
O2—C1—C2—N1	−3.8 (3)	C12—C13—C14—O7	0.9 (3)