catena-Poly[[diaqua­nickel(II)]-bis[μ-(4-pyridylsulfanyl)acetato-κ²N:O;κ²O:N]]

The Ni atom in the title compound, [Ni(C₇H₆NO₂S)₂(H₂O)₂]_n, occupies a special position on an inversion centre and has an octa­hedral coordination formed by two water mol­ecules and two pyridyl N and two carboxyl­ate O atoms belonging to four different anionic ligands. Each ligand has a bidentate bridging function, so that each Ni atom is connected to each of its two Ni neighbours by two ligand bridges, thus producing infinite chains running along the a axis in the crystal structure. O—H...O bonds link the chains into a three-dimensional framework.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.084
• wR factor = 0.191
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT731_ALERT_1_B Bond    Calc     0.85(9), Rep     0.85(2) ......       4.50 su-Ra
              O3   -H6      1.555   1.555
PLAT735_ALERT_1_B D-H     Calc     0.85(9), Rep     0.85(2) ......       4.50 su-Ra
              O3   -H6      1.555   1.555

Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.50 Ratio
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         12
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          1
            O3  -NI1 -O3  -O2      7.00  0.00   3.555   1.555   1.555   3.655
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O3  -NI1 -O3  -O2      5.00  0.00   3.555   1.555   1.555   2.655
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            N1  -NI1 -N1  -C5      9.00  0.00   3.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         20
            N1  -NI1 -N1  -C1      9.00  0.00   3.555   1.555   1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(6), Rep     0.85(2) ......       3.00 su-Ra
              O3   -H3      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(6), Rep     0.85(2) ......       3.00 su-Ra
              O3   -H3      1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.97(9), Rep     1.97(4) ......       2.25 su-Ra
              H6   -O2      1.555   2.655
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.18 Ratio
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      13.00 Deg.
              O2   -O3   -H3      3.655   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      12.00 Deg.
              O2   -O3   -H6      2.655   1.555   1.555

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Three compounds obtained by the reaction of pyridin-4-ylthioacetic acid with nickel(II) salts have been recently crystallographically characterized, namely one zwitterionic complex [Ni(C₇H₆NO₂S)₂(H₂O)₄] (Zhang et al., 2004) and two coordination polymers, [Ni(C₇H₆NO₂S)₂(H₂O)]_n (Huang et al., 2004a) and [Ni₂(C₇H₆NO₂S)₄(H₂O)₂]_n (Huang et al., 2004b). Herein we report the structure of a new Ni(II) complex (I) with pyridin-4-ylthioacetato ligand.

In the crystal structure of the title compound, the Ni1 atom occupies a special position in the inversion centre and has an octahedral coordination formed by two water molecules, as well as two pyridyl N and two carboxylate O atoms belonging to four different anionic ligands. Each ligand has a bidentate bridging function, so that each Ni atom is connected to each of its two Ni neighbours by two ligand bridges, thus producing infinite chains running along the a-axis in the crystal structure (Fig. 1). The O—H···O bonds link the chains into a three-dimensional framework (Table 2, Fig. 2).

Related literature

For related literature, see: Huang et al. (2004a,b); Zhang et al. (2004).

S2. Experimental

Nickel(II) acetate (50 mg, 0.2 mmol), pyridin-4-ylthioacetic acid (39 mg, 0.2 mmol) and NaOH (8 mg, 0.2 mmol) were dissolved in 10 ml of water. The solution was placed in a Teflon-lined stainless-steel bomb (23 ml) and heated at 423 K for 48 h. After cooling to room temperature, green crystals of (I) precipitated from the solution in about 60% yield.

S3. Refinement

The water H atoms were located and refined, subject to an O—H = 0.85±0.02 Å restraint. The aromatic and aliphatic H atoms were placed at calculated positions (C—H 0.93 Å and 0.97 Å respectively) and refined using the riding-model approximation with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 1997a); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Infinite chains in the crystal structure of (I) with atom-labelling scheme, showing the coordination sphere of metal and coordination mode of the ligand. Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as small spheres of arbitrary radius. Hydrogen bonds are shown as dashed lines [Symmetry codes: (i): x - 1, y, z; (ii): 1 - x, -y, -z; (iii): -x, -y, -z].

Fig. 2. The packing diagram of the title compound viewed down the a-axis. Hydrogen bonds are shown as dashed lines.

catena-Poly[[diaquanickel(II)]-bis[µ-(4-pyridylsulfanyl)acetato- κ²N:O;κ²O:N]]

Crystal data

[Ni(C7H6NO2S)2(H2O)2]	F(000) = 444
Mr = 431.12	Dx = 1.689 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2522 reflections
a = 8.9232 (9) Å	θ = 2.3–25.0°
b = 10.6901 (10) Å	µ = 1.42 mm^−1
c = 8.8887 (9) Å	T = 298 K
β = 90.378 (3)°	Prism, green
V = 847.87 (14) Å^3	0.32 × 0.24 × 0.16 mm
Z = 2

Data collection

BRUKER SMART CCD Apex II diffractometer	1489 independent reflections
Radiation source: fine-focus sealed tube	1198 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 8.40 pixels mm^-1	θmax = 25.0°, θmin = 2.3°
ω scans	h = −10→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −11→12
Tmin = 0.658, Tmax = 0.804	l = −10→10
2425 measured reflections

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + 14.8565P] where P = (Fo^2 + 2Fc^2)/3
1489 reflections	(Δ/σ)max < 0.001
123 parameters	Δρmax = 0.96 e Å^−3
2 restraints	Δρmin = −0.91 e Å^−3

Special details

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
Ni1	0.0000	0.0000	0.0000	0.0233 (4)
S1	0.5686 (2)	−0.1649 (2)	0.4472 (2)	0.0294 (6)
O1	0.8661 (6)	−0.0028 (6)	0.1907 (7)	0.0311 (14)
O2	0.8051 (7)	−0.2052 (6)	0.2088 (7)	0.0315 (15)
O3	0.0489 (7)	0.1845 (6)	0.0462 (7)	0.0287 (14)
N1	0.1893 (8)	−0.0633 (7)	0.1246 (8)	0.0298 (18)
C1	0.3188 (9)	0.0012 (9)	0.1215 (9)	0.0271 (19)
H1	0.3263	0.0683	0.0555	0.033*
C2	0.4433 (10)	−0.0276 (9)	0.2126 (11)	0.033 (2)
H2	0.5317	0.0179	0.2049	0.040*
C3	0.4312 (9)	−0.1255 (8)	0.3141 (10)	0.0246 (19)
C4	0.3014 (10)	−0.1952 (9)	0.3123 (10)	0.031 (2)
H4	0.2924	−0.2647	0.3745	0.037*
C5	0.1847 (10)	−0.1616 (9)	0.2178 (10)	0.031 (2)
H5	0.0980	−0.2100	0.2189	0.037*
C6	0.7218 (10)	−0.0638 (9)	0.4016 (10)	0.030 (2)
H6A	0.6842	0.0212	0.3952	0.036*
H6B	0.7939	−0.0665	0.4838	0.036*
C7	0.8041 (9)	−0.0940 (8)	0.2550 (9)	0.0243 (19)
H3	0.110 (7)	0.201 (8)	−0.025 (6)	0.02 (2)*
H6	0.100 (11)	0.202 (11)	0.124 (8)	0.07 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0199 (8)	0.0251 (8)	0.0249 (8)	−0.0015 (7)	−0.0033 (6)	−0.0003 (7)
S1	0.0232 (11)	0.0395 (13)	0.0255 (11)	0.0049 (10)	−0.0031 (9)	0.0067 (10)
O1	0.029 (3)	0.032 (3)	0.032 (3)	0.000 (3)	0.000 (3)	0.001 (3)
O2	0.037 (4)	0.030 (4)	0.028 (3)	−0.001 (3)	0.003 (3)	−0.003 (3)
O3	0.031 (4)	0.031 (4)	0.025 (3)	−0.004 (3)	−0.003 (3)	−0.009 (3)
N1	0.021 (4)	0.033 (4)	0.035 (4)	0.002 (3)	0.000 (3)	0.000 (3)
C1	0.021 (4)	0.031 (4)	0.029 (5)	−0.004 (4)	−0.005 (3)	0.004 (4)
C2	0.022 (4)	0.035 (6)	0.043 (5)	0.000 (4)	−0.001 (4)	0.003 (4)
C3	0.017 (4)	0.026 (5)	0.030 (5)	0.006 (3)	−0.002 (3)	−0.007 (4)
C4	0.033 (5)	0.027 (5)	0.032 (5)	−0.004 (4)	0.005 (4)	0.007 (4)
C5	0.020 (4)	0.034 (5)	0.037 (5)	−0.005 (4)	0.001 (4)	0.015 (4)
C6	0.023 (5)	0.034 (5)	0.031 (5)	0.004 (4)	0.000 (4)	0.002 (4)
C7	0.015 (4)	0.033 (5)	0.024 (4)	0.002 (4)	−0.009 (3)	0.006 (4)

Geometric parameters (Å, º)

Ni1—O3^i	2.060 (6)	O3—H6	0.85 (2)
Ni1—O1^ii	2.081 (6)	N1—C5	1.339 (11)
Ni1—O3	2.060 (6)	N1—C1	1.346 (11)
Ni1—O1^iii	2.081 (6)	C1—C2	1.404 (12)
Ni1—N1^i	2.125 (7)	C1—H1	0.9300
Ni1—N1	2.125 (7)	C2—C3	1.386 (12)
S1—C3	1.749 (8)	C2—H2	0.9300
S1—C6	1.792 (9)	C3—C4	1.378 (12)
O1—C7	1.260 (10)	C4—C5	1.382 (12)
O1—Ni1^iv	2.081 (6)	C4—H4	0.9300
O2—C7	1.258 (11)	C5—H5	0.9300
O3—O2^ii	2.631 (9)	C6—C7	1.535 (12)
O3—O2^v	2.792 (8)	C6—H6A	0.9700
O3—H3	0.85 (2)	C6—H6B	0.9700
O3—Ni1—O3^i	180.0 (3)	C5—N1—C1	116.4 (7)
O3—Ni1—O1^ii	91.5 (3)	C5—N1—Ni1	123.0 (6)
O3^i—Ni1—O1^ii	88.5 (3)	C1—N1—Ni1	120.4 (6)
O3—Ni1—O1^iii	88.5 (3)	N1—C1—C2	123.5 (8)
O3^i—Ni1—O1^iii	91.5 (3)	N1—C1—H1	118.2
O1^ii—Ni1—O1^iii	180.0 (3)	C2—C1—H1	118.2
O3—Ni1—N1^i	88.0 (3)	C3—C2—C1	118.4 (8)
O3^i—Ni1—N1^i	92.0 (3)	C3—C2—H2	120.8
O1^ii—Ni1—N1^i	91.7 (3)	C1—C2—H2	120.8
O1^iii—Ni1—N1^i	88.3 (3)	C4—C3—C2	118.0 (8)
O3—Ni1—N1	92.0 (3)	C4—C3—S1	117.6 (7)
O3^i—Ni1—N1	88.0 (3)	C2—C3—S1	124.4 (7)
O1^ii—Ni1—N1	88.3 (3)	C3—C4—C5	119.8 (8)
O1^iii—Ni1—N1	91.7 (3)	C3—C4—H4	120.1
N1^i—Ni1—N1	180.0 (6)	C5—C4—H4	120.1
C3—S1—C6	103.5 (4)	N1—C5—C4	123.6 (8)
C7—O1—Ni1^iv	129.6 (6)	N1—C5—H5	118.2
Ni1—O3—O2^ii	90.8 (3)	C4—C5—H5	118.2
Ni1—O3—O2^v	131.1 (3)	C7—C6—S1	115.8 (7)
O2^ii—O3—O2^v	113.9 (3)	C7—C6—H6A	108.3
Ni1—O3—H3	101 (6)	S1—C6—H6A	108.3
O2^ii—O3—H3	13 (6)	C7—C6—H6B	108.3
O2^v—O3—H3	101 (6)	S1—C6—H6B	108.3
Ni1—O3—H6	119 (9)	H6A—C6—H6B	107.4
O2^ii—O3—H6	115 (8)	O2—C7—O1	125.4 (8)
O2^v—O3—H6	12 (8)	O2—C7—C6	118.7 (8)
H3—O3—H6	102 (10)	O1—C7—C6	115.9 (8)
O3^i—Ni1—O3—O2^ii	72 (100)	N1^i—Ni1—N1—C1	94 (100)
O1^ii—Ni1—O3—O2^ii	6.2 (3)	C5—N1—C1—C2	−2.0 (13)
O1^iii—Ni1—O3—O2^ii	−173.8 (3)	Ni1—N1—C1—C2	173.2 (7)
N1^i—Ni1—O3—O2^ii	−85.5 (3)	N1—C1—C2—C3	−1.8 (14)
N1—Ni1—O3—O2^ii	94.5 (3)	C1—C2—C3—C4	4.8 (13)
O3^i—Ni1—O3—O2^v	−52 (100)	C1—C2—C3—S1	−174.0 (7)
O1^ii—Ni1—O3—O2^v	−117.2 (4)	C6—S1—C3—C4	175.0 (7)
O1^iii—Ni1—O3—O2^v	62.8 (4)	C6—S1—C3—C2	−6.2 (9)
N1^i—Ni1—O3—O2^v	151.2 (4)	C2—C3—C4—C5	−4.1 (13)
N1—Ni1—O3—O2^v	−28.8 (4)	S1—C3—C4—C5	174.8 (7)
O3—Ni1—N1—C5	137.4 (7)	C1—N1—C5—C4	2.7 (14)
O3^i—Ni1—N1—C5	−42.6 (7)	Ni1—N1—C5—C4	−172.3 (7)
O1^ii—Ni1—N1—C5	−131.1 (7)	C3—C4—C5—N1	0.3 (15)
O1^iii—Ni1—N1—C5	48.9 (7)	C3—S1—C6—C7	−70.8 (7)
N1^i—Ni1—N1—C5	−91 (100)	Ni1^iv—O1—C7—O2	−4.3 (12)
O3—Ni1—N1—C1	−37.5 (7)	Ni1^iv—O1—C7—C6	175.6 (5)
O3^i—Ni1—N1—C1	142.5 (7)	S1—C6—C7—O2	−27.7 (10)
O1^ii—Ni1—N1—C1	54.0 (7)	S1—C6—C7—O1	152.4 (6)
O1^iii—Ni1—N1—C1	−126.0 (7)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) x−1, y, z; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^ii	0.85 (2)	1.81 (3)	2.631 (9)	161 (8)
O3—H6···O2^v	0.85 (2)	1.97 (4)	2.792 (8)	163 (12)

Symmetry codes: (ii) −x+1, −y, −z; (v) −x+1, y+1/2, −z+1/2.