Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023550/ya2052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023550/ya2052asup2.hkl |
CCDC reference: 651360
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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.
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 Uiso(H) = 1.2Ueq(C).
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).
For related literature, see: Huang et al. (2004a,b); Zhang et al. (2004).
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.
[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) Å3 | 0.32 × 0.24 × 0.16 mm |
Z = 2 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.084 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + 14.8565P] where P = (Fo2 + 2Fc2)/3 |
1489 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.96 e Å−3 |
2 restraints | Δρmin = −0.91 e Å−3 |
[Ni(C7H6NO2S)2(H2O)2] | V = 847.87 (14) Å3 |
Mr = 431.12 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9232 (9) Å | µ = 1.42 mm−1 |
b = 10.6901 (10) Å | T = 298 K |
c = 8.8887 (9) Å | 0.32 × 0.24 × 0.16 mm |
β = 90.378 (3)° |
BRUKER SMART CCD Apex II diffractometer | 1489 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1198 reflections with I > 2σ(I) |
Tmin = 0.658, Tmax = 0.804 | Rint = 0.050 |
2425 measured reflections |
R[F2 > 2σ(F2)] = 0.084 | 2 restraints |
wR(F2) = 0.191 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + 14.8565P] where P = (Fo2 + 2Fc2)/3 |
1489 reflections | Δρmax = 0.96 e Å−3 |
123 parameters | Δρmin = −0.91 e Å−3 |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Ni1—O3i | 2.060 (6) | O3—H6 | 0.85 (2) |
Ni1—O1ii | 2.081 (6) | N1—C5 | 1.339 (11) |
Ni1—O3 | 2.060 (6) | N1—C1 | 1.346 (11) |
Ni1—O1iii | 2.081 (6) | C1—C2 | 1.404 (12) |
Ni1—N1i | 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—Ni1iv | 2.081 (6) | C4—H4 | 0.9300 |
O2—C7 | 1.258 (11) | C5—H5 | 0.9300 |
O3—O2ii | 2.631 (9) | C6—C7 | 1.535 (12) |
O3—O2v | 2.792 (8) | C6—H6A | 0.9700 |
O3—H3 | 0.85 (2) | C6—H6B | 0.9700 |
O3—Ni1—O3i | 180.0 (3) | C5—N1—C1 | 116.4 (7) |
O3—Ni1—O1ii | 91.5 (3) | C5—N1—Ni1 | 123.0 (6) |
O3i—Ni1—O1ii | 88.5 (3) | C1—N1—Ni1 | 120.4 (6) |
O3—Ni1—O1iii | 88.5 (3) | N1—C1—C2 | 123.5 (8) |
O3i—Ni1—O1iii | 91.5 (3) | N1—C1—H1 | 118.2 |
O1ii—Ni1—O1iii | 180.0 (3) | C2—C1—H1 | 118.2 |
O3—Ni1—N1i | 88.0 (3) | C3—C2—C1 | 118.4 (8) |
O3i—Ni1—N1i | 92.0 (3) | C3—C2—H2 | 120.8 |
O1ii—Ni1—N1i | 91.7 (3) | C1—C2—H2 | 120.8 |
O1iii—Ni1—N1i | 88.3 (3) | C4—C3—C2 | 118.0 (8) |
O3—Ni1—N1 | 92.0 (3) | C4—C3—S1 | 117.6 (7) |
O3i—Ni1—N1 | 88.0 (3) | C2—C3—S1 | 124.4 (7) |
O1ii—Ni1—N1 | 88.3 (3) | C3—C4—C5 | 119.8 (8) |
O1iii—Ni1—N1 | 91.7 (3) | C3—C4—H4 | 120.1 |
N1i—Ni1—N1 | 180.0 (6) | C5—C4—H4 | 120.1 |
C3—S1—C6 | 103.5 (4) | N1—C5—C4 | 123.6 (8) |
C7—O1—Ni1iv | 129.6 (6) | N1—C5—H5 | 118.2 |
Ni1—O3—O2ii | 90.8 (3) | C4—C5—H5 | 118.2 |
Ni1—O3—O2v | 131.1 (3) | C7—C6—S1 | 115.8 (7) |
O2ii—O3—O2v | 113.9 (3) | C7—C6—H6A | 108.3 |
Ni1—O3—H3 | 101 (6) | S1—C6—H6A | 108.3 |
O2ii—O3—H3 | 13 (6) | C7—C6—H6B | 108.3 |
O2v—O3—H3 | 101 (6) | S1—C6—H6B | 108.3 |
Ni1—O3—H6 | 119 (9) | H6A—C6—H6B | 107.4 |
O2ii—O3—H6 | 115 (8) | O2—C7—O1 | 125.4 (8) |
O2v—O3—H6 | 12 (8) | O2—C7—C6 | 118.7 (8) |
H3—O3—H6 | 102 (10) | O1—C7—C6 | 115.9 (8) |
O3i—Ni1—O3—O2ii | 72 (100) | N1i—Ni1—N1—C1 | 94 (100) |
O1ii—Ni1—O3—O2ii | 6.2 (3) | C5—N1—C1—C2 | −2.0 (13) |
O1iii—Ni1—O3—O2ii | −173.8 (3) | Ni1—N1—C1—C2 | 173.2 (7) |
N1i—Ni1—O3—O2ii | −85.5 (3) | N1—C1—C2—C3 | −1.8 (14) |
N1—Ni1—O3—O2ii | 94.5 (3) | C1—C2—C3—C4 | 4.8 (13) |
O3i—Ni1—O3—O2v | −52 (100) | C1—C2—C3—S1 | −174.0 (7) |
O1ii—Ni1—O3—O2v | −117.2 (4) | C6—S1—C3—C4 | 175.0 (7) |
O1iii—Ni1—O3—O2v | 62.8 (4) | C6—S1—C3—C2 | −6.2 (9) |
N1i—Ni1—O3—O2v | 151.2 (4) | C2—C3—C4—C5 | −4.1 (13) |
N1—Ni1—O3—O2v | −28.8 (4) | S1—C3—C4—C5 | 174.8 (7) |
O3—Ni1—N1—C5 | 137.4 (7) | C1—N1—C5—C4 | 2.7 (14) |
O3i—Ni1—N1—C5 | −42.6 (7) | Ni1—N1—C5—C4 | −172.3 (7) |
O1ii—Ni1—N1—C5 | −131.1 (7) | C3—C4—C5—N1 | 0.3 (15) |
O1iii—Ni1—N1—C5 | 48.9 (7) | C3—S1—C6—C7 | −70.8 (7) |
N1i—Ni1—N1—C5 | −91 (100) | Ni1iv—O1—C7—O2 | −4.3 (12) |
O3—Ni1—N1—C1 | −37.5 (7) | Ni1iv—O1—C7—C6 | 175.6 (5) |
O3i—Ni1—N1—C1 | 142.5 (7) | S1—C6—C7—O2 | −27.7 (10) |
O1ii—Ni1—N1—C1 | 54.0 (7) | S1—C6—C7—O1 | 152.4 (6) |
O1iii—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2ii | 0.85 (2) | 1.81 (3) | 2.631 (9) | 161 (8) |
O3—H6···O2v | 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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C7H6NO2S)2(H2O)2] |
Mr | 431.12 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 8.9232 (9), 10.6901 (10), 8.8887 (9) |
β (°) | 90.378 (3) |
V (Å3) | 847.87 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.42 |
Crystal size (mm) | 0.32 × 0.24 × 0.16 |
Data collection | |
Diffractometer | BRUKER SMART CCD Apex II |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.658, 0.804 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2425, 1489, 1198 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.084, 0.191, 1.14 |
No. of reflections | 1489 |
No. of parameters | 123 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + 14.8565P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.96, −0.91 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL (Sheldrick, 1997a), SHELXTL.
Ni1—O1i | 2.081 (6) | Ni1—N1 | 2.125 (7) |
Ni1—O3 | 2.060 (6) | ||
O3—Ni1—O1i | 91.5 (3) | O1i—Ni1—N1ii | 91.7 (3) |
O3—Ni1—N1ii | 88.0 (3) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2i | 0.85 (2) | 1.81 (3) | 2.631 (9) | 161 (8) |
O3—H6···O2iii | 0.85 (2) | 1.97 (4) | 2.792 (8) | 163 (12) |
Symmetry codes: (i) −x+1, −y, −z; (iii) −x+1, y+1/2, −z+1/2. |
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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).