Acta Cryst.(2004). E60, m135±m136 DOI: 10.1107/S1600536803029039 Zhang, Fang, Wu and Ng [Ni(C7H6NO2S)2(H2O)4]
m135
metal-organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
Tetraaquabis(4-pyridylthioacetato)nickel(II)
Xian-Ming Zhang,aRui-Qin Fang,aHai-Shun Wuaand Seik Weng Ngb*
aSchool of Chemistry and Material Science,
Shanxi Normal University, Linfen 041004, People's Republic of China, andbDepartment of
Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
Correspondence e-mail: seikweng@um.edu.my
Key indicators
Single-crystal X-ray study T= 298 K
Mean(C±C) = 0.002 AÊ Rfactor = 0.026 wRfactor = 0.072
Data-to-parameter ratio = 12.0
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The Ni atom in the zwitterionic title compound, [Ni(C7H6
-NO2S)2(H2O)4], lies on a centre of symmetry. It is linked to the
pyridyl N atom of two anionic groups and to four water molecules in an octahedral environment. The zwitterions are connected by hydrogen bonds into a three-dimensional network structure.
Comment
The reaction of copper nitrate and the ammonium salt of 4-pyridylthioacetic acid yields [Cu(C7H6NO2S)2(H2O)2
-(NH3)2], which is zwitterionic, with the the
4-pyridylthio-acetate anion bonding through the pyridyl N atom. The amine donor in the molecule arises from the slight excess of ammonium hydroxide that was used to neutralize the carboxylic acid (Huanget al., 2004). A similar reaction with a nickel salt, but with sodium hydroxide in place of ammonium hydroxide, afforded the corresponding tetraaquanickel complex,viz.the title complex, (I) (Fig. 1), which also exists as a zwitterion. The octahedrally coordinated Ni atom lies on a centre of symmetry. Hydrogen bonds link the zwitterions into a three-dimensional network structure. Bond dimensions involving Ni are similar to those found in the zwitterionic tetraaquanicotinatonickel (Batten & Harris, 2001b) and tetraaquaisonicotinatonickel (Batten & Harris, 2001a; Minet al., 2001; Ng, 2003) complexes, which also feature extensive hydrogen-bonding interactions.
Experimental
A mixture of nickel sulfate hexahydrate (0.26 g, 1.0 mmol), 4-pyridylthioacetic acid (0.25 g, 1.5 mmol) and water (7 ml) was treated with drops of 2Nsodium hydroxide to give a pH of approximately 7. The solution was transferred into a 15 ml Te¯on-lined stainless-steel bomb, which was then heated at 433 K for 96 h. After cooling to room temperature, blue crystals separated from the solution in about 50% yield. CHN analysis: C 35.94, H 4.36, N 5.96, S 13.64%; calculated for C14H20N2NiO8S2: C 36.00, H 4.32, N 6.00, S 13.73%.
Crystal data
[Ni(C7H6NO2S)2(H2O)4] Mr= 467.15
Monoclinic,P21=a a= 7.4924 (5) AÊ b= 10.4589 (7) AÊ c= 12.1369 (8) AÊ
= 107.393 (1)
V= 907.6 (1) AÊ3 Z= 2
Dx= 1.709 Mg mÿ3
MoKradiation Cell parameters from 3212
re¯ections
= 2.6±26.9
= 1.35 mmÿ1 T= 298 (2) K Plate, blue
0.350.190.09 mm
Data collection
Bruker SMART APEX area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.753,Tmax= 0.889 5157 measured re¯ections
1960 independent re¯ections 1813 re¯ections withI> 2(I) Rint= 0.015
max= 27.0 h=ÿ8!9 k=ÿ13!11 l=ÿ15!15
Re®nement
Re®nement onF2 R[F2> 2(F2)] = 0.026 wR(F2) = 0.072 S= 1.04 1960 re¯ections 164 parameters
All H-atom parameters re®ned
w= 1/[2(F
o2) + (0.0462P)2
+ 0.1843P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.37 e AÊÿ3
min=ÿ0.17 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Ni1ÐO1w 2.071 (1)
Ni1ÐO2w 2.044 (1) Ni1ÐN1 2.106 (1) O1wÐNi1ÐO1wi 180
O1wÐNi1ÐO2w 89.1 (1) O1wÐNi1ÐO2wi 90.9 (1) O1wÐNi1ÐN1 91.0 (1) O1wÐNi1ÐN1i 89.0 (1)
O2wÐNi1ÐO2wi 180 O2wÐNi1ÐN1 87.5 (1) O2wÐNi1ÐN1i 92.5 (1) N1ÐNi1ÐN1i 180
Symmetry code: (i) 1ÿx;1ÿy;1ÿz.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O1wÐH1w1 O1ii 0.84 (1) 1.93 (1) 2.759 (2) 168 (3) O1wÐH1w2 O1iii 0.84 (1) 2.02 (1) 2.842 (2) 165 (2) O2wÐH2w1 O2iv 0.83 (1) 1.92 (1) 2.744 (2) 168 (2) O2wÐH2w2 O2ii 0.84 (1) 1.89 (1) 2.729 (2) 177 (3) Symmetry codes: (ii) 2ÿx;1ÿy;2ÿz; (iii)3
2ÿx;yÿ12;2ÿz; (iv)x;y;zÿ1.
The crystal used in the measurements diffracted suf®ciently strongly for all H atoms to be located and re®ned with distance restraints [OÐH = 0.85 (1) AÊ and CÐH = 0.95 (1) AÊ].
Data collection:SMART(Bruker, 2001); cell re®nement:SMART; data reduction:SAINT(Bruker, 2001); method used to solve struc-ture: difference Fourier, with Ni at (1
2,12,12); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEPII (Johnson, 1976); software used to prepare material for publication:SHELXL97.
References
Batten, S. R. & Harris, A. R. (2001a).Acta Cryst.E57, m7±m8. Batten, S. R. & Harris, A. R. (2001b).Acta Cryst.E57, m9±m11.
Bruker (2001).SAINTandSMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Huang, Y.-Q., Zhang, H., Chen, J.-G., Zou, W., Li, L., Wei, Z.-B. & Ng, S. W. (2004).Acta Cryst.E60, m133±m134.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Min, D., Yoon, S. S., Lee, C. Y., Han, W. S. & Lee, S. W. (2001).Bull. Korean Chem. Soc.22, 1041±1044.
Ng, S. W. (2003).Chin. J. Struct. Chem.22, 495.
Sheldrick, G. M. (1996).SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Figure 1
supporting information
sup-1 Acta Cryst. (2004). E60, m135–m136
supporting information
Acta Cryst. (2004). E60, m135–m136 [https://doi.org/10.1107/S1600536803029039]
Tetraaquabis(4-pyridylthioacetato)nickel(II)
Xian-Ming Zhang, Rui-Qin Fang, Hai-Shun Wu and Seik Weng Ng
Tetraaquabis(4-pyridylthioactetato)nickel(II)
Crystal data
[Ni(C7H6NO2S)2(H2O)4] Mr = 467.15
Monoclinic, P21/a Hall symbol: -P 2yab a = 7.4924 (5) Å b = 10.4589 (7) Å c = 12.1369 (8) Å β = 107.393 (1)° V = 907.6 (1) Å3 Z = 2
F(000) = 484 Dx = 1.709 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3212 reflections θ = 2.6–26.9°
µ = 1.35 mm−1 T = 298 K Plate, blue
0.35 × 0.19 × 0.09 mm
Data collection
Bruker SMART APEX area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.753, Tmax = 0.889
5157 measured reflections 1960 independent reflections 1813 reflections with I > 2σ(I) Rint = 0.015
θmax = 27.0°, θmin = 1.8° h = −8→9
k = −13→11 l = −15→15
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.026 wR(F2) = 0.072 S = 1.04 1960 reflections 164 parameters 10 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined w = 1/[σ2(F
o2) + (0.0462P)2 + 0.1843P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 0.37 e Å−3 Δρmin = −0.17 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Ni1 0.5000 0.5000 0.5000 0.0207 (1)
S1 0.91703 (6) 0.69526 (4) 1.03479 (3) 0.0314 (1)
O2 0.9398 (2) 0.51701 (14) 1.3212 (1) 0.0418 (3)
O1w 0.5797 (2) 0.31611 (11) 0.5572 (1) 0.0301 (3)
O2w 0.7633 (2) 0.53151 (15) 0.4890 (1) 0.0387 (3)
N1 0.5955 (2) 0.57068 (12) 0.6700 (1) 0.0251 (3)
C1 0.9667 (2) 0.60111 (16) 1.2541 (1) 0.0297 (3)
C2 0.8545 (2) 0.58104 (17) 1.1281 (1) 0.0313 (4)
C3 0.6892 (2) 0.68180 (16) 0.6934 (1) 0.0316 (4)
C4 0.7813 (2) 0.72242 (16) 0.8036 (1) 0.0307 (3)
C5 0.7802 (2) 0.64573 (15) 0.8975 (1) 0.0236 (3)
C6 0.6759 (2) 0.53384 (16) 0.8742 (1) 0.0264 (3)
C7 0.5875 (2) 0.50083 (14) 0.7607 (1) 0.0263 (3)
H1w1 0.691 (2) 0.318 (3) 0.600 (2) 0.065 (8)*
H1w2 0.517 (3) 0.277 (2) 0.594 (2) 0.061 (7)*
H2w1 0.801 (3) 0.526 (2) 0.431 (2) 0.048 (7)*
H2w2 0.852 (3) 0.515 (2) 0.548 (2) 0.056 (8)*
H2a 0.725 (2) 0.589 (2) 1.121 (2) 0.042 (6)*
H2b 0.878 (4) 0.495 (1) 1.110 (2) 0.053 (7)*
H3 0.698 (3) 0.731 (2) 0.630 (1) 0.046 (6)*
H4 0.845 (2) 0.802 (1) 0.814 (2) 0.036 (5)*
H6 0.669 (3) 0.475 (2) 0.932 (1) 0.035 (5)*
H7 0.525 (2) 0.421 (1) 0.747 (2) 0.027 (4)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ni1 0.0223 (2) 0.0242 (2) 0.0147 (2) −0.0004 (1) 0.0041 (1) 0.0010 (1)
S1 0.0354 (2) 0.0352 (2) 0.0196 (2) −0.0083 (2) 0.0021 (2) −0.0036 (2)
O1 0.0402 (7) 0.0397 (7) 0.0268 (6) 0.0042 (5) −0.0021 (5) −0.0075 (5)
O2 0.0422 (8) 0.0611 (9) 0.0216 (6) 0.0018 (6) 0.0086 (5) 0.0050 (5)
O1w 0.0353 (7) 0.0279 (6) 0.0241 (6) 0.0027 (5) 0.0044 (5) 0.0042 (4)
O2w 0.0258 (6) 0.0661 (8) 0.0243 (6) −0.0024 (6) 0.0080 (5) 0.0051 (6)
N1 0.0287 (6) 0.0276 (7) 0.0174 (6) −0.0006 (5) 0.0045 (5) 0.0002 (5)
C1 0.0280 (8) 0.0414 (9) 0.0183 (7) 0.0102 (7) 0.0046 (6) −0.0038 (6)
C2 0.0324 (8) 0.0397 (9) 0.0196 (7) −0.0015 (7) 0.0045 (6) −0.0002 (6)
C3 0.0409 (9) 0.0306 (8) 0.0217 (8) −0.0060 (7) 0.0070 (7) 0.0034 (6)
C4 0.0381 (9) 0.0279 (8) 0.0249 (8) −0.0084 (7) 0.0077 (7) −0.0003 (6)
C5 0.0229 (7) 0.0281 (8) 0.0180 (7) 0.0009 (6) 0.0036 (5) −0.0022 (6)
C6 0.0333 (8) 0.0259 (7) 0.0191 (7) −0.0010 (6) 0.0067 (6) 0.0015 (6)
C7 0.0310 (9) 0.0263 (8) 0.0203 (8) −0.0039 (6) 0.0057 (6) −0.0018 (5)
Geometric parameters (Å, º)
Ni1—O1w 2.071 (1) C4—C5 1.395 (2)
Ni1—O1wi 2.071 (1) C5—C6 1.389 (2)
Ni1—O2w 2.044 (1) C6—C7 1.382 (2)
Ni1—O2wi 2.044 (1) O1w—H1w1 0.84 (1)
Ni1—N1 2.106 (1) O1w—H1w2 0.84 (1)
supporting information
sup-3 Acta Cryst. (2004). E60, m135–m136
S1—C2 1.802 (2) O2w—H2w2 0.84 (1)
S1—C5 1.754 (2) C2—H2a 0.95 (1)
O1—C1 1.246 (2) C2—H2b 0.95 (1)
O2—C1 1.255 (2) C3—H3 0.95 (1)
N1—C7 1.337 (2) C4—H4 0.95 (1)
N1—C3 1.344 (2) C6—H6 0.95 (1)
C1—C2 1.523 (2) C7—H7 0.95 (1)
C3—C4 1.376 (2)
O1w—Ni1—O1wi 180 C6—C5—C4 117.3 (1)
O1w—Ni1—O2w 89.1 (1) C6—C5—S1 125.1 (1)
O1w—Ni1—O2wi 90.9 (1) C4—C5—S1 117.5 (1)
O1w—Ni1—N1 91.0 (1) C7—C6—C5 119.1 (1)
O1w—Ni1—N1i 89.0 (1) N1—C7—C6 123.9 (1)
O1wi—Ni1—O2w 90.9 (1) Ni1—O1w—H1w1 109 (2)
O1wi—Ni1—O2wi 89.1 (1) Ni1—O1w—H1w2 118 (2)
O1wi—Ni1—N1 89.0 (1) H1w1—O1w—H1w2 107 (2)
O1wi—Ni1—N1i 91.0 (1) Ni1—O2w—H2w1 129 (2)
O2w—Ni1—O2wi 180 Ni1—O2w—H2w2 117 (2)
O2w—Ni1—N1 87.5 (1) H2w1—O2w—H2w2 109 (3)
O2w—Ni1—N1i 92.5 (1) C1—C2—H2a 109 (1)
O2wi—Ni1—N1 92.5 (1) S1—C2—H2a 110 (1)
O2wi—Ni1—N1i 87.5 (1) C1—C2—H2b 106 (2)
N1—Ni1—N1i 180 S1—C2—H2b 113 (2)
C5—S1—C2 102.3 (1) H2a—C2—H2b 108 (2)
C7—N1—C3 116.6 (1) N1—C3—H3 117 (1)
C7—N1—Ni1 122.0 (1) C4—C3—H3 119 (1)
C3—N1—Ni1 120.9 (1) C3—C4—H4 119 (1)
O1—C1—O2 126.7 (2) C5—C4—H4 122 (1)
O1—C1—C2 119.3 (2) C7—C6—H6 118 (1)
O2—C1—C2 114.0 (2) C5—C6—H6 123 (1)
C1—C2—S1 111.7 (1) N1—C7—H7 118 (1)
N1—C3—C4 123.4 (1) C6—C7—H7 118 (1)
C3—C4—C5 119.5 (2)
O2w—Ni1—N1—C7 −121.8 (1) Ni1—N1—C3—C4 −168.9 (1)
O2wi—Ni1—N1—C7 58.2 (1) N1—C3—C4—C5 0.4 (3)
O1w—Ni1—N1—C7 −32.7 (1) C3—C4—C5—C6 −3.4 (2)
O1wi—Ni1—N1—C7 147.3 (1) C3—C4—C5—S1 174.4 (1)
O2w—Ni1—N1—C3 49.5 (1) C2—S1—C5—C6 −8.4 (2)
O2wi—Ni1—N1—C3 −130.5 (1) C2—S1—C5—C4 174.0 (1)
O1w—Ni1—N1—C3 138.5 (1) C4—C5—C6—C7 3.3 (2)
O1wi—Ni1—N1—C3 −41.5 (1) S1—C5—C6—C7 −174.3 (1)
O1—C1—C2—S1 6.2 (2) C3—N1—C7—C6 −2.9 (2)
C5—S1—C2—C1 176.8 (1) C5—C6—C7—N1 −0.1 (3)
C7—N1—C3—C4 2.8 (2)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1w—H1w1···O1ii 0.84 (1) 1.93 (1) 2.759 (2) 168 (3)
O1w—H1w2···O1iii 0.84 (1) 2.02 (1) 2.842 (2) 165 (2)
O2w—H2w1···O2iv 0.83 (1) 1.92 (1) 2.744 (2) 168 (2)
O2w—H2w2···O2ii 0.84 (1) 1.89 (1) 2.729 (2) 177 (3)
