metal-organic papers
Acta Cryst.(2004). E60, m933±m934 DOI: 10.1107/S1600536804013340 Yong-Qing Huanget al. [Ni(C7H6NO2S)2(H2O)]
m933
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
catena
-Poly[[aquanickel(II)]-di-
l
-(4-pyridyl-sulfanyl)acetato-
j
6N
:
O,O
;
O,O
000:
N
]
Yong-Qing Huang,aHui Zhang,a
Jian-Gu Chen,aWei Zouaand
Seik Weng Ngb*
aState Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, People's Republic of China, and bDepartment of Chemistry, University of
Malaya, 50603 Kuala Lumpur, Malaysia
Correspondence e-mail: seikweng@um.edu.my
Key indicators
Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.035
wRfactor = 0.095
Data-to-parameter ratio = 15.6
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 water-coordinated Ni atom in the title compound, [Ni(C7H6NO2S)2(H2O)]n, is covalently bonded to two
carboxylate groups (one binding in a monodentate mode and the other in a chelating mode); it is also linked to the N atoms of two other carboxylate anions in an octahedral environment. The compound adopts a linear chain architec-ture; adjacent chains are linked into layers by hydrogen bonds.
Comment
A number of compounds resulting from the reaction of pyridyl-4-thiolylacetic acid with metal salts have been crys-tallographically authenticated; some of these are neutral complexes whereas others are zwitterions (Qin et al., 2004; Zhanget al., 2004a,b).
Tetraaquabis(pyridyl-4-thiolylacetato)nickel(II), which exists as a zwitterion, was synthesized hydrothermally in a nearly neutral aqueous solvent system; the reaction when carried out at a lower temperature and for a shorter time gave the title polymeric compoundcatena
-(4-pyridylsulfanyl)acetato], (I) (Fig. 1), whose Ni atom is instead covalently linked to two carboxylate anions. One of the anions functions as a chelate [bite angle = 60.84 (6)]; its
two O atoms, the water molecule and the O atom of a monodentate carboxylate anion are coplanar; the pyridyl N atoms belonging to two other carboxylate anions lie on opposite sides of the plane, these interactions giving rise to a chain motif (Fig. 2).
Experimental
Nickel acetate (100 mg, 0.4 mmol), 4-pyridylthioacetic acid (68 mg, 0.4 mmol) and sodium hydroxide (16 mg, 0.4 mmol) were dissolved in a water±ethanol (12:5v/v) mixture (17 ml). The solution was placed in a Te¯on-lined stainless-steel bomb (23 ml). The bomb was heated at 393 K for 12 h and then cooled to room temperature. CHN elemental analyses on the green crystals found (calculated) for C14H14N2NiO5S2 (%): C 40.23 (40.70), H 3.42 (3.42), N 6.64 (6.78). IR (KBr): 3385, 2921, 1599, 1579, 1561, 1487, 1430, 1376, 1218, 1147, 1119, 1057, 817, 804, 724, 701, 589, 503 cmÿ1.
Crystal data
[Ni(C7H6NO2S)2(H2O)]
Mr= 413.10
Triclinic,P1
a= 8.1693 (4) AÊ
b= 10.3430 (5) AÊ
c= 10.6876 (5) AÊ
= 67.371 (1)
= 73.176 (1)
= 86.825 (1) V= 796.25 (7) AÊ3
Z= 2
Dx= 1.723 Mg mÿ3
MoKradiation Cell parameters from 5217
re¯ections
= 2.8±26.3
= 1.51 mmÿ1
T= 293 (2) K Prism, green
0.130.120.10 mm
Data collection
Bruker SMART APEX area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2001)
Tmin= 0.665,Tmax= 0.864 6789 measured re¯ections
3511 independent re¯ections 3266 re¯ections withI> 2(I)
Rint= 0.017
max= 27.5
h=ÿ10!10
k=ÿ13!13
l=ÿ13!13
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.035
wR(F2) = 0.095
S= 1.06 3511 re¯ections 225 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.056P)2
+ 0.2563P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.49 e AÊÿ3
min=ÿ0.26 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Ni1ÐO3 2.023 (2) Ni1ÐO1 2.094 (2) Ni1ÐO2 2.210 (2)
Ni1ÐO1w 2.049 (2) Ni1ÐN1i 2.099 (2) Ni1ÐN2ii 2.094 (2)
O1ÐNi1ÐO2 60.84 (6) O1ÐNi1ÐO3 166.10 (6) O1ÐNi1ÐO1w 98.41 (6) O1ÐNi1ÐN1i 88.55 (6) O1ÐNi1ÐN2ii 91.65 (6) O2ÐNi1ÐO3 105.37 (6) O2ÐNi1ÐO1w 158.89 (7) O2ÐNi1ÐN1i 86.52 (6)
O2ÐNi1ÐN2ii 92.02 (7) O3ÐNi1ÐN1i 88.82 (7) O3ÐNi1ÐN2ii 90.56 (7) O3ÐNi1ÐO1w 95.20 (7) O1wÐNi1ÐN1i 89.29 (7) O1wÐNi1ÐN2ii 92.43 (7) N1iÐNi1ÐN2ii 178.21 (7)
Symmetry codes: (i) 1ÿx;2ÿy;2ÿz; (ii) 1ÿx;1ÿy;1ÿz.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
O1wÐH1w2 O1iii 0.84 (1) 1.88 (1) 2.722 (2) 176 (3) O1wÐH1w1 O4 0.85 (1) 1.83 (2) 2.633 (2) 158 (3)
Symmetry code: (iii) 1ÿx;1ÿy;2ÿz.
The water H atoms were located in a difference map and re®ned with distance restraints of OÐH = 0.85 (1) AÊ and H H = 1.39 (1) AÊ. The aromatic (CÐH = 0.93 AÊ) and aliphatic (CÐH = 0.97 AÊ) H atoms were placed at calculated positions and re®ned using the riding-model approximation, withUiso= 1.2Ueq(C).
Data collection:SMART(Bruker, 2001); cell re®nement:SAINT
(Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
ORTEPII (Johnson, 1976); software used to prepare material for publication:SHELXL97.
The authors thank the National Science Foundation of China (Nos. 20171037 and 20073034), the Fujian Province Science Foundation (2002F016) and the University of Malaya for supporting this study.
References
Bruker (2001).SADABS, SAINTandSMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Qin, S. B., Ke, Y. X., Lu, S. M., Li, J. M., Pei, H. X., Wu, X. T. & Du, W. X. (2004).J.Mol. Struct.689, 75±80.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Zhang, X.-M., Fang, R.-Q., Wu, H.-S. & Ng, S. W. (2004a).Acta Cryst.E60, m135±m136.
Zhang, X.-M., Fang, R.-Q., Wu, H.-S. & Ng, S. W. (2004b).Acta Cryst.E60,
Figure 1
ORTEPII (Johnson, 1976) plot of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii. [Symmetry codes: (i) 1ÿx, 2ÿy, 2ÿz; (ii) 1ÿx, 1ÿy, 1ÿz.]
Figure 2
supporting information
sup-1
Acta Cryst. (2004). E60, m933–m934
supporting information
Acta Cryst. (2004). E60, m933–m934 [https://doi.org/10.1107/S1600536804013340]
catena
-Poly[[aquanickel(II)]-di-
µ
-(4-pyridylsulfanyl)acetato-
κ
6N
:
O,O
;
O,O
′
:
N
]
Yong-Qing Huang, Hui Zhang, Jian-Gu Chen, Wei Zou and Seik Weng Ng
catena-Poly[[aquanickel(II)]-di-µ-(4-pyridylsulfanyl)acetato]
Crystal data
[Ni(C7H6NO2S)2(H2O)]
Mr = 413.10
Triclinic, P1 Hall symbol: -P 1
a = 8.1693 (4) Å
b = 10.3430 (5) Å
c = 10.6876 (5) Å
α = 67.371 (1)°
β = 73.176 (1)°
γ = 86.825 (1)°
V = 796.25 (7) Å3
Z = 2
F(000) = 424
Dx = 1.723 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 5217 reflections
θ = 2.8–26.3°
µ = 1.51 mm−1
T = 293 K Prism, green
0.13 × 0.12 × 0.10 mm
Data collection
Bruker APEX area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001)
Tmin = 0.665, Tmax = 0.864
6789 measured reflections 3511 independent reflections 3266 reflections with I > 2σ(I)
Rint = 0.017
θmax = 27.5°, θmin = 2.1°
h = −10→10
k = −13→13
l = −13→13
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.035
wR(F2) = 0.095
S = 1.06 3511 reflections 225 parameters 2 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.056P)2 + 0.2563P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.49 e Å−3
Δρmin = −0.26 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
S1 0.87796 (9) 0.76461 (7) 1.06171 (8) 0.0427 (2)
S2 0.07987 (7) 0.77873 (6) 0.41886 (6) 0.0340 (1)
O1 0.6400 (2) 0.6852 (2) 0.9294 (2) 0.0308 (3)
O2 0.7493 (2) 0.8390 (2) 0.7145 (2) 0.0379 (4)
O3 0.4218 (2) 0.7779 (2) 0.6082 (2) 0.0318 (3)
O4 0.1770 (2) 0.6469 (2) 0.6941 (2) 0.0396 (4)
O1w 0.2967 (2) 0.5799 (2) 0.9134 (2) 0.0336 (3)
N1 0.6162 (2) 1.1238 (2) 1.1669 (2) 0.0301 (4)
N2 0.3642 (2) 0.4463 (2) 0.2762 (2) 0.0304 (4)
C1 0.7555 (3) 0.7773 (2) 0.8382 (2) 0.0294 (4)
C2 0.9081 (3) 0.8081 (3) 0.8771 (3) 0.0384 (5)
C3 0.7725 (3) 0.9048 (2) 1.0942 (2) 0.0310 (4)
C4 0.7327 (3) 1.0240 (2) 0.9941 (2) 0.0371 (5)
C5 0.6569 (3) 1.1294 (2) 1.0348 (2) 0.0376 (5)
C6 0.6526 (3) 1.0068 (2) 1.2639 (2) 0.0326 (5)
C7 0.7296 (3) 0.8973 (2) 1.2329 (2) 0.0349 (5)
C8 0.2769 (3) 0.7468 (2) 0.6042 (2) 0.0275 (4)
C9 0.2249 (3) 0.8486 (2) 0.4777 (2) 0.0345 (5)
C10 0.1975 (3) 0.6541 (2) 0.3642 (2) 0.0282 (4)
C11 0.1141 (3) 0.5710 (2) 0.3235 (2) 0.0329 (5)
C12 0.2002 (3) 0.4707 (2) 0.2810 (2) 0.0328 (5)
C13 0.4442 (3) 0.5272 (2) 0.3149 (3) 0.0358 (5)
C14 0.3678 (3) 0.6307 (2) 0.3585 (2) 0.0340 (5)
H1w1 0.240 (3) 0.583 (3) 0.857 (3) 0.06 (1)*
H1w2 0.320 (4) 0.498 (2) 0.959 (3) 0.07 (1)*
H2a 0.9418 0.9074 0.8268 0.046*
H2b 1.0026 0.7572 0.8436 0.046*
H4 0.7568 1.0328 0.9005 0.045*
H5 0.6326 1.2094 0.9658 0.045*
H6 0.6239 0.9996 1.3572 0.039*
H7 0.7530 0.8187 1.3039 0.042*
H9a 0.3279 0.8868 0.3992 0.041*
H9b 0.1728 0.9260 0.5013 0.041*
H11 0.0000 0.5832 0.3250 0.039*
H12 0.1414 0.4164 0.2539 0.039*
H13 0.5584 0.5127 0.3123 0.043*
H14 0.4297 0.6844 0.3840 0.041*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ni1 0.0293 (2) 0.0241 (2) 0.0255 (2) 0.0018 (1) −0.0103 (1) −0.0092 (1)
S1 0.0500 (4) 0.0401 (3) 0.0602 (4) 0.0187 (3) −0.0349 (3) −0.0312 (3)
S2 0.0364 (3) 0.0368 (3) 0.0390 (3) 0.0133 (2) −0.0199 (2) −0.0202 (2)
O1 0.033 (1) 0.028 (1) 0.032 (1) 0.000 (1) −0.014 (1) −0.009 (1)
O2 0.046 (1) 0.030 (1) 0.034 (1) 0.001 (1) −0.011 (1) −0.008 (1)
O3 0.035 (1) 0.034 (1) 0.028 (1) 0.001 (1) −0.013 (1) −0.011 (1)
supporting information
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Acta Cryst. (2004). E60, m933–m934
O1w 0.036 (1) 0.029 (1) 0.031 (1) 0.002 (1) −0.010 (1) −0.008 (1)
N1 0.031 (1) 0.028 (1) 0.032 (1) 0.002 (1) −0.011 (1) −0.012 (1)
N2 0.031 (1) 0.031 (1) 0.032 (1) 0.003 (1) −0.010 (1) −0.015 (1)
C1 0.035 (1) 0.020 (1) 0.037 (1) 0.006 (1) −0.012 (1) −0.015 (1)
C2 0.031 (1) 0.041 (1) 0.052 (1) 0.004 (1) −0.009 (1) −0.030 (1)
C3 0.029 (1) 0.030 (1) 0.042 (1) 0.004 (1) −0.016 (1) −0.018 (1)
C4 0.045 (1) 0.037 (1) 0.032 (1) 0.008 (1) −0.012 (1) −0.015 (1)
C5 0.046 (1) 0.032 (1) 0.031 (1) 0.008 (1) −0.012 (1) −0.009 (1)
C6 0.039 (1) 0.031 (1) 0.031 (1) 0.001 (1) −0.015 (1) −0.012 (1)
C7 0.044 (1) 0.028 (1) 0.039 (1) 0.005 (1) −0.022 (1) −0.012 (1)
C8 0.032 (1) 0.027 (1) 0.029 (1) 0.008 (1) −0.012 (1) −0.014 (1)
C9 0.045 (1) 0.028 (1) 0.037 (1) 0.006 (1) −0.021 (1) −0.013 (1)
C10 0.032 (1) 0.029 (1) 0.026 (1) 0.004 (1) −0.011 (1) −0.011 (1)
C11 0.031 (1) 0.038 (1) 0.036 (1) 0.005 (1) −0.014 (1) −0.017 (1)
C12 0.032 (1) 0.036 (1) 0.036 (1) 0.001 (1) −0.013 (1) −0.018 (1)
C13 0.027 (1) 0.041 (1) 0.045 (1) 0.004 (1) −0.012 (1) −0.021 (1)
C14 0.028 (1) 0.038 (1) 0.045 (1) 0.002 (1) −0.013 (1) −0.024 (1)
Geometric parameters (Å, º)
Ni1—O3 2.023 (2) C4—C5 1.376 (3)
Ni1—O1 2.094 (2) C6—C7 1.370 (3)
Ni1—O2 2.210 (2) C8—C9 1.518 (3)
Ni1—O1w 2.049 (2) C10—C11 1.384 (3)
Ni1—N1i 2.099 (2) C10—C14 1.387 (3)
Ni1—N2ii 2.094 (2) C11—C12 1.368 (3)
S1—C3 1.743 (2) C13—C14 1.377 (3)
S1—C2 1.790 (3) O1w—H1w1 0.85 (1)
S2—C10 1.745 (2) O1w—H1w2 0.84 (1)
S2—C9 1.788 (2) C2—H2a 0.97
O1—C1 1.265 (3) C2—H2b 0.97
O2—C1 1.243 (3) C4—H4 0.93
O3—C8 1.260 (3) C5—H5 0.93
O4—C8 1.238 (3) C6—H6 0.93
N1—C5 1.332 (3) C7—H7 0.93
N1—C6 1.342 (3) C9—H9a 0.97
N2—C13 1.335 (3) C9—H9b 0.97
N2—C12 1.339 (3) C11—H11 0.93
C1—C2 1.508 (3) C12—H12 0.93
C3—C4 1.383 (3) C13—H13 0.93
C3—C7 1.394 (3) C14—H14 0.93
O1—Ni1—O2 60.84 (6) O3—C8—C9 114.0 (2)
O1—Ni1—O3 166.10 (6) C8—C9—S2 116.3 (2)
O1—Ni1—O1w 98.41 (6) C11—C10—C14 117.1 (2)
O1—Ni1—N1i 88.55 (6) C11—C10—S2 117.5 (2)
O1—Ni1—N2ii 91.65 (6) C14—C10—S2 125.5 (2)
O2—Ni1—O1w 158.89 (7) N2—C12—C11 123.8 (2)
O2—Ni1—N1i 86.52 (6) N2—C13—C14 123.8 (2)
O2—Ni1—N2ii 92.02 (7) C13—C14—C10 119.3 (2)
O3—Ni1—N1i 88.82 (7) Ni1—O1w—H1w1 103 (2)
O3—Ni1—N2ii 90.56 (7) Ni1—O1w—H1w2 114 (2)
O3—Ni1—O1w 95.20 (7) H1w1—O1w—H1w2 113 (3)
O1w—Ni1—N1i 89.29 (7) C1—C2—H2a 108.3
O1w—Ni1—N2ii 92.43 (7) S1—C2—H2a 108.3
N1i—Ni1—N2ii 178.21 (7) C1—C2—H2b 108.3
C3—S1—C2 104.3 (1) S1—C2—H2b 108.3
C10—S2—C9 103.1 (1) H2a—C2—H2b 107.4
C1—O1—Ni1 91.5 (1) C5—C4—H4 120.4
C1—O2—Ni1 86.8 (1) C3—C4—H4 120.4
C8—O3—Ni1 126.4 (1) N1—C5—H5 118.0
C5—N1—C6 116.5 (2) C4—C5—H5 118.0
C5—N1—Ni1i 120.9 (2) N1—C6—H6 118.2
C6—N1—Ni1i 122.5 (2) C7—C6—H6 118.2
C13—N2—C12 116.2 (2) C6—C7—H7 120.3
C13—N2—Ni1ii 120.0 (2) C3—C7—H7 120.3
C12—N2—Ni1ii 123.7 (2) C8—C9—H9a 108.2
O2—C1—O1 120.9 (2) S2—C9—H9a 108.2
O2—C1—C2 119.1 (2) C8—C9—H9b 108.2
O1—C1—C2 119.9 (2) S2—C9—H9b 108.2
C1—C2—S1 116.1 (2) H9a—C9—H9b 107.4
C4—C3—C7 117.3 (2) C12—C11—H11 120.1
C4—C3—S1 125.9 (2) C10—C11—H11 120.1
C7—C3—S1 116.7 (2) N2—C12—H12 118.1
C5—C4—C3 119.1 (2) C11—C12—H12 118.1
N1—C5—C4 124.0 (2) N2—C13—H13 118.1
N1—C6—C7 123.5 (2) C14—C13—H13 118.1
C6—C7—C3 119.4 (2) C13—C14—H14 120.3
O4—C8—O3 126.1 (2) C10—C14—H14 120.3
O4—C8—C9 119.9 (2)
O3—Ni1—O1—C1 −7.4 (3) C6—N1—C5—C4 −0.2 (4)
O1w—Ni1—O1—C1 −175.6 (1) Ni1i—N1—C5—C4 −177.8 (2)
N2ii—Ni1—O1—C1 91.7 (1) C3—C4—C5—N1 −1.0 (4)
N1i—Ni1—O1—C1 −86.5 (1) C5—N1—C6—C7 0.9 (3)
O2—Ni1—O1—C1 0.3 (1) Ni1i—N1—C6—C7 178.5 (2)
O3—Ni1—O2—C1 177.8 (1) N1—C6—C7—C3 −0.5 (4)
O1w—Ni1—O2—C1 11.0 (2) C4—C3—C7—C6 −0.6 (3)
N2ii—Ni1—O2—C1 −91.1 (1) S1—C3—C7—C6 177.5 (2)
O1—Ni1—O2—C1 −0.3 (1) Ni1—O3—C8—O4 −18.4 (3)
N1i—Ni1—O2—C1 90.0 (1) Ni1—O3—C8—C9 159.1 (1)
O1w—Ni1—O3—C8 5.2 (2) O4—C8—C9—S2 −29.3 (3)
N2ii—Ni1—O3—C8 97.7 (2) O3—C8—C9—S2 153.0 (2)
O1—Ni1—O3—C8 −163.1 (2) C10—S2—C9—C8 −63.7 (2)
supporting information
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Acta Cryst. (2004). E60, m933–m934
O2—Ni1—O3—C8 −170.0 (2) C9—S2—C10—C14 −5.3 (2)
Ni1—O2—C1—O1 0.5 (2) C14—C10—C11—C12 0.4 (3)
Ni1—O2—C1—C2 177.2 (2) S2—C10—C11—C12 −179.4 (2)
Ni1—O1—C1—O2 −0.6 (2) C13—N2—C12—C11 −0.5 (3)
Ni1—O1—C1—C2 −177.2 (2) Ni1ii—N2—C12—C11 177.5 (2)
O2—C1—C2—S1 159.7 (2) C10—C11—C12—N2 0.2 (4)
O1—C1—C2—S1 −23.6 (3) C12—N2—C13—C14 0.2 (3)
C3—S1—C2—C1 −80.6 (2) Ni1ii—N2—C13—C14 −177.8 (2)
C2—S1—C3—C4 −3.2 (2) N2—C13—C14—C10 0.3 (4)
C2—S1—C3—C7 179.0 (2) C11—C10—C14—C13 −0.6 (3)
C7—C3—C4—C5 1.3 (4) S2—C10—C14—C13 179.1 (2)
S1—C3—C4—C5 −176.6 (2)
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1w—H1w2···O1iii 0.84 (1) 1.88 (1) 2.722 (2) 176 (3)
O1w—H1w1···O4 0.85 (1) 1.83 (2) 2.633 (2) 158 (3)
