metal-organic papers
Acta Cryst.(2005). E61, m509–m511 doi:10.1107/S1600536805004022 Fanet al. [Cu(C
7H4O6S)(C10H8N2)(H2O)2]
m509
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
Poly[[
cis
-diaqua(2,2
000-bipyridine)copper(II)]-l
-3-carboxylato-4-hydroxybenzenesulfonato]
Sai-Rong Fan,aLong-Guan Zhu,a* Hong-Ping Xiaoband
Seik Weng Ngc
aDepartment of Chemistry, Zhejiang University,
Hangzhou 310007, People’s Republic of China,
bSchool of Chemistry and Materials Science,
Wenzhou Normal College, Wenzhou 325027, People’s Republic of China, andcDepartment of
Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
Correspondence e-mail: chezlg@zju.edu.cn
Key indicators
Single-crystal X-ray study
T= 295 K
Mean(C–C) = 0.005 A˚
Rfactor = 0.052
wRfactor = 0.112
Data-to-parameter ratio = 15.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography
Printed in Great Britain – all rights reserved
The title complex, [Cu(C7H4O6S)(C10H8N2)(H2O)2]n, consists
of a polymeric neutral chain involving the 3-carboxylato-4-hydroxybenzenesulfonate ligand. The Cu atom shows a distorted octahedral coordination geometry, defined by two N atoms of the bipyridine, two O atoms of water molecules and the carboxyl O atom as well as one sulfonyl O atom of a symmetry-related bridging ligand. H atoms of water molecules
are involved in O—H O hydrogen bonding, building a three
dimensional network.
Comment
In a recent report on metal 3-carboxy-4-hydroxybenzene-sufonates, the authors reacted copper(II)
bis(3-carboxy-4-hydroxybenzenesulfonate) (prepared in situ) with two molar
equivalents of 2,20-bipyridine and obtained the expected bis-chelated compound but, of the two monoanions, only one is coordinated to the Cu atom, which is only five-coordinate (Gao et al., 2005). Without an abstracting reagent, a similar synthesis yielded the monochelated compound, but the
3-carboxy-4-hydroxybenzenesulfonate behaves here as a
dianion (Fig. 1).
In the title compound, (I), the doubly deprotonated
3-carboxylato-4-hydroxybenzenesulfonate group acts as a 2
-bridging ligand linking Cu atoms, forming a polymeric zigzag chain. The compound is isostructural with the cobalt(II) analog, whose structure has been described recently (Fanet al., 2005). H atoms of water molecules are involved in
inter-molecular O—H O hydrogen bonding, building a
three-dimensional network (Table 1 and Fig. 2). There are also
intramolecular O—H O hydrogen bonds between the
hydroxyl group and the carboxyl O atom coordinated to copper, and between one of the water molecules and the second carboxyl O atom (Table 1).
Experimental
A solution of copper acetate hydrate (0.041 g, 0.2 mmol) and 5-sulfosalicylic acid dihydrate (0.103 g, 0.4 mmol) dissolved in water (20 ml) was added to a methanol solution (5 ml) of 2,20-bipyridyl
(0.030 g, 0.2 mmol). The clear blue solution was left to stand for a day to allow the solvent to evaporate. Blue block-shaped crystals were
obtained. Analysis calculated for C17H16CuN2O8S: C 43.26, H 3.42, N
5.94%; found: C 42.63, H 3.47, N 5.96%.
Crystal data
[Cu(C7H4O6S)(C10H8N2)(H2O)2] Mr= 471.92
Monoclinic,P21=n a= 14.2339 (8) A˚
b= 7.7622 (4) A˚
c= 17.801 (1) A˚
= 110.940 (1) V= 1836.87 (17) A˚3
Z= 4
Dx= 1.707 Mg m
3
MoKradiation Cell parameters from 4713
reflections
= 2.3–28.3 = 1.35 mm1
T= 295 (2) K Block, blue
0.280.260.12 mm
Data collection
Bruker SMART APEX area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2002)
Tmin= 0.703,Tmax= 0.854
10938 measured reflections
4143 independent reflections 3855 reflections withI> 2(I)
Rint= 0.024 max= 27.5
h=18!18
k=9!10
l=23!14
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.052
wR(F2) = 0.112 S= 1.20 4143 reflections 275 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2(F
o2) + (0.0379P)2
+ 2.6968P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.63 e A˚ 3
min=0.40 e A˚ 3
Table 1
Hydrogen-bonding geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1W—H1W1 O2i
0.821 (18) 1.870 (19) 2.688 (3) 174 (4) O1W—H1W2 O2ii
0.83 (4) 1.89 (4) 2.717 (3) 178 (4) O2W—H2W1 O3i 0.848 (17) 2.001 (19) 2.810 (4) 159 (3) O2W—H2W2 O4 0.852 (18) 1.99 (2) 2.738 (4) 146 (3) O6—H6 O5 0.82 1.89 2.599 (3) 143
Symmetry codes: (i)x1 2;
3 2y;z
1
2; (ii) 1x;1y;2z.
Aromatic H atoms were positioned geometrically and were included in the refinement in the riding-model approximation [C— H = 0.93 A˚ andUiso(H) = 1.2Ueq(C)]. The water and hydroxy H atoms
were located in a difference Fourier map and refined with distance restraints of O—H = 0.85 (1) A˚ and H H = 1.39 (1) A˚ , and
Uiso(H) = 1.2Ueq(O).
Data collection:SMART(Bruker, 2002); cell refinement:SAINT
(Bruker, 2002); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication:SHELXL97.
We thank the National Natural Science Foundation of China (No. 50073019) and the University of Malaya for supporting this study.
References
Bruker (2002).SADABS, SAINTandSMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Burnett, M. N. & Johnson, C. K. (1996).ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
metal-organic papers
m510
Fanet al. [Cu(C [image:2.610.45.295.76.191.2]7H4O6S)(C10H8N2)(H2O)2] Acta Cryst.(2005). E61, m509–m511 Figure 2
CAMERON(Watkinet al., 1993) view of the packing, showing the O—
H O hydrogen-bonded (dashed lines) three-dimensional network. H
atoms not involved in hydrogen bonding have been omitted.
Figure 1
ORTEPIII(Burnett & Johnson, 1996) plot of a fragment of the polymeric chain of (I). Displacement ellipsoids are drawn at the 30% probability
level. H atoms have been omitted for clarity. [Symmetry codes: (i)x1
2, 1
2y, z 1 2; (ii)
1 2+x,
1 2y,
[image:2.610.45.296.253.622.2]Fan, S.-R., Zhu, L.-G., Xiao, H.-P. & Ng, S. W. (2005).Acta Cryst.E61, m435– m436.
Gao, S., Huo, L.-H., Zhao, H. & Ng, S. W. (2005).Acta Cryst.E61, m290– m292.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Watkin, D. M., Pearce, L. & Prout, C. K. (1993).CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.
metal-organic papers
Acta Cryst.(2005). E61, m509–m511 Fanet al. [Cu(C
supporting information
sup-1
Acta Cryst. (2005). E61, m509–m511
supporting information
Acta Cryst. (2005). E61, m509–m511 [https://doi.org/10.1107/S1600536805004022]
Poly[[
cis
-diaqua(2,2
′
-bipyridine)copper(II)]-µ-3-carboxylato-4-hydroxybenzene-sulfonato]
Sai-Rong Fan, Long-Guan Zhu, Hong-Ping Xiao and Seik Weng Ng
Poly[[cis-diaqua(2,2′-bipyridine)copper(II)]-µ-3-carboxylato-4- hydroxybenzenesulfonato]
Crystal data
[Cu(C7H4O6S)(C10H8N2)(H2O)2] Mr = 471.92
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 14.2339 (8) Å
b = 7.7622 (4) Å
c = 17.801 (1) Å
β = 110.940 (1)°
V = 1836.87 (17) Å3 Z = 4
F(000) = 964
Dx = 1.707 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4713 reflections
θ = 2.3–28.3°
µ = 1.35 mm−1 T = 295 K Block, blue
0.28 × 0.26 × 0.12 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, 2002)
Tmin = 0.703, Tmax = 0.854
10938 measured reflections 4143 independent reflections 3855 reflections with I > 2σ(I)
Rint = 0.024
θmax = 27.5°, θmin = 2.3° h = −18→18
k = −9→10
l = −23→14
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.052 wR(F2) = 0.112 S = 1.20 4143 reflections 275 parameters 6 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) + (0.0379P)2 + 2.6968P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.63 e Å−3
supporting information
sup-2
Acta Cryst. (2005). E61, m509–m511 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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cu1 0.41473 (3) 0.43810 (5) 0.67992 (2) 0.02594 (12) S1 0.79903 (5) 0.47741 (9) 1.14844 (4) 0.02252 (17) O1 0.84091 (17) 0.3277 (3) 1.19711 (13) 0.0332 (5) H1W1 0.298 (3) 0.659 (2) 0.699 (2) 0.040* H1W2 0.283 (3) 0.503 (4) 0.732 (2) 0.040* O2 0.76904 (17) 0.6060 (3) 1.19620 (14) 0.0312 (5) H2W1 0.477 (2) 0.794 (3) 0.669 (2) 0.037* H2W2 0.552 (2) 0.711 (4) 0.7302 (13) 0.037* O3 0.86249 (17) 0.5509 (3) 1.10858 (14) 0.0381 (6) O4 0.5985 (2) 0.6006 (4) 0.83827 (15) 0.0504 (7) O5 0.48314 (18) 0.3947 (3) 0.79452 (13) 0.0366 (6) O6 0.43908 (19) 0.1997 (3) 0.89597 (15) 0.0418 (6)
H6 0.4286 0.2432 0.8517 0.063*
O1W 0.3048 (2) 0.5534 (3) 0.70075 (16) 0.0374 (6) O2W 0.5126 (2) 0.7034 (4) 0.68134 (16) 0.0492 (7) N1 0.5126 (2) 0.3111 (4) 0.64346 (17) 0.0330 (6) N2 0.3418 (2) 0.4546 (4) 0.56064 (16) 0.0297 (6) C1 0.5980 (3) 0.2396 (6) 0.6905 (3) 0.0512 (10)
H1 0.6175 0.2524 0.7459 0.061*
C2 0.6591 (4) 0.1463 (7) 0.6598 (3) 0.0663 (14)
H2 0.7188 0.0975 0.6940 0.080*
C3 0.6302 (4) 0.1275 (6) 0.5784 (3) 0.0615 (13)
H3 0.6696 0.0637 0.5566 0.074*
C4 0.5433 (3) 0.2024 (5) 0.5290 (3) 0.0484 (10)
H4 0.5237 0.1923 0.4735 0.058*
C5 0.4847 (3) 0.2939 (4) 0.5629 (2) 0.0339 (8) C6 0.3882 (3) 0.3768 (4) 0.5159 (2) 0.0321 (7) C7 0.3473 (3) 0.3769 (6) 0.4324 (2) 0.0485 (10)
H7 0.3798 0.3221 0.4021 0.058*
C8 0.2571 (3) 0.4608 (6) 0.3959 (2) 0.0559 (12)
H8 0.2286 0.4640 0.3400 0.067*
C9 0.2092 (3) 0.5391 (6) 0.4407 (2) 0.0503 (10)
H9 0.1480 0.5949 0.4161 0.060*
supporting information
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Acta Cryst. (2005). E61, m509–m511
C14 0.5193 (2) 0.2755 (4) 0.95086 (19) 0.0273 (6) C15 0.5455 (2) 0.2172 (4) 1.02982 (19) 0.0295 (7) H15 0.5055 0.1353 1.0421 0.035* C16 0.6298 (2) 0.2792 (4) 1.08982 (18) 0.0273 (6) H16 0.6478 0.2367 1.1419 0.033* C17 0.5521 (2) 0.4770 (4) 0.84987 (19) 0.0285 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cu1 0.0293 (2) 0.0303 (2) 0.01867 (19) 0.00308 (15) 0.00907 (15) −0.00059 (15) S1 0.0235 (4) 0.0244 (4) 0.0182 (3) −0.0007 (3) 0.0058 (3) −0.0005 (3) O1 0.0349 (12) 0.0303 (12) 0.0265 (12) 0.0063 (10) 0.0014 (10) −0.0012 (10) O2 0.0404 (13) 0.0233 (11) 0.0307 (12) −0.0025 (9) 0.0136 (10) −0.0042 (9) O3 0.0314 (12) 0.0561 (16) 0.0271 (12) −0.0118 (11) 0.0109 (10) −0.0018 (11) O4 0.0543 (17) 0.0612 (18) 0.0249 (12) −0.0283 (14) 0.0012 (12) 0.0110 (12) O5 0.0422 (14) 0.0403 (13) 0.0185 (11) −0.0127 (11) 0.0002 (10) −0.0006 (10) O6 0.0397 (14) 0.0434 (14) 0.0307 (13) −0.0179 (11) −0.0018 (11) 0.0066 (11) O1W 0.0554 (16) 0.0252 (12) 0.0456 (15) 0.0100 (11) 0.0351 (13) 0.0075 (11) O2W 0.0594 (19) 0.0525 (17) 0.0351 (14) 0.0176 (14) 0.0161 (14) 0.0080 (13) N1 0.0354 (15) 0.0347 (15) 0.0344 (15) 0.0058 (12) 0.0192 (13) 0.0051 (12) N2 0.0340 (15) 0.0338 (14) 0.0231 (13) −0.0035 (12) 0.0126 (12) 0.0008 (11) C1 0.048 (2) 0.063 (3) 0.046 (2) 0.018 (2) 0.0217 (19) 0.013 (2) C2 0.056 (3) 0.068 (3) 0.087 (4) 0.031 (2) 0.041 (3) 0.026 (3) C3 0.068 (3) 0.056 (3) 0.085 (4) 0.013 (2) 0.057 (3) 0.002 (3) C4 0.061 (3) 0.045 (2) 0.056 (3) −0.0074 (19) 0.041 (2) −0.0097 (19) C5 0.0424 (19) 0.0317 (17) 0.0369 (19) −0.0076 (15) 0.0254 (16) −0.0027 (14) C6 0.0411 (19) 0.0336 (17) 0.0263 (16) −0.0126 (15) 0.0178 (15) −0.0045 (14) C7 0.062 (3) 0.058 (2) 0.0311 (19) −0.013 (2) 0.0238 (19) −0.0107 (18) C8 0.063 (3) 0.071 (3) 0.0244 (18) −0.019 (2) 0.0043 (19) 0.000 (2) C9 0.042 (2) 0.064 (3) 0.034 (2) −0.0045 (19) 0.0002 (17) 0.0100 (19) C10 0.0359 (18) 0.043 (2) 0.0327 (18) 0.0013 (15) 0.0108 (15) 0.0067 (16) C11 0.0214 (14) 0.0246 (14) 0.0189 (14) −0.0001 (11) 0.0038 (11) −0.0027 (11) C12 0.0238 (14) 0.0254 (15) 0.0223 (14) −0.0019 (12) 0.0072 (12) 0.0019 (12) C13 0.0249 (14) 0.0262 (15) 0.0194 (14) 0.0001 (12) 0.0064 (12) −0.0005 (12) C14 0.0235 (15) 0.0261 (15) 0.0286 (16) −0.0011 (12) 0.0048 (13) −0.0008 (13) C15 0.0298 (16) 0.0284 (16) 0.0297 (17) −0.0057 (13) 0.0100 (14) 0.0041 (13) C16 0.0294 (16) 0.0307 (16) 0.0204 (14) 0.0008 (13) 0.0073 (13) 0.0051 (13) C17 0.0272 (15) 0.0337 (17) 0.0226 (15) 0.0002 (13) 0.0062 (13) 0.0017 (13)
Geometric parameters (Å, º)
Cu1—O1W 1.950 (2) C2—H2 0.9300
Cu1—O5 1.950 (2) C3—C4 1.365 (6)
Cu1—N1 1.994 (3) C3—H3 0.9300
Cu1—N2 2.007 (3) C4—C5 1.387 (5)
Cu1—O1i 2.384 (2) C4—H4 0.9300
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Acta Cryst. (2005). E61, m509–m511
S1—O3 1.450 (2) C6—C7 1.389 (5)
S1—O2 1.470 (2) C7—C8 1.377 (6)
S1—C11 1.768 (3) C7—H7 0.9300
O1—Cu1ii 2.384 (2) C8—C9 1.364 (6)
O4—C17 1.223 (4) C8—H8 0.9300
O5—C17 1.285 (4) C9—C10 1.381 (5)
O6—C14 1.344 (4) C9—H9 0.9300
O6—H6 0.8200 C10—H10 0.9300
O1W—H1W1 0.821 (18) C11—C12 1.379 (4) O1W—H1W2 0.83 (4) C11—C16 1.389 (4) O2W—H2W1 0.848 (17) C12—C13 1.396 (4) O2W—H2W2 0.852 (18) C12—H12 0.9300
N1—C1 1.327 (5) C13—C14 1.402 (4)
N1—C5 1.350 (4) C13—C17 1.500 (4)
N2—C10 1.339 (4) C14—C15 1.395 (4)
N2—C6 1.346 (4) C15—C16 1.377 (4)
C1—C2 1.386 (6) C15—H15 0.9300
C1—H1 0.9300 C16—H16 0.9300
C2—C3 1.366 (7)
O1W—Cu1—O5 90.85 (11) C5—C4—H4 120.5 O1W—Cu1—N1 171.82 (12) N1—C5—C4 121.2 (4) O5—Cu1—N1 96.28 (11) N1—C5—C6 114.8 (3) O1W—Cu1—N2 91.43 (11) C4—C5—C6 124.0 (3) O5—Cu1—N2 173.69 (11) N2—C6—C7 121.7 (3) N1—Cu1—N2 81.07 (11) N2—C6—C5 114.5 (3) O1W—Cu1—O1i 87.27 (9) C7—C6—C5 123.8 (3)
O5—Cu1—O1i 78.14 (9) C8—C7—C6 118.0 (4)
N1—Cu1—O1i 90.29 (10) C8—C7—H7 121.0
N2—Cu1—O1i 96.09 (9) C6—C7—H7 121.0
O1—S1—O3 114.48 (15) C9—C8—C7 120.7 (4) O1—S1—O2 110.01 (13) C9—C8—H8 119.6 O3—S1—O2 112.10 (14) C7—C8—H8 119.6 O1—S1—C11 105.73 (14) C8—C9—C10 118.4 (4) O3—S1—C11 106.94 (14) C8—C9—H9 120.8 O2—S1—C11 107.07 (14) C10—C9—H9 120.8 S1—O1—Cu1ii 136.51 (14) N2—C10—C9 122.2 (4)
C17—O5—Cu1 132.5 (2) N2—C10—H10 118.9
C14—O6—H6 109.5 C9—C10—H10 118.9
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Acta Cryst. (2005). E61, m509–m511
C6—N2—Cu1 114.8 (2) O6—C14—C15 116.3 (3) N1—C1—C2 122.2 (4) O6—C14—C13 124.1 (3) N1—C1—H1 118.9 C15—C14—C13 119.7 (3) C2—C1—H1 118.9 C16—C15—C14 120.9 (3) C3—C2—C1 118.7 (4) C16—C15—H15 119.5
C3—C2—H2 120.6 C14—C15—H15 119.5
C1—C2—H2 120.6 C15—C16—C11 119.7 (3) C4—C3—C2 119.8 (4) C15—C16—H16 120.2
C4—C3—H3 120.1 C11—C16—H16 120.2
C2—C3—H3 120.1 O4—C17—O5 124.8 (3)
C3—C4—C5 119.1 (4) O4—C17—C13 120.6 (3) C3—C4—H4 120.5 O5—C17—C13 114.6 (3)
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1W—H1W1···O2iii 0.82 (2) 1.87 (2) 2.688 (3) 174 (4)
O1W—H1W2···O2iv 0.83 (4) 1.89 (4) 2.717 (3) 178 (4)
O2W—H2W1···O3iii 0.85 (2) 2.00 (2) 2.810 (4) 159 (3)
O2W—H2W2···O4 0.85 (2) 1.99 (2) 2.738 (4) 146 (3)
O6—H6···O5 0.82 1.89 2.599 (3) 143