Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050763/bh2137sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050763/bh2137Isup2.hkl |
CCDC reference: 667188
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.047
- wR factor = 0.105
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of P1 = ... S PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.19
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For related literature about the metal phosphonates chemistry, see: Clearfield (1998); Maeda (2004); Mao (2007). A related chemistry using two bridging ligands has been developed: Du et al. (2006a, 2006b); Du, Li, Liu & Mao (2007); Du, Xu, Li & Mao (2007). For complexes structurally related to the title compound, see: Drumel et al. (1996); Zhong et al. (2005).
A mixture of Cu(OAc)2 (65 mg, 0.36 mmol), 3-phosphono-benzenesulfonic acid (86 mg, 0.36 mmol) and 4,4'-bipy (50 mg, 0.32 mmol) in 10 ml distilled water with an initial pH value of ca. 3.5, was put into a Parr Teflon-lined autoclave (23 ml) and heated at 413 K for 4 days. Blue brick-shaped crystals of the title polymer were collected in a ca. 12% yield based on Cu. Analysis calculated for C16H15O7N2P1S1Cu1: C 40.55, H 3.19, N 5.91%; found: C 40.64, H 3.30, N 5.82%.
H atoms bonded to C atoms were positioned geometrically and included in the refinement using a riding-model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(carrier C). Water H atoms were located in a difference map and refined with O—H and H···H distances restrained to 0.85 (1) and 1.39 (1) Å, respectively, and Uiso(H) = 1.5Ueq(O1W). H atom of protonated HPO3 group was positioned geometrically (O—H = 0.82 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.5Ueq(O2).
The chemistry of metal phosphonates has been a research field of rapid expansion in recent years, mainly due to their potential applications in the area of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry, and materials chemistry (Clearfield, 1998; Maeda, 2004; Mao, 2007). The strategy of attaching functional groups such as amine, hydroxyl or carboxylate groups to the phosphonic acid can lead to a number of new metal phosphonates with micro-porous or open-framework structures. However, reports on the use of sulfonate group as a functional group to build metal phosphonate open frameworks are almost unknown to date. Recently, our increasing attention has been devoted to the metal coordination chemistry of phenylphosphonic acid ligand bonded to a sulfonate group, which can adopt a variety of coordination modes and form a variety of metal cluster compounds when an ancillary ligand, such as 1,10-phenanthroline or 4,4'-bipyridyl (4,4'-bipy), is also applied (Du et al., 2006a, 2006b; Du, Li, Liu & Mao, 2007; Du, Xu, Li & Mao, 2007). As an expansion of our previous work, we have also obtained a CuII sulfonate-phosphonate by applying this synthetic route. Herein, we report its synthesis and crystal structure.
The structure of the title compound features a layered architecture. The asymmetric unit contains one CuII ion, one [O3S—C6H4—PO3H]2- dianion, one 4,4'-bipy molecule, and one coordinated water molecule. CuII ion is five-coordinated with one phosphonate O atom from one [O3S—C6H4—PO3H]2- anion, one sulfonate O atom from a symmetry related [O3S—C6H4—PO3H]2- anion, two N atoms from two symmetry related 4,4'-bipy ligands, and one water molecule (Fig. 1). The coordination geometry around Cu can be described as a slightly distorted square-pyramid. The square plane is formed by one phosphonate O atom, two N atoms and the water molecule. The apical position is occupied by a sulfonate O atom. The Cu—O [1.964 (3)–2.234 (3) Å] and Cu—N [1.992 (3)–1.994 (3) Å] bond lengths are comparable to those reported for other CuII sulfonate/phosphonates complexes (Drumel et al., 1996; Zhong et al., 2005).
The phosphonate group is not completely deprotonated, as required for charge balance. The [O3S—C6H4—PO3H]2- ligand is bidentate and bridges two CuII ions via one phosphonate O atom and one sulfonate O atom. These bridges result in the formation of a one-dimensional helical chain along [010] (Fig. 2). These helical chains are further connected by bidentate bridging 4,4'-bipy ligands, to form a layered architecture (Fig. 3). The layered structure features an eight-membered ring including four CuII ions, two [O3S—C6H4—PO3H]2- anions and two 4,4'-bipy ligands. Between the layers, hydrogen bonds are formed, involving phosphonate O atom O2, sulfonate O atom O6 and the water molecule O1W (Fig. 4; Table 2). The O···O contacts range from 2.595 (4) to 2.701 (5) Å. Such a complex hydrogen-bond network is likely to contribute to the overall stability of the crystal structure and prevents guest molecules entering into the interstitial voids between the layers.
For related literature about the metal phosphonates chemistry, see: Clearfield (1998); Maeda (2004); Mao (2007). A related chemistry using two bridging ligands has been developed: Du et al. (2006a, 2006b); Du, Li, Liu & Mao (2007); Du, Xu, Li & Mao (2007). For complexes structurally related to the title compound, see: Drumel et al. (1996); Zhong et al. (2005).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2004).
[Cu(C6H5O6PS)(C10H8N2)(H2O)] | F(000) = 964 |
Mr = 473.87 | Dx = 1.790 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3426 reflections |
a = 10.9824 (2) Å | θ = 2.3–25.7° |
b = 11.2924 (3) Å | µ = 1.50 mm−1 |
c = 15.1189 (3) Å | T = 293 K |
β = 110.331 (1)° | Brick, blue |
V = 1758.20 (7) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 4 |
Bruker SMART APEXII CCD diffractometer | 3351 independent reflections |
Radiation source: fine-focus sealed tube | 2413 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
narrow frame method scans | θmax = 25.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.645, Tmax = 0.741 | k = −13→10 |
9468 measured reflections | l = −18→18 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0375P)2 + 2.653P] where P = (Fo2 + 2Fc2)/3 |
3351 reflections | (Δ/σ)max < 0.001 |
261 parameters | Δρmax = 0.82 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
[Cu(C6H5O6PS)(C10H8N2)(H2O)] | V = 1758.20 (7) Å3 |
Mr = 473.87 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.9824 (2) Å | µ = 1.50 mm−1 |
b = 11.2924 (3) Å | T = 293 K |
c = 15.1189 (3) Å | 0.30 × 0.25 × 0.20 mm |
β = 110.331 (1)° |
Bruker SMART APEXII CCD diffractometer | 3351 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2413 reflections with I > 2σ(I) |
Tmin = 0.645, Tmax = 0.741 | Rint = 0.052 |
9468 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.82 e Å−3 |
3351 reflections | Δρmin = −0.52 e Å−3 |
261 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | −0.25750 (5) | 0.30566 (5) | 0.18344 (3) | 0.02307 (16) | |
P1 | −0.12583 (11) | 0.29056 (10) | 0.03360 (7) | 0.0269 (3) | |
S1 | 0.33196 (10) | 0.04087 (10) | 0.19138 (8) | 0.0301 (3) | |
N1 | −0.0778 (3) | 0.2833 (3) | 0.2746 (2) | 0.0218 (8) | |
N2 | 0.5660 (3) | 0.2033 (3) | 0.5851 (2) | 0.0266 (8) | |
C1 | 0.0481 (4) | 0.2855 (4) | 0.0959 (3) | 0.0250 (10) | |
C2 | 0.1169 (4) | 0.1801 (4) | 0.1125 (3) | 0.0260 (10) | |
H2A | 0.0747 | 0.1098 | 0.0877 | 0.031* | |
C3 | 0.2487 (4) | 0.1789 (4) | 0.1661 (3) | 0.0229 (9) | |
C4 | 0.3123 (4) | 0.2822 (4) | 0.2027 (3) | 0.0310 (11) | |
H4A | 0.3997 | 0.2807 | 0.2400 | 0.037* | |
C5 | 0.2458 (5) | 0.3879 (4) | 0.1837 (4) | 0.0413 (12) | |
H5A | 0.2893 | 0.4582 | 0.2070 | 0.050* | |
C6 | 0.1144 (4) | 0.3905 (4) | 0.1301 (3) | 0.0362 (11) | |
H6A | 0.0705 | 0.4624 | 0.1170 | 0.043* | |
C7 | −0.0052 (4) | 0.3733 (4) | 0.3224 (3) | 0.0309 (10) | |
H7A | −0.0419 | 0.4484 | 0.3162 | 0.037* | |
C8 | 0.1217 (4) | 0.3587 (4) | 0.3804 (3) | 0.0332 (11) | |
H8A | 0.1693 | 0.4237 | 0.4118 | 0.040* | |
C14 | 0.4058 (4) | 0.3201 (4) | 0.4718 (3) | 0.0390 (12) | |
H11A | 0.3841 | 0.3917 | 0.4398 | 0.047* | |
C13 | 0.5286 (4) | 0.3021 (5) | 0.5364 (3) | 0.0416 (12) | |
H12A | 0.5887 | 0.3631 | 0.5463 | 0.050* | |
C12 | 0.4804 (4) | 0.1147 (4) | 0.5676 (3) | 0.0319 (11) | |
H13A | 0.5055 | 0.0437 | 0.6000 | 0.038* | |
C11 | 0.3556 (4) | 0.1246 (4) | 0.5027 (3) | 0.0305 (10) | |
H14A | 0.2994 | 0.0603 | 0.4913 | 0.037* | |
C10 | 0.3146 (4) | 0.2293 (4) | 0.4552 (3) | 0.0243 (10) | |
C9 | 0.1792 (4) | 0.2478 (4) | 0.3922 (3) | 0.0234 (9) | |
C15 | 0.1028 (4) | 0.1546 (4) | 0.3436 (3) | 0.0258 (10) | |
H17A | 0.1362 | 0.0781 | 0.3496 | 0.031* | |
C16 | −0.0228 (4) | 0.1768 (4) | 0.2864 (3) | 0.0277 (10) | |
H18A | −0.0725 | 0.1135 | 0.2539 | 0.033* | |
O1 | −0.1830 (3) | 0.3664 (3) | 0.09164 (19) | 0.0294 (7) | |
O2 | −0.1690 (3) | 0.1599 (3) | 0.0405 (2) | 0.0424 (9) | |
H2B | −0.2074 | 0.1342 | −0.0126 | 0.064* | |
O3 | −0.1557 (3) | 0.3310 (3) | −0.0648 (2) | 0.0389 (8) | |
O4 | 0.2841 (3) | −0.0182 (3) | 0.2586 (2) | 0.0396 (8) | |
O5 | 0.4693 (3) | 0.0663 (3) | 0.2314 (3) | 0.0547 (10) | |
O6 | 0.2960 (4) | −0.0212 (3) | 0.1014 (2) | 0.0618 (11) | |
O1W | −0.3168 (3) | 0.2021 (4) | 0.2649 (2) | 0.0486 (10) | |
H1WB | −0.273 (5) | 0.185 (5) | 0.324 (4) | 0.054 (17)* | |
H1WA | −0.397 (6) | 0.170 (5) | 0.251 (4) | 0.063 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0101 (2) | 0.0324 (3) | 0.0205 (3) | −0.0011 (2) | −0.00244 (19) | 0.0020 (2) |
P1 | 0.0194 (6) | 0.0349 (7) | 0.0226 (6) | 0.0000 (5) | 0.0025 (5) | 0.0020 (5) |
S1 | 0.0210 (6) | 0.0277 (6) | 0.0382 (6) | −0.0018 (4) | 0.0059 (5) | 0.0023 (5) |
N1 | 0.0148 (17) | 0.033 (2) | 0.0160 (16) | −0.0025 (15) | 0.0030 (14) | 0.0025 (15) |
N2 | 0.0147 (18) | 0.033 (2) | 0.0252 (18) | 0.0031 (16) | −0.0021 (15) | −0.0043 (17) |
C1 | 0.022 (2) | 0.030 (3) | 0.023 (2) | −0.0005 (18) | 0.0080 (18) | 0.0015 (18) |
C2 | 0.021 (2) | 0.025 (2) | 0.029 (2) | −0.0062 (18) | 0.0053 (18) | 0.0022 (19) |
C3 | 0.020 (2) | 0.027 (2) | 0.021 (2) | −0.0010 (18) | 0.0071 (17) | 0.0046 (18) |
C4 | 0.015 (2) | 0.039 (3) | 0.037 (3) | −0.0042 (19) | 0.0058 (19) | −0.004 (2) |
C5 | 0.028 (3) | 0.029 (3) | 0.062 (3) | −0.008 (2) | 0.010 (2) | −0.013 (2) |
C6 | 0.027 (3) | 0.030 (3) | 0.049 (3) | 0.002 (2) | 0.011 (2) | 0.001 (2) |
C7 | 0.020 (2) | 0.029 (3) | 0.036 (3) | 0.0048 (19) | 0.0006 (19) | −0.002 (2) |
C8 | 0.017 (2) | 0.036 (3) | 0.037 (3) | −0.0040 (19) | −0.004 (2) | −0.005 (2) |
C14 | 0.021 (2) | 0.036 (3) | 0.047 (3) | −0.002 (2) | −0.004 (2) | 0.012 (2) |
C13 | 0.019 (2) | 0.045 (3) | 0.050 (3) | −0.006 (2) | −0.003 (2) | 0.004 (3) |
C12 | 0.022 (2) | 0.035 (3) | 0.029 (2) | 0.006 (2) | −0.0031 (19) | 0.002 (2) |
C11 | 0.020 (2) | 0.033 (3) | 0.030 (2) | −0.0035 (19) | −0.0018 (19) | −0.003 (2) |
C10 | 0.014 (2) | 0.032 (3) | 0.021 (2) | 0.0032 (17) | −0.0010 (17) | −0.0025 (18) |
C9 | 0.014 (2) | 0.033 (2) | 0.020 (2) | 0.0025 (18) | 0.0029 (17) | 0.0034 (19) |
C15 | 0.021 (2) | 0.024 (2) | 0.024 (2) | 0.0040 (17) | −0.0022 (18) | 0.0002 (18) |
C16 | 0.022 (2) | 0.032 (3) | 0.023 (2) | −0.0041 (19) | 0.0001 (18) | −0.0043 (19) |
O1 | 0.0221 (16) | 0.0367 (18) | 0.0262 (16) | 0.0022 (13) | 0.0045 (13) | 0.0057 (13) |
O2 | 0.0341 (19) | 0.037 (2) | 0.046 (2) | −0.0052 (15) | 0.0014 (16) | 0.0017 (15) |
O3 | 0.038 (2) | 0.053 (2) | 0.0217 (16) | −0.0008 (16) | 0.0048 (14) | 0.0050 (14) |
O4 | 0.0273 (18) | 0.043 (2) | 0.048 (2) | 0.0022 (15) | 0.0118 (15) | 0.0174 (16) |
O5 | 0.0181 (18) | 0.044 (2) | 0.095 (3) | −0.0030 (15) | 0.0114 (19) | 0.012 (2) |
O6 | 0.094 (3) | 0.039 (2) | 0.042 (2) | 0.009 (2) | 0.012 (2) | −0.0112 (18) |
O1W | 0.0240 (19) | 0.075 (3) | 0.035 (2) | −0.0198 (18) | −0.0045 (16) | 0.021 (2) |
Cu1—O1 | 1.964 (3) | C5—H5A | 0.9300 |
Cu1—O1W | 1.966 (3) | C6—H6A | 0.9300 |
Cu1—N1 | 1.992 (3) | C7—C8 | 1.374 (6) |
Cu1—N2i | 1.994 (3) | C7—H7A | 0.9300 |
Cu1—O4ii | 2.234 (3) | C8—C9 | 1.386 (6) |
P1—O3 | 1.480 (3) | C8—H8A | 0.9300 |
P1—O1 | 1.510 (3) | C14—C13 | 1.378 (6) |
P1—O2 | 1.564 (3) | C14—C10 | 1.394 (6) |
P1—C1 | 1.813 (4) | C14—H11A | 0.9300 |
S1—O5 | 1.446 (3) | C13—H12A | 0.9300 |
S1—O4 | 1.457 (3) | C12—C11 | 1.385 (5) |
S1—O6 | 1.458 (4) | C12—H13A | 0.9300 |
S1—C3 | 1.780 (4) | C11—C10 | 1.375 (6) |
N1—C16 | 1.329 (5) | C11—H14A | 0.9300 |
N1—C7 | 1.338 (5) | C10—C9 | 1.476 (5) |
N2—C13 | 1.321 (6) | C9—C15 | 1.387 (6) |
N2—C12 | 1.335 (6) | C15—C16 | 1.372 (5) |
N2—Cu1iii | 1.994 (3) | C15—H17A | 0.9300 |
C1—C2 | 1.385 (6) | C16—H18A | 0.9300 |
C1—C6 | 1.393 (6) | O2—O6iv | 2.631 (5) |
C2—C3 | 1.392 (6) | O2—H2B | 0.8200 |
C2—H2A | 0.9300 | O4—Cu1v | 2.234 (3) |
C3—C4 | 1.373 (6) | O1W—O3vi | 2.595 (4) |
C4—C5 | 1.377 (6) | O1W—O5vii | 2.701 (5) |
C4—H4A | 0.9300 | O1W—H1WB | 0.87 (5) |
C5—C6 | 1.389 (6) | O1W—H1WA | 0.90 (6) |
O1—Cu1—O1W | 163.85 (15) | C5—C6—H6A | 119.9 |
O1—Cu1—N1 | 88.69 (12) | C1—C6—H6A | 119.9 |
O1W—Cu1—N1 | 87.45 (14) | N1—C7—C8 | 122.4 (4) |
O1—Cu1—N2i | 91.53 (13) | N1—C7—H7A | 118.8 |
O1W—Cu1—N2i | 89.36 (14) | C8—C7—H7A | 118.8 |
N1—Cu1—N2i | 169.20 (15) | C7—C8—C9 | 120.4 (4) |
O1—Cu1—O4ii | 96.31 (12) | C7—C8—H8A | 119.8 |
O1W—Cu1—O4ii | 99.62 (15) | C9—C8—H8A | 119.8 |
N1—Cu1—O4ii | 94.27 (12) | C13—C14—C10 | 119.0 (4) |
N2i—Cu1—O4ii | 96.43 (13) | C13—C14—H11A | 120.5 |
O3—P1—O1 | 114.69 (18) | C10—C14—H11A | 120.5 |
O3—P1—O2 | 113.07 (19) | N2—C13—C14 | 123.9 (4) |
O1—P1—O2 | 107.39 (18) | N2—C13—H12A | 118.1 |
O3—P1—C1 | 110.94 (18) | C14—C13—H12A | 118.1 |
O1—P1—C1 | 106.94 (17) | N2—C12—C11 | 122.3 (4) |
O2—P1—C1 | 102.99 (19) | N2—C12—H13A | 118.8 |
O5—S1—O4 | 112.1 (2) | C11—C12—H13A | 118.8 |
O5—S1—O6 | 113.0 (2) | C10—C11—C12 | 120.2 (4) |
O4—S1—O6 | 112.6 (2) | C10—C11—H14A | 119.9 |
O5—S1—C3 | 107.4 (2) | C12—C11—H14A | 119.9 |
O4—S1—C3 | 105.49 (19) | C11—C10—C14 | 117.0 (4) |
O6—S1—C3 | 105.6 (2) | C11—C10—C9 | 122.2 (4) |
C16—N1—C7 | 117.2 (3) | C14—C10—C9 | 120.8 (4) |
C16—N1—Cu1 | 120.2 (3) | C8—C9—C15 | 116.9 (4) |
C7—N1—Cu1 | 122.6 (3) | C8—C9—C10 | 121.5 (4) |
C13—N2—C12 | 117.5 (4) | C15—C9—C10 | 121.5 (4) |
C13—N2—Cu1iii | 119.4 (3) | C16—C15—C9 | 119.0 (4) |
C12—N2—Cu1iii | 123.0 (3) | C16—C15—H17A | 120.5 |
C2—C1—C6 | 118.8 (4) | C9—C15—H17A | 120.5 |
C2—C1—P1 | 122.1 (3) | N1—C16—C15 | 124.1 (4) |
C6—C1—P1 | 119.1 (3) | N1—C16—H18A | 118.0 |
C1—C2—C3 | 120.4 (4) | C15—C16—H18A | 118.0 |
C1—C2—H2A | 119.8 | P1—O1—Cu1 | 124.93 (18) |
C3—C2—H2A | 119.8 | P1—O2—O6iv | 126.43 (19) |
C4—C3—C2 | 120.4 (4) | P1—O2—H2B | 109.5 |
C4—C3—S1 | 120.4 (3) | S1—O4—Cu1v | 144.0 (2) |
C2—C3—S1 | 119.1 (3) | Cu1—O1W—O3vi | 116.55 (17) |
C3—C4—C5 | 119.6 (4) | Cu1—O1W—O5vii | 132.54 (18) |
C3—C4—H4A | 120.2 | O3vi—O1W—O5vii | 110.66 (16) |
C5—C4—H4A | 120.2 | Cu1—O1W—H1WB | 126 (3) |
C4—C5—C6 | 120.5 (4) | O5vii—O1W—H1WB | 101 (3) |
C4—C5—H5A | 119.7 | Cu1—O1W—H1WA | 127 (3) |
C6—C5—H5A | 119.7 | O3vi—O1W—H1WA | 117 (3) |
C5—C6—C1 | 120.1 (4) | H1WB—O1W—H1WA | 107 (5) |
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x, y+1/2, −z+1/2; (iii) x+1, −y+1/2, z+1/2; (iv) −x, −y, −z; (v) −x, y−1/2, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3vi | 0.87 (5) | 1.74 (6) | 2.595 (4) | 166 (5) |
O1W—H1WA···O5vii | 0.90 (6) | 1.82 (6) | 2.701 (5) | 163 (5) |
O2—H2B···O6iv | 0.82 | 1.86 | 2.631 (5) | 156 |
Symmetry codes: (iv) −x, −y, −z; (vi) x, −y+1/2, z+1/2; (vii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C6H5O6PS)(C10H8N2)(H2O)] |
Mr | 473.87 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.9824 (2), 11.2924 (3), 15.1189 (3) |
β (°) | 110.331 (1) |
V (Å3) | 1758.20 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.50 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.645, 0.741 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9468, 3351, 2413 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.611 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.106, 1.09 |
No. of reflections | 3351 |
No. of parameters | 261 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.82, −0.52 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004) and DIAMOND (Brandenburg, 1999), SHELXTL (Bruker, 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3i | 0.87 (5) | 1.74 (6) | 2.595 (4) | 166 (5) |
O1W—H1WA···O5ii | 0.90 (6) | 1.82 (6) | 2.701 (5) | 163 (5) |
O2—H2B···O6iii | 0.82 | 1.86 | 2.631 (5) | 155.7 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z; (iii) −x, −y, −z. |
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The chemistry of metal phosphonates has been a research field of rapid expansion in recent years, mainly due to their potential applications in the area of catalysis, ion exchange, proton conductivity, intercalation chemistry, photochemistry, and materials chemistry (Clearfield, 1998; Maeda, 2004; Mao, 2007). The strategy of attaching functional groups such as amine, hydroxyl or carboxylate groups to the phosphonic acid can lead to a number of new metal phosphonates with micro-porous or open-framework structures. However, reports on the use of sulfonate group as a functional group to build metal phosphonate open frameworks are almost unknown to date. Recently, our increasing attention has been devoted to the metal coordination chemistry of phenylphosphonic acid ligand bonded to a sulfonate group, which can adopt a variety of coordination modes and form a variety of metal cluster compounds when an ancillary ligand, such as 1,10-phenanthroline or 4,4'-bipyridyl (4,4'-bipy), is also applied (Du et al., 2006a, 2006b; Du, Li, Liu & Mao, 2007; Du, Xu, Li & Mao, 2007). As an expansion of our previous work, we have also obtained a CuII sulfonate-phosphonate by applying this synthetic route. Herein, we report its synthesis and crystal structure.
The structure of the title compound features a layered architecture. The asymmetric unit contains one CuII ion, one [O3S—C6H4—PO3H]2- dianion, one 4,4'-bipy molecule, and one coordinated water molecule. CuII ion is five-coordinated with one phosphonate O atom from one [O3S—C6H4—PO3H]2- anion, one sulfonate O atom from a symmetry related [O3S—C6H4—PO3H]2- anion, two N atoms from two symmetry related 4,4'-bipy ligands, and one water molecule (Fig. 1). The coordination geometry around Cu can be described as a slightly distorted square-pyramid. The square plane is formed by one phosphonate O atom, two N atoms and the water molecule. The apical position is occupied by a sulfonate O atom. The Cu—O [1.964 (3)–2.234 (3) Å] and Cu—N [1.992 (3)–1.994 (3) Å] bond lengths are comparable to those reported for other CuII sulfonate/phosphonates complexes (Drumel et al., 1996; Zhong et al., 2005).
The phosphonate group is not completely deprotonated, as required for charge balance. The [O3S—C6H4—PO3H]2- ligand is bidentate and bridges two CuII ions via one phosphonate O atom and one sulfonate O atom. These bridges result in the formation of a one-dimensional helical chain along [010] (Fig. 2). These helical chains are further connected by bidentate bridging 4,4'-bipy ligands, to form a layered architecture (Fig. 3). The layered structure features an eight-membered ring including four CuII ions, two [O3S—C6H4—PO3H]2- anions and two 4,4'-bipy ligands. Between the layers, hydrogen bonds are formed, involving phosphonate O atom O2, sulfonate O atom O6 and the water molecule O1W (Fig. 4; Table 2). The O···O contacts range from 2.595 (4) to 2.701 (5) Å. Such a complex hydrogen-bond network is likely to contribute to the overall stability of the crystal structure and prevents guest molecules entering into the interstitial voids between the layers.