




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813009604/xu5692sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536813009604/xu5692Isup2.hkl |
![]() | Chemdraw file https://doi.org/10.1107/S1600536813009604/xu5692Isup3.cdx |
CCDC reference: 819440
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.032
- wR factor = 0.085
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O4W - H4WA ... ?
Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cu1
Alert level G PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension . 2 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF ? PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............ 8 PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X) Cu1 -- O1W .. 5.2 su PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 8 PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) . 1.21 Ratio PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 16
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 7 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 3 ALERT type 4 Improvement, methodology, query or suggestion 3 ALERT type 5 Informative message, check
2-Carboxymethylsulfanyl nicotinic acid (1.0 mmol) in H2O (10 ml) was stirred under basic condition in which NH3.H2O was needed to keep pH value of 11. CuCl2.2H2O was added and stirred for 2 h. The resulting solution was placed for 2 days, and the crystals were filtered off, giving blue crystals of the title compound for X-ray analysis.
The carbon-bound H-atoms were positioned geometrically and included in the refinement using a riding model [aromatic C—H 0.93 Å and aliphatic C—H 0.97 Å, Uiso(H) = 1.2Ueq(C)]. The oxygen-bound H-atoms was located in a difference Fourier maps and refined with the O—H distance restrained to 0.83 (2) Å and Uiso(H) = 1.2Ueq(O).
2-Carboxymethylsulfanylnicotinic acid is prepared from 2-mercaptonanicotinic acid (Wang & Feng, 2010). 2-Mercaptonanicotinic acid is a multifunctional ligand, and some complexes containing 2-mercaptonanicotinate ligand have been previously investigated (Humphrey et al., 2006; Sun et al., 2011).
The 2-carboxymethylsulfanylnicotinic acid is an interesting ligand because of its potential versatile coordinate behavior. Recently, only three metal compounds have been reported about 2-carboxymethylsulfanyl nicotinic acid (Jiang et al., 2012). Herein, we report the synthesis and structure of the title compound.
A perspective view of (I) is presented in Fig.1. The asymmetric unit consists of one CuII ion, one (C8H5NO4S)2- ligands, one coordinated water molecule, and three lattice water molecules. As shown in Fig. 2, each pair of Cu2+ ion is µ-linked by four carboxylic groups of the individual (C8H5NO4S)2- ligands with Cu···Cu distances of 2.6524 (15) Å. The (C8H5NO4S)2- ligands bridge adjacent dinuclear units in a head-to-tail fashion to form a two-dimensional layer on the bc plane, and further linked into the three-dimensional architecture by O—H···O/N/S hydrogen bonds (Fig.3).
For background to the 2-[(carboxymethyl)sulfanyl]nicotinato ligand, see: Wang & Feng (2010). For related compounds, see: Jiang et al. (2012). For metal complexes with 2-mercaptonanicotinate ligands, see: Humphrey et al. (2006); Sun et al. (2011).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.
[Cu(C8H5NO4S)(H2O)]·3H2O | F(000) = 708 |
Mr = 346.82 | Dx = 1.779 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3501 reflections |
a = 9.940 (7) Å | θ = 2.1–27.6° |
b = 16.639 (9) Å | µ = 1.88 mm−1 |
c = 7.876 (4) Å | T = 296 K |
β = 96.28 (5)° | Plate, blue |
V = 1294.8 (13) Å3 | 0.25 × 0.09 × 0.06 mm |
Z = 4 |
Bruker SMART APEXII area-detector diffractometer | 2973 independent reflections |
Radiation source: fine-focus sealed tube | 2331 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ω scans | θmax = 27.6°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −11→12 |
Tmin = 0.812, Tmax = 0.892 | k = −21→21 |
20324 measured reflections | l = −10→10 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0455P)2 + 0.2317P] where P = (Fo2 + 2Fc2)/3 |
2973 reflections | (Δ/σ)max = 0.001 |
172 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu(C8H5NO4S)(H2O)]·3H2O | V = 1294.8 (13) Å3 |
Mr = 346.82 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.940 (7) Å | µ = 1.88 mm−1 |
b = 16.639 (9) Å | T = 296 K |
c = 7.876 (4) Å | 0.25 × 0.09 × 0.06 mm |
β = 96.28 (5)° |
Bruker SMART APEXII area-detector diffractometer | 2973 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2331 reflections with I > 2σ(I) |
Tmin = 0.812, Tmax = 0.892 | Rint = 0.054 |
20324 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.37 e Å−3 |
2973 reflections | Δρmin = −0.32 e Å−3 |
172 parameters |
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 | ||
Cu1 | 1.10928 (3) | 0.455426 (15) | 0.48878 (4) | 0.02469 (11) | |
S1 | 0.96122 (7) | 0.21713 (3) | 0.44052 (8) | 0.03032 (16) | |
O1 | 0.97500 (18) | 0.37850 (10) | 0.3866 (2) | 0.0338 (4) | |
O1W | 1.2932 (2) | 0.39085 (12) | 0.4498 (3) | 0.0473 (5) | |
H1WA | 1.2787 | 0.3469 | 0.4037 | 0.057* | |
H1WB | 1.3419 | 0.4141 | 0.3845 | 0.057* | |
O2 | 0.7893 (2) | 0.45444 (10) | 0.3972 (3) | 0.0369 (4) | |
O3 | 1.0779 (2) | 0.08898 (11) | 0.2128 (2) | 0.0374 (4) | |
O4 | 0.89346 (19) | 0.01319 (10) | 0.2319 (2) | 0.0328 (4) | |
N1 | 0.7301 (2) | 0.17934 (12) | 0.2526 (3) | 0.0341 (5) | |
C1 | 0.5606 (3) | 0.27286 (16) | 0.1366 (4) | 0.0398 (7) | |
H1A | 0.4768 | 0.2817 | 0.0745 | 0.048* | |
C2 | 0.7636 (3) | 0.32137 (14) | 0.2965 (3) | 0.0267 (5) | |
C3 | 0.6384 (3) | 0.33602 (16) | 0.2060 (4) | 0.0348 (6) | |
H3A | 0.6068 | 0.3885 | 0.1919 | 0.042* | |
C4 | 0.6114 (3) | 0.19624 (16) | 0.1627 (4) | 0.0393 (7) | |
H4A | 0.5600 | 0.1536 | 0.1147 | 0.047* | |
C5 | 0.8059 (3) | 0.24081 (14) | 0.3179 (3) | 0.0260 (5) | |
C6 | 0.8489 (3) | 0.38985 (13) | 0.3664 (3) | 0.0268 (5) | |
C7 | 0.9514 (3) | 0.10887 (14) | 0.4500 (3) | 0.0319 (6) | |
H7A | 1.0178 | 0.0897 | 0.5403 | 0.038* | |
H7B | 0.8626 | 0.0938 | 0.4794 | 0.038* | |
C8 | 0.9757 (3) | 0.06765 (14) | 0.2838 (3) | 0.0286 (5) | |
O2W | 0.6123 (3) | −0.00071 (16) | 0.2997 (4) | 0.0759 (8) | |
H2WA | 0.6385 | −0.0244 | 0.3907 | 0.091* | |
H2WB | 0.6774 | 0.0299 | 0.2886 | 0.091* | |
O3W | 0.3765 (3) | 0.07734 (18) | 0.3764 (4) | 0.0831 (9) | |
H3WA | 0.3048 | 0.0589 | 0.3329 | 0.100* | |
H3WB | 0.4364 | 0.0491 | 0.3424 | 0.100* | |
O4W | 0.2538 (3) | 0.24845 (18) | 0.2749 (5) | 0.1001 (11) | |
H4WA | 0.2766 | 0.2280 | 0.1881 | 0.120* | |
H4WB | 0.1699 | 0.2362 | 0.2691 | 0.120* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02945 (19) | 0.01710 (15) | 0.02766 (18) | 0.00031 (11) | 0.00377 (12) | 0.00057 (11) |
S1 | 0.0364 (4) | 0.0231 (3) | 0.0307 (4) | 0.0012 (3) | 0.0001 (3) | −0.0052 (2) |
O1 | 0.0335 (11) | 0.0208 (8) | 0.0472 (12) | −0.0032 (7) | 0.0043 (9) | −0.0036 (7) |
O1W | 0.0429 (12) | 0.0403 (11) | 0.0603 (14) | 0.0085 (9) | 0.0123 (10) | −0.0024 (9) |
O2 | 0.0382 (11) | 0.0238 (9) | 0.0469 (12) | 0.0011 (8) | −0.0026 (9) | −0.0080 (8) |
O3 | 0.0434 (12) | 0.0363 (10) | 0.0337 (10) | −0.0079 (9) | 0.0093 (9) | −0.0118 (8) |
O4 | 0.0412 (11) | 0.0248 (8) | 0.0330 (10) | −0.0010 (8) | 0.0066 (8) | −0.0051 (7) |
N1 | 0.0417 (14) | 0.0242 (10) | 0.0357 (13) | −0.0065 (9) | 0.0016 (10) | −0.0041 (9) |
C1 | 0.0335 (16) | 0.0393 (15) | 0.0444 (17) | −0.0048 (12) | −0.0052 (13) | −0.0017 (12) |
C2 | 0.0320 (14) | 0.0234 (12) | 0.0254 (13) | −0.0021 (10) | 0.0056 (10) | −0.0014 (9) |
C3 | 0.0357 (16) | 0.0275 (13) | 0.0410 (16) | −0.0008 (11) | 0.0027 (12) | 0.0011 (11) |
C4 | 0.0424 (17) | 0.0338 (14) | 0.0403 (16) | −0.0121 (12) | −0.0012 (13) | −0.0045 (12) |
C5 | 0.0308 (14) | 0.0242 (11) | 0.0238 (12) | −0.0016 (10) | 0.0066 (10) | −0.0016 (9) |
C6 | 0.0398 (16) | 0.0188 (11) | 0.0221 (12) | −0.0042 (10) | 0.0039 (11) | 0.0023 (9) |
C7 | 0.0499 (17) | 0.0225 (12) | 0.0234 (13) | 0.0016 (11) | 0.0039 (12) | −0.0010 (9) |
C8 | 0.0388 (15) | 0.0202 (11) | 0.0263 (13) | 0.0065 (10) | 0.0015 (11) | −0.0008 (9) |
O2W | 0.0679 (18) | 0.0680 (17) | 0.097 (2) | −0.0153 (14) | 0.0337 (15) | −0.0023 (15) |
O3W | 0.0590 (18) | 0.0867 (19) | 0.098 (2) | −0.0033 (15) | −0.0178 (15) | −0.0172 (17) |
O4W | 0.069 (2) | 0.090 (2) | 0.150 (3) | −0.0265 (17) | 0.048 (2) | −0.055 (2) |
Cu1—O1 | 1.958 (2) | N1—C5 | 1.340 (3) |
Cu1—O2i | 1.9682 (19) | C1—C4 | 1.379 (4) |
Cu1—O3ii | 1.9687 (19) | C1—C3 | 1.382 (4) |
Cu1—O4iii | 1.9836 (19) | C1—H1A | 0.9300 |
Cu1—O1W | 2.171 (2) | C2—C3 | 1.386 (4) |
Cu1—Cu1i | 2.6524 (15) | C2—C5 | 1.410 (3) |
S1—C5 | 1.773 (3) | C2—C6 | 1.489 (3) |
S1—C7 | 1.806 (3) | C3—H3A | 0.9300 |
O1—C6 | 1.261 (3) | C4—H4A | 0.9300 |
O1W—H1WA | 0.8228 | C7—C8 | 1.521 (3) |
O1W—H1WB | 0.8384 | C7—H7A | 0.9700 |
O2—C6 | 1.263 (3) | C7—H7B | 0.9700 |
O2—Cu1i | 1.9682 (19) | O2W—H2WA | 0.8345 |
O3—C8 | 1.263 (3) | O2W—H2WB | 0.8359 |
O3—Cu1iv | 1.9687 (19) | O3W—H3WA | 0.8165 |
O4—C8 | 1.258 (3) | O3W—H3WB | 0.8253 |
O4—Cu1v | 1.9836 (19) | O4W—H4WA | 0.8176 |
N1—C4 | 1.337 (4) | O4W—H4WB | 0.8547 |
O1—Cu1—O2i | 167.93 (8) | C3—C2—C5 | 117.9 (2) |
O1—Cu1—O3ii | 87.44 (9) | C3—C2—C6 | 119.9 (2) |
O2i—Cu1—O3ii | 90.03 (9) | C5—C2—C6 | 122.2 (2) |
O1—Cu1—O4iii | 90.75 (9) | C1—C3—C2 | 120.1 (2) |
O2i—Cu1—O4iii | 89.31 (9) | C1—C3—H3A | 119.9 |
O3ii—Cu1—O4iii | 168.14 (8) | C2—C3—H3A | 119.9 |
O1—Cu1—O1W | 99.49 (9) | N1—C4—C1 | 124.1 (3) |
O2i—Cu1—O1W | 92.56 (9) | N1—C4—H4A | 117.9 |
O3ii—Cu1—O1W | 99.18 (9) | C1—C4—H4A | 117.9 |
O4iii—Cu1—O1W | 92.69 (9) | N1—C5—C2 | 122.1 (2) |
O1—Cu1—Cu1i | 82.33 (7) | N1—C5—S1 | 117.35 (19) |
O2i—Cu1—Cu1i | 85.74 (7) | C2—C5—S1 | 120.48 (19) |
O3ii—Cu1—Cu1i | 86.50 (7) | O1—C6—O2 | 125.7 (2) |
O4iii—Cu1—Cu1i | 81.64 (7) | O1—C6—C2 | 116.7 (2) |
O1W—Cu1—Cu1i | 174.09 (6) | O2—C6—C2 | 117.5 (2) |
C5—S1—C7 | 101.32 (12) | C8—C7—S1 | 113.56 (17) |
C6—O1—Cu1 | 125.29 (16) | C8—C7—H7A | 108.9 |
Cu1—O1W—H1WA | 113.2 | S1—C7—H7A | 108.9 |
Cu1—O1W—H1WB | 114.3 | C8—C7—H7B | 108.9 |
H1WA—O1W—H1WB | 103.0 | S1—C7—H7B | 108.9 |
C6—O2—Cu1i | 120.56 (18) | H7A—C7—H7B | 107.7 |
C8—O3—Cu1iv | 120.36 (16) | O4—C8—O3 | 125.7 (2) |
C8—O4—Cu1v | 125.43 (17) | O4—C8—C7 | 116.5 (2) |
C4—N1—C5 | 118.0 (2) | O3—C8—C7 | 117.8 (2) |
C4—C1—C3 | 117.6 (3) | H2WA—O2W—H2WB | 101.8 |
C4—C1—H1A | 121.2 | H3WA—O3W—H3WB | 106.2 |
C3—C1—H1A | 121.2 | H4WA—O4W—H4WB | 102.4 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) x, −y+1/2, z−1/2; (v) −x+2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4Wvi | 0.82 | 1.93 | 2.747 (4) | 174 |
O1W—H1WB···O2Wiii | 0.84 | 2.11 | 2.899 (4) | 156 |
O2W—H2WA···O3Wvii | 0.83 | 2.05 | 2.843 (5) | 157 |
O2W—H2WB···O4 | 0.84 | 2.26 | 2.911 (4) | 135 |
O2W—H2WB···N1 | 0.84 | 2.56 | 3.253 (4) | 141 |
O3W—H3WA···O3viii | 0.82 | 2.40 | 3.110 (4) | 146 |
O3W—H3WB···O2W | 0.83 | 2.00 | 2.803 (5) | 165 |
O4W—H4WB···S1viii | 0.85 | 2.62 | 3.356 (4) | 146 |
Symmetry codes: (iii) −x+2, y+1/2, −z+1/2; (vi) x+1, y, z; (vii) −x+1, −y, −z+1; (viii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H5NO4S)(H2O)]·3H2O |
Mr | 346.82 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 9.940 (7), 16.639 (9), 7.876 (4) |
β (°) | 96.28 (5) |
V (Å3) | 1294.8 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.88 |
Crystal size (mm) | 0.25 × 0.09 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.812, 0.892 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20324, 2973, 2331 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.085, 1.04 |
No. of reflections | 2973 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.32 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008.
Cu1—O1 | 1.958 (2) | Cu1—O4iii | 1.9836 (19) |
Cu1—O2i | 1.9682 (19) | Cu1—O1W | 2.171 (2) |
Cu1—O3ii | 1.9687 (19) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4Wiv | 0.82 | 1.93 | 2.747 (4) | 174 |
O1W—H1WB···O2Wiii | 0.84 | 2.11 | 2.899 (4) | 156 |
O2W—H2WA···O3Wv | 0.83 | 2.05 | 2.843 (5) | 157 |
O2W—H2WB···O4 | 0.84 | 2.26 | 2.911 (4) | 135 |
O2W—H2WB···N1 | 0.84 | 2.56 | 3.253 (4) | 141 |
O3W—H3WA···O3vi | 0.82 | 2.40 | 3.110 (4) | 146 |
O3W—H3WB···O2W | 0.83 | 2.00 | 2.803 (5) | 165 |
O4W—H4WB···S1vi | 0.85 | 2.62 | 3.356 (4) | 146 |
Symmetry codes: (iii) −x+2, y+1/2, −z+1/2; (iv) x+1, y, z; (v) −x+1, −y, −z+1; (vi) x−1, y, z. |
2-Carboxymethylsulfanylnicotinic acid is prepared from 2-mercaptonanicotinic acid (Wang & Feng, 2010). 2-Mercaptonanicotinic acid is a multifunctional ligand, and some complexes containing 2-mercaptonanicotinate ligand have been previously investigated (Humphrey et al., 2006; Sun et al., 2011).
The 2-carboxymethylsulfanylnicotinic acid is an interesting ligand because of its potential versatile coordinate behavior. Recently, only three metal compounds have been reported about 2-carboxymethylsulfanyl nicotinic acid (Jiang et al., 2012). Herein, we report the synthesis and structure of the title compound.
A perspective view of (I) is presented in Fig.1. The asymmetric unit consists of one CuII ion, one (C8H5NO4S)2- ligands, one coordinated water molecule, and three lattice water molecules. As shown in Fig. 2, each pair of Cu2+ ion is µ-linked by four carboxylic groups of the individual (C8H5NO4S)2- ligands with Cu···Cu distances of 2.6524 (15) Å. The (C8H5NO4S)2- ligands bridge adjacent dinuclear units in a head-to-tail fashion to form a two-dimensional layer on the bc plane, and further linked into the three-dimensional architecture by O—H···O/N/S hydrogen bonds (Fig.3).