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The square-pyramidal environment of the metal in the copper(II) saccharinate neutral complex with 2,4'-bipyridine, [Cu(C7H4NO3S)2(C10H8N2)2(H2O)], consists of trans-oriented N-saccharinate and 2,4'-bi­pyridine ligand pairs and an apical aqua mol­ecule. A crystallographic twofold rotation axis passes through Cu and the aqua ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801020657/ci6083sup1.cif
Contains datablocks I, cu24

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801020657/ci6083Isup2.hkl
Contains datablock I

CCDC reference: 180516

Key indicators

  • Single-crystal X-ray study
  • T = 95 K
  • Mean [sigma](C-C) = 0.007 Å
  • R factor = 0.048
  • wR factor = 0.104
  • Data-to-parameter ratio = 17.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
STRVAL_01 From the CIF: _refine_ls_abs_structure_Flack 0.340 From the CIF: _refine_ls_abs_structure_Flack_su 0.020 Alert C Flack test results are ambiguous. PLAT_213 Alert C Atom C4 has ADP max/min Ratio ........... 3.10 prolate PLAT_213 Alert C Atom C16 has ADP max/min Ratio ........... 3.30 prolate PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 93.00 A   3 PLAT_733 Alert C Torsion Calc -7.4(7), Rep -7.5(3) .... 2.33 s.u-Ratio N1 -CU1 -N1 -C1 2.657 1.555 1.555 1.555 PLAT_733 Alert C Torsion Calc -16.9(9), Rep -16.9(3) .... 3.00 s.u-Ratio N2 -CU1 -N2 -C12 2.657 1.555 1.555 1.555 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.57 From the CIF: _reflns_number_total 4029 Count of symmetry unique reflns 2145 Completeness (_total/calc) 187.83% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1884 Fraction of Friedel pairs measured 0.878 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
6 Alert Level C = Please check

Comment top

The deprotonated anion of saccharin (o-sulfobenzimide) binds to a plethora of metal cations to form compounds whose structures can be conveniently probed by infrared spectroscopy (Naumov & Jovanovski, 2000, 2001). The compounds are coordinately unsaturated; among these, the copper(II) derivative has been well documented to form adducts, particularly with N-heterocycles (Naumov, Jovanovski, Drew & Ng, 2001; Naumov, Jovanovski, Ristova et al., 2001). On the other hand, one N-heterocycle that has not been used for binding is the 4,4'-bipyridine ligand; in our hands, the spacer ligand afforded a structure displaying a rhombic grid that encapsulates a dichloromethane molecule (Naumov, Jovanovski, Hanna et al., 2001). We then extended this study to the 2,4'-bipyridine analog, which should adopt a helical conformation if a similar metal–ligand bonding is retained as we noted in other systems; the 4,4'-isomer yields layer motifs whereas the 2,4'-isomer is able to furnish chains (Fun et al., 1999).

Coordination through the 2-N atom is not favored in the title compound, (I), and the ligand coordinates instead only through the 4-N atom (Fig. 1). The fifth coordinate site of the square-pyramidal geometry with trans-oriented pairs of N-saccharinate and bipyridine ligands is taken up by a coordinated water molecule.

Experimental top

Tetraaquabis(o-sulfobenzimidate)copper(II) dihydrate was synthesized from the reaction of copper(II) nitrate and sodium o-sulfobenzimidate in water in high yield (Naumov & Jovanovski, 2001). A small quantity of the compound (ca 0.05 g) was dissolved in warm ethanol (50 ml). An amount of 2,4'-bipyridine corresponding to twice the amount of the copper compound was dissolved in dichloromethane (5 ml) and the solution was laid over 10 ml portions of a filtered solution of the copper reagent. Individual attempts invariably resulted in small amount of wing-shaped crystals that were mixed with regularly shaped crystals. Both types gave the same element analyses. The diffraction measurements were carried out on a regularly shaped specimen. Elemental CHN analysis (calculated/found): C 53.85/53.77, H 3.46/3.27, N 11.08/10.86%.

Refinement top

Of the 4029 reflections, 2139 were Friedel pairs. The water H atom was located and refined. The other H atoms were generated geometrically, U(H) = 1.2Ueq(C). The elemental CHN analysis confirmed the composition, eliminating the possibility of residual solvent molecules in the solvent- accessible voids. The somewhat larger ADP max/min ratio for C4 and C14 is an artifact of the quality of the crystallographic data.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) plot at the 50% probability level.
Aquabis(2,4'-bipyridine)di(o-sulfobenzimidato)copper(II) top
Crystal data top
[Cu(C7H4NO3S)2(C10H8N2)2(H2O)]F(000) = 778
Mr = 758.27Dx = 1.429 Mg m3
Monoclinic, C2Mo Kα radiation, λ = 0.71073 Å
a = 12.5758 (3) ÅCell parameters from 5360 reflections
b = 12.2526 (2) Åθ = 1.8–27.6°
c = 11.6563 (3) ŵ = 0.79 mm1
β = 101.140 (1)°T = 95 K
V = 1762.23 (7) Å3Plate, blue
Z = 20.18 × 0.18 × 0.04 mm
Data collection top
Siemens CCD area-detector
diffractometer
4029 independent reflections
Radiation source: fine-focus sealed tube3056 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.094
ω scansθmax = 27.6°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1616
Tmin = 0.870, Tmax = 0.969k = 1515
8924 measured reflectionsl = 1415
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0197P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max < 0.001
4029 reflectionsΔρmax = 0.56 e Å3
231 parametersΔρmin = 0.94 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.34 (2)
Crystal data top
[Cu(C7H4NO3S)2(C10H8N2)2(H2O)]V = 1762.23 (7) Å3
Mr = 758.27Z = 2
Monoclinic, C2Mo Kα radiation
a = 12.5758 (3) ŵ = 0.79 mm1
b = 12.2526 (2) ÅT = 95 K
c = 11.6563 (3) Å0.18 × 0.18 × 0.04 mm
β = 101.140 (1)°
Data collection top
Siemens CCD area-detector
diffractometer
4029 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3056 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.969Rint = 0.094
8924 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.104Δρmax = 0.56 e Å3
S = 0.95Δρmin = 0.94 e Å3
4029 reflectionsAbsolute structure: Flack (1983)
231 parametersAbsolute structure parameter: 0.34 (2)
1 restraint
Special details top

Geometry. The pyridyl rings are twisted by 28.1 (2) °.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.49995 (5)1.00000.0106 (2)
S10.4303 (1)0.42281 (9)0.72832 (8)0.0157 (2)
O10.4144 (2)0.6996 (2)0.8457 (3)0.026 (1)
O20.3457 (2)0.3467 (2)0.7389 (3)0.025 (1)
O30.5352 (2)0.3781 (2)0.7242 (3)0.024 (1)
O1w0.50000.3145 (4)1.00000.016 (1)
N10.4400 (2)0.5167 (3)0.8292 (3)0.011 (1)
N20.3487 (2)0.5163 (3)1.0340 (3)0.012 (1)
N30.0007 (3)0.6316 (3)1.1525 (3)0.017 (1)
C10.4119 (3)0.6175 (4)0.7843 (4)0.016 (1)
C20.3798 (3)0.6156 (4)0.6535 (4)0.020 (1)
C30.3442 (4)0.7023 (4)0.5793 (4)0.036 (1)
C40.3170 (4)0.6765 (6)0.4582 (5)0.053 (2)
C50.3261 (4)0.5736 (6)0.4176 (5)0.047 (2)
C60.3612 (3)0.4866 (6)0.4919 (4)0.035 (1)
C70.3866 (3)0.5119 (4)0.6102 (3)0.020 (1)
C80.2839 (3)0.4295 (4)1.0293 (3)0.018 (1)
C90.1850 (3)0.4331 (4)1.0660 (4)0.018 (1)
C100.1511 (3)0.5297 (3)1.1088 (3)0.014 (1)
C110.2171 (3)0.6209 (3)1.1094 (3)0.013 (1)
C120.3151 (3)0.6114 (3)1.0726 (3)0.013 (1)
C130.0498 (3)0.5343 (3)1.1563 (4)0.015 (1)
C140.0112 (3)0.4409 (4)1.2032 (4)0.025 (1)
C150.0815 (4)0.4476 (4)1.2499 (5)0.034 (1)
C160.1336 (4)0.5477 (4)1.2466 (5)0.036 (1)
C170.0920 (3)0.6361 (4)1.1967 (4)0.025 (1)
H1w0.508 (4)0.276 (4)1.056 (4)0.02 (1)*
H30.33840.77430.60770.043*
H40.29160.73300.40390.063*
H50.30800.56060.33580.056*
H60.36740.41460.46360.042*
H80.30610.36270.99980.022*
H90.14110.36961.06160.021*
H110.19500.68951.13500.016*
H120.36000.67411.07470.016*
H140.04840.37341.20310.030*
H150.10890.38541.28340.040*
H160.19740.55531.27830.043*
H170.12950.70361.19340.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0104 (3)0.0126 (4)0.0091 (4)0.0000.0023 (3)0.000
S10.0175 (5)0.0195 (6)0.0105 (5)0.0007 (4)0.0033 (4)0.0016 (5)
O10.032 (2)0.014 (2)0.032 (2)0.000 (1)0.006 (2)0.000 (1)
O20.026 (2)0.023 (2)0.025 (2)0.009 (1)0.005 (2)0.005 (1)
O30.022 (2)0.030 (2)0.021 (2)0.009 (1)0.007 (1)0.001 (1)
O1w0.021 (2)0.011 (2)0.018 (3)0.0000.010 (2)0.000
N10.013 (1)0.010 (2)0.010 (2)0.000 (1)0.004 (1)0.001 (1)
N20.011 (1)0.013 (2)0.013 (2)0.001 (1)0.002 (1)0.001 (1)
N30.014 (2)0.016 (2)0.022 (2)0.003 (1)0.006 (2)0.002 (2)
C10.011 (2)0.015 (2)0.024 (2)0.001 (2)0.008 (2)0.002 (2)
C20.014 (2)0.029 (3)0.017 (2)0.003 (2)0.003 (2)0.011 (2)
C30.032 (3)0.039 (3)0.036 (3)0.006 (2)0.005 (2)0.024 (3)
C40.038 (3)0.081 (5)0.039 (3)0.006 (3)0.006 (3)0.044 (4)
C50.041 (3)0.084 (5)0.014 (3)0.006 (3)0.002 (2)0.017 (3)
C60.028 (2)0.062 (4)0.015 (2)0.003 (3)0.004 (2)0.000 (3)
C70.014 (2)0.033 (3)0.013 (2)0.001 (2)0.005 (2)0.010 (2)
C80.016 (2)0.018 (2)0.022 (2)0.004 (2)0.008 (2)0.008 (2)
C90.016 (2)0.014 (2)0.026 (2)0.005 (2)0.009 (2)0.003 (2)
C100.012 (2)0.017 (2)0.012 (2)0.001 (2)0.003 (2)0.004 (2)
C110.016 (2)0.010 (2)0.013 (2)0.001 (2)0.001 (2)0.004 (2)
C120.012 (2)0.014 (2)0.013 (2)0.003 (2)0.001 (2)0.002 (2)
C130.012 (2)0.019 (2)0.015 (2)0.002 (2)0.003 (2)0.001 (2)
C140.022 (2)0.016 (2)0.040 (3)0.004 (2)0.016 (2)0.007 (2)
C150.032 (3)0.023 (3)0.056 (3)0.002 (2)0.033 (3)0.011 (2)
C160.021 (2)0.031 (3)0.064 (4)0.000 (2)0.030 (3)0.004 (3)
C170.017 (2)0.021 (3)0.040 (3)0.005 (2)0.013 (2)0.003 (2)
Geometric parameters (Å, º) top
Cu1—N11.999 (3)C8—C91.392 (5)
Cu1—N1i1.999 (3)C9—C101.384 (6)
Cu1—N22.027 (3)C10—C111.392 (5)
Cu1—N2i2.027 (3)C10—C131.485 (5)
Cu1—O1w2.272 (4)C11—C121.386 (5)
S1—O31.437 (3)C13—C141.395 (6)
S1—O21.438 (3)C14—C151.382 (6)
S1—N11.633 (3)C15—C161.388 (6)
S1—C71.760 (4)C16—C171.379 (6)
O1—C11.232 (5)O1w—H1w0.79 (4)
N1—C11.361 (5)C3—H30.9500
N2—C81.335 (5)C4—H40.9500
N2—C121.347 (5)C5—H50.9500
N3—C171.347 (5)C6—H60.9500
N3—C131.347 (5)C8—H80.9500
C1—C21.500 (6)C9—H90.9500
C2—C71.375 (7)C11—H110.9500
C2—C31.388 (6)C12—H120.9500
C3—C41.423 (8)C14—H140.9500
C4—C51.359 (8)C15—H150.9500
C5—C61.390 (8)C16—H160.9500
C6—C71.389 (6)C17—H170.9500
N1—Cu1—N1i168.2 (2)C11—C10—C9117.7 (4)
N1—Cu1—N289.8 (1)C11—C10—C13121.4 (4)
N1—Cu1—N2i89.0 (1)C9—C10—C13120.9 (3)
N1—Cu1—O1w95.9 (1)C12—C11—C10119.7 (4)
N1i—Cu1—N289.0 (1)N2—C12—C11122.1 (4)
N1i—Cu1—N2i89.8 (1)N3—C13—C14122.8 (4)
N1i—Cu1—O1w95.9 (1)N3—C13—C10117.0 (4)
N2—Cu1—N2i168.6 (2)C14—C13—C10120.2 (3)
N2—Cu1—O1w95.7 (1)C15—C14—C13119.3 (4)
N2i—Cu1—O1w95.7 (1)C14—C15—C16118.1 (4)
O3—S1—O2117.0 (2)C17—C16—C15119.3 (4)
O3—S1—N1110.6 (2)N3—C17—C16123.4 (4)
O2—S1—N1110.4 (2)Cu1—O1w—H1w127 (3)
O3—S1—C7111.1 (2)C2—C3—H3122.1
O2—S1—C7110.2 (2)C4—C3—H3122.1
N1—S1—C795.4 (2)C5—C4—H4119.0
C1—N1—S1112.7 (3)C3—C4—H4119.0
C1—N1—Cu1119.7 (3)C4—C5—H5118.9
S1—N1—Cu1127.3 (2)C6—C5—H5118.9
C8—N2—C12118.3 (3)C7—C6—H6122.2
C8—N2—Cu1120.1 (3)C5—C6—H6122.2
C12—N2—Cu1121.2 (3)N2—C8—H8118.8
C17—N3—C13117.1 (4)C9—C8—H8118.8
O1—C1—N1122.9 (4)C8—C9—H9120.2
O1—C1—C2125.1 (4)C10—C9—H9120.2
N1—C1—C2112.0 (4)C12—C11—H11120.1
C7—C2—C3120.9 (4)C10—C11—H11120.1
C7—C2—C1111.4 (4)N2—C12—H12118.9
C3—C2—C1127.7 (5)C11—C12—H12118.9
C2—C3—C4115.8 (5)C15—C14—H14120.3
C5—C4—C3122.0 (5)C13—C14—H14120.3
C4—C5—C6122.2 (5)C14—C15—H15120.9
C7—C6—C5115.6 (6)C16—C15—H15120.9
C2—C7—C6123.5 (5)C17—C16—H16120.3
C2—C7—S1108.5 (3)C15—C16—H16120.3
C6—C7—S1128.0 (5)N3—C17—H17118.3
N2—C8—C9122.5 (4)C16—C17—H17118.3
C8—C9—C10119.6 (4)
O3—S1—N1—C1115.4 (3)C3—C2—C7—C61.4 (7)
O2—S1—N1—C1113.5 (3)C1—C2—C7—C6179.8 (4)
C7—S1—N1—C10.4 (3)C3—C2—C7—S1178.2 (4)
O3—S1—N1—Cu158.3 (3)C1—C2—C7—S10.2 (4)
O2—S1—N1—Cu172.8 (2)C5—C6—C7—C21.0 (7)
C7—S1—N1—Cu1173.3 (2)C5—C6—C7—S1178.6 (4)
N1i—Cu1—N1—C17.5 (3)O3—S1—C7—C2114.9 (3)
N2—Cu1—N1—C176.8 (3)O2—S1—C7—C2113.8 (3)
N2i—Cu1—N1—C191.9 (3)N1—S1—C7—C20.3 (3)
O1w—Cu1—N1—C1172.5 (3)O3—S1—C7—C665.6 (4)
N1i—Cu1—N1—S1165.8 (2)O2—S1—C7—C665.8 (4)
N2—Cu1—N1—S1109.8 (2)N1—S1—C7—C6179.9 (4)
N2i—Cu1—N1—S181.5 (2)C12—N2—C8—C92.0 (6)
O1w—Cu1—N1—S114.2 (2)Cu1—N2—C8—C9171.6 (3)
N1—Cu1—N2—C885.6 (3)N2—C8—C9—C100.2 (6)
N1i—Cu1—N2—C8106.2 (3)C8—C9—C10—C112.1 (6)
N2i—Cu1—N2—C8169.6 (3)C8—C9—C10—C13175.7 (4)
O1w—Cu1—N2—C810.4 (3)C9—C10—C11—C122.8 (6)
N1—Cu1—N2—C12101.0 (3)C13—C10—C11—C12175.1 (3)
N1i—Cu1—N2—C1267.2 (3)C8—N2—C12—C111.3 (5)
N2i—Cu1—N2—C1216.9 (3)Cu1—N2—C12—C11172.2 (3)
O1w—Cu1—N2—C12163.1 (3)C10—C11—C12—N21.1 (6)
S1—N1—C1—O1179.5 (3)C17—N3—C13—C140.0 (6)
Cu1—N1—C1—O15.2 (5)C17—N3—C13—C10179.3 (3)
S1—N1—C1—C20.3 (4)C11—C10—C13—N328.0 (5)
Cu1—N1—C1—C2173.9 (2)C9—C10—C13—N3154.2 (4)
O1—C1—C2—C7179.2 (4)C11—C10—C13—C14151.3 (4)
N1—C1—C2—C70.1 (5)C9—C10—C13—C1426.5 (6)
O1—C1—C2—C32.6 (7)N3—C13—C14—C151.1 (7)
N1—C1—C2—C3178.4 (4)C10—C13—C14—C15178.2 (4)
C7—C2—C3—C40.6 (7)C13—C14—C15—C160.9 (7)
C1—C2—C3—C4178.7 (4)C14—C15—C16—C170.4 (8)
C2—C3—C4—C50.5 (8)C13—N3—C17—C161.3 (7)
C3—C4—C5—C60.9 (9)C15—C16—C17—N31.5 (8)
C4—C5—C6—C70.2 (8)
Symmetry code: (i) x+1, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w···N3ii0.79 (4)2.11 (4)2.862 (5)158 (4)
Symmetry code: (ii) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Cu(C7H4NO3S)2(C10H8N2)2(H2O)]
Mr758.27
Crystal system, space groupMonoclinic, C2
Temperature (K)95
a, b, c (Å)12.5758 (3), 12.2526 (2), 11.6563 (3)
β (°) 101.140 (1)
V3)1762.23 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.79
Crystal size (mm)0.18 × 0.18 × 0.04
Data collection
DiffractometerSiemens CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.870, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
8924, 4029, 3056
Rint0.094
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.104, 0.95
No. of reflections4029
No. of parameters231
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.56, 0.94
Absolute structureFlack (1983)
Absolute structure parameter0.34 (2)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—N11.999 (3)Cu1—O1w2.272 (4)
Cu1—N22.027 (3)
N1—Cu1—N1i168.2 (2)N1—Cu1—O1w95.9 (1)
N1—Cu1—N289.8 (1)N2—Cu1—N2i168.6 (2)
N1—Cu1—N2i89.0 (1)N2—Cu1—O1w95.7 (1)
Symmetry code: (i) x+1, y, z+2.
 

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