Diaqua­bis(4-oxidopyridinium-3-sulfon­ato-κ²O,O′)cobalt(II) hexa­hydrate

The Co^II atom in the title zwitterionic compound, [Co(C₅H₄NO₄S)₂(H₂O)₂]·6H₂O, is located on an inversion centre, and exists in an octa­hedral coordination geometry owing to chelation by the monoanion and coordination by water. A three-dimensional hydrogen-bonding framework is formed through O—H...O and N—H...O hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.030
• wR factor = 0.115
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, pyridinesulfonates have been widely used to synthesize metal complexes, such as 2-pyridinesulfonate (Delgado et al., 2006), 3-pyridinesulfonate (Cotton et al., 1992), 4-pyridinesulfonate (Lu et al., 2007) However, there is no report based on hydroxypyridonesulfonic acid which is derivated from pyridinesulfonate. Herein, we reported the synthesis and structure of a new complex, [Co(4-HPSH)₂(H₂O)₂].6H₂O, obtained by the reaction of 4-hydroxypyridone-3-sulfonic acid (4-HPSH₂) and cobalt chloride hexahydrate in aqueous solution.

As illustrated in Fig. 1, the Co^II atom lies on an inversion center and displays an octahedral geometry defined by two sulfonyl O atoms and hydroxyl O atoms of different 4-HPSH^- ligands and two water molecules. The distances of Co1—O_sulfonato bonds are slightly longer than that of Co1—O_hydroxyl and Co—O_water. A three-dimensional supramolecular network structure is formed through the extended hydrogen-bonding interactions between water molecules and N,O atoms of 4-HPSH^- ligands (Table 2).

Related literature

There are no crystallographic reports to date of complexes of hydroxypyridineylsulfonic acid. For metal complexes of the related pyridinesulfonic acid, see: Delgado et al. (2006); Cotton et al. (1992); Lu et al. (2007).

S2. Experimental

The title complex was prepared by the addition of cobalt chloride hexahydrate (2.38 g, 10 mmol) to a hot aqueous solution of 4-hydroxypyridone-3-sulfonaic acid (1.75 g, 10 mmol); the pH was adjusted to 6 with 0.1 M sodium hydroxide. The solution was allowed to evaporate at room temperature. Pink prismatic crystals separated from the filtered solution after several days. CH&N analysis. Calc. for C₁₀H₂₄N₂O₁₆S₂Co: C 21.78, H 4.39, N 5.08%; Found: C 21.75, H 4.34, N 5.11%.

S3. Refinement

Carbon-bond H atoms were placed in calculated positions, C—H = 0.93 and U_iso(H) = 1.2U_eq(C), and were included in the refinement in the riding-model approximation. The H atoms of water molecules and nitrogen atoms of 4-HPSH₂ were located in difference Fourier map and refined with the O—H and N—H distance restrained to 0.85 (1) and 0.86 (1) Å, and with U_iso(H) = 1.5U_eq(O,N).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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 (Sheldrick, 1997).

Figures

Fig. 1. Molecular structure of the title compound with 30% probability ellipsoid for the non-H atoms.

Diaqua(4-oxidopyridinium-3-sulfonato-κ²O,O')cobaltate(II) hexahydrate

Crystal data

[Co(C5H4NO4S)2(H2O)2]·6H2O	Z = 1
Mr = 551.36	F(000) = 285
Triclinic, P1	Dx = 1.771 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7825 (16) Å	Cell parameters from 4752 reflections
b = 8.4697 (17) Å	θ = 3.1–27.5°
c = 8.7952 (18) Å	µ = 1.12 mm^−1
α = 90.97 (3)°	T = 295 K
β = 110.17 (3)°	Prism, pink
γ = 106.65 (3)°	0.36 × 0.24 × 0.18 mm
V = 517.0 (2) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	2344 independent reflections
Radiation source: fine-focus sealed tube	2180 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −10→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.690, Tmax = 0.825	l = −11→11
5086 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0657P)^2 + 0.2777P] where P = (Fo^2 + 2Fc^2)/3
2344 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.49 e Å^−3
9 restraints	Δρmin = −0.51 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.0000	0.0000	0.02233 (15)
S1	0.92641 (8)	0.15049 (7)	0.25659 (7)	0.02739 (17)
O1W	0.3658 (3)	0.1085 (3)	0.1158 (2)	0.0408 (5)
H1W1	0.249 (2)	0.057 (4)	0.098 (4)	0.061*
H1W2	0.420 (4)	0.165 (4)	0.209 (2)	0.061*
O2W	0.5537 (4)	0.3487 (3)	0.3767 (3)	0.0561 (6)
H2W1	0.559 (7)	0.448 (3)	0.355 (5)	0.084*
H2W2	0.506 (7)	0.330 (5)	0.451 (4)	0.084*
O3W	1.2937 (3)	0.9351 (3)	0.4386 (3)	0.0503 (5)
H3W1	1.2279	1.0011	0.4081	0.076*
H3W2	1.3059	0.9221	0.5370	0.076*
O4W	1.4313 (3)	0.3181 (3)	0.6517 (3)	0.0473 (5)
H4W1	1.318 (3)	0.254 (4)	0.606 (4)	0.071*
H4W2	1.489 (5)	0.286 (5)	0.740 (3)	0.071*
O1	0.7299 (2)	0.0442 (2)	0.23120 (19)	0.0287 (4)
O2	1.0019 (3)	0.0900 (3)	0.1464 (3)	0.0456 (5)
O3	1.0490 (3)	0.1798 (3)	0.4275 (2)	0.0464 (5)
O4	0.6346 (2)	0.2346 (2)	−0.0464 (2)	0.0314 (4)
N1	1.0347 (3)	0.6376 (3)	0.2655 (3)	0.0407 (5)
H1N	1.1202	0.7233	0.3298	0.049*
C1	1.0364 (4)	0.4848 (3)	0.3030 (3)	0.0343 (5)
H1	1.1288	0.4733	0.3991	0.041*
C2	0.9046 (3)	0.3462 (3)	0.2023 (3)	0.0252 (4)
C3	0.7598 (3)	0.3593 (3)	0.0541 (3)	0.0257 (4)
C4	0.7656 (4)	0.5256 (3)	0.0240 (3)	0.0376 (6)
H4	0.6744	0.5434	−0.0695	0.045*
C5	0.9011 (4)	0.6580 (3)	0.1287 (4)	0.0419 (6)
H5	0.9017	0.7648	0.1055	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0205 (2)	0.0197 (2)	0.0217 (2)	0.00253 (15)	0.00473 (16)	0.00120 (15)
S1	0.0201 (3)	0.0250 (3)	0.0310 (3)	0.0059 (2)	0.0029 (2)	0.0034 (2)
O1W	0.0252 (9)	0.0478 (11)	0.0439 (10)	0.0069 (8)	0.0105 (8)	−0.0119 (9)
O2W	0.0698 (16)	0.0414 (12)	0.0494 (13)	0.0074 (11)	0.0211 (11)	−0.0064 (10)
O3W	0.0423 (11)	0.0433 (12)	0.0565 (13)	0.0059 (9)	0.0136 (9)	−0.0001 (9)
O4W	0.0455 (12)	0.0397 (11)	0.0385 (11)	0.0036 (9)	0.0011 (9)	0.0093 (8)
O1	0.0230 (8)	0.0310 (8)	0.0260 (8)	0.0041 (6)	0.0048 (6)	0.0068 (6)
O2	0.0384 (10)	0.0407 (10)	0.0684 (14)	0.0170 (8)	0.0286 (10)	0.0066 (10)
O3	0.0366 (10)	0.0378 (10)	0.0386 (10)	0.0030 (8)	−0.0109 (8)	0.0065 (8)
O4	0.0317 (9)	0.0227 (8)	0.0269 (8)	−0.0003 (6)	0.0021 (6)	0.0039 (6)
N1	0.0416 (12)	0.0235 (10)	0.0412 (12)	−0.0029 (9)	0.0073 (10)	−0.0059 (9)
C1	0.0303 (12)	0.0306 (12)	0.0313 (11)	0.0025 (9)	0.0041 (9)	−0.0014 (9)
C2	0.0231 (10)	0.0215 (10)	0.0269 (10)	0.0037 (8)	0.0069 (8)	0.0014 (8)
C3	0.0238 (10)	0.0241 (10)	0.0256 (10)	0.0035 (8)	0.0079 (8)	0.0034 (8)
C4	0.0399 (14)	0.0272 (12)	0.0374 (13)	0.0067 (10)	0.0067 (11)	0.0085 (10)
C5	0.0500 (16)	0.0227 (11)	0.0462 (15)	0.0054 (11)	0.0140 (12)	0.0041 (10)

Geometric parameters (Å, º)

Co1—O1W	2.0551 (19)	O3W—H3W2	0.8500
Co1—O1	2.1349 (18)	O4W—H4W1	0.84 (3)
Co1—O4	2.0833 (17)	O4W—H4W2	0.85 (3)
Co1—O1W^i	2.0551 (19)	O4—C3	1.277 (3)
Co1—O4^i	2.0833 (17)	N1—C1	1.343 (4)
Co1—O1^i	2.1349 (18)	N1—C5	1.344 (4)
S1—O3	1.447 (2)	N1—H1N	0.8600
S1—O2	1.448 (2)	C1—C2	1.365 (3)
S1—O1	1.4722 (17)	C1—H1	0.9300
S1—C2	1.771 (2)	C2—C3	1.430 (3)
O1W—H1W1	0.847 (10)	C3—C4	1.429 (3)
O1W—H1W2	0.840 (10)	C4—C5	1.354 (4)
O2W—H2W1	0.86 (3)	C4—H4	0.9300
O2W—H2W2	0.85 (5)	C5—H5	0.9300
O3W—H3W1	0.8500
O1W^i—Co1—O1W	180.00 (9)	H2W1—O2W—H2W2	108 (5)
O1W—Co1—O4^i	91.22 (8)	H3W1—O3W—H3W2	107.8
O4—Co1—O4^i	180.00 (10)	H4W1—O4W—H4W2	111 (4)
O1W—Co1—O4	88.78 (8)	S1—O1—Co1	121.86 (10)
O1W—Co1—O1^i	93.30 (8)	C3—O4—Co1	129.23 (15)
O4—Co1—O1^i	91.40 (7)	C1—N1—C5	120.8 (2)
O1W—Co1—O1	86.70 (8)	C1—N1—H1N	119.6
O4—Co1—O1	88.60 (7)	C5—N1—H1N	119.6
O1^i—Co1—O1	180.00 (11)	N1—C1—C2	121.1 (2)
O1W^i—Co1—O4^i	88.78 (8)	N1—C1—H1	119.5
O1W^i—Co1—O4	91.22 (8)	C2—C1—H1	119.5
O1W^i—Co1—O1^i	86.70 (8)	C1—C2—C3	121.0 (2)
O4^i—Co1—O1^i	88.60 (7)	C1—C2—S1	117.73 (18)
O1W^i—Co1—O1	93.30 (8)	C3—C2—S1	121.24 (17)
O4^i—Co1—O1	91.40 (7)	O4—C3—C4	121.4 (2)
O3—S1—O2	115.28 (14)	O4—C3—C2	123.9 (2)
O3—S1—O1	111.26 (12)	C4—C3—C2	114.7 (2)
O2—S1—O1	111.36 (12)	C5—C4—C3	121.4 (2)
O3—S1—C2	105.95 (12)	C5—C4—H4	119.3
O2—S1—C2	106.48 (12)	C3—C4—H4	119.3
O1—S1—C2	105.79 (10)	N1—C5—C4	121.1 (2)
Co1—O1W—H1W1	117 (2)	N1—C5—H5	119.4
Co1—O1W—H1W2	125 (2)	C4—C5—H5	119.4
H1W1—O1W—H1W2	111.0 (17)
O3—S1—O1—Co1	171.90 (12)	O2—S1—C2—C1	−105.7 (2)
O2—S1—O1—Co1	−57.99 (15)	O1—S1—C2—C1	135.74 (19)
C2—S1—O1—Co1	57.30 (14)	O3—S1—C2—C3	−165.5 (2)
O1W^i—Co1—O1—S1	61.02 (13)	O2—S1—C2—C3	71.3 (2)
O1W—Co1—O1—S1	−118.98 (13)	O1—S1—C2—C3	−47.2 (2)
O4—Co1—O1—S1	−30.12 (12)	Co1—O4—C3—C4	−146.7 (2)
O4^i—Co1—O1—S1	149.88 (12)	Co1—O4—C3—C2	33.9 (3)
O1W^i—Co1—O4—C3	−113.9 (2)	C1—C2—C3—O4	178.8 (2)
O1W—Co1—O4—C3	66.1 (2)	S1—C2—C3—O4	1.9 (3)
O1^i—Co1—O4—C3	159.4 (2)	C1—C2—C3—C4	−0.6 (3)
O1—Co1—O4—C3	−20.6 (2)	S1—C2—C3—C4	−177.48 (19)
C5—N1—C1—C2	1.0 (4)	O4—C3—C4—C5	−178.5 (3)
N1—C1—C2—C3	−0.4 (4)	C2—C3—C4—C5	0.9 (4)
N1—C1—C2—S1	176.6 (2)	C1—N1—C5—C4	−0.6 (5)
O3—S1—C2—C1	17.5 (2)	C3—C4—C5—N1	−0.4 (5)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O2^ii	0.85 (1)	2.19 (3)	2.896 (3)	140 (3)
O1W—H1W1···O2^i	0.85 (1)	2.37 (2)	2.982 (3)	130 (3)
O1W—H1W2···O2W	0.84 (1)	1.91 (2)	2.714 (3)	161 (4)
O2W—H2W1···O4W^iii	0.86 (3)	1.96 (3)	2.809 (3)	168 (4)
O2W—H2W2···O4W^ii	0.85 (5)	2.04 (4)	2.880 (4)	170 (5)
O3W—H3W1···O3^iv	0.85	2.37	3.175 (3)	158
O3W—H3W2···O1^iii	0.85	2.18	2.978 (3)	157
O4W—H4W1···O3	0.84 (3)	2.05 (2)	2.827 (3)	154 (3)
O4W—H4W2···O4^v	0.85 (3)	1.96 (3)	2.805 (3)	174 (4)
N1—H1N···O3W	0.86	1.90	2.752 (3)	169

Symmetry codes: (i) −x+1, −y, −z; (ii) x−1, y, z; (iii) −x+2, −y+1, −z+1; (iv) x, y+1, z; (v) x+1, y, z+1.