catena-Poly[[diaqua­bis[(4-nitro­phenyl­sulfin­yl)acetato-κO]zinc(II)]-μ-4,4′-bipyridine-κ²N:N′]

In the title coordination polymer, [Zn(C₈H₆NO₅S)₂(C₁₀H₈N₂)(H₂O)₂]_n, each Zn^II ion is in a slightly distorted octa­hedral coordination environment, formed by two carboxy­late O atoms from two (4-nitro­phenyl­sulfin­yl)acetate ligands, two N atoms from bipyridine ligands and two water mol­ecules. The Zn^II ions and the bipryidine ligands lie on crystallographic twofold axes with the Zn^II ions linked by bipyridine ligands into a one-dimensional chain structure. In the crystal structure, inter­molecular O—H...O hydrogen bonds link one-dimensional chains into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.077
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.80 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           27.44
           From the CIF: _reflns_number_total               3335
           Count of symmetry unique reflns         1773
           Completeness (_total/calc)            188.10%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1562
           Fraction of Friedel pairs measured     0.881
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   0 ALERT type 5 Informative message, check

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S1. Comment

4,4'-Bipyridine and organic aromatic carboxylic acid ligands are often used in syntheses to bridge metal atoms and these compound can demonstrate fascinating network topologies and potential application in the field of host–guest chemistry, ion exchange and catalysis (Ghosh et al., 2005). Simple carboxylic acids containing the 4-nitrophenyl group exhibit a variety of supramolecular aggregation patterns (Glidewell et al., 2002). Recently, our attention has been focused on 4-nitrophenylsulfinyl acetic acid, whose crystal structure has been reported previously (Glidewell et al., 2003).

Complex(I) consists of linear chains formed through 4,4'-bipy ligands linking six-coordinate Zn^II ions (Fig. 1). The ZnII ion has slightly distorted octahedral geometry. Two N donors of two 4,4'-bipy ligands and two coordinated water molecules lie in the equatorial plane, while two O-atom donors of two (4-nitrophenylsulfinyl)acetate ligands are in the axial positions.

These one-dimensional chains are connected into a three dimensional network via intermolecular O—H···O hydrogen bonds(Table 1),(Fig. 2).

Related literature

For synthetic background, see: Ghosh et al. (2005), and for previously published structures related to the topic, see: Glidewell et al. (2002, 2003). For preparation details, see: Nobles & Thompson (1965).

S2. Experimental

(4-Nitrophenylsulfanyl)acetic acid was prepared by a nucleophilic reaction of chloroacetic acid and 4-nitrothiophenol under basic conditions. (4-nitrophenylsulfanyl)acetic acid was then oxidized using 30% aqueous hydrogen peroxide in acetic anhydride solution, producing 4-nitrophenylsulfinyl acetic acid (Nobles & Thompson, 1965). Zinc nitrate hexahydrate (0.586 g, 2 mmol) and (4-nitrophenylsulfinyl)acetic acid (0.458 g, 2 mmol) and 4,4'-bipyridine (0.312 g, 2 mmol) were dissolved in water and the pH was adjusted to 6 with 0.01M sodium hydroxide, colorless crystals separated from the filtered solution after several days.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, withwith C—H = 0.93 Å (aromatic C) or C—H = 0.97 Å (methylene C), and with U_iso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map but they were treated as riding on their parent atoms with O—H = 0.85 Å and with U_iso(H) = 1.5Ueq(O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Part of the polymeric structure of the title complex, with the atomlabelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented as spheres of arbitrary radii. [Symmetry codes: (I) -x, -y + 2, z; (II) x, y,z - 1; (III)-x, -y + 2, z - 1, (IV) x, y, z + 1].
	Fig. 2. A partial packing plot of (I). Dashed lines indicate the donor to acceptor non-bonded contacts invloved in hydrogen bonding. H atoms have been omitted.

catena-Poly[[diaquabis[(4-nitrophenylsulfinyl)acetato-κO]zinc(II)]- µ-4,4'-bipyridine-κ²N:N']

Crystal data

[Zn(C8H6NO5S)2(C10H8N2)(H2O)2]	F(000) = 2928
Mr = 713.98	Dx = 1.604 Mg m^−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 12942 reflections
a = 20.079 (4) Å	θ = 6.3–54.9°
b = 25.646 (5) Å	µ = 1.04 mm^−1
c = 11.485 (2) Å	T = 293 K
V = 5914 (2) Å^3	Block, colourless
Z = 8	0.28 × 0.23 × 0.20 mm

Data collection

Rigaku RAXIS-RAPID diffractometer	3335 independent reflections
Radiation source: fine-focus sealed tube	3138 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −26→26
Tmin = 0.761, Tmax = 0.822	k = −33→33
14073 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.047P)^2 + 4.1913P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.005
3335 reflections	Δρmax = 0.55 e Å^−3
206 parameters	Δρmin = −0.32 e Å^−3
13 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.022 (14)

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.

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.

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

	x	y	z	Uiso*/Ueq
C1	0.02856 (17)	0.72739 (13)	0.5181 (3)	0.0284 (7)
C2	0.0666 (2)	0.70549 (15)	0.4295 (3)	0.0362 (8)
H1	0.0647	0.7189	0.3544	0.043*
C3	0.10728 (19)	0.66355 (14)	0.4545 (3)	0.0374 (9)
H2	0.1334	0.6484	0.3969	0.045*
C4	0.1084 (2)	0.64463 (14)	0.5672 (3)	0.0338 (8)
C5	0.0714 (2)	0.66611 (15)	0.6570 (3)	0.0398 (9)
H3	0.0733	0.6524	0.7319	0.048*
C6	0.0315 (2)	0.70887 (15)	0.6312 (3)	0.0364 (8)
H4	0.0069	0.7250	0.6897	0.044*
C7	0.03217 (17)	0.83002 (12)	0.4745 (4)	0.0310 (7)
H5	0.0590	0.8310	0.5448	0.037*
H6	0.0614	0.8232	0.4091	0.037*
C8	−0.00307 (18)	0.88235 (12)	0.4576 (3)	0.0280 (7)
C9	0.0212 (2)	1.04111 (14)	0.7267 (4)	0.0370 (8)
H7	0.0369	1.0699	0.6860	0.044*
C10	0.0210 (2)	1.04293 (17)	0.8483 (4)	0.0414 (9)
H8	0.0349	1.0729	0.8869	0.050*
C11	0.0000	1.0000	0.9105 (5)	0.0300 (13)
C12	0.0000	1.0000	1.0404 (5)	0.0359 (14)
C13	0.0321 (2)	0.96088 (16)	1.1036 (4)	0.0383 (9)
H9	0.0536	0.9338	1.0650	0.046*
C14	0.03179 (19)	0.96264 (14)	1.2234 (4)	0.0355 (8)
H10	0.0545	0.9369	1.2643	0.043*
N1	0.1489 (2)	0.59871 (17)	0.5925 (4)	0.0506 (9)
N2	0.0000	1.0000	0.6666 (4)	0.0264 (10)
N3	0.0000	1.0000	1.2837 (4)	0.0308 (11)
O1	−0.06561 (15)	0.78963 (11)	0.5975 (3)	0.0472 (7)
O2	−0.06099 (15)	0.88136 (10)	0.4182 (3)	0.0446 (7)
O3	0.03031 (12)	0.92181 (8)	0.4850 (2)	0.0302 (5)
O4	0.1760 (2)	0.57580 (17)	0.5154 (4)	0.0837 (12)
O5	0.1539 (2)	0.58524 (18)	0.6938 (4)	0.0845 (12)
O6	0.10205 (11)	1.02344 (9)	0.4739 (2)	0.0324 (5)
H12	0.1267	1.0044	0.4314	0.049*
H11	0.0976	1.0551	0.4537	0.049*
S2	−0.02931 (4)	0.77903 (3)	0.48577 (9)	0.0311 (2)
Zn1	0.0000	1.0000	0.47672 (3)	0.02310 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0334 (17)	0.0190 (14)	0.0327 (19)	−0.0014 (12)	0.0014 (15)	0.0027 (13)
C2	0.046 (2)	0.0311 (17)	0.0318 (18)	0.0040 (16)	0.0073 (17)	0.0063 (15)
C3	0.0390 (19)	0.0333 (18)	0.040 (2)	0.0061 (15)	0.0095 (16)	−0.0009 (15)
C4	0.0373 (18)	0.0277 (17)	0.0365 (19)	0.0073 (15)	−0.0023 (16)	0.0044 (15)
C5	0.048 (2)	0.039 (2)	0.0323 (19)	0.0122 (18)	0.0004 (17)	0.0072 (16)
C6	0.043 (2)	0.0346 (19)	0.032 (2)	0.0091 (16)	0.0062 (16)	0.0000 (15)
C7	0.0333 (16)	0.0209 (14)	0.0387 (17)	−0.0012 (12)	0.0007 (16)	−0.0004 (15)
C8	0.0412 (17)	0.0217 (14)	0.021 (2)	0.0032 (14)	0.0011 (14)	−0.0002 (12)
C9	0.056 (2)	0.0340 (18)	0.0209 (16)	−0.0072 (17)	−0.0033 (18)	0.0036 (15)
C10	0.065 (3)	0.037 (2)	0.0219 (19)	−0.010 (2)	−0.0070 (18)	−0.0022 (16)
C11	0.034 (3)	0.039 (3)	0.017 (3)	0.000 (2)	0.000	0.000
C12	0.046 (4)	0.041 (4)	0.020 (3)	−0.004 (2)	0.000	0.000
C13	0.052 (2)	0.039 (2)	0.0238 (18)	0.0089 (17)	0.0028 (17)	−0.0022 (16)
C14	0.0454 (19)	0.0375 (18)	0.0236 (17)	0.0085 (15)	0.0011 (18)	0.0042 (15)
N1	0.058 (2)	0.048 (2)	0.046 (2)	0.0266 (18)	0.0021 (18)	0.0042 (17)
N2	0.035 (3)	0.027 (2)	0.017 (2)	0.0019 (16)	0.000	0.000
N3	0.038 (3)	0.035 (3)	0.019 (2)	−0.0026 (17)	0.000	0.000
O1	0.0427 (15)	0.0356 (15)	0.063 (2)	0.0060 (12)	0.0208 (15)	0.0064 (14)
O2	0.0513 (15)	0.0249 (12)	0.0578 (17)	0.0043 (11)	−0.0216 (14)	−0.0069 (12)
O3	0.0410 (12)	0.0197 (9)	0.0299 (12)	0.0006 (9)	−0.0014 (12)	−0.0005 (10)
O4	0.0909 (16)	0.0800 (16)	0.0802 (17)	0.0424 (12)	0.0035 (13)	−0.0019 (12)
O5	0.0888 (16)	0.0848 (16)	0.0797 (17)	0.0400 (12)	0.0001 (13)	0.0060 (13)
O6	0.0356 (12)	0.0293 (11)	0.0323 (12)	0.0041 (9)	0.0041 (12)	0.0017 (11)
S2	0.0310 (4)	0.0203 (3)	0.0418 (5)	−0.0003 (3)	−0.0009 (4)	0.0015 (4)
Zn1	0.0327 (3)	0.0192 (2)	0.0174 (2)	−0.0002 (2)	0.000	0.000

Geometric parameters (Å, º)

C1—C6	1.384 (5)	C11—C10^i	1.379 (5)
C1—C2	1.391 (5)	C11—C12	1.492 (6)
C1—S2	1.801 (3)	C12—C13^i	1.396 (5)
C2—C3	1.381 (5)	C12—C13	1.396 (5)
C2—H1	0.9300	C13—C14	1.377 (6)
C3—C4	1.383 (5)	C13—H9	0.9300
C3—H2	0.9300	C14—N3	1.343 (5)
C4—C5	1.384 (6)	C14—H10	0.9300
C4—N1	1.460 (5)	N1—O4	1.194 (6)
C5—C6	1.390 (5)	N1—O5	1.217 (6)
C5—H3	0.9300	N2—C9^i	1.330 (4)
C6—H4	0.9300	N2—Zn1	2.181 (4)
C7—C8	1.530 (4)	N3—C14^i	1.343 (5)
C7—S2	1.803 (3)	N3—Zn1^ii	2.217 (5)
C7—H5	0.9700	O1—S2	1.500 (3)
C7—H6	0.9700	O3—Zn1	2.098 (2)
C8—O2	1.248 (5)	O6—Zn1	2.136 (2)
C8—O3	1.254 (4)	O6—H12	0.8500
C9—N2	1.330 (4)	O6—H11	0.8501
C9—C10	1.397 (6)	Zn1—O3^i	2.098 (2)
C9—H7	0.9300	Zn1—O6^i	2.136 (2)
C10—C11	1.379 (5)	Zn1—N3^iii	2.217 (5)
C10—H8	0.9300
C6—C1—C2	121.6 (3)	C13—C12—C11	121.3 (3)
C6—C1—S2	118.3 (3)	C14—C13—C12	119.6 (4)
C2—C1—S2	120.0 (3)	C14—C13—H9	120.2
C3—C2—C1	119.2 (4)	C12—C13—H9	120.2
C3—C2—H1	120.4	N3—C14—C13	122.7 (4)
C1—C2—H1	120.4	N3—C14—H10	118.6
C2—C3—C4	118.5 (3)	C13—C14—H10	118.6
C2—C3—H2	120.7	O4—N1—O5	122.0 (4)
C4—C3—H2	120.7	O4—N1—C4	120.3 (4)
C3—C4—C5	123.3 (3)	O5—N1—C4	117.7 (4)
C3—C4—N1	118.5 (4)	C9—N2—C9^i	117.5 (5)
C5—C4—N1	118.1 (3)	C9—N2—Zn1	121.3 (2)
C4—C5—C6	117.7 (3)	C9^i—N2—Zn1	121.3 (2)
C4—C5—H3	121.1	C14—N3—C14^i	117.9 (5)
C6—C5—H3	121.1	C14—N3—Zn1^ii	121.0 (3)
C1—C6—C5	119.6 (4)	C14^i—N3—Zn1^ii	121.0 (3)
C1—C6—H4	120.2	C8—O3—Zn1	127.2 (2)
C5—C6—H4	120.2	Zn1—O6—H12	113.9
C8—C7—S2	109.2 (2)	Zn1—O6—H11	100.0
C8—C7—H5	109.8	H12—O6—H11	117.0
S2—C7—H5	109.8	O1—S2—C1	105.68 (17)
C8—C7—H6	109.8	O1—S2—C7	105.22 (18)
S2—C7—H6	109.8	C1—S2—C7	96.11 (15)
H5—C7—H6	108.3	O3—Zn1—O3^i	174.79 (15)
O2—C8—O3	127.3 (3)	O3—Zn1—O6^i	90.57 (9)
O2—C8—C7	117.3 (3)	O3^i—Zn1—O6^i	89.50 (9)
O3—C8—C7	115.4 (3)	O3—Zn1—O6	89.50 (9)
N2—C9—C10	122.9 (4)	O3^i—Zn1—O6	90.57 (9)
N2—C9—H7	118.5	O6^i—Zn1—O6	178.29 (15)
C10—C9—H7	118.5	O3—Zn1—N2	87.39 (7)
C11—C10—C9	119.5 (4)	O3^i—Zn1—N2	87.39 (7)
C11—C10—H8	120.3	O6^i—Zn1—N2	90.86 (7)
C9—C10—H8	120.3	O6—Zn1—N2	90.86 (7)
C10^i—C11—C10	117.6 (5)	O3—Zn1—N3^iii	92.61 (7)
C10^i—C11—C12	121.2 (3)	O3^i—Zn1—N3^iii	92.61 (7)
C10—C11—C12	121.2 (3)	O6^i—Zn1—N3^iii	89.14 (7)
C13^i—C12—C13	117.4 (5)	O6—Zn1—N3^iii	89.14 (7)
C13^i—C12—C11	121.3 (3)	N2—Zn1—N3^iii	180.000 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H12···O1^iv	0.85	1.88	2.731 (4)	176
O6—H11···O2^i	0.85	1.83	2.655 (4)	162

Symmetry codes: (i) −x, −y+2, z; (iv) x+1/4, −y+7/4, z−1/4.