Poly[(dimethyl­formamide)(μ4-2,2′-sulfanediyldibenzoato)nickel(II)]

Xie, J.-B.

doi:10.1107/S1600536810007749

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m368

doi:10.1107/S1600536810007749

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Poly[(dimethylformamide)(μ₄-2,2′-sulfanediyldibenzoato)nickel(II)]

Jiang-Bo Xie ^a ^*

^aCollege of Materials Science and Engineering, North University of China, Taiyuan, Shanxi, 030051, People's Republic of China
^*Correspondence e-mail: xjb209@126.com

(Received 25 February 2010; accepted 1 March 2010; online 6 March 2010)

The title centrosymmetric dinuclear Ni^II complex, [Ni(C₁₄H₈O₄S)(C₃H₇NO)]_n, was prepared via reaction of Ni(NO₃)₂·6H₂O and thiosalicylic acid, with H₂O and dimethylformamide (DMF) as the mixed solvent. The central Ni^II ion is five-coordinated by five O atoms from DMF and from the carboxylate groups of the organic ligand. The symmetry-related coordination polyhedra interlink into centrosymmetric dimeric units and these, in turn, are linked into infinite chains propagating parallel to [100].

Related literature

For high-dimensional coordination polymers, see: Li et al. (2009 , 2010 ).

Experimental

Crystal data

[Ni(C₁₄H₈O₄S)(C₃H₇NO)]
M_r = 808.12
Triclinic, $[P \overline 1]$
a = 8.5196 (2) Å
b = 10.5240 (2) Å
c = 11.0138 (3) Å
α = 67.241 (1)°
β = 79.0410 (11)°
γ = 71.796 (1)°
V = 862.33 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.19 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.701, T_max = 0.794
11190 measured reflections
3350 independent reflections
2553 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.079
S = 1.01
3350 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810007749/bg2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007749/bg2334Isup2.hkl

checkCIF report

Comment top

Organic carboxylates as ligands attract much attention not only because of versatile coordination modes but also owing to their ability to facilitate the formation of high-dimensional coordination polymers (Li et al., 2009; Li et al., 2010). One such example, namely, thiosalicylic acid, is a semi-rigid, multidentate ligand that can provide up to four donor atoms with variable coordination modes. Unlike the imidazole-4,5-dicarboxylic acid and benzimidazole-5,6-dicarboxylic acid with nitrogen and oxygen coordinated dots, the thiosalicylic acid only has oxygen coordinated dot. So it can form low-dimensional compound. This is therefore considered as an excellent candidate for generating one-dimensional compound with chain structure.

In the title complex, the Ni^II atom is coordinated by one oxygen atom from one DMF ligand and four oxygen atoms from the thiosalicylic acid carboxylates, giving a centrosymmetric dimeric structure with a Ni···Ni distance of 2.6374 (7) Å (Fig. 1). A one-dimensional infinite chain is formed due to the bidentate bridging mode shown by all the thiosalicylic acid carboxylates (Fig. 2). The Ni—O bond distances vary from 1.947 (2) Å to 2.129 (2) Å. The O—Ni—O angles are in the range of 88.16 (9) to 168.24 (8) °. As far as we know, examples of dinuclear Ni^II complex bridged by thiosalicylic acid and DMF have not been characterized so far.

Related literature top

For high-dimensional coordination polymers see Li et al. (2009, 2010).

Experimental top

A solution obtained by dissolving 0.145 g (0.5 mmol) Ni(NO₃)₂.6H₂O in 4 ml DMF and 10 ml H₂O was added. The mixture was stirred until complete dissolution. To the stirred solution was added equimolar quantities 0.136 g (0.5 mmol) thiosalicylic acid. The green solution was then under 160 °C for 72 h in a 23 ml Teflon-lined stainless-steel autoclave. Afterthe reaction, the bomb was cooled to room temperature in a rate of 5 °C per hour. Green prismatic crystals were collected and dried in air. Yield: ca.82 % on the basis of Ni.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Displacement ellipsoid plot (40% probability level) of the title compound(I), with atom numbering of structurally unique non-H.
	Fig. 2. The packing diagram of the title compound (I).

Poly[(dimethylformamide)(µ₄-2,2'-sulfanediyldibenzoato)nickel(II)] top

Crystal data top

[Ni(C₁₄H₈O₄S)(C₃H₇NO)]	Z = 1
M_r = 808.12	F(000) = 416
Triclinic, P1	D_x = 1.556 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5196 (2) Å	Cell parameters from 2701 reflections
b = 10.5240 (2) Å	θ = 2.4–22.3°
c = 11.0138 (3) Å	µ = 1.27 mm⁻¹
α = 67.241 (1)°	T = 298 K
β = 79.0410 (11)°	Block, green
γ = 71.796 (1)°	0.30 × 0.25 × 0.19 mm
V = 862.33 (3) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3350 independent reflections
Radiation source: fine-focus sealed tube	2553 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scan	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→10
T_min = 0.701, T_max = 0.794	k = −12→12
11190 measured reflections	l = −13→13

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0295P)² + 0.4P] where P = (F_o² + 2F_c²)/3
3350 reflections	(Δ/σ)_max = 0.001
228 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Ni(C₁₄H₈O₄S)(C₃H₇NO)]	γ = 71.796 (1)°
M_r = 808.12	V = 862.33 (3) Å³
Triclinic, P1	Z = 1
a = 8.5196 (2) Å	Mo Kα radiation
b = 10.5240 (2) Å	µ = 1.27 mm⁻¹
c = 11.0138 (3) Å	T = 298 K
α = 67.241 (1)°	0.30 × 0.25 × 0.19 mm
β = 79.0410 (11)°

Data collection top

Bruker APEXII area-detector diffractometer	3350 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	2553 reflections with I > 2σ(I)
T_min = 0.701, T_max = 0.794	R_int = 0.035
11190 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.01	Δρ_max = 0.44 e Å⁻³
3350 reflections	Δρ_min = −0.35 e Å⁻³
228 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.37381 (4)	0.57945 (3)	0.55076 (3)	0.03249 (12)
S1	−0.02998 (9)	0.75102 (9)	0.29878 (7)	0.0481 (2)
O1	0.2572 (2)	0.5904 (2)	0.40641 (19)	0.0499 (5)
O2	0.4743 (3)	0.4593 (2)	0.3200 (2)	0.0551 (6)
O3	−0.3145 (3)	0.5998 (2)	0.33626 (19)	0.0501 (5)
O4	−0.5286 (2)	0.7322 (2)	0.4242 (2)	0.0521 (5)
O5	0.1675 (3)	0.7125 (2)	0.6255 (2)	0.0547 (6)
N1	−0.1056 (3)	0.8241 (3)	0.6247 (3)	0.0535 (7)
C1	0.3275 (4)	0.5360 (3)	0.3199 (3)	0.0417 (7)
C2	0.2315 (3)	0.5674 (3)	0.2057 (3)	0.0381 (6)
C3	0.3089 (4)	0.5029 (3)	0.1132 (3)	0.0501 (8)
H3	0.4126	0.4380	0.1281	0.060*
C4	0.2369 (4)	0.5317 (4)	0.0004 (3)	0.0561 (8)
H4	0.2922	0.4894	−0.0614	0.067*
C5	0.0810 (4)	0.6248 (3)	−0.0189 (3)	0.0553 (8)
H5	0.0308	0.6456	−0.0948	0.066*
C6	−0.0010 (4)	0.6872 (3)	0.0722 (3)	0.0494 (8)
H6	−0.1072	0.7477	0.0582	0.059*
C7	0.0723 (3)	0.6616 (3)	0.1858 (3)	0.0411 (7)
C8	−0.2076 (4)	0.8749 (3)	0.2161 (3)	0.0429 (7)
C9	−0.1898 (4)	1.0066 (3)	0.1271 (3)	0.0571 (9)
H9	−0.0855	1.0235	0.1077	0.069*
C10	−0.3225 (5)	1.1122 (4)	0.0670 (3)	0.0665 (10)
H10	−0.3077	1.1993	0.0069	0.080*
C11	−0.4766 (4)	1.0887 (3)	0.0962 (3)	0.0620 (9)
H11	−0.5668	1.1595	0.0550	0.074*
C12	−0.4984 (4)	0.9601 (3)	0.1866 (3)	0.0529 (8)
H12	−0.6039	0.9455	0.2069	0.063*
C13	−0.3648 (3)	0.8520 (3)	0.2478 (3)	0.0388 (7)
C14	−0.4029 (4)	0.7160 (3)	0.3450 (3)	0.0399 (7)
C15	0.0244 (4)	0.7207 (3)	0.6097 (3)	0.0472 (7)
H15	0.0070	0.6507	0.5859	0.057*
C16	−0.2706 (4)	0.8325 (4)	0.5980 (4)	0.0821 (12)
H16A	−0.2647	0.7545	0.5709	0.123*
H16B	−0.3115	0.9213	0.5289	0.123*
H16C	−0.3440	0.8271	0.6765	0.123*
C17	−0.0867 (4)	0.9353 (4)	0.6631 (4)	0.0730 (11)
H17A	0.0279	0.9356	0.6498	0.110*
H17B	−0.1239	0.9177	0.7546	0.110*
H17C	−0.1515	1.0264	0.6103	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0266 (2)	0.0328 (2)	0.0312 (2)	−0.00384 (15)	−0.00182 (14)	−0.00739 (15)
S1	0.0385 (5)	0.0590 (5)	0.0440 (4)	−0.0096 (4)	−0.0055 (3)	−0.0165 (4)
O1	0.0380 (12)	0.0645 (14)	0.0418 (12)	−0.0035 (11)	−0.0075 (9)	−0.0189 (11)
O2	0.0390 (13)	0.0620 (14)	0.0583 (14)	0.0012 (11)	−0.0136 (10)	−0.0217 (11)
O3	0.0488 (13)	0.0383 (12)	0.0507 (13)	−0.0109 (10)	0.0077 (10)	−0.0083 (10)
O4	0.0458 (13)	0.0440 (12)	0.0561 (13)	−0.0135 (10)	0.0116 (11)	−0.0125 (10)
O5	0.0396 (13)	0.0615 (14)	0.0619 (14)	−0.0011 (11)	−0.0042 (11)	−0.0302 (12)
N1	0.0392 (16)	0.0548 (17)	0.0596 (17)	−0.0016 (13)	−0.0001 (13)	−0.0230 (14)
C1	0.0382 (18)	0.0402 (17)	0.0422 (17)	−0.0145 (15)	−0.0034 (14)	−0.0062 (14)
C2	0.0373 (17)	0.0401 (16)	0.0344 (15)	−0.0146 (14)	−0.0054 (12)	−0.0058 (13)
C3	0.0479 (19)	0.0488 (19)	0.0492 (19)	−0.0120 (16)	−0.0056 (15)	−0.0124 (16)
C4	0.059 (2)	0.066 (2)	0.0479 (19)	−0.0171 (19)	−0.0054 (16)	−0.0247 (17)
C5	0.064 (2)	0.061 (2)	0.0452 (18)	−0.0191 (19)	−0.0137 (16)	−0.0157 (17)
C6	0.0444 (19)	0.056 (2)	0.0467 (18)	−0.0127 (16)	−0.0133 (15)	−0.0122 (16)
C7	0.0380 (17)	0.0432 (17)	0.0398 (16)	−0.0177 (14)	−0.0025 (13)	−0.0068 (13)
C8	0.0430 (18)	0.0410 (17)	0.0387 (16)	−0.0096 (14)	−0.0039 (13)	−0.0084 (14)
C9	0.056 (2)	0.055 (2)	0.055 (2)	−0.0266 (18)	0.0023 (17)	−0.0072 (17)
C10	0.075 (3)	0.044 (2)	0.060 (2)	−0.018 (2)	−0.001 (2)	0.0035 (17)
C11	0.059 (2)	0.0440 (19)	0.057 (2)	0.0006 (17)	−0.0058 (18)	−0.0013 (16)
C12	0.0407 (19)	0.0497 (19)	0.055 (2)	−0.0071 (16)	−0.0006 (15)	−0.0090 (16)
C13	0.0368 (17)	0.0370 (16)	0.0371 (16)	−0.0094 (14)	0.0002 (13)	−0.0088 (13)
C14	0.0338 (17)	0.0419 (18)	0.0397 (16)	−0.0105 (14)	−0.0036 (13)	−0.0090 (14)
C15	0.048 (2)	0.0482 (19)	0.0381 (17)	−0.0065 (16)	0.0032 (15)	−0.0155 (15)
C16	0.045 (2)	0.111 (3)	0.092 (3)	−0.013 (2)	−0.004 (2)	−0.044 (3)
C17	0.060 (2)	0.064 (2)	0.094 (3)	−0.0011 (19)	0.003 (2)	−0.042 (2)

Geometric parameters (Å, º) top

Ni1—O2ⁱ	1.947 (2)	C5—C6	1.373 (4)
Ni1—O4ⁱⁱ	1.9695 (19)	C5—H5	0.9300
Ni1—O3ⁱⁱⁱ	1.9751 (19)	C6—C7	1.400 (4)
Ni1—O1	1.9790 (19)	C6—H6	0.9300
Ni1—O5	2.129 (2)	C8—C9	1.389 (4)
Ni1—Ni1ⁱ	2.6374 (6)	C8—C13	1.390 (4)
S1—C7	1.781 (3)	C9—C10	1.371 (4)
S1—C8	1.786 (3)	C9—H9	0.9300
O1—C1	1.259 (3)	C10—C11	1.368 (5)
O2—C1	1.258 (3)	C10—H10	0.9300
O3—C14	1.249 (3)	C11—C12	1.379 (4)
O4—C14	1.258 (3)	C11—H11	0.9300
O5—C15	1.236 (3)	C12—C13	1.391 (4)
N1—C15	1.325 (4)	C12—H12	0.9300
N1—C17	1.450 (4)	C13—C14	1.507 (4)
N1—C16	1.460 (4)	C15—H15	0.9300
C1—C2	1.504 (4)	C16—H16A	0.9600
C2—C3	1.391 (4)	C16—H16B	0.9600
C2—C7	1.405 (4)	C16—H16C	0.9600
C3—C4	1.375 (4)	C17—H17A	0.9600
C3—H3	0.9300	C17—H17B	0.9600
C4—C5	1.379 (4)	C17—H17C	0.9600
C4—H4	0.9300

O2ⁱ—Ni1—O4ⁱⁱ	90.48 (9)	C7—C6—H6	119.4
O2ⁱ—Ni1—O3ⁱⁱⁱ	88.17 (9)	C6—C7—C2	118.1 (3)
O4ⁱⁱ—Ni1—O3ⁱⁱⁱ	168.24 (8)	C6—C7—S1	120.9 (2)
O2ⁱ—Ni1—O1	168.07 (8)	C2—C7—S1	121.0 (2)
O4ⁱⁱ—Ni1—O1	89.02 (9)	C9—C8—C13	118.9 (3)
O3ⁱⁱⁱ—Ni1—O1	89.89 (8)	C9—C8—S1	117.6 (2)
O2ⁱ—Ni1—O5	97.16 (8)	C13—C8—S1	123.1 (2)
O4ⁱⁱ—Ni1—O5	97.19 (8)	C10—C9—C8	121.5 (3)
O3ⁱⁱⁱ—Ni1—O5	94.56 (8)	C10—C9—H9	119.2
O1—Ni1—O5	94.73 (8)	C8—C9—H9	119.2
O2ⁱ—Ni1—Ni1ⁱ	84.58 (6)	C11—C10—C9	119.6 (3)
O4ⁱⁱ—Ni1—Ni1ⁱ	81.54 (6)	C11—C10—H10	120.2
O3ⁱⁱⁱ—Ni1—Ni1ⁱ	86.70 (6)	C9—C10—H10	120.2
O1—Ni1—Ni1ⁱ	83.56 (6)	C10—C11—C12	120.1 (3)
O5—Ni1—Ni1ⁱ	177.88 (6)	C10—C11—H11	120.0
C7—S1—C8	102.75 (13)	C12—C11—H11	120.0
C1—O1—Ni1	123.11 (19)	C11—C12—C13	120.9 (3)
C1—O2—Ni1ⁱ	123.63 (19)	C11—C12—H12	119.6
C14—O3—Ni1ⁱⁱⁱ	119.78 (18)	C13—C12—H12	119.6
C14—O4—Ni1^iv	125.92 (19)	C8—C13—C12	119.0 (3)
C15—O5—Ni1	120.6 (2)	C8—C13—C14	124.6 (3)
C15—N1—C17	120.9 (3)	C12—C13—C14	116.4 (2)
C15—N1—C16	120.9 (3)	O3—C14—O4	126.0 (3)
C17—N1—C16	118.2 (3)	O3—C14—C13	118.5 (2)
O2—C1—O1	124.9 (3)	O4—C14—C13	115.4 (3)
O2—C1—C2	117.1 (3)	O5—C15—N1	123.4 (3)
O1—C1—C2	118.0 (3)	O5—C15—H15	118.3
C3—C2—C7	119.1 (3)	N1—C15—H15	118.3
C3—C2—C1	117.4 (3)	N1—C16—H16A	109.5
C7—C2—C1	123.5 (3)	N1—C16—H16B	109.5
C4—C3—C2	122.1 (3)	H16A—C16—H16B	109.5
C4—C3—H3	118.9	N1—C16—H16C	109.5
C2—C3—H3	118.9	H16A—C16—H16C	109.5
C3—C4—C5	118.5 (3)	H16B—C16—H16C	109.5
C3—C4—H4	120.7	N1—C17—H17A	109.5
C5—C4—H4	120.7	N1—C17—H17B	109.5
C6—C5—C4	120.9 (3)	H17A—C17—H17B	109.5
C6—C5—H5	119.6	N1—C17—H17C	109.5
C4—C5—H5	119.6	H17A—C17—H17C	109.5
C5—C6—C7	121.2 (3)	H17B—C17—H17C	109.5
C5—C6—H6	119.4

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

Experimental details

Crystal data
Chemical formula	[Ni(C₁₄H₈O₄S)(C₃H₇NO)]
M_r	808.12
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.5196 (2), 10.5240 (2), 11.0138 (3)
α, β, γ (°)	67.241 (1), 79.0410 (11), 71.796 (1)
V (Å³)	862.33 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.30 × 0.25 × 0.19

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.701, 0.794
No. of measured, independent and observed [I > 2σ(I)] reflections	11190, 3350, 2553
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.079, 1.01
No. of reflections	3350
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Acknowledgements

The project was supported by the Science Foundation of North University of China.

References

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Li, Z.-Y., Dai, J.-W., Qiu, H.-H., Yue, S.-T. & Liu, Y.-L. (2010). Inorg. Chem. Commun. 13, 452–455. Web of Science CSD CrossRef CAS Google Scholar
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