Literature DB >> 21582704

Bis(thio-semicarbazide)nickel(II) bis-[2-(thio-semicarbazonometh-yl)benzene-sulfonate] dihydrate.

Abstract

In the title compound, [Ni(CH(5)N(3)S)(2)](C(8)H(8)N(3)O(3)S(2))(2)·2H(2)O, the Ni(II) atom lies on a inversion centre and is four-coordinated by two N and two S atoms of two thio-semicarbazide ligands in an almost square-planar coordination. In the crystal structure, the molecules are linked into a three-dimensional network via C-H⋯O, C-H⋯N, N-H⋯O, N-H⋯S and O-H⋯O hydrogen bonds.

Entities: Chemical Disease Species

Year: 2009 PMID： 21582704 PMCID： PMC2969405 DOI： 10.1107/S1600536809022144

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the design and synthesis of organic–inorganic hybrid materials and their potential practical applications, see: Hagrman et al. (1998 ▶); Ranford et al. (1998 ▶).

Experimental

Crystal data

[Ni(CH5N3S)2](C8H8N3O3S2)2·2H2O M = 793.61 Triclinic, a = 7.3853 (8) Å b = 9.9043 (11) Å c = 11.3140 (18) Å α = 86.670 (2)° β = 77.611 (1)° γ = 75.177 (1)° V = 781.40 (17) Å3 Z = 1 Mo Kα radiation μ = 1.09 mm−1 T = 298 K 0.33 × 0.21 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.716, T max = 0.872 4091 measured reflections 2717 independent reflections 2268 reflections with I > 2σ(I) R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.029 wR(F 2) = 0.078 S = 1.03 2717 reflections 205 parameters H-atom parameters constrained Δρmax = 0.30 e Å−3 Δρmin = −0.25 e Å−3 Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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: SHELXTL. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022144/at2808sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022144/at2808Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(CH₅N₃S)₂](C₈H₈N₃O₃S₂)₂·2H₂O	Z = 1
M_r = 793.61	F(000) = 410
Triclinic, P1	D_x = 1.686 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3853 (8) Å	Cell parameters from 2430 reflections
b = 9.9043 (11) Å	θ = 2.8–28.3°
c = 11.3140 (18) Å	µ = 1.09 mm⁻¹
α = 86.670 (2)°	T = 298 K
β = 77.611 (1)°	Block, light green
γ = 75.177 (1)°	0.33 × 0.21 × 0.13 mm
V = 781.40 (17) Å³

Bruker SMART CCD area-detector diffractometer	2717 independent reflections
Radiation source: fine-focus sealed tube	2268 reflections with I > 2σ(I)
graphite	R_int = 0.014
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
T_min = 0.716, T_max = 0.872	k = −11→10
4091 measured reflections	l = −13→13

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0372P)² + 0.4266P] where P = (F_o² + 2F_c²)/3
2717 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

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	U_iso*/U_eq
Ni1	0.5000	0.0000	1.0000	0.02441 (13)
S1	0.34631 (9)	0.48280 (6)	0.21469 (5)	0.02605 (16)
S2	−0.17224 (10)	1.04164 (7)	0.68768 (6)	0.03721 (19)
S3	0.26167 (9)	−0.01235 (7)	0.91972 (6)	0.03314 (17)
N1	0.0111 (3)	0.8006 (2)	0.58317 (19)	0.0340 (5)
H1	−0.0018	0.8437	0.5161	0.041*
N2	0.1084 (3)	0.6619 (2)	0.58171 (19)	0.0303 (5)
N3	−0.0510 (4)	0.7954 (2)	0.7884 (2)	0.0484 (7)
H3A	0.0034	0.7075	0.7846	0.058*
H3B	−0.0972	0.8354	0.8577	0.058*
N4	0.2869 (3)	0.2479 (2)	0.9094 (2)	0.0334 (5)
H4	0.2478	0.3364	0.8989	0.040*
N5	0.4569 (3)	0.1917 (2)	0.95422 (19)	0.0290 (5)
H5A	0.4527	0.2420	1.0189	0.035*
H5B	0.5575	0.2025	0.8969	0.035*
N6	0.0401 (3)	0.2105 (2)	0.8361 (2)	0.0408 (6)
H6A	0.0047	0.2983	0.8208	0.049*
H6B	−0.0232	0.1547	0.8197	0.049*
O1	0.4008 (3)	0.61284 (18)	0.21793 (16)	0.0365 (4)
O2	0.4767 (3)	0.38730 (18)	0.12150 (15)	0.0338 (4)
O3	0.1474 (3)	0.50454 (19)	0.20417 (17)	0.0375 (5)
O4	0.8292 (3)	0.46182 (19)	0.06672 (18)	0.0421 (5)
H4C	0.7240	0.4388	0.0908	0.051*
H4D	0.8465	0.4734	−0.0095	0.051*
C1	−0.0636 (4)	0.8689 (3)	0.6882 (2)	0.0302 (6)
C2	0.1743 (4)	0.6065 (3)	0.4783 (2)	0.0317 (6)
H2	0.1525	0.6586	0.4094	0.038*
C3	0.2855 (3)	0.4598 (3)	0.4667 (2)	0.0270 (5)
C4	0.3691 (3)	0.3944 (2)	0.3547 (2)	0.0251 (5)
C5	0.4773 (4)	0.2568 (3)	0.3488 (2)	0.0345 (6)
H5	0.5331	0.2144	0.2740	0.041*
C6	0.5023 (4)	0.1825 (3)	0.4542 (3)	0.0399 (7)
H6	0.5753	0.0906	0.4501	0.048*
C7	0.4188 (4)	0.2450 (3)	0.5650 (3)	0.0421 (7)
H7	0.4347	0.1947	0.6357	0.051*
C8	0.3117 (4)	0.3820 (3)	0.5717 (2)	0.0362 (6)
H8	0.2563	0.4231	0.6470	0.043*
C9	0.1903 (4)	0.1618 (3)	0.8844 (2)	0.0277 (5)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0261 (2)	0.0197 (2)	0.0281 (3)	−0.00600 (18)	−0.00623 (18)	−0.00112 (18)
S1	0.0318 (3)	0.0230 (3)	0.0241 (3)	−0.0083 (3)	−0.0059 (3)	0.0011 (2)
S2	0.0469 (4)	0.0278 (4)	0.0327 (4)	−0.0011 (3)	−0.0082 (3)	−0.0037 (3)
S3	0.0340 (4)	0.0228 (3)	0.0468 (4)	−0.0076 (3)	−0.0168 (3)	0.0003 (3)
N1	0.0434 (13)	0.0259 (12)	0.0269 (12)	−0.0008 (10)	−0.0041 (10)	−0.0013 (9)
N2	0.0330 (12)	0.0240 (11)	0.0307 (12)	−0.0052 (9)	−0.0015 (9)	−0.0023 (9)
N3	0.0765 (19)	0.0295 (13)	0.0277 (13)	−0.0020 (12)	0.0002 (12)	0.0000 (10)
N4	0.0385 (13)	0.0198 (11)	0.0445 (13)	−0.0046 (9)	−0.0188 (11)	0.0049 (9)
N5	0.0340 (12)	0.0276 (11)	0.0288 (11)	−0.0116 (9)	−0.0093 (9)	0.0012 (9)
N6	0.0429 (14)	0.0279 (12)	0.0567 (16)	−0.0054 (10)	−0.0258 (12)	0.0017 (11)
O1	0.0544 (12)	0.0267 (10)	0.0301 (10)	−0.0180 (9)	−0.0033 (9)	0.0025 (8)
O2	0.0408 (11)	0.0333 (10)	0.0267 (9)	−0.0107 (8)	−0.0032 (8)	−0.0040 (8)
O3	0.0351 (10)	0.0386 (11)	0.0395 (11)	−0.0074 (8)	−0.0133 (8)	0.0083 (9)
O4	0.0365 (11)	0.0407 (11)	0.0508 (12)	−0.0116 (9)	−0.0104 (9)	0.0009 (9)
C1	0.0329 (14)	0.0282 (14)	0.0292 (14)	−0.0086 (11)	−0.0039 (11)	−0.0020 (11)
C2	0.0365 (15)	0.0286 (14)	0.0281 (14)	−0.0054 (11)	−0.0067 (11)	0.0027 (11)
C3	0.0283 (13)	0.0273 (13)	0.0268 (13)	−0.0091 (10)	−0.0061 (10)	0.0018 (10)
C4	0.0261 (12)	0.0230 (13)	0.0275 (13)	−0.0077 (10)	−0.0075 (10)	0.0035 (10)
C5	0.0387 (15)	0.0277 (14)	0.0340 (15)	−0.0036 (12)	−0.0060 (12)	−0.0008 (11)
C6	0.0433 (16)	0.0236 (14)	0.0476 (18)	0.0003 (12)	−0.0104 (13)	0.0077 (12)
C7	0.0465 (17)	0.0413 (17)	0.0355 (16)	−0.0059 (14)	−0.0112 (13)	0.0119 (13)
C8	0.0419 (16)	0.0369 (16)	0.0256 (14)	−0.0058 (12)	−0.0038 (12)	0.0023 (11)
C9	0.0310 (14)	0.0263 (13)	0.0245 (13)	−0.0055 (11)	−0.0046 (11)	−0.0026 (10)

Ni1—N5ⁱ	1.903 (2)	N5—H5A	0.9000
Ni1—N5	1.903 (2)	N5—H5B	0.9000
Ni1—S3ⁱ	2.1788 (7)	N6—C9	1.310 (3)
Ni1—S3	2.1788 (7)	N6—H6A	0.8600
S1—O1	1.4487 (18)	N6—H6B	0.8600
S1—O3	1.4590 (19)	O4—H4C	0.8500
S1—O2	1.4655 (18)	O4—H4D	0.8500
S1—C4	1.784 (2)	C2—C3	1.472 (3)
S2—C1	1.694 (3)	C2—H2	0.9300
S3—C9	1.720 (2)	C3—C8	1.400 (4)
N1—C1	1.340 (3)	C3—C4	1.400 (3)
N1—N2	1.377 (3)	C4—C5	1.390 (3)
N1—H1	0.8600	C5—C6	1.385 (4)
N2—C2	1.265 (3)	C5—H5	0.9300
N3—C1	1.319 (3)	C6—C7	1.378 (4)
N3—H3A	0.8600	C6—H6	0.9300
N3—H3B	0.8600	C7—C8	1.382 (4)
N4—C9	1.320 (3)	C7—H7	0.9300
N4—N5	1.423 (3)	C8—H8	0.9300
N4—H4	0.8600

N5ⁱ—Ni1—N5	180.000 (1)	C9—N6—H6B	120.0
N5ⁱ—Ni1—S3ⁱ	88.41 (6)	H6A—N6—H6B	120.0
N5—Ni1—S3ⁱ	91.59 (6)	H4C—O4—H4D	108.2
N5ⁱ—Ni1—S3	91.59 (6)	N3—C1—N1	117.1 (2)
N5—Ni1—S3	88.41 (6)	N3—C1—S2	123.0 (2)
S3ⁱ—Ni1—S3	180.000 (1)	N1—C1—S2	119.80 (19)
O1—S1—O3	112.53 (11)	N2—C2—C3	120.2 (2)
O1—S1—O2	112.54 (11)	N2—C2—H2	119.9
O3—S1—O2	111.48 (11)	C3—C2—H2	119.9
O1—S1—C4	107.61 (11)	C8—C3—C4	118.1 (2)
O3—S1—C4	107.07 (11)	C8—C3—C2	119.0 (2)
O2—S1—C4	105.09 (11)	C4—C3—C2	123.0 (2)
C9—S3—Ni1	97.45 (9)	C5—C4—C3	120.6 (2)
C1—N1—N2	120.6 (2)	C5—C4—S1	117.17 (19)
C1—N1—H1	119.7	C3—C4—S1	122.23 (18)
N2—N1—H1	119.7	C6—C5—C4	120.1 (2)
C2—N2—N1	116.0 (2)	C6—C5—H5	119.9
C1—N3—H3A	120.0	C4—C5—H5	119.9
C1—N3—H3B	120.0	C7—C6—C5	119.9 (2)
H3A—N3—H3B	120.0	C7—C6—H6	120.0
C9—N4—N5	118.9 (2)	C5—C6—H6	120.0
C9—N4—H4	120.6	C6—C7—C8	120.3 (3)
N5—N4—H4	120.6	C6—C7—H7	119.8
N4—N5—Ni1	115.48 (15)	C8—C7—H7	119.8
N4—N5—H5A	108.4	C7—C8—C3	120.9 (3)
Ni1—N5—H5A	108.4	C7—C8—H8	119.5
N4—N5—H5B	108.4	C3—C8—H8	119.5
Ni1—N5—H5B	108.4	N6—C9—N4	119.8 (2)
H5A—N5—H5B	107.5	N6—C9—S3	121.3 (2)
C9—N6—H6A	120.0	N4—C9—S3	118.86 (19)

N5ⁱ—Ni1—S3—C9	174.91 (10)	O3—S1—C4—C5	111.1 (2)
N5—Ni1—S3—C9	−5.09 (10)	O2—S1—C4—C5	−7.5 (2)
C1—N1—N2—C2	−179.7 (2)	O1—S1—C4—C3	51.3 (2)
C9—N4—N5—Ni1	−10.8 (3)	O3—S1—C4—C3	−69.9 (2)
S3ⁱ—Ni1—N5—N4	−171.05 (16)	O2—S1—C4—C3	171.4 (2)
S3—Ni1—N5—N4	8.95 (16)	C3—C4—C5—C6	0.5 (4)
N2—N1—C1—N3	−4.5 (4)	S1—C4—C5—C6	179.4 (2)
N2—N1—C1—S2	176.70 (18)	C4—C5—C6—C7	0.3 (4)
N1—N2—C2—C3	178.2 (2)	C5—C6—C7—C8	−0.6 (5)
N2—C2—C3—C8	1.9 (4)	C6—C7—C8—C3	0.1 (4)
N2—C2—C3—C4	−177.2 (2)	C4—C3—C8—C7	0.7 (4)
C8—C3—C4—C5	−1.0 (4)	C2—C3—C8—C7	−178.4 (3)
C2—C3—C4—C5	178.1 (2)	N5—N4—C9—N6	−175.8 (2)
C8—C3—C4—S1	−179.8 (2)	N5—N4—C9—S3	5.8 (3)
C2—C3—C4—S1	−0.8 (3)	Ni1—S3—C9—N6	−177.3 (2)
O1—S1—C4—C5	−127.7 (2)	Ni1—S3—C9—N4	1.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2ⁱⁱ	0.86	2.73	3.475 (2)	147
N3—H3A···N2	0.86	2.29	2.643 (3)	105
N3—H3A···O4ⁱⁱⁱ	0.86	2.58	3.224 (3)	132
N4—H4···O4ⁱⁱⁱ	0.86	1.97	2.794 (3)	160
O4—H4C···O2	0.85	1.97	2.819 (3)	172
O4—H4D···O3^iv	0.85	2.19	3.036 (3)	172
O4—H4D···O4^v	0.85	2.58	2.903 (3)	104
N5—H5A···O2^vi	0.90	1.97	2.837 (3)	163
N5—H5B···O1ⁱⁱⁱ	0.90	2.23	2.893 (3)	130
N6—H6A···O3^vii	0.86	2.03	2.866 (3)	165
N6—H6B···S2^viii	0.86	2.50	3.298 (2)	156
C2—H2···O1	0.93	2.50	3.066 (3)	119
C5—H5···O2	0.93	2.38	2.811 (3)	108
C8—H8···N2	0.93	2.48	2.790 (4)	100

Ni1—N5	1.903 (2)
Ni1—S3	2.1788 (7)

N5ⁱ—Ni1—N5	180
N5ⁱ—Ni1—S3	91.59 (6)
N5—Ni1—S3	88.41 (6)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2ⁱⁱ	0.86	2.73	3.475 (2)	147
N3—H3A⋯N2	0.86	2.29	2.643 (3)	105
N3—H3A⋯O4ⁱⁱⁱ	0.86	2.58	3.224 (3)	132
N4—H4⋯O4ⁱⁱⁱ	0.86	1.97	2.794 (3)	160
O4—H4C⋯O2	0.85	1.97	2.819 (3)	172
O4—H4D⋯O3^iv	0.85	2.19	3.036 (3)	172
O4—H4D⋯O4^v	0.85	2.58	2.903 (3)	104
N5—H5A⋯O2^vi	0.90	1.97	2.837 (3)	163
N5—H5B⋯O1ⁱⁱⁱ	0.90	2.23	2.893 (3)	130
N6—H6A⋯O3^vii	0.86	2.03	2.866 (3)	165
N6—H6B⋯S2^viii	0.86	2.50	3.298 (2)	156
C2—H2⋯O1	0.93	2.50	3.066 (3)	119
C5—H5⋯O2	0.93	2.38	2.811 (3)	108
C8—H8⋯N2	0.93	2.48	2.790 (4)	100

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Dicopper(II) Complexes of the Antitumor Analogues Acylbis(salicylaldehyde hydrazones) and Crystal Structures of Monomeric [Cu(2)(1,3-propanedioyl bis(salicylaldehyde hydrazone))(H(2)O)(2)].(ClO(4))(2).3H(2)O and Polymeric [{Cu(2)(1,6-hexanedioyl bis(salicylaldehyde hydrazone))(C(2)H(5)OH)(2)}(m)()].(ClO(4))(2)(m)().m(C(2)H(5)OH).

Authors: John D. Ranford; Jagadese J. Vittal; Yu M. Wang
Journal: Inorg Chem Date: 1998-03-23 Impact factor: 5.165

2 in total