Diaqua­bis(1,1,4-trimethyl­thio­semicarbazide)nickel(II) dinitrate

Burrows, A.D.; Harrington, R.W.; Mahon, M.F.

doi:10.1107/S1600536805002965

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages m551-m553

https://doi.org/10.1107/S1600536805002965

Diaquabis(1,1,4-trimethylthiosemicarbazide)nickel(II) dinitrate

Andrew D. Burrows,^a Ross W. Harrington ^a ^*‡ and Mary F. Mahon ^a

^aDepartment of Chemistry, University of Bath, Claverton Down, Bath BA1 7AY, England
^*Correspondence e-mail: r.w.harrington@ncl.ac.uk

(Received 12 January 2005; accepted 26 January 2005; online 19 February 2005)

The determination of the crystal structure of the title compound, [Ni(C₄H₁₁N₃S)₂(H₂O)₂](NO₃)₂, reveals a distorted octahedral geometry around the Ni centre, which lies on an inversion centre, with water molecules occupying the axial positions. Hydrogen bonding is observed between the 1,1,4-trimethylthiosemicarbazide NH groups and the nitrate anions, and also between the coordinated water molecules and the anions.

Comment

The title compound, (I), was formed as part of our investigations into the crystal engineering of nickel bis(thiosemicarbazide) dicarboxylates, in which the Ni-containing cations and dicarboxylate anions are linked through charge-augmented hydrogen bonds (Allen et al., 1999 ; Burrows et al., 2000 , 2004 ).

The asymmetric unit in (I) consists of a nickel(II) centre, to which is co-ordinated one 1,1,4-trimethylthiosemicarbazide ligand, via the S and dimethylamine N atoms, and one water molecule. A nitrate anion completes the asymmetric unit. The remainder of the molecular unit is generated by transformation through a crystallographic inversion centre, on which the metal is located. The structure of (I) is shown in Fig. 1.

The geometry around the Ni centre is distorted octahedral, with bond angles ranging from 82.95 (3) to 97.05 (3)°. Each nitrate anion forms hydrogen bonds to three separate Ni^II species. The presence of parallel N—H donors (D) on the 1,1,4-trimethylthiosemicarbazide ligand and parallel O acceptors (A) on the nitrates facilitates the formation of DD:AA interactions, graph set R₂²(8) (Etter, 1990 ), which link the cations and anions. Each of the remaining AA faces of the nitrates is involved in a single O—H⋯O interaction with coordinated water molecules

The combination of the DD:AA hydrogen bonds with one such O—H⋯O interaction results in the formation of `slipped' hydrogen-bonded chains along the crystallographic a axis, as illustrated in Fig. 2. Within the chains are hydrogen-bonded rings of graph set R₄²(16). The `slipped' description of these chains is relative to chains observed in networks formed from reactions with linear dicarboxylates, such as fumarate or terephthalate, where the cations are linked solely via DD:AA interactions to the anion carboxylate groups (Allen et al., 1999; Burrows et al., 2004). The formation of the three-dimensional structure is faciliated by the second O—H⋯O interaction, graph set R₆⁵(23), illustrated in Fig. 3. Thus all of the hydrogen-bond donors are satisfied. By contrast, not all of the hydrogen-bond acceptors available to the O atoms of the nitrate anion are utilized, O2 being the only atom to form two interactions, with atoms H3 and H4B. In the cases of atoms O1 and O3, only one hydrogen bond is formed. Details of the hydrogen bonding are given in Table 1.

Figure 1
A view of the molecule of (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are represented by small spheres. [Symmetry code: (i) x + 1, y + 1, z + 1.]

Figure 2
Interactions (dashed lines) forming hydrogen-bonded chains in (I)

Figure 3
Hydrogen-bond interactions (dashed lines) in the formation of the R₆⁵(23) graph set.

Experimental

Equimolar aqueous solutions of bis(1,1,4-trimethylthiosemicarbazide)nickel(II) nitrate (Burrows et al, 2004) and the sodium salt of either succinic or itaconic acid were allowed to evaporate slowly over a period of two weeks. In both cases, the formation of green crystals of (I) resulted. Analysis by single-crystal X-ray diffraction revealed the identity of the products and confirmed that the dicarboxylate was not incorporated into the crystalline material in either case.

Crystal data

[Ni(C₄H₁₁N₃S)₂(H₂O)₂](NO₃)₂
M_r = 485.20
Monoclinic, P 2₁ /c
a = 9.464 (2) Å
b = 12.358 (2) Å
c = 9.775 (2) Å
β = 117.7671 (13)°
V = 1011.60 (4) Å³
Z = 2
D_x = 1.593 Mg m⁻³
Mo Kα radiation
Cell parameters from 1024 reflections
θ = 4.1–27.5°
μ = 1.22 mm⁻¹
T = 170 (2) K
Block, green
0.30 × 0.30 × 0.30 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(Blessing, 1995 )T_min = 0.697, T_max = 0.697
15 566 measured reflections
2317 independent reflections
2203 reflections with I > 2σ(I)
R_int = 0.025
θ_max = 27.5°
h = −12 → 12
k = −15 → 16
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.056
S = 1.06
2317 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0213P)² + 0.4059P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.0133 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3ⁱ	0.862 (15)	1.913 (15)	2.7703 (14)	173 (2)
O4—H4B⋯O2	0.847 (15)	1.875 (16)	2.7074 (14)	167 (2)
N2—H2⋯O1ⁱⁱ	0.866 (13)	2.103 (14)	2.9565 (16)	168.6 (15)
N3—H3⋯O2ⁱⁱ	0.867 (13)	1.990 (14)	2.8551 (15)	175.6 (15)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

The positions of the water, amino and amido H atoms were located in a difference map and refined isotropically, subject to a distance restraint of 0.89 (2) Å. H atoms on all C atoms were included in calculated positions, constrained to an ideal geometry with C—H distances of 0.98 Å and with U_iso(H) = 1.5U_eq(C). Each group was allowed to rotate freely about its C—N bond.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Bruker, 2001 ), printCIF and local programs.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805002965/wk6043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805002965/wk6043Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001), printCIF and local programs.

Diaquabis(1,1,4-trimethylthiosemicarbazide)nickel(II) dinitrate top

Crystal data top

[Ni(C₄H₁₁N₃S)₂(H₂O)₂](NO₃)₂	F(000) = 508
M_r = 485.20	D_x = 1.593 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 1024 reflections
a = 9.4640 (2) Å	θ = 4.1–27.5°
b = 12.3580 (2) Å	µ = 1.22 mm⁻¹
c = 9.7750 (2) Å	T = 170 K
β = 117.7671 (13)°	Block, green
V = 1011.60 (4) Å³	0.30 × 0.30 × 0.30 mm
Z = 2

Data collection top

Nonius KappaCCD area-detector diffractometer	2317 independent reflections
Radiation source: sealed tube	2203 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 27.5°, θ_min = 4.1°
Absorption correction: multi-scan from symmetry-related measurements (Blessing, 1995)	h = −12→12
T_min = 0.697, T_max = 0.697	k = −15→16
15566 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom & difmap
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0213P)² + 0.4059P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2317 reflections	Δρ_max = 0.26 e Å⁻³
144 parameters	Δρ_min = −0.26 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0133 (16)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.01900 (9)
S1	0.45094 (4)	0.47524 (3)	0.71566 (4)	0.02431 (10)
O1	0.01934 (13)	0.22074 (10)	0.58796 (14)	0.0439 (3)
O2	0.09424 (12)	0.32177 (9)	0.45410 (13)	0.0415 (3)
O3	0.24872 (12)	0.19351 (9)	0.59396 (12)	0.0354 (2)
O4	0.30050 (12)	0.40960 (8)	0.36503 (12)	0.0301 (2)
H4A	0.280 (2)	0.3818 (16)	0.2767 (19)	0.056 (6)*
H4B	0.246 (2)	0.3740 (16)	0.398 (2)	0.061 (6)*
N1	0.33577 (12)	0.63500 (9)	0.45151 (12)	0.0229 (2)
N2	0.23053 (14)	0.61040 (10)	0.51535 (13)	0.0275 (2)
H2	0.1510 (17)	0.6543 (13)	0.4910 (19)	0.032 (4)*
N3	0.18327 (14)	0.54724 (10)	0.70802 (13)	0.0276 (2)
H3	0.0975 (17)	0.5861 (13)	0.6625 (18)	0.031 (4)*
N4	0.12171 (13)	0.24468 (9)	0.54663 (12)	0.0265 (2)
C1	0.27924 (15)	0.54831 (10)	0.64284 (14)	0.0224 (2)
C2	0.20559 (18)	0.47758 (13)	0.83646 (17)	0.0328 (3)
H2A	0.1880	0.4021	0.8019	0.049*
H2B	0.1292	0.4978	0.8735	0.049*
H2C	0.3146	0.4860	0.9205	0.049*
C3	0.41701 (18)	0.73925 (11)	0.51787 (18)	0.0325 (3)
H3A	0.3370	0.7965	0.4923	0.049*
H3B	0.4889	0.7575	0.4746	0.049*
H3C	0.4788	0.7325	0.6305	0.049*
C4	0.23263 (17)	0.64895 (12)	0.28301 (16)	0.0315 (3)
H4C	0.1528	0.7051	0.2653	0.047*
H4D	0.1786	0.5805	0.2381	0.047*
H4E	0.2983	0.6705	0.2343	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01794 (13)	0.01924 (14)	0.01906 (13)	−0.00020 (7)	0.00798 (10)	−0.00053 (7)
S1	0.02300 (17)	0.02794 (18)	0.02205 (17)	0.00512 (12)	0.01056 (13)	0.00483 (12)
O1	0.0389 (6)	0.0526 (7)	0.0514 (7)	0.0139 (5)	0.0305 (5)	0.0202 (5)
O2	0.0262 (5)	0.0448 (6)	0.0486 (7)	0.0051 (4)	0.0132 (5)	0.0236 (5)
O3	0.0315 (5)	0.0403 (6)	0.0359 (5)	0.0147 (4)	0.0169 (4)	0.0088 (4)
O4	0.0284 (5)	0.0326 (5)	0.0300 (5)	−0.0108 (4)	0.0143 (4)	−0.0081 (4)
N1	0.0239 (5)	0.0238 (5)	0.0234 (5)	0.0027 (4)	0.0130 (4)	0.0038 (4)
N2	0.0248 (5)	0.0316 (6)	0.0307 (6)	0.0097 (5)	0.0168 (5)	0.0096 (5)
N3	0.0261 (6)	0.0310 (6)	0.0291 (6)	0.0056 (5)	0.0157 (5)	0.0059 (5)
N4	0.0259 (5)	0.0287 (6)	0.0225 (5)	0.0022 (4)	0.0093 (4)	−0.0002 (4)
C1	0.0229 (6)	0.0216 (6)	0.0223 (6)	−0.0006 (5)	0.0102 (5)	−0.0008 (5)
C2	0.0353 (8)	0.0380 (8)	0.0308 (7)	−0.0002 (6)	0.0203 (6)	0.0055 (6)
C3	0.0374 (7)	0.0209 (7)	0.0404 (8)	0.0020 (5)	0.0193 (6)	0.0005 (5)
C4	0.0314 (7)	0.0369 (8)	0.0255 (7)	0.0107 (6)	0.0127 (6)	0.0099 (6)

Geometric parameters (Å, º) top

Ni1—S1	2.3802 (3)	N2—H2	0.866 (13)
Ni1—S1ⁱ	2.3802 (3)	N2—C1	1.3487 (16)
Ni1—O4	2.0573 (10)	N3—H3	0.867 (13)
Ni1—O4ⁱ	2.0573 (10)	N3—C1	1.3305 (16)
Ni1—N1	2.1765 (10)	N3—C2	1.4543 (18)
Ni1—N1ⁱ	2.1765 (10)	C2—H2A	0.9800
S1—C1	1.6985 (13)	C2—H2B	0.9800
O1—N4	1.2467 (15)	C2—H2C	0.9800
O2—N4	1.2547 (15)	C3—H3A	0.9800
O3—N4	1.2412 (14)	C3—H3B	0.9800
O4—H4A	0.862 (15)	C3—H3C	0.9800
O4—H4B	0.847 (15)	C4—H4C	0.9800
N1—N2	1.4328 (14)	C4—H4D	0.9800
N1—C3	1.4857 (17)	C4—H4E	0.9800
N1—C4	1.4823 (17)

S1—Ni1—S1ⁱ	180.0	H3—N3—C1	115.7 (11)
S1—Ni1—O4	89.93 (3)	H3—N3—C2	119.7 (11)
S1ⁱ—Ni1—O4	90.07 (3)	C1—N3—C2	124.22 (12)
S1ⁱ—Ni1—O4ⁱ	89.93 (3)	O1—N4—O2	118.85 (11)
S1—Ni1—O4ⁱ	90.07 (3)	O1—N4—O3	121.48 (11)
S1—Ni1—N1	82.95 (3)	O2—N4—O3	119.67 (11)
S1ⁱ—Ni1—N1ⁱ	82.95 (3)	S1—C1—N2	122.56 (9)
S1ⁱ—Ni1—N1	97.05 (3)	S1—C1—N3	121.82 (10)
S1—Ni1—N1ⁱ	97.05 (3)	N2—C1—N3	115.62 (11)
O4—Ni1—O4ⁱ	180.00 (5)	N3—C2—H2A	109.5
O4—Ni1—N1	85.85 (4)	N3—C2—H2B	109.5
O4—Ni1—N1ⁱ	94.15 (4)	N3—C2—H2C	109.5
O4ⁱ—Ni1—N1ⁱ	85.85 (4)	H2A—C2—H2B	109.5
O4ⁱ—Ni1—N1	94.15 (4)	H2A—C2—H2C	109.5
N1—Ni1—N1ⁱ	180.0	H2B—C2—H2C	109.5
Ni1—S1—C1	95.96 (4)	N1—C3—H3A	109.5
Ni1—O4—H4A	124.9 (14)	N1—C3—H3B	109.5
Ni1—O4—H4B	125.0 (15)	N1—C3—H3C	109.5
H4A—O4—H4B	106 (2)	H3A—C3—H3B	109.5
Ni1—N1—N2	108.26 (7)	H3A—C3—H3C	109.5
Ni1—N1—C3	113.44 (8)	H3B—C3—H3C	109.5
Ni1—N1—C4	111.40 (8)	N1—C4—H4C	109.5
N2—N1—C3	108.49 (10)	N1—C4—H4D	109.5
N2—N1—C4	106.09 (10)	N1—C4—H4E	109.5
C3—N1—C4	108.85 (11)	H4C—C4—H4D	109.5
N1—N2—H2	116.0 (11)	H4C—C4—H4E	109.5
N1—N2—C1	121.02 (10)	H4D—C4—H4E	109.5
H2—N2—C1	119.3 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3ⁱⁱ	0.86 (2)	1.91 (2)	2.7703 (14)	173 (2)
O4—H4B···O2	0.85 (2)	1.88 (2)	2.7074 (14)	167 (2)
N2—H2···O1ⁱⁱⁱ	0.87 (1)	2.10 (1)	2.9565 (16)	169 (2)
N3—H3···O2ⁱⁱⁱ	0.87 (1)	1.99 (1)	2.8551 (15)	176 (2)

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

Footnotes

‡Current address: School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne NE1 7RU, England.

Acknowledgements

The EPSRC is thanked for funding.

References

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