Tetrakis­(1H-pyrazole-κN²)bis(thio­cyanato-κN)nickel(II)

In the title mononuclear complex, [Ni(NCS)₂(C₃H₄N₂)₄], the six-coordinate Ni^II atom assumes an octa­hedral geometry and is located on an inversion centre. The crystal packing is stabilized by N—H...S, N—H...N and C—H...S hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.093
• Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C1      ..       6.58 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.06

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Metal complexes containing thiocyanate with pyrazole and its derivatives as ligands play a pivotal role in the area of modern coordination chemistry (Zarbaa et al., 2004; Shi et al., 2006). The interest in this area prompted us to synthesize the title complex, and here we report its crystal structure (Fig. 1).

The Ni^II atom lies on an inversion centre and assumes a slightly distorted octahedral geometry (Table 1). Table 2 and Fig. 2 give information on N—H···S, N—H···N and C—H···S hydrogen bonds, which form a supramolecular three-dimensional structure.

Related literature

For related crystal structures, see: Zarbaa et al. (2004); Shi et al. (2006).

S2. Experimental

Pyrazole (0.1053 g, 1.55 mmol), NaNCS (0.0711 g, 0.877 mmol) and Ni(ClO₄)₂.6H₂O (0.1568 g, 0.429 mmol) were dissolved in 3 × 5 ml H₂O, and the three solutions were mixed together and stirred for a few minutes. Blue single crystals were obtained after the mixed solution had been allowed to stand at room temperature for two weeks.

S3. Refinement

H atoms of N—H were located in a difference Fourier map and refined as riding in their as-found positions, with U_iso(H) = 1.2U_eq(N). Other H atoms were placed in calculated positions, and refined as riding, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures

	Fig. 1. The molecular structure of (I) showing the atom numbering scheme with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x + 1/2, -y + 3/2, -z].
	Fig. 2. The hydrogen bonding (dashed lines).

Tetrakis(1H-pyrazole-κN²)bis(thiocyanato-κN)nickel(II)

Crystal data

[Ni(NCS)2(C3H4N2)4]	F(000) = 920
Mr = 447.20	Dx = 1.477 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2696 reflections
a = 14.046 (3) Å	θ = 2.5–26.7°
b = 10.863 (2) Å	µ = 1.19 mm^−1
c = 14.862 (3) Å	T = 298 K
β = 117.485 (2)°	Bar, blue
V = 2011.6 (7) Å^3	0.48 × 0.26 × 0.21 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2188 independent reflections
Radiation source: fine-focus sealed tube	1867 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.598, Tmax = 0.788	k = −13→9
5718 measured reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.6564P] where P = (Fo^2 + 2Fc^2)/3
2188 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

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
Ni1	0.2500	0.7500	0.0000	0.04033 (14)
S1	0.45000 (6)	0.38423 (6)	0.09641 (6)	0.0763 (2)
N1	0.26313 (13)	0.71955 (15)	0.14564 (13)	0.0470 (4)
N3	0.36411 (14)	0.61469 (16)	0.02753 (14)	0.0539 (4)
N2	0.20074 (15)	0.78111 (17)	0.17699 (14)	0.0529 (4)
H1	0.1537	0.8281	0.1356	0.064*
C1	0.40149 (15)	0.51988 (19)	0.05644 (14)	0.0442 (4)
N4	0.37288 (14)	0.88231 (16)	0.05969 (14)	0.0519 (4)
C2	0.32207 (17)	0.6455 (2)	0.22228 (16)	0.0559 (5)
H2	0.3734	0.5911	0.2226	0.067*
N5	0.47618 (16)	0.8519 (2)	0.10443 (19)	0.0836 (7)
H8	0.4916	0.7781	0.1016	0.100*
C5	0.3738 (2)	1.0024 (2)	0.0677 (2)	0.0794 (8)
H5	0.3127	1.0514	0.0437	0.095*
C3	0.2974 (2)	0.6598 (2)	0.30146 (18)	0.0671 (6)
H3	0.3281	0.6189	0.3634	0.081*
C4	0.2183 (2)	0.7468 (2)	0.2695 (2)	0.0658 (7)
H4	0.1835	0.7764	0.3053	0.079*
C7	0.5409 (2)	0.9486 (3)	0.1390 (3)	0.1087 (12)
H7	0.6155	0.9476	0.1722	0.130*
C6	0.4781 (3)	1.0467 (3)	0.1170 (3)	0.1089 (12)
H6	0.4996	1.1284	0.1315	0.131*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0391 (2)	0.0375 (2)	0.0467 (2)	0.00696 (12)	0.02175 (16)	0.00747 (13)
S1	0.0814 (5)	0.0640 (4)	0.0994 (5)	0.0357 (3)	0.0553 (4)	0.0367 (3)
N1	0.0448 (9)	0.0493 (9)	0.0499 (9)	0.0059 (7)	0.0245 (8)	0.0063 (7)
N3	0.0521 (10)	0.0495 (10)	0.0652 (11)	0.0147 (8)	0.0313 (9)	0.0107 (8)
N2	0.0497 (10)	0.0582 (10)	0.0568 (10)	0.0081 (8)	0.0295 (9)	0.0064 (8)
C1	0.0416 (10)	0.0532 (12)	0.0426 (10)	0.0075 (8)	0.0235 (8)	0.0053 (8)
N4	0.0457 (9)	0.0501 (10)	0.0572 (10)	0.0012 (7)	0.0213 (8)	0.0070 (8)
C2	0.0537 (12)	0.0603 (13)	0.0536 (12)	0.0111 (9)	0.0246 (10)	0.0127 (9)
N5	0.0479 (11)	0.0571 (12)	0.120 (2)	0.0010 (9)	0.0165 (12)	0.0125 (12)
C5	0.0638 (15)	0.0527 (14)	0.117 (2)	−0.0021 (11)	0.0375 (16)	−0.0044 (14)
C3	0.0697 (15)	0.0800 (16)	0.0511 (12)	0.0017 (12)	0.0273 (11)	0.0135 (11)
C4	0.0672 (15)	0.0827 (18)	0.0581 (14)	−0.0035 (11)	0.0379 (13)	−0.0009 (11)
C7	0.0530 (15)	0.0742 (19)	0.160 (3)	−0.0144 (14)	0.0157 (18)	0.001 (2)
C6	0.081 (2)	0.0628 (18)	0.161 (3)	−0.0235 (16)	0.037 (2)	−0.015 (2)

Geometric parameters (Å, º)

Ni1—N3^i	2.0716 (16)	N4—N5	1.329 (3)
Ni1—N3	2.0716 (16)	C2—C3	1.381 (3)
Ni1—N4^i	2.1020 (17)	C2—H2	0.930
Ni1—N4	2.1020 (17)	N5—C7	1.327 (3)
Ni1—N1^i	2.1120 (17)	N5—H8	0.8361
Ni1—N1	2.1120 (17)	C5—C6	1.387 (4)
S1—C1	1.617 (2)	C5—H5	0.930
N1—C2	1.326 (2)	C3—C4	1.366 (4)
N1—N2	1.345 (2)	C3—H3	0.930
N3—C1	1.146 (2)	C4—H4	0.930
N2—C4	1.333 (3)	C7—C6	1.324 (4)
N2—H1	0.8364	C7—H7	0.930
N4—C5	1.309 (3)	C6—H6	0.930
N3^i—Ni1—N3	180.0	C5—N4—Ni1	133.71 (17)
N3^i—Ni1—N4^i	89.54 (8)	N5—N4—Ni1	122.36 (14)
N3—Ni1—N4^i	90.46 (8)	N1—C2—C3	111.2 (2)
N3^i—Ni1—N4	90.46 (8)	N1—C2—H2	124.4
N3—Ni1—N4	89.54 (8)	C3—C2—H2	124.4
N4^i—Ni1—N4	180.00 (7)	C7—N5—N4	113.0 (2)
N3^i—Ni1—N1^i	89.59 (7)	C7—N5—H8	129.1
N3—Ni1—N1^i	90.41 (7)	N4—N5—H8	117.5
N4^i—Ni1—N1^i	90.47 (7)	N4—C5—C6	110.9 (3)
N4—Ni1—N1^i	89.53 (7)	N4—C5—H5	124.6
N3^i—Ni1—N1	90.41 (7)	C6—C5—H5	124.6
N3—Ni1—N1	89.59 (7)	C4—C3—C2	105.4 (2)
N4^i—Ni1—N1	89.53 (7)	C4—C3—H3	127.3
N4—Ni1—N1	90.47 (7)	C2—C3—H3	127.3
N1^i—Ni1—N1	180.00 (9)	N2—C4—C3	106.6 (2)
C2—N1—N2	104.61 (17)	N2—C4—H4	126.7
C2—N1—Ni1	134.41 (15)	C3—C4—H4	126.7
N2—N1—Ni1	120.96 (13)	C6—C7—N5	106.4 (3)
C1—N3—Ni1	152.96 (16)	C6—C7—H7	126.8
C4—N2—N1	112.21 (18)	N5—C7—H7	126.8
C4—N2—H1	129.5	C7—C6—C5	105.8 (3)
N1—N2—H1	117.9	C7—C6—H6	127.1
N3—C1—S1	177.92 (19)	C5—C6—H6	127.1
C5—N4—N5	103.89 (19)
N3^i—Ni1—N1—C2	−178.9 (2)	N1—Ni1—N4—C5	−95.1 (3)
N3—Ni1—N1—C2	1.1 (2)	N3^i—Ni1—N4—N5	172.6 (2)
N4^i—Ni1—N1—C2	91.5 (2)	N3—Ni1—N4—N5	−7.4 (2)
N4—Ni1—N1—C2	−88.5 (2)	N1^i—Ni1—N4—N5	−97.82 (19)
N3^i—Ni1—N1—N2	2.81 (16)	N1—Ni1—N4—N5	82.18 (19)
N3—Ni1—N1—N2	−177.19 (16)	N2—N1—C2—C3	0.1 (3)
N4^i—Ni1—N1—N2	−86.73 (16)	Ni1—N1—C2—C3	−178.42 (16)
N4—Ni1—N1—N2	93.27 (16)	C5—N4—N5—C7	−0.5 (4)
N4^i—Ni1—N3—C1	−45.5 (4)	Ni1—N4—N5—C7	−178.5 (2)
N4—Ni1—N3—C1	134.5 (4)	N5—N4—C5—C6	0.5 (4)
N1^i—Ni1—N3—C1	−136.0 (4)	Ni1—N4—C5—C6	178.1 (2)
N1—Ni1—N3—C1	44.0 (4)	N1—C2—C3—C4	0.5 (3)
C2—N1—N2—C4	−0.7 (3)	N1—N2—C4—C3	1.0 (3)
Ni1—N1—N2—C4	178.07 (15)	C2—C3—C4—N2	−0.9 (3)
N3^i—Ni1—N4—C5	−4.7 (3)	N4—N5—C7—C6	0.4 (4)
N3—Ni1—N4—C5	175.3 (3)	N5—C7—C6—C5	−0.1 (5)
N1^i—Ni1—N4—C5	84.9 (3)	N4—C5—C6—C7	−0.2 (5)

Symmetry code: (i) −x+1/2, −y+3/2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N3^i	0.84	2.40	2.966 (3)	125
N2—H1···S1^ii	0.84	2.71	3.346 (2)	134
C6—H6···S1^iii	0.93	2.85	3.686 (3)	150

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) x−1/2, y+1/2, z; (iii) x, y+1, z.