Poly[bis­[μ₂-5-(pyrimidin-2-yl)tetra­zolato]nickel(II)]

In the title compound, [Ni(C₅H₃N₆)₂]_n, the Ni^II atom is located on an inversion centre and exhibits a distorted octa­hedral geometry. The crystal structure features a two-dimensional square-grid-like network. The compound is isostructural with the iron(II) and cobalt(II) analogues, whose structures and magnetic properties have been reported [Rodríguez, Kivekäsb & Colacio (2005). Chem. Commun. pp. 5228–5230].

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.053
• wR factor = 0.105
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.79
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      34.00 A   3 

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.791
            Tmax scaled      0.791 Tmin scaled      0.771
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.15

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Poly[5-(pyrimidin-2-yl)tetrazolato]nickel(II)], (I) (Fig. 1), is isostructural with the iron(II) and cobalt(II) analogs (Rodríguez et al., 2005). The three structures feature a two-dimensional square-grid-like network, in which each metal atom is located on an inversion centre and exhibits a distorted octahedral geometry. Each metal atom bonds to four ligands, and each ligand is coordinated to two metal atoms through one of the pyrimidyl nitrogen atoms and the 1-positon tetrazole nitrogen atom in cis position for one, and one 3-position tetrazole nitrogen atom for the other.

Related literature

For compound preparation, see: Demko & Sharpless (2001). For related literature, see: Rodríguez et al. (2005).

S2. Experimental

The ligand, 2-(1H-tetrazol-5-yl)pyrimidine (L), was synthesized according to the literature method (Demko & Sharpless, 2001). A mixture of NiCl₂.6H₂O (48 mg, 0.2 mmol) and ligand L (60 mg, 0.4 mmol) in water (10 ml) was placed in a Teflon-lined stainless-steel Parr bomb that was heated at 413 K for 72 h. The bomb was then cooled to room temperature. Pink crystals were isolated in about 20% yield.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions (C—H = 0.93 Å) and refined in the riding-model approximation, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Part of the two-dimensional network structure of (I). Displacement ellipsoids are drawn at the 40% probability level. [symmetry codes: (A) -x, 1 - y, 1 - z; (B) 1/2 + x, 1/2 - y, 1 - z.]

Poly[bis[µ₂-5-(pyrimidin-2-yl)tetrazolato]nickel(II)]

Crystal data

[Ni(C5H3N6)2]	F(000) = 712
Mr = 352.98	Dx = 1.745 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3035 reflections
a = 8.2054 (16) Å	θ = 2.5–26.4°
b = 9.1736 (18) Å	µ = 1.47 mm^−1
c = 17.846 (4) Å	T = 293 K
V = 1343.3 (5) Å^3	Block, pink
Z = 4	0.18 × 0.16 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1598 independent reflections
Radiation source: fine-focus sealed tube	1396 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 27.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→9
Tmin = 0.974, Tmax = 1.000	k = −12→10
9528 measured reflections	l = −23→22

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.032P)^2 + 2.6446P] where P = (Fo^2 + 2Fc^2)/3
1598 reflections	(Δ/σ)max = 0.001
106 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.40 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	0.0000	0.5000	0.5000	0.00927 (16)
N1	−0.1491 (3)	0.3232 (3)	0.48286 (15)	0.0130 (6)
C2	−0.0291 (4)	0.3372 (3)	0.35937 (19)	0.0142 (6)
N6	0.0456 (3)	0.4562 (3)	0.38656 (15)	0.0116 (5)
N5	−0.0129 (3)	0.2818 (3)	0.29133 (16)	0.0196 (6)
C5	0.1446 (4)	0.5280 (3)	0.3397 (2)	0.0175 (7)
H5	0.1993	0.6105	0.3565	0.021*
C1	−0.1385 (4)	0.2677 (3)	0.41376 (17)	0.0121 (6)
C4	0.1666 (4)	0.4812 (4)	0.2669 (2)	0.0213 (7)
H4	0.2334	0.5320	0.2338	0.026*
N2	−0.2581 (3)	0.2430 (3)	0.51904 (14)	0.0128 (5)
N4	−0.2388 (3)	0.1549 (3)	0.40478 (15)	0.0148 (6)
C3	0.0857 (4)	0.3563 (4)	0.2450 (2)	0.0236 (8)
H3	0.1000	0.3225	0.1963	0.028*
N3	−0.3114 (3)	0.1428 (3)	0.47178 (16)	0.0126 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0094 (3)	0.0073 (3)	0.0111 (3)	0.0006 (2)	−0.0003 (2)	−0.0005 (2)
N1	0.0116 (12)	0.0106 (11)	0.0169 (15)	0.0001 (10)	0.0008 (10)	−0.0004 (10)
C2	0.0143 (14)	0.0136 (14)	0.0148 (16)	−0.0025 (12)	0.0006 (12)	0.0005 (12)
N6	0.0129 (12)	0.0080 (11)	0.0139 (14)	0.0016 (9)	−0.0010 (10)	0.0007 (9)
N5	0.0216 (15)	0.0220 (14)	0.0153 (15)	−0.0032 (12)	0.0039 (12)	−0.0051 (11)
C5	0.0191 (16)	0.0108 (14)	0.0227 (18)	0.0004 (12)	0.0033 (13)	0.0008 (12)
C1	0.0129 (14)	0.0127 (14)	0.0106 (16)	−0.0006 (12)	0.0002 (12)	−0.0003 (11)
C4	0.0224 (17)	0.0219 (16)	0.0195 (18)	0.0017 (14)	0.0079 (14)	0.0040 (14)
N2	0.0118 (12)	0.0114 (12)	0.0152 (14)	−0.0031 (10)	0.0012 (11)	−0.0004 (10)
N4	0.0157 (13)	0.0153 (12)	0.0134 (14)	−0.0015 (11)	0.0024 (11)	−0.0015 (10)
C3	0.0272 (18)	0.0290 (18)	0.0146 (18)	−0.0029 (16)	0.0060 (14)	−0.0019 (15)
N3	0.0138 (12)	0.0095 (11)	0.0144 (14)	−0.0033 (10)	0.0018 (10)	−0.0013 (10)

Geometric parameters (Å, º)

Ni1—N1^i	2.054 (3)	N6—C5	1.338 (4)
Ni1—N1	2.054 (3)	N5—C3	1.344 (4)
Ni1—N3^ii	2.089 (2)	C5—C4	1.382 (5)
Ni1—N3^iii	2.089 (2)	C5—H5	0.93
Ni1—N6^i	2.098 (3)	C1—N4	1.332 (4)
Ni1—N6	2.098 (3)	C4—C3	1.381 (5)
N1—N2	1.326 (3)	C4—H4	0.93
N1—C1	1.337 (4)	N2—N3	1.322 (4)
C2—N5	1.323 (4)	N4—N3	1.340 (4)
C2—N6	1.343 (4)	C3—H3	0.93
C2—C1	1.468 (4)	N3—Ni1^iv	2.089 (2)
N1^i—Ni1—N1	180	C5—N6—C2	116.8 (3)
N1^i—Ni1—N3^ii	88.98 (10)	C5—N6—Ni1	128.1 (2)
N1—Ni1—N3^ii	91.02 (10)	C2—N6—Ni1	115.0 (2)
N1^i—Ni1—N3^iii	91.02 (10)	C2—N5—C3	115.5 (3)
N1—Ni1—N3^iii	88.98 (10)	N6—C5—C4	121.0 (3)
N3^ii—Ni1—N3^iii	180	N6—C5—H5	119.5
N1^i—Ni1—N6^i	79.12 (10)	C4—C5—H5	119.5
N1—Ni1—N6^i	100.88 (10)	N4—C1—N1	111.5 (3)
N3^ii—Ni1—N6^i	88.87 (10)	N4—C1—C2	129.5 (3)
N3^iii—Ni1—N6^i	91.13 (10)	N1—C1—C2	119.0 (3)
N1^i—Ni1—N6	100.88 (10)	C3—C4—C5	117.4 (3)
N1—Ni1—N6	79.12 (10)	C3—C4—H4	121.3
N3^ii—Ni1—N6	91.13 (10)	C5—C4—H4	121.3
N3^iii—Ni1—N6	88.87 (10)	N3—N2—N1	107.4 (2)
N6^i—Ni1—N6	180	C1—N4—N3	103.4 (2)
N2—N1—C1	106.4 (2)	N5—C3—C4	122.5 (3)
N2—N1—Ni1	140.1 (2)	N5—C3—H3	118.7
C1—N1—Ni1	113.5 (2)	C4—C3—H3	118.7
N5—C2—N6	126.7 (3)	N2—N3—N4	111.4 (2)
N5—C2—C1	120.1 (3)	N2—N3—Ni1^iv	121.8 (2)
N6—C2—C1	113.2 (3)	N4—N3—Ni1^iv	126.6 (2)
N3^ii—Ni1—N1—N2	−85.7 (3)	C2—N6—C5—C4	0.5 (5)
N3^iii—Ni1—N1—N2	94.3 (3)	Ni1—N6—C5—C4	177.2 (2)
N6^i—Ni1—N1—N2	3.4 (3)	N2—N1—C1—N4	0.5 (3)
N6—Ni1—N1—N2	−176.6 (3)	Ni1—N1—C1—N4	−179.06 (19)
N3^ii—Ni1—N1—C1	93.6 (2)	N2—N1—C1—C2	178.4 (3)
N3^iii—Ni1—N1—C1	−86.4 (2)	Ni1—N1—C1—C2	−1.2 (3)
N6^i—Ni1—N1—C1	−177.3 (2)	N5—C2—C1—N4	−4.5 (5)
N6—Ni1—N1—C1	2.7 (2)	N6—C2—C1—N4	175.3 (3)
N5—C2—N6—C5	1.3 (5)	N5—C2—C1—N1	178.0 (3)
C1—C2—N6—C5	−178.4 (3)	N6—C2—C1—N1	−2.2 (4)
N5—C2—N6—Ni1	−175.8 (3)	N6—C5—C4—C3	−1.4 (5)
C1—C2—N6—Ni1	4.4 (3)	C1—N1—N2—N3	−0.4 (3)
N1^i—Ni1—N6—C5	−0.8 (3)	Ni1—N1—N2—N3	178.9 (2)
N1—Ni1—N6—C5	179.2 (3)	N1—C1—N4—N3	−0.3 (3)
N3^ii—Ni1—N6—C5	88.4 (3)	C2—C1—N4—N3	−177.9 (3)
N3^iii—Ni1—N6—C5	−91.6 (3)	C2—N5—C3—C4	0.8 (5)
N1^i—Ni1—N6—C2	176.0 (2)	C5—C4—C3—N5	0.7 (5)
N1—Ni1—N6—C2	−4.0 (2)	N1—N2—N3—N4	0.2 (3)
N3^ii—Ni1—N6—C2	−94.8 (2)	N1—N2—N3—Ni1^iv	−174.80 (18)
N3^iii—Ni1—N6—C2	85.2 (2)	C1—N4—N3—N2	0.0 (3)
N6—C2—N5—C3	−2.0 (5)	C1—N4—N3—Ni1^iv	174.8 (2)
C1—C2—N5—C3	177.8 (3)

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