Poly[bis-(methanol-κO)tris-(μ-pyrimidine-κN:N')tetra-kis(thio-cyanato-κN)dinickel(II)].

In the crystal structure of the title compound, [Ni(2)(NCS)(4)(C(4)H(4)N(2))(3)(CH(3)OH)(2)](n), each nickel(II) cation is coordinated by three N-bonded pyrimidine ligands, two N-bonded thio-cyanate anions and one O-bonded methanol mol-ecule in a distorted octa-hedral environment. The asymmetric unit consists of one nickel cation, two thio-cyanate anions and one methanol mol-ecule in general positions, as well as one pyrimidine ligand located around a twofold rotation axis. The crystal structure consists of μ-N:N' pyrimidine-bridged zigzag-like nickel thio-cyanate chains; these are further linked by μ-N:N-bridging pyrimidine ligands into layers which are stacked perpendicular to the b axis. The layers are connected via weak O-H⋯S hydrogen bonding.

Related literature

For related pyrimidine structures, see: Lloret et al. (1998 ▶); Näther et al. (2007 ▶); Näther & Greve (2003 ▶). For general background, see: Wriedt et al. (2008 ▶) and literature cited therein.

Experimental

Crystal data

[Ni2(NCS)4(C4H4N2)3(CH4O)2]

M = 654.10

Orthorhombic,

a = 20.0624 (4) Å

b = 32.5018 (6) Å

c = 8.0268 (2) Å

V = 5233.99 (19) Å3

Z = 8

Mo Kα radiation

μ = 1.80 mm−1

T = 80 K

0.19 × 0.09 × 0.03 mm

Data collection

Stoe IPDS-2 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.813, T max = 0.936

26228 measured reflections

3743 independent reflections

3659 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.048

S = 1.09

3743 reflections

170 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1746 Friedel pairs

Flack parameter: 0.092 (7)

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▶; 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: XCIF in SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005674/si2156sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005674/si2156Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni2(NCS)4(C4H4N2)3(CH4O)2]	F(000) = 2672
Mr = 654.10	Dx = 1.660 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 26829 reflections
a = 20.0624 (4) Å	θ = 2.4–30.2°
b = 32.5018 (6) Å	µ = 1.80 mm−1
c = 8.0268 (2) Å	T = 80 K
V = 5233.99 (19) Å3	Needle, green
Z = 8	0.19 × 0.09 × 0.03 mm

Stoe IPDS-2 diffractometer	3743 independent reflections
Radiation source: fine-focus sealed tube	3659 reflections with I > 2σ(I)
graphite	Rint = 0.043
ω scans	θmax = 29.8°, θmin = 2.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −28→28
Tmin = 0.813, Tmax = 0.936	k = −45→45
26228 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.048	w = 1/[σ2(Fo2) + (0.0258P)2 + 3.6623P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
3743 reflections	Δρmax = 0.34 e Å−3
170 parameters	Δρmin = −0.21 e Å−3
1 restraint	Absolute structure: Flack (1983), 1746 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.0917 (74)

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	Uiso*/Ueq
Ni1	0.606548 (9)	0.227000 (5)	0.78384 (2)	0.01902 (4)
N1	0.55175 (7)	0.27249 (4)	0.65206 (17)	0.0215 (2)
N2	0.47332 (7)	0.29025 (4)	0.44204 (17)	0.0223 (2)
C1	0.50701 (7)	0.26330 (4)	0.5344 (2)	0.0221 (2)
H1	0.4985	0.2350	0.5149	0.026*
C2	0.48569 (8)	0.33035 (5)	0.4691 (2)	0.0254 (3)
H2	0.4634	0.3505	0.4036	0.030*
C3	0.52997 (9)	0.34281 (5)	0.5898 (2)	0.0270 (3)
H3	0.5379	0.3712	0.6103	0.032*
C4	0.56250 (9)	0.31286 (5)	0.6799 (2)	0.0256 (3)
H4	0.5933	0.3208	0.7638	0.031*
N11	0.69268 (6)	0.24119 (4)	0.64396 (16)	0.0216 (2)
C11	0.7500	0.2500	0.7204 (3)	0.0221 (4)
H11	0.7500	0.2500	0.8388	0.027*
C13	0.7500	0.2500	0.3882 (3)	0.0322 (5)
H13	0.7500	0.2500	0.2698	0.039*
C14	0.69298 (8)	0.24151 (6)	0.4778 (2)	0.0275 (3)
H14	0.6528	0.2357	0.4196	0.033*
N21	0.58003 (7)	0.18291 (4)	0.61601 (18)	0.0257 (3)
C21	0.55990 (7)	0.15388 (4)	0.5486 (2)	0.0223 (3)
S21	0.53215 (3)	0.113396 (13)	0.45037 (6)	0.03346 (9)
N31	0.63443 (7)	0.26781 (4)	0.96274 (18)	0.0249 (3)
C31	0.63460 (8)	0.29113 (5)	1.07238 (19)	0.0228 (3)
S31	0.63423 (3)	0.323347 (15)	1.22718 (6)	0.03821 (11)
O41	0.66278 (7)	0.18126 (4)	0.90523 (16)	0.0300 (3)
C41	0.67557 (12)	0.17680 (6)	1.0780 (3)	0.0418 (5)
H41A	0.6591	0.2011	1.1375	0.063*
H41B	0.7237	0.1740	1.0962	0.063*
H41C	0.6528	0.1522	1.1198	0.063*
H1O4	0.6830 (14)	0.1640 (8)	0.854 (3)	0.047 (7)*

	U11	U22	U33	U12	U13	U23
Ni1	0.01457 (7)	0.02028 (8)	0.02220 (8)	−0.00051 (7)	−0.00029 (7)	−0.00255 (7)
N1	0.0171 (6)	0.0219 (6)	0.0254 (6)	−0.0014 (4)	−0.0012 (4)	0.0006 (5)
N2	0.0169 (6)	0.0217 (5)	0.0282 (6)	−0.0005 (5)	−0.0006 (5)	0.0003 (5)
C1	0.0175 (6)	0.0196 (5)	0.0291 (6)	−0.0006 (4)	−0.0011 (6)	−0.0018 (6)
C2	0.0253 (8)	0.0222 (6)	0.0287 (7)	0.0000 (5)	0.0014 (6)	0.0019 (6)
C3	0.0329 (9)	0.0193 (6)	0.0287 (7)	−0.0039 (6)	0.0002 (6)	−0.0016 (5)
C4	0.0276 (8)	0.0239 (6)	0.0254 (7)	−0.0048 (6)	−0.0021 (6)	−0.0014 (5)
N11	0.0165 (6)	0.0253 (6)	0.0231 (6)	−0.0003 (5)	0.0005 (5)	−0.0011 (4)
C11	0.0173 (9)	0.0262 (9)	0.0230 (9)	0.0002 (7)	0.000	0.000
C13	0.0257 (12)	0.0499 (15)	0.0208 (10)	−0.0044 (10)	0.000	0.000
C14	0.0202 (7)	0.0376 (8)	0.0247 (7)	−0.0016 (6)	−0.0022 (6)	−0.0019 (6)
N21	0.0230 (6)	0.0245 (6)	0.0296 (7)	−0.0003 (5)	−0.0028 (5)	−0.0053 (5)
C21	0.0183 (6)	0.0246 (6)	0.0239 (6)	0.0029 (5)	0.0015 (5)	0.0018 (5)
S21	0.0355 (2)	0.02680 (18)	0.0381 (2)	−0.00436 (16)	−0.00331 (18)	−0.00964 (16)
N31	0.0222 (6)	0.0263 (6)	0.0262 (6)	−0.0024 (5)	0.0006 (5)	−0.0035 (5)
C31	0.0177 (6)	0.0241 (6)	0.0265 (8)	−0.0009 (5)	0.0005 (5)	0.0012 (5)
S31	0.0431 (3)	0.0360 (2)	0.0355 (2)	−0.00220 (19)	0.00501 (19)	−0.01510 (18)
O41	0.0285 (6)	0.0306 (6)	0.0308 (6)	0.0096 (5)	−0.0014 (5)	0.0020 (5)
C41	0.0516 (12)	0.0336 (9)	0.0403 (10)	0.0021 (8)	−0.0217 (9)	0.0030 (7)

Ni1—N31	2.0334 (14)	N11—C14	1.334 (2)
Ni1—N21	2.0376 (13)	N11—C11	1.3346 (16)
Ni1—O41	2.1053 (12)	C11—N11iii	1.3346 (16)
Ni1—N11	2.1118 (13)	C11—H11	0.9500
Ni1—N2i	2.1200 (13)	C13—C14	1.379 (2)
Ni1—N1	2.1244 (13)	C13—C14iii	1.379 (2)
N1—C1	1.337 (2)	C13—H13	0.9500
N1—C4	1.348 (2)	C14—H14	0.9500
N2—C1	1.332 (2)	N21—C21	1.160 (2)
N2—C2	1.3444 (19)	C21—S21	1.6320 (16)
N2—Ni1ii	2.1200 (13)	N31—C31	1.161 (2)
C1—H1	0.9500	C31—S31	1.6250 (16)
C2—C3	1.376 (2)	O41—C41	1.418 (2)
C2—H2	0.9500	O41—H1O4	0.80 (3)
C3—C4	1.377 (2)	C41—H41A	0.9800
C3—H3	0.9500	C41—H41B	0.9800
C4—H4	0.9500	C41—H41C	0.9800
N31—Ni1—N21	176.02 (6)	C4—C3—H3	121.0
N31—Ni1—O41	89.22 (6)	N1—C4—C3	121.66 (15)
N21—Ni1—O41	87.09 (5)	N1—C4—H4	119.2
N31—Ni1—N11	90.45 (5)	C3—C4—H4	119.2
N21—Ni1—N11	90.90 (6)	C14—N11—C11	117.02 (16)
O41—Ni1—N11	87.81 (5)	C14—N11—Ni1	122.48 (11)
N31—Ni1—N2i	87.56 (5)	C11—N11—Ni1	120.49 (12)
N21—Ni1—N2i	90.73 (5)	N11—C11—N11iii	125.2 (2)
O41—Ni1—N2i	86.62 (5)	N11—C11—H11	117.4
N11—Ni1—N2i	174.11 (5)	N11iii—C11—H11	117.4
N31—Ni1—N1	92.29 (5)	C14—C13—C14iii	117.1 (2)
N21—Ni1—N1	91.44 (5)	C14—C13—H13	121.4
O41—Ni1—N1	177.66 (5)	C14iii—C13—H13	121.4
N11—Ni1—N1	90.39 (5)	N11—C14—C13	121.79 (16)
N2i—Ni1—N1	95.23 (5)	N11—C14—H14	119.1
C1—N1—C4	116.23 (14)	C13—C14—H14	119.1
C1—N1—Ni1	122.94 (10)	C21—N21—Ni1	166.20 (14)
C4—N1—Ni1	120.79 (11)	N21—C21—S21	178.86 (16)
C1—N2—C2	117.01 (14)	C31—N31—Ni1	164.08 (13)
C1—N2—Ni1ii	122.90 (10)	N31—C31—S31	179.26 (16)
C2—N2—Ni1ii	119.50 (11)	C41—O41—Ni1	128.45 (12)
N2—C1—N1	125.96 (13)	C41—O41—H1O4	110 (2)
N2—C1—H1	117.0	Ni1—O41—H1O4	121.7 (19)
N1—C1—H1	117.0	O41—C41—H41A	109.5
N2—C2—C3	121.22 (15)	O41—C41—H41B	109.5
N2—C2—H2	119.4	H41A—C41—H41B	109.5
C3—C2—H2	119.4	O41—C41—H41C	109.5
C2—C3—C4	117.90 (14)	H41A—C41—H41C	109.5
C2—C3—H3	121.0	H41B—C41—H41C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O41—H1O4···S21iv	0.80 (3)	2.50 (3)	3.2474 (14)	154 (2)

Table 1

Selected geometric parameters (Å, °)

Ni1—N31	2.0334 (14)
Ni1—N21	2.0376 (13)
Ni1—O41	2.1053 (12)
Ni1—N11	2.1118 (13)
Ni1—N2i	2.1200 (13)
Ni1—N1	2.1244 (13)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O41—H1O4⋯S21ii	0.80 (3)	2.50 (3)	3.2474 (14)	154 (2)

Symmetry code: (ii) .