Pyridinium bis-(pyridine-κN)tetra-kis-(thio-cyanato-κN)ferrate(III).

In the title compound, (C5H6N)[Fe(NCS)4(C5H5N)2], the Fe(III) ion is coordinated by four thio-cyanate N atoms and two pyridine N atoms in a trans arrangement, forming an FeN6 polyhedron with a slightly distorted octa-hedral geometry. Charge balance is achieved by one pyridinium cation bound to the complex anion via N-H⋯S hydrogen bonding. The asymmetric unit consists of one Fe(III) cation, four thio-cyanate anions, two coordinated pyridine mol-ecules and one pyridinium cation. The structure exhibits π-π inter-actions between pyridine rings [centroid-centroid distances = 3.7267 (2), 3.7811 (2) and 3.8924 (2) Å]. The N atom and a neighboring C atom of the pyridinium cation are statistically disordered with an occupancy ratio of 0.58 (2):0.42 (2).

Related literature

For the use of materials with mol­ecular assemblies comprising cationic and anionic modules, see: Fritsky et al. (1998 ▶, 2004 ▶); Strotmeyer et al. (2003 ▶); Kanderal et al. (2005 ▶). For FeII–thio­cyanate complexes with aromatic N-donor ligands indicating spin crossover, see: Gamez et al. (2009 ▶). For related structures, see: Petrusenko et al. (1997 ▶); Moroz et al. (2010 ▶); Penkova et al. (2010 ▶); Shylin et al. (2013 ▶).

Experimental

Crystal data

(C5H6N)[Fe(NCS)4(C5H5N)2]

M = 526.48

Monoclinic,

a = 10.7650 (7) Å

b = 14.0424 (8) Å

c = 15.7266 (9) Å

β = 103.244 (3)°

V = 2314.1 (2) Å3

Z = 4

Mo Kα radiation

μ = 1.03 mm−1

T = 120 K

0.21 × 0.14 × 0.07 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.814, T max = 0.929

17377 measured reflections

4739 independent reflections

3027 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.065

S = 0.92

4739 reflections

281 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1997 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813011628/xu5698sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011628/xu5698Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813011628/xu5698Isup3.cdx

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

(C5H6N)[Fe(NCS)4(C5H5N)2]	F(000) = 1076
Mr = 526.48	Dx = 1.511 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3249 reflections
a = 10.7650 (7) Å	θ = 2.5–26.9°
b = 14.0424 (8) Å	µ = 1.03 mm−1
c = 15.7266 (9) Å	T = 120 K
β = 103.244 (3)°	Block, red
V = 2314.1 (2) Å3	0.21 × 0.14 × 0.07 mm
Z = 4

Bruker Kappa APEXII DUO CCD diffractometer	4739 independent reflections
Radiation source: fine-focus sealed tube	3027 reflections with I > 2σ(I)
Curved graphite crystal monochromator	Rint = 0.065
Detector resolution: 16 pixels mm-1	θmax = 26.4°, θmin = 2.0°
φ scans and ω scans with κ offset	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −17→17
Tmin = 0.814, Tmax = 0.929	l = −19→16
17377 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065	H-atom parameters constrained
S = 0.92	w = 1/[σ2(Fo2) + (0.024P)2] where P = (Fo2 + 2Fc2)/3
4739 reflections	(Δ/σ)max = 0.001
281 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.36 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	Uiso*/Ueq	Occ. (<1)
Fe1	0.02757 (4)	0.74386 (2)	0.35673 (2)	0.01575 (10)
S1	−0.26742 (7)	0.99542 (5)	0.35060 (4)	0.02555 (18)
S2	0.33249 (7)	0.49516 (5)	0.37979 (4)	0.02563 (18)
S3	0.41585 (7)	0.90657 (5)	0.34609 (4)	0.02646 (18)
S4	−0.37170 (7)	0.61072 (5)	0.37071 (5)	0.03125 (19)
N1	−0.02004 (18)	0.75765 (14)	0.21626 (11)	0.0158 (5)
N2	0.0714 (2)	0.71819 (13)	0.49668 (12)	0.0160 (5)
N3	−0.0733 (2)	0.86076 (15)	0.37176 (13)	0.0227 (5)
N4	0.1344 (2)	0.62743 (14)	0.34665 (13)	0.0212 (5)
N5	0.1848 (2)	0.82818 (14)	0.36327 (12)	0.0204 (5)
N6	−0.1316 (2)	0.66311 (14)	0.34861 (13)	0.0224 (5)
N7	0.2005 (2)	0.26981 (16)	0.34397 (14)	0.0236 (7)	0.58 (2)
H7A	0.1943	0.3257	0.3180	0.028*	0.58 (2)
N7A	0.2499 (2)	0.26424 (16)	0.43092 (15)	0.0236 (7)	0.42 (2)
H7AA	0.2757	0.3165	0.4606	0.028*	0.42 (2)
C12	0.2170 (3)	0.57121 (17)	0.36058 (15)	0.0181 (6)
C14	−0.2322 (3)	0.64138 (17)	0.35776 (15)	0.0185 (6)
C11	−0.1543 (3)	0.91796 (17)	0.36277 (14)	0.0171 (6)
C13	0.2810 (3)	0.86161 (17)	0.35567 (15)	0.0183 (6)
C5	−0.0212 (2)	0.68043 (17)	0.16522 (15)	0.0185 (6)
H5	0.0013	0.6204	0.1923	0.022*
C1	−0.0523 (2)	0.84165 (17)	0.17635 (15)	0.0192 (6)
H1	−0.0526	0.8967	0.2114	0.023*
C15	0.2499 (2)	0.26424 (16)	0.43092 (15)	0.0236 (7)	0.58 (2)
H15	0.2777	0.3207	0.4630	0.028*	0.58 (2)
C15A	0.2005 (2)	0.26981 (16)	0.34397 (14)	0.0236 (7)	0.42 (2)
H15A	0.1938	0.3301	0.3159	0.028*	0.42 (2)
C6	0.1024 (2)	0.78922 (17)	0.55371 (15)	0.0187 (6)
H6	0.1088	0.8517	0.5320	0.022*
C10	0.0651 (3)	0.63017 (18)	0.52842 (16)	0.0220 (6)
H10	0.0438	0.5788	0.4884	0.026*
C4	−0.0536 (2)	0.68502 (18)	0.07530 (15)	0.0207 (6)
H4	−0.0546	0.6290	0.0413	0.025*
C3	−0.0846 (2)	0.77183 (18)	0.03525 (16)	0.0232 (6)
H3	−0.1053	0.7768	−0.0266	0.028*
C8	0.1183 (3)	0.68517 (18)	0.67526 (16)	0.0246 (6)
H8	0.1336	0.6740	0.7364	0.030*
C7	0.1258 (3)	0.77584 (17)	0.64337 (15)	0.0227 (6)
H7	0.1466	0.8283	0.6821	0.027*
C2	−0.0849 (2)	0.85126 (18)	0.08662 (15)	0.0208 (6)
H2	−0.1073	0.9118	0.0607	0.025*
C16	0.2603 (3)	0.18020 (18)	0.47284 (17)	0.0272 (7)
H16	0.2947	0.1771	0.5341	0.033*
C19	0.1606 (3)	0.19118 (18)	0.29654 (17)	0.0268 (7)
H19	0.1259	0.1959	0.2355	0.032*
C9	0.0882 (3)	0.61079 (18)	0.61679 (16)	0.0245 (7)
H9	0.0834	0.5474	0.6369	0.029*
C17	0.2203 (3)	0.09859 (19)	0.42586 (17)	0.0303 (7)
H17	0.2271	0.0387	0.4546	0.036*
C18	0.1707 (3)	0.10391 (18)	0.33741 (17)	0.0301 (7)
H18	0.1436	0.0478	0.3047	0.036*

	U11	U22	U33	U12	U13	U23
Fe1	0.01694 (19)	0.01441 (19)	0.01572 (17)	0.00150 (16)	0.00334 (13)	−0.00003 (15)
S1	0.0250 (4)	0.0179 (4)	0.0332 (4)	0.0067 (3)	0.0055 (3)	0.0014 (3)
S2	0.0244 (4)	0.0204 (4)	0.0326 (4)	0.0075 (3)	0.0075 (3)	0.0044 (3)
S3	0.0224 (4)	0.0271 (4)	0.0307 (4)	−0.0042 (3)	0.0077 (3)	0.0048 (3)
S4	0.0240 (4)	0.0326 (4)	0.0386 (4)	−0.0042 (3)	0.0104 (3)	0.0080 (3)
N1	0.0135 (12)	0.0135 (11)	0.0204 (11)	−0.0022 (9)	0.0042 (8)	−0.0012 (9)
N2	0.0197 (13)	0.0120 (11)	0.0163 (10)	−0.0010 (9)	0.0039 (9)	0.0003 (9)
N3	0.0276 (14)	0.0194 (12)	0.0216 (12)	0.0044 (11)	0.0071 (10)	0.0003 (10)
N6	0.0251 (15)	0.0219 (12)	0.0192 (12)	−0.0014 (11)	0.0030 (10)	0.0001 (10)
N5	0.0216 (14)	0.0203 (12)	0.0187 (11)	−0.0004 (10)	0.0033 (9)	0.0013 (9)
N4	0.0239 (14)	0.0186 (12)	0.0209 (12)	0.0031 (11)	0.0048 (10)	−0.0014 (10)
C12	0.0216 (16)	0.0162 (14)	0.0165 (13)	−0.0051 (12)	0.0044 (11)	−0.0002 (11)
C14	0.0257 (18)	0.0139 (14)	0.0145 (13)	0.0025 (12)	0.0014 (12)	−0.0010 (11)
C11	0.0233 (16)	0.0172 (14)	0.0105 (12)	−0.0051 (12)	0.0033 (11)	−0.0020 (10)
C13	0.0258 (17)	0.0151 (13)	0.0133 (13)	0.0056 (13)	0.0026 (11)	0.0011 (11)
C5	0.0186 (15)	0.0141 (13)	0.0223 (14)	−0.0044 (12)	0.0037 (11)	−0.0004 (11)
C1	0.0206 (16)	0.0148 (14)	0.0223 (14)	−0.0033 (12)	0.0055 (11)	−0.0003 (11)
C15	0.0283 (16)	0.0215 (15)	0.0229 (14)	−0.0032 (12)	0.0100 (11)	−0.0042 (11)
N7	0.0261 (15)	0.0195 (14)	0.0273 (15)	0.0031 (11)	0.0102 (11)	0.0026 (11)
N7A	0.0283 (16)	0.0215 (15)	0.0229 (14)	−0.0032 (12)	0.0100 (11)	−0.0042 (11)
C15A	0.0261 (15)	0.0195 (14)	0.0273 (15)	0.0031 (11)	0.0102 (11)	0.0026 (11)
C6	0.0186 (15)	0.0144 (13)	0.0233 (14)	−0.0005 (11)	0.0051 (11)	0.0013 (11)
C10	0.0243 (16)	0.0194 (14)	0.0220 (14)	−0.0008 (12)	0.0047 (12)	0.0002 (12)
C4	0.0211 (16)	0.0198 (15)	0.0209 (14)	−0.0049 (12)	0.0041 (11)	−0.0082 (12)
C3	0.0217 (16)	0.0288 (16)	0.0177 (13)	−0.0087 (12)	0.0014 (11)	0.0024 (12)
C8	0.0242 (17)	0.0326 (16)	0.0171 (13)	0.0022 (13)	0.0047 (12)	0.0040 (13)
C7	0.0249 (16)	0.0229 (15)	0.0189 (14)	−0.0007 (12)	0.0023 (12)	−0.0060 (12)
C2	0.0207 (16)	0.0189 (14)	0.0223 (14)	−0.0019 (12)	0.0036 (12)	0.0037 (12)
C16	0.0354 (19)	0.0279 (16)	0.0213 (14)	0.0020 (14)	0.0125 (13)	0.0014 (13)
C19	0.0294 (18)	0.0295 (16)	0.0231 (14)	0.0027 (14)	0.0094 (12)	−0.0024 (13)
C9	0.0303 (17)	0.0186 (15)	0.0248 (15)	0.0010 (13)	0.0065 (12)	0.0079 (12)
C17	0.044 (2)	0.0209 (16)	0.0305 (16)	0.0029 (14)	0.0187 (14)	0.0070 (13)
C18	0.041 (2)	0.0208 (16)	0.0314 (16)	−0.0046 (14)	0.0131 (14)	−0.0068 (13)

Fe1—N1	2.1591 (18)	C15—H15	0.9500
Fe1—N2	2.1727 (19)	N7—C19	1.346 (3)
Fe1—N3	2.012 (2)	N7—H7A	0.8800
Fe1—N4	2.026 (2)	C6—C7	1.387 (3)
Fe1—N5	2.049 (2)	C6—H6	0.9500
Fe1—N6	2.034 (2)	C10—C9	1.382 (3)
S1—C11	1.611 (3)	C10—H10	0.9500
S2—C12	1.614 (3)	C4—C3	1.377 (3)
S3—C13	1.621 (3)	C4—H4	0.9500
S4—C14	1.620 (3)	C3—C2	1.378 (3)
N1—C1	1.344 (3)	C3—H3	0.9500
N1—C5	1.347 (3)	C8—C7	1.378 (3)
N2—C6	1.332 (3)	C8—C9	1.380 (3)
N2—C10	1.341 (3)	C8—H8	0.9500
N3—C11	1.170 (3)	C7—H7	0.9500
N6—C14	1.165 (3)	C2—H2	0.9500
N5—C13	1.168 (3)	C16—C17	1.378 (3)
N4—C12	1.172 (3)	C16—H16	0.9500
C5—C4	1.378 (3)	C19—C18	1.377 (3)
C5—H5	0.9500	C19—H19	0.9500
C1—C2	1.380 (3)	C9—H9	0.9500
C1—H1	0.9500	C17—C18	1.373 (4)
C15—C16	1.344 (3)	C17—H17	0.9500
C15—N7	1.351 (3)	C18—H18	0.9500
N3—Fe1—N4	177.50 (9)	C19—N7—H7A	119.5
N3—Fe1—N6	89.58 (9)	C15—N7—H7A	119.5
N4—Fe1—N6	91.74 (9)	N2—C6—C7	122.8 (2)
N3—Fe1—N5	89.11 (9)	N2—C6—H6	118.6
N4—Fe1—N5	89.60 (9)	C7—C6—H6	118.6
N6—Fe1—N5	178.43 (9)	N2—C10—C9	122.9 (2)
N3—Fe1—N1	92.24 (8)	N2—C10—H10	118.5
N4—Fe1—N1	89.90 (8)	C9—C10—H10	118.5
N6—Fe1—N1	89.24 (8)	C3—C4—C5	119.2 (2)
N5—Fe1—N1	89.96 (8)	C3—C4—H4	120.4
N3—Fe1—N2	90.81 (8)	C5—C4—H4	120.4
N4—Fe1—N2	87.13 (8)	C4—C3—C2	118.8 (2)
N6—Fe1—N2	87.45 (8)	C4—C3—H3	120.6
N5—Fe1—N2	93.43 (8)	C2—C3—H3	120.6
N1—Fe1—N2	175.48 (7)	C7—C8—C9	118.8 (2)
C1—N1—C5	117.51 (19)	C7—C8—H8	120.6
C1—N1—Fe1	122.14 (16)	C9—C8—H8	120.6
C5—N1—Fe1	120.33 (15)	C8—C7—C6	118.9 (2)
C6—N2—C10	117.8 (2)	C8—C7—H7	120.6
C6—N2—Fe1	121.38 (15)	C6—C7—H7	120.6
C10—N2—Fe1	120.83 (15)	C3—C2—C1	119.1 (2)
C11—N3—Fe1	162.43 (19)	C3—C2—H2	120.5
C14—N6—Fe1	158.7 (2)	C1—C2—H2	120.5
C13—N5—Fe1	165.7 (2)	C15—C16—C17	119.1 (2)
C12—N4—Fe1	161.67 (19)	C15—C16—H16	120.4
N4—C12—S2	179.0 (2)	C17—C16—H16	120.4
N6—C14—S4	179.7 (3)	N7—C19—C18	119.4 (2)
N3—C11—S1	179.1 (2)	N7—C19—H19	120.3
N5—C13—S3	179.0 (2)	C18—C19—H19	120.3
N1—C5—C4	122.6 (2)	C8—C9—C10	118.8 (2)
N1—C5—H5	118.7	C8—C9—H9	120.6
C4—C5—H5	118.7	C10—C9—H9	120.6
N1—C1—C2	122.8 (2)	C18—C17—C16	119.9 (2)
N1—C1—H1	118.6	C18—C17—H17	120.0
C2—C1—H1	118.6	C16—C17—H17	120.0
C16—C15—N7	121.1 (2)	C17—C18—C19	119.5 (2)
C16—C15—H15	119.4	C17—C18—H18	120.3
N7—C15—H15	119.4	C19—C18—H18	120.3
C19—N7—C15	121.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···S3i	0.88	2.82	3.532 (2)	139
N7—H7A···S2	0.88	2.86	3.462 (2)	127
N7A—H7AA···S4ii	0.88	2.81	3.558 (2)	144
N7A—H7AA···S2	0.88	2.94	3.504 (2)	124

Table 1

Selected bond lengths (Å)

Fe1—N1	2.1591 (18)
Fe1—N2	2.1727 (19)
Fe1—N3	2.012 (2)
Fe1—N4	2.026 (2)
Fe1—N5	2.049 (2)
Fe1—N6	2.034 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7A⋯S3i	0.88	2.82	3.532 (2)	139
N7—H7A⋯S2	0.88	2.86	3.462 (2)	127
N7A—H7AA⋯S4ii	0.88	2.81	3.558 (2)	144
N7A—H7AA⋯S2	0.88	2.94	3.504 (2)	124

Symmetry codes: (i) ; (ii) .