Pyridinium bis-(pyridine-κN)tetra-kis-(thio-cyanato-κN)ferrate(III)-pyrazine-2-carbo-nitrile-pyridine (1/4/1).

In the title compound, (C5H6N)[Fe(NCS)4(C5H5N)2]·4C5H3N3·C5H5N, the Fe(III) ion is located on an inversion centre and is six-coordinated by four N atoms of the thio-cyanate ligands and two pyridine N atoms in a trans arrangement, forming a slightly distorted octa-hedral geometry. A half-occupied H atom attached to a pyridinium cation forms an N-H⋯N hydrogen bond with a centrosymmetrically-related pyridine unit. Four pyrazine-2-carbo-nitrile mol-ecules crystallize per complex anion. In the crystal, π-π stacking inter-actions are present [centroid-centroid distances = 3.6220 (9), 3.6930 (9), 3.5532 (9), 3.5803 (9) and 3.5458 (8) Å].

Related literature

For the use of mol­ecular assemblies comprising cationic and anionic modules, see: Fritsky et al. (1998 ▶, 2004 ▶); Kanderal et al. (2005 ▶). For FeII–thio­cyanate complexes with aromatic N-donor ligands indicating spin crossover, see: Gamez et al. (2009 ▶); Niel et al. (2001 ▶). For related structures, see: Moroz et al. (2010 ▶); Penkova et al. (2010 ▶); Petrusenko et al. (1997 ▶); Real et al. (1991 ▶).

Experimental

Crystal data

(C5H6N)[Fe(NCS)4(C5H5N)2]·4C5H3N3·C5H5N

M = 1025.99

Triclinic,

a = 8.1766 (2) Å

b = 11.9362 (3) Å

c = 12.7519 (3) Å

α = 102.982 (1)°

β = 97.799 (1)°

γ = 97.684 (1)°

V = 1184.02 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.55 mm−1

T = 120 K

0.38 × 0.19 × 0.17 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.818, T max = 0.910

18588 measured reflections

5482 independent reflections

4470 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.076

S = 1.01

5482 reflections

313 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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/S1600536813010362/hy2622sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010362/hy2622Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813010362/hy2622Isup3.cdx

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

(C5H6N)[Fe(NCS)4(C5H5N)2]·4C5H3N3·C5H5N	Z = 1
Mr = 1025.99	F(000) = 527
Triclinic, P1	Dx = 1.439 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1766 (2) Å	Cell parameters from 7810 reflections
b = 11.9362 (3) Å	θ = 2.6–27.6°
c = 12.7519 (3) Å	µ = 0.55 mm−1
α = 102.982 (1)°	T = 120 K
β = 97.799 (1)°	Block, red
γ = 97.684 (1)°	0.38 × 0.19 × 0.17 mm
V = 1184.02 (5) Å3

Bruker Kappa APEXII DUO CCD diffractometer	5482 independent reflections
Radiation source: fine-focus sealed tube	4470 reflections with I > 2σ(I)
Curved graphite crystal monochromator	Rint = 0.024
Detector resolution: 16 pixels mm-1	θmax = 27.7°, θmin = 1.7°
φ and ω scans with κ offset	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
Tmin = 0.818, Tmax = 0.910	l = −16→16
18588 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0363P)2 + 0.3715P] where P = (Fo2 + 2Fc2)/3
5482 reflections	(Δ/σ)max = 0.001
313 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Experimental. Hydrogen atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95 Å, N—H = 0.88 Å, and Uiso = 1.2 Ueq(parent atom). The highest peak is located 0.70 Å from atom C18 and the deepest hole is located 0.48 Å from atom Fe1.

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	0.5000	0.5000	0.5000	0.01474 (8)
S1	0.18557 (5)	0.25687 (4)	0.16391 (3)	0.02717 (11)
S2	0.31797 (5)	0.74869 (4)	0.27623 (4)	0.02695 (11)
N1	0.72282 (15)	0.50545 (11)	0.43036 (10)	0.0163 (3)
N2	0.38008 (16)	0.37328 (11)	0.36553 (11)	0.0200 (3)
N3	0.42809 (15)	0.62208 (11)	0.42297 (11)	0.0193 (3)
N4	0.86353 (18)	0.50989 (12)	0.04639 (11)	0.0279 (3)
H4N	0.9528	0.5042	0.0153	0.033*	0.50
N5	0.40216 (18)	0.10177 (12)	0.42369 (12)	0.0278 (3)
N6	0.09833 (17)	−0.12537 (12)	0.62053 (11)	0.0271 (3)
N7	0.90967 (18)	0.11755 (13)	−0.07429 (12)	0.0302 (3)
N8	0.59044 (17)	−0.09046 (12)	0.13024 (11)	0.0237 (3)
N9	0.67103 (17)	0.14539 (11)	0.12764 (11)	0.0220 (3)
N10	0.15882 (17)	0.11284 (12)	0.62270 (11)	0.0224 (3)
C1	0.29957 (18)	0.32456 (13)	0.28113 (12)	0.0173 (3)
C2	0.80428 (18)	0.60594 (13)	0.41827 (12)	0.0193 (3)
H2	0.7656	0.6766	0.4459	0.023*
C3	0.94253 (19)	0.60979 (14)	0.36697 (13)	0.0213 (3)
H3	0.9981	0.6821	0.3597	0.026*
C4	0.99889 (19)	0.50744 (14)	0.32645 (13)	0.0214 (3)
H4	1.0925	0.5080	0.2897	0.026*
C5	0.9167 (2)	0.40386 (14)	0.34019 (13)	0.0225 (3)
H5	0.9541	0.3323	0.3142	0.027*
C6	0.77991 (19)	0.40658 (13)	0.39215 (12)	0.0197 (3)
H6	0.7235	0.3354	0.4014	0.024*
C7	0.6803 (2)	0.62600 (15)	0.12971 (14)	0.0297 (4)
H7	0.6508	0.7007	0.1539	0.036*
C8	0.5837 (2)	0.52690 (15)	0.14229 (13)	0.0271 (4)
H8	0.4869	0.5328	0.1754	0.032*
C9	0.38283 (18)	0.67553 (13)	0.36185 (12)	0.0176 (3)
C10	0.8197 (2)	0.61399 (15)	0.08152 (14)	0.0283 (4)
H10	0.8867	0.6817	0.0730	0.034*
C11	0.32510 (19)	0.07281 (13)	0.48410 (13)	0.0204 (3)
C12	0.22339 (18)	0.03216 (13)	0.55739 (12)	0.0183 (3)
C13	0.1944 (2)	−0.08487 (14)	0.55571 (13)	0.0238 (3)
H13	0.2437	−0.1378	0.5074	0.029*
C14	0.0340 (2)	−0.04577 (15)	0.68615 (13)	0.0255 (4)
H14	−0.0350	−0.0704	0.7338	0.031*
C15	0.0642 (2)	0.07162 (15)	0.68746 (13)	0.0252 (4)
H15	0.0157	0.1246	0.7363	0.030*
C16	0.7703 (2)	0.41443 (15)	0.05894 (15)	0.0309 (4)
H16	0.8024	0.3407	0.0344	0.037*
C17	0.6293 (2)	0.42005 (15)	0.10637 (14)	0.0292 (4)
H17	0.5645	0.3511	0.1142	0.035*
C18	0.72593 (18)	0.05927 (13)	0.06193 (12)	0.0182 (3)
C19	0.53568 (19)	−0.00576 (14)	0.19602 (12)	0.0209 (3)
H19	0.4667	−0.0256	0.2456	0.025*
C20	0.5757 (2)	0.11054 (14)	0.19485 (12)	0.0221 (3)
H20	0.5334	0.1675	0.2439	0.026*
C21	0.68690 (19)	−0.05677 (14)	0.06260 (12)	0.0211 (3)
H21	0.7296	−0.1138	0.0139	0.025*
C22	0.82945 (19)	0.09294 (14)	−0.01369 (13)	0.0219 (3)

	U11	U22	U33	U12	U13	U23
Fe1	0.01377 (15)	0.01447 (15)	0.01549 (15)	0.00130 (11)	0.00307 (11)	0.00305 (12)
S1	0.0231 (2)	0.0345 (2)	0.0178 (2)	0.00335 (17)	0.00294 (16)	−0.00485 (17)
S2	0.0290 (2)	0.0289 (2)	0.0305 (2)	0.00821 (18)	0.00977 (18)	0.01836 (18)
N1	0.0150 (6)	0.0167 (6)	0.0168 (6)	0.0016 (5)	0.0026 (5)	0.0042 (5)
N2	0.0187 (6)	0.0182 (7)	0.0213 (7)	0.0017 (5)	0.0032 (5)	0.0018 (5)
N3	0.0177 (6)	0.0178 (7)	0.0224 (7)	0.0020 (5)	0.0045 (5)	0.0050 (5)
N4	0.0315 (8)	0.0282 (8)	0.0275 (8)	0.0064 (6)	0.0127 (6)	0.0086 (6)
N5	0.0284 (8)	0.0291 (8)	0.0268 (7)	0.0039 (6)	0.0103 (6)	0.0062 (6)
N6	0.0268 (8)	0.0264 (8)	0.0279 (8)	−0.0001 (6)	0.0022 (6)	0.0108 (6)
N7	0.0279 (8)	0.0364 (9)	0.0255 (7)	−0.0008 (6)	0.0082 (6)	0.0076 (6)
N8	0.0275 (7)	0.0216 (7)	0.0223 (7)	0.0020 (6)	0.0076 (6)	0.0054 (6)
N9	0.0244 (7)	0.0212 (7)	0.0212 (7)	0.0048 (5)	0.0052 (6)	0.0054 (6)
N10	0.0244 (7)	0.0238 (7)	0.0204 (7)	0.0061 (6)	0.0061 (5)	0.0059 (6)
C1	0.0160 (7)	0.0161 (7)	0.0215 (8)	0.0043 (6)	0.0085 (6)	0.0041 (6)
C2	0.0181 (8)	0.0165 (7)	0.0228 (8)	0.0018 (6)	0.0025 (6)	0.0048 (6)
C3	0.0174 (8)	0.0209 (8)	0.0259 (8)	−0.0004 (6)	0.0037 (6)	0.0083 (7)
C4	0.0145 (7)	0.0285 (9)	0.0223 (8)	0.0026 (6)	0.0059 (6)	0.0076 (7)
C5	0.0210 (8)	0.0217 (8)	0.0257 (8)	0.0070 (6)	0.0064 (7)	0.0045 (7)
C6	0.0206 (8)	0.0166 (8)	0.0219 (8)	0.0018 (6)	0.0045 (6)	0.0054 (6)
C7	0.0383 (10)	0.0239 (9)	0.0268 (9)	0.0102 (8)	0.0048 (8)	0.0038 (7)
C8	0.0264 (9)	0.0330 (10)	0.0236 (8)	0.0089 (7)	0.0064 (7)	0.0073 (7)
C9	0.0144 (7)	0.0164 (7)	0.0219 (8)	0.0011 (6)	0.0081 (6)	0.0023 (6)
C10	0.0363 (10)	0.0226 (9)	0.0265 (9)	0.0023 (7)	0.0065 (7)	0.0081 (7)
C11	0.0201 (8)	0.0194 (8)	0.0204 (8)	0.0036 (6)	0.0017 (6)	0.0029 (6)
C12	0.0158 (7)	0.0227 (8)	0.0158 (7)	0.0024 (6)	0.0007 (6)	0.0054 (6)
C13	0.0231 (8)	0.0232 (8)	0.0238 (8)	0.0032 (7)	0.0029 (7)	0.0042 (7)
C14	0.0191 (8)	0.0380 (10)	0.0202 (8)	0.0004 (7)	0.0017 (6)	0.0124 (7)
C15	0.0238 (8)	0.0337 (10)	0.0202 (8)	0.0080 (7)	0.0072 (7)	0.0073 (7)
C16	0.0364 (10)	0.0219 (9)	0.0371 (10)	0.0087 (7)	0.0108 (8)	0.0081 (8)
C17	0.0307 (9)	0.0255 (9)	0.0337 (10)	0.0032 (7)	0.0079 (8)	0.0119 (8)
C18	0.0153 (7)	0.0238 (8)	0.0149 (7)	0.0019 (6)	0.0016 (6)	0.0049 (6)
C19	0.0179 (8)	0.0277 (9)	0.0168 (7)	0.0021 (6)	0.0038 (6)	0.0055 (6)
C20	0.0228 (8)	0.0263 (9)	0.0178 (8)	0.0085 (7)	0.0056 (6)	0.0028 (6)
C21	0.0231 (8)	0.0211 (8)	0.0187 (8)	0.0045 (6)	0.0056 (6)	0.0021 (6)
C22	0.0207 (8)	0.0235 (8)	0.0197 (8)	0.0014 (6)	0.0025 (6)	0.0039 (6)

Fe1—N3	2.0370 (13)	C6—H6	0.9500
Fe1—N2	2.0424 (13)	C7—C10	1.375 (2)
Fe1—N1	2.1320 (12)	C7—C8	1.385 (2)
S1—C1	1.6229 (16)	C7—H7	0.9500
S2—C9	1.6220 (16)	C8—C17	1.374 (2)
N1—C6	1.3412 (19)	C8—H8	0.9500
N1—C2	1.3430 (19)	C10—H10	0.9500
N2—C1	1.164 (2)	C11—C12	1.452 (2)
N3—C9	1.166 (2)	C12—N10	1.340 (2)
N4—C10	1.336 (2)	C12—C13	1.380 (2)
N4—C16	1.337 (2)	C13—H13	0.9500
N4—H4N	0.8800	C14—C15	1.386 (2)
N5—C11	1.142 (2)	C14—H14	0.9500
N6—C14	1.332 (2)	C15—N10	1.333 (2)
N6—C13	1.337 (2)	C15—H15	0.9500
N7—C22	1.141 (2)	C16—C17	1.375 (2)
N8—C19	1.330 (2)	C16—H16	0.9500
N8—C21	1.3355 (19)	C17—H17	0.9500
C2—C3	1.381 (2)	C18—N9	1.3411 (19)
C2—H2	0.9500	C19—C20	1.387 (2)
C3—C4	1.380 (2)	C19—H19	0.9500
C3—H3	0.9500	C20—N9	1.331 (2)
C4—C5	1.385 (2)	C20—H20	0.9500
C4—H4	0.9500	C21—C18	1.381 (2)
C5—C6	1.376 (2)	C21—H21	0.9500
C5—H5	0.9500	C22—C18	1.453 (2)
N3i—Fe1—N3	179.999 (1)	N1—C6—H6	118.6
N3i—Fe1—N2i	88.77 (5)	C5—C6—H6	118.6
N3—Fe1—N2i	91.23 (5)	C10—C7—C8	118.63 (16)
N3i—Fe1—N2	91.23 (5)	C10—C7—H7	120.7
N3—Fe1—N2	88.77 (5)	C8—C7—H7	120.7
N2i—Fe1—N2	180.0	C17—C8—C7	119.32 (16)
N3i—Fe1—N1	90.30 (5)	C17—C8—H8	120.3
N3—Fe1—N1	89.70 (5)	C7—C8—H8	120.3
N2i—Fe1—N1	90.58 (5)	N3—C9—S2	179.33 (15)
N2—Fe1—N1	89.42 (5)	N4—C10—C7	121.91 (16)
N3i—Fe1—N1i	89.70 (5)	N4—C10—H10	119.0
N3—Fe1—N1i	90.30 (5)	C7—C10—H10	119.0
N2i—Fe1—N1i	89.42 (5)	N5—C11—C12	177.71 (17)
N2—Fe1—N1i	90.58 (5)	N10—C12—C13	123.29 (14)
N1—Fe1—N1i	180.0	N10—C12—C11	116.65 (14)
C6—N1—C2	118.34 (13)	C13—C12—C11	120.04 (14)
C6—N1—Fe1	120.20 (10)	N6—C13—C12	121.47 (15)
C2—N1—Fe1	121.37 (10)	N6—C13—H13	119.3
C1—N2—Fe1	163.20 (12)	C12—C13—H13	119.3
C9—N3—Fe1	167.56 (12)	N6—C14—C15	122.38 (15)
C10—N4—C16	119.32 (15)	N6—C14—H14	118.8
C10—N4—H4N	120.3	C15—C14—H14	118.8
C16—N4—H4N	120.3	N10—C15—C14	122.39 (15)
C14—N6—C13	115.74 (14)	N10—C15—H15	118.8
C19—N8—C21	115.86 (14)	C14—C15—H15	118.8
N2—C1—S1	179.41 (14)	C15—N10—C12	114.73 (14)
N7—C22—C18	178.82 (18)	N4—C16—C17	121.84 (16)
N8—C21—C18	121.37 (14)	N4—C16—H16	119.1
N8—C21—H21	119.3	C17—C16—H16	119.1
C18—C21—H21	119.3	C8—C17—C16	118.98 (16)
N1—C2—C3	122.04 (14)	C8—C17—H17	120.5
N1—C2—H2	119.0	C16—C17—H17	120.5
C3—C2—H2	119.0	N9—C18—C21	123.30 (14)
C4—C3—C2	119.23 (14)	N9—C18—C22	116.67 (14)
C4—C3—H3	120.4	C21—C18—C22	120.03 (14)
C2—C3—H3	120.4	N8—C19—C20	122.36 (14)
C3—C4—C5	118.89 (14)	N8—C19—H19	118.8
C3—C4—H4	120.6	C20—C19—H19	118.8
C5—C4—H4	120.6	N9—C20—C19	122.46 (14)
C6—C5—C4	118.72 (15)	N9—C20—H20	118.8
C6—C5—H5	120.6	C19—C20—H20	118.8
C4—C5—H5	120.6	C20—N9—C18	114.64 (13)
N1—C6—C5	122.77 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4N···N4ii	0.88	1.80	2.677 (3)	179

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4N⋯N4i	0.88	1.80	2.677 (3)	179

Symmetry code: (i) .