Pyridinium bis­(pyridine-κN)tetra­kis­(thio­cyanato-κN)ferrate(III)

Shylin, S.I.; Gural'skiy, I.A.; Haukka, M.; Kapshuk, A.A.; Prisyazhnaya, E.V.

doi:10.1107/S1600536813011628

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m298-m299

doi:10.1107/S1600536813011628

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Pyridinium bis(pyridine-κN)tetrakis(thiocyanato-κN)ferrate(III)

Sergii I. Shylin,^a ^* Il'ya A. Gural'skiy,^a Matti Haukka,^b Anatoliy A. Kapshuk ^a and Elena V. Prisyazhnaya ^c

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska 64/13, 01601 Kyiv, Ukraine, ^bDepartment of Chemistry, University of Jyväskylä, PO Box 35, FI-40014 Jyväskyä, Finland, and ^cKyiv National University of Construction and Architecture, Department of Chemistry, Povitroflotsky Avenue 31, 03680 Kyiv, Ukraine
^*Correspondence e-mail: shylin@univ.kiev.ua

(Received 25 April 2013; accepted 28 April 2013; online 4 May 2013)

In the title compound, (C₅H₆N)[Fe(NCS)₄(C₅H₅N)₂], the Fe^III ion is coordinated by four thiocyanate N atoms and two pyridine N atoms in a trans arrangement, forming an FeN₆ polyhedron with a slightly distorted octahedral 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 thiocyanate anions, two coordinated pyridine molecules and one pyridinium cation. The structure exhibits π–π interactions 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 Fe^II–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_r = 526.48
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.065
S = 0.92
4739 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813011628/xu5698sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813011628/xu5698Isup3.cdx

checkCIF report

Comment top

Molecular assemblies consisting of cationic and anionic modules are of great interest for crystal engineering and molecular magnetism (Strotmeyer et al., 2003; Fritsky et al., 2004). Target properties of such compounds can be tuned by different types of intermolecular interactions, such as coordination and hydrogen bonds, π–π and lone pair – π contacts, etc. (Fritsky et al., 1998; Kanderal et al., 2005). In certain cases, even the existence of spin crossover in these complexes can be observed. Therefore, Fe^II isothiocyanate complexes with aromatic N-donor ligands attract much attention considering the possible metal ion spin state modulation by variation of a ligand (Gamez et al., 2009). Herein, we attempted to synthesize Fe^II thiocyanate complex with 1,5-naphthyridine, however, the reaction of it and [Fe^II(NCS)₂(py)₄] (py = pyridine) in CHCl₃ in air led to the oxidation of Fe^II and to the formation of the title compound.

The compound consists of complex anion [Fe(NCS)₄(py)₂]^- and pyridinium cation the N7 atom of which is disordered over two alternative sites with the occupancy ratio of 0.58 (2): 0.42 (2). The Fe^III ion is sixfold coordinated by four N atoms of thiocyanate anions forming the equatorial plane and two N atoms of two pyridine ligands occupying axial positions (Fig. 1). The distances between Fe^III ion and N atoms of the thiocyanate anions are shorter than those between Fe^III and N atoms of the pyridine ligands (Table 1), hence FeN₆ octahedron is slightly distorted. A similar distortion of the coordination polyhedron was reported for the related compound (Hpy)[Fe(NCS)₄(py)₂]_.4(cnpz).(py), where cnpz = pyrazine-2-carbonitrile (Shylin et al., 2013). The thiocyanate ligands are only bound through N atoms and are quasi-linear, while the Fe–NCS linkages are bent [Fe1—N3—C11 = 162.43 (19)°, Fe1—N4—C12 = 161.67 (19)°, Fe1—N5—C13 = 165.7 (2)°, Fe1—N6—C14 = 158.7 (2)°]. These structural features are typical for the complexes where the NCS group is N-bound (Petrusenko et al., 1997). The C—N and C—C bond lengths in the coordinated pyridine ligands are normal and close to the values observed in the related structures (Moroz et al., 2010; Penkova et al., 2010).

In the title compound pyridine ligands and pyridinium cations interact with one another via π–π stacking, with distances between the centroids of 3.7267 (2), 3.7811 (2) and 3.8924 (2) Å (Fig. 2). Pyridinium cations are also bound to the anionic complex through a number of N—H···S hydrogen bonds (Table 2).

Related literature top

For use of molecular assemblies comprising cationic and anionic modules, see: Fritsky et al. (1998, 2004); Strotmeyer et al. (2003); Kanderal et al. (2005). For Fe^II–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 top

Crystals of the title compound were obtained by adding 1,5-naphthyridine (26 mg, 0.2 mmol) to tetrakis(pyridine)bis(isothiocyanato)iron(II) [Fe(NCS)₂(py)₄] (48.8 mg, 0.1 mmol) in CHCl₃ (5 ml). The solution was left to evaporate in air. In one day this yielded red crystals that were collected, washed with water and dried in air. Yield is 16 mg (30% relative to Fe).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal structure of the title compound showing hydrogen bonds and π–π contacts as dashed lines (carmine = Fe, yellow = S, blue = N, light-grey = C, grey = H).

Pyridinium bis(pyridine-κN)tetrakis(thiocyanato-κN)ferrate(III) top

Crystal data top

(C₅H₆N)[Fe(NCS)₄(C₅H₅N)₂]	F(000) = 1076
M_r = 526.48	D_x = 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

Data collection top

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	R_int = 0.065
Detector resolution: 16 pixels mm^-1	θ_max = 26.4°, θ_min = 2.0°
ϕ scans and ω scans with κ offset	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −17→17
T_min = 0.814, T_max = 0.929	l = −19→16
17377 measured reflections

Refinement top

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(F_o²) + (0.024P)²] where P = (F_o² + 2F_c²)/3
4739 reflections	(Δ/σ)_max = 0.001
281 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

(C₅H₆N)[Fe(NCS)₄(C₅H₅N)₂]	V = 2314.1 (2) Å³
M_r = 526.48	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.7650 (7) Å	µ = 1.03 mm⁻¹
b = 14.0424 (8) Å	T = 120 K
c = 15.7266 (9) Å	0.21 × 0.14 × 0.07 mm
β = 103.244 (3)°

Data collection top

Bruker Kappa APEXII DUO CCD diffractometer	4739 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3027 reflections with I > 2σ(I)
T_min = 0.814, T_max = 0.929	R_int = 0.065
17377 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 0.92	Δρ_max = 0.33 e Å⁻³
4739 reflections	Δρ_min = −0.36 e Å⁻³
281 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	(C₅H₆N)[Fe(NCS)₄(C₅H₅N)₂]
M_r	526.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	10.7650 (7), 14.0424 (8), 15.7266 (9)
β (°)	103.244 (3)
V (Å³)	2314.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.21 × 0.14 × 0.07

Data collection
Diffractometer	Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.814, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	17377, 4739, 3027
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.065, 0.92
No. of reflections	4739
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1997).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7A···S3ⁱ	0.88	2.82	3.532 (2)	139.1
N7—H7A···S2	0.88	2.86	3.462 (2)	127.3
N7A—H7AA···S4ⁱⁱ	0.88	2.81	3.558 (2)	143.8
N7A—H7AA···S2	0.88	2.94	3.504 (2)	123.7

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

References

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Volume 69| Part 6| June 2013| Pages m298-m299

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