Bis[5-chloro-2-(phenyl­diazenyl-κN2)pyridine-κN]bis­(thio­cyanato-κN)iron(II)

Vittaya, L.; Leesakul, N.; Pakawatchai, C.; Saithong, S.; Hansongnern, K.

doi:10.1107/S1600536812014286

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m555-m556

doi:10.1107/S1600536812014286

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Bis[5-chloro-2-(phenyldiazenyl-κN²)pyridine-κN]bis(thiocyanato-κN)iron(II)

Luksamee Vittaya,^a ^* Nararak Leesakul,^b Chaveng Pakawatchai,^b Saowanit Saithong ^b and Kanidtha Hansongnern ^b

^aFaculty of Science and Fisheries Technology, Rajamangala University of Technology Srivijaya, Sikao, Trang 92150, Thailand, and ^bDepartment of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: nokluksamee@hotmail.com

(Received 29 March 2012; accepted 2 April 2012; online 13 April 2012)

In the title complex, [Fe(NCS)₂(C₁₁H₈ClN₃)₂], the Fe^II atom is coordinated by two N atoms from the thiocyanate ligands and four N atoms from two chelating 5-chloro-2-(phenyldiazenyl)pyridine ligands, generating a fairly regular FeN₆ octahedral coordination geometry. The thiocyanate ions are in a cis disposition and the pyridine N atoms are in a trans orientation. In the crystal, a short intermolecular Cl⋯S contact [3.366 (3) Å] is observed.

Related literature

For background to diazenyl complexes, see: Krause & Krause (1980 ); Santra et al. (1999 ); Hotze, Caspers et al. (2004 ); Hotze, Kooijman et al. (2004 ). For applications of diazenyl compounds, see: Erkkila et al. (1999 ); Wong & Giandomenico (1999 ); Velder et al. (2000 ); Barf & Sheldon (1995 ). For structures of related diazenylimine complexes, see: Hansongnern et al. (2008 ); Ray et al. (2005 ); Senapoti et al. (2002). For background to diazenyl complexes, see: Byabartta et al. (2001 ).

Experimental

Crystal data

[Fe(NCS)₂(C₁₁H₈ClN₃)₂]
M_r = 607.34
Monoclinic, P 2₁ /n
a = 9.5151 (3) Å
b = 23.7391 (9) Å
c = 12.1550 (4) Å
β = 96.209 (1)°
V = 2729.46 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.34 × 0.17 × 0.09 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.916, T_max = 1.000
29379 measured reflections
4809 independent reflections
4189 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.110
S = 1.08
4809 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Selected bond lengths (Å)

Fe1—N3	1.900 (2)
Fe1—N6	1.917 (2)
Fe1—N4	1.936 (2)
Fe1—N7	1.941 (2)
Fe1—N1	1.945 (2)
Fe1—N8	1.952 (2)

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014286/hb6716sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014286/hb6716Isup2.hkl

checkCIF report

Comment top

Azoimine (—N=N—C=N—) compounds are famously used as effective ligands in synthesization of transition metal complexes owing of their strong π-acidity (Krause and Krause 1980; Santra et al., 1999; Hotze, Caspers et al., 2004), stability and various applications like DNA probing (Erkkila et al., 1999), chemotherapeutic drugs (Wong et al., 1999), anticancer activity (Hotze, Kooijman et al., 2004) and powerful catalysts in epoxidation reaction of olefin to give epoxide (Barf and Sheldon 1995). The diazenylimine complexes are mostly found in octahedral geometry with d⁶ metal ions (Hansongnern et al., 2008; Ray et al., 2005; Senapoti et al., 2002).

Herein, we report the synthesis and crystal structure of a new Fe(II) complex with 5-chloro-2-(phenyldiazenyl) pyridine, (C₁₁H₈N₃Cl₁: Clazpy), an azoimine ligand. Regarding to the title compound, the molecular structure of [Fe(Clazpy)₂(NCS)₂] is a distorted octahedral complex (Scheme 1 and Fig.1). The chelating coordination is observed by two N atoms from pyridine rings [Fe(1)—N(1) = 1.945 (2) Å and Fe(1)—N(4) = 1.936 (2) Å] and other two N atoms from diazenyl moiety [Fe(1)—N(3) = 1.900 (2) Å and Fe(1)—N(6) = 1.917 (2) Å in trans arrangement while two N atoms of both thiocyanato ligands are in cis geometry [Fe(1)—N(7) = 1.941 (2) Å, Fe(1)—N(8) = 1.952 (2) Å]. The dihedral angles between pyridine and phenyl rings of both Clazpy ligands are similar, with 53.83 (12)° and 52.53 (10)°. The bond lengths of Fe—N(NCS) (1.941 (2) Å and 1.952 (2) Å) are longer than that reported in the related complex, [Fe(MeaaiEt)₂(NCS)₂]; MeaaiEt = 1-ethyl-2(p-tolyldiazenyl)imiddiazenylle (Ray et al., 2005). The average Fe—N(py) and Fe—N(diazenyl) distances (1.9085 Å and 1.9405 Å) in [Fe(Clazpy)₂(NCS)₂] is shorter than that observed in [Fe(MeaaiEt)₂(NCS)₂], Fe—N(imiddiazenylle) = 2.103 (2) Å and Fe—N(diazenyl) = 2.371 (2) Å, supporting the strong σ-donor and π-acceptor property of Clazpy. The better π-back bonding from d⁶-Fe(II) to π* orbital of the Clazpy ligand makes slightly N=N distance to be longer comparison with MeaaiEt owing to the decreasing of N=N bond order, thus, the strength of the diazenyl bond decreases. All N(py)—Fe—N(py) and N(diazenyl)—Fe—NCS bond angles deviate from 180°, especially for N(6)—Fe(1)—N(8) = 168.44 (10)° during to the bite angle from the two Clazpy ligands. The torsion angles of pyridine-diazenyl-phenyl atoms, C(5)—N(2)—N(3)—C(6) and C(16)—N(5)—N(6)—C(17), are -176.4 (2) and -178.6 (2)°, respectively. In addition, the short contact between Cl(1) of clazpy and S(1) of isothiocyanato ligand are observed (Cl(1)···S(1) = 3.366 (3) Å) between two adjacent molecules.

Related literature top

For background to diazenyl complexes, see: Krause & Krause (1980); Santra et al. (1999); Hotze, Caspers et al. (2004); Hotze, Kooijman et al. (2004). For applications of diazenyl compounds, see: Erkkila et al. (1999); Wong & Giandomenico (1999); Velder et al. (2000); Barf & Sheldon (1995). For structures of related diazenylimine complexes, see: Hansongnern et al. (2008); Ray et al. (2005); Senapoti et al. (2002). For background to diazenyl complexes, see: Byabartta et al. (2001).

Experimental top

Methanolic solution (30 ml) of 5-chloro-2-(phenyldiazenyl)pyridine (Clazpy) (0.11 g, 0.50 mmol), FeSO₄.7H₂O (0.07 g, 0.25 mmol) and ammonium thiocynate (0.04 g, 0.53 mmol) was refluxed for 3 h. The filtrate was standing for overnight at room temperature. The green solids were precipitated and collected by filtration, washed it with methanol/water (1:1 v/v), and dried in vacuo for a day. The green solids were recrystallized in the mixture of CH₂Cl₂ and MeOH (1:2). The green crystals were obtained (yield 80%, 0.12 g). Anal. Calcd for FeC₂₄H₁₆N₈ S₂Cl₂: C, 47.47; H, 2.66; N, 18.45; S, 10.56. Found: C, 47.07; H, 2.56; N, 17.98; S, 10.39.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids plotted at the 50% probability level.
	Fig. 2. The short contact interactions of [Fe(Clazpy)₂(NCS)₂] .

Bis[5-chloro-2-(phenyldiazenyl-κN²)pyridine- κN]bis(thiocyanato-κN)iron(II) top

Crystal data top

[Fe(NCS)₂(C₁₁H₈ClN₃)₂]	F(000) = 1232
M_r = 607.34	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7953 reflections
a = 9.5151 (3) Å	θ = 2.3–25.4°
b = 23.7391 (9) Å	µ = 0.93 mm⁻¹
c = 12.1550 (4) Å	T = 293 K
β = 96.209 (1)°	Block, red-brown
V = 2729.46 (16) Å³	0.34 × 0.17 × 0.09 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4809 independent reflections
Radiation source: fine-focus sealed tube	4189 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Frames, each covering 0.3 ° in ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
T_min = 0.916, T_max = 1.000	k = −28→28
29379 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0511P)² + 2.004P] where P = (F_o² + 2F_c²)/3
4809 reflections	(Δ/σ)_max = 0.001
334 parameters	Δρ_max = 0.95 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[Fe(NCS)₂(C₁₁H₈ClN₃)₂]	V = 2729.46 (16) Å³
M_r = 607.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5151 (3) Å	µ = 0.93 mm⁻¹
b = 23.7391 (9) Å	T = 293 K
c = 12.1550 (4) Å	0.34 × 0.17 × 0.09 mm
β = 96.209 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	4809 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	4189 reflections with I > 2σ(I)
T_min = 0.916, T_max = 1.000	R_int = 0.027
29379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.08	Δρ_max = 0.95 e Å⁻³
4809 reflections	Δρ_min = −0.75 e Å⁻³
334 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 > 2σ(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 al data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.26710 (4)	0.199109 (16)	0.72956 (3)	0.03803 (13)
N1	0.4302 (2)	0.15150 (10)	0.77250 (18)	0.0439 (5)
N2	0.4637 (2)	0.22105 (11)	0.90825 (19)	0.0513 (6)
N3	0.3387 (2)	0.23370 (10)	0.86513 (17)	0.0415 (5)
N4	0.1056 (2)	0.24866 (10)	0.70140 (17)	0.0432 (5)
N5	−0.0086 (2)	0.16663 (12)	0.7497 (2)	0.0536 (6)
N6	0.1197 (2)	0.15144 (10)	0.77242 (18)	0.0451 (5)
N7	0.2284 (2)	0.16225 (10)	0.58695 (19)	0.0490 (6)
N8	0.3889 (2)	0.25196 (11)	0.66138 (19)	0.0470 (5)
S2	0.49476 (8)	0.34626 (3)	0.56230 (8)	0.0626 (2)
S1	0.20586 (13)	0.09807 (7)	0.39640 (12)	0.1316 (7)
C1	0.4725 (3)	0.10415 (13)	0.7267 (3)	0.0522 (7)
H1	0.4145	0.0873	0.6694	0.063*
C2	0.6012 (3)	0.07977 (14)	0.7631 (3)	0.0613 (9)
C3	0.6913 (3)	0.10504 (17)	0.8452 (3)	0.0713 (10)
H3	0.7798	0.0898	0.8675	0.086*
C4	0.6470 (3)	0.15305 (17)	0.8927 (3)	0.0667 (9)
H4	0.7047	0.1709	0.9488	0.080*
C5	0.5151 (3)	0.17485 (14)	0.8567 (2)	0.0494 (7)
C6	0.2817 (3)	0.28345 (12)	0.9103 (2)	0.0458 (6)
C7	0.3583 (4)	0.33294 (15)	0.9139 (3)	0.0676 (9)
H7	0.4501	0.3333	0.8943	0.081*
C8	0.2971 (5)	0.38131 (17)	0.9467 (4)	0.0913 (13)
H8	0.3475	0.4149	0.9496	0.110*
C9	0.1606 (5)	0.38048 (18)	0.9755 (3)	0.0905 (13)
H9	0.1187	0.4137	0.9958	0.109*
C10	0.0864 (4)	0.33076 (17)	0.9743 (3)	0.0717 (10)
H10	−0.0043	0.3303	0.9961	0.086*
C11	0.1460 (3)	0.28201 (14)	0.9411 (2)	0.0520 (7)
H11	0.0958	0.2483	0.9392	0.062*
C12	0.1023 (3)	0.30337 (13)	0.6782 (2)	0.0496 (7)
H12	0.1861	0.3220	0.6685	0.059*
C13	−0.0229 (3)	0.33307 (15)	0.6681 (3)	0.0611 (8)
C14	−0.1487 (4)	0.30664 (18)	0.6787 (3)	0.0751 (11)
H14	−0.2334	0.3265	0.6711	0.090*
C15	−0.1460 (3)	0.25012 (18)	0.7007 (3)	0.0711 (10)
H15	−0.2297	0.2307	0.7069	0.085*
C16	−0.0178 (3)	0.22207 (14)	0.7138 (2)	0.0519 (7)
C17	0.1347 (3)	0.09386 (12)	0.8076 (2)	0.0503 (7)
C18	0.0563 (4)	0.05231 (16)	0.7497 (3)	0.0752 (10)
H18	−0.0066	0.0612	0.6882	0.090*
C19	0.0737 (5)	−0.00269 (18)	0.7856 (4)	0.0987 (15)
H19	0.0232	−0.0313	0.7470	0.118*
C20	0.1640 (5)	−0.01550 (17)	0.8771 (5)	0.0998 (15)
H20	0.1738	−0.0527	0.9007	0.120*
C21	0.2400 (4)	0.02575 (16)	0.9341 (4)	0.0832 (11)
H21	0.3010	0.0167	0.9966	0.100*
C22	0.2266 (3)	0.08071 (13)	0.8994 (3)	0.0580 (8)
H22	0.2792	0.1089	0.9377	0.070*
C23	0.2177 (3)	0.13531 (15)	0.5084 (3)	0.0592 (8)
C24	0.4349 (3)	0.29088 (12)	0.6208 (2)	0.0423 (6)
Cl1	0.64768 (11)	0.01811 (4)	0.70172 (10)	0.0874 (3)
Cl2	−0.01594 (12)	0.40406 (4)	0.64356 (10)	0.0929 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0315 (2)	0.0475 (2)	0.0347 (2)	0.00046 (15)	0.00200 (14)	−0.00205 (15)
N1	0.0344 (11)	0.0541 (14)	0.0438 (12)	0.0022 (10)	0.0072 (9)	0.0068 (10)
N2	0.0360 (12)	0.0753 (17)	0.0416 (13)	−0.0022 (11)	−0.0004 (10)	0.0006 (12)
N3	0.0342 (11)	0.0558 (14)	0.0344 (11)	−0.0058 (10)	0.0034 (9)	0.0012 (10)
N4	0.0372 (12)	0.0567 (14)	0.0348 (11)	0.0067 (10)	−0.0001 (9)	−0.0054 (10)
N5	0.0361 (13)	0.0714 (17)	0.0526 (14)	−0.0047 (11)	0.0020 (10)	−0.0058 (12)
N6	0.0369 (12)	0.0562 (14)	0.0422 (12)	−0.0057 (10)	0.0040 (9)	−0.0072 (10)
N7	0.0446 (13)	0.0613 (15)	0.0404 (13)	0.0026 (11)	0.0017 (10)	−0.0108 (11)
N8	0.0423 (13)	0.0547 (14)	0.0447 (13)	0.0013 (11)	0.0084 (10)	0.0003 (11)
S2	0.0505 (4)	0.0526 (5)	0.0840 (6)	0.0021 (3)	0.0047 (4)	0.0187 (4)
S1	0.0840 (8)	0.1876 (15)	0.1193 (10)	0.0205 (8)	−0.0075 (7)	−0.1068 (11)
C1	0.0482 (16)	0.0534 (17)	0.0567 (18)	0.0057 (13)	0.0130 (13)	0.0084 (14)
C2	0.0548 (18)	0.066 (2)	0.067 (2)	0.0172 (16)	0.0222 (16)	0.0224 (16)
C3	0.0431 (17)	0.105 (3)	0.067 (2)	0.0237 (18)	0.0115 (16)	0.025 (2)
C4	0.0398 (16)	0.104 (3)	0.0553 (19)	0.0097 (17)	−0.0004 (14)	0.0079 (18)
C5	0.0355 (14)	0.0702 (19)	0.0423 (15)	−0.0004 (13)	0.0026 (12)	0.0084 (14)
C6	0.0485 (16)	0.0556 (17)	0.0330 (13)	−0.0068 (13)	0.0030 (11)	−0.0059 (12)
C7	0.066 (2)	0.071 (2)	0.067 (2)	−0.0203 (18)	0.0130 (17)	−0.0172 (17)
C8	0.122 (4)	0.066 (2)	0.088 (3)	−0.027 (2)	0.024 (3)	−0.024 (2)
C9	0.127 (4)	0.070 (3)	0.079 (3)	0.012 (3)	0.031 (3)	−0.023 (2)
C10	0.076 (2)	0.087 (3)	0.056 (2)	0.010 (2)	0.0224 (17)	−0.0098 (18)
C11	0.0513 (17)	0.0639 (19)	0.0417 (15)	−0.0032 (14)	0.0093 (12)	−0.0030 (13)
C12	0.0478 (16)	0.0626 (19)	0.0369 (14)	0.0100 (14)	−0.0019 (12)	−0.0028 (13)
C13	0.060 (2)	0.072 (2)	0.0484 (17)	0.0227 (17)	−0.0063 (14)	−0.0040 (15)
C14	0.048 (2)	0.102 (3)	0.072 (2)	0.0312 (19)	−0.0086 (16)	−0.005 (2)
C15	0.0358 (16)	0.100 (3)	0.075 (2)	0.0076 (17)	−0.0038 (15)	−0.003 (2)
C16	0.0358 (15)	0.073 (2)	0.0459 (16)	0.0016 (14)	−0.0026 (12)	−0.0059 (14)
C17	0.0450 (15)	0.0504 (17)	0.0568 (17)	−0.0108 (13)	0.0118 (13)	−0.0095 (13)
C18	0.069 (2)	0.071 (2)	0.083 (2)	−0.0176 (18)	−0.0039 (19)	−0.0160 (19)
C19	0.097 (3)	0.064 (3)	0.133 (4)	−0.033 (2)	0.001 (3)	−0.022 (3)
C20	0.101 (3)	0.055 (2)	0.141 (4)	−0.019 (2)	0.001 (3)	0.006 (3)
C21	0.091 (3)	0.061 (2)	0.095 (3)	−0.014 (2)	−0.003 (2)	0.016 (2)
C22	0.0599 (19)	0.0500 (18)	0.0631 (19)	−0.0108 (14)	0.0020 (15)	0.0015 (14)
C23	0.0355 (15)	0.078 (2)	0.063 (2)	0.0087 (14)	−0.0004 (13)	−0.0181 (17)
C24	0.0346 (13)	0.0487 (16)	0.0428 (14)	0.0077 (12)	0.0004 (11)	−0.0032 (12)
Cl1	0.0880 (7)	0.0692 (6)	0.1091 (8)	0.0340 (5)	0.0298 (6)	0.0175 (5)
Cl2	0.1028 (8)	0.0715 (6)	0.1004 (8)	0.0383 (6)	−0.0082 (6)	0.0028 (5)

Geometric parameters (Å, º) top

Fe1—N3	1.900 (2)	C6—C11	1.384 (4)
Fe1—N6	1.917 (2)	C7—C8	1.366 (5)
Fe1—N4	1.936 (2)	C7—H7	0.9300
Fe1—N7	1.941 (2)	C8—C9	1.381 (6)
Fe1—N1	1.945 (2)	C8—H8	0.9300
Fe1—N8	1.952 (2)	C9—C10	1.375 (6)
N1—C1	1.336 (4)	C9—H9	0.9300
N1—C5	1.352 (4)	C10—C11	1.369 (5)
N2—N3	1.282 (3)	C10—H10	0.9300
N2—C5	1.379 (4)	C11—H11	0.9300
N3—C6	1.433 (4)	C12—C13	1.378 (4)
N4—C12	1.329 (4)	C12—H12	0.9300
N4—C16	1.356 (4)	C13—C14	1.370 (5)
N5—N6	1.274 (3)	C13—Cl2	1.714 (4)
N5—C16	1.386 (4)	C14—C15	1.368 (5)
N6—C17	1.435 (4)	C14—H14	0.9300
N7—C23	1.144 (4)	C15—C16	1.384 (4)
N8—C24	1.156 (4)	C15—H15	0.9300
S2—C24	1.626 (3)	C17—C22	1.378 (4)
S1—C23	1.617 (3)	C17—C18	1.382 (4)
C1—C2	1.383 (4)	C18—C19	1.381 (6)
C1—H1	0.9300	C18—H18	0.9300
C2—C3	1.380 (5)	C19—C20	1.364 (6)
C2—Cl1	1.722 (4)	C19—H19	0.9300
C3—C4	1.365 (5)	C20—C21	1.361 (6)
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.384 (4)	C21—C22	1.373 (5)
C4—H4	0.9300	C21—H21	0.9300
C6—C7	1.380 (4)	C22—H22	0.9300

N3—Fe1—N6	102.92 (9)	C8—C7—H7	120.5
N3—Fe1—N4	95.39 (9)	C6—C7—H7	120.5
N6—Fe1—N4	79.44 (10)	C7—C8—C9	120.2 (4)
N3—Fe1—N7	169.99 (9)	C7—C8—H8	119.9
N6—Fe1—N7	84.43 (10)	C9—C8—H8	119.9
N4—Fe1—N7	92.62 (9)	C10—C9—C8	120.4 (4)
N3—Fe1—N1	79.49 (10)	C10—C9—H9	119.8
N6—Fe1—N1	99.78 (10)	C8—C9—H9	119.8
N4—Fe1—N1	174.56 (9)	C11—C10—C9	120.0 (3)
N7—Fe1—N1	92.66 (10)	C11—C10—H10	120.0
N3—Fe1—N8	85.23 (9)	C9—C10—H10	120.0
N6—Fe1—N8	168.44 (10)	C10—C11—C6	119.2 (3)
N4—Fe1—N8	91.75 (10)	C10—C11—H11	120.4
N7—Fe1—N8	88.54 (10)	C6—C11—H11	120.4
N1—Fe1—N8	89.68 (10)	N4—C12—C13	121.3 (3)
C1—N1—C5	118.6 (2)	N4—C12—H12	119.3
C1—N1—Fe1	130.1 (2)	C13—C12—H12	119.3
C5—N1—Fe1	111.03 (19)	C14—C13—C12	120.9 (3)
N3—N2—C5	111.1 (2)	C14—C13—Cl2	121.1 (3)
N2—N3—C6	114.1 (2)	C12—C13—Cl2	118.0 (3)
N2—N3—Fe1	118.86 (18)	C15—C14—C13	118.0 (3)
C6—N3—Fe1	125.00 (17)	C15—C14—H14	121.0
C12—N4—C16	118.5 (2)	C13—C14—H14	121.0
C12—N4—Fe1	129.2 (2)	C14—C15—C16	119.5 (3)
C16—N4—Fe1	112.2 (2)	C14—C15—H15	120.3
N6—N5—C16	111.3 (2)	C16—C15—H15	120.3
N5—N6—C17	113.3 (2)	N4—C16—C15	121.8 (3)
N5—N6—Fe1	119.1 (2)	N4—C16—N5	116.8 (2)
C17—N6—Fe1	126.25 (18)	C15—C16—N5	121.2 (3)
C23—N7—Fe1	171.1 (3)	C22—C17—C18	120.7 (3)
C24—N8—Fe1	164.8 (2)	C22—C17—N6	119.4 (2)
N1—C1—C2	121.0 (3)	C18—C17—N6	119.9 (3)
N1—C1—H1	119.5	C19—C18—C17	118.3 (4)
C2—C1—H1	119.5	C19—C18—H18	120.8
C3—C2—C1	120.6 (3)	C17—C18—H18	120.8
C3—C2—Cl1	120.9 (3)	C20—C19—C18	120.8 (4)
C1—C2—Cl1	118.5 (3)	C20—C19—H19	119.6
C4—C3—C2	118.2 (3)	C18—C19—H19	119.6
C4—C3—H3	120.9	C21—C20—C19	120.5 (4)
C2—C3—H3	120.9	C21—C20—H20	119.7
C3—C4—C5	119.3 (3)	C19—C20—H20	119.7
C3—C4—H4	120.4	C20—C21—C22	120.0 (4)
C5—C4—H4	120.4	C20—C21—H21	120.0
N1—C5—N2	117.2 (2)	C22—C21—H21	120.0
N1—C5—C4	122.2 (3)	C21—C22—C17	119.6 (3)
N2—C5—C4	120.5 (3)	C21—C22—H22	120.2
C7—C6—C11	121.1 (3)	C17—C22—H22	120.2
C7—C6—N3	119.6 (3)	N7—C23—S1	178.5 (3)
C11—C6—N3	119.1 (3)	N8—C24—S2	178.2 (2)
C8—C7—C6	119.0 (3)

N3—Fe1—N1—C1	173.6 (3)	Cl1—C2—C3—C4	−178.3 (3)
N6—Fe1—N1—C1	72.2 (2)	C2—C3—C4—C5	−0.6 (5)
N7—Fe1—N1—C1	−12.7 (2)	C1—N1—C5—N2	−174.8 (2)
N8—Fe1—N1—C1	−101.2 (2)	Fe1—N1—C5—N2	10.3 (3)
N3—Fe1—N1—C5	−12.28 (18)	C1—N1—C5—C4	3.5 (4)
N6—Fe1—N1—C5	−113.74 (19)	Fe1—N1—C5—C4	−171.4 (2)
N7—Fe1—N1—C5	161.45 (19)	N3—N2—C5—N1	0.3 (4)
N8—Fe1—N1—C5	72.93 (19)	N3—N2—C5—C4	−178.0 (3)
C5—N2—N3—C6	−176.4 (2)	C3—C4—C5—N1	−2.7 (5)
C5—N2—N3—Fe1	−11.8 (3)	C3—C4—C5—N2	175.6 (3)
N6—Fe1—N3—N2	111.7 (2)	N2—N3—C6—C7	53.0 (4)
N4—Fe1—N3—N2	−167.9 (2)	Fe1—N3—C6—C7	−110.6 (3)
N7—Fe1—N3—N2	−24.9 (7)	N2—N3—C6—C11	−132.3 (3)
N1—Fe1—N3—N2	14.0 (2)	Fe1—N3—C6—C11	64.1 (3)
N8—Fe1—N3—N2	−76.6 (2)	C11—C6—C7—C8	−1.1 (5)
N6—Fe1—N3—C6	−85.4 (2)	N3—C6—C7—C8	173.4 (3)
N4—Fe1—N3—C6	−5.0 (2)	C6—C7—C8—C9	−0.1 (6)
N7—Fe1—N3—C6	138.0 (5)	C7—C8—C9—C10	1.7 (7)
N1—Fe1—N3—C6	176.8 (2)	C8—C9—C10—C11	−2.1 (6)
N8—Fe1—N3—C6	86.3 (2)	C9—C10—C11—C6	0.8 (5)
N3—Fe1—N4—C12	67.2 (2)	C7—C6—C11—C10	0.8 (5)
N6—Fe1—N4—C12	169.3 (2)	N3—C6—C11—C10	−173.8 (3)
N7—Fe1—N4—C12	−106.8 (2)	C16—N4—C12—C13	0.8 (4)
N8—Fe1—N4—C12	−18.2 (2)	Fe1—N4—C12—C13	−175.3 (2)
N3—Fe1—N4—C16	−109.20 (19)	N4—C12—C13—C14	−1.9 (5)
N6—Fe1—N4—C16	−7.03 (18)	N4—C12—C13—Cl2	177.4 (2)
N7—Fe1—N4—C16	76.81 (19)	C12—C13—C14—C15	0.7 (5)
N8—Fe1—N4—C16	165.42 (19)	Cl2—C13—C14—C15	−178.5 (3)
C16—N5—N6—C17	−178.6 (2)	C13—C14—C15—C16	1.3 (5)
C16—N5—N6—Fe1	−11.1 (3)	C12—N4—C16—C15	1.3 (4)
N3—Fe1—N6—N5	103.7 (2)	Fe1—N4—C16—C15	178.1 (2)
N4—Fe1—N6—N5	10.6 (2)	C12—N4—C16—N5	−173.2 (2)
N7—Fe1—N6—N5	−83.1 (2)	Fe1—N4—C16—N5	3.6 (3)
N1—Fe1—N6—N5	−174.9 (2)	C14—C15—C16—N4	−2.4 (5)
N8—Fe1—N6—N5	−30.3 (6)	C14—C15—C16—N5	171.9 (3)
N3—Fe1—N6—C17	−90.5 (2)	N6—N5—C16—N4	4.5 (4)
N4—Fe1—N6—C17	176.3 (2)	N6—N5—C16—C15	−170.0 (3)
N7—Fe1—N6—C17	82.6 (2)	N5—N6—C17—C22	−133.9 (3)
N1—Fe1—N6—C17	−9.1 (2)	Fe1—N6—C17—C22	59.6 (3)
N8—Fe1—N6—C17	135.4 (5)	N5—N6—C17—C18	45.6 (4)
N3—Fe1—N8—C24	−87.5 (9)	Fe1—N6—C17—C18	−120.9 (3)
N6—Fe1—N8—C24	47.9 (11)	C22—C17—C18—C19	−0.8 (6)
N4—Fe1—N8—C24	7.8 (9)	N6—C17—C18—C19	179.8 (3)
N7—Fe1—N8—C24	100.4 (9)	C17—C18—C19—C20	1.2 (7)
N1—Fe1—N8—C24	−167.0 (9)	C18—C19—C20—C21	−0.7 (8)
C5—N1—C1—C2	−0.9 (4)	C19—C20—C21—C22	−0.3 (8)
Fe1—N1—C1—C2	172.8 (2)	C20—C21—C22—C17	0.8 (6)
N1—C1—C2—C3	−2.3 (5)	C18—C17—C22—C21	−0.2 (5)
N1—C1—C2—Cl1	179.0 (2)	N6—C17—C22—C21	179.2 (3)
C1—C2—C3—C4	3.1 (5)

Experimental details

Crystal data
Chemical formula	[Fe(NCS)₂(C₁₁H₈ClN₃)₂]
M_r	607.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.5151 (3), 23.7391 (9), 12.1550 (4)
β (°)	96.209 (1)
V (Å³)	2729.46 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.34 × 0.17 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.916, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	29379, 4809, 4189
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.110, 1.08
No. of reflections	4809
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.75

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Fe1—N3	1.900 (2)	Fe1—N7	1.941 (2)
Fe1—N6	1.917 (2)	Fe1—N1	1.945 (2)
Fe1—N4	1.936 (2)	Fe1—N8	1.952 (2)

Acknowledgements

We are grateful to the Faculty of Science and Fisheries Technology, Rajamangala University of Technology Srivijaya, for financial support. We express our thanks for partial financial support and the single-crystal X-ray diffractometer to the Center for Innovation in Chemistry (PERCH-CIC), Comission on Higher Education, Ministry of Education, Thailand.

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