2-Amino-4-ferrocenyl-thia-zole.

The title compound, [Fe(C5H5)(C8H7N2S)], was synthesized by the direct reaction of acetyl-ferrocene, thio-urea and resublimed iodine. The structure shows one mol-ecule in the asymmetric unit. The amino-thia-zole ring makes an angle of 14.53 (13)° with the ferrocenyl ring to which it is attached. In the crystal, pairs of complex mol-ecules inter-act via inter-molecular N-H⋯N hydrogen bonds, forming a cyclic dimer which then inter-acts with other dimers through C-H⋯π inter-actions. © Anzaldo et al. 2022.

Chemical context

Recently, the synthesis of new hybrid compounds based on a ferrocenyl group linked to a five-membered heterocyclic unit has drawn attention (Sánchez-Rodríguez et al., 2017 ▸; Shao et al., 2006a ▸). One important five-membered heterocycle is 2-amino­thia­zole, which is a versatile scaffold extensively used in various branches of chemistry including dyes and in the pharmaceutical industries. 2-Amino­thia­zole derivatives are widely used by medicinal chemists (Das et al., 2016 ▸) and have various applications in medicinal, agriculture and analytical chemistry. They are known to exhibit a wide variety of biological activities such as anti­viral, anti­bacterial, anti­fungal, anti­tubercular, herbicidal and insecticidal (Mishra et al., 2017 ▸; Ji Ram et al., 2019 ▸; Dondoni, 2010 ▸). Thia­zoles are also used as precursors or inter­mediates for the synthesis of a variety of heterocyclic compounds (Zeng et al., 2003 ▸). We report here the crystal and mol­ecular structure of 2-amino-4-ferrocenyl­thia­zole, which has not previously been reported.

Structural commentary

The title compound crystallizes in the monoclinic system, space group P21/c. The asymmetric unit contains one mol­ecular unit as shown in Fig. 1 ▸. The C15—S11—C12 bond angle of 88.6 (2)° reflects the presence of a non-delocalized lone pair of electrons and is similar to that observed in other thia­zoles. The length of the C12=N13 double bond is 1.306 (4) Å. The torsion angles in the amino substituted thia­zole ring are: 1.1 (3)° for N13—C12—S11—C15 and 1.7 (4)° for N13—C14—C15—S11. All bond lengths and angles confirm the sp 2 hybridization for all C and N atoms.

Figure 1

Structure of 2-amino-4-ferrocenyl­thia­zole. Displacement ellipsoids are drawn at the 30% probability level.

The ferrocene moiety is in the staggered conformation. The influence of the steric hindrance caused by the organic groups is reflected in the torsion angle C5—C1—C14—C15, 17.0 (5)°, compared with the C2—C1—C14—N13 torsion angle of 13.2 (4)°. The steric effect is also evident in the dihedral angle of 14.77 (17)° subtended by the planes of the heterocycle (C14/C15/S11/C12/N13) and the Cp plane (C1–C5).

Supra­molecular features

The structure is stabilized by inter­molecular hydrogen bonding (N—H⋯N) and C—H⋯π inter­actions. For C10—H10⋯Cg(C1–C5) the H-to-ring distance is 2.89 Å, as shown in Table 1 ▸. As a result of inter­molecular N—H⋯N inter­actions, a pseudo six-membered (N16/C12/N13/N16/C12/N13) ring is formed and this hydrogen bond, in addition to the C—H⋯π inter­action, produces a packing into supra­molecular layers parallel to the bc plane (Fig. 2 ▸). The structure presents very similar C=N distances and angles in the thia­zole ring, as reported earlier for some similar compounds (Sánchez-Rodríguez et al., 2017 ▸; Shao et al., 2006b ▸).

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C5 Cp ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N16—H16A⋯N13i	0.84 (2)	2.14 (2)	2.976 (4)	173 (4)
C10—H10⋯Cg1ii	0.98	2.89	3.703 (3)	141

Symmetry codes: (i) ; (ii) .

Figure 2

The packing of the title compound. The dotted lines indicate inter­molecular hydrogen bonds. All H atoms not involved in these inter­actions have been omitted for clarity.

Database survey

A search of the Cambridge Structural Database (CSD, version 5.43, update of November 2021; Groom et al., 2016 ▸) for 4-ferrocenyl thia­zoles gave eight hits. In six cases (GAVFIT, Yu et al., 2005 ▸; GAVFIT01, Yu et al., 2007 ▸; QAYSAL, Shao et al., 2006b ▸; QAYSAL01, Shao et al., 2006a ▸; RAPQAB, Shao et al., 2005 ▸; RAPQAB01, Shao et al., 2006a ▸), the thia­zole ring is substituted. In two cases there is no substitution in the thia­zole ring (GUPKAG, Xu et al., 2020 ▸ and PAWWEQ, Plazuk et al., 2005 ▸) with PAWWEQ being a diferrocenyl compound. In all eight cases, the bond lengths and angles confirm the sp hybridization for all C and N atoms.

Synthesis and crystallization

The title compound was synthesized according to the reported method (Chopra et al., 2015 ▸). The crude product was purified by column chromatography over silica and suitable crystals were obtained after recrystallization of the solid from a 1:1 hexane-di­chloro­methane mixture by slow evaporation. The compound 2-amino-4-ferrocenyl­thia­zole was further characterized by 1H NMR and IR–ATR. FT–IR (ATR, cm−1) ν 3099 (ArCH), 2921 (CH3), 1658 (C=N); 1H NMR (300 MHz, CDCl3): 4.62 (2H, t, subst. Cp); 4.25 (2H, t, subst. Cp); 4.10 (5H, s, subst. Cp); 5.00 (2H, –NH2), 6.35 (1H, C—H).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. N-bound H atoms were refined isotropically with U iso(H) = 1.2U eq(N). C-bound H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined with isotropically U iso(H) = 1.2U eq(C) using a riding model.

Table 2

Experimental details

Crystal data
Chemical formula	[Fe(C5H5)(C8H7N2S)]
M r	284.16
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	298
a, b, c (Å)	14.4024 (4), 7.9621 (2), 10.3584 (3)
β (°)	104.3453 (13)
V (Å3)	1150.80 (5)
Z	4
Radiation type	Mo Kα
μ (mm−1)	1.47
Crystal size (mm)	0.27 × 0.16 × 0.14
Data collection
Diffractometer	Bruker D8 Venture κ-geometry diffractometer 208039-01
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.656, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	17487, 3214, 1805
R int	0.102
(sin θ/λ)max (Å−1)	0.694
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.050, 0.091, 1.02
No. of reflections	3214
No. of parameters	160
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.44, −0.43

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), XP (Siemens, 1998 ▸) and CIFTAB (Sheldrick, 2013 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022007228/dj2046sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022007228/dj2046Isup3.hkl

CCDC reference: 1841501

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Fe(C5H5)(C8H7N2S)]	F(000) = 584
Mr = 284.16	Dx = 1.640 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.4024 (4) Å	Cell parameters from 5893 reflections
b = 7.9621 (2) Å	θ = 2.9–30.0°
c = 10.3584 (3) Å	µ = 1.47 mm−1
β = 104.3453 (13)°	T = 298 K
V = 1150.80 (5) Å3	Prism, orange
Z = 4	0.27 × 0.16 × 0.14 mm

Bruker D8 Venture κ-geometry diffractometer 208039-01	3214 independent reflections
Radiation source: micro-focus X-ray source	1805 reflections with I > 2σ(I)
Helios multilayer mirror monochromator	Rint = 0.102
Detector resolution: 52.0833 pixels mm-1	θmax = 29.6°, θmin = 2.9°
φ and ω–scans	h = −19→19
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −11→11
Tmin = 0.656, Tmax = 0.746	l = −14→14
17487 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)] = 0.050	Hydrogen site location: mixed
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.024P)2 + 0.7338P] where P = (Fo2 + 2Fc2)/3
3214 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.44 e Å−3
1 restraint	Δρmin = −0.43 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Fe1	0.17036 (3)	0.50999 (5)	0.21675 (4)	0.02688 (13)
C1	0.2361 (2)	0.7055 (3)	0.3316 (3)	0.0293 (7)
C2	0.2072 (2)	0.5816 (4)	0.4119 (3)	0.0347 (7)
H2	0.249851	0.519784	0.484765	0.042*
C3	0.1066 (2)	0.5605 (4)	0.3683 (3)	0.0378 (8)
H3	0.067801	0.482058	0.405807	0.045*
C5	0.1513 (2)	0.7608 (4)	0.2371 (3)	0.0354 (8)
H5	0.148594	0.845906	0.167931	0.043*
C4	0.0721 (2)	0.6712 (4)	0.2603 (3)	0.0390 (8)
H4	0.005144	0.683301	0.210031	0.047*
C6	0.2513 (2)	0.4562 (4)	0.0875 (3)	0.0390 (8)
H6	0.301224	0.528302	0.067788	0.047*
C7	0.2651 (2)	0.3335 (4)	0.1884 (3)	0.0401 (8)
H7	0.326028	0.304522	0.250824	0.048*
C8	0.1747 (2)	0.2590 (4)	0.1828 (3)	0.0436 (9)
H8	0.162060	0.169787	0.241401	0.052*
C9	0.1063 (2)	0.3352 (4)	0.0782 (3)	0.0417 (8)
H9	0.037655	0.309044	0.051734	0.050*
C10	0.1538 (2)	0.4568 (4)	0.0194 (3)	0.0388 (8)
H10	0.123912	0.530116	−0.055375	0.047*
S11	0.48146 (6)	0.92268 (11)	0.31997 (10)	0.0468 (3)
C12	0.4914 (2)	0.7406 (4)	0.4136 (3)	0.0340 (7)
N13	0.41026 (17)	0.6692 (3)	0.4162 (3)	0.0313 (6)
C14	0.3340 (2)	0.7625 (4)	0.3407 (3)	0.0301 (7)
C15	0.3588 (2)	0.9019 (4)	0.2849 (3)	0.0407 (8)
H15	0.315506	0.977392	0.234051	0.049*
N16	0.5779 (2)	0.6798 (4)	0.4780 (4)	0.0506 (9)
H16A	0.580 (2)	0.585 (3)	0.514 (3)	0.061*
H16B	0.627 (2)	0.732 (4)	0.469 (4)	0.061*

	U11	U22	U33	U12	U13	U23
Fe1	0.0253 (2)	0.0294 (2)	0.0264 (2)	0.00356 (18)	0.00735 (17)	−0.0012 (2)
C1	0.0303 (17)	0.0283 (16)	0.0294 (18)	0.0051 (12)	0.0075 (14)	−0.0029 (13)
C2	0.0349 (18)	0.0426 (18)	0.0263 (18)	0.0062 (14)	0.0071 (14)	−0.0018 (15)
C3	0.0341 (18)	0.050 (2)	0.035 (2)	0.0000 (15)	0.0180 (15)	−0.0075 (16)
C5	0.0387 (19)	0.0287 (16)	0.036 (2)	0.0100 (14)	0.0042 (16)	−0.0040 (14)
C4	0.0283 (18)	0.048 (2)	0.039 (2)	0.0094 (15)	0.0060 (15)	−0.0144 (17)
C6	0.042 (2)	0.040 (2)	0.042 (2)	0.0015 (14)	0.0252 (17)	−0.0056 (15)
C7	0.0376 (19)	0.0400 (19)	0.044 (2)	0.0147 (15)	0.0119 (16)	−0.0086 (16)
C8	0.056 (2)	0.0291 (17)	0.050 (2)	0.0014 (16)	0.0215 (19)	0.0012 (16)
C9	0.0375 (19)	0.0440 (19)	0.042 (2)	−0.0034 (16)	0.0062 (17)	−0.0154 (17)
C10	0.045 (2)	0.044 (2)	0.0284 (18)	0.0079 (15)	0.0102 (16)	−0.0009 (15)
S11	0.0426 (5)	0.0386 (5)	0.0569 (6)	−0.0050 (4)	0.0081 (4)	0.0175 (4)
C12	0.0351 (18)	0.0308 (16)	0.035 (2)	−0.0025 (14)	0.0062 (15)	0.0041 (14)
N13	0.0284 (14)	0.0299 (13)	0.0348 (16)	0.0007 (11)	0.0064 (12)	0.0043 (12)
C14	0.0329 (17)	0.0277 (16)	0.0289 (18)	0.0020 (13)	0.0060 (14)	−0.0040 (13)
C15	0.0385 (19)	0.0346 (18)	0.045 (2)	0.0035 (14)	0.0029 (16)	0.0112 (16)
N16	0.0283 (16)	0.0447 (18)	0.074 (2)	−0.0057 (13)	0.0045 (16)	0.0265 (17)

Fe1—C6	2.027 (3)	C6—C10	1.408 (4)
Fe1—C7	2.030 (3)	C6—C7	1.408 (4)
Fe1—C8	2.033 (3)	C6—H6	0.9800
Fe1—C5	2.034 (3)	C7—C8	1.419 (4)
Fe1—C2	2.040 (3)	C7—H7	0.9800
Fe1—C4	2.043 (3)	C8—C9	1.408 (4)
Fe1—C1	2.043 (3)	C8—H8	0.9800
Fe1—C10	2.043 (3)	C9—C10	1.409 (4)
Fe1—C3	2.045 (3)	C9—H9	0.9800
Fe1—C9	2.047 (3)	C10—H10	0.9800
C1—C2	1.417 (4)	S11—C15	1.721 (3)
C1—C5	1.432 (4)	S11—C12	1.730 (3)
C1—C14	1.462 (4)	C12—N13	1.306 (4)
C2—C3	1.417 (4)	C12—N16	1.349 (4)
C2—H2	0.9800	N13—C14	1.394 (3)
C3—C4	1.414 (4)	C14—C15	1.340 (4)
C3—H3	0.9800	C15—H15	0.9300
C5—C4	1.416 (4)	N16—H16A	0.84 (2)
C5—H5	0.9800	N16—H16B	0.84 (2)
C4—H4	0.9800
C6—Fe1—C7	40.61 (12)	C4—C3—H3	126.0
C6—Fe1—C8	68.33 (13)	C2—C3—H3	126.0
C7—Fe1—C8	40.88 (12)	Fe1—C3—H3	126.0
C6—Fe1—C5	112.99 (13)	C4—C5—C1	108.4 (3)
C7—Fe1—C5	143.86 (14)	C4—C5—Fe1	70.02 (17)
C8—Fe1—C5	173.68 (13)	C1—C5—Fe1	69.79 (16)
C6—Fe1—C2	131.49 (13)	C4—C5—H5	125.8
C7—Fe1—C2	108.54 (13)	C1—C5—H5	125.8
C8—Fe1—C2	115.77 (13)	Fe1—C5—H5	125.8
C5—Fe1—C2	68.37 (13)	C3—C4—C5	107.9 (3)
C6—Fe1—C4	145.32 (14)	C3—C4—Fe1	69.85 (17)
C7—Fe1—C4	173.96 (14)	C5—C4—Fe1	69.34 (17)
C8—Fe1—C4	135.13 (14)	C3—C4—H4	126.0
C5—Fe1—C4	40.64 (12)	C5—C4—H4	126.0
C2—Fe1—C4	68.26 (12)	Fe1—C4—H4	126.0
C6—Fe1—C1	106.63 (13)	C10—C6—C7	108.3 (3)
C7—Fe1—C1	112.38 (13)	C10—C6—Fe1	70.40 (18)
C8—Fe1—C1	145.08 (13)	C7—C6—Fe1	69.82 (18)
C5—Fe1—C1	41.12 (11)	C10—C6—H6	125.9
C2—Fe1—C1	40.62 (12)	C7—C6—H6	125.9
C4—Fe1—C1	68.84 (12)	Fe1—C6—H6	125.9
C6—Fe1—C10	40.46 (12)	C6—C7—C8	107.5 (3)
C7—Fe1—C10	68.14 (13)	C6—C7—Fe1	69.56 (17)
C8—Fe1—C10	67.91 (13)	C8—C7—Fe1	69.66 (18)
C5—Fe1—C10	108.79 (13)	C6—C7—H7	126.2
C2—Fe1—C10	170.67 (13)	C8—C7—H7	126.2
C4—Fe1—C10	115.84 (13)	Fe1—C7—H7	126.2
C1—Fe1—C10	131.53 (13)	C9—C8—C7	108.1 (3)
C6—Fe1—C3	171.70 (13)	C9—C8—Fe1	70.36 (18)
C7—Fe1—C3	133.85 (14)	C7—C8—Fe1	69.46 (18)
C8—Fe1—C3	111.39 (13)	C9—C8—H8	125.9
C5—Fe1—C3	68.26 (13)	C7—C8—H8	125.9
C2—Fe1—C3	40.58 (12)	Fe1—C8—H8	125.9
C4—Fe1—C3	40.48 (13)	C8—C9—C10	107.9 (3)
C1—Fe1—C3	68.58 (13)	C8—C9—Fe1	69.26 (18)
C10—Fe1—C3	147.70 (13)	C10—C9—Fe1	69.70 (18)
C6—Fe1—C9	68.10 (13)	C8—C9—H9	126.1
C7—Fe1—C9	68.31 (13)	C10—C9—H9	126.1
C8—Fe1—C9	40.38 (12)	Fe1—C9—H9	126.1
C5—Fe1—C9	133.72 (13)	C6—C10—C9	108.2 (3)
C2—Fe1—C9	147.76 (14)	C6—C10—Fe1	69.14 (18)
C4—Fe1—C9	111.42 (13)	C9—C10—Fe1	70.01 (18)
C1—Fe1—C9	171.57 (13)	C6—C10—H10	125.9
C10—Fe1—C9	40.29 (13)	C9—C10—H10	125.9
C3—Fe1—C9	117.46 (14)	Fe1—C10—H10	125.9
C2—C1—C5	106.9 (3)	C15—S11—C12	88.62 (15)
C2—C1—C14	126.6 (3)	N13—C12—N16	123.7 (3)
C5—C1—C14	126.4 (3)	N13—C12—S11	115.2 (2)
C2—C1—Fe1	69.56 (17)	N16—C12—S11	121.1 (2)
C5—C1—Fe1	69.09 (16)	C12—N13—C14	110.0 (3)
C14—C1—Fe1	125.0 (2)	C15—C14—N13	115.2 (3)
C3—C2—C1	108.7 (3)	C15—C14—C1	125.8 (3)
C3—C2—Fe1	69.93 (17)	N13—C14—C1	119.0 (3)
C1—C2—Fe1	69.82 (17)	C14—C15—S11	111.0 (2)
C3—C2—H2	125.6	C14—C15—H15	124.5
C1—C2—H2	125.6	S11—C15—H15	124.5
Fe1—C2—H2	125.6	C12—N16—H16A	118 (2)
C4—C3—C2	108.0 (3)	C12—N16—H16B	118 (2)
C4—C3—Fe1	69.67 (18)	H16A—N16—H16B	123 (3)
C2—C3—Fe1	69.49 (17)
C5—C1—C2—C3	0.0 (3)	C7—C8—C9—C10	−0.2 (4)
C14—C1—C2—C3	−178.4 (3)	Fe1—C8—C9—C10	59.2 (2)
Fe1—C1—C2—C3	−59.3 (2)	C7—C8—C9—Fe1	−59.4 (2)
C5—C1—C2—Fe1	59.2 (2)	C7—C6—C10—C9	0.5 (3)
C14—C1—C2—Fe1	−119.1 (3)	Fe1—C6—C10—C9	−59.3 (2)
C1—C2—C3—C4	0.0 (3)	C7—C6—C10—Fe1	59.8 (2)
Fe1—C2—C3—C4	−59.2 (2)	C8—C9—C10—C6	−0.2 (4)
C1—C2—C3—Fe1	59.2 (2)	Fe1—C9—C10—C6	58.8 (2)
C2—C1—C5—C4	0.0 (3)	C8—C9—C10—Fe1	−58.9 (2)
C14—C1—C5—C4	178.4 (3)	C15—S11—C12—N13	1.1 (3)
Fe1—C1—C5—C4	59.6 (2)	C15—S11—C12—N16	−179.0 (3)
C2—C1—C5—Fe1	−59.5 (2)	N16—C12—N13—C14	179.7 (3)
C14—C1—C5—Fe1	118.8 (3)	S11—C12—N13—C14	−0.4 (3)
C2—C3—C4—C5	0.0 (3)	C12—N13—C14—C15	−0.9 (4)
Fe1—C3—C4—C5	−59.1 (2)	C12—N13—C14—C1	−179.3 (3)
C2—C3—C4—Fe1	59.1 (2)	C2—C1—C14—C15	−165.0 (3)
C1—C5—C4—C3	0.0 (3)	C5—C1—C14—C15	17.0 (5)
Fe1—C5—C4—C3	59.4 (2)	Fe1—C1—C14—C15	105.6 (3)
C1—C5—C4—Fe1	−59.4 (2)	C2—C1—C14—N13	13.2 (4)
C10—C6—C7—C8	−0.6 (3)	C5—C1—C14—N13	−164.9 (3)
Fe1—C6—C7—C8	59.6 (2)	Fe1—C1—C14—N13	−76.2 (3)
C10—C6—C7—Fe1	−60.1 (2)	N13—C14—C15—S11	1.7 (4)
C6—C7—C8—C9	0.5 (4)	C1—C14—C15—S11	180.0 (2)
Fe1—C7—C8—C9	60.0 (2)	C12—S11—C15—C14	−1.6 (3)
C6—C7—C8—Fe1	−59.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N16—H16A···N13i	0.84 (2)	2.14 (2)	2.976 (4)	173 (4)
C10—H10···Cg1ii	0.98	2.89	3.703 (3)	141