Journal of Chemical Crystallography, Vol. 37, No. 6, June 2007 (
C 2007) DOI: 10.1007/s10870-006-9166-5

Syntheses and crystal structures of an organometallic thiosemicarbazone and an organometallic enehydrazide Yao-Cheng Shi,(1)∗ Hong-Jian Cheng,(1) Chun-Xia Sui,(1) and Bei-Bei Zhu(1) Received March 25, 2006; accepted October 17, 2006 Published Online March 13, 2007

Reactions of ferrocenoylacetone with thiosemicarbazide and isonicotinic acid hydrazide generate an organometallic thiosemicarbazone 1 and enehydrazide 2, respectively. The complexes 1 and 2, which can be formulated as [C5 H5 FeC5 H4 C(O)CH2 C(=NNHCSNH2 )CH3 ] and [C5 H5 FeC5 H4 C(O)CH=C(NHNHCOC5 H4 N-4)CH3 ], have been characterized by elemental analyses, IR, NMR, UV and were structurally characterized by single-crystal X-ray crystallography. Complex 1 (C15 H17 FeN3 OS) crystallizes in the monoclinic space group P21 /c, with lattice constants: a = 13.939(3) Å, b = 8.2600(17) Å, c = 13.176(3) Å, β = 94.83(3)◦ , V = 1511.7(6) Å3 , Z = 4, Dc = 1.508 g cm−3 , F(000) = 712, R1 = 0.0602, wR2 = 0.1526. Two intermolecular hydrogen bonds N–H · · · S (N · · · S = 3.356(8) and 3.499(7) Å, N–H · · · S = 168 and 170◦ ) form a chain in the [010] direction. The intermolecular hydrogen bond C–H · · · O (C · · · O = 3.432(10) Å, C–H · · · O = 151◦ ) leads to a [010] double-chain through each unit cell. The intermolecular hydrogen bond C–H · · · O (C · · · O = 3.359(10) Å, C–H · · · O = 173◦ ) makes the [010] double-chain pack along the c axis to result in a two-dimensional network. Complex 2 (C20 H19 FeN3 O2 ) crystallizes in the monoclinic space group P21 /c, with lattice constants: a = 14.091(2) Å, b = 10.024(2) Å, c = 13.806(2) Å, β = 112.41(2)◦ , V = 1802.8(6) Å3 , Z = 4, Dc = 1.434 g cm−3 , F(000) = 808, R1 = 0.0576, wR2 = 0.1593. The strong intramolecular hydrogen bond N–H · · · O from the enamine N atom and carbonyl O atom stabilizes the enehydrazide. The intermolecular hydrogen bonds N–H · · · O and C–H · · · O (N · · · O = 2.906(6) Å, N–H · · · O = 155◦ C · · · O = 3.364(6) Å, C–H · · · O = 153◦ ) generate a [010] chain. The intermolecular hydrogen bond N–H · · · O (N · · · O = 2.989(6) Å, N–H · · · O = 128◦ ) forms a [010] double-chain through each unit cell. The π · · · π stacking interation involving the pyridyl groups makes the [010] double-chain pack along the c axis to lead to a two-dimensional network. KEY WORDS: Ferrocenoylacetone; hydrazide; thiosemicarbazone; enehydrazide; X-ray crystallography.

Introduction (1)

∗

School of Chemistry, Yangzhou University, Yangzhou 225002, P.R. China. To whom correspondence should be addressed; e-mail: yzssyc@ yzcn.net

The products generated from the reactions of 1,3-dioxo compounds and hydrazides have attracted much interest due to their applications in 399 C 2007 Springer Science+Business Media, LLC 1074-1542/07/0600-0399/0


400 the synthesis of heterocyclic compounds and in coordination chemistry.1 – 3 It has been reported that the product of a β-dioxo compound and an acyl hydrazide is capable of existing as a tautomeric mixture of enehydrazide, acylhydrazone and 1-acyl-5-hydroxy-2-pyrazoline.1 However, they have not been structurally characterized by single-crystal X-ray crystallography. Because of few studies on reactions of organometallic 1,3diketones and acylhydrazides,4,5 we have initiated a systematical investigation into these reactions. As part of this work, herein we report the syntheses and crystal structures of an organometallic thiosemicarbazone from ferrocenoylacetone and thiosemicarbazide and an organometallic enehydrazide from ferrocenoylacetone and isonicotinic acid hydrazide. Experimental Reagents and general procedures All chemicals used were of reagent grade. Ferrocenoylacetone was synthesized by a literature method.4 Progress of the reaction was monitored by TLC. 1 H NMR spectra were determined with a Bruker Avance 600 spectrometer using TMS as external standard in CDCl3 . The IR spectra were recorded on a Perkin-Elmer 402 as a KBr disk in the range of 400–4000 cm−1 . The UV spectra were measured with a Shimadzu UV-240 spectrometer using a solution in DMF. Analyses for C, H and N were performed on an Elementa Vario EL III instrument. The melting points were measured with a Yanagimoto apparatus and are uncorrected. Synthesis of complex 1 Ferrocenoylacetone (1.047 g, 3.9 mmol) was added to a solution of thiosemicarbazide (0.353 g, 3.9 mmol) and a catalytic trace amount of acetic acid (2–3 drops) in 20 mL of ethanol, and then the mixture was refluxed for 3 h. The solvent was evaporated under vacuum, and the residue was recrystallized from petroleum ether (60–

Shi, Cheng, Sui, and Zhu 90◦ C) to afford 1.190 g (89.2%) of 1 as an orange solid. Prism single crystals were obtained from dichloromethane and acetone. M.p. 162.6– 163.5◦ C. Anal. Calcd. for C15 H17 FeN3 O: C, 52.49; H, 4.99; N, 12.24. Found: C, 52.27; H, 4.92; N, 12.25%. IR (KBr disk): ν(NH) 3421.15(s), 3218.31(m), 3130.39(m), ν(C=O) and ν(C=N) 1582 (vs, br), ν(C=S) 1068.98(m) cm−1 . UV (nm, in DMF): λmax (ε × 104 ) 259 (8.7), 275 (1.5) (Bband); 328 (1.9) (K-band).1 H NMR (DMSO): δ 1.967 (s, 3H, CH3 ), 3.742(s, 2H, CH2 ), 4.267 (s, 5H, C5 H5 ), 4.610 (s, 2H, (H3 , H4 ) of C5 H4 ring), 4.859 (s, 2H, (H2 , H5 ) of C5 H4 ring), 7.705, 8.163 (s, s, 1H, 1H, NH2 ), 10.177 (s, 1H, NH) ppm. Synthesis of complex 2 A solution of ferrocenoylacetone (1.891 g, 7 mmol), isonicotinic acid hydrazide (0.960 g, 7 mmol) and a catalytic amount of acetic acid (2–3 drops) in 20 mL of ethanol was refluxed for 8 h. The solvent was evaporated under vacuum, and the residue was recrystallized from dichloromethane and petroleum ether (60–90◦ C) to afford 2.225 g (82.6%) of 2 as a red crystalline solid. M.p. 176.0–178.2◦ C. Block single crystals were obtained from dichloromethane and acetone. Anal. Calcd. for C20 H19 FeN3 O2 : C, 61.72; H, 4.92; N, 10.80. Found: C, 61.33; H, 4.92; N, 10.50 %. IR (KBr disk): ν(amide NH) 3270.88 (m), ν(enamine NH) 3090.79 (m), ν(C=O) 1666.39 (vs), ν(C=N) and ν(C=C) 1596.15 (vs) cm−1 . UV (nm, in DMF): λmax (ε × 104 ) 274 (0.9) (Bband), 333 (1.2) (K-band).1 H NMR (DMSO–d6 ): δ 1.959 (s, 3H, CH3 ), 4.134 (s, 5H, C5 H5 ), 4.413 (s, 2H, 2 (H3 , H4 ) of C5 H4 ring), 4.737 (s, 2H, 2 (H2 , H5 ) of C5 H4 ring), 5.552 (s, 1H, CH), 7.744, 7.752 (d, 2H, (H3 , H5 ) of C5 H4 N ring), 8.743, 8.752 (d, 2H, (H2 , H6 ) of C5 H4 N ring), 10.904 (s, 1H, amide NH), 11.612 (s, 1H, enamine NH) ppm. Crystal structure determination X-ray data of both complexes were collected on an Enraf-Nonius CAD4 diffractometer

Syntheses and crystal structures of an organometallic thiosemicarbazone/enehydrazide

401

Table 1. Crystallographic Data for Complexes 1 and 2 Complex CCDC deposit no. Color/shape Formula Formula weight Crystal size (mm) Crystal system Space group Unit cell dimensions a (Å) b (Å) c (Å) β (◦ ) V (Å3 ) Z Dc (g cm−1 ) F (000) T(K) µ(Mo-Kα )(mm−1 ) Scan mode θ Range (◦ ) Limiting indices Absorption correction Reflections collected Independent reflections Independent reflections [I > 2.0σ (I)] Refinement method Data/restraints/parameters Final R indices [I > 2.0σ (I)] R indices (all data) GooF Largest diff.peak and hole (e Å−3 )

1

2

CCDC-602172 Orange/prism C15 H17 FeN3 OS 343.23 0.30 × 0.20 × 0.10 Monoclinic P21 /c

CCDC-602173 Red/block C20 H19 FeN3 O2 389.23 0.40 × 0.10 × 0.10 Monoclinic P21 /c

13.939(3) 8.2600(17) 13.176(3) 94.83(3) 1511.7(6) 4 1.508 712 295 1.137 ω-2θ 1.47; 24.97 −16 ≤ h ≤ 16, −9 ≤ k ≤ 0, 0 ≤ l ≤ 15 PSI-scan 2771 2645 1276 Full-matrix least-squares on F2 2645/0/191 R1 , 0.0602; wR2 , 0.1526 R1 , 0.1752; wR2 , 0.2019 0.902 0.46 and −0.38

14.091(2) 10.024(2) 13.806(2) 112.41(2) 1802.8(6) 4 1.434 808 295 0.855 ω-2θ 1.56; 24.99 −16 ≤ h ≤ 15, −11 ≤ k ≤ 0, 0 ≤ l ≤ 16 PSI-scan 3292 3147 2096 Full-matrix least-squares on F2 3147/0/236 R1 , 0.0576; wR2 , 0.1593 R1 , 0.1017; wR2 , 0.1889 1.05 0.67 and −0.72

at 295 K using graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). The data reduction were carried out with the XCAD-4 software.6 The structures were solved by direct methods after absorption correction by Psi-scan method7 and subsequently refined on F2 by using full-matrix least-squares methods. All non-hydrogen atoms were refined anisotropically, and hydrogen atoms were located at calculated positions and subsequently treated as riding atoms, with C–H = 0.93 (cyclopentadienyl), 0.96 (CH3 ) and 0.97 Å (CH2 ) and N–H = 0.86 Å at 295 K for complex 1 and C–H = .93 (cyclopentadienyl, olefinic and pyridyl) and 0.96 Å (CH3 ) and N–H = 0.86 Å at 295 K for compound 2 and Uiso (H) values set at 1.2Ueq (C, N).8 A summary of the data collec-

tions and structure refinement parameters is given in Table 1. ORTEP plots of complexes 1 and 2 with displacement ellipsoids at the 30% probability level were drawn using PLATON.9

Results and discussion Unlike the reaction of S-benzlydithiocarbazate with ferrocenoylacetone which results in a tautomeric mixture of enehydrazide and thioacylhydrazone (thiosemicarbazone) in solution,4 thiosemicarbazide yields only the thioacylhydrazone 1. Furthermore, isonicotinic acid hydrazide affords only the enehydrazide 2 (Scheme 1). The new complexes have been characterized

402

Shi, Cheng, Sui, and Zhu H2NNHCSNH2 C5H5FeC5H4COCH2C(=NNHCSNH2)CH3 C5H5FeC5H4COCH2COCH3

(1) H2NNHCOC5H4N-4 C5H5FeC5H4COCH=C(NHNHCO(C5H4N-4))CH3 (2)

Scheme 1.

by elemental analyses and IR, NMR, UV spectra. The 1 H NMR spectra show that in solution the new complexes exist in a thioacylhydrazone and an enehydrazide form, respectively. The IR spectra display that in the solid state each the new complex exists in the same form as in solution. More importantly, their structures have been unambiguously determined by single-crystal X-ray crystallography. The molecular structure of complex 1 is shown in Fig. 1. Selected bond distances and angles are listed in Table 2. The O–C(5) and N(3)–C(3) bond distances of 1.218(9) and 1.274(10) Å are very close to those of the related C5 H5 FeC5 H4 C(O)CH2 C (=NNHCS2 CH2 Ph)CH3 ] complex (1.221(4) and 1.271(5) Å, respectively), indicating these are typical double bonds.4,5 As in the above com-

plex, the C=N bond adopts the E configuration (Fig. 1). Bond distances of the NNHCSNH2 moiety in complex 1 (1.398(9), 1.322(10), 1.682(8) and 1.342 (9) Å) are similar to those in the compound 4-[(N-hydroxyethyl-N-methyl)amino] benzaldehyde thiosemicarbazone (The values are 1.391(3), 1.337(3), 1.680(3) and 1.342(3) Å, respectively).10 The mean C–C distances in the substituted cyclopentadienyl and cyclopentadienyl group (1.421(11) and 1.400 (13) Å) are close to the 1.41 Å distance observed in ferrocene. However, the average distances of iron to carbon in the ferrocenyl group with and without the side-chain (2.039(8) and 2.036(9) Å) are slightly shorter than the 2.045 Å distance in ferrocene.5 The C(5)–C(6) distance is 1.466(11) Å shorter than 1.48 Å of Csp2–Csp2 single bond, suggesting that the carbonyl group is partially involved

Fig. 1. Molecular structure of complex 1.

Syntheses and crystal structures of an organometallic thiosemicarbazone/enehydrazide Table 2.

Selected Bond Distances (Å) and Angles (◦ ) for Complex 1

S–C(1) O–C(5) N(1)–C(1) N(2)–C(1) N(2)–N(3) N(3)–C(3) C(2)–C(3) C(1)–N(2)–N(3) C(3)–N(3)–N(2) N(1)–C(1)–N(2) N(1)–C(1)–S N(2)–C(1)–S N(3)–C(3)–C(2) N(3)–C(3)–C(4) C(2)–C(3)–C(4)

1.682 (8) 1.218 (9) 1.322 (10) 1.342 (9) 1.398 (9) 1.274 (10) 1.489 (12) 117.0 (6) 117.8 (7) 117.6 (8) 121.3 (7) 121.0 (6) 128.1 (8) 114.2 (8) 117.7 (7)

C(3)–C(4) C(4)–C(5) C(5)–C(6) C(7) · · · Oiii C(9) · · · · · · Oiv N(1) · · · Si N(2) · · · Sii C(3)–C(4)–C(5) O–C(5)–C(4) O–C(5)–C(6) C(4)–C(5)–C(6) C(7)–H(7) · · · Oiii C(9)–H(9) · · · Oiv N(1)–H(1B) · · · Si N(2)–H(2) · · · Sii

1.520 (11) 1.513 (11) 1.466 (11) 3.432(10) 3.359(10) 3.356 (8) 3.499 (7) 111.6 (7) 121.2 (8) 120.3 (8) 118.3 (8) 151 173 168 170

Note. Symmetry codes: (i) −x, −1/2 + y, 3/2 − z; (ii) −x, 1/2 + y, 3/2 − z; Symmetry codes: (iii) 1 − x, 1 − y, 1 − z; (iv) x, 1/2 − y, − 1/2 + z.

in the conjugation of the substituted cyclopentadienyl group. This is further supported by the small dihedral angle between the O–C(4)–C(5) plane and the substituted cyclopentadienyl group (14.6(9)◦ ). The cyclopentadienyl groups form a dihedral angle of 2.3(5)◦ and therefore they are nearly parallel. The CH3 (CH2 )C(=N) plane and the NHCSNH2 plane are not coplanar, making an angle of 6.8(5)◦ . As shown in Fig. 2, the intermolecular hydrogen bonds N(1)–H(1B) · · · Si and N(2)– H(2) · · · Sii form a [010] chain having edge-fused centrosymmetric R2 2 (8) rings (Fig. 2; Table 2; Symmetry codes: (i) − x, − 1/2 + y, 3/2 − z; (ii) − x, 1/2 + y, 3/2 − z; N(1) · · · Si = 3.356 (8) Å; N(2) · · · Sii = 3.499 (7) Å).11 The intermolecular hydrogen bond C(7)– H(7) · · · Oiii generates a [010] double-chain having centrosymmetric R2 2 (10) rings through each unit cell. The intermolecular hydrogen bond C(9)–H(9) · · · Oiv leads to a [001] chain (Fig. 2; Table 2; Symmetry codes: (iii) 1 − x, 1 − y, 1 − z; (iv) x, 1/2 − y, − 1/2 + z; C(7) · · · Oiii = 3.432(10) ; C(9) · · · Oiv = 3.359 (10) Å). Therefore the above-mentioned intermolecular hydrogen bonds produce a twodimensional network.

403

The molecular structure of complex 2 is shown in Fig. 3. Selected bond distances and angles are listed in Table 3. The bond distances and angles of the O=C–C=C–N system in complex 2 are similar to the corresponding values of the previously reported enaminones, the bond distances in the O=C–C=C–N skeleton indicate electron delocalization. 4,5 The mean C–C distances in the substituted cyclopentadienyl and cyclopentadienyl group (1.420(8) and 1.401 (9) Å) are close to 1.41 Å in ferrocene. However, the average distances of iron to carbon in the ferrocenyl group with and without the side-chain (2.038(5) and 2.037(6) Å) are slightly shorter than 2.045 Å in ferrocene. The dihedral angle between the cyclopentadienyl groups is 0.4(4)◦ and shows that they are parallel to each other as in complex 1. The dihedral angles between the O=C–C=C–N skeleton and the planes of the N(2)–C(15)–O(2) group and the substituted cyclopentadienyl group are 73.1(3) and 27.2(3)◦ , respectively. Planes of the N(2)–C(15)–O(2) group and the pyridine group form a dihedral angle of 10.4(3)◦ , suggesting that the amide group is not involved in the conjugation of the pyridine group. This is in agreement wih that the C(15)–C(16) bond distance of 1.496(6) Å is a typical single bond. As in the enaminones previously reported, complex 2 shows the strong intramolecular hydrogen bond N(1)–H(1N) · · · O(1) (Fig. 3; Table 3; N(1) · · · O(1) = 2.682(6) Å). The intermolecular hydrogen bonds N(2)– H(2N) · · · O(2) and C(17)–H(17) · · · O(2)ii generate a [010] chain having R2 1 (7) rings.11 Furthermore, intermolecular hydrogen bond N(1)–H(1N) · · · O(1)i forms a [010] doublechain having centrosymmetric R2 2 (4) rings through each unit cell. The π · · · π stacking interaction involving the pyridyl groups Cg(3) · · · Cg(3)iii makes the [010] double-chain pack along [001], thus resulting in the infinite two-dimensional network in the (100) plane (Fig. 4; Table 3; Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, 1/2 + y, 3/2 − z; (iii) 1 − x, 1 − y, 2 − z; N(1) · · · O(1)i = 2.989(6) Å;

404

Shi, Cheng, Sui, and Zhu

Fig. 2. Packing diagram of complex 1. Dashed lines indicate hydrogen bonds. Atoms marked with an asterisk (∗ ), dollar sign ($), ampersand (&) or sign (#) are at the symmetry positions (1 − x, 1 − y, 1 − z), ( −x, −1/2 + y, 3/2 − z), ( −x, 1/2 + y, 3/2 − z) and (x, 1/2 − y, −1/2 + z), respectively.

N(2) · · · O(2)ii = 2.906(6); C(17) · · · O(2) ii = 3.364(6); Cg(3) · · · Cg(3)iii = .566(4) Å, Cg(3) is centroid of the pyridyl group).

Supplementary material Full crystallographic data (CCDC No. 602172 for complex 1 and CCDC No. 602173 for complex 2) have been deposited at the Cambridge Crystallographic Database Centre and are available on request from the Director, CCDC, 12

Fig. 3. Molecular structure of complex 2.

Syntheses and crystal structures of an organometallic thiosemicarbazone/enehydrazide

405

Table 3. Selected Bond Distances (Å) and Angles (◦ ) for Complex 2 O(1)–C(11) O(2)–C(15) N(1)–C(13) N(1)–N(2) N(2)–C(15) C(10)–C(11) C(11)–C(12)

1.242 (6) 1.221 (6) 1.339 (6) 1.385 (5) 1.343 (6) 1.479 (7) 1.430 (7)

C(13)–N(1)–N(2) C(15)–N(2)–N(1) O(1)–C(11)–C(12) O(1)–C(11)–C(10) C(10)–C(11)–C(12) C(11)–C(12)–C(13) N(1)–C(13)–C(12) N(1)–C(13)–C(14)

121.3 (4) 119.7 (4) 123.0 (5) 119.2 (5) 117.8 (4) 124.4 (5) 121.3 (5) 117.5 (5)

C(12)–C(13) C(13)–C(14) C(15)–C(16) N(1) · · · O(1) N(1) · · · O(1)i N(2) · · · O(2)ii

1.375 (7) 1.495 (8) 1.496 (6) 2.682(6) 2.989(6) 2.906(6)

C(12)–C(13)–C(14) O(2)–C(15)–N(2) O(2)–C(15)–C(16) N(2)–C(15)–C(16) N(1)–H(1N) · · · O(1) N(1)–H(1N) · · · O(1)i N(2)–H(2N) · · · O(2)ii

121.1 (5) 122.1 (4) 121.1 (5) 116.8 (4) 131 128 155

Note. Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, 1/2 + y, 3/2 − z.

Union Road, Cambridge, CB2 1EZ, UK (Fax: + 44-1223-336-033; Email:[email protected] or http://www.ccdc.cam.ac.uk).

Acknowledgments The authors thank the National Nature Science Foundation of China (No. 20572091) and Nature Science Foundation of Jiangsu Province (No. 05KJB150151) for financial support of this work.

References

Fig. 4. Packing diagram of complex 2. Dashed lines indicate hydrogen bonds. Atoms marked with an asterisk (∗ ), dollar sign ($) or ampersand (&) are at the symmetry positions (1 − x, 1 − y, 1 − z), (1 − x, 1/2 + y, 3/2 − z) and (1 − x, − 1/2 + y, 3/2 − z), respectively.

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