Crystal structures of two substituted thia-zolidine derivatives.

In the first of the compounds reported herein, namely 6'-ferrocenyl-6a'-nitro-6',6a',6b',7',9',11a'-hexa-hydro-2H-spiro-[ace-naphthyl-ene-1,11'-chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zol]-2-one, [Fe(C5H5)(C29H21N2O4S)], (I), the thia-zolidine ring adopts a twist conformation on the methine N-C atoms. In the second compound, viz. 6'-(4-methoxy-phen-yl)-6a'-nitro-6',6a',6b',7',9',11a'-hexa-hydro-2H-spiro-[ace-naphthyl-ene-1,11'-chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zol]-2-one, [Fe(C5H5)(C26H19N2O5S)], (II), the thia-zolidine ring adopts an envelope conformation with a methine C atom as the flap. In both compounds, the pyrrolidine ring adopts a twist conformation on the thia-zolidine and tetra-hydro-pyran C atoms. The mean planes of the thia-zolidine and pyrrolidine rings subtend angles of 67.30 (1) and 62.95 (7)° in (I) and (II), respectively, while the mean plane of the pyrrolidine ring makes dihedral angles of 76.53 (1) and 87.74 (7)° with the ace-naphthyl-ene ring system in (I) and (II), respectively. In both compounds, an intra-molecular C-H⋯O hydrogen bond forms an S(7) ring motif. In the crystal of (I), mol-ecules are linked via two different C-H⋯O hydrogen bonds, forming chains along [001] and [100]. In (II), they are linked through C-H⋯O hydrogen bonds, forming dimers with an R 2 (2)(10) ring motif while C-H⋯π inter-actions link the mol-ecules in a head-to-tail fashion, forming chains along the a-axis direction.

Crystal structures of two triazola-dioxola-benzena-cyclo-nona-phanes.

In the title compounds, C25H29BrN5O7, (I) [systematic name: (Z)-1(5)-bromo-3(2),3(2)-dimethyl-2(1)-nitro-2(2),2(3),2(5),2(6),2(7),2(7a),3(3a),3(5),3(6),3(6a)-deca-hydro-2(1) H,6(1) H-4,9-dioxa-2(3,2)-pyrrolizina-6(4,1)-triazola-3(5,6)-furo[2,3-d][1,3]dioxola-1(1,2)-benzena-cyclo-nona-phane], and C24H29N5O7S, (II) [systematic name: (Z)-3(2),3(2)-dimethyl-2(7)-nitro-2(5),2(6),2(7),2(7a),3(3a),3(5),3(6),3(6a)-octa-hydro-2(1) H,2(3) H,6(1) H-4,9-dioxa-2(5,6)-pyrrolo-[1,2-c]thia-zola-6(4,1)-triazola-3(5,6)-furo[2,3-d][1,3]dioxola-1(1,2)-benzena-cyclo-nona-phane], the triazole rings adopt almost planar conformations. In (I), the fused pyrrolidine rings adopt envelope conformations with the C atoms opposite the fused N-C bond as the flap in each ring, and their mean planes are inclined to one another by 52.8 (3)°. In (II), the pyrrolidine and thia-zole rings are both twisted on the fused N-C bond, and their mean planes are inclined to one another by 70.8 (2)°. In both (I) and (II), the furan ring adopts an envelope conformation with the adjacent C atom of the macrocycle as the flap. In the crystal of (I), mol-ecules are linked via C-H⋯N and C-H⋯O hydrogen bonds, forming sheets parallel to (10-1), while in (II), mol-ecules are linked via C-H⋯N and C-H⋯O hydrogen bonds, forming helical chains propagating along [010], which are linked via C-H⋯S hydrogen bonds, forming slabs parallel to (001).

Crystal structure of 6-(4-chloro-phen-yl)-6a-nitro-6,6a,6b,7,9,11a-hexa-hydro-spiro[chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zole-11,11'-indeno-[1,2-b]quinoxaline] chloro-form monosolvate.

In the title compound, C33H23ClN4O3S·CHCl3, the thia-zole ring adopts an envelope conformation with the N atom as the flap, and the pyrrolidine ring adopts a half-chair conformation. The thia-zole ring mean plane makes a dihedral angle of 59.31 (1)° with the pyrrolidine ring mean plane, 71.67 (1)° with the chromene ring and 82.59 (1)° with the chloro-benzene ring. An intra-molecular C-H⋯N hydrogen bond occurs. In the crystal, a second C-H⋯N hydrogen bond links the main and solvent mol-ecules. The solvent chloroform molecule is disordered about two positions with an occupancy ratio of 0.508 (14):0.492 (14).

Synthesis and antimicrobial evaluation of novel bis-ß-lactam grafted macrocycles.

A series of macrocyclic bis-ß-lactams has been synthesized in three good yielding steps using a Staudinger [2+2] cycloaddition reaction of ketene derived from phenoxyacetyl chloride as the key step. The reaction provided a diastereomeric mixture of cis-anti-cis (C2-symmetry) and cis-syn-cis (meso) bis-ß-lactam grafted macrocycles which were screened for their in vitro antibacterial and antifungal activities against four human pathogenic bacteria and two pathogenic fungi. Compounds 6a and 6b exhibited antibacterial activity at lower concentration against four bacterial pathogens and compounds 10b and 12a showed antifungal activity against two fungal pathogens when compared to reference control.

Allyl 2-(2,2-dimethyl-3a,6a-di-hydro-furo[3,2-d][1,3]dioxol-5-yl)-4-oxo-4H-chromene-3-carboxyl-ate.

In the title compound, C20H18O7, the dioxolane ring adopts an envelope conformation with the dimethyl-substituted C atom as the flap, and its mean plane makes a dihedral angle of 73.25 (2)° with the pyran ring mean plane. The furan ring makes dihedral angles of 67.43 (12) and 6.20 (11)° with the mean plane of the dioxolane and pyran rings, respectively. The O atom attached to the pyran ring deviates by 0.0219 (2) Šfrom its mean plane. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds, forming chains along [010] and enclosing R 2 (2)(9) loops. They stack along the a axis with π-π inter-actions involving the 4H-chromene units [centroid-centroid distances of 3.6389 (13) and 3.6555 (13) Å]. The terminal CH2=CH- atoms of the allyl acetate group are disordered over two sets of sites with a refined occupancy ratio of 0.717 (6):0.283 (6).

Methyl 2-(2,2-dimethyl-3a,6a-di-hydro-furo[3,2-d][1,3]dioxol-5-yl)-4-oxo-4H-chromene-3-carboxyl-ate.

In the title mol-ecule, C18H16O7, the dioxolane ring adopts an envelope conformation with the dimethyl-substituted C atom as the flap. The furan ring is almost coplanar with the pyran ring, with a dihedral angle of 1.04 (10)° between the planes, and it makes a dihedral angle of 67.97 (11)° with the mean plane of the dioxolane ring. The latter makes a dihedral angle of 67.15 (10)° with the pyran ring. The O atom attached to the pyran ring deviates by -0.009 (1) Å. The crystal packing features C-H⋯O hydrogen bonds, forming a three-dimensional structure. The meth-oxy-carbonyl atoms are disordered over two positions, with a refined occupancy ratio of 0.508 (18):0.492 (18).

2-Ferrocenyl-3-nitro-2H-chromene.

In the title compound, [Fe(C5H5)(C14H10NO3)], the cyclo-penta-dienyl rings are in an eclipsed conformation and the pyran ring adopts a half-chair conformation. The mean plane of the pyran ring makes dihedral angles of 79.33 (1) and 80.73 (1)°, respectively, with the substituted and unsubstituted cyclo-penta-dienyl rings. In the crystal, pairs of C-H⋯O hydrogen bonds link the mol-ecules into inversion dimers with R 2 (2)(16) motifs.

2-Methyl-4-(naphthalen-2-yl)-3a-nitro-3,3a,4,9b-tetra-hydro-2H-spiro-[chromeno[3,4-c]pyrrole-1,3'-indolin]-2'-one.

In the title compound, C29H23N3O4, the 2-methylpyrrolidine ring adopts a twist conformation on the N-C bond involving the spiro C atom, while the hydropyran ring adopts an envelope conformation with the methine C atom bonded to the O atom as the flap. The mean plane of the indoline-2-one ring system is almost perpendicular to the mean plane of the pyrrolidine ring, making a dihedral angle of 89.73 (8)°. The latter ring makes dihedral angles of 47.80 (8) with the naphthalene ring system and 32.38 (8)° with the hydropyran ring mean plane. There is an intra-molecular C-H⋯O hydrogen bond involving the indoline-2-one O atom. In the crystal, adjacent mol-ecules are linked via N-H⋯O hydrogen bonds, forming chains propagating along [100]. The chains are linked via weak C-H⋯O hydrogen bonds, forming two-dimensional networks, lying parallel to (101), and consolidated by C-H⋯π inter-actions.

6-(4-Meth-oxy-phen-yl)-6a-nitro-6,6a,6b,7,8,9,10,12a-octa-hydro-spiro-[chromeno[3,4-a]indolizine-12,3'-indolin]-2'-one.

In the title compound, C29H27N3O5, the hydropyran ring adopts an envelope conformation with the methine C atom bearing the para-meth-oxy-benzene ring as the flap. The central pyrrolidine ring has a twist conformation on the N-C bond involving the spiro C atom. The piperidine ring adopts a chair conformation. An intra-molecular C-H⋯O contact closes an S(7) ring. In the crystal, inversion dimers linked by C-H⋯O inter-actions generate R 2 (2)(18) loops and N-H⋯O hydrogen bonds connect the dimers into [100] chains.

8,13,26-Trioxa-23-thia-21-aza-penta-cyclo-[18.6.0.0(2,7).0(14,19).0(21,25)]hexa-cosa-2(7),3,5,14,16,18-hexa-ene.

In the title compound, C21H23NO3S, both the thia-zole and oxazolidine rings adopt twist conformations. The mean plane of the thia-zole ring makes a dihedral angle of 61.02 (7)° with the oxazolidine ring mean plane, and dihedral angles of 22.72 (6) and 75.07 (6)° with the benzene rings. The benzene rings are almost perpendicular to one another, making a dihedral angle of 89.14 (6)°. There are bifurcated intra-molecular C-H⋯O hydrogen bonds in the mol-ecular structure. In the crystal, mol-ecules are linked via C-H⋯π inter-actions, forming chains propagating along [100].

8,11,24-Trioxa-21-thia-19-aza-penta-cyclo-[16.6.0.0(2,7).0(12,17).0(19,23)]tetra-cosa-2(7),3,5,12,14,16-hexa-ene.

In the title compound, C19H19NO3S, the thia-zole and oxazolidine rings each adopt an envelope conformation, with the S and O atoms as the respective flap atoms. The thia-zole and oxazolidine rings (all atoms) make a dihedral angle of 66.39 (11)° while the phenyl rings subtend a dihedral angle of 22.71 (10)°.

6a-Nitro-6-phenyl-6,6a,6b,7,8,9,10,12a-octa-hydro-spiro-[chromeno[3,4-a]indol-izine-12,3'-indolin]-2'-one.

In the title compound, C28H25N3O4, the central pyrrolidine ring adopts adopts an envelope conformation with the N atom as the flap and the piperidine ring adopts a chair conformation. The pendant pyrrolidine ring is almost planar (r.m.s. deviation = 0.008 Å). An intra-molecular C-H⋯O inter-action closes an S(6) ring. In the crystal, inversion dimers linked by pairs of N-H⋯O hydrogen bonds generate R 2 (2)(8) loops.

(1S,3'S,3a'R,6'S)-6'-(2-Chloro-phen-yl)-3'-[(2R,3S)-1-(4-meth-oxy-phen-yl)-4-oxo-3-phenyl-azetidin-2-yl]-2-oxo-3',3'a,4',6'-tetra-hydro-2H,2'H-spiro-[ace-naphthyl-ene-1,1'-pyrrolo-[1,2-c][1,3]thia-zole]-2',2'-dicarbo-nitrile.

The mol-ecular conformation of the title compound, C41H29ClN4O3S, is stabilized by intra-molecular C-H⋯O and C-H⋯Cl hydrogen bonds. The thia-zole ring adopts an envelope conformation with the N atom as the flap, while the pyrrolidine ring has a twisted conformation on the N-C bond involving the spiro C atom. The ß la-ctam ring makes dihedral angles of 39.74 (15) and 16.21 (16)° with the mean planes of the thia-zole and pyrrolidine rings, respectively. The thia-zole ring mean plane makes dihedral angles of 23.79 (13) and 70.88 (13) ° with the pyrrolidine and cyclo-pentane rings, respectively, while the pyrrolidine ring makes a dihedral angle of 85.63 (13)° with the cyclo-pentane ring. The O atom attached to the ß la-ctam ring deviates from its mean plane by 0.040 (2) Å, while the O atom attached to the cyclo-pentane ring deviates from its mean plane by 0.132 (2) Å. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains along [010], and C-H⋯π and π-π inter-actions [centroid-centroid distance = 3.6928 (17) Å].

Ethyl 27-oxo-15-oxa-2,20-diaza-hexa-cyclo-[18.6.1.0(1,8).0(2,6).0(9,14).0(21,26)]hepta-cosa-9,11,13,21,23,25-hexa-ene-7-carboxyl-ate.

In the title compound, C27H30N2O4, the pyrrolidine ring adopts a twisted conformation. The indoline ring system is almost perpendicular to the mean plane of the pyrrolidine ring, making a dihedral angle of 81.7 (8)°. In the crystal, mol-ecules are linked into centrosymmetric dimers with graph-set motif R2(2)(16) via pairs of C-H⋯O hydrogen bonds. The terminal ethyl group of the ester group is disordered over two sets of sites, with a site-occupancy ratio of 0.587 (11):0.413 (11).

Ethyl 8,13-dioxa-21-aza-penta-cyclo-[18.5.1.0(2,7).0(14,19).0(21,25)]hexa-cosa-2(7),3,5,14,16,18-hexa-ene-26-carboxyl-ate.

In the title compound, C26H31NO4, the five-membered rings of the central pyrrolizine system adopt N-envelope conformations. The ethyl acetate group adopts an extended conformation. The dihedral angle between the benzene rings is 36.6 (1)°. In the crystal, C-H⋯O hydrogen bonds form a zigzag chain running along the b-axis directions. The crystal structure is futher consolidated by C-H⋯π inter-actions.

(E)-1-Ferrocenyl-3-[2-(2-hy-droxy-eth-oxy)phen-yl]prop-2-en-1-one.

In the title compound, [Fe(C5H5)(C16H15O3)], the cyclo-penta-dienyl rings are in an eclipsed conformation and the benzene ring makes dihedral angles of 10.84 (9) and 12.35 (9)°, respectively, with the substituted and unsubstituted cyclo-penta-dienyl rings. In the crystal, mol-ecules form inversion dimers through pairs of O-H⋯O hydrogen bonds. Weak C-H⋯O hydrogen bonds are observed between the dimers.

Methyl 11-hy-droxy-9-[1-(4-meth-oxy-phen-yl)-4-oxo-3-phenyl-azetidin-2-yl]-18-oxo-10-oxa-2-aza-penta-cyclo-[9.7.0.0(1,8).0(2,6).0(12,17)]octa-deca-12(17),13,15-triene-8-carboxyl-ate.

In the title compound, C34H32N2O7, the furan ring adopts a twist conformation and both the pyrrolidine rings adopt envelope conformations with O and C as flap atoms. The ß-lactam ring makes a dihedral angles of 80.20 (10)° with the furan ring, of 75.55 (10)° with the pyrrolidine ring, of 12.26 (10)° with the meth-oxy-phenyl ring and of 73.77 (13)° with the phenyl ring. The O atom attached to the ß-lactam ring deviates by 0.0385 (13) Šfrom the ring plane. The mol-ecular conformation is stabilized by intra-molecular O-H⋯N and C-H⋯O hydrogen bonds. The packing of the crystal is stabilized by inter-molecular C-H⋯O hydrogen bonds, which form a chain running along the b axis.

(3E)-11,16-Dioxatricyclo-[15.4.0.0(5,10)]henicosa-1(21),3,5,7,9,17,19-heptaen-2-one.

The title compound, C19H18O3, crystallizes with three mol-ecules (A, B and C) in the asymmetric unit. The carbonyl O atom shows positional disorder over two sites in mol-ecules A and B; the site-occupancy ratios are 0.76 (3):0.24 (3) and 0.86 (3):0.14 (3), respectively. The ethyl-ene fragments in each mol-ecule have an E conformation, while the C-O-C-C torsion angles indicate near planarity. The dihedral angles formed by the aromatic rings are 20.0 (1), 23.7 (1) and 16.1 (1)° for mol-ecules A, B and C, respectively. Intra-molecular C-H⋯O hydrogen bonds occur in each mol-ecule.

1-(4-{2-[(E)-3-(4-Chloro-phen-yl)-3-oxo-prop-1-en-1-yl]phen-oxy}but-yl)-1H-indole-3-carbaldehyde.

In the title compound, C(28)H(24)ClNO(3), the dihedral angles between the central benzene ring and the indole ring system and the chlorobenzene ring are 70.81 (5) and 78.62 (5)°, respectively. The mol-ecular structure is stabilized by a weak intra-molecular C-H⋯O inter-action. In the crystal, pairs of C-H⋯O hydrogen bonds link the mol-ecules into inversion dimers with an R(2) (2)(14) motif.

2,15-Dioxa-7,18,19,20,23-penta-aza-hepta-cyclo-[21.6.1.1(17,20).0(1,8).0(3,7).0(9,14).0(24,29)]hentriaconta-9,11,13,17(31),18,24,26,28-octaen-30-one.

In the title compound, C24H23N5O3, the oxindole ring system is nearly planar, with a dihedral angle between the two fused rings of 3.3 (1)°. In the fused pyrrolo-oxazole ring system, the oxazole and pyrrolidine rings adopt envelope conformations with the spiro C atom and one of the methyl-ene C atoms, respectively, as the flap atoms. In the crystal, mol-ecules are linked into a helical chain along the b axis via C-H⋯O inter-actions generating R 2 (1)(7) and R 2 (2)(8) ring motifs.