Experimental. Crystal data

Transcription

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN ,3 0 -[1,2-Phenylenebis(methylene)]bis(1- octylbenzimidazolium) dibromide monohydrate Rosenani A. Haque, a Muhammad Adnan Iqbal, a Hoong-Kun Fun b * and Suhana Arshad b a School of Chemical Sciences, Universiti Sains Malaysia, Penang, Malaysia, and b X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, USM, Penang, Malaysia Correspondence hkfun@usm.my Received 22 February 2012; accepted 24 February 2012 Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.052; wr factor = 0.161; data-to-parameter ratio = Experimental Crystal data C 38 H 52 N Br H 2 O M r = Triclinic, P1 a = (4) Å b = (12) Å c = (8) Å = (3) = (2) Data collection Bruker SMART APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.451, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 416 parameters = (3) V = (19) Å 3 Z =2 Mo K radiation = 2.24 mm 1 T = 100 K mm measured reflections independent reflections 8816 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 2.62 e Å 3 min = 1.68 e Å 3 In the title hydrated molecular salt, C 38 H 52 N Br H 2 O, the central benzene ring of the dication makes dihedral angles of (13) and (12) with the pendant benzimidazol-3- ium rings. The conformations of the octyl side chains are completely different. In the crystal, the components are linked by O HBr, C HBr and C HO hydrogen bonds into a two-dimensional network lying parallel to the ac plane. Aromatic stacking interactions are also observed [shortest centroid-to-centroid separation = (16) Å]. Related literature For related structures, see: Haque et al. (2012); Iqbal et al. (2012); Haque et al. (2011). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA O1W H1W1Br (5) 2.50 (5) (3) 173 (4) O1W H2W1Br (5) 2.52 (5) (3) 177 (5) C7 H7ABr (3) 154 C15 H15ABr (3) 134 C16 H16ABr (3) 143 C2 H2ABr2 i (3) 155 C4 H4AO1W ii (4) 133 C8 H8ABr1 iii (3) 169 C8 H8BBr2 iii (3) 159 C19 H19ABr2 iv (3) 167 C21 H21ABr2 v (3) 155 C31 H31ABr2 v (3) 154 Symmetry codes: (i) x þ 2; y þ 1; z þ 1; (ii) x þ 3; y þ 1; z þ 1; (iii) x þ 1; y; z; (iv) x þ 2; y þ 1; z; (v) x þ 1; y þ 1; z. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009). RAH thanks the Universiti Sains Malaysia (USM) for Research University (RU) grants Nos. 1001/PKI MIA/ and 1001/PKIMIA/ MAI is grateful to (IPS) USM for financial support [a fellowship, grant No. USM.IPS/JWT/1/19 (JLD 6), and a research attachment fund, grant No. P-KM0018/10(R)-308/AIPS/415401]. HKF and SA thank the Universiti Sains Malaysia (USM) for Research University Grant No. 1001/PFIZIK/ SA also thanks the Malaysian government and USM for an award through the Academic Staff Training Scheme (ASTS). Thomson Reuters ResearcherID: A Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6650). o924 Haque et al. doi: /s

2 organic compounds References Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, Haque, R. A., Iqbal, M. A., Budagumpi, S., Hemamalini, M. & Fun, H.-K. (2012). Acta Cryst. E68, o573. Haque, R. A., Iqbal, M. A., Hemamalini, M. & Fun, H.-K. (2011). Acta Cryst. E67, o1814 o1815. Iqbal, M. A., Haque, R. A., Fun, H.-K. & Chia, T. S. (2012). Acta Cryst. E68, o466 o467. Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, Haque et al. C 38 H 52 N Br H 2 O o925

3 supporting information [ 3,3 -[1,2-Phenylenebis(methylene)]bis(1-octylbenzimidazolium) dibromide monohydrate Rosenani A. Haque, Muhammad Adnan Iqbal, Hoong-Kun Fun and Suhana Arshad S1. Comment As a part of our ongoing studies, we have previously reported crystal structures of ortho-xylyl linked bisbenzimidazolium salts with ethyl (Haque et al., 2012), propyl (Iqbal et al., 2012), and heptyl (Haque et al., 2011) substitutions. In this paper we describe single-crystal X-ray diffraction study of the title compound, (I) (Fig. 1). Bond lengths and angles are comparable to the related structure (Haque et al., 2011). The central benzene (C9 C14) ring makes dihedral angles of (13) and (12) with the terminal 1H-benzo[d]imidazol-3-ium (N1/N2/C1 C7) and (N3/N4/C16 C22) rings, respectively. The crystal structure is shown in Fig. 2. The cations, anions and water molecules are linked by intermolecular O H Br, C H Br and C H O hydrogen bonds (Table 1) into a two-dimensional network parallel to the ac plane. π π interactions of Cg1 Cg3 = (18) Å (symmetry code: 3 - x, 1 - y, 1 - z), Cg3 Cg3 = (18) Å (symmetry code: 3 - x, 1 - y, 1 - z), Cg2 Cg4 = (17) Å (symmetry code: 2 - x, 1 - y, -z) and Cg4 Cg4 = (16) Å (symmetry code: 2 - x, 1 - y, -z) further stabilized the structure. [Cg1, Cg2, Cg3 and Cg4 is the centroid of the N1/N2/C1/C6/C7, N3/N4/C16/C17/C22, C1 C6 and C17 C22 rings, respectively]. S2. Experimental A mixture of benzimidazole (5.90 g, 50 mmol) and finely ground potassium hydroxide (4.50 g, 80 mmol) in 50 ml of DMSO was stirred at room temperature (27 28 C) for 30 min. 1-Bromoctane (8.70 ml, 50 mmol) was added drop-wise into this consistently stirred mixture with further stirring for 2 h at the same temperature. The mixture was then poured into water (700 ml) and was extracted by chloroform (5 30 ml). The extract was dried by filtering through five plies of Whatman filter papers. This process was repeated twice to collect crystal a clear solution which was evaporated under reduced pressure to get N-octylbenzimidazole (1) as a thick yellowish fluid. Furthermore, a mixture of 1 (4.04 g, 20 mmol) and 1,2-bis(bromomethyl)benzene (2.64 g, 10 mmol) in 1,4-dioxane (50 ml) was refluxed at 100 C for 18 h. After cooling the reaction mixture to room temperature, the desired compound (2.2Br) appeared as white crystalline powder. The salt was filtered and washed by fresh 1,4-dioxane (3 5 ml), dried at room temperature for 24 h. The product was collected as white crystalline powder (7.42 g, 97.76%). Saturated solution of 2.2Br in methanol (0.5 ml) was exposed to diethyl ether vapours (vapour diffusion) at room temperature to get colourless blocks of (I). Single crystals were also obtained by slow evaporation of saturated solution of 2.2Br in MeOH/CH 3 CN (70:30) and by evaporating saturated solution of title compound in d 6 -DMSO at room temperature. S3. Refinement The H atoms of the water molecule were located in a difference Fourier map and refined freely [O H = 0.84 (5) and 0.83 (5) Å]. All the other H atoms were positioned geometrically [C H = Å] and refined using a riding model sup-1

4 with U iso (H) = 1.2 or 1.5U eq (C). A rotating group model was applied to the methyl groups. Figure 1 The molecular structure of the title compound, showing 30% probability displacement ellipsoids. sup-2

5 Figure 2 The crystal packing of the title compound. Those H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity. 3,3 -[1,2-Phenylenebis(methylene)]bis(1-octylbenzimidazolium) dibromide monohydrate Crystal data C 38 H 52 N Br H 2 O M r = Triclinic, P1 Hall symbol: -P 1 a = (4) Å b = (12) Å c = (8) Å α = (3) β = (2) γ = (3) V = (19) Å 3 Z = 2 F(000) = 776 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9861 reflections θ = µ = 2.24 mm 1 sup-3

6 T = 100 K Block, colourless Data collection Bruker SMART APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2009) T min = 0.451, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 416 parameters 0 restraints Primary atom site location: structure-invariant direct methods mm measured reflections independent reflections 8816 reflections with I > 2σ(I) R int = θ max = 30.0, θ min = 1.5 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.1139P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 2.62 e Å 3 Δρ min = 1.68 e Å 3 Special details Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at (1) K. 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 ) x y z U iso */U eq Br (3) (19) (18) (9) Br (3) (19) (17) (9) N (3) (16) (15) (4) N (3) (16) (14) (4) N (2) (15) (14) (4) N (3) (15) (14) (4) C (3) (18) (17) (5) C (3) (2) (18) (5) H2A * C (4) (2) (18) (5) H3A * sup-4

7 C (3) (2) (19) (5) H4A * C (3) (19) (18) (5) H5A * C (3) (18) (16) (4) C (3) (19) (18) (5) H7A * C (3) (19) (16) (5) H8A * H8B * C (3) (18) (16) (4) C (3) (2) (18) (5) H10A * C (3) (2) (19) (5) H11A * C (3) (19) (18) (5) H12A * C (3) (19) (17) (5) H13A * C (3) (18) (16) (4) C (3) (19) (17) (5) H15A * H15B * C (3) (18) (17) (4) H16A * C (3) (17) (16) (4) C (3) (19) (18) (5) H18A * C (3) (19) (18) (5) H19A * C (3) (19) (18) (5) H20A * C (3) (18) (17) (5) H21A * C (3) (17) (17) (4) C (3) (2) (19) (5) H23A * H23B * C (4) (2) (2) (6) H24A * H24B * C (4) (2) (19) (5) H25A * H25B * C (4) (2) (19) (5) H26A * H26B * C (4) (2) (19) (5) sup-5

8 H27A * H27B * C (3) (2) (18) (5) H28A * H28B * C (4) (2) (19) (5) H29A * H29B * C (4) (2) (2) (6) H30A * H30B * H30C * C (3) (19) (18) (5) H31A * H31B * C (3) (19) (18) (5) H32A * H32B * C (3) (2) (19) (5) H33A * H33B * C (3) (2) (19) (5) H34A * H34B * C (3) (2) (2) (5) H35A * H35B * C (3) (2) (2) (6) H36A * H36B * C (4) (2) (2) (6) H37A * H37B * C (4) (3) (2) (7) H38A * H38B * H38C * O1W (3) (18) (17) (5) H1W (5) (3) (3) (12)* H2W (6) (3) (3) (11)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Br (14) (15) (15) (10) (10) (11) Br (14) (14) (14) (10) (10) (11) N (10) (10) (9) (8) (8) (8) N (10) (9) (9) (7) (8) (8) sup-6

9 N (9) (10) (9) (7) (8) (8) N (9) (9) (9) (7) (8) (8) C (11) (11) (11) (9) (9) (9) C (14) (12) (11) (10) (10) (10) C (14) (12) (11) (10) (10) (10) C (12) (12) (12) (9) (10) (10) C (11) (12) (11) (9) (9) (10) C (11) (10) (10) (8) (9) (9) C (11) (11) (11) (9) (9) (9) C (11) (12) (10) (9) (9) (9) C (11) (11) (10) (9) (9) (9) C (12) (12) (12) (10) (10) (10) C (14) (12) (12) (10) (11) (10) C (13) (11) (11) (9) (10) (9) C (12) (12) (11) (9) (9) (10) C (11) (11) (10) (9) (9) (9) C (11) (11) (11) (9) (9) (9) C (11) (11) (10) (9) (9) (9) C (11) (10) (10) (8) (9) (8) C (12) (11) (11) (9) (9) (9) C (12) (11) (12) (9) (10) (10) C (13) (11) (11) (9) (10) (9) C (12) (11) (11) (9) (9) (9) C (11) (10) (10) (8) (9) (9) C (12) (12) (12) (10) (10) (10) C (15) (12) (14) (11) (12) (11) C (14) (12) (13) (10) (11) (10) C (14) (12) (13) (10) (11) (10) C (14) (12) (12) (10) (11) (10) C (13) (12) (12) (10) (10) (10) C (14) (13) (12) (11) (11) (11) C (14) (14) (13) (11) (11) (12) C (11) (11) (11) (9) (9) (9) C (11) (12) (12) (9) (9) (10) C (13) (13) (12) (10) (10) (11) C (13) (13) (13) (10) (10) (11) C (13) (13) (13) (10) (11) (11) C (13) (13) (14) (10) (11) (11) C (15) (13) (14) (11) (12) (11) C (18) (16) (15) (14) (13) (13) O1W (11) (12) (13) (9) (9) (10) Geometric parameters (Å, º) N1 C (3) C23 C (4) N1 C (3) C23 H23A N1 C (3) C23 H23B N2 C (3) C24 C (4) sup-7

10 N2 C (3) C24 H24A N2 C (3) C24 H24B N3 C (3) C25 C (4) N3 C (3) C25 H25A N3 C (3) C25 H25B N4 C (3) C26 C (4) N4 C (3) C26 H26A N4 C (3) C26 H26B C1 C (3) C27 C (4) C1 C (3) C27 H27A C2 C (4) C27 H27B C2 H2A C28 C (4) C3 C (4) C28 H28A C3 H3A C28 H28B C4 C (4) C29 C (4) C4 H4A C29 H29A C5 C (3) C29 H29B C5 H5A C30 H30A C7 H7A C30 H30B C8 C (3) C30 H30C C8 H8A C31 C (3) C8 H8B C31 H31A C9 C (4) C31 H31B C9 C (3) C32 C (4) C10 C (4) C32 H32A C10 H10A C32 H32B C11 C (4) C33 C (4) C11 H11A C33 H33A C12 C (4) C33 H33B C12 H12A C34 C (4) C13 C (3) C34 H34A C13 H13A C34 H34B C14 C (3) C35 C (4) C15 H15A C35 H35A C15 H15B C35 H35B C16 H16A C36 C (4) C17 C (3) C36 H36A C17 C (3) C36 H36B C18 C (4) C37 C (4) C18 H18A C37 H37A C19 C (4) C37 H37B C19 H19A C38 H38A C20 C (4) C38 H38B C20 H20A C38 H38C C21 C (3) O1W H1W (5) C21 H21A O1W H2W (5) C7 N1 C (2) C23 C24 H24A sup-8

11 C7 N1 C (2) C25 C24 H24A C1 N1 C (2) C23 C24 H24B C7 N2 C (2) C25 C24 H24B C7 N2 C (2) H24A C24 H24B C6 N2 C (2) C26 C25 C (2) C16 N3 C (2) C26 C25 H25A C16 N3 C (2) C24 C25 H25A C17 N3 C (2) C26 C25 H25B C16 N4 C (2) C24 C25 H25B C16 N4 C (2) H25A C25 H25B C22 N4 C (2) C27 C26 C (2) N1 C1 C (2) C27 C26 H26A N1 C1 C (2) C25 C26 H26A C2 C1 C (2) C27 C26 H26B C3 C2 C (2) C25 C26 H26B C3 C2 H2A H26A C26 H26B C1 C2 H2A C26 C27 C (2) C2 C3 C (2) C26 C27 H27A C2 C3 H3A C28 C27 H27A C4 C3 H3A C26 C27 H27B C5 C4 C (3) C28 C27 H27B C5 C4 H4A H27A C27 H27B C3 C4 H4A C29 C28 C (2) C4 C5 C (2) C29 C28 H28A C4 C5 H5A C27 C28 H28A C6 C5 H5A C29 C28 H28B C1 C6 N (2) C27 C28 H28B C1 C6 C (2) H28A C28 H28B N2 C6 C (2) C28 C29 C (2) N2 C7 N (2) C28 C29 H29A N2 C7 H7A C30 C29 H29A N1 C7 H7A C28 C29 H29B N2 C8 C (2) C30 C29 H29B N2 C8 H8A H29A C29 H29B C9 C8 H8A C29 C30 H30A N2 C8 H8B C29 C30 H30B C9 C8 H8B H30A C30 H30B H8A C8 H8B C29 C30 H30C C10 C9 C (2) H30A C30 H30C C10 C9 C (2) H30B C30 H30C C14 C9 C (2) N4 C31 C (2) C11 C10 C (2) N4 C31 H31A C11 C10 H10A C32 C31 H31A C9 C10 H10A N4 C31 H31B C12 C11 C (2) C32 C31 H31B C12 C11 H11A H31A C31 H31B C10 C11 H11A C31 C32 C (2) C11 C12 C (2) C31 C32 H32A sup-9

12 C11 C12 H12A C33 C32 H32A C13 C12 H12A C31 C32 H32B C14 C13 C (2) C33 C32 H32B C14 C13 H13A H32A C32 H32B C12 C13 H13A C32 C33 C (2) C13 C14 C (2) C32 C33 H33A C13 C14 C (2) C34 C33 H33A C9 C14 C (2) C32 C33 H33B N3 C15 C (19) C34 C33 H33B N3 C15 H15A H33A C33 H33B C14 C15 H15A C35 C34 C (2) N3 C15 H15B C35 C34 H34A C14 C15 H15B C33 C34 H34A H15A C15 H15B C35 C34 H34B N4 C16 N (2) C33 C34 H34B N4 C16 H16A H34A C34 H34B N3 C16 H16A C34 C35 C (2) C18 C17 N (2) C34 C35 H35A C18 C17 C (2) C36 C35 H35A N3 C17 C (2) C34 C35 H35B C19 C18 C (2) C36 C35 H35B C19 C18 H18A H35A C35 H35B C17 C18 H18A C37 C36 C (2) C18 C19 C (2) C37 C36 H36A C18 C19 H19A C35 C36 H36A C20 C19 H19A C37 C36 H36B C21 C20 C (2) C35 C36 H36B C21 C20 H20A H36A C36 H36B C19 C20 H20A C38 C37 C (3) C20 C21 C (2) C38 C37 H37A C20 C21 H21A C36 C37 H37A C22 C21 H21A C38 C37 H37B N4 C22 C (2) C36 C37 H37B N4 C22 C (2) H37A C37 H37B C17 C22 C (2) C37 C38 H38A N1 C23 C (2) C37 C38 H38B N1 C23 H23A H38A C38 H38B C24 C23 H23A C37 C38 H38C N1 C23 H23B H38A C38 H38C C24 C23 H23B H38B C38 H38C H23A C23 H23B H1W1 O1W H2W1 108 (4) C23 C24 C (2) C7 N1 C1 C (3) C9 C14 C15 N (2) C23 N1 C1 C2 2.6 (4) C22 N4 C16 N3 0.3 (3) C7 N1 C1 C6 0.7 (3) C31 N4 C16 N (2) C23 N1 C1 C (2) C17 N3 C16 N4 0.4 (3) N1 C1 C2 C (3) C15 N3 C16 N (2) sup-10

13 C6 C1 C2 C3 0.2 (4) C16 N3 C17 C (3) C1 C2 C3 C4 0.2 (4) C15 N3 C17 C (4) C2 C3 C4 C5 0.1 (4) C16 N3 C17 C (3) C3 C4 C5 C6 0.5 (4) C15 N3 C17 C (2) N1 C1 C6 N2 0.9 (3) N3 C17 C18 C (2) C2 C1 C6 N (2) C22 C17 C18 C (4) N1 C1 C6 C (2) C17 C18 C19 C (4) C2 C1 C6 C5 0.1 (4) C18 C19 C20 C (4) C7 N2 C6 C1 0.8 (3) C19 C20 C21 C (4) C8 N2 C6 C (2) C16 N4 C22 C (3) C7 N2 C6 C (3) C31 N4 C22 C (2) C8 N2 C6 C5 6.5 (4) C16 N4 C22 C (2) C4 C5 C6 C1 0.5 (4) C31 N4 C22 C (4) C4 C5 C6 N (2) C18 C17 C22 N (2) C6 N2 C7 N1 0.3 (3) N3 C17 C22 N4 0.1 (3) C8 N2 C7 N (2) C18 C17 C22 C (4) C1 N1 C7 N2 0.3 (3) N3 C17 C22 C (2) C23 N1 C7 N (2) C20 C21 C22 N (2) C7 N2 C8 C (4) C20 C21 C22 C (3) C6 N2 C8 C (2) C7 N1 C23 C (3) N2 C8 C9 C (3) C1 N1 C23 C (3) N2 C8 C9 C (3) N1 C23 C24 C (2) C14 C9 C10 C (4) C23 C24 C25 C (2) C8 C9 C10 C (2) C24 C25 C26 C (3) C9 C10 C11 C (4) C25 C26 C27 C (2) C10 C11 C12 C (4) C26 C27 C28 C (2) C11 C12 C13 C (4) C27 C28 C29 C (2) C12 C13 C14 C9 0.9 (4) C16 N4 C31 C (3) C12 C13 C14 C (2) C22 N4 C31 C (3) C10 C9 C14 C (4) N4 C31 C32 C (3) C8 C9 C14 C (2) C31 C32 C33 C (2) C10 C9 C14 C (2) C32 C33 C34 C (3) C8 C9 C14 C (4) C33 C34 C35 C (2) C16 N3 C15 C (3) C34 C35 C36 C (2) C17 N3 C15 C (3) C35 C36 C37 C (4) C13 C14 C15 N (3) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O1W H1W1 Br (5) 2.50 (5) (3) 173 (4) O1W H2W1 Br (5) 2.52 (5) (3) 177 (5) C7 H7A Br (3) 154 C15 H15A Br (3) 134 C16 H16A Br (3) 143 C2 H2A Br2 i (3) 155 C4 H4A O1W ii (4) 133 C8 H8A Br1 iii (3) 169 sup-11

14 C8 H8B Br2 iii (3) 159 C19 H19A Br2 iv (3) 167 C21 H21A Br2 v (3) 155 C31 H31A Br2 v (3) 154 Symmetry codes: (i) x+2, y+1, z+1; (ii) x+3, y+1, z+1; (iii) x+1, y, z; (iv) x+2, y+1, z; (v) x+1, y+1, z. sup-12