N-(2-Fluoro-benz-yloxy)-1,3,5-trimethyl-2,6-diphenyl-piperidin-4-imine.

In the title compound, C(27)H(29)FN(2)O, the piperidine ring has a twisted boat conformation and all ring substituents occupy equatorial positions. The dihedral angle formed between the phenyl rings is 66.71 (12)°, and the phenyl rings form dihedral angles of 46.60 (13) and 43.75 (13)° with the fluoro-benzene ring, which occupies a position coplanar to the meth-oxy(methyl-idene)amine residue [N-O-C-C torsion angle = -179.5 (2)°]. In the crystal, a complex network of C-H⋯π inter-actions connects the mol-ecules into a three-dimensional architecture.

Related literature

For the biological activity of mol­ecules having a 2,6-diaryl­piperidine core, see: Ramachandran et al. (2011 ▶); Ramalingan et al. (2004 ▶). For the structures of related chloro and bromo derivatives, see: Ramalingan et al. (2012a ▶,b ▶). For the synthesis, see: Ramalingan et al. (2006 ▶).

Experimental

Crystal data

C27H29FN2O

M = 416.52

Orthorhombic,

a = 7.4004 (3) Å

b = 22.4857 (9) Å

c = 13.4465 (5) Å

V = 2237.54 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 100 K

0.30 × 0.20 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.930, T max = 1.000

14812 measured reflections

2693 independent reflections

2311 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.101

S = 1.03

2693 reflections

280 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029327/pv2563sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029327/pv2563Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812029327/pv2563Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C27H29FN2O	F(000) = 888
Mr = 416.52	Dx = 1.236 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4254 reflections
a = 7.4004 (3) Å	θ = 2.4–27.5°
b = 22.4857 (9) Å	µ = 0.08 mm−1
c = 13.4465 (5) Å	T = 100 K
V = 2237.54 (15) Å3	Prism, colourless
Z = 4	0.30 × 0.20 × 0.15 mm

Agilent SuperNova Dual diffractometer with an Atlas detector	2693 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2311 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.058
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.9°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −21→29
Tmin = 0.930, Tmax = 1.000	l = −17→16
14812 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0469P)2 + 0.573P] where P = (Fo2 + 2Fc2)/3
2693 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.21 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

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 > σ(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 ALL data will be even larger.

	x	y	z	Uiso*/Ueq
F1	0.1682 (3)	0.76313 (8)	−0.25008 (12)	0.0369 (5)
O1	0.1493 (2)	0.83790 (8)	0.03234 (14)	0.0210 (4)
N1	0.1480 (3)	0.90124 (9)	0.03729 (17)	0.0177 (5)
N2	−0.1331 (3)	0.95190 (9)	0.25393 (16)	0.0142 (4)
C1	0.1633 (4)	0.72749 (12)	−0.1681 (2)	0.0222 (6)
C2	0.1639 (4)	0.66675 (13)	−0.1813 (2)	0.0282 (6)
H2	0.1681	0.6499	−0.2461	0.034*
C3	0.1585 (4)	0.63103 (13)	−0.0983 (2)	0.0295 (7)
H3	0.1583	0.5890	−0.1054	0.035*
C4	0.1533 (4)	0.65620 (14)	−0.0041 (2)	0.0329 (7)
H4	0.1498	0.6315	0.0531	0.040*
C5	0.1534 (4)	0.71756 (12)	0.0062 (2)	0.0259 (6)
H5	0.1503	0.7345	0.0709	0.031*
C6	0.1578 (4)	0.75462 (12)	−0.0761 (2)	0.0191 (5)
C7	0.1582 (4)	0.82144 (11)	−0.06990 (19)	0.0209 (6)
H7A	0.2699	0.8375	−0.1003	0.025*
H7B	0.0531	0.8378	−0.1063	0.025*
C8	0.1264 (3)	0.91809 (11)	0.12724 (19)	0.0154 (5)
C9	0.1013 (3)	0.87766 (11)	0.21545 (18)	0.0156 (5)
H9	0.0246	0.8435	0.1933	0.019*
C10	−0.0016 (3)	0.90997 (10)	0.29954 (19)	0.0153 (5)
H10	0.0868	0.9332	0.3402	0.018*
C11	−0.0404 (3)	1.00355 (11)	0.20744 (18)	0.0147 (5)
H11	0.0010	1.0308	0.2616	0.018*
C12	0.1286 (3)	0.98411 (11)	0.14558 (18)	0.0149 (5)
H12	0.1226	1.0046	0.0796	0.018*
C13	0.3042 (3)	1.00342 (12)	0.1971 (2)	0.0207 (6)
H13A	0.4080	0.9908	0.1571	0.031*
H13B	0.3112	0.9850	0.2631	0.031*
H13C	0.3055	1.0468	0.2042	0.031*
C14	0.2820 (4)	0.85183 (12)	0.2516 (2)	0.0227 (6)
H14A	0.3420	0.8313	0.1965	0.034*
H14B	0.2596	0.8236	0.3058	0.034*
H14C	0.3594	0.8841	0.2756	0.034*
C15	−0.2592 (4)	0.97521 (12)	0.3285 (2)	0.0212 (5)
H15A	−0.3437	1.0028	0.2966	0.032*
H15B	−0.1915	0.9962	0.3804	0.032*
H15C	−0.3267	0.9422	0.3583	0.032*
C16	−0.0951 (3)	0.86507 (11)	0.36609 (19)	0.0146 (5)
C17	−0.2307 (3)	0.82735 (11)	0.3303 (2)	0.0173 (5)
H17	−0.2665	0.8297	0.2626	0.021*
C18	−0.3132 (4)	0.78652 (11)	0.3928 (2)	0.0200 (6)
H18	−0.4060	0.7614	0.3678	0.024*
C19	−0.2608 (4)	0.78218 (12)	0.4915 (2)	0.0222 (6)
H19	−0.3162	0.7537	0.5338	0.027*
C20	−0.1280 (3)	0.81934 (11)	0.5284 (2)	0.0202 (6)
H20	−0.0924	0.8167	0.5961	0.024*
C21	−0.0465 (3)	0.86073 (11)	0.46574 (19)	0.0169 (5)
H21	0.0439	0.8865	0.4915	0.020*
C22	−0.1760 (3)	1.03673 (11)	0.14343 (18)	0.0149 (5)
C23	−0.2317 (4)	1.09396 (11)	0.16686 (19)	0.0178 (5)
H23	−0.1837	1.1133	0.2239	0.021*
C24	−0.3578 (4)	1.12344 (12)	0.1073 (2)	0.0197 (6)
H24	−0.3947	1.1627	0.1239	0.024*
C25	−0.4290 (4)	1.09576 (11)	0.0244 (2)	0.0210 (6)
H25	−0.5152	1.1157	−0.0160	0.025*
C26	−0.3732 (3)	1.03838 (12)	0.0005 (2)	0.0193 (5)
H26	−0.4219	1.0191	−0.0564	0.023*
C27	−0.2472 (3)	1.00917 (11)	0.05908 (18)	0.0163 (5)
H27	−0.2090	0.9702	0.0417	0.020*

	U11	U22	U33	U12	U13	U23
F1	0.0700 (14)	0.0239 (9)	0.0167 (8)	0.0023 (9)	0.0004 (8)	−0.0001 (7)
O1	0.0322 (10)	0.0142 (9)	0.0167 (9)	0.0021 (7)	0.0041 (8)	−0.0017 (8)
N1	0.0206 (11)	0.0131 (10)	0.0193 (11)	0.0022 (8)	0.0011 (9)	−0.0004 (9)
N2	0.0139 (10)	0.0147 (10)	0.0140 (10)	0.0006 (8)	0.0016 (8)	0.0014 (8)
C1	0.0282 (14)	0.0208 (14)	0.0178 (13)	0.0010 (11)	0.0016 (12)	0.0011 (11)
C2	0.0357 (16)	0.0258 (15)	0.0232 (15)	0.0015 (12)	−0.0042 (13)	−0.0069 (12)
C3	0.0397 (18)	0.0186 (14)	0.0301 (16)	0.0014 (12)	−0.0004 (14)	−0.0046 (12)
C4	0.0461 (18)	0.0248 (16)	0.0279 (16)	0.0032 (14)	0.0007 (14)	0.0069 (13)
C5	0.0372 (17)	0.0217 (14)	0.0189 (14)	0.0021 (12)	0.0022 (12)	−0.0044 (11)
C6	0.0182 (13)	0.0200 (13)	0.0192 (12)	0.0039 (10)	0.0001 (10)	−0.0017 (11)
C7	0.0320 (15)	0.0170 (13)	0.0137 (12)	0.0016 (11)	0.0044 (11)	−0.0012 (11)
C8	0.0104 (11)	0.0172 (13)	0.0186 (12)	0.0018 (9)	−0.0002 (10)	−0.0008 (10)
C9	0.0159 (12)	0.0149 (12)	0.0160 (12)	0.0006 (9)	0.0029 (10)	0.0008 (10)
C10	0.0146 (12)	0.0159 (12)	0.0152 (11)	0.0000 (9)	−0.0006 (9)	0.0005 (10)
C11	0.0169 (12)	0.0136 (12)	0.0136 (11)	−0.0004 (9)	−0.0008 (10)	−0.0014 (10)
C12	0.0166 (12)	0.0135 (12)	0.0146 (12)	0.0008 (10)	0.0004 (10)	0.0026 (10)
C13	0.0172 (12)	0.0217 (14)	0.0233 (14)	−0.0043 (10)	0.0018 (12)	−0.0005 (12)
C14	0.0210 (13)	0.0249 (14)	0.0220 (13)	0.0073 (11)	0.0010 (11)	0.0037 (12)
C15	0.0219 (13)	0.0211 (13)	0.0206 (13)	0.0044 (11)	0.0074 (11)	0.0033 (11)
C16	0.0146 (12)	0.0132 (12)	0.0161 (12)	0.0022 (9)	0.0025 (10)	0.0009 (10)
C17	0.0186 (12)	0.0172 (12)	0.0161 (11)	0.0014 (10)	−0.0001 (10)	−0.0010 (10)
C18	0.0153 (12)	0.0168 (13)	0.0278 (14)	−0.0022 (10)	0.0014 (11)	−0.0007 (11)
C19	0.0219 (14)	0.0174 (13)	0.0271 (15)	0.0019 (11)	0.0072 (12)	0.0063 (11)
C20	0.0220 (13)	0.0225 (13)	0.0162 (12)	0.0050 (10)	0.0017 (11)	0.0014 (11)
C21	0.0163 (12)	0.0170 (13)	0.0173 (12)	0.0003 (10)	−0.0001 (10)	−0.0001 (10)
C22	0.0160 (12)	0.0153 (12)	0.0135 (12)	−0.0015 (9)	0.0050 (10)	0.0017 (10)
C23	0.0206 (13)	0.0168 (13)	0.0160 (12)	−0.0027 (10)	0.0029 (10)	0.0004 (10)
C24	0.0234 (14)	0.0135 (13)	0.0223 (14)	0.0037 (10)	0.0064 (11)	0.0029 (11)
C25	0.0180 (13)	0.0249 (14)	0.0200 (13)	0.0048 (11)	0.0025 (11)	0.0056 (11)
C26	0.0189 (13)	0.0228 (13)	0.0162 (12)	0.0001 (10)	−0.0035 (11)	0.0006 (11)
C27	0.0177 (12)	0.0148 (12)	0.0164 (12)	−0.0020 (10)	0.0013 (10)	0.0011 (10)

F1—C1	1.363 (3)	C13—H13A	0.9800
O1—C7	1.425 (3)	C13—H13B	0.9800
O1—N1	1.426 (3)	C13—H13C	0.9800
N1—C8	1.278 (3)	C14—H14A	0.9800
N2—C15	1.467 (3)	C14—H14B	0.9800
N2—C11	1.487 (3)	C14—H14C	0.9800
N2—C10	1.487 (3)	C15—H15A	0.9800
C1—C2	1.377 (4)	C15—H15B	0.9800
C1—C6	1.381 (4)	C15—H15C	0.9800
C2—C3	1.376 (4)	C16—C21	1.391 (3)
C2—H2	0.9500	C16—C17	1.399 (4)
C3—C4	1.388 (4)	C17—C18	1.386 (4)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.387 (4)	C18—C19	1.387 (4)
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.386 (4)	C19—C20	1.382 (4)
C5—H5	0.9500	C19—H19	0.9500
C6—C7	1.505 (4)	C20—C21	1.392 (4)
C7—H7A	0.9900	C20—H20	0.9500
C7—H7B	0.9900	C21—H21	0.9500
C8—C9	1.506 (4)	C22—C23	1.388 (3)
C8—C12	1.505 (3)	C22—C27	1.396 (4)
C9—C14	1.536 (4)	C23—C24	1.397 (4)
C9—C10	1.545 (3)	C23—H23	0.9500
C9—H9	1.0000	C24—C25	1.381 (4)
C10—C16	1.516 (3)	C24—H24	0.9500
C10—H10	1.0000	C25—C26	1.392 (4)
C11—C22	1.518 (3)	C25—H25	0.9500
C11—C12	1.564 (3)	C26—C27	1.386 (4)
C11—H11	1.0000	C26—H26	0.9500
C12—C13	1.536 (3)	C27—H27	0.9500
C12—H12	1.0000
C7—O1—N1	107.75 (18)	C11—C12—H12	107.9
C8—N1—O1	110.0 (2)	C12—C13—H13A	109.5
C15—N2—C11	107.57 (18)	C12—C13—H13B	109.5
C15—N2—C10	111.1 (2)	H13A—C13—H13B	109.5
C11—N2—C10	111.54 (18)	C12—C13—H13C	109.5
F1—C1—C2	118.6 (2)	H13A—C13—H13C	109.5
F1—C1—C6	117.8 (2)	H13B—C13—H13C	109.5
C2—C1—C6	123.6 (3)	C9—C14—H14A	109.5
C3—C2—C1	118.3 (3)	C9—C14—H14B	109.5
C3—C2—H2	120.9	H14A—C14—H14B	109.5
C1—C2—H2	120.9	C9—C14—H14C	109.5
C2—C3—C4	120.2 (3)	H14A—C14—H14C	109.5
C2—C3—H3	119.9	H14B—C14—H14C	109.5
C4—C3—H3	119.9	N2—C15—H15A	109.5
C5—C4—C3	119.8 (3)	N2—C15—H15B	109.5
C5—C4—H4	120.1	H15A—C15—H15B	109.5
C3—C4—H4	120.1	N2—C15—H15C	109.5
C6—C5—C4	121.2 (3)	H15A—C15—H15C	109.5
C6—C5—H5	119.4	H15B—C15—H15C	109.5
C4—C5—H5	119.4	C21—C16—C17	118.3 (2)
C1—C6—C5	116.8 (2)	C21—C16—C10	119.8 (2)
C1—C6—C7	119.4 (2)	C17—C16—C10	121.9 (2)
C5—C6—C7	123.8 (2)	C18—C17—C16	120.6 (2)
O1—C7—C6	108.2 (2)	C18—C17—H17	119.7
O1—C7—H7A	110.1	C16—C17—H17	119.7
C6—C7—H7A	110.1	C19—C18—C17	120.2 (3)
O1—C7—H7B	110.1	C19—C18—H18	119.9
C6—C7—H7B	110.1	C17—C18—H18	119.9
H7A—C7—H7B	108.4	C20—C19—C18	120.0 (2)
N1—C8—C9	125.6 (2)	C20—C19—H19	120.0
N1—C8—C12	116.5 (2)	C18—C19—H19	120.0
C9—C8—C12	117.9 (2)	C19—C20—C21	119.7 (3)
C8—C9—C14	111.7 (2)	C19—C20—H20	120.2
C8—C9—C10	110.7 (2)	C21—C20—H20	120.2
C14—C9—C10	112.0 (2)	C16—C21—C20	121.2 (2)
C8—C9—H9	107.4	C16—C21—H21	119.4
C14—C9—H9	107.4	C20—C21—H21	119.4
C10—C9—H9	107.4	C23—C22—C27	119.0 (2)
N2—C10—C16	111.5 (2)	C23—C22—C11	121.6 (2)
N2—C10—C9	108.59 (19)	C27—C22—C11	119.5 (2)
C16—C10—C9	110.12 (19)	C22—C23—C24	120.6 (2)
N2—C10—H10	108.8	C22—C23—H23	119.7
C16—C10—H10	108.8	C24—C23—H23	119.7
C9—C10—H10	108.8	C25—C24—C23	120.2 (2)
N2—C11—C22	108.50 (19)	C25—C24—H24	119.9
N2—C11—C12	111.97 (18)	C23—C24—H24	119.9
C22—C11—C12	111.37 (19)	C24—C25—C26	119.4 (2)
N2—C11—H11	108.3	C24—C25—H25	120.3
C22—C11—H11	108.3	C26—C25—H25	120.3
C12—C11—H11	108.3	C27—C26—C25	120.5 (2)
C8—C12—C13	111.2 (2)	C27—C26—H26	119.7
C8—C12—C11	110.75 (19)	C25—C26—H26	119.7
C13—C12—C11	110.9 (2)	C26—C27—C22	120.4 (2)
C8—C12—H12	107.9	C26—C27—H27	119.8
C13—C12—H12	107.9	C22—C27—H27	119.8
C7—O1—N1—C8	175.2 (2)	N1—C8—C12—C13	−107.0 (3)
F1—C1—C2—C3	−179.8 (3)	C9—C8—C12—C13	72.4 (3)
C6—C1—C2—C3	0.2 (4)	N1—C8—C12—C11	129.2 (2)
C1—C2—C3—C4	−0.3 (4)	C9—C8—C12—C11	−51.5 (3)
C2—C3—C4—C5	0.1 (5)	N2—C11—C12—C8	14.6 (3)
C3—C4—C5—C6	0.2 (5)	C22—C11—C12—C8	−107.1 (2)
F1—C1—C6—C5	−179.8 (3)	N2—C11—C12—C13	−109.4 (2)
C2—C1—C6—C5	0.2 (4)	C22—C11—C12—C13	128.9 (2)
F1—C1—C6—C7	−0.2 (4)	N2—C10—C16—C21	−122.1 (2)
C2—C1—C6—C7	179.8 (3)	C9—C10—C16—C21	117.3 (2)
C4—C5—C6—C1	−0.4 (4)	N2—C10—C16—C17	57.9 (3)
C4—C5—C6—C7	−180.0 (3)	C9—C10—C16—C17	−62.8 (3)
N1—O1—C7—C6	−179.5 (2)	C21—C16—C17—C18	−0.4 (4)
C1—C6—C7—O1	179.1 (2)	C10—C16—C17—C18	179.7 (2)
C5—C6—C7—O1	−1.3 (4)	C16—C17—C18—C19	−0.7 (4)
O1—N1—C8—C9	−1.4 (3)	C17—C18—C19—C20	1.1 (4)
O1—N1—C8—C12	177.92 (18)	C18—C19—C20—C21	−0.4 (4)
N1—C8—C9—C14	79.6 (3)	C17—C16—C21—C20	1.0 (4)
C12—C8—C9—C14	−99.7 (3)	C10—C16—C21—C20	−179.0 (2)
N1—C8—C9—C10	−154.8 (2)	C19—C20—C21—C16	−0.6 (4)
C12—C8—C9—C10	25.9 (3)	N2—C11—C22—C23	113.8 (2)
C15—N2—C10—C16	47.3 (3)	C12—C11—C22—C23	−122.5 (2)
C11—N2—C10—C16	167.3 (2)	N2—C11—C22—C27	−66.0 (3)
C15—N2—C10—C9	168.8 (2)	C12—C11—C22—C27	57.7 (3)
C11—N2—C10—C9	−71.1 (2)	C27—C22—C23—C24	0.3 (4)
C8—C9—C10—N2	33.5 (3)	C11—C22—C23—C24	−179.5 (2)
C14—C9—C10—N2	158.9 (2)	C22—C23—C24—C25	0.2 (4)
C8—C9—C10—C16	155.9 (2)	C23—C24—C25—C26	−0.3 (4)
C14—C9—C10—C16	−78.7 (3)	C24—C25—C26—C27	−0.1 (4)
C15—N2—C11—C22	−70.3 (2)	C25—C26—C27—C22	0.7 (4)
C10—N2—C11—C22	167.55 (19)	C23—C22—C27—C26	−0.8 (4)
C15—N2—C11—C12	166.4 (2)	C11—C22—C27—C26	179.0 (2)
C10—N2—C11—C12	44.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···Cg1i	0.99	2.96	3.721 (3)	135
C13—H13A···Cg2ii	0.98	2.91	3.577 (3)	127
C18—H18···Cg3iii	0.95	2.90	3.700 (3)	143
C21—H21···Cg2iv	0.95	2.51	3.446 (3)	167
C25—H25···Cg3v	0.95	2.74	3.654 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

Cg1–Cg3 are the centroids of the C1–C6, C16–C21 and C22–C27 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cg1i	0.99	2.96	3.721 (3)	135
C13—H13A⋯Cg2ii	0.98	2.91	3.577 (3)	127
C18—H18⋯Cg3iii	0.95	2.90	3.700 (3)	143
C21—H21⋯Cg2iv	0.95	2.51	3.446 (3)	167
C25—H25⋯Cg3v	0.95	2.74	3.654 (3)	160

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .