3-Isopropyl-1-{2-[(1-methyl-1H-tetra-zol-5-yl)sulfan-yl]acet-yl}-2,6-di-phenyl-piperidin-4-one hemihydrate.

In the title compound, C24H27N5O2S·0.5H2O, the piperidine ring adopts a distorted boat conformation. The phenyl rings subtend dihedral angles of 69.7 (1) and 88.7 (1)° with the best plane through the piperidine moiety. In the crystal, symmetry-related mol-ecules are linked through a network of C-H⋯O and C-H⋯N inter-actions, the former connecting them into zigzag chains along the c-axis direction and the latter forming an R (2) 2(4)motif. The dimer formation (C-H⋯N) and the repetition of symmetry-related molecules (C-H⋯O) along the b-axis direction stabilize the packing mode. The water mol-ecule is located on a twofold rotation axis.

Related literature

For the biological activity of piperidine derivatives, see: Aridoss et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C24H27N5O2S·0.5H2O

M = 458.57

Monoclinic,

a = 28.7522 (9) Å

b = 11.1809 (4) Å

c = 16.5584 (5) Å

β = 115.303 (2)°

V = 4812.4 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.17 mm−1

T = 293 K

0.22 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.964, T max = 0.972

22058 measured reflections

6013 independent reflections

4157 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.146

S = 1.04

6013 reflections

297 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813026500/bt6930sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026500/bt6930Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813026500/bt6930Isup3.cml

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

C24H27N5O2S·0.5H2O	F(000) = 1944
Mr = 458.57	Dx = 1.266 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4157 reflections
a = 28.7522 (9) Å	θ = 2.5–28.5°
b = 11.1809 (4) Å	µ = 0.17 mm−1
c = 16.5584 (5) Å	T = 293 K
β = 115.303 (2)°	Block, white crystalline
V = 4812.4 (3) Å3	0.22 × 0.19 × 0.17 mm
Z = 8

Bruker SMART APEXII CCD diffractometer	6013 independent reflections
Radiation source: fine-focus sealed tube	4157 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scans	θmax = 28.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −38→37
Tmin = 0.964, Tmax = 0.972	k = −14→14
22058 measured reflections	l = −22→22

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.146	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0657P)2 + 3.1292P] where P = (Fo2 + 2Fc2)/3
6013 reflections	(Δ/σ)max < 0.001
297 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.25 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
C2	0.36794 (6)	0.31060 (16)	0.37251 (12)	0.0412 (4)
H2	0.3603	0.2457	0.3289	0.049*
C3	0.40052 (7)	0.40262 (18)	0.35071 (12)	0.0492 (4)
H3	0.4339	0.3659	0.3635	0.059*
C4	0.41000 (7)	0.51029 (18)	0.41040 (13)	0.0519 (5)
C5	0.37256 (7)	0.52979 (16)	0.45051 (12)	0.0465 (4)
H5A	0.3715	0.6147	0.4617	0.056*
H5B	0.3856	0.4894	0.5078	0.056*
C6	0.31739 (6)	0.48676 (14)	0.39456 (11)	0.0388 (4)
H6	0.3012	0.5417	0.3441	0.047*
C7	0.28781 (6)	0.49375 (15)	0.45121 (11)	0.0402 (4)
C8	0.25431 (7)	0.58770 (17)	0.43993 (14)	0.0519 (5)
H8	0.2485	0.6437	0.3951	0.062*
C9	0.22951 (9)	0.5988 (2)	0.49479 (18)	0.0661 (6)
H9	0.2071	0.6625	0.4868	0.079*
C10	0.23757 (9)	0.5170 (2)	0.56082 (17)	0.0682 (6)
H10	0.2211	0.5253	0.5981	0.082*
C11	0.27031 (9)	0.4222 (2)	0.57168 (15)	0.0638 (6)
H11	0.2755	0.3657	0.6159	0.077*
C12	0.29535 (8)	0.41052 (17)	0.51762 (13)	0.0508 (4)
H12	0.3175	0.3464	0.5257	0.061*
C13	0.39463 (6)	0.25381 (16)	0.46536 (12)	0.0439 (4)
C14	0.36763 (7)	0.16991 (17)	0.48954 (14)	0.0525 (5)
H14	0.3345	0.1489	0.4490	0.063*
C15	0.38885 (9)	0.1164 (2)	0.57293 (15)	0.0640 (6)
H15	0.3698	0.0611	0.5883	0.077*
C16	0.43792 (9)	0.1451 (2)	0.63289 (16)	0.0708 (6)
H16	0.4522	0.1097	0.6891	0.085*
C17	0.46572 (8)	0.2261 (2)	0.60943 (16)	0.0712 (7)
H17	0.4991	0.2450	0.6498	0.085*
C18	0.44445 (7)	0.28039 (19)	0.52588 (14)	0.0570 (5)
H18	0.4638	0.3349	0.5106	0.068*
C19	0.37600 (8)	0.4421 (2)	0.25143 (14)	0.0598 (5)
H19	0.3441	0.4849	0.2402	0.072*
C20	0.36228 (12)	0.3358 (3)	0.18807 (16)	0.0836 (8)
H20A	0.3481	0.3639	0.1275	0.125*
H20B	0.3374	0.2867	0.1968	0.125*
H20C	0.3927	0.2896	0.2000	0.125*
C21	0.41134 (12)	0.5283 (3)	0.2321 (2)	0.1060 (11)
H21A	0.4432	0.4888	0.2434	0.159*
H21B	0.4181	0.5971	0.2701	0.159*
H21C	0.3950	0.5530	0.1707	0.159*
C22	0.27371 (6)	0.31101 (15)	0.30215 (11)	0.0386 (4)
C23	0.22425 (6)	0.37998 (17)	0.27937 (12)	0.0456 (4)
H23A	0.2283	0.4620	0.2643	0.055*
H23B	0.2159	0.3808	0.3303	0.055*
C24	0.12585 (7)	0.41117 (17)	0.17409 (13)	0.0499 (4)
C25	0.06530 (10)	0.3638 (2)	0.01369 (17)	0.0818 (8)
H25A	0.0921	0.3667	−0.0062	0.123*
H25B	0.0352	0.4030	−0.0292	0.123*
H25C	0.0573	0.2819	0.0199	0.123*
N1	0.31787 (5)	0.36569 (12)	0.35824 (9)	0.0368 (3)
N2	0.12550 (7)	0.48754 (19)	0.23410 (14)	0.0695 (5)
N3	0.08016 (8)	0.5478 (2)	0.19371 (18)	0.0833 (6)
N4	0.05421 (7)	0.51015 (18)	0.11397 (18)	0.0799 (6)
N5	0.08241 (6)	0.42381 (15)	0.09937 (12)	0.0600 (5)
O1	0.44618 (6)	0.57684 (16)	0.42809 (13)	0.0792 (5)
O2	0.27217 (5)	0.21064 (12)	0.27106 (9)	0.0508 (3)
S1	0.173492 (17)	0.30767 (4)	0.18556 (3)	0.04999 (15)
O1W	0.0000	0.7061 (7)	0.2500	0.373 (7)
H1W	0.0172	0.6692	0.2298	0.560*

	U11	U22	U33	U12	U13	U23
C2	0.0302 (8)	0.0449 (9)	0.0444 (9)	−0.0009 (7)	0.0121 (7)	−0.0003 (7)
C3	0.0349 (9)	0.0609 (12)	0.0488 (10)	−0.0035 (8)	0.0152 (8)	0.0055 (8)
C4	0.0369 (9)	0.0564 (11)	0.0538 (11)	−0.0119 (8)	0.0110 (8)	0.0054 (8)
C5	0.0403 (9)	0.0427 (9)	0.0481 (9)	−0.0116 (7)	0.0109 (8)	−0.0033 (7)
C6	0.0345 (8)	0.0355 (8)	0.0397 (8)	−0.0034 (6)	0.0093 (7)	0.0020 (6)
C7	0.0379 (8)	0.0378 (9)	0.0405 (8)	−0.0080 (7)	0.0125 (7)	−0.0056 (6)
C8	0.0477 (10)	0.0447 (10)	0.0582 (11)	−0.0021 (8)	0.0178 (9)	−0.0059 (8)
C9	0.0559 (12)	0.0567 (13)	0.0906 (16)	−0.0078 (10)	0.0360 (12)	−0.0249 (12)
C10	0.0721 (14)	0.0690 (14)	0.0807 (15)	−0.0302 (12)	0.0491 (13)	−0.0313 (12)
C11	0.0796 (15)	0.0617 (13)	0.0586 (12)	−0.0225 (11)	0.0377 (12)	−0.0074 (10)
C12	0.0568 (11)	0.0444 (10)	0.0514 (10)	−0.0058 (8)	0.0234 (9)	−0.0009 (8)
C13	0.0315 (8)	0.0431 (9)	0.0488 (9)	0.0015 (7)	0.0091 (7)	0.0029 (7)
C14	0.0369 (9)	0.0475 (10)	0.0594 (11)	−0.0039 (8)	0.0076 (9)	0.0079 (8)
C15	0.0550 (12)	0.0554 (12)	0.0684 (13)	−0.0029 (10)	0.0138 (11)	0.0173 (10)
C16	0.0609 (13)	0.0701 (14)	0.0577 (12)	0.0018 (11)	0.0028 (11)	0.0188 (11)
C17	0.0433 (11)	0.0793 (15)	0.0615 (13)	−0.0053 (11)	−0.0057 (10)	0.0118 (11)
C18	0.0340 (9)	0.0624 (12)	0.0614 (12)	−0.0061 (8)	0.0077 (9)	0.0094 (10)
C19	0.0508 (11)	0.0727 (14)	0.0510 (11)	−0.0044 (10)	0.0170 (9)	0.0103 (10)
C20	0.096 (2)	0.0965 (19)	0.0498 (12)	−0.0058 (16)	0.0236 (13)	0.0015 (12)
C21	0.104 (2)	0.139 (3)	0.0702 (16)	−0.043 (2)	0.0331 (16)	0.0237 (17)
C22	0.0305 (8)	0.0454 (9)	0.0335 (7)	−0.0032 (7)	0.0076 (6)	0.0004 (7)
C23	0.0312 (8)	0.0503 (10)	0.0426 (9)	−0.0025 (7)	0.0036 (7)	−0.0051 (8)
C24	0.0332 (9)	0.0517 (10)	0.0541 (10)	−0.0021 (8)	0.0085 (8)	0.0071 (8)
C25	0.0601 (14)	0.0748 (16)	0.0668 (14)	0.0057 (12)	−0.0146 (12)	0.0038 (12)
N1	0.0279 (6)	0.0386 (7)	0.0373 (7)	−0.0025 (5)	0.0077 (5)	−0.0008 (5)
N2	0.0495 (10)	0.0756 (13)	0.0749 (12)	0.0097 (9)	0.0185 (9)	−0.0033 (10)
N3	0.0576 (12)	0.0761 (14)	0.1063 (17)	0.0158 (11)	0.0254 (12)	−0.0021 (13)
N4	0.0472 (10)	0.0623 (12)	0.1054 (17)	0.0130 (9)	0.0089 (11)	0.0096 (11)
N5	0.0376 (8)	0.0515 (9)	0.0681 (11)	0.0017 (7)	0.0009 (8)	0.0113 (8)
O1	0.0542 (9)	0.0838 (11)	0.0987 (12)	−0.0338 (8)	0.0320 (9)	−0.0138 (9)
O2	0.0399 (7)	0.0483 (7)	0.0540 (7)	−0.0035 (5)	0.0104 (6)	−0.0138 (6)
S1	0.0327 (2)	0.0534 (3)	0.0470 (3)	−0.00136 (19)	0.00093 (18)	−0.0049 (2)
O1W	0.275 (9)	0.202 (7)	0.68 (2)	0.000	0.242 (13)	0.000

C2—N1	1.489 (2)	C16—C17	1.370 (3)
C2—C13	1.532 (2)	C16—H16	0.9300
C2—C3	1.535 (2)	C17—C18	1.390 (3)
C2—H2	0.9800	C17—H17	0.9300
C3—C4	1.507 (3)	C18—H18	0.9300
C3—C19	1.551 (3)	C19—C20	1.522 (3)
C3—H3	0.9800	C19—C21	1.530 (3)
C4—O1	1.209 (2)	C19—H19	0.9800
C4—C5	1.503 (3)	C20—H20A	0.9600
C5—C6	1.533 (2)	C20—H20B	0.9600
C5—H5A	0.9700	C20—H20C	0.9600
C5—H5B	0.9700	C21—H21A	0.9600
C6—N1	1.484 (2)	C21—H21B	0.9600
C6—C7	1.514 (2)	C21—H21C	0.9600
C6—H6	0.9800	C22—O2	1.228 (2)
C7—C8	1.383 (3)	C22—N1	1.357 (2)
C7—C12	1.385 (3)	C22—C23	1.517 (2)
C8—C9	1.379 (3)	C23—S1	1.8052 (17)
C8—H8	0.9300	C23—H23A	0.9700
C9—C10	1.367 (4)	C23—H23B	0.9700
C9—H9	0.9300	C24—N2	1.313 (3)
C10—C11	1.378 (3)	C24—N5	1.338 (2)
C10—H10	0.9300	C24—S1	1.741 (2)
C11—C12	1.374 (3)	C25—N5	1.452 (3)
C11—H11	0.9300	C25—H25A	0.9600
C12—H12	0.9300	C25—H25B	0.9600
C13—C14	1.382 (3)	C25—H25C	0.9600
C13—C18	1.385 (2)	N2—N3	1.362 (3)
C14—C15	1.384 (3)	N3—N4	1.279 (3)
C14—H14	0.9300	N4—N5	1.347 (3)
C15—C16	1.372 (3)	O1W—H1W	0.8163
C15—H15	0.9300
N1—C2—C13	111.48 (14)	C17—C16—H16	120.2
N1—C2—C3	109.35 (14)	C15—C16—H16	120.2
C13—C2—C3	114.81 (14)	C16—C17—C18	120.61 (19)
N1—C2—H2	106.9	C16—C17—H17	119.7
C13—C2—H2	106.9	C18—C17—H17	119.7
C3—C2—H2	106.9	C13—C18—C17	120.36 (19)
C4—C3—C2	109.80 (15)	C13—C18—H18	119.8
C4—C3—C19	109.92 (17)	C17—C18—H18	119.8
C2—C3—C19	113.18 (15)	C20—C19—C21	110.3 (2)
C4—C3—H3	107.9	C20—C19—C3	111.99 (19)
C2—C3—H3	107.9	C21—C19—C3	111.05 (18)
C19—C3—H3	107.9	C20—C19—H19	107.8
O1—C4—C5	120.56 (19)	C21—C19—H19	107.8
O1—C4—C3	123.12 (19)	C3—C19—H19	107.8
C5—C4—C3	116.29 (15)	C19—C20—H20A	109.5
C4—C5—C6	116.04 (15)	C19—C20—H20B	109.5
C4—C5—H5A	108.3	H20A—C20—H20B	109.5
C6—C5—H5A	108.3	C19—C20—H20C	109.5
C4—C5—H5B	108.3	H20A—C20—H20C	109.5
C6—C5—H5B	108.3	H20B—C20—H20C	109.5
H5A—C5—H5B	107.4	C19—C21—H21A	109.5
N1—C6—C7	113.78 (13)	C19—C21—H21B	109.5
N1—C6—C5	110.17 (14)	H21A—C21—H21B	109.5
C7—C6—C5	108.64 (14)	C19—C21—H21C	109.5
N1—C6—H6	108.0	H21A—C21—H21C	109.5
C7—C6—H6	108.0	H21B—C21—H21C	109.5
C5—C6—H6	108.0	O2—C22—N1	123.69 (16)
C8—C7—C12	118.77 (18)	O2—C22—C23	119.90 (15)
C8—C7—C6	119.93 (16)	N1—C22—C23	116.41 (14)
C12—C7—C6	121.23 (16)	C22—C23—S1	108.28 (12)
C9—C8—C7	120.4 (2)	C22—C23—H23A	110.0
C9—C8—H8	119.8	S1—C23—H23A	110.0
C7—C8—H8	119.8	C22—C23—H23B	110.0
C10—C9—C8	120.5 (2)	S1—C23—H23B	110.0
C10—C9—H9	119.7	H23A—C23—H23B	108.4
C8—C9—H9	119.7	N2—C24—N5	108.97 (18)
C9—C10—C11	119.5 (2)	N2—C24—S1	127.57 (15)
C9—C10—H10	120.3	N5—C24—S1	123.46 (16)
C11—C10—H10	120.3	N5—C25—H25A	109.5
C12—C11—C10	120.5 (2)	N5—C25—H25B	109.5
C12—C11—H11	119.8	H25A—C25—H25B	109.5
C10—C11—H11	119.8	N5—C25—H25C	109.5
C11—C12—C7	120.4 (2)	H25A—C25—H25C	109.5
C11—C12—H12	119.8	H25B—C25—H25C	109.5
C7—C12—H12	119.8	C22—N1—C6	121.37 (13)
C14—C13—C18	118.14 (17)	C22—N1—C2	118.73 (14)
C14—C13—C2	118.02 (15)	C6—N1—C2	119.27 (13)
C18—C13—C2	123.84 (17)	C24—N2—N3	105.37 (19)
C13—C14—C15	121.32 (18)	N4—N3—N2	111.0 (2)
C13—C14—H14	119.3	N3—N4—N5	106.89 (18)
C15—C14—H14	119.3	C24—N5—N4	107.78 (19)
C16—C15—C14	120.0 (2)	C24—N5—C25	130.34 (19)
C16—C15—H15	120.0	N4—N5—C25	121.86 (18)
C14—C15—H15	120.0	C24—S1—C23	96.05 (9)
C17—C16—C15	119.6 (2)
N1—C2—C3—C4	59.75 (18)	C2—C13—C18—C17	179.1 (2)
C13—C2—C3—C4	−66.4 (2)	C16—C17—C18—C13	0.4 (4)
N1—C2—C3—C19	−63.5 (2)	C4—C3—C19—C20	−176.12 (19)
C13—C2—C3—C19	170.36 (17)	C2—C3—C19—C20	−53.0 (2)
C2—C3—C4—O1	155.9 (2)	C4—C3—C19—C21	60.0 (3)
C19—C3—C4—O1	−79.0 (2)	C2—C3—C19—C21	−176.8 (2)
C2—C3—C4—C5	−22.2 (2)	O2—C22—C23—S1	−14.3 (2)
C19—C3—C4—C5	102.97 (19)	N1—C22—C23—S1	166.62 (12)
O1—C4—C5—C6	151.13 (19)	O2—C22—N1—C6	−179.37 (15)
C3—C4—C5—C6	−30.8 (2)	C23—C22—N1—C6	−0.3 (2)
C4—C5—C6—N1	45.1 (2)	O2—C22—N1—C2	9.8 (2)
C4—C5—C6—C7	170.36 (15)	C23—C22—N1—C2	−171.18 (14)
N1—C6—C7—C8	−135.30 (16)	C7—C6—N1—C22	61.59 (19)
C5—C6—C7—C8	101.58 (18)	C5—C6—N1—C22	−176.13 (14)
N1—C6—C7—C12	47.8 (2)	C7—C6—N1—C2	−127.61 (15)
C5—C6—C7—C12	−75.3 (2)	C5—C6—N1—C2	−5.3 (2)
C12—C7—C8—C9	0.9 (3)	C13—C2—N1—C22	−107.47 (17)
C6—C7—C8—C9	−176.10 (17)	C3—C2—N1—C22	124.49 (16)
C7—C8—C9—C10	−0.2 (3)	C13—C2—N1—C6	81.48 (17)
C8—C9—C10—C11	−0.7 (3)	C3—C2—N1—C6	−46.55 (19)
C9—C10—C11—C12	1.0 (3)	N5—C24—N2—N3	0.1 (2)
C10—C11—C12—C7	−0.3 (3)	S1—C24—N2—N3	−179.61 (17)
C8—C7—C12—C11	−0.7 (3)	C24—N2—N3—N4	0.3 (3)
C6—C7—C12—C11	176.30 (17)	N2—N3—N4—N5	−0.6 (3)
N1—C2—C13—C14	55.1 (2)	N2—C24—N5—N4	−0.4 (2)
C3—C2—C13—C14	−179.87 (17)	S1—C24—N5—N4	179.29 (15)
N1—C2—C13—C18	−125.88 (19)	N2—C24—N5—C25	177.7 (2)
C3—C2—C13—C18	−0.8 (3)	S1—C24—N5—C25	−2.5 (3)
C18—C13—C14—C15	2.1 (3)	N3—N4—N5—C24	0.6 (3)
C2—C13—C14—C15	−178.76 (19)	N3—N4—N5—C25	−177.7 (2)
C13—C14—C15—C16	−1.1 (4)	N2—C24—S1—C23	−19.8 (2)
C14—C15—C16—C17	−0.4 (4)	N5—C24—S1—C23	160.54 (17)
C15—C16—C17—C18	0.7 (4)	C22—C23—S1—C24	−176.64 (13)
C14—C13—C18—C17	−1.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25C···O1i	0.96	2.47	3.406 (3)	166
C18—H18···O1ii	0.93	2.54	3.312 (2)	140
C25—H25B···N4iii	0.96	2.54	3.472 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25C⋯O1i	0.96	2.47	3.406 (3)	166
C18—H18⋯O1ii	0.93	2.54	3.312 (2)	140
C25—H25B⋯N4iii	0.96	2.54	3.472 (3)	165

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