4,4-Dimethyl-2-tosyl-1,2,3,3a,4,11b-hexa-hydro-11H-pyrrolo[3,4-c]pyrano[5,6-c]chromen-11-one 0.125-hydrate.

In the title compound, C(23)H(23)NO(5)S·0.125H(2)O, the pyrrolidine ring has a twist conformation and the dihydro-pyran ring adopts a half-chair conformation; the two rings are cis-fused. The mol-ecule adopts a folded conformation. The sulfonyl-bound phenyl ring and the pyran ring of the coumarin ring system are stacked over one another, with a centroid-centroid distance of 3.7470 (7) Å; the dihedral angle between the two rings is 18.93 (2)°. An intra-molecular C-H⋯O hydrogen bond is observed. The solvent water mol-ecule, lying on a twofold rotation axis, is only partially occupied with an occupancy of 0.125 (relative occupancy with respect to the main molecule) and is involved in O-H⋯O and C-H⋯O hydrogen bonding.

Related literature

For the biological activity of pyran­ocoumarin compounds, see: Kawaii et al. (2001 ▶); Hossain et al. (1996 ▶); Goel et al. (1997 ▶); Su et al. (2009 ▶); Xu et al. (2006 ▶). For asymmetry parameters, see: Duax et al. (1976 ▶).

Experimental

Crystal data

C23H23NO5S·0.125H2O

M = 427.74

Tetragonal,

a = 15.1932 (2) Å

c = 17.7180 (3) Å

V = 4089.91 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 100 K

0.50 × 0.44 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.845, T max = 0.976

97892 measured reflections

6004 independent reflections

5114 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.109

S = 1.05

6004 reflections

282 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044730/bt5116sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044730/bt5116Isup2.hkl

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

C23H23NO5S·0.125H2O	Dx = 1.389 Mg m−3
Mr = 427.74	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/n	Cell parameters from 9971 reflections
Hall symbol: -P 4bc	θ = 2.2–29.7°
a = 15.1932 (2) Å	µ = 0.20 mm−1
c = 17.7180 (3) Å	T = 100 K
V = 4089.91 (10) Å3	Block, colourless
Z = 8	0.50 × 0.44 × 0.13 mm
F(000) = 1802

Bruker SMART APEXII CCD area-detector diffractometer	6004 independent reflections
Radiation source: fine-focus sealed tube	5114 reflections with I > 2σ(I)
graphite	Rint = 0.058
φ and ω scans	θmax = 30.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −19→21
Tmin = 0.845, Tmax = 0.976	k = −19→21
97892 measured reflections	l = −24→25

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0592P)2 + 1.3394P] where P = (Fo2 + 2Fc2)/3
6004 reflections	(Δ/σ)max = 0.001
282 parameters	Δρmax = 0.44 e Å−3
1 restraint	Δρmin = −0.36 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	Occ. (<1)
S1	0.581635 (19)	0.56278 (2)	0.395952 (15)	0.02140 (8)
O1	0.62409 (6)	0.47960 (7)	0.40829 (5)	0.0292 (2)
O2	0.61326 (6)	0.63995 (7)	0.43408 (5)	0.0313 (2)
O3	0.30418 (6)	0.47680 (5)	0.26574 (4)	0.01818 (16)
O4	0.35320 (6)	0.73448 (6)	0.20657 (5)	0.02448 (19)
O5	0.35668 (6)	0.77642 (6)	0.32563 (5)	0.02305 (18)
N1	0.47990 (6)	0.55091 (7)	0.42058 (5)	0.01870 (19)
C1	0.43048 (8)	0.47357 (8)	0.39346 (6)	0.0190 (2)
H1A	0.4416	0.4226	0.4250	0.023*
H1B	0.4460	0.4595	0.3418	0.023*
C2	0.33383 (7)	0.50282 (7)	0.39921 (6)	0.0168 (2)
H2	0.3125	0.4905	0.4503	0.020*
C3	0.33722 (7)	0.60314 (7)	0.38784 (6)	0.0165 (2)
H3	0.2865	0.6312	0.4120	0.020*
C4	0.42234 (8)	0.62880 (8)	0.42864 (6)	0.0191 (2)
H4A	0.4489	0.6801	0.4054	0.023*
H4B	0.4111	0.6414	0.4814	0.023*
C5	0.27372 (8)	0.45698 (7)	0.34279 (6)	0.0180 (2)
C6	0.32304 (7)	0.56163 (7)	0.25100 (6)	0.0161 (2)
C7	0.33841 (7)	0.62372 (7)	0.30463 (6)	0.0163 (2)
C8	0.58331 (7)	0.58347 (8)	0.29825 (6)	0.0191 (2)
C9	0.56995 (11)	0.66848 (9)	0.27189 (7)	0.0313 (3)
H9	0.5634	0.7150	0.3056	0.038*
C10	0.56654 (12)	0.68315 (9)	0.19508 (8)	0.0387 (4)
H10	0.5564	0.7399	0.1775	0.046*
C11	0.57777 (10)	0.61547 (9)	0.14336 (7)	0.0284 (3)
C12	0.59130 (8)	0.53099 (8)	0.17059 (7)	0.0211 (2)
H12	0.5989	0.4848	0.1367	0.025*
C13	0.59373 (8)	0.51415 (8)	0.24766 (6)	0.0195 (2)
H13	0.6022	0.4571	0.2653	0.023*
C14	0.57659 (14)	0.63433 (12)	0.05996 (8)	0.0496 (5)
H14A	0.5511	0.5853	0.0337	0.074*
H14B	0.6357	0.6435	0.0425	0.074*
H14C	0.5422	0.6862	0.0505	0.074*
C15	0.17906 (8)	0.48882 (8)	0.34908 (7)	0.0229 (2)
H15A	0.1432	0.4582	0.3130	0.034*
H15B	0.1768	0.5509	0.3391	0.034*
H15C	0.1575	0.4775	0.3991	0.034*
C16	0.27884 (9)	0.35747 (8)	0.34841 (7)	0.0244 (2)
H16A	0.2400	0.3315	0.3119	0.037*
H16B	0.2617	0.3393	0.3982	0.037*
H16C	0.3381	0.3386	0.3387	0.037*
C17	0.32585 (7)	0.58344 (8)	0.17165 (6)	0.0180 (2)
C18	0.31166 (8)	0.52190 (8)	0.11395 (6)	0.0211 (2)
H18	0.3007	0.4633	0.1258	0.025*
C19	0.31403 (9)	0.54850 (9)	0.03950 (7)	0.0252 (3)
H19	0.3041	0.5078	0.0013	0.030*
C20	0.33121 (10)	0.63606 (10)	0.02134 (7)	0.0307 (3)
H20	0.3327	0.6532	−0.0290	0.037*
C21	0.34609 (10)	0.69774 (9)	0.07730 (7)	0.0307 (3)
H21	0.3584	0.7560	0.0651	0.037*
C22	0.34229 (8)	0.67083 (8)	0.15238 (6)	0.0223 (2)
C23	0.35020 (8)	0.71478 (8)	0.28241 (6)	0.0190 (2)
O1W	0.7500	0.7500	0.4887 (3)	0.0379 (14)	0.25
H1W1	0.714 (5)	0.723 (5)	0.463 (4)	0.057*	0.25

	U11	U22	U33	U12	U13	U23
S1	0.01678 (14)	0.03109 (17)	0.01633 (13)	0.00006 (10)	−0.00130 (9)	0.00123 (10)
O1	0.0219 (4)	0.0431 (6)	0.0225 (4)	0.0104 (4)	−0.0003 (3)	0.0089 (4)
O2	0.0238 (5)	0.0462 (6)	0.0241 (4)	−0.0101 (4)	−0.0015 (3)	−0.0076 (4)
O3	0.0253 (4)	0.0136 (4)	0.0156 (3)	−0.0018 (3)	0.0003 (3)	0.0007 (3)
O4	0.0349 (5)	0.0179 (4)	0.0207 (4)	−0.0063 (3)	−0.0050 (3)	0.0041 (3)
O5	0.0261 (4)	0.0163 (4)	0.0267 (4)	−0.0019 (3)	−0.0023 (3)	−0.0015 (3)
N1	0.0163 (4)	0.0216 (5)	0.0182 (4)	0.0010 (4)	−0.0001 (3)	0.0003 (3)
C1	0.0199 (5)	0.0190 (5)	0.0181 (5)	0.0011 (4)	−0.0008 (4)	0.0009 (4)
C2	0.0188 (5)	0.0164 (5)	0.0152 (4)	0.0000 (4)	0.0006 (4)	0.0013 (4)
C3	0.0178 (5)	0.0157 (5)	0.0161 (4)	0.0005 (4)	0.0008 (4)	−0.0007 (4)
C4	0.0208 (5)	0.0195 (5)	0.0169 (5)	0.0003 (4)	−0.0013 (4)	−0.0022 (4)
C5	0.0214 (5)	0.0162 (5)	0.0164 (5)	−0.0020 (4)	0.0005 (4)	0.0027 (4)
C6	0.0161 (5)	0.0148 (5)	0.0173 (5)	0.0006 (4)	−0.0008 (4)	0.0018 (4)
C7	0.0167 (5)	0.0152 (5)	0.0171 (5)	0.0003 (4)	−0.0011 (4)	0.0013 (4)
C8	0.0175 (5)	0.0223 (5)	0.0175 (5)	−0.0005 (4)	0.0009 (4)	0.0016 (4)
C9	0.0501 (9)	0.0184 (6)	0.0253 (6)	0.0008 (5)	0.0106 (6)	−0.0021 (5)
C10	0.0695 (11)	0.0195 (6)	0.0272 (6)	0.0099 (6)	0.0134 (7)	0.0065 (5)
C11	0.0404 (8)	0.0249 (6)	0.0200 (5)	0.0089 (5)	0.0051 (5)	0.0053 (5)
C12	0.0240 (6)	0.0204 (5)	0.0190 (5)	0.0016 (4)	0.0005 (4)	−0.0004 (4)
C13	0.0201 (5)	0.0183 (5)	0.0201 (5)	0.0014 (4)	0.0004 (4)	0.0027 (4)
C14	0.0861 (14)	0.0409 (9)	0.0217 (6)	0.0300 (9)	0.0102 (7)	0.0097 (6)
C15	0.0194 (5)	0.0235 (6)	0.0256 (6)	−0.0029 (4)	−0.0004 (4)	0.0019 (4)
C16	0.0322 (7)	0.0161 (5)	0.0250 (6)	−0.0025 (4)	−0.0019 (5)	0.0029 (4)
C17	0.0184 (5)	0.0194 (5)	0.0162 (5)	−0.0007 (4)	−0.0012 (4)	0.0021 (4)
C18	0.0237 (6)	0.0209 (5)	0.0188 (5)	0.0017 (4)	−0.0024 (4)	0.0008 (4)
C19	0.0290 (6)	0.0290 (6)	0.0177 (5)	0.0018 (5)	−0.0036 (4)	−0.0004 (4)
C20	0.0389 (8)	0.0351 (7)	0.0180 (5)	−0.0040 (6)	−0.0036 (5)	0.0072 (5)
C21	0.0424 (8)	0.0273 (7)	0.0225 (6)	−0.0088 (5)	−0.0046 (5)	0.0090 (5)
C22	0.0266 (6)	0.0207 (6)	0.0195 (5)	−0.0039 (4)	−0.0039 (4)	0.0030 (4)
C23	0.0188 (5)	0.0173 (5)	0.0208 (5)	−0.0010 (4)	−0.0023 (4)	0.0027 (4)
O1W	0.055 (4)	0.037 (3)	0.022 (2)	−0.029 (3)	0.000	0.000

S1—O1	1.4355 (10)	C9—C10	1.3799 (19)
S1—O2	1.4359 (10)	C9—H9	0.93
S1—N1	1.6161 (10)	C10—C11	1.3878 (19)
S1—C8	1.7597 (12)	C10—H10	0.93
O3—C6	1.3459 (13)	C11—C12	1.3865 (17)
O3—C5	1.4727 (13)	C11—C14	1.5054 (18)
O4—C22	1.3728 (14)	C12—C13	1.3897 (15)
O4—C23	1.3774 (14)	C12—H12	0.93
O5—C23	1.2137 (14)	C13—H13	0.93
N1—C1	1.4749 (15)	C14—H14A	0.96
N1—C4	1.4784 (15)	C14—H14B	0.96
C1—C2	1.5376 (16)	C14—H14C	0.96
C1—H1A	0.97	C15—H15A	0.96
C1—H1B	0.97	C15—H15B	0.96
C2—C5	1.5225 (15)	C15—H15C	0.96
C2—C3	1.5382 (15)	C16—H16A	0.96
C2—H2	0.98	C16—H16B	0.96
C3—C7	1.5072 (14)	C16—H16C	0.96
C3—C4	1.5320 (16)	C17—C22	1.3935 (16)
C3—H3	0.98	C17—C18	1.4021 (16)
C4—H4A	0.97	C18—C19	1.3800 (16)
C4—H4B	0.97	C18—H18	0.93
C5—C16	1.5172 (16)	C19—C20	1.3934 (19)
C5—C15	1.5215 (17)	C19—H19	0.93
C6—C7	1.3592 (15)	C20—C21	1.383 (2)
C6—C17	1.4449 (14)	C20—H20	0.93
C7—C23	1.4497 (15)	C21—C22	1.3929 (16)
C8—C9	1.3883 (17)	C21—H21	0.93
C8—C13	1.3920 (16)	O1W—H1W1	0.83 (2)
O1—S1—O2	119.79 (6)	C8—C9—H9	120.4
O1—S1—N1	106.89 (6)	C9—C10—C11	121.80 (12)
O2—S1—N1	106.50 (6)	C9—C10—H10	119.1
O1—S1—C8	107.49 (6)	C11—C10—H10	119.1
O2—S1—C8	108.18 (6)	C12—C11—C10	118.31 (12)
N1—S1—C8	107.42 (5)	C12—C11—C14	121.30 (12)
C6—O3—C5	116.27 (8)	C10—C11—C14	120.38 (12)
C22—O4—C23	121.68 (9)	C11—C12—C13	121.08 (11)
C1—N1—C4	111.59 (9)	C11—C12—H12	119.5
C1—N1—S1	119.20 (8)	C13—C12—H12	119.5
C4—N1—S1	120.17 (8)	C12—C13—C8	119.36 (11)
N1—C1—C2	103.55 (9)	C12—C13—H13	120.3
N1—C1—H1A	111.1	C8—C13—H13	120.3
C2—C1—H1A	111.1	C11—C14—H14A	109.5
N1—C1—H1B	111.1	C11—C14—H14B	109.5
C2—C1—H1B	111.1	H14A—C14—H14B	109.5
H1A—C1—H1B	109.0	C11—C14—H14C	109.5
C5—C2—C1	113.40 (9)	H14A—C14—H14C	109.5
C5—C2—C3	112.79 (9)	H14B—C14—H14C	109.5
C1—C2—C3	104.22 (9)	C5—C15—H15A	109.5
C5—C2—H2	108.7	C5—C15—H15B	109.5
C1—C2—H2	108.7	H15A—C15—H15B	109.5
C3—C2—H2	108.7	C5—C15—H15C	109.5
C7—C3—C4	113.50 (9)	H15A—C15—H15C	109.5
C7—C3—C2	109.51 (9)	H15B—C15—H15C	109.5
C4—C3—C2	102.63 (9)	C5—C16—H16A	109.5
C7—C3—H3	110.3	C5—C16—H16B	109.5
C4—C3—H3	110.3	H16A—C16—H16B	109.5
C2—C3—H3	110.3	C5—C16—H16C	109.5
N1—C4—C3	104.48 (9)	H16A—C16—H16C	109.5
N1—C4—H4A	110.9	H16B—C16—H16C	109.5
C3—C4—H4A	110.9	C22—C17—C18	118.96 (10)
N1—C4—H4B	110.9	C22—C17—C6	117.53 (10)
C3—C4—H4B	110.9	C18—C17—C6	123.50 (10)
H4A—C4—H4B	108.9	C19—C18—C17	119.85 (11)
O3—C5—C16	104.38 (9)	C19—C18—H18	120.1
O3—C5—C15	107.45 (9)	C17—C18—H18	120.1
C16—C5—C15	111.13 (10)	C18—C19—C20	120.34 (12)
O3—C5—C2	109.06 (9)	C18—C19—H19	119.8
C16—C5—C2	112.46 (9)	C20—C19—H19	119.8
C15—C5—C2	111.93 (9)	C21—C20—C19	120.80 (11)
O3—C6—C7	124.44 (10)	C21—C20—H20	119.6
O3—C6—C17	114.50 (9)	C19—C20—H20	119.6
C7—C6—C17	121.06 (10)	C20—C21—C22	118.62 (12)
C6—C7—C23	119.59 (10)	C20—C21—H21	120.7
C6—C7—C3	122.54 (10)	C22—C21—H21	120.7
C23—C7—C3	117.72 (9)	O4—C22—C21	117.14 (11)
C9—C8—C13	120.26 (11)	O4—C22—C17	121.43 (10)
C9—C8—S1	119.68 (9)	C21—C22—C17	121.41 (11)
C13—C8—S1	119.99 (9)	O5—C23—O4	116.44 (10)
C10—C9—C8	119.17 (12)	O5—C23—C7	125.11 (11)
C10—C9—H9	120.4	O4—C23—C7	118.45 (10)
O1—S1—N1—C1	−47.47 (10)	O2—S1—C8—C9	−31.08 (12)
O2—S1—N1—C1	−176.63 (8)	N1—S1—C8—C9	83.53 (12)
C8—S1—N1—C1	67.65 (10)	O1—S1—C8—C13	21.34 (11)
O1—S1—N1—C4	168.19 (8)	O2—S1—C8—C13	152.02 (10)
O2—S1—N1—C4	39.03 (10)	N1—S1—C8—C13	−93.37 (10)
C8—S1—N1—C4	−76.69 (9)	C13—C8—C9—C10	0.5 (2)
C4—N1—C1—C2	−10.44 (11)	S1—C8—C9—C10	−176.44 (12)
S1—N1—C1—C2	−157.62 (7)	C8—C9—C10—C11	−1.3 (3)
N1—C1—C2—C5	152.39 (9)	C9—C10—C11—C12	1.1 (3)
N1—C1—C2—C3	29.36 (10)	C9—C10—C11—C14	−178.00 (17)
C5—C2—C3—C7	−39.60 (12)	C10—C11—C12—C13	−0.1 (2)
C1—C2—C3—C7	83.82 (10)	C14—C11—C12—C13	178.96 (14)
C5—C2—C3—C4	−160.46 (9)	C11—C12—C13—C8	−0.66 (19)
C1—C2—C3—C4	−37.03 (10)	C9—C8—C13—C12	0.48 (18)
C1—N1—C4—C3	−12.70 (12)	S1—C8—C13—C12	177.37 (9)
S1—N1—C4—C3	134.11 (8)	O3—C6—C17—C22	178.02 (10)
C7—C3—C4—N1	−87.73 (11)	C7—C6—C17—C22	−1.85 (16)
C2—C3—C4—N1	30.35 (10)	O3—C6—C17—C18	−0.97 (16)
C6—O3—C5—C16	−166.93 (9)	C7—C6—C17—C18	179.16 (11)
C6—O3—C5—C15	74.98 (11)	C22—C17—C18—C19	−0.09 (18)
C6—O3—C5—C2	−46.55 (12)	C6—C17—C18—C19	178.89 (11)
C1—C2—C5—O3	−60.12 (12)	C17—C18—C19—C20	0.55 (19)
C3—C2—C5—O3	58.06 (12)	C18—C19—C20—C21	0.0 (2)
C1—C2—C5—C16	55.17 (12)	C19—C20—C21—C22	−0.9 (2)
C3—C2—C5—C16	173.35 (9)	C23—O4—C22—C21	179.72 (12)
C1—C2—C5—C15	−178.89 (9)	C23—O4—C22—C17	1.34 (18)
C3—C2—C5—C15	−60.71 (12)	C20—C21—C22—O4	−176.96 (13)
C5—O3—C6—C7	18.19 (15)	C20—C21—C22—C17	1.4 (2)
C5—O3—C6—C17	−161.67 (9)	C18—C17—C22—O4	177.39 (11)
O3—C6—C7—C23	−174.40 (10)	C6—C17—C22—O4	−1.65 (17)
C17—C6—C7—C23	5.45 (16)	C18—C17—C22—C21	−0.91 (19)
O3—C6—C7—C3	0.98 (17)	C6—C17—C22—C21	−179.95 (12)
C17—C6—C7—C3	−179.17 (10)	C22—O4—C23—O5	−176.80 (11)
C4—C3—C7—C6	124.43 (11)	C22—O4—C23—C7	2.28 (16)
C2—C3—C7—C6	10.40 (15)	C6—C7—C23—O5	173.33 (11)
C4—C3—C7—C23	−60.11 (13)	C3—C7—C23—O5	−2.27 (17)
C2—C3—C7—C23	−174.13 (10)	C6—C7—C23—O4	−5.67 (16)
O1—S1—C8—C9	−161.76 (11)	C3—C7—C23—O4	178.73 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O5	0.97	2.47	3.0588 (15)	119
O1W—H1W1···O2	0.83 (2)	2.05 (8)	2.837 (2)	161 (8)
C16—H16B···O1Wi	0.96	2.43	3.345 (5)	160
C16—H16B···O1Wii	0.96	2.43	3.345 (5)	160
C14—H14B···O1Wiii	0.96	2.44	3.282 (2)	147
C14—H14B···O1Wiv	0.96	2.44	3.282 (2)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O5	0.97	2.47	3.0588 (15)	119
O1W—H1W1⋯O2	0.83 (2)	2.05 (8)	2.837 (2)	161 (8)
C16—H16B⋯O1Wi	0.96	2.43	3.345 (5)	160
C16—H16B⋯O1Wii	0.96	2.43	3.345 (5)	160
C14—H14B⋯O1Wiii	0.96	2.44	3.282 (2)	147
C14—H14B⋯O1Wiv	0.96	2.44	3.282 (2)	147

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