A P212121 polymorph of (+)-clusianone.

The title compound, C33H42O4 [systematic name: (1S,5S,7R)-3-benzoyl-4-hy-droxy-8,8-dimethyl-1,5,7-tris-(3-methyl-but-2--enyl)bi-cyclo-[3.3.1]nona-3-ene-2,9-dione], has a central bi-cyclo-[3.3.1]nonane-2,4,9-trione surrounded by tetra-prenyl-ated and benzoyl groups. The compound was recrystallized several times in methanol using both a slow evaporation method and with a crystal-seeding technique. This subsequently produced diffraction-quality crystals which crystallize in the ortho-rhom-bic space group P212121, in contrast to a previous report of a structure determination in the Pna21 space group [McCandlish et al. (1976 ▶). Acta Cryst. B32, 1793-1801]. The title compound has a melting point of 365-366 K, and a specific rotation [α](20) value of +51.94°. A strong intra-molecular O-H⋯O hydrogen bond is noted. In the crystal, mol-ecules are assembled in the ab plane by weak C-H⋯O inter-actions.

Related literature

For related structural studies, see: McCandlish et al. (1976 ▶); Santos et al. (1998 ▶, 2001 ▶). For background to Clusiaceae metabolites, see: Monache et al. (1991 ▶); de Oliveira et al. (1996 ▶). For discussion of polycyclic polyprenylated acyl­phloroglucinols, including their biological properties, see: Piccinelli et al. (2005 ▶); Garnsey et al. (2011 ▶); Simpkins (2013 ▶).

Experimental

Crystal data

C33H42O4

M = 502.69

Orthorhombic,

a = 9.2035 (2) Å

b = 13.4629 (2) Å

c = 22.9607 (5) Å

V = 2844.96 (10) Å3

Z = 4

Cu Kα radiation

μ = 0.59 mm−1

T = 100 K

0.21 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2002 ▶) T min = 0.86, T max = 0.95

39826 measured reflections

5498 independent reflections

5269 reflections with I > 2.0σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 0.96

5498 reflections

335 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 2383 Friedel pairs

Absolute structure parameter: −0.04 (15)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶; Cooper et al., 2010 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813031036/tk5270sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813031036/tk5270Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813031036/tk5270Isup3.cml

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

C33H42O4	Dx = 1.174 Mg m−3
Mr = 502.69	Melting point: 365 K
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 19011 reflections
a = 9.2035 (2) Å	θ = 3–71°
b = 13.4629 (2) Å	µ = 0.59 mm−1
c = 22.9607 (5) Å	T = 100 K
V = 2844.96 (10) Å3	Prismatic, colourless
Z = 4	0.21 × 0.14 × 0.08 mm
F(000) = 1088

Oxford Diffraction Gemini diffractometer	5498 independent reflections
Radiation source: Cu Ka	5269 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 71.6°, θmin = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2002)	h = −11→11
Tmin = 0.86, Tmax = 0.95	k = −16→16
39826 measured reflections	l = −28→28

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034	Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.04P)2 + 1.02P] , where P = (max(Fo2,0) + 2Fc2)/3
wR(F2) = 0.084	(Δ/σ)max = 0.001
S = 0.96	Δρmax = 0.24 e Å−3
5498 reflections	Δρmin = −0.18 e Å−3
335 parameters	Absolute structure: Flack (1983), 2383 Friedel pairs
0 restraints	Absolute structure parameter: −0.04 (15)
Primary atom site location: other

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat with a nominal stability of 0.1 K.

	x	y	z	Uiso*/Ueq
O1	1.01156 (11)	0.23087 (8)	0.70014 (5)	0.0254
H1	0.9976	0.3386	0.7123	0.0500*
C2	0.89022 (15)	0.21427 (11)	0.67631 (6)	0.0196
C3	0.87580 (15)	0.11723 (10)	0.64619 (6)	0.0196
C4	0.81066 (17)	0.10926 (12)	0.59161 (7)	0.0252
C5	0.81469 (18)	0.01993 (13)	0.56225 (7)	0.0333
C6	0.87951 (19)	−0.06283 (13)	0.58714 (8)	0.0364
C7	0.94348 (19)	−0.05514 (12)	0.64160 (8)	0.0338
C8	0.94353 (17)	0.03472 (11)	0.67054 (7)	0.0260
C9	0.78010 (15)	0.29113 (10)	0.67650 (6)	0.0189
C10	0.82224 (15)	0.38637 (11)	0.69421 (6)	0.0200
O11	0.95023 (11)	0.40387 (7)	0.71561 (4)	0.0244
C12	0.72277 (16)	0.47533 (10)	0.69123 (6)	0.0207
C13	0.60033 (16)	0.45383 (10)	0.64825 (6)	0.0204
O14	0.56632 (12)	0.51181 (7)	0.61064 (5)	0.0285
C15	0.51798 (15)	0.35827 (10)	0.66056 (6)	0.0198
C16	0.62421 (15)	0.26982 (10)	0.66719 (6)	0.0187
O17	0.57659 (11)	0.18581 (7)	0.66667 (5)	0.0232
C18	0.43562 (16)	0.37607 (10)	0.72158 (6)	0.0215
C19	0.55121 (16)	0.40042 (10)	0.76906 (6)	0.0211
C20	0.64960 (16)	0.48756 (11)	0.75201 (6)	0.0220
C21	0.48510 (17)	0.42104 (11)	0.83005 (7)	0.0255
C22	0.59687 (18)	0.41885 (11)	0.87765 (7)	0.0268
C23	0.61287 (19)	0.35035 (12)	0.91878 (7)	0.0297
C24	0.7280 (2)	0.36145 (15)	0.96492 (8)	0.0415
C25	0.5211 (2)	0.25871 (14)	0.92400 (9)	0.0454
C26	0.32752 (17)	0.46277 (12)	0.71414 (7)	0.0286
C27	0.35104 (16)	0.28311 (12)	0.73993 (7)	0.0275
C28	0.41309 (16)	0.33433 (10)	0.60982 (6)	0.0227
C29	0.48887 (16)	0.31514 (11)	0.55260 (7)	0.0234
C30	0.48971 (16)	0.23037 (11)	0.52250 (6)	0.0235
C31	0.41774 (19)	0.13577 (11)	0.54147 (7)	0.0297
C32	0.56841 (18)	0.22262 (12)	0.46514 (7)	0.0286
C33	0.80586 (17)	0.57064 (11)	0.67524 (6)	0.0238
C34	0.90501 (18)	0.55841 (11)	0.62358 (6)	0.0269
C35	1.03353 (17)	0.60074 (10)	0.61558 (6)	0.0242
C36	1.10148 (18)	0.67277 (11)	0.65730 (7)	0.0283
C37	1.1235 (2)	0.57708 (12)	0.56262 (7)	0.0336
H41	0.7629	0.1648	0.5747	0.0322*
H51	0.7720	0.0154	0.5245	0.0408*
H61	0.8767	−0.1239	0.5662	0.0448*
H71	0.9882	−0.1120	0.6603	0.0423*
H81	0.9888	0.0410	0.7073	0.0323*
H191	0.6141	0.3413	0.7739	0.0240*
H201	0.7285	0.4939	0.7814	0.0255*
H202	0.5948	0.5492	0.7515	0.0250*
H211	0.4404	0.4855	0.8298	0.0302*
H212	0.4098	0.3724	0.8376	0.0308*
H221	0.6650	0.4724	0.8783	0.0333*
H241	0.7808	0.4252	0.9604	0.0629*
H242	0.6826	0.3587	1.0029	0.0630*
H243	0.7968	0.3064	0.9624	0.0633*
H251	0.4774	0.2571	0.9626	0.0712*
H252	0.4405	0.2558	0.8975	0.0712*
H253	0.5783	0.1996	0.9203	0.0711*
H261	0.2489	0.4460	0.6869	0.0435*
H262	0.3726	0.5228	0.7009	0.0443*
H263	0.2793	0.4760	0.7516	0.0424*
H271	0.2827	0.2989	0.7720	0.0415*
H272	0.4133	0.2300	0.7529	0.0415*
H273	0.2935	0.2588	0.7065	0.0413*
H281	0.3488	0.3913	0.6046	0.0275*
H282	0.3528	0.2790	0.6214	0.0274*
H291	0.5415	0.3699	0.5369	0.0295*
H311	0.3450	0.1161	0.5121	0.0463*
H312	0.3641	0.1421	0.5785	0.0443*
H313	0.4882	0.0812	0.5462	0.0471*
H321	0.5028	0.1978	0.4355	0.0443*
H322	0.6530	0.1781	0.4687	0.0436*
H323	0.6061	0.2878	0.4517	0.0438*
H331	0.8619	0.5902	0.7093	0.0268*
H332	0.7355	0.6225	0.6683	0.0297*
H341	0.8682	0.5150	0.5937	0.0329*
H361	1.1371	0.7325	0.6379	0.0438*
H362	1.1884	0.6436	0.6753	0.0454*
H363	1.0391	0.6926	0.6877	0.0428*
H371	1.1424	0.6355	0.5392	0.0501*
H372	1.0793	0.5284	0.5373	0.0518*
H373	1.2186	0.5520	0.5739	0.0518*

	U11	U22	U33	U12	U13	U23
O1	0.0188 (5)	0.0295 (5)	0.0279 (5)	0.0028 (4)	−0.0055 (4)	−0.0029 (4)
C2	0.0186 (7)	0.0247 (7)	0.0157 (6)	−0.0013 (6)	0.0009 (5)	0.0033 (5)
C3	0.0143 (6)	0.0228 (7)	0.0216 (7)	0.0013 (6)	0.0031 (5)	0.0010 (5)
C4	0.0223 (7)	0.0281 (8)	0.0250 (7)	0.0033 (6)	−0.0014 (6)	−0.0008 (6)
C5	0.0277 (8)	0.0415 (9)	0.0307 (8)	0.0014 (7)	−0.0041 (7)	−0.0124 (7)
C6	0.0330 (9)	0.0281 (8)	0.0480 (10)	0.0050 (7)	0.0038 (8)	−0.0156 (7)
C7	0.0331 (9)	0.0251 (7)	0.0432 (9)	0.0107 (7)	0.0017 (7)	0.0014 (7)
C8	0.0231 (7)	0.0299 (8)	0.0251 (7)	0.0045 (6)	−0.0002 (6)	0.0012 (6)
C9	0.0199 (7)	0.0209 (7)	0.0160 (6)	0.0006 (5)	0.0006 (5)	0.0015 (5)
C10	0.0192 (6)	0.0250 (7)	0.0157 (6)	−0.0026 (6)	0.0016 (5)	0.0013 (5)
O11	0.0215 (5)	0.0246 (5)	0.0270 (5)	−0.0021 (4)	−0.0028 (4)	−0.0040 (4)
C12	0.0222 (7)	0.0186 (7)	0.0215 (7)	−0.0026 (5)	0.0020 (6)	−0.0015 (5)
C13	0.0213 (7)	0.0186 (6)	0.0214 (7)	0.0034 (6)	0.0024 (6)	−0.0028 (5)
O14	0.0349 (6)	0.0215 (5)	0.0291 (6)	0.0015 (4)	−0.0056 (5)	0.0039 (4)
C15	0.0170 (6)	0.0196 (6)	0.0227 (7)	0.0005 (5)	−0.0002 (5)	−0.0006 (5)
C16	0.0194 (6)	0.0199 (6)	0.0169 (6)	0.0011 (5)	0.0005 (5)	−0.0007 (5)
O17	0.0195 (5)	0.0185 (5)	0.0318 (6)	−0.0007 (4)	0.0004 (4)	−0.0005 (4)
C18	0.0181 (7)	0.0214 (7)	0.0248 (7)	0.0010 (6)	0.0026 (6)	−0.0010 (5)
C19	0.0213 (7)	0.0179 (6)	0.0242 (7)	0.0021 (5)	0.0028 (6)	−0.0005 (5)
C20	0.0236 (7)	0.0200 (7)	0.0223 (7)	0.0000 (6)	0.0018 (6)	−0.0023 (5)
C21	0.0270 (7)	0.0222 (7)	0.0272 (7)	0.0026 (6)	0.0057 (6)	−0.0009 (6)
C22	0.0305 (8)	0.0241 (7)	0.0259 (7)	−0.0004 (6)	0.0081 (6)	−0.0059 (6)
C23	0.0340 (8)	0.0285 (8)	0.0267 (8)	0.0077 (7)	0.0078 (7)	−0.0029 (6)
C24	0.0491 (11)	0.0477 (10)	0.0278 (9)	0.0143 (9)	0.0009 (8)	−0.0037 (8)
C25	0.0507 (12)	0.0352 (10)	0.0503 (11)	0.0003 (9)	0.0050 (10)	0.0126 (8)
C26	0.0232 (7)	0.0291 (8)	0.0335 (8)	0.0066 (6)	0.0013 (7)	−0.0016 (7)
C27	0.0225 (8)	0.0293 (8)	0.0306 (8)	−0.0031 (6)	0.0043 (6)	−0.0013 (7)
C28	0.0178 (7)	0.0214 (6)	0.0290 (8)	0.0030 (5)	−0.0052 (6)	−0.0002 (6)
C29	0.0196 (7)	0.0252 (7)	0.0254 (7)	−0.0011 (6)	−0.0056 (6)	0.0039 (6)
C30	0.0187 (7)	0.0283 (7)	0.0235 (7)	0.0022 (6)	−0.0060 (6)	0.0012 (6)
C31	0.0312 (8)	0.0258 (7)	0.0322 (8)	0.0000 (7)	0.0025 (7)	−0.0028 (6)
C32	0.0283 (8)	0.0328 (8)	0.0247 (7)	−0.0003 (7)	−0.0015 (6)	0.0001 (6)
C33	0.0282 (8)	0.0199 (7)	0.0232 (7)	−0.0041 (6)	0.0019 (6)	−0.0015 (6)
C34	0.0381 (9)	0.0209 (6)	0.0217 (7)	−0.0045 (6)	0.0022 (7)	−0.0021 (6)
C35	0.0327 (8)	0.0173 (6)	0.0227 (7)	0.0020 (6)	0.0033 (6)	0.0028 (5)
C36	0.0280 (8)	0.0250 (7)	0.0317 (8)	−0.0024 (6)	0.0034 (6)	−0.0012 (6)
C37	0.0409 (9)	0.0267 (8)	0.0332 (9)	−0.0057 (7)	0.0124 (8)	−0.0030 (6)

O1—C2	1.2635 (17)	C23—C24	1.506 (3)
H1—O11	0.984	C23—C25	1.500 (3)
C2—C3	1.4842 (19)	C24—H241	0.992
C2—C9	1.448 (2)	C24—H242	0.968
C3—C4	1.393 (2)	C24—H243	0.977
C3—C8	1.391 (2)	C25—H251	0.974
C4—C5	1.379 (2)	C25—H252	0.960
C4—H41	0.950	C25—H253	0.958
C5—C6	1.387 (3)	C26—H261	0.983
C5—H51	0.953	C26—H262	0.958
C6—C7	1.386 (3)	C26—H263	0.984
C6—H61	0.953	C27—H271	0.992
C7—C8	1.380 (2)	C27—H272	0.964
C7—H71	0.969	C27—H273	0.988
C8—H81	0.945	C28—C29	1.510 (2)
C9—C10	1.400 (2)	C28—H281	0.975
C9—C16	1.479 (2)	C28—H282	0.967
C10—O11	1.2979 (17)	C29—C30	1.334 (2)
C10—C12	1.509 (2)	C29—H291	0.953
C12—C13	1.526 (2)	C30—C31	1.500 (2)
C12—C20	1.5582 (19)	C30—C32	1.507 (2)
C12—C33	1.5381 (19)	C31—H311	0.987
C13—O14	1.2054 (18)	C31—H312	0.987
C13—C15	1.5198 (19)	C31—H313	0.986
C15—C16	1.5482 (19)	C32—H321	0.969
C15—C18	1.6110 (19)	C32—H322	0.986
C15—C28	1.5469 (19)	C32—H323	0.993
C16—O17	1.2131 (17)	C33—C34	1.506 (2)
C18—C19	1.558 (2)	C33—H331	0.973
C18—C26	1.543 (2)	C33—H332	0.966
C18—C27	1.533 (2)	C34—C35	1.326 (2)
C19—C20	1.5328 (19)	C34—H341	0.964
C19—C21	1.552 (2)	C35—C36	1.500 (2)
C19—H191	0.990	C35—C37	1.505 (2)
C20—H201	0.994	C36—H361	0.977
C20—H202	0.971	C36—H362	0.982
C21—C22	1.501 (2)	C36—H363	0.943
C21—H211	0.961	C37—H371	0.969
C21—H212	0.969	C37—H372	0.966
C22—C23	1.328 (2)	C37—H373	0.973
C22—H221	0.955
O1—C2—C3	115.88 (13)	C22—C23—C25	124.43 (16)
O1—C2—C9	119.39 (13)	C24—C23—C25	114.94 (15)
C3—C2—C9	124.59 (12)	C23—C24—H241	110.9
C2—C3—C4	121.69 (13)	C23—C24—H242	109.1
C2—C3—C8	118.39 (13)	H241—C24—H242	109.8
C4—C3—C8	119.53 (14)	C23—C24—H243	109.8
C3—C4—C5	119.68 (15)	H241—C24—H243	109.4
C3—C4—H41	120.4	H242—C24—H243	107.7
C5—C4—H41	119.9	C23—C25—H251	108.9
C4—C5—C6	120.70 (15)	C23—C25—H252	114.7
C4—C5—H51	119.3	H251—C25—H252	104.9
C6—C5—H51	120.0	C23—C25—H253	111.5
C5—C6—C7	119.63 (15)	H251—C25—H253	106.8
C5—C6—H61	118.2	H252—C25—H253	109.5
C7—C6—H61	122.1	C18—C26—H261	111.8
C6—C7—C8	120.00 (15)	C18—C26—H262	113.2
C6—C7—H71	121.4	H261—C26—H262	108.1
C8—C7—H71	118.6	C18—C26—H263	109.3
C3—C8—C7	120.41 (14)	H261—C26—H263	105.5
C3—C8—H81	119.0	H262—C26—H263	108.7
C7—C8—H81	120.6	C18—C27—H271	110.6
C2—C9—C10	117.48 (13)	C18—C27—H272	112.9
C2—C9—C16	122.67 (13)	H271—C27—H272	107.8
C10—C9—C16	119.24 (13)	C18—C27—H273	109.2
C9—C10—O11	121.85 (13)	H271—C27—H273	108.0
C9—C10—C12	123.08 (13)	H272—C27—H273	108.3
O11—C10—C12	115.06 (12)	C15—C28—C29	113.75 (11)
H1—O11—C10	102.2	C15—C28—H281	107.9
C10—C12—C13	109.07 (11)	C29—C28—H281	107.9
C10—C12—C20	107.79 (11)	C15—C28—H282	108.1
C13—C12—C20	106.27 (11)	C29—C28—H282	111.9
C10—C12—C33	111.80 (12)	H281—C28—H282	107.0
C13—C12—C33	111.78 (12)	C28—C29—C30	126.86 (14)
C20—C12—C33	109.91 (11)	C28—C29—H291	115.6
C12—C13—O14	122.17 (13)	C30—C29—H291	117.5
C12—C13—C15	114.12 (11)	C29—C30—C31	124.98 (14)
O14—C13—C15	123.50 (13)	C29—C30—C32	120.98 (14)
C13—C15—C16	110.76 (11)	C31—C30—C32	114.03 (13)
C13—C15—C18	105.69 (11)	C30—C31—H311	109.2
C16—C15—C18	109.03 (11)	C30—C31—H312	113.4
C13—C15—C28	110.33 (11)	H311—C31—H312	105.8
C16—C15—C28	107.93 (11)	C30—C31—H313	112.0
C18—C15—C28	113.10 (11)	H311—C31—H313	108.7
C15—C16—C9	118.54 (12)	H312—C31—H313	107.4
C15—C16—O17	119.21 (13)	C30—C32—H321	109.7
C9—C16—O17	122.20 (13)	C30—C32—H322	110.4
C15—C18—C19	108.57 (11)	H321—C32—H322	110.0
C15—C18—C26	108.64 (12)	C30—C32—H323	112.3
C19—C18—C26	111.01 (12)	H321—C32—H323	107.7
C15—C18—C27	110.89 (12)	H322—C32—H323	106.7
C19—C18—C27	109.04 (12)	C12—C33—C34	113.47 (12)
C26—C18—C27	108.70 (12)	C12—C33—H331	107.3
C18—C19—C20	112.70 (11)	C34—C33—H331	110.0
C18—C19—C21	113.66 (12)	C12—C33—H332	108.0
C20—C19—C21	108.97 (11)	C34—C33—H332	110.8
C18—C19—H191	108.0	H331—C33—H332	107.0
C20—C19—H191	107.4	C33—C34—C35	127.09 (14)
C21—C19—H191	105.7	C33—C34—H341	114.5
C19—C20—C12	113.78 (11)	C35—C34—H341	118.4
C19—C20—H201	108.9	C34—C35—C36	124.15 (14)
C12—C20—H201	107.5	C34—C35—C37	120.78 (14)
C19—C20—H202	110.5	C36—C35—C37	115.06 (14)
C12—C20—H202	107.7	C35—C36—H361	112.4
H201—C20—H202	108.2	C35—C36—H362	110.5
C19—C21—C22	112.63 (12)	H361—C36—H362	104.3
C19—C21—H211	108.9	C35—C36—H363	113.8
C22—C21—H211	108.4	H361—C36—H363	108.0
C19—C21—H212	108.7	H362—C36—H363	107.3
C22—C21—H212	110.3	C35—C37—H371	112.1
H211—C21—H212	107.8	C35—C37—H372	113.5
C21—C22—C23	127.39 (15)	H371—C37—H372	106.9
C21—C22—H221	116.5	C35—C37—H373	110.7
C23—C22—H221	116.1	H371—C37—H373	105.5
C22—C23—C24	120.62 (16)	H372—C37—H373	107.6

D—H···A	D—H	H···A	D···A	D—H···A
O11—H1···O1	0.98	1.48	2.4227 (14)	158
C27—H273···O1i	0.99	2.63	3.330 (2)	128
C36—H363···O1ii	0.94	2.67	3.523 (2)	151
C8—H81···O11iii	0.95	2.62	3.300 (2)	129
C21—H211···O17iv	0.96	2.70	3.610 (2)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H1⋯O1	0.98	1.48	2.4227 (14)	158
C27—H273⋯O1i	0.99	2.63	3.330 (2)	128
C36—H363⋯O1ii	0.94	2.67	3.523 (2)	151
C8—H81⋯O11iii	0.95	2.62	3.300 (2)	129
C21—H211⋯O17iv	0.96	2.70	3.610 (2)	158

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