Dimethyl 3,3'-(phenyl-methyl-ene)bis-(1H-indole-2-carboxyl-ate).

In the title compound, C27H22N2O4, the two indole ring systems are approximately perpendicular to each other, with a dihedral angle of 84.5 (5)° between their planes; the benzene ring is twisted with respect to the two indole ring systems at angles of 78.5 (5) and 86.5 (3)°. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, weak C-H⋯O and C-H⋯N hydrogen bonds, and C-H⋯π inter-actions into a three-dimensional supra-molecular architecture.

Related literature

For applications of indole derivatives, see: Poter et al. (1977 ▶); Sundberg (1996 ▶); Chang et al. (1999 ▶); Ge et al. (1999 ▶); Ni (2008 ▶); Sun et al. (2012 ▶).

Experimental

Crystal data

C27H22N2O4

M = 438.47

Monoclinic,

a = 13.604 (3) Å

b = 15.560 (3) Å

c = 11.274 (2) Å

β = 112.66 (3)°

V = 2202.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonis CAD-4 diffractometer

4196 measured reflections

4021 independent reflections

2322 reflections with I > 2σ(I)

R int = 0.028

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.181

S = 1.00

4021 reflections

298 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024471/xu5723sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024471/xu5723Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813024471/xu5723Isup3.cml

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

C27H22N2O4	F(000) = 920
Mr = 438.47	Dx = 1.322 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 13.604 (3) Å	θ = 9–13°
b = 15.560 (3) Å	µ = 0.09 mm−1
c = 11.274 (2) Å	T = 293 K
β = 112.66 (3)°	Block, colorless
V = 2202.2 (8) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Enraf–Nonis CAD-4 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 25.4°, θmin = 1.6°
Graphite monochromator	h = −16→0
ω/2θ scans	k = 0→18
4196 measured reflections	l = −12→13
4021 independent reflections	3 standard reflections every 200 reflections
2322 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.181	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.088P)2] where P = (Fo2 + 2Fc2)/3
4021 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.22 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
O1	0.52156 (18)	−0.10234 (15)	0.9162 (2)	0.0504 (7)
N1	0.3221 (2)	−0.07271 (18)	0.8973 (3)	0.0470 (8)
H1A	0.3563	−0.1099	0.9548	0.056*
C1	0.3029 (2)	0.08122 (19)	0.6386 (3)	0.0351 (7)
H1B	0.3709	0.1108	0.6826	0.042*
O2	0.52350 (18)	0.01567 (15)	0.8016 (2)	0.0478 (6)
N2	0.3660 (2)	−0.00463 (17)	0.3694 (3)	0.0422 (7)
H2A	0.3961	−0.0012	0.3150	0.051*
C2	0.2866 (3)	0.0248 (2)	0.7391 (3)	0.0371 (8)
O3	0.4526 (2)	0.18689 (16)	0.5589 (3)	0.0593 (7)
C3	0.1909 (3)	0.0105 (2)	0.7638 (3)	0.0377 (8)
O4	0.46982 (19)	0.14311 (15)	0.3787 (2)	0.0502 (6)
C4	0.0870 (3)	0.0436 (2)	0.7147 (3)	0.0456 (9)
H4A	0.0657	0.0822	0.6464	0.055*
C5	0.0171 (3)	0.0181 (2)	0.7694 (4)	0.0539 (10)
H5A	−0.0517	0.0403	0.7376	0.065*
C6	0.0467 (3)	−0.0403 (2)	0.8713 (4)	0.0545 (10)
H6A	−0.0024	−0.0558	0.9064	0.065*
C7	0.1462 (3)	−0.0749 (2)	0.9201 (4)	0.0533 (10)
H7A	0.1659	−0.1139	0.9878	0.064*
C8	0.2178 (3)	−0.0499 (2)	0.8649 (3)	0.0411 (8)
C9	0.3638 (3)	−0.0263 (2)	0.8228 (3)	0.0397 (8)
C10	0.4765 (3)	−0.0341 (2)	0.8434 (3)	0.0417 (8)
C11	0.6316 (3)	−0.1198 (2)	0.9398 (4)	0.0545 (10)
H11A	0.6544	−0.1702	0.9924	0.082*
H11B	0.6746	−0.0717	0.9832	0.082*
H11C	0.6390	−0.1290	0.8595	0.082*
C12	0.3159 (2)	0.02960 (19)	0.5322 (3)	0.0346 (7)
C13	0.2685 (2)	−0.0511 (2)	0.4786 (3)	0.0373 (8)
C14	0.1994 (3)	−0.1099 (2)	0.5024 (3)	0.0462 (9)
H14A	0.1743	−0.0993	0.5669	0.055*
C15	0.1699 (3)	−0.1824 (2)	0.4296 (4)	0.0556 (10)
H15A	0.1243	−0.2211	0.4454	0.067*
C16	0.2062 (3)	−0.2005 (2)	0.3313 (4)	0.0570 (10)
H16A	0.1843	−0.2506	0.2833	0.068*
C17	0.2733 (3)	−0.1452 (2)	0.3054 (3)	0.0485 (9)
H17A	0.2985	−0.1573	0.2413	0.058*
C18	0.3028 (2)	−0.0704 (2)	0.3775 (3)	0.0402 (8)
C19	0.3741 (2)	0.0555 (2)	0.4624 (3)	0.0360 (7)
C20	0.4351 (3)	0.1350 (2)	0.4750 (3)	0.0394 (8)
C21	0.5280 (3)	0.2203 (3)	0.3776 (4)	0.0608 (11)
H21A	0.5483	0.2193	0.3050	0.091*
H21B	0.5907	0.2235	0.4553	0.091*
H21C	0.4838	0.2695	0.3718	0.091*
C22	0.2189 (3)	0.1521 (2)	0.5862 (3)	0.0380 (8)
C23	0.1452 (3)	0.1525 (3)	0.4629 (4)	0.0649 (12)
H23A	0.1441	0.1072	0.4087	0.078*
C24	0.0724 (4)	0.2182 (3)	0.4161 (4)	0.0899 (17)
H24A	0.0223	0.2164	0.3321	0.108*
C25	0.0744 (4)	0.2856 (3)	0.4939 (5)	0.0797 (14)
H25A	0.0268	0.3309	0.4626	0.096*
C26	0.1465 (4)	0.2865 (3)	0.6181 (5)	0.0688 (12)
H26A	0.1469	0.3319	0.6719	0.083*
C27	0.2187 (3)	0.2202 (2)	0.6638 (4)	0.0493 (9)
H27A	0.2679	0.2216	0.7484	0.059*

	U11	U22	U33	U12	U13	U23
O1	0.0438 (14)	0.0483 (15)	0.0580 (15)	0.0155 (12)	0.0183 (12)	0.0135 (12)
N1	0.0547 (19)	0.0451 (18)	0.0455 (17)	0.0053 (14)	0.0240 (15)	0.0124 (14)
C1	0.0370 (17)	0.0347 (18)	0.0341 (17)	0.0010 (14)	0.0144 (14)	−0.0007 (14)
O2	0.0478 (14)	0.0516 (15)	0.0512 (14)	0.0058 (12)	0.0270 (12)	0.0081 (12)
N2	0.0465 (16)	0.0447 (17)	0.0440 (16)	−0.0025 (14)	0.0270 (14)	−0.0041 (14)
C2	0.0411 (19)	0.0375 (18)	0.0357 (17)	0.0040 (15)	0.0180 (15)	−0.0005 (15)
O3	0.082 (2)	0.0447 (15)	0.0680 (17)	−0.0167 (14)	0.0468 (16)	−0.0162 (14)
C3	0.0401 (19)	0.0353 (18)	0.0395 (18)	−0.0035 (15)	0.0174 (15)	−0.0030 (15)
O4	0.0603 (16)	0.0501 (15)	0.0481 (14)	−0.0144 (12)	0.0296 (12)	−0.0017 (12)
C4	0.042 (2)	0.049 (2)	0.046 (2)	−0.0019 (17)	0.0178 (17)	0.0003 (17)
C5	0.042 (2)	0.059 (2)	0.065 (2)	−0.0045 (18)	0.0251 (19)	−0.001 (2)
C6	0.057 (2)	0.054 (2)	0.063 (2)	−0.014 (2)	0.036 (2)	−0.006 (2)
C7	0.066 (3)	0.045 (2)	0.058 (2)	−0.007 (2)	0.034 (2)	0.0022 (19)
C8	0.045 (2)	0.0383 (19)	0.0454 (19)	−0.0016 (16)	0.0233 (16)	−0.0006 (16)
C9	0.046 (2)	0.0394 (19)	0.0384 (18)	0.0004 (16)	0.0211 (16)	0.0003 (15)
C10	0.051 (2)	0.041 (2)	0.0364 (18)	0.0078 (17)	0.0204 (17)	−0.0025 (16)
C11	0.047 (2)	0.054 (2)	0.058 (2)	0.0163 (18)	0.0154 (19)	0.0062 (19)
C12	0.0355 (17)	0.0329 (17)	0.0352 (17)	0.0026 (14)	0.0135 (14)	0.0023 (14)
C13	0.0368 (18)	0.0350 (18)	0.0411 (18)	0.0036 (15)	0.0161 (15)	−0.0015 (15)
C14	0.048 (2)	0.043 (2)	0.051 (2)	−0.0051 (17)	0.0229 (18)	0.0006 (17)
C15	0.050 (2)	0.047 (2)	0.072 (3)	−0.0076 (18)	0.025 (2)	−0.005 (2)
C16	0.057 (2)	0.043 (2)	0.064 (3)	−0.0056 (19)	0.015 (2)	−0.0113 (19)
C17	0.051 (2)	0.048 (2)	0.047 (2)	0.0008 (18)	0.0193 (18)	−0.0101 (18)
C18	0.0360 (18)	0.0386 (19)	0.0448 (19)	0.0019 (15)	0.0140 (15)	−0.0013 (16)
C19	0.0399 (18)	0.0335 (18)	0.0370 (17)	0.0037 (15)	0.0174 (15)	0.0006 (15)
C20	0.0399 (19)	0.039 (2)	0.043 (2)	0.0038 (15)	0.0203 (16)	0.0043 (17)
C21	0.067 (3)	0.057 (2)	0.064 (3)	−0.016 (2)	0.032 (2)	0.005 (2)
C22	0.0425 (19)	0.0363 (18)	0.0433 (19)	0.0023 (15)	0.0256 (16)	0.0028 (15)
C23	0.070 (3)	0.078 (3)	0.042 (2)	0.033 (2)	0.016 (2)	−0.003 (2)
C24	0.100 (4)	0.116 (4)	0.047 (3)	0.064 (3)	0.021 (2)	0.011 (3)
C25	0.100 (4)	0.073 (3)	0.079 (3)	0.048 (3)	0.049 (3)	0.028 (3)
C26	0.087 (3)	0.049 (3)	0.084 (3)	0.018 (2)	0.049 (3)	−0.002 (2)
C27	0.054 (2)	0.043 (2)	0.051 (2)	0.0056 (18)	0.0204 (18)	−0.0040 (18)

O1—C10	1.338 (4)	C11—H11B	0.9600
O1—C11	1.442 (4)	C11—H11C	0.9600
N1—C8	1.369 (4)	C12—C19	1.375 (4)
N1—C9	1.385 (4)	C12—C13	1.435 (4)
N1—H1A	0.8600	C13—C14	1.410 (4)
C1—C12	1.510 (4)	C13—C18	1.420 (4)
C1—C2	1.516 (4)	C14—C15	1.361 (5)
C1—C22	1.532 (4)	C14—H14A	0.9300
C1—H1B	0.9800	C15—C16	1.405 (5)
O2—C10	1.210 (4)	C15—H15A	0.9300
N2—C18	1.363 (4)	C16—C17	1.366 (5)
N2—C19	1.378 (4)	C16—H16A	0.9300
N2—H2A	0.8600	C17—C18	1.387 (5)
C2—C9	1.364 (4)	C17—H17A	0.9300
C2—C3	1.450 (4)	C19—C20	1.465 (5)
O3—C20	1.196 (4)	C21—H21A	0.9600
C3—C4	1.402 (4)	C21—H21B	0.9600
C3—C8	1.412 (4)	C21—H21C	0.9600
O4—C20	1.346 (4)	C22—C23	1.365 (5)
O4—C21	1.441 (4)	C22—C27	1.376 (5)
C4—C5	1.376 (5)	C23—C24	1.378 (5)
C4—H4A	0.9300	C23—H23A	0.9300
C5—C6	1.398 (5)	C24—C25	1.361 (6)
C5—H5A	0.9300	C24—H24A	0.9300
C6—C7	1.360 (5)	C25—C26	1.365 (6)
C6—H6A	0.9300	C25—H25A	0.9300
C7—C8	1.398 (5)	C26—C27	1.381 (5)
C7—H7A	0.9300	C26—H26A	0.9300
C9—C10	1.465 (5)	C27—H27A	0.9300
C11—H11A	0.9600
C10—O1—C11	117.4 (3)	C13—C12—C1	129.0 (3)
C8—N1—C9	109.1 (3)	C14—C13—C18	117.7 (3)
C8—N1—H1A	125.5	C14—C13—C12	135.4 (3)
C9—N1—H1A	125.5	C18—C13—C12	106.9 (3)
C12—C1—C2	112.4 (2)	C15—C14—C13	119.1 (3)
C12—C1—C22	111.9 (3)	C15—C14—H14A	120.4
C2—C1—C22	113.8 (3)	C13—C14—H14A	120.4
C12—C1—H1B	106.0	C14—C15—C16	122.0 (3)
C2—C1—H1B	106.0	C14—C15—H15A	119.0
C22—C1—H1B	106.0	C16—C15—H15A	119.0
C18—N2—C19	109.1 (3)	C17—C16—C15	120.7 (3)
C18—N2—H2A	125.4	C17—C16—H16A	119.7
C19—N2—H2A	125.4	C15—C16—H16A	119.7
C9—C2—C3	106.7 (3)	C16—C17—C18	118.0 (3)
C9—C2—C1	124.0 (3)	C16—C17—H17A	121.0
C3—C2—C1	129.3 (3)	C18—C17—H17A	121.0
C4—C3—C8	118.1 (3)	N2—C18—C17	129.7 (3)
C4—C3—C2	135.4 (3)	N2—C18—C13	107.8 (3)
C8—C3—C2	106.5 (3)	C17—C18—C13	122.5 (3)
C20—O4—C21	116.7 (3)	C12—C19—N2	110.0 (3)
C5—C4—C3	118.9 (3)	C12—C19—C20	128.5 (3)
C5—C4—H4A	120.6	N2—C19—C20	121.5 (3)
C3—C4—H4A	120.6	O3—C20—O4	123.3 (3)
C4—C5—C6	121.8 (4)	O3—C20—C19	125.4 (3)
C4—C5—H5A	119.1	O4—C20—C19	111.3 (3)
C6—C5—H5A	119.1	O4—C21—H21A	109.5
C7—C6—C5	121.1 (3)	O4—C21—H21B	109.5
C7—C6—H6A	119.5	H21A—C21—H21B	109.5
C5—C6—H6A	119.5	O4—C21—H21C	109.5
C6—C7—C8	117.8 (3)	H21A—C21—H21C	109.5
C6—C7—H7A	121.1	H21B—C21—H21C	109.5
C8—C7—H7A	121.1	C23—C22—C27	117.6 (3)
N1—C8—C7	129.6 (3)	C23—C22—C1	122.9 (3)
N1—C8—C3	107.9 (3)	C27—C22—C1	119.5 (3)
C7—C8—C3	122.4 (3)	C22—C23—C24	122.1 (4)
C2—C9—N1	109.7 (3)	C22—C23—H23A	118.9
C2—C9—C10	129.7 (3)	C24—C23—H23A	118.9
N1—C9—C10	120.6 (3)	C25—C24—C23	119.5 (4)
O2—C10—O1	124.1 (3)	C25—C24—H24A	120.3
O2—C10—C9	124.3 (3)	C23—C24—H24A	120.3
O1—C10—C9	111.6 (3)	C24—C25—C26	119.8 (4)
O1—C11—H11A	109.5	C24—C25—H25A	120.1
O1—C11—H11B	109.5	C26—C25—H25A	120.1
H11A—C11—H11B	109.5	C25—C26—C27	120.1 (4)
O1—C11—H11C	109.5	C25—C26—H26A	119.9
H11A—C11—H11C	109.5	C27—C26—H26A	119.9
H11B—C11—H11C	109.5	C22—C27—C26	120.9 (4)
C19—C12—C13	106.3 (3)	C22—C27—H27A	119.5
C19—C12—C1	124.6 (3)	C26—C27—H27A	119.5
C12—C1—C2—C9	69.5 (4)	C19—C12—C13—C18	0.7 (3)
C22—C1—C2—C9	−161.9 (3)	C1—C12—C13—C18	177.6 (3)
C12—C1—C2—C3	−107.8 (4)	C18—C13—C14—C15	0.9 (5)
C22—C1—C2—C3	20.8 (5)	C12—C13—C14—C15	179.8 (3)
C9—C2—C3—C4	178.2 (4)	C13—C14—C15—C16	0.0 (5)
C1—C2—C3—C4	−4.2 (6)	C14—C15—C16—C17	0.1 (6)
C9—C2—C3—C8	0.4 (4)	C15—C16—C17—C18	−1.0 (5)
C1—C2—C3—C8	178.1 (3)	C19—N2—C18—C17	−179.1 (3)
C8—C3—C4—C5	2.0 (5)	C19—N2—C18—C13	0.5 (4)
C2—C3—C4—C5	−175.6 (3)	C16—C17—C18—N2	−178.5 (3)
C3—C4—C5—C6	−0.6 (5)	C16—C17—C18—C13	2.0 (5)
C4—C5—C6—C7	−0.5 (6)	C14—C13—C18—N2	178.5 (3)
C5—C6—C7—C8	0.2 (6)	C12—C13—C18—N2	−0.7 (3)
C9—N1—C8—C7	−175.0 (3)	C14—C13—C18—C17	−1.9 (5)
C9—N1—C8—C3	2.1 (4)	C12—C13—C18—C17	178.9 (3)
C6—C7—C8—N1	178.0 (3)	C13—C12—C19—N2	−0.4 (4)
C6—C7—C8—C3	1.3 (5)	C1—C12—C19—N2	−177.5 (3)
C4—C3—C8—N1	−179.8 (3)	C13—C12—C19—C20	177.8 (3)
C2—C3—C8—N1	−1.5 (4)	C1—C12—C19—C20	0.6 (5)
C4—C3—C8—C7	−2.4 (5)	C18—N2—C19—C12	−0.1 (4)
C2—C3—C8—C7	175.8 (3)	C18—N2—C19—C20	−178.4 (3)
C3—C2—C9—N1	0.8 (4)	C21—O4—C20—O3	−1.9 (5)
C1—C2—C9—N1	−177.0 (3)	C21—O4—C20—C19	178.0 (3)
C3—C2—C9—C10	−176.8 (3)	C12—C19—C20—O3	8.2 (6)
C1—C2—C9—C10	5.4 (5)	N2—C19—C20—O3	−173.9 (3)
C8—N1—C9—C2	−1.8 (4)	C12—C19—C20—O4	−171.7 (3)
C8—N1—C9—C10	176.0 (3)	N2—C19—C20—O4	6.3 (4)
C11—O1—C10—O2	−3.5 (5)	C12—C1—C22—C23	17.2 (5)
C11—O1—C10—C9	177.5 (3)	C2—C1—C22—C23	−111.7 (4)
C2—C9—C10—O2	12.8 (6)	C12—C1—C22—C27	−160.6 (3)
N1—C9—C10—O2	−164.6 (3)	C2—C1—C22—C27	70.6 (4)
C2—C9—C10—O1	−168.2 (3)	C27—C22—C23—C24	−0.1 (6)
N1—C9—C10—O1	14.4 (4)	C1—C22—C23—C24	−177.9 (4)
C2—C1—C12—C19	−150.7 (3)	C22—C23—C24—C25	1.0 (8)
C22—C1—C12—C19	79.7 (4)	C23—C24—C25—C26	−1.7 (8)
C2—C1—C12—C13	32.8 (4)	C24—C25—C26—C27	1.4 (7)
C22—C1—C12—C13	−96.8 (4)	C23—C22—C27—C26	−0.1 (5)
C19—C12—C13—C14	−178.3 (4)	C1—C22—C27—C26	177.8 (3)
C1—C12—C13—C14	−1.3 (6)	C25—C26—C27—C22	−0.5 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2i	0.86	2.02	2.870 (4)	169
C11—H11A···O3ii	0.96	2.60	3.221 (4)	123
C11—H11B···N1iii	0.96	2.61	3.443 (5)	145
C11—H11C···O4i	0.96	2.53	3.333 (5)	142
C5—H5A···Cg4iv	0.93	2.76	3.659 (4)	164
C11—H11B···Cg1iii	0.96	2.55	3.366 (4)	143
C21—H21B···Cg4i	0.96	2.73	3.516 (5)	139

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg4 are the centroids of the N1-pyrrole and C15-benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2i	0.86	2.02	2.870 (4)	169
C11—H11A⋯O3ii	0.96	2.60	3.221 (4)	123
C11—H11B⋯N1iii	0.96	2.61	3.443 (5)	145
C11—H11C⋯O4i	0.96	2.53	3.333 (5)	142
C5—H5A⋯Cg4iv	0.93	2.76	3.659 (4)	164
C11—H11B⋯Cg1iii	0.96	2.55	3.366 (4)	143
C21—H21B⋯Cg4i	0.96	2.73	3.516 (5)	139

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