Bis[(3-chloro-benz-yl)ammonium] 2-phenyl-propane-dioate dihydrate.

In the asymmetric unit of the title compound, 2C(7)H(9)ClN(+)·C(9)H(6)O(4) (2-)·2H(2)O, there are two crystallographically independent cations, one dianion and two water mol-ecules. The dihedral angle between the two carboxyl-ate groups of the dianion is 78.1 (2)°. In the crystal, the components are held together by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, forming a layer parallel to the bc plane, with the hydro-philic and hydro-phobic groups located in the inner and outer regions of the layers, respectively.

Related literature

For related structures, see: Ueda et al. (2005 ▶); Gotoh & Ishida (2009 ▶).

Experimental

Crystal data

2C7H9ClN+·C9H6O4 2−·2H2O

M = 499.39

Monoclinic,

a = 17.3487 (7) Å

b = 9.7903 (5) Å

c = 14.3496 (6) Å

β = 103.3832 (12)°

V = 2371.07 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 93 K

0.36 × 0.25 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID-II diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.809, T max = 0.969

22684 measured reflections

5404 independent reflections

4801 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.03

5404 reflections

312 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.28 e Å−3

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810029764/zl2291sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029764/zl2291Isup2.hkl

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

2C7H9ClN+·C9H6O42−·2H2O	F(000) = 1048.00
Mr = 499.39	Dx = 1.399 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 19587 reflections
a = 17.3487 (7) Å	θ = 3.2–27.5°
b = 9.7903 (5) Å	µ = 0.32 mm−1
c = 14.3496 (6) Å	T = 93 K
β = 103.3832 (12)°	Block, colorless
V = 2371.07 (17) Å3	0.36 × 0.25 × 0.10 mm
Z = 4

Rigaku R-AXIS RAPID-II diffractometer	4801 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −22→22
Tmin = 0.809, Tmax = 0.969	k = −12→12
22684 measured reflections	l = −17→18
5404 independent reflections

Refinement on F2	312 parameters
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.030	w = 1/[σ2(Fo2) + (0.045P)2 + 0.8144P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.080	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.35 e Å−3
5404 reflections	Δρmin = −0.28 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
Cl1	0.439729 (18)	0.35812 (3)	0.16174 (2)	0.02351 (8)
Cl2	0.456436 (18)	0.67256 (3)	0.58413 (2)	0.02689 (9)
O1	0.01868 (5)	0.88588 (8)	0.27920 (6)	0.01579 (17)
O2	0.12915 (5)	0.76812 (8)	0.33753 (6)	0.01682 (17)
O3	0.10538 (5)	1.13611 (8)	0.50629 (6)	0.01916 (18)
O4	0.11331 (5)	0.90909 (8)	0.52121 (6)	0.01844 (18)
O5	−0.03654 (5)	0.85786 (9)	0.08701 (6)	0.01747 (17)
H5A	−0.0194 (10)	0.8553 (16)	0.1434 (13)	0.021*
H5B	−0.0583 (9)	0.7825 (18)	0.0693 (11)	0.021*
O6	−0.06079 (6)	0.68283 (9)	0.36504 (7)	0.02034 (18)
H6A	−0.0353 (10)	0.7262 (17)	0.3327 (12)	0.024*
H6B	−0.0720 (9)	0.7440 (17)	0.4024 (12)	0.024*
N1	0.10896 (6)	0.55243 (10)	0.20825 (7)	0.01391 (19)
H1A	0.1134	0.6328	0.2409	0.021*
H1B	0.0613	0.5135	0.2079	0.021*
H1C	0.1126	0.5684	0.1469	0.021*
N2	0.09606 (6)	0.61282 (10)	0.50244 (7)	0.0162 (2)
H2A	0.1111	0.6780	0.4650	0.024*
H2B	0.0510	0.6400	0.5193	0.024*
H2C	0.0869	0.5329	0.4693	0.024*
C1	0.09030 (7)	0.87682 (11)	0.32604 (7)	0.0126 (2)
C2	0.12851 (6)	1.00848 (11)	0.37329 (8)	0.0127 (2)
H2	0.1016	1.0877	0.3352	0.015*
C3	0.11362 (6)	1.01818 (11)	0.47553 (8)	0.0136 (2)
C4	0.21663 (7)	1.01807 (11)	0.37713 (8)	0.0138 (2)
C5	0.24195 (7)	1.08640 (12)	0.30411 (8)	0.0173 (2)
H5	0.2040	1.1274	0.2534	0.021*
C6	0.32227 (8)	1.09505 (13)	0.30482 (10)	0.0225 (3)
H6	0.3387	1.1402	0.2541	0.027*
C7	0.37820 (7)	1.03784 (13)	0.37942 (10)	0.0238 (3)
H7	0.4330	1.0452	0.3806	0.029*
C8	0.35360 (7)	0.96960 (13)	0.45254 (9)	0.0227 (3)
H8	0.3918	0.9301	0.5037	0.027*
C9	0.27344 (7)	0.95889 (12)	0.45108 (9)	0.0188 (2)
H9	0.2572	0.9109	0.5008	0.023*
C10	0.25586 (7)	0.50774 (12)	0.25364 (8)	0.0152 (2)
C11	0.30228 (7)	0.42829 (12)	0.20729 (8)	0.0170 (2)
H11	0.2804	0.3502	0.1715	0.020*
C12	0.38073 (7)	0.46418 (12)	0.21377 (8)	0.0171 (2)
C13	0.41351 (7)	0.58019 (12)	0.26201 (9)	0.0195 (2)
H13	0.4672	0.6038	0.2655	0.023*
C14	0.36614 (7)	0.66165 (13)	0.30541 (9)	0.0215 (3)
H14	0.3874	0.7430	0.3374	0.026*
C15	0.28821 (7)	0.62547 (12)	0.30251 (9)	0.0188 (2)
H15	0.2569	0.6808	0.3338	0.023*
C16	0.17387 (7)	0.45831 (12)	0.25573 (9)	0.0175 (2)
H16A	0.1651	0.3681	0.2238	0.021*
H16B	0.1710	0.4456	0.3233	0.021*
C17	0.23541 (7)	0.54046 (12)	0.56655 (8)	0.0163 (2)
C18	0.30291 (7)	0.62186 (12)	0.58334 (8)	0.0175 (2)
H18	0.3022	0.7109	0.6094	0.021*
C19	0.37141 (7)	0.57119 (13)	0.56150 (9)	0.0197 (2)
C20	0.37432 (8)	0.44271 (13)	0.52259 (9)	0.0227 (3)
H20	0.4216	0.4105	0.5074	0.027*
C21	0.30677 (8)	0.36155 (13)	0.50613 (9)	0.0227 (3)
H21	0.3077	0.2730	0.4794	0.027*
C22	0.23794 (7)	0.40932 (12)	0.52858 (9)	0.0191 (2)
H22	0.1923	0.3527	0.5181	0.023*
C23	0.16042 (7)	0.59252 (12)	0.59052 (8)	0.0176 (2)
H23A	0.1425	0.5264	0.6332	0.021*
H23B	0.1715	0.6803	0.6253	0.021*

	U11	U22	U33	U12	U13	U23
Cl1	0.01977 (15)	0.02374 (15)	0.02822 (16)	0.00445 (11)	0.00803 (12)	−0.00380 (12)
Cl2	0.01780 (15)	0.02676 (17)	0.03560 (18)	−0.00173 (11)	0.00518 (13)	0.00059 (13)
O1	0.0139 (4)	0.0185 (4)	0.0145 (4)	0.0003 (3)	0.0021 (3)	−0.0018 (3)
O2	0.0175 (4)	0.0127 (4)	0.0199 (4)	0.0010 (3)	0.0035 (3)	−0.0034 (3)
O3	0.0283 (5)	0.0130 (4)	0.0172 (4)	0.0028 (3)	0.0073 (4)	−0.0026 (3)
O4	0.0290 (5)	0.0124 (4)	0.0146 (4)	−0.0008 (3)	0.0065 (3)	0.0003 (3)
O5	0.0221 (4)	0.0164 (4)	0.0127 (4)	−0.0040 (3)	0.0017 (3)	−0.0005 (3)
O6	0.0251 (5)	0.0176 (4)	0.0199 (4)	−0.0012 (3)	0.0084 (4)	−0.0022 (3)
N1	0.0148 (4)	0.0134 (4)	0.0135 (4)	−0.0012 (4)	0.0031 (4)	−0.0012 (3)
N2	0.0158 (5)	0.0133 (5)	0.0197 (5)	0.0012 (4)	0.0043 (4)	0.0015 (4)
C1	0.0146 (5)	0.0151 (5)	0.0088 (5)	−0.0007 (4)	0.0044 (4)	−0.0011 (4)
C2	0.0157 (5)	0.0101 (5)	0.0119 (5)	0.0011 (4)	0.0027 (4)	0.0003 (4)
C3	0.0136 (5)	0.0139 (5)	0.0129 (5)	−0.0004 (4)	0.0020 (4)	−0.0017 (4)
C4	0.0162 (5)	0.0100 (5)	0.0149 (5)	−0.0005 (4)	0.0028 (4)	−0.0031 (4)
C5	0.0200 (6)	0.0140 (5)	0.0180 (5)	−0.0005 (4)	0.0045 (5)	−0.0008 (4)
C6	0.0238 (6)	0.0185 (6)	0.0286 (6)	−0.0024 (5)	0.0127 (5)	−0.0013 (5)
C7	0.0167 (6)	0.0196 (6)	0.0356 (7)	−0.0015 (5)	0.0074 (5)	−0.0074 (5)
C8	0.0193 (6)	0.0204 (6)	0.0252 (6)	0.0036 (5)	−0.0016 (5)	−0.0021 (5)
C9	0.0204 (6)	0.0176 (6)	0.0174 (5)	0.0006 (4)	0.0022 (5)	0.0005 (4)
C10	0.0147 (5)	0.0146 (5)	0.0153 (5)	0.0004 (4)	0.0012 (4)	0.0030 (4)
C11	0.0182 (5)	0.0143 (5)	0.0177 (5)	−0.0007 (4)	0.0022 (5)	−0.0003 (4)
C12	0.0172 (5)	0.0162 (5)	0.0177 (5)	0.0036 (4)	0.0038 (4)	0.0015 (4)
C13	0.0140 (5)	0.0191 (6)	0.0247 (6)	−0.0015 (4)	0.0028 (5)	0.0010 (5)
C14	0.0200 (6)	0.0166 (6)	0.0265 (6)	−0.0024 (4)	0.0027 (5)	−0.0042 (5)
C15	0.0179 (6)	0.0178 (6)	0.0208 (6)	0.0010 (4)	0.0046 (5)	−0.0022 (4)
C16	0.0159 (5)	0.0152 (5)	0.0210 (6)	−0.0002 (4)	0.0036 (5)	0.0039 (4)
C17	0.0181 (5)	0.0166 (5)	0.0134 (5)	0.0041 (4)	0.0023 (4)	0.0027 (4)
C18	0.0197 (6)	0.0154 (5)	0.0168 (5)	0.0024 (4)	0.0028 (5)	0.0009 (4)
C19	0.0174 (5)	0.0212 (6)	0.0192 (6)	0.0007 (5)	0.0014 (5)	0.0040 (5)
C20	0.0201 (6)	0.0243 (6)	0.0237 (6)	0.0072 (5)	0.0053 (5)	0.0009 (5)
C21	0.0262 (6)	0.0172 (6)	0.0231 (6)	0.0052 (5)	0.0025 (5)	−0.0024 (5)
C22	0.0194 (6)	0.0165 (5)	0.0196 (6)	0.0007 (4)	0.0007 (5)	0.0003 (4)
C23	0.0182 (5)	0.0175 (5)	0.0165 (5)	0.0018 (4)	0.0031 (5)	−0.0006 (4)

Cl1—C12	1.7427 (12)	C8—C9	1.3899 (17)
Cl2—C19	1.7448 (13)	C8—H8	0.9500
O1—C1	1.2714 (14)	C9—H9	0.9500
O2—C1	1.2501 (14)	C10—C11	1.3941 (16)
O3—C3	1.2559 (14)	C10—C15	1.3975 (16)
O4—C3	1.2538 (14)	C10—C16	1.5095 (16)
O5—H5A	0.795 (18)	C11—C12	1.3878 (16)
O5—H5B	0.840 (18)	C11—H11	0.9500
O6—H6A	0.828 (18)	C12—C13	1.3822 (17)
O6—H6B	0.855 (17)	C13—C14	1.3914 (18)
N1—C16	1.4921 (14)	C13—H13	0.9500
N1—H1A	0.9100	C14—C15	1.3888 (17)
N1—H1B	0.9100	C14—H14	0.9500
N1—H1C	0.9100	C15—H15	0.9500
N2—C23	1.4935 (15)	C16—H16A	0.9900
N2—H2A	0.9100	C16—H16B	0.9900
N2—H2B	0.9100	C17—C18	1.3906 (17)
N2—H2C	0.9100	C17—C22	1.3994 (16)
C1—C2	1.5338 (15)	C17—C23	1.5092 (16)
C2—C4	1.5199 (15)	C18—C19	1.3889 (17)
C2—C3	1.5503 (15)	C18—H18	0.9500
C2—H2	1.0000	C19—C20	1.3818 (18)
C4—C9	1.3960 (16)	C20—C21	1.3901 (19)
C4—C5	1.3969 (16)	C20—H20	0.9500
C5—C6	1.3937 (17)	C21—C22	1.3880 (18)
C5—H5	0.9500	C21—H21	0.9500
C6—C7	1.3858 (19)	C22—H22	0.9500
C6—H6	0.9500	C23—H23A	0.9900
C7—C8	1.3916 (19)	C23—H23B	0.9900
C7—H7	0.9500
H5A—O5—H5B	108.4 (15)	C15—C10—C16	121.68 (11)
H6A—O6—H6B	102.7 (15)	C12—C11—C10	119.51 (11)
C16—N1—H1A	109.5	C12—C11—H11	120.2
C16—N1—H1B	109.5	C10—C11—H11	120.2
H1A—N1—H1B	109.5	C13—C12—C11	121.67 (11)
C16—N1—H1C	109.5	C13—C12—Cl1	119.33 (9)
H1A—N1—H1C	109.5	C11—C12—Cl1	118.99 (9)
H1B—N1—H1C	109.5	C12—C13—C14	118.56 (11)
C23—N2—H2A	109.5	C12—C13—H13	120.7
C23—N2—H2B	109.5	C14—C13—H13	120.7
H2A—N2—H2B	109.5	C15—C14—C13	120.81 (11)
C23—N2—H2C	109.5	C15—C14—H14	119.6
H2A—N2—H2C	109.5	C13—C14—H14	119.6
H2B—N2—H2C	109.5	C14—C15—C10	120.02 (11)
O2—C1—O1	124.07 (10)	C14—C15—H15	120.0
O2—C1—C2	119.50 (10)	C10—C15—H15	120.0
O1—C1—C2	116.40 (9)	N1—C16—C10	114.08 (9)
C4—C2—C1	113.34 (9)	N1—C16—H16A	108.7
C4—C2—C3	110.39 (9)	C10—C16—H16A	108.7
C1—C2—C3	108.67 (9)	N1—C16—H16B	108.7
C4—C2—H2	108.1	C10—C16—H16B	108.7
C1—C2—H2	108.1	H16A—C16—H16B	107.6
C3—C2—H2	108.1	C18—C17—C22	119.48 (11)
O4—C3—O3	125.78 (10)	C18—C17—C23	120.18 (11)
O4—C3—C2	117.67 (9)	C22—C17—C23	120.33 (11)
O3—C3—C2	116.51 (10)	C19—C18—C17	119.10 (11)
C9—C4—C5	118.66 (11)	C19—C18—H18	120.4
C9—C4—C2	121.95 (10)	C17—C18—H18	120.4
C5—C4—C2	119.39 (10)	C20—C19—C18	121.97 (12)
C6—C5—C4	120.74 (11)	C20—C19—Cl2	118.99 (10)
C6—C5—H5	119.6	C18—C19—Cl2	119.04 (10)
C4—C5—H5	119.6	C19—C20—C21	118.74 (11)
C7—C6—C5	120.08 (12)	C19—C20—H20	120.6
C7—C6—H6	120.0	C21—C20—H20	120.6
C5—C6—H6	120.0	C22—C21—C20	120.31 (12)
C6—C7—C8	119.63 (12)	C22—C21—H21	119.8
C6—C7—H7	120.2	C20—C21—H21	119.8
C8—C7—H7	120.2	C21—C22—C17	120.38 (11)
C9—C8—C7	120.34 (12)	C21—C22—H22	119.8
C9—C8—H8	119.8	C17—C22—H22	119.8
C7—C8—H8	119.8	N2—C23—C17	111.54 (9)
C8—C9—C4	120.53 (11)	N2—C23—H23A	109.3
C8—C9—H9	119.7	C17—C23—H23A	109.3
C4—C9—H9	119.7	N2—C23—H23B	109.3
C11—C10—C15	119.37 (11)	C17—C23—H23B	109.3
C11—C10—C16	118.79 (10)	H23A—C23—H23B	108.0
O2—C1—C2—C4	35.03 (14)	C10—C11—C12—C13	−2.61 (18)
O1—C1—C2—C4	−147.07 (10)	C10—C11—C12—Cl1	176.06 (9)
O2—C1—C2—C3	−88.10 (12)	C11—C12—C13—C14	0.44 (18)
O1—C1—C2—C3	89.81 (11)	Cl1—C12—C13—C14	−178.22 (10)
C4—C2—C3—O4	−89.86 (12)	C12—C13—C14—C15	1.64 (19)
C1—C2—C3—O4	35.02 (13)	C13—C14—C15—C10	−1.55 (19)
C4—C2—C3—O3	87.97 (12)	C11—C10—C15—C14	−0.64 (18)
C1—C2—C3—O3	−147.15 (10)	C16—C10—C15—C14	174.74 (11)
C1—C2—C4—C9	−85.18 (13)	C11—C10—C16—N1	−119.05 (12)
C3—C2—C4—C9	36.99 (14)	C15—C10—C16—N1	65.55 (14)
C1—C2—C4—C5	93.96 (12)	C22—C17—C18—C19	0.32 (17)
C3—C2—C4—C5	−143.87 (10)	C23—C17—C18—C19	179.41 (10)
C9—C4—C5—C6	0.20 (17)	C17—C18—C19—C20	0.70 (18)
C2—C4—C5—C6	−178.97 (10)	C17—C18—C19—Cl2	−179.13 (9)
C4—C5—C6—C7	−1.26 (18)	C18—C19—C20—C21	−0.84 (19)
C5—C6—C7—C8	1.21 (19)	Cl2—C19—C20—C21	178.99 (10)
C6—C7—C8—C9	−0.12 (19)	C19—C20—C21—C22	−0.04 (19)
C7—C8—C9—C4	−0.95 (18)	C20—C21—C22—C17	1.05 (19)
C5—C4—C9—C8	0.90 (17)	C18—C17—C22—C21	−1.18 (18)
C2—C4—C9—C8	−179.95 (11)	C23—C17—C22—C21	179.73 (11)
C15—C10—C11—C12	2.67 (17)	C18—C17—C23—N2	113.48 (12)
C16—C10—C11—C12	−172.85 (10)	C22—C17—C23—N2	−67.43 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.91	1.89	2.7789 (13)	165
N1—H1B···O1i	0.91	1.91	2.7891 (14)	163
N1—H1C···O4ii	0.91	1.82	2.7286 (13)	175
N2—H2A···O2	0.91	2.12	2.9783 (13)	157
N2—H2A···O4	0.91	2.40	2.9220 (13)	117
N2—H2B···O5iii	0.91	1.98	2.8530 (14)	159
N2—H2C···O5i	0.91	2.01	2.8863 (13)	162
O5—H5A···O1	0.795 (18)	1.931 (18)	2.7158 (12)	169.2 (16)
O5—H5B···O3i	0.841 (17)	1.868 (17)	2.6818 (12)	162.6 (15)
O6—H6A···O1	0.828 (17)	2.060 (17)	2.8559 (13)	161.0 (16)
O6—H6B···O3iv	0.856 (17)	1.945 (17)	2.7948 (13)	172.3 (16)
C9—H9···O4	0.95	2.58	3.2035 (15)	123
C15—H15···O2	0.95	2.39	3.2341 (15)	148
C22—H22···O3v	0.95	2.58	3.4936 (15)	160
C23—H23A···O6vi	0.99	2.49	3.3424 (15)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.91	1.89	2.7789 (13)	165
N1—H1B⋯O1i	0.91	1.91	2.7891 (14)	163
N1—H1C⋯O4ii	0.91	1.82	2.7286 (13)	175
N2—H2A⋯O2	0.91	2.12	2.9783 (13)	157
N2—H2A⋯O4	0.91	2.40	2.9220 (13)	117
N2—H2B⋯O5iii	0.91	1.98	2.8530 (14)	159
N2—H2C⋯O5i	0.91	2.01	2.8863 (13)	162
O5—H5A⋯O1	0.795 (18)	1.931 (18)	2.7158 (12)	169.2 (16)
O5—H5B⋯O3i	0.841 (17)	1.868 (17)	2.6818 (12)	162.6 (15)
O6—H6A⋯O1	0.828 (17)	2.060 (17)	2.8559 (13)	161.0 (16)
O6—H6B⋯O3iv	0.856 (17)	1.945 (17)	2.7948 (13)	172.3 (16)
C9—H9⋯O4	0.95	2.58	3.2035 (15)	123
C15—H15⋯O2	0.95	2.39	3.2341 (15)	148
C22—H22⋯O3v	0.95	2.58	3.4936 (15)	160
C23—H23A⋯O6vi	0.99	2.49	3.3424 (15)	144

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