Tetra-aqua-bis-(N,N-dimethyl-formamide-κO)zinc(II) bis-[(2-{3-[2-(carboxyl-ato-meth-oxy-κ(2)O,O')phen-yl]pyrazol-1-yl-κN(2)}acetato-κO)chloridozincate(II)].

The asymmetric unit of the title compound, [Zn(C(3)H(7)NO)(2)(H(2)O)(4)][Zn(C(13)H(10)N(2)O(5))Cl](2), is composed of a single anion and half a cation. The Zn(II) atom in the monoanion has a distorted triganol-pyramidal geometry, being coordinated by three O atoms and one N atom from one 2-{3-[2-(carboxyl-ato-meth-oxy)phen-yl]pyrazol-1-yl}acetate ligand and one Cl atom. In the dication, the Zn(II) atom is located on an inversion center and is coordinated by six O atoms in a slightly distorted octa-hedral geometry. In the crystal, the ions are linked by O-H⋯O hydrogen bonds, forming a two-dimensional network lying parallel to the ab plane. There are also C-H⋯O and C-H⋯Cl inter-actions present, which lead to the formation of a three-dimensional structure.

Related literature

For potential applications of <span class="Chemical">pyrazole derivatives in advanced materials, see: Su et al. (2000 ▶); Tong et al. (2003 ▶). For the τ-descriptor of <class="Chemical">span class="Chemical">penta-coordinated metal atoms, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Zn(C3H7NO)2(H2O)4][Zn(C13<span class="Species">H10N2O5)Cl]2

M = 1033.79

Triclinic,

a = 8.0040 (16) Å

b = 8.7276 (17) Å

c = 15.782 (3) Å

α = 90.06 (3)°

β = 101.22 (3)°

γ = 107.95 (3)°

V = 1026.6 (3) Å3

Z = 1

Mo Kα radiation

μ = 1.95 mm−1

T = 291 K

0.25 × 0.22 × 0.21 mm

Data collection

Rigaku <span class="Chemical">Mercury diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.642, T max = 0.686

10740 measured reflections

4704 independent reflections

3632 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.168

S = 1.07

4704 reflections

265 parameters

23 restraints

H-atom parameters constrained

Δρmax = 1.99 e Å−3

Δρmin = −0.73 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and CrystalStructure (Rigaku/MSC, 2004 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023045/su2397sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023045/su2397Isup2.hkl

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

[Zn(C3H7NO)2(H2O)4][Zn(C13H10N2O5)Cl]2	Z = 1
Mr = 1033.79	F(000) = 528
Triclinic, P1	Dx = 1.672 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0040 (16) Å	Cell parameters from 10740 reflections
b = 8.7276 (17) Å	θ = 3.1–27.5°
c = 15.782 (3) Å	µ = 1.95 mm−1
α = 90.06 (3)°	T = 291 K
β = 101.22 (3)°	Block, colourless
γ = 107.95 (3)°	0.25 × 0.22 × 0.21 mm
V = 1026.6 (3) Å3

Rigaku Mercury diffractometer	4704 independent reflections
Radiation source: fine-focus sealed tube	3632 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −10→10
Tmin = 0.642, Tmax = 0.686	k = −11→11
10740 measured reflections	l = −20→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
4704 reflections	(Δ/σ)max < 0.001
265 parameters	Δρmax = 1.99 e Å−3
23 restraints	Δρmin = −0.73 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Zn2	0.28061 (6)	0.71444 (5)	0.29770 (3)	0.0271 (2)
Cl1	0.04523 (14)	0.78125 (14)	0.32248 (8)	0.0415 (4)
O1	0.2909 (4)	0.5528 (3)	0.41252 (18)	0.0343 (9)
O2	0.3455 (4)	0.8648 (4)	0.20287 (18)	0.0371 (9)
O3	0.5276 (4)	1.0071 (5)	0.1224 (2)	0.0509 (13)
O4	0.2013 (4)	0.4924 (3)	0.24461 (19)	0.0365 (9)
O5	0.0503 (4)	0.2338 (4)	0.2575 (2)	0.0459 (11)
N1	0.5313 (4)	0.8109 (4)	0.3703 (2)	0.0283 (10)
N2	0.6622 (4)	0.9126 (4)	0.3366 (2)	0.0301 (10)
C1	0.7964 (5)	1.0017 (5)	0.3987 (3)	0.0361 (12)
C2	0.7530 (6)	0.9617 (5)	0.4766 (3)	0.0350 (12)
C3	0.5845 (5)	0.8392 (4)	0.4578 (2)	0.0249 (11)
C4	0.4840 (5)	0.7501 (5)	0.5203 (3)	0.0277 (11)
C5	0.5382 (6)	0.8039 (5)	0.6081 (3)	0.0336 (12)
C6	0.4588 (7)	0.7199 (6)	0.6715 (3)	0.0413 (16)
C7	0.3213 (7)	0.5759 (6)	0.6478 (3)	0.0432 (16)
C8	0.2595 (6)	0.5178 (5)	0.5621 (3)	0.0348 (12)
C9	0.3411 (5)	0.6049 (5)	0.4985 (2)	0.0273 (11)
C10	0.6618 (6)	0.9009 (6)	0.2440 (3)	0.0398 (14)
C11	0.4999 (5)	0.9281 (5)	0.1858 (3)	0.0339 (12)
C12	0.1551 (5)	0.4021 (4)	0.3845 (3)	0.0281 (11)
C13	0.1363 (6)	0.3744 (5)	0.2887 (3)	0.0348 (12)
Zn1	1.00000	0.00000	0.00000	0.0325 (2)
O6	1.0708 (8)	0.2476 (5)	−0.0070 (4)	0.094 (2)
O7	0.7437 (5)	−0.0088 (7)	0.0101 (2)	0.0810 (19)
O8	1.0867 (5)	0.0342 (4)	0.13520 (19)	0.0494 (11)
N3	1.2254 (6)	0.4929 (5)	−0.0348 (3)	0.0660 (18)
C14	1.1206 (6)	0.3353 (5)	−0.0562 (3)	0.101 (3)
C15	1.3142 (14)	0.5932 (12)	0.0394 (5)	0.117 (4)
C16	1.2371 (14)	0.5717 (13)	−0.1167 (5)	0.127 (5)
H1A	0.90130	1.07770	0.39000	0.0430*
H2A	0.82010	1.00570	0.53090	0.0420*
H5A	0.63130	0.90010	0.62420	0.0400*
H6A	0.49700	0.75920	0.72910	0.0500*
H7A	0.26940	0.51700	0.69030	0.0520*
H8A	0.16510	0.42230	0.54690	0.0420*
H10A	0.66620	0.79470	0.22870	0.0480*
H10B	0.76960	0.97980	0.23300	0.0480*
H12A	0.04210	0.40420	0.39730	0.0340*
H12B	0.18820	0.31550	0.41460	0.0340*
H7B	0.66940	−0.02460	−0.04690	0.1210*
H7C	0.74740	0.09090	0.03730	0.1210*
H8B	1.21120	0.04140	0.15010	0.0740*
H8C	1.07190	0.13250	0.15470	0.0740*
H14A	1.08940	0.28160	−0.11290	0.1510*
H15A	1.30250	0.53170	0.08960	0.1750*
H15B	1.26260	0.67830	0.04230	0.1750*
H15C	1.43890	0.63880	0.03760	0.1750*
H16A	1.17280	0.49420	−0.16430	0.1900*
H16B	1.36070	0.61470	−0.12100	0.1900*
H16C	1.18550	0.65770	−0.11810	0.1900*

	U11	U22	U33	U12	U13	U23
Zn2	0.0249 (3)	0.0290 (3)	0.0234 (3)	0.0051 (2)	0.0009 (2)	0.0017 (2)
Cl1	0.0314 (5)	0.0477 (7)	0.0473 (7)	0.0147 (5)	0.0092 (5)	−0.0004 (5)
O1	0.0401 (16)	0.0295 (15)	0.0255 (14)	0.0018 (12)	0.0031 (12)	0.0017 (12)
O2	0.0267 (14)	0.0531 (19)	0.0271 (15)	0.0065 (13)	0.0048 (12)	0.0146 (14)
O3	0.0330 (17)	0.083 (3)	0.0349 (18)	0.0130 (17)	0.0115 (14)	0.0271 (17)
O4	0.0455 (17)	0.0321 (16)	0.0290 (15)	0.0076 (13)	0.0084 (13)	−0.0017 (12)
O5	0.0502 (19)	0.0320 (17)	0.0456 (19)	−0.0007 (14)	0.0089 (15)	−0.0144 (14)
N1	0.0214 (15)	0.0339 (18)	0.0270 (17)	0.0061 (14)	0.0030 (13)	0.0041 (14)
N2	0.0237 (16)	0.0361 (19)	0.0286 (18)	0.0079 (14)	0.0033 (14)	0.0075 (14)
C1	0.025 (2)	0.033 (2)	0.040 (2)	−0.0009 (17)	−0.0014 (18)	0.0049 (19)
C2	0.029 (2)	0.034 (2)	0.034 (2)	0.0038 (17)	−0.0023 (17)	−0.0019 (18)
C3	0.0261 (18)	0.0230 (18)	0.0244 (19)	0.0099 (15)	−0.0013 (15)	0.0002 (15)
C4	0.0262 (19)	0.029 (2)	0.028 (2)	0.0126 (16)	−0.0004 (16)	0.0002 (16)
C5	0.039 (2)	0.036 (2)	0.024 (2)	0.0140 (18)	−0.0012 (17)	−0.0048 (17)
C6	0.046 (3)	0.053 (3)	0.026 (2)	0.019 (2)	0.0041 (19)	−0.004 (2)
C7	0.046 (3)	0.058 (3)	0.030 (2)	0.017 (2)	0.017 (2)	0.013 (2)
C8	0.035 (2)	0.037 (2)	0.031 (2)	0.0090 (19)	0.0075 (18)	0.0018 (18)
C9	0.029 (2)	0.032 (2)	0.0230 (19)	0.0133 (17)	0.0040 (16)	0.0000 (16)
C10	0.029 (2)	0.056 (3)	0.035 (2)	0.012 (2)	0.0103 (18)	0.013 (2)
C11	0.029 (2)	0.045 (2)	0.026 (2)	0.0102 (19)	0.0038 (17)	0.0036 (18)
C12	0.0272 (19)	0.0220 (19)	0.032 (2)	0.0034 (15)	0.0057 (16)	0.0013 (16)
C13	0.031 (2)	0.034 (2)	0.040 (2)	0.0138 (18)	0.0027 (18)	−0.0043 (19)
Zn1	0.0342 (4)	0.0339 (4)	0.0301 (4)	0.0116 (3)	0.0071 (3)	0.0034 (3)
O6	0.133 (4)	0.050 (3)	0.098 (4)	0.022 (3)	0.030 (3)	0.031 (2)
O7	0.050 (2)	0.177 (5)	0.0319 (19)	0.058 (3)	0.0093 (17)	0.007 (2)
O8	0.070 (2)	0.061 (2)	0.0268 (16)	0.0414 (19)	−0.0013 (15)	−0.0040 (15)
N3	0.073 (3)	0.039 (2)	0.090 (4)	0.014 (2)	0.032 (3)	0.002 (2)
C14	0.116 (5)	0.069 (4)	0.113 (5)	0.017 (4)	0.031 (4)	0.004 (4)
C15	0.168 (8)	0.130 (7)	0.066 (5)	0.082 (6)	0.001 (5)	−0.018 (5)
C16	0.157 (9)	0.163 (9)	0.052 (5)	0.049 (7)	0.005 (5)	0.022 (5)

Zn2—Cl1	2.2373 (14)	C1—C2	1.359 (7)
Zn2—O1	2.302 (3)	C2—C3	1.416 (6)
Zn2—O2	2.029 (3)	C3—C4	1.466 (6)
Zn2—O4	1.973 (3)	C4—C5	1.403 (7)
Zn2—N1	2.027 (3)	C4—C9	1.409 (6)
Zn1—O6	2.067 (4)	C5—C6	1.380 (7)
Zn1—O7	2.066 (4)	C6—C7	1.385 (7)
Zn1—O8	2.102 (3)	C7—C8	1.384 (7)
Zn1—O6i	2.067 (4)	C8—C9	1.401 (6)
Zn1—O7i	2.066 (4)	C10—C11	1.519 (7)
Zn1—O8i	2.102 (3)	C12—C13	1.502 (7)
O1—C9	1.372 (4)	C1—H1A	0.9300
O1—C12	1.427 (5)	C2—H2A	0.9300
O2—C11	1.271 (5)	C5—H5A	0.9300
O3—C11	1.233 (6)	C6—H6A	0.9300
O4—C13	1.276 (5)	C7—H7A	0.9300
O5—C13	1.252 (5)	C8—H8A	0.9300
O6—C14	1.132 (7)	C10—H10B	0.9700
O7—H7B	0.9600	C10—H10A	0.9700
O7—H7C	0.9600	C12—H12B	0.9700
O8—H8C	0.9600	C12—H12A	0.9700
O8—H8B	0.9600	C14—H14A	0.9600
N1—N2	1.347 (5)	C15—H15A	0.9600
N1—C3	1.362 (4)	C15—H15B	0.9600
N2—C1	1.339 (6)	C15—H15C	0.9600
N2—C10	1.464 (6)	C16—H16A	0.9600
N3—C15	1.390 (10)	C16—H16B	0.9600
N3—C16	1.470 (10)	C16—H16C	0.9600
N3—C14	1.374 (6)
Cl1—Zn2—O1	94.96 (9)	C3—C4—C5	119.3 (4)
Cl1—Zn2—O2	99.10 (11)	C4—C5—C6	122.6 (4)
Cl1—Zn2—O4	110.29 (11)	C5—C6—C7	118.8 (4)
Cl1—Zn2—N1	122.65 (10)	C6—C7—C8	121.3 (4)
O1—Zn2—O2	164.05 (13)	C7—C8—C9	119.1 (4)
O1—Zn2—O4	74.99 (11)	O1—C9—C4	116.2 (3)
O1—Zn2—N1	75.37 (12)	O1—C9—C8	122.5 (4)
O2—Zn2—O4	106.75 (13)	C4—C9—C8	121.2 (3)
O2—Zn2—N1	90.64 (13)	N2—C10—C11	114.2 (4)
O4—Zn2—N1	120.51 (14)	O2—C11—C10	119.1 (4)
O7—Zn1—O7i	180.00	O2—C11—O3	124.1 (4)
O7—Zn1—O8i	89.06 (15)	O3—C11—C10	116.8 (4)
O6i—Zn1—O8	90.8 (2)	O1—C12—C13	108.3 (3)
O7i—Zn1—O8	89.06 (15)	O4—C13—O5	124.6 (4)
O8—Zn1—O8i	180.00	O5—C13—C12	115.8 (4)
O6i—Zn1—O7i	90.4 (2)	O4—C13—C12	119.6 (4)
O6i—Zn1—O8i	89.2 (2)	C2—C1—H1A	126.00
O7i—Zn1—O8i	90.94 (15)	N2—C1—H1A	126.00
O7—Zn1—O8	90.94 (15)	C1—C2—H2A	127.00
O6i—Zn1—O7	89.6 (2)	C3—C2—H2A	127.00
O6—Zn1—O7	90.4 (2)	C6—C5—H5A	119.00
O6—Zn1—O8	89.2 (2)	C4—C5—H5A	119.00
O6—Zn1—O6i	180.00	C5—C6—H6A	121.00
O6—Zn1—O7i	89.6 (2)	C7—C6—H6A	121.00
O6—Zn1—O8i	90.8 (2)	C8—C7—H7A	119.00
Zn2—O1—C12	106.2 (2)	C6—C7—H7A	119.00
C9—O1—C12	120.6 (3)	C7—C8—H8A	120.00
Zn2—O1—C9	125.9 (2)	C9—C8—H8A	120.00
Zn2—O2—C11	127.5 (3)	N2—C10—H10A	109.00
Zn2—O4—C13	119.3 (3)	C11—C10—H10B	109.00
Zn1—O6—C14	135.3 (5)	H10A—C10—H10B	108.00
H7B—O7—H7C	109.00	N2—C10—H10B	109.00
Zn1—O7—H7C	110.00	C11—C10—H10A	109.00
Zn1—O7—H7B	109.00	C13—C12—H12A	110.00
H8B—O8—H8C	109.00	O1—C12—H12B	110.00
Zn1—O8—H8B	109.00	O1—C12—H12A	110.00
Zn1—O8—H8C	109.00	C13—C12—H12B	110.00
N2—N1—C3	106.0 (3)	H12A—C12—H12B	108.00
Zn2—N1—C3	129.2 (3)	O6—C14—N3	123.6 (5)
Zn2—N1—N2	120.7 (2)	O6—C14—H14A	111.00
N1—N2—C1	111.5 (3)	N3—C14—H14A	125.00
N1—N2—C10	121.0 (3)	N3—C15—H15A	109.00
C1—N2—C10	126.8 (4)	N3—C15—H15B	110.00
C14—N3—C16	106.6 (5)	N3—C15—H15C	109.00
C14—N3—C15	138.4 (6)	H15A—C15—H15B	109.00
C15—N3—C16	115.0 (6)	H15A—C15—H15C	109.00
N2—C1—C2	108.2 (4)	H15B—C15—H15C	109.00
C1—C2—C3	105.7 (4)	N3—C16—H16A	109.00
N1—C3—C2	108.6 (3)	N3—C16—H16B	109.00
N1—C3—C4	124.3 (3)	N3—C16—H16C	109.00
C2—C3—C4	127.0 (3)	H16A—C16—H16B	110.00
C3—C4—C9	123.7 (4)	H16A—C16—H16C	110.00
C5—C4—C9	116.9 (4)	H16B—C16—H16C	109.00
Cl1—Zn2—O1—C9	−69.9 (3)	Zn2—N1—N2—C10	−29.1 (5)
Cl1—Zn2—O1—C12	79.9 (2)	C3—N1—N2—C1	1.0 (4)
O4—Zn2—O1—C9	−179.6 (4)	Zn2—N1—N2—C1	160.1 (3)
O4—Zn2—O1—C12	−29.8 (2)	N2—N1—C3—C4	−177.7 (4)
N1—Zn2—O1—C9	52.6 (3)	C3—N1—N2—C10	171.8 (4)
N1—Zn2—O1—C12	−157.7 (3)	Zn2—N1—C3—C2	−156.8 (3)
Cl1—Zn2—O2—C11	150.2 (3)	Zn2—N1—C3—C4	25.6 (6)
O4—Zn2—O2—C11	−95.3 (4)	N2—N1—C3—C2	−0.1 (4)
N1—Zn2—O2—C11	27.0 (4)	N1—N2—C10—C11	61.6 (5)
Cl1—Zn2—O4—C13	−66.6 (4)	C1—N2—C10—C11	−129.1 (4)
O1—Zn2—O4—C13	23.2 (3)	C10—N2—C1—C2	−171.6 (4)
O2—Zn2—O4—C13	−173.3 (3)	N1—N2—C1—C2	−1.4 (5)
N1—Zn2—O4—C13	85.7 (4)	C15—N3—C14—O6	6.5 (13)
Cl1—Zn2—N1—N2	−111.0 (3)	C16—N3—C14—O6	−171.4 (7)
Cl1—Zn2—N1—C3	42.7 (4)	N2—C1—C2—C3	1.3 (5)
O1—Zn2—N1—N2	162.5 (3)	C1—C2—C3—N1	−0.7 (5)
O1—Zn2—N1—C3	−43.8 (3)	C1—C2—C3—C4	176.8 (4)
O2—Zn2—N1—N2	−9.8 (3)	N1—C3—C4—C5	−171.2 (4)
O2—Zn2—N1—C3	143.9 (3)	N1—C3—C4—C9	13.3 (6)
O4—Zn2—N1—N2	100.2 (3)	C2—C3—C4—C5	11.7 (7)
O4—Zn2—N1—C3	−106.1 (3)	C2—C3—C4—C9	−163.8 (4)
O7i—Zn1—O6—C14	60.2 (8)	C3—C4—C9—O1	−3.7 (6)
O8i—Zn1—O6—C14	−30.8 (8)	C3—C4—C5—C6	−175.1 (5)
O7—Zn1—O6—C14	−119.8 (8)	C9—C4—C5—C6	0.7 (7)
O8—Zn1—O6—C14	149.3 (8)	C5—C4—C9—C8	−0.9 (6)
C12—O1—C9—C4	176.1 (4)	C3—C4—C9—C8	174.6 (4)
C9—O1—C12—C13	−177.2 (4)	C5—C4—C9—O1	−179.3 (4)
C12—O1—C9—C8	−2.2 (6)	C4—C5—C6—C7	0.7 (8)
Zn2—O1—C12—C13	31.1 (4)	C5—C6—C7—C8	−1.8 (8)
Zn2—O1—C9—C4	−38.1 (5)	C6—C7—C8—C9	1.6 (8)
Zn2—O1—C9—C8	143.6 (4)	C7—C8—C9—O1	178.1 (4)
Zn2—O2—C11—O3	173.3 (3)	C7—C8—C9—C4	−0.2 (7)
Zn2—O2—C11—C10	−4.1 (6)	N2—C10—C11—O2	−42.3 (6)
Zn2—O4—C13—O5	165.2 (4)	N2—C10—C11—O3	140.2 (4)
Zn2—O4—C13—C12	−12.3 (6)	O1—C12—C13—O4	−16.5 (6)
Zn1—O6—C14—N3	−152.5 (5)	O1—C12—C13—O5	165.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3ii	0.96	1.83	2.710 (5)	151
O8—H8B···O2iii	0.96	2.21	2.941 (5)	132
O8—H8C···O5iv	0.96	1.91	2.715 (5)	140
C2—H2A···Cl1v	0.93	2.79	3.668 (5)	159
C10—H10B···O5vi	0.97	2.59	3.511 (6)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O3i	0.96	1.83	2.710 (5)	151
O8—H8B⋯O2ii	0.96	2.21	2.941 (5)	132
O8—H8C⋯O5iii	0.96	1.91	2.715 (5)	140
C2—H2A⋯Cl1iv	0.93	2.79	3.668 (5)	159
C10—H10B⋯O5v	0.97	2.59	3.511 (6)	159

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