New fluorescent compounds based on zinc thio­cyanate: influence of structure on spectral properties

New coordination compounds based on zinc thio­cyanate, namely (acetone thio­semicarbazone-κ²N¹,S)bis­(iso­thio­cyanato-κN)zinc(II) monohydrate, [Zn(NCS)₂(C₄H₉N₃S)]·H₂O, (I), and di­aqua­tetra­kis­(urea-κO)zinc(II) tetra­kis­(iso­thio­cyanato-κN)zinc(II), [Zn(CH₄N₂O)₄(H₂O)₂][Zn(NCS)₄], (II), were synthesized and studied by UV–Vis, fluorescence and IR spectroscopy. Coordination salt (II) forms a rare system composed of two different coordination units of the same metal and it is the first example of a compound with two completely different zinc coordination units, of which one contains a tetra­kis­(urea)zinc unit. Both (I) and (II) possess fluorescence properties and produce blue and green emissions, respectively, upon irradiation with violet light. The spectral properties were correlated with the observed mol­ecular and supra­molecular structures. The acetone thio­semicarbazone ligand of (I) exhibits (upon coordination) red shifts of bands corresponding to N=C and C=S stretching vibration frequencies, which is not typical for chelating mol­ecules.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2009).

(Acetone thiosemicarbazone-κ²N¹,S)bis(isothiocyanato-κN)zinc(II) monohydrate (I)

Crystal data

[Zn(NCS)2(C4H9N3S)]·H2O	F(000) = 672
Mr = 330.75	Dx = 1.662 Mg m^−3 Dm = 1.65 Mg m^−3 Dm measured by Berman density torsion balance
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.0831 (1) Å	Cell parameters from 12061 reflections
b = 17.4525 (2) Å	θ = 4.4–78.9°
c = 7.6133 (1) Å	µ = 6.94 mm^−1
β = 99.480 (1)°	T = 100 K
V = 1321.46 (3) Å^3	Needle, orange
Z = 4	0.51 × 0.03 × 0.02 mm

Data collection

Synergy Dualflex Pilatus 200K diffractometer	2509 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	Rint = 0.041
ω scans	θmax = 79.0°, θmin = 4.5°
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −12→12
Tmin = 0.674, Tmax = 1.000	k = −20→22
18106 measured reflections	l = −9→8
2729 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: mixed
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0385P)^2 + 0.6876P] where P = (Fo^2 + 2Fc^2)/3
2729 reflections	(Δ/σ)max = 0.001
162 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.24956 (2)	0.39025 (2)	0.71910 (3)	0.02073 (9)
S1	0.12971 (5)	0.49395 (2)	0.78916 (6)	0.02267 (11)
C1	0.15338 (17)	0.54833 (10)	0.6097 (2)	0.0201 (3)
N1	0.09589 (18)	0.61627 (9)	0.5832 (2)	0.0252 (3)
H1A	0.107 (2)	0.6413 (14)	0.496 (4)	0.030*
H1B	0.043 (3)	0.6292 (14)	0.648 (4)	0.030*
N2	0.22916 (15)	0.52571 (9)	0.4887 (2)	0.0210 (3)
H2	0.227 (2)	0.5501 (13)	0.396 (3)	0.025*
N3	0.29015 (15)	0.45396 (8)	0.5019 (2)	0.0202 (3)
C2	0.36288 (18)	0.43604 (11)	0.3844 (2)	0.0222 (4)
C3	0.3874 (2)	0.48830 (12)	0.2373 (3)	0.0284 (4)
H3A	0.3058	0.4942	0.1535	0.043*
H3B	0.4559	0.4668	0.1782	0.043*
H3C	0.4163	0.5374	0.2859	0.043*
C4	0.4271 (2)	0.35890 (12)	0.3967 (3)	0.0290 (4)
H4A	0.4046	0.3321	0.4980	0.043*
H4B	0.5229	0.3645	0.4098	0.043*
H4C	0.3950	0.3304	0.2904	0.043*
N5	0.15868 (16)	0.29557 (9)	0.6303 (2)	0.0266 (3)
C5	0.12986 (17)	0.23143 (10)	0.6127 (2)	0.0205 (4)
S5	0.08928 (5)	0.14099 (3)	0.59089 (6)	0.02474 (12)
N6	0.41618 (16)	0.35917 (9)	0.8679 (2)	0.0255 (3)
C6	0.51482 (19)	0.33565 (11)	0.9495 (2)	0.0229 (4)
S6	0.65321 (5)	0.30372 (3)	1.06693 (7)	0.03105 (13)
O1	0.16900 (16)	0.64445 (9)	0.2396 (2)	0.0320 (3)
H1O	0.232 (3)	0.6633 (17)	0.189 (4)	0.048*
H1P	0.107 (3)	0.6374 (17)	0.165 (4)	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.02507 (15)	0.01493 (14)	0.02130 (15)	0.00018 (8)	0.00120 (10)	0.00146 (9)
S1	0.0311 (2)	0.0182 (2)	0.0193 (2)	0.00283 (17)	0.00584 (17)	0.00226 (16)
C1	0.0222 (8)	0.0176 (8)	0.0190 (9)	−0.0012 (7)	−0.0006 (7)	−0.0005 (7)
N1	0.0339 (9)	0.0210 (8)	0.0210 (9)	0.0058 (7)	0.0051 (7)	0.0025 (6)
N2	0.0280 (8)	0.0172 (7)	0.0173 (8)	0.0022 (6)	0.0025 (6)	0.0038 (6)
N3	0.0240 (7)	0.0164 (7)	0.0194 (7)	0.0005 (6)	0.0014 (6)	−0.0001 (6)
C2	0.0245 (9)	0.0226 (9)	0.0184 (9)	−0.0032 (7)	0.0005 (7)	−0.0026 (7)
C3	0.0361 (10)	0.0280 (10)	0.0221 (10)	−0.0034 (8)	0.0083 (8)	−0.0019 (8)
C4	0.0318 (10)	0.0275 (10)	0.0284 (10)	0.0050 (8)	0.0070 (8)	−0.0019 (8)
N5	0.0299 (8)	0.0199 (8)	0.0286 (9)	0.0002 (6)	0.0010 (7)	0.0000 (6)
C5	0.0223 (8)	0.0210 (9)	0.0180 (8)	0.0019 (7)	0.0027 (7)	−0.0003 (7)
S5	0.0320 (2)	0.0168 (2)	0.0250 (2)	−0.00316 (17)	0.00355 (18)	−0.00254 (16)
N6	0.0271 (8)	0.0244 (8)	0.0243 (8)	0.0022 (6)	0.0020 (7)	0.0032 (6)
C6	0.0281 (10)	0.0227 (9)	0.0193 (9)	−0.0036 (7)	0.0082 (7)	−0.0013 (7)
S6	0.0245 (2)	0.0428 (3)	0.0248 (3)	0.00211 (19)	0.00090 (19)	0.0068 (2)
O1	0.0301 (7)	0.0376 (8)	0.0273 (8)	−0.0028 (6)	0.0020 (6)	0.0106 (6)

Geometric parameters (Å, º)

Zn1—N6	1.9424 (16)	C2—C3	1.496 (3)
Zn1—N5	1.9554 (16)	C3—H3A	0.9600
Zn1—N3	2.0881 (15)	C3—H3B	0.9600
Zn1—S1	2.2875 (5)	C3—H3C	0.9600
S1—C1	1.7125 (18)	C4—H4A	0.9600
C1—N1	1.321 (2)	C4—H4B	0.9600
C1—N2	1.349 (2)	C4—H4C	0.9600
N1—H1A	0.82 (3)	N5—C5	1.159 (2)
N1—H1B	0.82 (3)	C5—S5	1.6321 (18)
N2—N3	1.391 (2)	N6—C6	1.158 (3)
N2—H2	0.82 (2)	C6—S6	1.6265 (19)
N3—C2	1.286 (2)	O1—H1O	0.86 (3)
C2—C4	1.490 (3)	O1—H1P	0.78 (3)
N6—Zn1—N5	106.07 (7)	N3—C2—C3	123.81 (17)
N6—Zn1—N3	110.30 (6)	C4—C2—C3	118.32 (17)
N5—Zn1—N3	108.53 (6)	C2—C3—H3A	109.5
N6—Zn1—S1	121.63 (5)	C2—C3—H3B	109.5
N5—Zn1—S1	120.91 (5)	H3A—C3—H3B	109.5
N3—Zn1—S1	86.75 (4)	C2—C3—H3C	109.5
C1—S1—Zn1	95.97 (6)	H3A—C3—H3C	109.5
N1—C1—N2	116.26 (17)	H3B—C3—H3C	109.5
N1—C1—S1	120.25 (15)	C2—C4—H4A	109.5
N2—C1—S1	123.48 (14)	C2—C4—H4B	109.5
C1—N1—H1A	119.2 (17)	H4A—C4—H4B	109.5
C1—N1—H1B	117.9 (18)	C2—C4—H4C	109.5
H1A—N1—H1B	122 (3)	H4A—C4—H4C	109.5
C1—N2—N3	120.47 (15)	H4B—C4—H4C	109.5
C1—N2—H2	119.7 (16)	C5—N5—Zn1	161.92 (15)
N3—N2—H2	118.7 (16)	N5—C5—S5	179.22 (18)
C2—N3—N2	117.67 (15)	C6—N6—Zn1	174.96 (16)
C2—N3—Zn1	129.08 (13)	N6—C6—S6	179.00 (19)
N2—N3—Zn1	113.25 (11)	H1O—O1—H1P	107 (3)
N3—C2—C4	117.87 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.82 (3)	2.15 (3)	2.875 (2)	148 (2)
N1—H1B···S5^i	0.82 (3)	2.58 (3)	3.3694 (19)	164 (2)
N2—H2···O1	0.82 (2)	2.06 (2)	2.807 (2)	151 (2)
O1—H1O···S6^ii	0.86 (3)	2.49 (3)	3.2948 (16)	156 (3)
O1—H1P···S5^iii	0.78 (3)	2.54 (3)	3.3102 (16)	169 (3)

Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x+1, −y+1, −z+1; (iii) −x, y+1/2, −z+1/2.

Diaquatetrakis(urea-κO)zinc(II) tetrakis(isothiocyanato-κN)zinc(II) (II)

Crystal data

[Zn(CH4N2O)4(H2O)2][Zn(NCS)4]	F(000) = 1296
Mr = 639.34	Dx = 1.789 Mg m^−3 Dm = 1.77 Mg m^−3 Dm measured by Berman density torsion balance
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.8246 (8) Å	Cell parameters from 6085 reflections
b = 5.0239 (2) Å	θ = 4.2–31.6°
c = 21.6451 (8) Å	µ = 2.42 mm^−1
β = 90.074 (4)°	T = 100 K
V = 2373.27 (16) Å^3	Prism, orange
Z = 4	0.33 × 0.16 × 0.07 mm

Data collection

Synergy Dualflex Pilatus 200K diffractometer	3061 reflections with I > 2σ(I)
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	Rint = 0.019
ω scans	θmax = 31.9°, θmin = 3.7°
Absorption correction: gaussian (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −31→29
Tmin = 0.710, Tmax = 1.000	k = −5→7
9207 measured reflections	l = −30→32
3261 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.018	Hydrogen site location: difference Fourier map
wR(F^2) = 0.049	Only H-atom coordinates refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0251P)^2 + 1.7969P] where P = (Fo^2 + 2Fc^2)/3
3261 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn11	0.5000	0.41640 (4)	0.2500	0.01200 (5)
S11	0.66268 (2)	1.01492 (7)	0.20317 (2)	0.01485 (7)
C11	0.60834 (5)	0.8023 (2)	0.21995 (5)	0.0115 (2)
N11	0.57044 (5)	0.6474 (2)	0.23202 (5)	0.0149 (2)
S12	0.44851 (2)	−0.20314 (6)	0.09188 (2)	0.01339 (7)
C12	0.46842 (5)	0.0232 (2)	0.14286 (5)	0.0117 (2)
N12	0.48223 (5)	0.1836 (2)	0.17888 (5)	0.0150 (2)
Zn1	0.7500	0.2500	0.5000	0.00780 (5)
O1	0.82066 (4)	0.03747 (17)	0.44970 (4)	0.01022 (15)
N1	0.66314 (5)	0.4268 (2)	0.33194 (5)	0.0152 (2)
H1A	0.6414 (8)	0.548 (4)	0.3479 (8)	0.018*
H1B	0.6541 (8)	0.352 (4)	0.2986 (8)	0.018*
N2	0.72654 (5)	0.0715 (2)	0.35449 (5)	0.01269 (19)
H2A	0.7611 (8)	0.029 (4)	0.3719 (8)	0.015*
H2B	0.7204 (7)	0.007 (4)	0.3168 (8)	0.015*
C1	0.70303 (5)	0.3107 (2)	0.37040 (5)	0.0101 (2)
O2	0.71709 (4)	0.42341 (17)	0.42081 (4)	0.01119 (16)
N3	0.91109 (5)	−0.0934 (2)	0.40849 (5)	0.0155 (2)
H3A	0.8912 (8)	−0.196 (4)	0.3845 (8)	0.019*
H3B	0.9488 (8)	−0.053 (4)	0.4012 (8)	0.019*
N4	0.90855 (5)	0.2547 (2)	0.47682 (6)	0.0177 (2)
H4A	0.9465 (8)	0.277 (4)	0.4702 (8)	0.021*
H4B	0.8898 (8)	0.349 (4)	0.4992 (8)	0.021*
C2	0.87851 (5)	0.0693 (2)	0.44476 (5)	0.0098 (2)
O7	0.69391 (4)	−0.08130 (17)	0.48458 (4)	0.00983 (15)
H7A	0.6923 (8)	−0.195 (4)	0.5094 (8)	0.015*
H7B	0.6947 (7)	−0.156 (4)	0.4525 (8)	0.015*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn11	0.01217 (9)	0.01078 (10)	0.01305 (9)	0.000	−0.00047 (7)	0.000
S11	0.01435 (13)	0.01553 (15)	0.01466 (13)	−0.00276 (10)	0.00064 (10)	0.00070 (11)
C11	0.0124 (5)	0.0125 (5)	0.0095 (5)	0.0036 (4)	−0.0022 (4)	−0.0016 (4)
N11	0.0151 (4)	0.0141 (5)	0.0156 (5)	0.0008 (4)	−0.0002 (4)	−0.0008 (4)
S12	0.01223 (13)	0.01390 (14)	0.01404 (13)	−0.00084 (10)	−0.00063 (10)	−0.00153 (11)
C12	0.0098 (5)	0.0124 (5)	0.0130 (5)	0.0005 (4)	0.0007 (4)	0.0045 (4)
N12	0.0159 (5)	0.0139 (5)	0.0153 (5)	−0.0003 (4)	−0.0003 (4)	0.0013 (4)
Zn1	0.00829 (8)	0.00612 (9)	0.00897 (9)	−0.00006 (6)	−0.00101 (6)	0.00045 (6)
O1	0.0089 (3)	0.0104 (4)	0.0113 (4)	0.0000 (3)	0.0003 (3)	0.0001 (3)
N1	0.0168 (5)	0.0160 (5)	0.0129 (5)	0.0054 (4)	−0.0044 (4)	−0.0023 (4)
N2	0.0140 (4)	0.0127 (5)	0.0114 (4)	0.0019 (4)	−0.0034 (4)	−0.0020 (4)
C1	0.0091 (4)	0.0109 (5)	0.0103 (5)	−0.0016 (4)	0.0005 (4)	0.0020 (4)
O2	0.0144 (4)	0.0097 (4)	0.0095 (3)	0.0012 (3)	−0.0023 (3)	0.0002 (3)
N3	0.0117 (4)	0.0180 (5)	0.0170 (5)	−0.0002 (4)	0.0032 (4)	−0.0055 (4)
N4	0.0098 (4)	0.0177 (6)	0.0255 (6)	−0.0017 (4)	0.0028 (4)	−0.0096 (4)
C2	0.0112 (5)	0.0096 (5)	0.0087 (4)	0.0008 (4)	0.0002 (4)	0.0022 (4)
O7	0.0118 (4)	0.0076 (4)	0.0100 (4)	−0.0009 (3)	−0.0004 (3)	−0.0002 (3)

Geometric parameters (Å, º)

Zn11—N11	1.9656 (11)	N1—C1	1.3377 (15)
Zn11—N11^i	1.9656 (11)	N1—H1A	0.847 (19)
Zn11—N12^i	1.9714 (11)	N1—H1B	0.838 (18)
Zn11—N12	1.9714 (11)	N2—C1	1.3511 (16)
S11—C11	1.6372 (13)	N2—H2A	0.869 (17)
C11—N11	1.1657 (17)	N2—H2B	0.889 (17)
S12—C12	1.6425 (13)	C1—O2	1.2668 (14)
C12—N12	1.1608 (17)	N3—C2	1.3382 (16)
Zn1—O2	2.0518 (8)	N3—H3A	0.851 (18)
Zn1—O2^ii	2.0519 (8)	N3—H3B	0.862 (18)
Zn1—O7^ii	2.0926 (8)	N4—C2	1.3337 (16)
Zn1—O7	2.0926 (8)	N4—H4A	0.848 (19)
Zn1—O1^ii	2.1697 (8)	N4—H4B	0.79 (2)
Zn1—O1	2.1697 (8)	O7—H7A	0.784 (19)
O1—C2	1.2773 (13)	O7—H7B	0.789 (18)
N11—Zn11—N11^i	107.62 (7)	O1—Zn1—O1^ii	180.00 (4)
N11—Zn11—N12^i	110.60 (4)	C2—O1—Zn1	133.14 (8)
N11^i—Zn11—N12^i	110.42 (4)	C1—N1—H1A	115.1 (12)
N11—Zn11—N12	110.42 (4)	C1—N1—H1B	119.5 (13)
N11^i—Zn11—N12	110.60 (4)	H1A—N1—H1B	123.0 (17)
N12^i—Zn11—N12	107.21 (6)	C1—N2—H2A	116.0 (12)
N11—C11—S11	178.77 (12)	C1—N2—H2B	120.1 (11)
C11—N11—Zn11	173.75 (10)	H2A—N2—H2B	115.9 (15)
N12—C12—S12	179.70 (12)	O2—C1—N1	119.85 (11)
C12—N12—Zn11	170.75 (10)	O2—C1—N2	121.70 (10)
O2—Zn1—O2^ii	180.0	N1—C1—N2	118.43 (11)
O2—Zn1—O7^ii	89.97 (3)	C1—O2—Zn1	127.87 (8)
O2^ii—Zn1—O7^ii	90.02 (3)	C2—N3—H3A	117.3 (12)
O2—Zn1—O7	90.03 (3)	C2—N3—H3B	118.2 (12)
O2^ii—Zn1—O7	89.98 (3)	H3A—N3—H3B	121.1 (16)
O7—Zn1—O7^ii	180.00 (4)	C2—N4—H4A	119.0 (12)
O2—Zn1—O1^ii	87.82 (3)	C2—N4—H4B	118.8 (13)
O2^ii—Zn1—O1^ii	92.18 (3)	H4A—N4—H4B	121.9 (18)
O7^ii—Zn1—O1^ii	86.82 (3)	O1—C2—N4	121.95 (11)
O7—Zn1—O1^ii	93.18 (3)	O1—C2—N3	119.92 (11)
O2—Zn1—O1	92.18 (3)	N4—C2—N3	118.07 (11)
O2^ii—Zn1—O1	87.82 (3)	Zn1—O7—H7A	119.8 (13)
O7^ii—Zn1—O1	93.18 (3)	Zn1—O7—H7B	120.2 (13)
O7—Zn1—O1	86.82 (3)	H7A—O7—H7B	105.0 (18)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S12^iii	0.847 (19)	2.668 (19)	3.4820 (12)	161.7 (16)
N1—H1B···S11^iv	0.838 (18)	2.677 (19)	3.4713 (12)	158.8 (16)
N2—H2A···O1	0.869 (17)	2.127 (17)	2.9129 (13)	150.1 (15)
N2—H2B···S11^iv	0.889 (17)	2.762 (17)	3.5692 (10)	151.7 (14)
N3—H3A···S11^v	0.851 (18)	2.661 (18)	3.5066 (12)	172.1 (15)
N3—H3B···S12^vi	0.862 (18)	2.853 (18)	3.6376 (12)	152.2 (16)
N3—H3B···N12^vii	0.862 (18)	2.651 (18)	3.2039 (15)	123.1 (15)
N4—H4A···S12^vi	0.848 (19)	2.660 (19)	3.4639 (12)	158.8 (16)
N4—H4B···S12^viii	0.79 (2)	2.970 (19)	3.4687 (12)	123.2 (15)
N4—H4B···O7^ii	0.79 (2)	2.195 (19)	2.8975 (14)	147.9 (17)
O7—H7A···O1^ix	0.784 (19)	1.956 (19)	2.7162 (12)	163.1 (17)
O7—H7B···N2	0.789 (18)	2.507 (17)	3.0052 (14)	122.4 (16)
O7—H7B···O2^iv	0.789 (18)	2.277 (19)	2.8904 (12)	135.2 (16)

Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1; (iii) −x+1, y+1, −z+1/2; (iv) x, y−1, z; (v) −x+3/2, y−3/2, −z+1/2; (vi) −x+3/2, y+1/2, −z+1/2; (vii) −x+3/2, y−1/2, −z+1/2; (viii) x+1/2, −y+1/2, z+1/2; (ix) −x+3/2, −y−1/2, −z+1.