Crystal structure of [butane-2,3-dione bis­(4-methyl­thio­semicarbazonato)-κ4S,N1,N1′,S′](pyridine-κN)zinc(II)

Brown, O.C.; Tocher, D.A.; Blower, P.J.; Went, M.J.

doi:10.1107/S2056989015019234

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages 1349-1351

https://doi.org/10.1107/S2056989015019234

Open

access

Crystal structure of [butane-2,3-dione bis(4-methylthiosemicarbazonato)-κ⁴S,N¹,N^1′,S′](pyridine-κN)zinc(II)

Oliver C. Brown,^a Derek A. Tocher,^b Philip J. Blower ^c and Michael J. Went ^a ^*

^aUniversity of Kent, School of Physical Sciences, Canterbury CT2 7NH, England, ^bDepartment of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, England, and ^cKing's College London, Division of Imaging Sciences and Biomedical Engineering, 4th Floor Lambeth Wing, St Thomas' Hospital, London SE1 7EH, England
^*Correspondence e-mail: m.j.went@kent.ac.uk

Edited by T. J. Prior, University of Hull, England (Received 27 September 2015; accepted 12 October 2015; online 17 October 2015)

In the structure of the title complex, [Zn(C₈H₁₄N₆S₂)(C₅H₅N)], the Zn^II ion has a pseudo-square-pyramidal coordination environment and is displaced by 0.490 Å from the plane of best fit defined by the bis(thiosemicarbazonate) N₂S₂ donor atoms. Chains sustained by intermolecular N—H⋯N and N—H⋯S hydrogen-bonding interactions extend parallel to [10-1].

Keywords: crystal structure; bis(thiosemicarbazone); copper; zinc; hypoxia; PET.

CCDC reference: 1430734

1. Chemical context

Bis(thiosemicarbazonato)copper complexes labelled with ^60/62/64Cu isotopes are useful radiopharmaceuticals for imaging blood flow and hypoxic tissues in vivo (Dearling et al., 2002 ). Bis(thiosemicarbazonato)zinc complexes can act as precursors for bis(thiosemicarbazonato)copper complexes by reaction with copper acetate in water (Holland et al., 2007 ). This synthetic approach can be very useful in the quick, clean synthesis of radio-copper complexes, particularly if the copper isotope has a short half live. A solid-phase synthesis has been developed based on the attachment of a bis(thiosemicarbazonato)zinc complex to 4-(dimethylamino)pyridine functionalized polystyrene resin and elution of the desired radio-copper complex by the addition of a [⁶⁴Cu]copper acetate solution (Betts et al., 2008 ). A number of different polymers for zinc–copper bis(thiosemicarbazonato) transmetalation reactions have been tested and a pyridyl system was found to be optimal (Aphaiwong et al., 2012 ). This communication reports the crystal structure of a zinc bis(thiosemicarbazonato) pyridine complex, [Zn(C₈H₁₄N₆S₂)(C₅H₅N)]. Comparison of the infra-red and Raman spectra indicates that [butane-2,3-dione bis(4-methylthiosemicarbazonato)]zinc(II) coordinates to poly(4-vinylpyridine) (Brown 2015 ).

2. Structural commentary

The molecular structure of [butane-2,3-dione bis(4-methylthiosemicarbazonato)]pyridinezinc is shown in Fig. 1. The Zn^II ion lies in a pseudo-square-pyramidal coordination and is displaced by 0.490 Å from the plane of best fit defined by the bis(thiosemicarbazonate) N₂S₂ donor atoms. In the related 4-(dimethylamino)pyridine complex, the displacement is 0.517 Å (Betts et al., 2008). The Zn–pyridine bond is shorter [2.0900 (18) Å] than the other two bonds to atoms N3 and N4. It is apparent that the ligand cavity is too small to fit the Zn^II ideally, resulting in an N—Zn—N angle of only 74.45 (7)° which may contribute to the ready transmetalations that result in Cu^II complexes with angles of approximately 80° (Blower et al., 2003 ). A comparison of the vibrational spectroscopy of poly(4-vinylpyridine), [butane-2,3-dione bis(4-methylthiosemicarbazonato)]zinc(II) and [butane-2,3-dione bis(4-methylthiosemicarbazonato)]zinc(II) on poly(4-vinylpyridine) can be found in the supporting information.

Figure 1
The molecular structure of the title complex.

3. Supramolecular features

The molecules form a chain via N6—H6⋯S1 (2.65 Å) and N1—H1⋯N5 (2.21 Å) hydrogen bonds (Table 1), as has been seen previously in related Cu^II bis(thiosemicarbazonate) complexes (Blower et al., 2003), with weaker interactions between the chains [H6A⋯S2( $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z) = 2.88 Å and H12⋯N5(−x, 1 − y, 1 − z) = 2.67 Å] (see Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N5ⁱ	0.86	2.21	2.988 (3)	150
N6—H6⋯S1ⁱⁱ	0.86	2.65	3.500 (2)	167
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The chain structure of the title complex formed by N—H⋯N and N—H⋯S hydrogen bonds. The chain direction is parallel to [10 $[\overline1]$ ].

4. Synthesis and crystallization

[Butane-2,3-dione bis(4-methylthiosemicarbazonato)]zinc (0.194 g, 0.60 mmol) was dissolved in DMSO (2 ml). Pyridine (0.06 ml, 0.059 g, 0.70 mol) was added to the solution and left to stir overnight. Water (5 ml) was added to solution. The crystalline precipitate was recovered via filtration, washed with ethanol (1 × 10 ml) and diethyl ether (5 × 10 ml). The solid was dried in air. A yellow solid (0.125 g) was recovered (52% yield).

5. Spectroscopic data

¹H NMR (DMSO-d₆, 400 MHz): δ 8.49 (2H, m, H_(2,6) pyridyl), 7.79 (2H, m, H₍₄₎ pyridyl), 7.39 (2H, m, H_(3,5) pyridyl), 7.18 (2H, s, H₃C-NH), 2.79 (6H, m, HN-CH₃), 2.26 (6H, s, N=C—CH₃). ¹³C {¹H} NMR (DMSO-d₆, 100 MHz): δ 149.72 (C_(2,6) pyridyl), 137.57 (C₍₄₎ pyridyl), 124.90 (C_(3,5) pyridyl), 29.81 (HN—CH₃), 14.47 (N=C—CH₃). IR (cm⁻¹) 3273 (w), 3217 (w), 3001 (w), 2938 (w), 1603 (w), 1530 (m), 1510 (m), 1476 (m), 1447 (m), 1396 (m), 1337 (m), 1250 (s), 1213 (s), 1157 (m), 1072 (s), 1040 (s), 1013 (m), 974 (m), 839 (m), 760 (m), 694 (s), 648 (m), 635 (m), 590 (m), 446 (s). Raman (632.81 nm): cm⁻¹ = 3285 (w), 1613 (w), 1544 (s), 1513 (s), 1478 (m), 1377 (w), 1337 (w), 1285 (m), 1254 (m), 1217 (w), 1190 (w), 1037 (w), 1013 (w), 989 (w),841 (w), 795 (w), 726 (w), 592 (w), 538 (w), 448 (w), 375 (w), 334 (w), 289 (w). Found for Zn₁C₁₃H₁₉N₇S₂: C, 38.8; H, 4.6; N, 24.3. Calculated for Zn₁C₁₃H₁₉N₇S₂: C, 38.8; H, 4.75; N, 24.3%. UV–Vis: λ_max/nm (DMSO) 314 (∊/dm³ mol⁻¹ cm⁻¹ 12 600) and 434 (12 800).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were included in idealized positions and refined as riding: N—H = 0.86 Å, C—H = 0.93 (aromatic) or 0.96 (methyl) Å; U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl). Methyl H atoms were generated in idealized positions and refined as rotating groups. [please check added text]

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(C₈H₁₄N₆S₂)(C₅H₅N)]
M_r	402.84
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	10.1466 (2), 13.9076 (3), 12.7775 (3)
β (°)	104.756 (2)
V (Å³)	1743.64 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.27
Crystal size (mm)	0.26 × 0.04 × 0.02

Data collection
Diffractometer	Agilent SuperNova Dual Source diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.775, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12050, 3445, 3020
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.074, 1.04
No. of reflections	3445
No. of parameters	212
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.42
Computer programs: (CrysAlis PRO; Agilent, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1430734

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019234/pj2023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019234/pj2023Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015019234/pj2023sup3.pdf

checkCIF report

Computing details top

Data collection: (CrysAlis PRO; Agilent, 2014); cell refinement: (CrysAlis PRO; Agilent, 2014); data reduction: (CrysAlis PRO; Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

[Butane-2,3-dione bis(4-methylthiosemicarbazonato)-κ⁴S,N¹,N^1',S'](pyridine-κN)zinc(II) top

Crystal data top

[Zn(C₈H₁₄N₆S₂)(C₅H₅N)]	F(000) = 832
M_r = 402.84	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.1466 (2) Å	Cell parameters from 6492 reflections
b = 13.9076 (3) Å	θ = 4.8–73.0°
c = 12.7775 (3) Å	µ = 4.27 mm⁻¹
β = 104.756 (2)°	T = 150 K
V = 1743.64 (7) Å³	Needle, clear yellow
Z = 4	0.26 × 0.04 × 0.02 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3445 independent reflections
Radiation source: sealed X-ray tube, SuperNova (Cu) X-ray Source	3020 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.041
Detector resolution: 5.2031 pixels mm^-1	θ_max = 73.6°, θ_min = 4.8°
ω scans	h = −7→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −16→17
T_min = 0.775, T_max = 1.000	l = −15→15
12050 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.032P)² + 1.1359P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3445 reflections	Δρ_max = 0.36 e Å⁻³
212 parameters	Δρ_min = −0.42 e Å⁻³
0 restraints

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.30020 (3)	0.73515 (2)	0.47000 (2)	0.01926 (9)
S1	0.44685 (5)	0.79566 (4)	0.36852 (4)	0.02284 (12)
S2	0.14259 (6)	0.85069 (4)	0.50133 (4)	0.02449 (13)
N1	0.68465 (19)	0.71828 (14)	0.37359 (15)	0.0248 (4)
H1	0.6813	0.7600	0.3233	0.030*
N2	0.59011 (19)	0.65189 (13)	0.50031 (15)	0.0235 (4)
N3	0.47831 (18)	0.65526 (13)	0.54215 (14)	0.0203 (4)
N4	0.26884 (18)	0.68075 (13)	0.61711 (14)	0.0213 (4)
N5	0.15519 (18)	0.70523 (13)	0.65027 (14)	0.0215 (4)
N6	−0.02309 (19)	0.80647 (14)	0.62535 (15)	0.0257 (4)
H6	−0.0411	0.7758	0.6785	0.031*
N7	0.17142 (18)	0.64416 (13)	0.35929 (14)	0.0213 (4)
C1	0.8028 (2)	0.65595 (18)	0.4039 (2)	0.0301 (5)
H1A	0.8662	0.6725	0.3624	0.045*
H1B	0.7748	0.5903	0.3898	0.045*
H1C	0.8457	0.6638	0.4796	0.045*
C2	0.5800 (2)	0.71402 (15)	0.42040 (17)	0.0214 (4)
C3	0.4771 (2)	0.60479 (15)	0.62697 (16)	0.0211 (4)
C4	0.5913 (3)	0.54130 (19)	0.6841 (2)	0.0344 (6)
H4A	0.5647	0.4752	0.6712	0.052*
H4B	0.6127	0.5542	0.7604	0.052*
H4C	0.6700	0.5537	0.6575	0.052*
C5	0.3557 (2)	0.61910 (15)	0.66955 (16)	0.0200 (4)
C6	0.3438 (2)	0.56830 (17)	0.76987 (17)	0.0251 (4)
H6A	0.4086	0.5947	0.8314	0.038*
H6B	0.3618	0.5010	0.7639	0.038*
H6C	0.2533	0.5766	0.7788	0.038*
C7	0.0907 (2)	0.78126 (15)	0.59668 (17)	0.0215 (4)
C8	−0.1183 (2)	0.88087 (17)	0.57441 (18)	0.0269 (5)
H8A	−0.1695	0.8591	0.5046	0.040*
H8B	−0.0689	0.9381	0.5662	0.040*
H8C	−0.1794	0.8946	0.6188	0.040*
C9	0.1317 (2)	0.67116 (17)	0.25522 (18)	0.0264 (5)
H9	0.1650	0.7287	0.2350	0.032*
C10	0.0434 (2)	0.61722 (18)	0.17651 (19)	0.0313 (5)
H10	0.0177	0.6381	0.1050	0.038*
C11	−0.0057 (2)	0.53150 (17)	0.2068 (2)	0.0301 (5)
H11	−0.0652	0.4937	0.1558	0.036*
C12	0.0346 (2)	0.50294 (17)	0.3136 (2)	0.0301 (5)
H12	0.0030	0.4455	0.3356	0.036*
C13	0.1226 (2)	0.56104 (16)	0.38725 (18)	0.0247 (4)
H13	0.1492	0.5417	0.4592	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01595 (15)	0.02595 (15)	0.01686 (14)	0.00116 (10)	0.00599 (10)	0.00201 (10)
S1	0.0201 (3)	0.0283 (3)	0.0226 (2)	0.00170 (19)	0.0101 (2)	0.00528 (19)
S2	0.0234 (3)	0.0268 (3)	0.0264 (3)	0.0057 (2)	0.0122 (2)	0.0057 (2)
N1	0.0194 (9)	0.0345 (10)	0.0227 (9)	0.0000 (7)	0.0097 (7)	0.0049 (7)
N2	0.0193 (9)	0.0316 (10)	0.0219 (8)	0.0020 (7)	0.0095 (7)	0.0024 (7)
N3	0.0158 (9)	0.0268 (9)	0.0191 (8)	0.0023 (7)	0.0060 (7)	0.0020 (7)
N4	0.0202 (9)	0.0270 (9)	0.0186 (8)	0.0011 (7)	0.0081 (7)	0.0002 (7)
N5	0.0149 (9)	0.0318 (9)	0.0201 (8)	0.0022 (7)	0.0088 (7)	0.0010 (7)
N6	0.0182 (9)	0.0365 (10)	0.0246 (9)	0.0064 (8)	0.0098 (7)	0.0051 (8)
N7	0.0159 (9)	0.0259 (9)	0.0221 (8)	0.0001 (7)	0.0050 (7)	−0.0005 (7)
C1	0.0169 (11)	0.0405 (13)	0.0358 (12)	0.0037 (9)	0.0118 (9)	0.0010 (10)
C2	0.0176 (10)	0.0268 (10)	0.0209 (10)	−0.0029 (8)	0.0069 (8)	−0.0028 (8)
C3	0.0178 (10)	0.0270 (10)	0.0192 (9)	0.0017 (8)	0.0060 (8)	0.0019 (8)
C4	0.0292 (13)	0.0448 (14)	0.0331 (12)	0.0165 (11)	0.0149 (10)	0.0157 (11)
C5	0.0179 (10)	0.0257 (10)	0.0165 (9)	−0.0013 (8)	0.0047 (8)	−0.0002 (8)
C6	0.0185 (11)	0.0355 (12)	0.0210 (10)	0.0003 (9)	0.0047 (8)	0.0051 (9)
C7	0.0183 (11)	0.0295 (11)	0.0171 (9)	−0.0006 (8)	0.0055 (8)	−0.0036 (8)
C8	0.0209 (11)	0.0346 (12)	0.0263 (11)	0.0062 (9)	0.0077 (9)	−0.0014 (9)
C9	0.0230 (12)	0.0300 (11)	0.0247 (11)	−0.0010 (9)	0.0034 (9)	0.0025 (9)
C10	0.0255 (12)	0.0408 (13)	0.0242 (11)	0.0011 (10)	0.0004 (9)	0.0004 (9)
C11	0.0203 (11)	0.0334 (12)	0.0346 (12)	−0.0013 (9)	0.0032 (9)	−0.0096 (10)
C12	0.0240 (12)	0.0258 (11)	0.0410 (13)	−0.0018 (9)	0.0094 (10)	−0.0021 (10)
C13	0.0197 (11)	0.0274 (11)	0.0280 (11)	0.0017 (9)	0.0080 (8)	0.0037 (9)

Geometric parameters (Å, º) top

Zn1—S1	2.3635 (6)	C1—H1C	0.9600
Zn1—S2	2.3718 (6)	C3—C4	1.491 (3)
Zn1—N3	2.1218 (18)	C3—C5	1.482 (3)
Zn1—N4	2.1241 (17)	C4—H4A	0.9600
Zn1—N7	2.0900 (18)	C4—H4B	0.9600
S1—C2	1.760 (2)	C4—H4C	0.9600
S2—C7	1.738 (2)	C5—C6	1.495 (3)
N1—H1	0.8600	C6—H6A	0.9600
N1—C1	1.450 (3)	C6—H6B	0.9600
N1—C2	1.347 (3)	C6—H6C	0.9600
N2—N3	1.372 (3)	C8—H8A	0.9600
N2—C2	1.321 (3)	C8—H8B	0.9600
N3—C3	1.294 (3)	C8—H8C	0.9600
N4—N5	1.369 (2)	C9—H9	0.9300
N4—C5	1.288 (3)	C9—C10	1.385 (3)
N5—C7	1.337 (3)	C10—H10	0.9300
N6—H6	0.8600	C10—C11	1.385 (4)
N6—C7	1.344 (3)	C11—H11	0.9300
N6—C8	1.452 (3)	C11—C12	1.379 (4)
N7—C9	1.341 (3)	C12—H12	0.9300
N7—C13	1.341 (3)	C12—C13	1.382 (3)
C1—H1A	0.9600	C13—H13	0.9300
C1—H1B	0.9600

S1—Zn1—S2	113.40 (2)	C5—C3—C4	120.98 (18)
N3—Zn1—S1	80.75 (5)	C3—C4—H4A	109.5
N3—Zn1—S2	144.85 (5)	C3—C4—H4B	109.5
N3—Zn1—N4	74.45 (7)	C3—C4—H4C	109.5
N4—Zn1—S1	150.39 (5)	H4A—C4—H4B	109.5
N4—Zn1—S2	80.36 (5)	H4A—C4—H4C	109.5
N7—Zn1—S1	102.52 (5)	H4B—C4—H4C	109.5
N7—Zn1—S2	101.09 (5)	N4—C5—C3	114.89 (18)
N7—Zn1—N3	107.07 (7)	N4—C5—C6	124.51 (19)
N7—Zn1—N4	100.05 (7)	C3—C5—C6	120.51 (18)
C2—S1—Zn1	95.38 (7)	C5—C6—H6A	109.5
C7—S2—Zn1	94.57 (7)	C5—C6—H6B	109.5
C1—N1—H1	118.4	C5—C6—H6C	109.5
C2—N1—H1	118.4	H6A—C6—H6B	109.5
C2—N1—C1	123.16 (19)	H6A—C6—H6C	109.5
C2—N2—N3	111.67 (18)	H6B—C6—H6C	109.5
N2—N3—Zn1	123.07 (13)	N5—C7—S2	127.03 (16)
C3—N3—Zn1	117.35 (14)	N5—C7—N6	114.16 (19)
C3—N3—N2	119.53 (18)	N6—C7—S2	118.75 (17)
N5—N4—Zn1	120.87 (13)	N6—C8—H8A	109.5
C5—N4—Zn1	117.43 (14)	N6—C8—H8B	109.5
C5—N4—N5	121.53 (18)	N6—C8—H8C	109.5
C7—N5—N4	112.29 (17)	H8A—C8—H8B	109.5
C7—N6—H6	117.1	H8A—C8—H8C	109.5
C7—N6—C8	125.71 (19)	H8B—C8—H8C	109.5
C8—N6—H6	117.1	N7—C9—H9	118.5
C9—N7—Zn1	118.66 (15)	N7—C9—C10	122.9 (2)
C13—N7—Zn1	123.45 (15)	C10—C9—H9	118.5
C13—N7—C9	117.86 (19)	C9—C10—H10	120.8
N1—C1—H1A	109.5	C11—C10—C9	118.4 (2)
N1—C1—H1B	109.5	C11—C10—H10	120.8
N1—C1—H1C	109.5	C10—C11—H11	120.4
H1A—C1—H1B	109.5	C12—C11—C10	119.1 (2)
H1A—C1—H1C	109.5	C12—C11—H11	120.4
H1B—C1—H1C	109.5	C11—C12—H12	120.6
N1—C2—S1	114.89 (16)	C11—C12—C13	118.9 (2)
N2—C2—S1	127.89 (17)	C13—C12—H12	120.6
N2—C2—N1	117.2 (2)	N7—C13—C12	122.8 (2)
N3—C3—C4	124.0 (2)	N7—C13—H13	118.6
N3—C3—C5	114.89 (18)	C12—C13—H13	118.6

Zn1—S1—C2—N1	173.89 (15)	N4—N5—C7—N6	178.74 (18)
Zn1—S1—C2—N2	−7.9 (2)	N5—N4—C5—C3	−176.54 (18)
Zn1—S2—C7—N5	17.1 (2)	N5—N4—C5—C6	−0.1 (3)
Zn1—S2—C7—N6	−165.88 (16)	N7—C9—C10—C11	−0.1 (4)
Zn1—N3—C3—C4	177.10 (18)	C1—N1—C2—S1	−179.04 (17)
Zn1—N3—C3—C5	−6.8 (2)	C1—N1—C2—N2	2.6 (3)
Zn1—N4—N5—C7	−15.4 (2)	C2—N2—N3—Zn1	8.8 (2)
Zn1—N4—C5—C3	8.2 (2)	C2—N2—N3—C3	−174.17 (19)
Zn1—N4—C5—C6	−175.37 (16)	C4—C3—C5—N4	175.3 (2)
Zn1—N7—C9—C10	−178.02 (18)	C4—C3—C5—C6	−1.3 (3)
Zn1—N7—C13—C12	178.17 (17)	C5—N4—N5—C7	169.43 (19)
N2—N3—C3—C4	−0.1 (3)	C8—N6—C7—S2	7.9 (3)
N2—N3—C3—C5	175.95 (18)	C8—N6—C7—N5	−174.7 (2)
N3—N2—C2—S1	1.0 (3)	C9—N7—C13—C12	0.2 (3)
N3—N2—C2—N1	179.17 (18)	C9—C10—C11—C12	0.0 (4)
N3—C3—C5—N4	−0.9 (3)	C10—C11—C12—C13	0.2 (3)
N3—C3—C5—C6	−177.50 (19)	C11—C12—C13—N7	−0.4 (3)
N4—N5—C7—S2	−4.1 (3)	C13—N7—C9—C10	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N5ⁱ	0.86	2.21	2.988 (3)	150
N6—H6···S1ⁱⁱ	0.86	2.65	3.500 (2)	167

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

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Aphaiwong, A., Moloney, M. G. & Christlieb, M. (2012). J. Mater. Chem. 22, 24627–24636. Web of Science CrossRef CAS Google Scholar
Betts, H. M., Barnard, P. J., Bayly, S. R., Dilworth, J. R., Gee, A. D. & Holland, J. P. (2008). Angew. Chem. Int. Ed. 47, 8416–8419. Web of Science CSD CrossRef CAS Google Scholar
Blower, P. J., Castle, T. C., Cowley, A. R., Dilworth, J. R., Donnelly, P. S., Labisbal, E., Sowrey, F. E., Teat, S. J. & Went, M. J. (2003). Dalton Trans. pp. 4416–4425. Web of Science CSD CrossRef Google Scholar
Brown, O. C. (2015). PhD thesis, University of Kent, England. Google Scholar
Dearling, J. L. J., Lewis, J. S., Mullen, G. E. D., Welch, M. J. & Blower, P. J. (2002). J. Biol. Inorg. Chem. 7, 249–259. Web of Science CrossRef PubMed CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Holland, J. P., Aigbirhio, F. I., Betts, H. M., Bonnitcha, P. D., Burke, P., Christlieb, M., Churchill, G. C., Cowley, A. R., Dilworth, J. R., Donnelly, P. S., Green, J. C., Peach, J. M., Vasudevan, S. R. & Warren, J. E. (2007). Inorg. Chem. 46, 465–485. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.