Diacetatobis­(tri­methyl­ene­thio­urea)­zinc(II) monohydrate

In the title compound, [Zn(CH₃COO)₂(C₄H₈N₂S)₂]·H₂O, the Zn atom is tetrahedrally coordinated in the ZnO₂S₂ form. N—H...O and O—H...O intramolecular and intermolecular hydrogen bonds are formed by the four N atoms and the water mol­ecule. N—H...O intermolecular hydrogen bonds and C—H...S and C—H...O intermolecular interactions interconnect columns formed by the mol­ecules into layers. Adjacent layers are then linked by other N—H...O and O—H...O intermolecular hydrogen bonds to form a three-dimensional framework throughout the structure. The orientations of the acetate planes are such that the Zn atom lies within them.

S1. Comment

Complexes of metal acetate with thioamides such as bis(acetato)bis(ethylenethiourea)cobalt(II) (Holt, et al., 1970) and bis(acetato)bis(thiourea)zinc(II) (Cavalca, et al., 1967) show weak metal–oxygen interactions in addition to the normal metal–oxygen bond with the acetato group. Our interest in the structures of zinc(II) halides complexed with S-donor ligands led us to the X-ray crystallographic investigation of the title complex, (I). It is also interesting to see the effects of the presence of the weak zinc–oxygen interactions and the water molecules on the structure.

Scheme I

The average lengths of the thioamide N—C [1.319 (4) Å] and S—C [1.734 (4) Å] bonds in the trimethylenethiourea ligands are comparable to the values reported in the free ligand [N—C = 1.334 (6), S—C = 1.722 (7) Å; Dias & Truter, 1964). The reduction of π-electron density in the exocyclic S—C bond for the S atom coordinated to a metal atom results in the lengthening of the S—C bond. This reduction contributes to increased π-electron density in the thioamide N—C bonds, and the corresponding shortening of these N—C bonds. The average Zn—S and Zn—O bond lengths, 2.333 (1) and 1.981 (3) Å, respectively, are comparable with the average values reported in the complexes of [Zn(C₂Cl₃O₂)₂(CH₄N₂S)₂]·H₂O [Zn—S = 2.304 (2), Zn—O = 2.006 (5) Å; Potočňák et al., 1994], Zn[SC(NHCH₂)₂]₂S₂O₃ [Zn—S = 2.320 (8), Zn—O = 2.022 (18) Å; Baggio et al., 1974] and [Zn(C₆H₅COO)₂{CS(NH₂)₂}₂] [Zn—S = 2.367 (1), Zn—O = 1.964 (2) Å; Černák et al., 1995].

The Zn atom is coordinated by a S atom from each of two trimetylenethiourea ligands and one O atom from each of two acetate groups. This ZnO₂S₂ coordination forms a distorted tetrahedron with the angles around the Zn atom ranging from 93.48 (10) to 121.17 (8)°. This type of coordination is also observed in the structures reported by Černák et al. (1995) and Potočňák et al. (1994).

In the crystal, all the N atoms of the thioamide ligands and the water molecules act as hydrogen donors to form N—H···O and O—H···O intramolecular and intermolecular hydrogen bonds. There are also C—H···S and C—H···O intermolecular interactions observed in the crystal (Table 2). Within the asymmetric unit, the water molecule forms an intermolecular O1W-H2W1···O4 hydrogen bond with the Zn complex. The molecules are stacked into columns along the a axis. These columns are interconnected by the N3—H3A···O3(-1/2 + x, 1/2 - y, -1/2 + z) hydrogen bond and the C4—H4D···S2(1/2 + x, 1/2 - y, 1/2 + z) and C10—H10B···O1(-1/2 + x, 1/2 - y, -1/2 + z) interactions into layers which lie perpendicular to the b axis. The layers are then linked by the water molecules through N2—H2A···O1W(1 - x, 1 - y, -z) and O1W-H1W1···O2(-1/2 + x, 1/2 - y, 1/2 + z) interactions. These hydrogen bonds and interactions form a three-dimensional framework throughout the structure.

The Zn1 atom is also involved in weaker interactions with the other two O atoms, O2 and O4, from the carboxylate ligands (Table 3). The Zn1—O1—C1 and Zn1—O3—C3 bond angles are 124.4 (2) and 119.7 (2)°, respectively. The orientation of the planes of the two acetates are determined by the Zn1—O1, Zn1—O2, Zn1—O3 and Zn1—O4 interactions (Cavalca et al., 1967). The two acetate groups are nearly co-planar, the dihedral angle between them being 11.1 (3)°. The Zn1 atom lies 0.116 (1) and 0.075 (1) Å from the acetate planes defined by O1, O2, C1 and C2, and O3, O4, C3 and C4, respectively. As a result, the orientations of the acetate planes are such that Zn1 lies virtually on them. This observation is also reported by Cavalca et al. (1967) [Zn···O = 2.996 (5) and 2.891 (9) Å, Zn—O—C = 119.4 (6) and 118.2 (7)°, Zn–Plane_acetates = 0.095 and 0.036 Å]. Other short contacts observed in the structure are listed in Table 3.

S2. Experimental

Solutions of zinc acetate (0.257 g, 1.17 mmol) and tetrahydropyrimidine-2-thione (0.271 g, 2.34 mmol) in acetonitrile were mixed in a 1:2 molar ratio in a 50 ml flask and the mixture was stirred for about 30 minutes. The solution was then filtered into another flask and left to evaporate slowly. After a few days, some single crystals were collected, washed with hexane and dried (m.p. 400 K).

S3. Refinement

After checking their presence in the difference map, the positions of all H atoms of the Zn complex were geometrically idealized and allowed to ride on their parent atoms with C—H distances in the range 0.96–0.97 Å, N—H distances of 0.88 Å and fixed displacement parameters defined by U_iso(H) = 1.2U_eq(parent atom) or 1.5U_eq(C_methyl). The H atoms of the water molecule were refined isotropically. Owing to large fraction of weak data at higher angles, the 2θ maximum was limited to 50°. The highest peak and the deepest hole are 0.97 and 1.03 Å from O3 and Zn1, respectively. Atom C11 in one of the trimethylenethiourea rings is disordered and was refined with an occupancy ratio of 0.75:0.25.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995), PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. The open bonds depict the alternate disordered arrangement involving C11.
	Fig. 2. The three-dimensional framework viewed down the a axis, showing the hydrogen bonding and intermolecular contacts.

Diacetatobis(trimethylenethiourea)zinc(II) Monohydrate

Crystal data

C12H22N4O4S2Zn·H2O	Dx = 1.453 Mg m^−3
Mr = 433.84	Melting point: 400K K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.7517 (1) Å	Cell parameters from 8192 reflections
b = 17.3654 (2) Å	θ = 2.0–29.4°
c = 13.0543 (2) Å	µ = 1.48 mm^−1
β = 90.837 (1)°	T = 293 K
V = 1983.74 (4) Å^3	Slab, colourless
Z = 4	0.16 × 0.12 × 0.10 mm
F(000) = 904

Data collection

Siemens SMART CCD area-detector diffractometer	3495 independent reflections
Radiation source: fine-focus sealed tube	2645 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.097
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 2.0°
ω scans	h = −9→10
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −20→19
Tmin = 0.798, Tmax = 0.867	l = −15→10
11176 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0693P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3495 reflections	Δρmax = 0.54 e Å^−3
238 parameters	Δρmin = −1.37 e Å^−3
2 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0165 (16)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.57847 (4)	0.250169 (19)	0.53877 (3)	0.0358 (2)
S1	0.76157 (11)	0.31906 (6)	0.44927 (7)	0.0499 (3)
S2	0.34630 (11)	0.24216 (5)	0.44875 (8)	0.0451 (3)
O1	0.6330 (3)	0.14138 (14)	0.56550 (18)	0.0507 (7)
O2	0.6449 (4)	0.10394 (15)	0.4038 (2)	0.0618 (8)
O3	0.5858 (3)	0.27839 (14)	0.68607 (17)	0.0464 (6)
O4	0.4660 (3)	0.38806 (15)	0.65645 (18)	0.0536 (7)
N1	0.6499 (4)	0.23990 (17)	0.2885 (3)	0.0505 (9)
H1A	0.6629	0.2006	0.3277	0.061*
N2	0.6875 (4)	0.36776 (18)	0.2620 (2)	0.0531 (8)
H2A	0.7165	0.4118	0.2855	0.064*
N3	0.1875 (3)	0.34003 (17)	0.3369 (2)	0.0432 (7)
H3A	0.1687	0.2998	0.3005	0.052*
N4	0.3255 (4)	0.39478 (16)	0.4667 (2)	0.0487 (8)
H4A	0.3880	0.3885	0.5175	0.058*
C1	0.6593 (5)	0.0923 (2)	0.4966 (3)	0.0492 (9)
C2	0.7095 (7)	0.0134 (2)	0.5336 (4)	0.0832 (16)
H2B	0.8057	0.0177	0.5694	0.125*
H2C	0.7204	−0.0203	0.4759	0.125*
H2D	0.6343	−0.0071	0.5789	0.125*
C3	0.5250 (4)	0.34119 (19)	0.7156 (3)	0.0389 (8)
C4	0.5290 (5)	0.3577 (3)	0.8281 (3)	0.0589 (11)
H4B	0.4762	0.3176	0.8638	0.088*
H4C	0.4801	0.4061	0.8408	0.088*
H4D	0.6332	0.3599	0.8519	0.088*
C5	0.6940 (4)	0.30764 (19)	0.3243 (3)	0.0419 (8)
C6	0.5805 (7)	0.2266 (3)	0.1874 (3)	0.0710 (14)
H6A	0.4992	0.1889	0.1925	0.085*
H6B	0.6566	0.2067	0.1411	0.085*
C7	0.5176 (6)	0.3007 (3)	0.1467 (3)	0.0680 (13)
H7A	0.4268	0.3147	0.1842	0.082*
H7B	0.4888	0.2945	0.0751	0.082*
C8	0.6346 (6)	0.3636 (3)	0.1570 (3)	0.0702 (13)
H8A	0.7199	0.3531	0.1126	0.084*
H8B	0.5898	0.4125	0.1367	0.084*
C9	0.2838 (4)	0.33344 (19)	0.4158 (2)	0.0370 (8)
C10	0.1116 (5)	0.4125 (2)	0.3085 (3)	0.0573 (10)
H10A	0.0151	0.4168	0.3437	0.069*	0.75
H10B	0.0910	0.4135	0.2353	0.069*	0.75
H10C	0.0046	0.4031	0.2925	0.069*	0.25
H10D	0.1591	0.4344	0.2485	0.069*	0.25
C11A	0.2140 (8)	0.4780 (3)	0.3380 (5)	0.0673 (17)	0.75
H11A	0.2990	0.4797	0.2912	0.081*	0.75
H11B	0.1576	0.5258	0.3305	0.081*	0.75
C11B	0.1257 (18)	0.4666 (9)	0.3961 (13)	0.049 (4)	0.25
H11C	0.0956	0.5174	0.3725	0.059*	0.25
H11D	0.0534	0.4510	0.4478	0.059*	0.25
C12	0.2750 (6)	0.4727 (2)	0.4445 (3)	0.0680 (13)
H12A	0.3601	0.5080	0.4531	0.082*	0.75
H12B	0.1962	0.4875	0.4922	0.082*	0.75
H12C	0.2691	0.5025	0.5072	0.082*	0.25
H12D	0.3459	0.4980	0.3990	0.082*	0.25
O1W	0.2152 (4)	0.47623 (19)	0.7228 (3)	0.0646 (8)
H1W1	0.182 (7)	0.457 (4)	0.779 (4)	0.14 (3)*
H2W1	0.277 (6)	0.446 (3)	0.707 (5)	0.12 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0469 (3)	0.0312 (3)	0.0292 (3)	0.00422 (16)	−0.0008 (2)	−0.00182 (14)
S1	0.0564 (6)	0.0465 (6)	0.0466 (6)	−0.0130 (4)	−0.0005 (4)	0.0017 (4)
S2	0.0473 (6)	0.0366 (5)	0.0511 (7)	−0.0026 (4)	−0.0114 (4)	−0.0032 (4)
O1	0.0792 (19)	0.0347 (13)	0.0382 (15)	0.0122 (12)	−0.0008 (12)	−0.0029 (11)
O2	0.108 (2)	0.0390 (15)	0.0391 (17)	−0.0013 (15)	0.0103 (14)	−0.0018 (11)
O3	0.0658 (17)	0.0402 (14)	0.0332 (14)	0.0130 (13)	−0.0029 (11)	−0.0062 (11)
O4	0.0799 (18)	0.0445 (15)	0.0358 (14)	0.0166 (13)	−0.0117 (12)	−0.0011 (11)
N1	0.080 (3)	0.0390 (18)	0.0323 (19)	−0.0068 (15)	0.0064 (16)	0.0036 (12)
N2	0.073 (2)	0.0404 (18)	0.046 (2)	−0.0016 (16)	0.0104 (16)	0.0070 (14)
N3	0.0529 (18)	0.0409 (17)	0.0357 (17)	−0.0010 (14)	−0.0077 (13)	−0.0043 (13)
N4	0.069 (2)	0.0394 (17)	0.0375 (17)	0.0030 (15)	−0.0204 (14)	−0.0047 (13)
C1	0.065 (2)	0.0324 (19)	0.050 (3)	0.0035 (17)	0.0095 (18)	0.0001 (17)
C2	0.139 (5)	0.046 (3)	0.065 (3)	0.033 (3)	0.002 (3)	0.004 (2)
C3	0.049 (2)	0.0343 (18)	0.0338 (19)	−0.0006 (16)	−0.0030 (15)	−0.0059 (15)
C4	0.078 (3)	0.066 (3)	0.032 (2)	0.024 (2)	−0.0161 (18)	−0.0139 (18)
C5	0.047 (2)	0.0363 (19)	0.043 (2)	−0.0018 (16)	0.0124 (16)	0.0032 (16)
C6	0.114 (4)	0.057 (3)	0.042 (3)	−0.022 (3)	0.011 (2)	−0.004 (2)
C7	0.075 (3)	0.093 (4)	0.035 (2)	0.000 (3)	−0.007 (2)	0.002 (2)
C8	0.111 (4)	0.051 (2)	0.049 (3)	0.011 (3)	0.017 (2)	0.012 (2)
C9	0.0406 (18)	0.0412 (19)	0.0294 (18)	−0.0015 (15)	0.0044 (14)	0.0004 (14)
C10	0.067 (3)	0.054 (3)	0.051 (2)	0.007 (2)	−0.0092 (19)	0.0046 (19)
C11A	0.092 (5)	0.048 (3)	0.062 (4)	−0.005 (3)	−0.032 (4)	0.014 (3)
C11B	0.048 (9)	0.047 (9)	0.052 (10)	0.008 (7)	−0.001 (7)	0.005 (7)
C12	0.103 (4)	0.040 (2)	0.060 (3)	0.004 (2)	−0.027 (2)	−0.0026 (19)
O1W	0.089 (2)	0.0424 (16)	0.063 (2)	0.0147 (16)	0.0091 (17)	0.0125 (15)

Geometric parameters (Å, º)

Zn1—O1	1.978 (2)	C4—H4C	0.9600
Zn1—O3	1.984 (2)	C4—H4D	0.9600
Zn1—S1	2.328 (1)	C6—C7	1.494 (7)
Zn1—S2	2.337 (1)	C6—H6A	0.9700
S1—C5	1.739 (4)	C6—H6B	0.9700
S2—C9	1.729 (3)	C7—C8	1.502 (6)
O1—C1	1.263 (4)	C7—H7A	0.9700
O2—C1	1.233 (4)	C7—H7B	0.9700
O3—C3	1.276 (4)	C8—H8A	0.9700
O4—C3	1.230 (4)	C8—H8B	0.9700
N1—C5	1.322 (4)	C10—C11B	1.484 (16)
N1—C6	1.463 (6)	C10—C11A	1.496 (7)
N1—H1A	0.8600	C10—H10A	0.9700
N2—C5	1.324 (4)	C10—H10B	0.9700
N2—C8	1.442 (6)	C10—H10C	0.9700
N2—H2A	0.8600	C10—H10D	0.9700
N3—C9	1.326 (4)	C11A—C12	1.485 (7)
N3—C10	1.468 (5)	C11A—H11A	0.9700
N3—H3A	0.8600	C11A—H11B	0.9700
N4—C9	1.305 (4)	C11B—C12	1.447 (16)
N4—C12	1.452 (5)	C11B—H11C	0.9700
N4—H4A	0.8600	C11B—H11D	0.9700
C1—C2	1.516 (5)	C12—H12A	0.9700
C2—H2B	0.9600	C12—H12B	0.9700
C2—H2C	0.9600	C12—H12C	0.9700
C2—H2D	0.9600	C12—H12D	0.9700
C3—C4	1.497 (5)	O1W—H1W1	0.86 (4)
C4—H4B	0.9600	O1W—H2W1	0.79 (4)
O1—Zn1—O3	93.48 (10)	C8—C7—H7A	109.6
O1—Zn1—S1	114.42 (8)	C6—C7—H7B	109.6
O3—Zn1—S1	110.28 (8)	C8—C7—H7B	109.6
O1—Zn1—S2	103.74 (8)	H7A—C7—H7B	108.1
O3—Zn1—S2	121.17 (8)	N2—C8—C7	109.3 (3)
S1—Zn1—S2	112.22 (4)	N2—C8—H8A	109.8
C5—S1—Zn1	100.68 (12)	C7—C8—H8A	109.8
C9—S2—Zn1	109.89 (12)	N2—C8—H8B	109.8
C1—O1—Zn1	124.4 (2)	C7—C8—H8B	109.8
C3—O3—Zn1	119.7 (2)	H8A—C8—H8B	108.3
C5—N1—C6	125.1 (3)	N4—C9—N3	119.7 (3)
C5—N1—H1A	117.5	N4—C9—S2	122.4 (3)
C6—N1—H1A	117.5	N3—C9—S2	117.9 (3)
C5—N2—C8	123.7 (3)	N3—C10—C11B	108.4 (6)
C5—N2—H2A	118.2	N3—C10—C11A	108.7 (4)
C8—N2—H2A	118.2	N3—C10—H10A	110.0
C9—N3—C10	123.4 (3)	C11A—C10—H10A	110.0
C9—N3—H3A	118.3	N3—C10—H10B	110.0
C10—N3—H3A	118.3	C11A—C10—H10B	110.0
C9—N4—C12	125.2 (3)	H10A—C10—H10B	108.3
C9—N4—H4A	117.4	N3—C10—H10C	110.0
C12—N4—H4A	117.4	C11B—C10—H10C	110.0
O2—C1—O1	124.9 (3)	N3—C10—H10D	110.0
O2—C1—C2	119.1 (4)	C11B—C10—H10D	110.0
O1—C1—C2	116.0 (4)	H10C—C10—H10D	108.4
C1—C2—H2B	109.5	C12—C11A—C10	113.6 (5)
C1—C2—H2C	109.5	C12—C11A—H11A	108.9
H2B—C2—H2C	109.5	C10—C11A—H11A	108.9
C1—C2—H2D	109.5	C12—C11A—H11B	108.9
H2B—C2—H2D	109.5	C10—C11A—H11B	108.9
H2C—C2—H2D	109.5	H11A—C11A—H11B	107.7
O4—C3—O3	123.3 (3)	C12—C11B—C10	116.6 (11)
O4—C3—C4	119.6 (3)	C12—C11B—H11C	108.1
O3—C3—C4	117.1 (3)	C10—C11B—H11C	108.1
C3—C4—H4B	109.5	C12—C11B—H11D	108.1
C3—C4—H4C	109.5	C10—C11B—H11D	108.1
H4B—C4—H4C	109.5	H11C—C11B—H11D	107.3
C3—C4—H4D	109.5	C11B—C12—N4	106.8 (7)
H4B—C4—H4D	109.5	N4—C12—C11A	110.4 (4)
H4C—C4—H4D	109.5	N4—C12—H12A	109.6
N1—C5—N2	118.4 (4)	C11A—C12—H12A	109.6
N1—C5—S1	121.8 (3)	N4—C12—H12B	109.6
N2—C5—S1	119.8 (3)	C11A—C12—H12B	109.6
N1—C6—C7	109.3 (4)	H12A—C12—H12B	108.1
N1—C6—H6A	109.8	C11B—C12—H12C	110.4
C7—C6—H6A	109.8	N4—C12—H12C	110.4
N1—C6—H6B	109.8	C11B—C12—H12D	110.4
C7—C6—H6B	109.8	N4—C12—H12D	110.4
H6A—C6—H6B	108.3	H12C—C12—H12D	108.6
C6—C7—C8	110.3 (4)	H1W1—O1W—H2W1	102 (6)
C6—C7—H7A	109.6
O1—Zn1—S1—C5	93.70 (15)	Zn1—S1—C5—N1	−46.2 (3)
O3—Zn1—S1—C5	−162.48 (14)	Zn1—S1—C5—N2	134.5 (3)
S2—Zn1—S1—C5	−24.15 (13)	C5—N1—C6—C7	−19.8 (6)
O1—Zn1—S2—C9	−178.43 (13)	N1—C6—C7—C8	48.7 (5)
O3—Zn1—S2—C9	78.81 (15)	C5—N2—C8—C7	30.2 (6)
S1—Zn1—S2—C9	−54.40 (13)	C6—C7—C8—N2	−53.9 (5)
O3—Zn1—O1—C1	−173.9 (3)	C12—N4—C9—N3	0.0 (6)
S1—Zn1—O1—C1	−59.8 (3)	C12—N4—C9—S2	−178.7 (3)
S2—Zn1—O1—C1	62.8 (3)	C10—N3—C9—N4	−6.3 (5)
O1—Zn1—O3—C3	−164.1 (3)	C10—N3—C9—S2	172.4 (3)
S1—Zn1—O3—C3	78.2 (3)	Zn1—S2—C9—N4	−24.5 (3)
S2—Zn1—O3—C3	−55.8 (3)	Zn1—S2—C9—N3	156.8 (2)
Zn1—O1—C1—O2	−5.1 (6)	C9—N3—C10—C11B	−15.7 (9)
Zn1—O1—C1—C2	176.0 (3)	C9—N3—C10—C11A	30.5 (6)
Zn1—O3—C3—O4	−3.1 (5)	N3—C10—C11A—C12	−48.8 (7)
Zn1—O3—C3—C4	177.7 (3)	N3—C10—C11B—C12	45.8 (14)
C6—N1—C5—N2	−5.9 (6)	C10—C11B—C12—N4	−50.6 (14)
C6—N1—C5—S1	174.8 (4)	C9—N4—C12—C11B	27.5 (9)
C8—N2—C5—N1	0.1 (6)	C9—N4—C12—C11A	−19.4 (7)
C8—N2—C5—S1	179.4 (3)	C10—C11A—C12—N4	44.0 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.86	1.96	2.801 (4)	166
N4—H4A···O4	0.86	1.93	2.752 (4)	160
O1W—H2W1···O4	0.78 (5)	2.05 (5)	2.823 (4)	167 (5)
N2—H2A···O1W^i	0.86	2.04	2.846 (5)	156
N3—H3A···O3^ii	0.86	2.14	2.974 (4)	164
O1W—H1W1···O2^iii	0.86 (6)	1.97 (6)	2.818 (5)	167 (6)
C4—H4D···S2^iv	0.96	2.86	3.615 (5)	137
C10—H10B···O1^ii	0.97	2.45	3.315 (5)	149

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