Bis­(diethyl­enetri­amine-κ³N)­nickel(II) 5-amino-1,3,4-thia­diazo­le-2-sulfonamidate chloride monohydrate

In the X-ray crystal structure of the title complex, [Ni(C₄H₁₃N₃)₂](C₂H₃N₄O₂S₂)Cl·H₂O, the coordination polyhedron is composed of non-centrosymmetric [Ni(diethyl­enetri­amine)₂]²⁺ cations in which the tri­amine ligands coordinate to the metal centre as tridentate ligands in a facial position. The Ni^II ions are linked to six N atoms in an octahedral arrangement, slightly compressed in one extreme. The sulfon­amide behaves as a counter-ion instead of as a ligand. Important information about the deprotonated sulfon­amide group conformation has been obtained.

S1. Comment

Heterocyclic sulfonamides constitute an important group of carbonic anhydrase inhibitors. The inhibition of this enzyme by sulfonamide drugs finds clinical application in the treatment of glaucoma, epilepsy and other disorders. Acetazolamide (5-acetamido-1,3,4-thiadiazole-2-sulfonamide) has shown to be one of the most potent inhibitors (Evelhoch et al., 1981). The search for new sulfonamides with major pharmacological potency, low toxicity and few side effects still continues (Jallon, 1997). Hats (5-amino-1,3,4- thiadiazole-2-sulfonamide), an acetazolamide analogue, has shown to be more potent than acetazolamide as anticonvulsant in mice, although its low inhibition ability on carbonic anhydrase (Chufán, Pedregosa, Baldini & Bruno-Blanch et al., 1999).

The knowledge of the interactions of sulfonamides with carbonic anhydrase (or its structural models) is of great pharmacological and therapeutic interest. Thus, metallic complexes with Hats were synthesized and some crystal structures were determined (Chufán et al., 1997; Borja et al., 1998; Chufán, 1999). The crystal structure of [Zn(ats)₂(NH₃)]·H₂O in which the sulfonamide presents two different coordination behaviours: as monodentate ligand through the N-sulfonamido atom and as a bridging ligand, linking the zinc ions through the N-sulfonamido and the N-thiadiazole atoms are reported (Borja et al., 1998). Recently, we have synthesized a new copper complex, [Cu(ats)₂(dipn)] (dipn = dipropylenetriamine), where the sulfonamide also shows two coordination modes: as monodentate ligand in the same way that in the zinc(II) complex described above and as a bridging ligand, linking the copper ions through the O-sulfonamido and the N-sulfonamido atoms (Chufán, Pedregosa, Ferrer & Borrás et al., 1999).

In the present paper, we report the crystal structure of [Ni(dien)₂](ats)(Cl)·H₂O (dien = diethylenetriamine), (I), in which the sulfonamide behaves as a counter-ion instead of a ligand. It is noteworthy that this is the first reported metal complex structure where the Hats sulfonamide acts as a counter-ion. \sch

The main structural difference between the sulfonamidate anion and the free sulfonamide is the shortening of the N—S bond, see Table 1. This is due to deprotonation of the sulfonamido group and subsequent delocalization of the negative charge through the N—S bond. This phenomenon is also present in [Zn(ats)₂(NH₃)]·H₂O, but in an attenuate way because of the N-sulfonamido atom being in a coordination site. The increasing of the (C—S) exocyclic bond is also attributed to electronic delocalization after deprotonation. These facts are evidence that structural properties are more affected by deprotonation than by coordination effects, as was concluded by vibrational spectroscopy for similar metal complexes (Chufán, Pedregosa, Ferrer & Borrás et al., 1999).

The coordination polyhedron consists of [Ni(dien)₂]²⁺ unities, in which the diethylenetriamine coordinates to the metal center as a tridentate ligand in facial position. The Ni^II ions are linked to six N atoms, forming NiN₆ cromophores with octahedral geometry. On the other hand, the comparison between the differences of the angles at Ni (see Table 1) are due to the spanning of the dimethylene groups.

The analogous complex [Cu(dipn)(ats)₂] was synthesized with the same metal:triamine:sulfonamide molar ratio (1:2:2) and similar experimental conditions. The reason by which in the copper(II) complex the bis(triamine) is not formed, is related with the fact that the copper(II) ion is subject to Jahn-Teller effect whose typical distortion is an elongation along one fourfold axis, so that there is a planar array of four short Cu—L bonds and two trans long ones (Cotton & Wilkinson, 1988).

S2. Experimental

The title complex, [Ni(dien)₂](ats)Cl·H₂O, was prepared by mixing nickel(II) chloride hexahydrate (1 mmol), diethylenetriamine (2 mmol) and 5-amino-1,3,4-thiadiazole-2-sulfonamide (2 mmol) in ethanol (50 ml), at room temperature. Single crystals were obtained after one month from the resulting pale purple solution.

S3. Refinement

All hydrogen atoms were localized geometrically and refined as riding, except H331 and the water H atoms that were located in subsequent difference Fourier maps. These atoms were refined.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1997); cell refinement: CAD-4 Software; data reduction: Process in Omolen (Nonius, 1997); program(s) used to solve structure: DIRDIF (Beurskens, 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. View (ORTEPII; Johnson, 1976) of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 50% probability level; H atoms are drawn as small circles of arbitrary radius.

Bis(diethylenetriamine)nickel(II) 5-amino-1,3,4-thiadiazole-2- sulfonamidate chloride hydrate.

Crystal data

[Ni(C4H13N3)2](C2H3N4O2S2)Cl·H2O	F(000) = 1024
Mr = 497.73	Dx = 1.567 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.378 (6) Å	Cell parameters from 25 reflections
b = 11.099 (10) Å	θ = 1.8–25.0°
c = 23.042 (12) Å	µ = 1.28 mm^−1
β = 99.44 (5)°	T = 293 K
V = 2114 (3) Å^3	Prismatic, red
Z = 4	0.15 × 0.10 × 0.10 mm

Data collection

Enraf-Nonius Cad-4 difractometer diffractometer	2685 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.8°
Graphite monochromator	h = 0→9
ω–2θ scans	k = 0→13
Absorption correction: ψ scan (North et al., 1968)	l = −27→26
Tmin = 0.774, Tmax = 0.880	60 standard reflections every 1000 reflections
3706 measured reflections	intensity decay: 0.1%
3706 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 4.4405P] where P = (Fo^2 + 2Fc^2)/3
3706 reflections	(Δ/σ)max = 0.042
264 parameters	Δρmax = 0.67 e Å^−3
6 restraints	Δρmin = −0.50 e Å^−3

Special details

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
Ni	0.40181 (9)	0.30325 (7)	0.84560 (3)	0.0268 (3)
N11	0.1522 (7)	0.3011 (6)	0.8507 (3)	0.0459 (15)
H11A	0.1285	0.3586	0.8755	0.071 (10)*
H11B	0.0929	0.3141	0.8150	0.071 (10)*
N12	0.4079 (6)	0.1676 (5)	0.9112 (2)	0.0336 (13)
H12	0.4530	0.0995	0.8990	0.028 (12)*
N13	0.4679 (7)	0.4136 (5)	0.9208 (2)	0.0423 (15)
H13A	0.5670	0.4448	0.9206	0.071 (10)*
H13B	0.3974	0.4751	0.9199	0.075 (11)*
C11	0.1176 (10)	0.1805 (9)	0.8727 (4)	0.070 (3)
H111	0.0134	0.1822	0.8859	0.076 (7)*
H112	0.1109	0.1229	0.8408	0.076 (7)*
C12	0.2413 (9)	0.1408 (8)	0.9213 (4)	0.056 (2)
H121	0.2307	0.0546	0.9267	0.076 (7)*
H122	0.2232	0.1802	0.9572	0.076 (7)*
C13	0.5105 (9)	0.2139 (7)	0.9640 (3)	0.0487 (19)
H131	0.6232	0.2085	0.9593	0.076 (7)*
H132	0.4956	0.1653	0.9977	0.076 (7)*
C14	0.4681 (10)	0.3432 (7)	0.9744 (3)	0.052 (2)
H141	0.3621	0.3470	0.9861	0.076 (7)*
H142	0.5463	0.3766	1.0060	0.076 (7)*
N21	0.3750 (7)	0.1739 (4)	0.7766 (2)	0.0336 (13)
H21A	0.3576	0.1007	0.7913	0.071 (10)*
H21B	0.2885	0.1929	0.7496	0.071 (10)*
N22	0.6447 (6)	0.3024 (5)	0.8293 (3)	0.0367 (13)
H22	0.7122	0.2965	0.8644	0.028 (12)*
N23	0.3840 (7)	0.4509 (5)	0.7883 (3)	0.0417 (15)
H23A	0.2967	0.4417	0.7602	0.071 (10)*
H23B	0.3703	0.5186	0.8084	0.071 (10)*
C21	0.5194 (9)	0.1697 (6)	0.7487 (3)	0.0458 (19)
H211	0.5104	0.2292	0.7175	0.076 (7)*
H212	0.5284	0.0908	0.7313	0.076 (7)*
C22	0.6688 (9)	0.1947 (7)	0.7935 (4)	0.0478 (19)
H221	0.6925	0.1254	0.8191	0.076 (7)*
H222	0.7605	0.2079	0.7734	0.076 (7)*
C23	0.6735 (9)	0.4190 (7)	0.8024 (4)	0.050 (2)
H231	0.7637	0.4110	0.7811	0.076 (7)*
H232	0.7030	0.4783	0.8332	0.076 (7)*
C24	0.5278 (11)	0.4632 (7)	0.7609 (3)	0.059 (2)
H241	0.5427	0.5471	0.7512	0.076 (7)*
H242	0.5147	0.4168	0.7248	0.076 (7)*
S3	0.4583 (2)	−0.16955 (14)	0.82795 (7)	0.0355 (4)
O31	0.3478 (6)	−0.0730 (5)	0.8377 (3)	0.0607 (16)
O32	0.5118 (7)	−0.1628 (7)	0.7720 (2)	0.083 (2)
N33	0.4032 (8)	−0.2958 (5)	0.8401 (3)	0.0537 (18)
H331	0.346 (17)	−0.274 (15)	0.875 (5)	0.23 (8)*
C41	0.6403 (7)	−0.1369 (5)	0.8782 (3)	0.0297 (14)
S4	0.7967 (2)	−0.23924 (15)	0.88958 (8)	0.0420 (5)
N41	0.6663 (7)	−0.0382 (5)	0.9071 (2)	0.0358 (13)
N42	0.8190 (6)	−0.0338 (5)	0.9405 (2)	0.0365 (13)
C42	0.9014 (8)	−0.1323 (6)	0.9360 (3)	0.0334 (15)
N5	1.0510 (7)	−0.1509 (5)	0.9644 (3)	0.0522 (18)
H51	1.0990	−0.0962	0.9874	0.062 (18)*
H52	1.0997	−0.2176	0.9599	0.062 (18)*
Cl	0.1326 (2)	0.58261 (17)	0.91968 (9)	0.0515 (5)
O6	0.8403 (9)	0.4150 (7)	0.9406 (3)	0.085 (2)
H61	0.943 (7)	0.444 (11)	0.935 (6)	0.14 (3)*
H62	0.847 (15)	0.437 (11)	0.9807 (18)	0.14 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0324 (5)	0.0197 (4)	0.0267 (4)	0.0026 (3)	0.0000 (3)	−0.0042 (3)
N11	0.034 (3)	0.057 (4)	0.045 (4)	0.005 (3)	0.001 (3)	−0.008 (3)
N12	0.044 (3)	0.030 (3)	0.027 (3)	0.002 (2)	0.006 (2)	−0.003 (2)
N13	0.046 (3)	0.036 (3)	0.042 (3)	0.007 (3)	−0.003 (3)	−0.016 (3)
C11	0.054 (5)	0.087 (7)	0.072 (6)	−0.024 (5)	0.015 (5)	0.003 (6)
C12	0.055 (5)	0.062 (5)	0.051 (5)	−0.004 (4)	0.013 (4)	0.009 (4)
C13	0.056 (5)	0.055 (5)	0.032 (4)	0.009 (4)	−0.002 (3)	−0.003 (4)
C14	0.064 (5)	0.054 (5)	0.036 (4)	0.009 (4)	0.000 (4)	−0.019 (4)
N21	0.046 (3)	0.026 (3)	0.027 (3)	−0.001 (2)	0.003 (2)	−0.003 (2)
N22	0.032 (3)	0.035 (3)	0.042 (3)	0.004 (2)	0.002 (2)	0.004 (3)
N23	0.052 (4)	0.027 (3)	0.041 (3)	0.000 (3)	−0.011 (3)	0.005 (3)
C21	0.067 (5)	0.035 (4)	0.041 (4)	0.000 (3)	0.025 (4)	−0.015 (3)
C22	0.050 (4)	0.039 (4)	0.058 (5)	0.008 (3)	0.020 (4)	0.002 (4)
C23	0.051 (5)	0.044 (4)	0.058 (5)	−0.016 (4)	0.016 (4)	0.003 (4)
C24	0.095 (7)	0.038 (4)	0.042 (5)	0.000 (4)	0.006 (4)	0.016 (4)
S3	0.0405 (9)	0.0345 (9)	0.0289 (8)	0.0026 (7)	0.0022 (7)	0.0010 (7)
O31	0.061 (3)	0.047 (3)	0.066 (4)	0.013 (3)	−0.014 (3)	−0.002 (3)
O32	0.069 (4)	0.148 (7)	0.031 (3)	−0.032 (4)	0.004 (3)	0.002 (4)
N33	0.066 (4)	0.030 (3)	0.059 (4)	−0.004 (3)	−0.010 (4)	−0.009 (3)
C41	0.037 (4)	0.024 (3)	0.029 (3)	−0.001 (3)	0.004 (3)	0.000 (3)
S4	0.0468 (10)	0.0301 (9)	0.0444 (10)	0.0071 (8)	−0.0067 (8)	−0.0144 (8)
N41	0.047 (3)	0.027 (3)	0.031 (3)	0.002 (2)	−0.001 (2)	−0.007 (2)
N42	0.041 (3)	0.025 (3)	0.040 (3)	0.003 (2)	−0.004 (3)	−0.010 (2)
C42	0.036 (4)	0.032 (4)	0.031 (3)	0.001 (3)	0.001 (3)	−0.007 (3)
N5	0.048 (4)	0.036 (3)	0.064 (4)	0.011 (3)	−0.017 (3)	−0.022 (3)
Cl	0.0525 (11)	0.0430 (10)	0.0589 (12)	0.0088 (9)	0.0091 (9)	−0.0080 (9)
O6	0.081 (5)	0.108 (6)	0.060 (4)	−0.041 (4)	−0.008 (4)	0.001 (4)

Geometric parameters (Å, º)

Ni—N23	2.094 (5)	N22—H22	0.9100
Ni—N11	2.114 (6)	N23—C24	1.455 (13)
Ni—N13	2.123 (5)	N23—H23A	0.9000
Ni—N21	2.126 (5)	N23—H23B	0.9000
Ni—N22	2.129 (6)	C21—C22	1.514 (12)
Ni—N12	2.129 (5)	C21—H211	0.9700
N11—C11	1.474 (10)	C21—H212	0.9700
N11—H11A	0.9000	C22—H221	0.9700
N11—H11B	0.9000	C22—H222	0.9700
N12—C13	1.461 (9)	C23—C24	1.506 (12)
N12—C12	1.484 (13)	C23—H231	0.9700
N12—H12	0.9100	C23—H232	0.9700
N13—C14	1.465 (10)	C24—H241	0.9700
N13—H13A	0.9000	C24—H242	0.9700
N13—H13B	0.9000	S3—O32	1.432 (6)
C11—C12	1.463 (12)	S3—O31	1.459 (7)
C11—H111	0.9700	S3—N33	1.513 (7)
C11—H112	0.9700	S3—C41	1.792 (10)
C12—H121	0.9700	N33—H331	1.03 (13)
C12—H122	0.9700	C41—N41	1.283 (8)
C13—C14	1.507 (10)	C41—S4	1.723 (9)
C13—H131	0.9700	S4—C42	1.738 (7)
C13—H132	0.9700	N41—N42	1.383 (11)
C14—H141	0.9700	N42—C42	1.304 (8)
C14—H142	0.9700	C42—N5	1.333 (11)
N21—C21	1.463 (12)	N5—H51	0.8600
N21—H21A	0.9000	N5—H52	0.8600
N21—H21B	0.9000	O6—H61	0.95 (8)
N22—C23	1.472 (8)	O6—H62	0.95 (6)
N22—C22	1.484 (9)
N23—Ni—N11	94.2 (2)	C21—N21—H21B	109.5
N23—Ni—N13	92.6 (2)	Ni—N21—H21B	109.5
N11—Ni—N13	95.0 (2)	H21A—N21—H21B	108.1
N23—Ni—N21	94.0 (2)	C23—N22—C22	115.3 (6)
N11—Ni—N21	93.0 (2)	C23—N22—Ni	107.3 (4)
N13—Ni—N21	169.2 (2)	C22—N22—Ni	108.4 (4)
N23—Ni—N22	82.2 (2)	C23—N22—H22	109.0
N11—Ni—N22	173.1 (3)	C22—N22—H22	109.0
N13—Ni—N22	91.0 (2)	Ni—N22—H22	109.0
N21—Ni—N22	81.5 (2)	C24—N23—Ni	111.6 (4)
N23—Ni—N12	172.9 (2)	C24—N23—H23A	109.4
N11—Ni—N12	82.0 (2)	Ni—N23—H23A	109.4
N13—Ni—N12	81.8 (2)	C24—N23—H23B	109.4
N21—Ni—N12	92.2 (2)	Ni—N23—H23B	109.4
N22—Ni—N12	102.1 (2)	H23A—N23—H23B	108.0
C11—N11—Ni	106.2 (4)	N21—C21—C22	110.4 (6)
C11—N11—H11A	110.5	N21—C21—H211	109.6
Ni—N11—H11A	110.5	C22—C21—H211	109.6
C11—N11—H11B	110.5	N21—C21—H212	109.6
Ni—N11—H11B	110.5	C22—C21—H212	109.6
H11A—N11—H11B	108.7	H211—C21—H212	108.1
C13—N12—C12	112.7 (6)	N22—C22—C21	111.3 (5)
C13—N12—Ni	106.3 (4)	N22—C22—H221	109.4
C12—N12—Ni	109.6 (4)	C21—C22—H221	109.4
C13—N12—H12	109.4	N22—C22—H222	109.4
C12—N12—H12	109.4	C21—C22—H222	109.4
Ni—N12—H12	109.4	H221—C22—H222	108.0
C14—N13—Ni	110.1 (4)	N22—C23—C24	112.9 (6)
C14—N13—H13A	109.6	N22—C23—H231	109.0
Ni—N13—H13A	109.6	C24—C23—H231	109.0
C14—N13—H13B	109.6	N22—C23—H232	109.0
Ni—N13—H13B	109.6	C24—C23—H232	109.0
H13A—N13—H13B	108.1	H231—C23—H232	107.8
C12—C11—N11	113.0 (7)	N23—C24—C23	110.3 (7)
C12—C11—H111	109.0	N23—C24—H241	109.6
N11—C11—H111	109.0	C23—C24—H241	109.6
C12—C11—H112	109.0	N23—C24—H242	109.6
N11—C11—H112	109.0	C23—C24—H242	109.6
H111—C11—H112	107.8	H241—C24—H242	108.1
C11—C12—N12	112.8 (7)	O32—S3—O31	113.2 (4)
C11—C12—H121	109.0	O32—S3—N33	111.5 (4)
N12—C12—H121	109.0	O31—S3—N33	115.5 (5)
C11—C12—H122	109.0	O32—S3—C41	102.2 (3)
N12—C12—H122	109.0	O31—S3—C41	104.2 (3)
H121—C12—H122	107.8	N33—S3—C41	108.8 (3)
N12—C13—C14	110.8 (5)	S3—N33—H331	100 (10)
N12—C13—H131	109.5	N41—C41—S4	114.7 (5)
C14—C13—H131	109.5	N41—C41—S3	124.1 (4)
N12—C13—H132	109.5	S4—C41—S3	120.7 (3)
C14—C13—H132	109.5	C41—S4—C42	86.7 (4)
H131—C13—H132	108.1	C41—N41—N42	112.9 (5)
N13—C14—C13	109.9 (5)	C42—N42—N41	111.9 (5)
N13—C14—H141	109.7	N42—C42—N5	123.7 (6)
C13—C14—H141	109.7	N42—C42—S4	113.8 (5)
N13—C14—H142	109.7	N5—C42—S4	122.5 (5)
C13—C14—H142	109.7	C42—N5—H51	120.0
H141—C14—H142	108.2	C42—N5—H52	120.0
C21—N21—Ni	110.6 (4)	H51—N5—H52	120.0
C21—N21—H21A	109.5	H61—O6—H62	106 (8)
Ni—N21—H21A	109.5
N23—Ni—N11—C11	161.6 (5)	N12—Ni—N22—C23	−159.1 (5)
N13—Ni—N11—C11	−105.8 (5)	N23—Ni—N22—C22	−109.9 (4)
N21—Ni—N11—C11	66.9 (5)	N13—Ni—N22—C22	157.2 (5)
N12—Ni—N11—C11	−24.8 (4)	N21—Ni—N22—C22	−15.1 (5)
N11—Ni—N12—C13	−117.9 (5)	N12—Ni—N22—C22	75.5 (5)
N13—Ni—N12—C13	−21.6 (4)	N11—Ni—N23—C24	−164.8 (4)
N21—Ni—N12—C13	149.4 (4)	N13—Ni—N23—C24	100.0 (5)
N22—Ni—N12—C13	67.4 (5)	N21—Ni—N23—C24	−71.5 (5)
N11—Ni—N12—C12	4.1 (4)	N22—Ni—N23—C24	9.7 (4)
N13—Ni—N12—C12	100.4 (4)	Ni—N21—C21—C22	33.5 (6)
N21—Ni—N12—C12	−88.6 (4)	C23—N22—C22—C21	−83.0 (7)
N22—Ni—N12—C12	−170.7 (4)	Ni—N22—C22—C21	36.9 (6)
N23—Ni—N13—C14	170.9 (4)	N21—C21—C22—N22	−47.5 (7)
N11—Ni—N13—C14	76.4 (4)	C22—N22—C23—C24	84.0 (7)
N21—Ni—N13—C14	−61.0 (13)	Ni—N22—C23—C24	−37.2 (8)
N22—Ni—N13—C14	−106.5 (4)	Ni—N23—C24—C23	−31.7 (7)
N12—Ni—N13—C14	−4.7 (4)	N22—C23—C24—N23	46.2 (8)
Ni—N11—C11—C12	43.5 (8)	O32—S3—C41—N41	108.1 (6)
N11—C11—C12—N12	−42.4 (9)	O31—S3—C41—N41	−10.3 (6)
C13—N12—C12—C11	137.6 (7)	N33—S3—C41—N41	−133.6 (6)
Ni—N12—C12—C11	18.5 (8)	O32—S3—C41—S4	−70.5 (5)
C12—N12—C13—C14	−75.1 (7)	O31—S3—C41—S4	171.1 (3)
Ni—N12—C13—C14	44.9 (6)	N33—S3—C41—S4	47.2 (5)
Ni—N13—C14—C13	30.0 (7)	N41—C41—S4—C42	−1.3 (5)
N12—C13—C14—N13	−51.2 (8)	S3—C41—S4—C42	177.4 (4)
N23—Ni—N21—C21	71.4 (4)	S4—C41—N41—N42	1.6 (6)
N11—Ni—N21—C21	165.9 (4)	S3—C41—N41—N42	−177.1 (4)
N13—Ni—N21—C21	−56.6 (12)	C41—N41—N42—C42	−0.9 (7)
N22—Ni—N21—C21	−10.5 (4)	N41—N42—C42—N5	−178.8 (6)
N12—Ni—N21—C21	−112.1 (4)	N41—N42—C42—S4	−0.1 (6)
N23—Ni—N22—C23	15.1 (5)	C41—S4—C42—N42	0.8 (5)
N13—Ni—N22—C23	−77.4 (5)	C41—S4—C42—N5	179.5 (6)
N21—Ni—N22—C23	110.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11A···Cl	0.90	2.68	3.521 (7)	155
N12—H12···O31	0.91	2.46	3.158 (8)	134
N12—H12···N41	0.91	2.33	3.16 (1)	150
N13—H13A···O6	0.90	2.29	3.08 (2)	146
N13—H13B···Cl	0.90	2.52	3.374 (7)	159
N21—H21A···O31	0.90	2.21	3.108 (8)	171
N22—H22···O6	0.91	2.31	3.08 (1)	141
N23—H23A···O31^i	0.90	2.38	3.23 (1)	156
N21—H21B···N33^i	0.90	2.40	3.28 (1)	162
N11—H11B···O32^i	0.90	2.07	2.964 (9)	171
N21—H21B···S3^i	0.90	2.93	3.796 (7)	162
N23—H23A···S3^i	0.90	2.96	3.83 (1)	161
O6—H62···Cl^ii	0.95 (6)	2.28 (5)	3.190 (8)	160 (10)
N23—H23B···N33^iii	0.90	2.19	3.048 (9)	160
N5—H51···N42^iv	0.86	2.22	3.066 (9)	166
N5—H52···Cl^v	0.86	2.44	3.242 (7)	156
O6—H61···Cl^vi	0.95 (7)	2.28 (7)	3.174 (8)	157 (10)

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