(μ-2,2′,2′′,2′′′-{[Pyrazine-2,3,5,6-tetra­yltetra­kis(methyl­ene)]tetra­kis(sulfanedi­yl)}tetra­acetato)bis­[aqua­nickel(II)] hepta­hydrate

Reaction of the ligand 2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetra­yltetra­kis­(methyl­ene)]tetra­kis­(sulfanedi­yl)}tetra­acetic acid (H₄L1), with NiCl₂ leads to the formation of a binuclear complex, (μ-2,2′,2′′,2′′′-{[pyrazine-2,3,5,6-tetra­yltetra­kis­(methyl­ene)]tetra­kis­(sulfanedi­yl)}tetra­acetato-κ⁵O,S,N¹,S′,O′:κ⁵O′′,S′′,N⁴,S′′′,O′′′)bis[aqua­nickel(II)] hepta­hydrate, {[Ni₂(C₁₆H₁₆N₂O₈S₄)(H₂O)₂]·7H₂O} (I). It crystallizes with two half mol­ecules in the asymmetric unit. The complete mol­ecules are generated by inversion symmetry, with the center of the pyrazine rings being located at crystallographic centres of inversion. The ligand coordinates two Ni^II ions in a bis-penta­dentate manner and the sixfold coordination sphere of each nickel(II) atom (NiS₂O₃N) is completed by a water mol­ecule. The complex crystallized as a hepta-hydrate. The binuclear complexes are linked by O_water—H...O_carbon­yl hydrogen bonds, forming layers parallel to the (101) plane. This layered structure is additionally stabilized by weak C—H...O hydrogen bonds. Further O—H...O hydrogen bonds involving binuclear complexes and solvent water mol­ecules, together with weak C—H...S hydrogen bonds, link the layers to form a supra­molecular framework.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.096
• Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT417_ALERT_2_C Short Inter D-H..H-D       H7WA     ..H9WA     .       2.13 Ang.
                                                      x,y,z  =      1_555 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      3.262 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          4 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.007 Degree
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --S1       .        6.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Ni1      --S2       .        7.3 s.u.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........         18 Note
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       2.12 Info
PLAT794_ALERT_5_G Tentative Bond Valency for Ni2       (II)      .       2.15 Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        101 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  13 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL023_ALERT_1_A There is a mismatched ^ on line 21354
               Foundation; University of Neuch^atel</span>
              If you require a ^ then it should be escaped
              with a \, i.e. \^
              Otherwise there must be a matching closing ~, e.g. ^12^C

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

(µ-2,2',2'',2'''-{[Pyrazine-2,3,5,6-tetrayltetrakis(methylene)]tetrakis(sulfanediyl)}tetraacetato-κ⁵O,S,N¹,S',O':κ⁵O'',S'',N⁴,S''',O''')bis[aquanickel(II)] heptahydrate

Crystal data

[Ni2(C16H16N2O8S4)(H2O)2]·7H2O	Z = 2
Mr = 772.11	F(000) = 800
Triclinic, P1	Dx = 1.814 Mg m^−3
a = 8.6799 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4092 (10) Å	Cell parameters from 19267 reflections
c = 14.7210 (13) Å	θ = 2.3–25.9°
α = 90.308 (7)°	µ = 1.71 mm^−1
β = 103.619 (7)°	T = 153 K
γ = 93.801 (7)°	Needle, purple
V = 1413.4 (2) Å^3	0.49 × 0.06 × 0.06 mm

Data collection

STOE IPDS 2 diffractometer	7779 independent reflections
Radiation source: fine-focus sealed tube	6120 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.052
φ + ω scans	θmax = 29.5°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements) (ShxAbs; Spek, 2020)	h = −12→11
Tmin = 0.261, Tmax = 0.714	k = −15→13
19974 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 1.0506P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
7779 reflections	Δρmax = 0.74 e Å^−3
443 parameters	Δρmin = −0.64 e Å^−3
2 restraints	Extinction correction: (SHELXL-2018/3; Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (6)

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.

Refinement. H atoms of coordinated and non-coordinated water molecules were all located from difference-Fourier maps and freely refined. The C-bound H atoms were included in calculated positions and treated as riding on their parent C atom: C—H = 0.97 - 0.99 Å with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	Uiso*/Ueq
Ni1	0.53221 (4)	0.24084 (3)	0.38618 (2)	0.01578 (8)
S1	0.80929 (7)	0.27577 (5)	0.45193 (4)	0.01770 (12)
S2	0.25256 (8)	0.24883 (6)	0.32588 (5)	0.01966 (13)
O1	0.6527 (3)	0.09177 (18)	0.64400 (14)	0.0260 (4)
O2	0.5239 (2)	0.15751 (16)	0.50754 (13)	0.0189 (3)
O3	0.4421 (3)	0.4074 (2)	0.13485 (16)	0.0374 (5)
O4	0.5504 (2)	0.31920 (17)	0.26639 (13)	0.0218 (4)
O1W	0.5614 (2)	0.07971 (17)	0.33656 (14)	0.0214 (4)
H1WA	0.493 (5)	0.021 (4)	0.347 (3)	0.044 (12)*
H1WB	0.562 (5)	0.074 (4)	0.280 (4)	0.049 (13)*
N1	0.5120 (2)	0.39964 (18)	0.45117 (14)	0.0150 (4)
C1	0.6427 (3)	0.4640 (2)	0.49454 (16)	0.0150 (4)
C2	0.8013 (3)	0.4274 (2)	0.48542 (19)	0.0187 (5)
H2A	0.878607	0.443243	0.546080	0.022*
H2B	0.836746	0.477764	0.438614	0.022*
C3	0.8088 (3)	0.1985 (2)	0.5586 (2)	0.0243 (5)
H3A	0.881017	0.134074	0.562820	0.029*
H3B	0.854011	0.253460	0.611882	0.029*
C4	0.6478 (3)	0.1460 (2)	0.57012 (18)	0.0186 (5)
C5	0.3695 (3)	0.4333 (2)	0.45563 (17)	0.0157 (4)
C6	0.2232 (3)	0.3583 (2)	0.40844 (18)	0.0191 (5)
H6A	0.142444	0.410319	0.375290	0.023*
H6B	0.179663	0.317800	0.457218	0.023*
C7	0.2684 (3)	0.3386 (3)	0.22634 (19)	0.0267 (6)
H7A	0.195741	0.302037	0.169739	0.032*
H7B	0.230429	0.416684	0.235880	0.032*
C8	0.4334 (3)	0.3569 (3)	0.20767 (19)	0.0233 (5)
Ni2	0.08393 (4)	0.76880 (3)	0.11162 (2)	0.01682 (8)
S3	−0.17445 (8)	0.74194 (6)	0.13855 (4)	0.01891 (13)
S4	0.33203 (7)	0.76930 (6)	0.07086 (4)	0.01819 (12)
O5	−0.2463 (2)	0.9086 (2)	−0.09705 (16)	0.0298 (5)
O6	−0.0227 (2)	0.85094 (17)	−0.00750 (13)	0.0211 (4)
O7	0.4137 (2)	0.62254 (19)	0.31716 (15)	0.0272 (4)
O8	0.1895 (2)	0.67823 (17)	0.22496 (13)	0.0208 (4)
O2W	0.1272 (3)	0.92039 (18)	0.18933 (14)	0.0230 (4)
H2WA	0.159 (6)	0.984 (4)	0.162 (3)	0.052 (13)*
H2WB	0.187 (7)	0.910 (5)	0.245 (4)	0.078 (18)*
N2	0.0311 (2)	0.60923 (18)	0.04172 (14)	0.0161 (4)
C9	−0.1108 (3)	0.5517 (2)	0.03476 (17)	0.0161 (4)
C10	−0.2367 (3)	0.6057 (2)	0.07259 (18)	0.0191 (5)
H10A	−0.276242	0.548113	0.113293	0.023*
H10B	−0.326835	0.620196	0.019548	0.023*
C11	−0.2527 (4)	0.8505 (3)	0.0556 (2)	0.0288 (6)
H11A	−0.365699	0.826762	0.027239	0.035*
H11B	−0.249215	0.926009	0.089668	0.035*
C12	−0.1675 (3)	0.8705 (2)	−0.02232 (19)	0.0209 (5)
C13	0.1429 (3)	0.5602 (2)	0.00845 (17)	0.0162 (4)
C14	0.3030 (3)	0.6239 (2)	0.01658 (19)	0.0201 (5)
H14A	0.321931	0.630870	−0.046967	0.024*
H14B	0.384762	0.574769	0.052830	0.024*
C15	0.4378 (3)	0.7395 (3)	0.18853 (18)	0.0231 (5)
H15A	0.528662	0.692942	0.185131	0.028*
H15B	0.481816	0.815165	0.220452	0.028*
C16	0.3408 (3)	0.6741 (2)	0.24832 (18)	0.0189 (5)
O3W	0.2116 (3)	0.1139 (2)	0.53431 (19)	0.0364 (5)
H3WA	0.310 (5)	0.107 (3)	0.531 (3)	0.030 (9)*
H3WB	0.186 (8)	0.056 (6)	0.578 (5)	0.09 (2)*
O4W	0.9679 (3)	0.5567 (2)	0.29921 (16)	0.0274 (4)
H4WA	1.041 (6)	0.603 (4)	0.278 (3)	0.047 (12)*
H4WB	0.893 (6)	0.597 (4)	0.310 (4)	0.058 (14)*
O5W	0.5598 (3)	0.0350 (2)	0.15764 (15)	0.0283 (4)
H5WA	0.649 (8)	0.081 (6)	0.143 (4)	0.09 (2)*
H5WB	0.487 (6)	0.068 (4)	0.129 (4)	0.054 (14)*
O6W	0.7456 (3)	0.6695 (2)	0.36273 (17)	0.0315 (5)
H6WA	0.648 (6)	0.654 (4)	0.349 (3)	0.042 (12)*
H6WB	0.763 (6)	0.738 (5)	0.391 (4)	0.068 (16)*
O7W	0.8648 (3)	0.1299 (2)	0.16038 (19)	0.0370 (5)
H7WA	0.867 (6)	0.202 (2)	0.178 (3)	0.050 (13)*
H7WB	0.923 (7)	0.132 (5)	0.112 (4)	0.078 (17)*
O8W	0.9536 (3)	0.0333 (3)	0.3655 (3)	0.0467 (7)
H8WA	0.939 (8)	0.059 (6)	0.310 (2)	0.10 (2)*
H8WB	1.022 (9)	0.070 (7)	0.410 (5)	0.11 (3)*
O9W	0.8291 (3)	0.3532 (2)	0.20860 (18)	0.0339 (5)
H9WA	0.745 (7)	0.338 (5)	0.224 (4)	0.065 (16)*
H9WB	0.878 (6)	0.411 (4)	0.241 (3)	0.048 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01756 (15)	0.01571 (15)	0.01319 (15)	0.00010 (11)	0.00220 (11)	−0.00087 (11)
S1	0.0181 (3)	0.0171 (3)	0.0182 (3)	0.0016 (2)	0.0048 (2)	−0.0015 (2)
S2	0.0195 (3)	0.0176 (3)	0.0199 (3)	−0.0013 (2)	0.0015 (2)	−0.0045 (2)
O1	0.0324 (10)	0.0244 (10)	0.0177 (9)	−0.0046 (8)	0.0007 (8)	0.0025 (8)
O2	0.0206 (8)	0.0201 (9)	0.0149 (8)	−0.0013 (7)	0.0026 (7)	0.0003 (7)
O3	0.0421 (13)	0.0489 (14)	0.0205 (10)	0.0069 (11)	0.0048 (9)	0.0131 (10)
O4	0.0244 (9)	0.0253 (9)	0.0157 (8)	0.0010 (7)	0.0050 (7)	0.0047 (7)
O1W	0.0266 (9)	0.0174 (9)	0.0198 (9)	−0.0006 (7)	0.0052 (8)	−0.0035 (7)
N1	0.0163 (9)	0.0135 (9)	0.0143 (9)	−0.0011 (7)	0.0027 (7)	−0.0014 (7)
C1	0.0169 (10)	0.0150 (10)	0.0127 (10)	0.0012 (8)	0.0026 (8)	0.0007 (8)
C2	0.0157 (11)	0.0177 (11)	0.0223 (12)	0.0001 (9)	0.0040 (9)	−0.0017 (9)
C3	0.0232 (13)	0.0220 (12)	0.0256 (13)	0.0001 (10)	0.0021 (10)	0.0045 (10)
C4	0.0230 (12)	0.0168 (11)	0.0144 (11)	−0.0009 (9)	0.0021 (9)	−0.0011 (9)
C5	0.0173 (10)	0.0153 (10)	0.0136 (10)	−0.0011 (8)	0.0025 (8)	0.0000 (8)
C6	0.0190 (11)	0.0203 (12)	0.0167 (11)	−0.0003 (9)	0.0020 (9)	−0.0029 (9)
C7	0.0271 (13)	0.0351 (15)	0.0164 (12)	0.0059 (11)	0.0011 (10)	−0.0008 (11)
C8	0.0281 (13)	0.0262 (13)	0.0142 (11)	0.0017 (10)	0.0020 (10)	0.0005 (10)
Ni2	0.01780 (15)	0.01761 (16)	0.01431 (15)	0.00035 (11)	0.00256 (11)	−0.00098 (11)
S3	0.0210 (3)	0.0200 (3)	0.0168 (3)	0.0014 (2)	0.0069 (2)	−0.0016 (2)
S4	0.0185 (3)	0.0189 (3)	0.0162 (3)	−0.0023 (2)	0.0031 (2)	−0.0005 (2)
O5	0.0248 (10)	0.0340 (11)	0.0279 (11)	0.0016 (8)	0.0008 (8)	0.0106 (9)
O6	0.0209 (9)	0.0234 (9)	0.0189 (9)	0.0030 (7)	0.0040 (7)	0.0032 (7)
O7	0.0284 (10)	0.0290 (10)	0.0222 (10)	0.0049 (8)	0.0008 (8)	0.0059 (8)
O8	0.0205 (9)	0.0243 (9)	0.0164 (8)	−0.0017 (7)	0.0026 (7)	0.0015 (7)
O2W	0.0312 (10)	0.0183 (9)	0.0177 (9)	−0.0001 (8)	0.0025 (8)	−0.0027 (7)
N2	0.0165 (9)	0.0170 (9)	0.0140 (9)	0.0007 (7)	0.0019 (7)	−0.0008 (8)
C9	0.0165 (10)	0.0179 (11)	0.0128 (10)	−0.0002 (8)	0.0017 (8)	−0.0002 (9)
C10	0.0170 (11)	0.0212 (12)	0.0192 (11)	0.0003 (9)	0.0046 (9)	−0.0045 (9)
C11	0.0299 (14)	0.0270 (14)	0.0347 (16)	0.0108 (11)	0.0155 (12)	0.0101 (12)
C12	0.0229 (12)	0.0168 (11)	0.0228 (12)	0.0009 (9)	0.0047 (10)	0.0044 (10)
C13	0.0170 (10)	0.0175 (11)	0.0135 (10)	0.0007 (8)	0.0024 (8)	−0.0004 (9)
C14	0.0190 (11)	0.0215 (12)	0.0197 (12)	−0.0032 (9)	0.0056 (9)	−0.0053 (10)
C15	0.0184 (11)	0.0314 (14)	0.0170 (12)	−0.0032 (10)	0.0009 (9)	−0.0020 (10)
C16	0.0213 (11)	0.0191 (11)	0.0145 (11)	0.0004 (9)	0.0009 (9)	−0.0024 (9)
O3W	0.0268 (11)	0.0366 (13)	0.0473 (14)	0.0028 (9)	0.0113 (10)	0.0092 (11)
O4W	0.0258 (10)	0.0272 (10)	0.0281 (11)	−0.0019 (8)	0.0052 (8)	0.0017 (8)
O5W	0.0287 (11)	0.0321 (11)	0.0239 (10)	0.0034 (9)	0.0058 (8)	−0.0033 (9)
O6W	0.0272 (11)	0.0402 (13)	0.0276 (11)	0.0041 (9)	0.0066 (9)	0.0044 (10)
O7W	0.0386 (13)	0.0311 (12)	0.0462 (14)	−0.0009 (10)	0.0208 (11)	−0.0050 (11)
O8W	0.0367 (14)	0.0421 (15)	0.061 (2)	−0.0031 (11)	0.0130 (14)	0.0098 (14)
O9W	0.0352 (12)	0.0336 (12)	0.0345 (12)	−0.0043 (10)	0.0132 (10)	−0.0071 (10)

Geometric parameters (Å, º)

Ni1—O1W	2.0276 (19)	S3—C10	1.810 (3)
Ni1—O2	2.0423 (18)	S4—C15	1.805 (3)
Ni1—O4	2.0158 (19)	S4—C14	1.814 (3)
Ni1—N1	2.081 (2)	O5—C12	1.248 (3)
Ni1—S1	2.3775 (7)	O6—C12	1.260 (3)
Ni1—S2	2.3883 (8)	O7—C16	1.236 (3)
S1—C3	1.805 (3)	O8—C16	1.281 (3)
S1—C2	1.806 (3)	O2W—H2WA	0.88 (5)
S2—C6	1.809 (3)	O2W—H2WB	0.88 (6)
S2—C7	1.819 (3)	N2—C13	1.337 (3)
O1—C4	1.248 (3)	N2—C9	1.338 (3)
O2—C4	1.255 (3)	C9—C13^ii	1.405 (3)
O3—C8	1.235 (3)	C9—C10	1.502 (3)
O4—C8	1.270 (3)	C10—H10A	0.9900
O1W—H1WA	0.90 (5)	C10—H10B	0.9900
O1W—H1WB	0.83 (5)	C11—C12	1.515 (4)
N1—C1	1.333 (3)	C11—H11A	0.9900
N1—C5	1.335 (3)	C11—H11B	0.9900
C1—C5^i	1.403 (3)	C13—C14	1.503 (3)
C1—C2	1.500 (3)	C14—H14A	0.9900
C2—H2A	0.9900	C14—H14B	0.9900
C2—H2B	0.9900	C15—C16	1.521 (4)
C3—C4	1.531 (4)	C15—H15A	0.9900
C3—H3A	0.9900	C15—H15B	0.9900
C3—H3B	0.9900	O3W—H3WA	0.87 (4)
C5—C6	1.503 (3)	O3W—H3WB	0.98 (7)
C6—H6A	0.9900	O4W—H4WA	0.91 (5)
C6—H6B	0.9900	O4W—H4WB	0.86 (5)
C7—C8	1.523 (4)	O5W—H5WA	0.97 (7)
C7—H7A	0.9900	O5W—H5WB	0.80 (5)
C7—H7B	0.9900	O6W—H6WA	0.83 (5)
Ni2—O2W	2.033 (2)	O6W—H6WB	0.87 (6)
Ni2—O6	2.0440 (19)	O7W—H7WA	0.857 (19)
Ni2—O8	2.0287 (19)	O7W—H7WB	0.97 (6)
Ni2—N2	2.057 (2)	O8W—H8WA	0.85 (2)
Ni2—S4	2.3674 (7)	O8W—H8WB	0.86 (8)
Ni2—S3	2.3685 (7)	O9W—H9WA	0.82 (6)
S3—C11	1.795 (3)	O9W—H9WB	0.84 (5)
O4—Ni1—O1W	92.71 (8)	O2W—Ni2—N2	175.03 (9)
O4—Ni1—O2	177.15 (8)	O6—Ni2—N2	89.81 (8)
O1W—Ni1—O2	85.47 (8)	O8—Ni2—S4	85.30 (6)
O4—Ni1—N1	92.73 (8)	O2W—Ni2—S4	97.60 (6)
O1W—Ni1—N1	173.94 (8)	O6—Ni2—S4	93.64 (6)
O2—Ni1—N1	88.99 (8)	N2—Ni2—S4	86.11 (6)
O4—Ni1—S1	91.86 (6)	O8—Ni2—S3	94.92 (6)
O1W—Ni1—S1	92.11 (6)	O2W—Ni2—S3	91.04 (6)
O2—Ni1—S1	86.03 (6)	O6—Ni2—S3	85.63 (6)
N1—Ni1—S1	85.03 (6)	N2—Ni2—S3	85.28 (6)
O4—Ni1—S2	84.80 (6)	S4—Ni2—S3	171.37 (3)
O1W—Ni1—S2	99.55 (6)	C11—S3—C10	102.65 (14)
O2—Ni1—S2	97.65 (6)	C11—S3—Ni2	93.29 (10)
N1—Ni1—S2	83.62 (6)	C10—S3—Ni2	98.05 (8)
S1—Ni1—S2	167.99 (3)	C15—S4—C14	101.74 (13)
C3—S1—C2	103.12 (13)	C15—S4—Ni2	93.14 (9)
C3—S1—Ni1	95.52 (9)	C14—S4—Ni2	97.06 (8)
C2—S1—Ni1	96.06 (8)	C12—O6—Ni2	119.89 (17)
C6—S2—C7	101.48 (13)	C16—O8—Ni2	120.83 (17)
C6—S2—Ni1	96.67 (9)	Ni2—O2W—H2WA	117 (3)
C7—S2—Ni1	95.58 (10)	Ni2—O2W—H2WB	112 (4)
C4—O2—Ni1	121.22 (17)	H2WA—O2W—H2WB	113 (5)
C8—O4—Ni1	123.77 (18)	C13—N2—C9	120.3 (2)
Ni1—O1W—H1WA	116 (3)	C13—N2—Ni2	119.43 (17)
Ni1—O1W—H1WB	117 (3)	C9—N2—Ni2	120.15 (16)
H1WA—O1W—H1WB	106 (4)	N2—C9—C13^ii	119.9 (2)
C1—N1—C5	119.7 (2)	N2—C9—C10	120.7 (2)
C1—N1—Ni1	119.71 (16)	C13^ii—C9—C10	119.5 (2)
C5—N1—Ni1	120.41 (16)	C9—C10—S3	115.48 (18)
N1—C1—C5^i	120.2 (2)	C9—C10—H10A	108.4
N1—C1—C2	118.9 (2)	S3—C10—H10A	108.4
C5^i—C1—C2	120.9 (2)	C9—C10—H10B	108.4
C1—C2—S1	116.34 (18)	S3—C10—H10B	108.4
C1—C2—H2A	108.2	H10A—C10—H10B	107.5
S1—C2—H2A	108.2	C12—C11—S3	115.45 (19)
C1—C2—H2B	108.2	C12—C11—H11A	108.4
S1—C2—H2B	108.2	S3—C11—H11A	108.4
H2A—C2—H2B	107.4	C12—C11—H11B	108.4
C4—C3—S1	116.69 (19)	S3—C11—H11B	108.4
C4—C3—H3A	108.1	H11A—C11—H11B	107.5
S1—C3—H3A	108.1	O5—C12—O6	124.2 (3)
C4—C3—H3B	108.1	O5—C12—C11	116.9 (2)
S1—C3—H3B	108.1	O6—C12—C11	118.9 (2)
H3A—C3—H3B	107.3	N2—C13—C9^ii	119.8 (2)
O1—C4—O2	124.7 (2)	N2—C13—C14	120.6 (2)
O1—C4—C3	114.8 (2)	C9^ii—C13—C14	119.5 (2)
O2—C4—C3	120.5 (2)	C13—C14—S4	116.43 (18)
N1—C5—C1^i	120.1 (2)	C13—C14—H14A	108.2
N1—C5—C6	119.1 (2)	S4—C14—H14A	108.2
C1^i—C5—C6	120.7 (2)	C13—C14—H14B	108.2
C5—C6—S2	115.43 (17)	S4—C14—H14B	108.2
C5—C6—H6A	108.4	H14A—C14—H14B	107.3
S2—C6—H6A	108.4	C16—C15—S4	115.77 (18)
C5—C6—H6B	108.4	C16—C15—H15A	108.3
S2—C6—H6B	108.4	S4—C15—H15A	108.3
H6A—C6—H6B	107.5	C16—C15—H15B	108.3
C8—C7—S2	116.14 (19)	S4—C15—H15B	108.3
C8—C7—H7A	108.3	H15A—C15—H15B	107.4
S2—C7—H7A	108.3	O7—C16—O8	124.6 (3)
C8—C7—H7B	108.3	O7—C16—C15	117.7 (2)
S2—C7—H7B	108.3	O8—C16—C15	117.8 (2)
H7A—C7—H7B	107.4	H3WA—O3W—H3WB	108 (4)
O3—C8—O4	124.9 (3)	H4WA—O4W—H4WB	111 (4)
O3—C8—C7	116.4 (3)	H5WA—O5W—H5WB	101 (5)
O4—C8—C7	118.7 (2)	H6WA—O6W—H6WB	107 (4)
O8—Ni2—O2W	90.24 (8)	H7WA—O7W—H7WB	104 (5)
O8—Ni2—O6	176.47 (8)	H8WA—O8W—H8WB	120 (7)
O2W—Ni2—O6	93.24 (8)	H9WA—O9W—H9WB	109 (5)
O8—Ni2—N2	86.76 (8)
N1—C1—C2—S1	−20.9 (3)	Ni1—S2—C7—C8	9.7 (2)
N1—C5—C6—S2	−14.8 (3)	Ni1—O4—C8—O3	178.4 (2)
S1—C3—C4—O2	−0.1 (3)	Ni1—O4—C8—C7	−2.2 (4)
S2—C7—C8—O4	−6.7 (4)	S2—C7—C8—O3	172.7 (2)
N2—C13—C14—S4	−1.3 (3)	C13—N2—C9—C13^ii	−0.6 (4)
N2—C9—C10—S3	−7.0 (3)	Ni2—N2—C9—C13^ii	−176.41 (18)
S4—C15—C16—O8	−21.9 (3)	C13—N2—C9—C10	179.5 (2)
S3—C11—C12—O6	−27.6 (4)	Ni2—N2—C9—C10	3.7 (3)
C5—N1—C1—C5^i	−0.2 (4)	C13^ii—C9—C10—S3	173.09 (19)
Ni1—N1—C1—C5^i	−175.32 (17)	C11—S3—C10—C9	101.2 (2)
C5—N1—C1—C2	−177.5 (2)	Ni2—S3—C10—C9	6.0 (2)
Ni1—N1—C1—C2	7.4 (3)	C10—S3—C11—C12	−72.7 (3)
C5^i—C1—C2—S1	161.87 (19)	Ni2—S3—C11—C12	26.3 (2)
C3—S1—C2—C1	−76.6 (2)	Ni2—O6—C12—O5	−172.1 (2)
Ni1—S1—C2—C1	20.51 (19)	Ni2—O6—C12—C11	9.8 (3)
C2—S1—C3—C4	96.0 (2)	S3—C11—C12—O5	154.2 (2)
Ni1—S1—C3—C4	−1.6 (2)	C9—N2—C13—C9^ii	0.6 (4)
Ni1—O2—C4—O1	−176.6 (2)	Ni2—N2—C13—C9^ii	176.44 (18)
Ni1—O2—C4—C3	2.3 (3)	C9—N2—C13—C14	−179.6 (2)
S1—C3—C4—O1	178.92 (19)	Ni2—N2—C13—C14	−3.7 (3)
C1—N1—C5—C1^i	0.2 (4)	C9^ii—C13—C14—S4	178.57 (19)
Ni1—N1—C5—C1^i	175.29 (17)	C15—S4—C14—C13	99.1 (2)
C1—N1—C5—C6	−178.5 (2)	Ni2—S4—C14—C13	4.4 (2)
Ni1—N1—C5—C6	−3.4 (3)	C14—S4—C15—C16	−71.2 (2)
C1^i—C5—C6—S2	166.52 (19)	Ni2—S4—C15—C16	26.7 (2)
C7—S2—C6—C5	−75.9 (2)	Ni2—O8—C16—O7	178.7 (2)
Ni1—S2—C6—C5	21.24 (19)	Ni2—O8—C16—C15	0.2 (3)
C6—S2—C7—C8	107.7 (2)	S4—C15—C16—O7	159.5 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1^iii	0.90 (5)	1.78 (5)	2.672 (3)	174 (4)
O1W—H1WB···O5W	0.83 (5)	1.85 (5)	2.677 (3)	170 (5)
O2W—H2WA···O5^iv	0.88 (5)	1.80 (5)	2.673 (3)	168 (4)
O2W—H2WB···O1^i	0.88 (6)	1.88 (6)	2.742 (3)	168 (6)
O3W—H3WA···O2	0.87 (4)	2.02 (4)	2.842 (3)	157 (4)
O3W—H3WB···O8W^iii	0.98 (7)	1.87 (7)	2.785 (4)	154 (6)
O4W—H4WA···O8^v	0.91 (5)	1.83 (5)	2.733 (3)	172 (4)
O4W—H4WB···O6W	0.86 (5)	1.88 (5)	2.724 (3)	166 (5)
O5W—H5WA···O7W	0.97 (7)	1.88 (7)	2.785 (3)	154 (6)
O5W—H5WB···O5^ii	0.80 (5)	2.06 (5)	2.776 (3)	149 (5)
O6W—H6WA···O7	0.83 (5)	1.98 (5)	2.814 (3)	178 (4)
O6W—H6WB···O3W^i	0.87 (6)	1.98 (6)	2.849 (4)	173 (5)
O7W—H7WA···O9W	0.86 (2)	1.85 (2)	2.698 (3)	169 (5)
O7W—H7WB···O6^vi	0.97 (6)	1.94 (6)	2.899 (3)	174 (5)
O8W—H8WA···O7W	0.85 (2)	2.32 (2)	3.159 (5)	173 (6)
O8W—H8WB···O3W^v	0.86 (8)	2.19 (8)	3.019 (4)	164 (7)
O9W—H9WA···O4	0.82 (6)	1.93 (6)	2.752 (3)	174 (6)
O9W—H9WB···O4W	0.84 (5)	1.90 (5)	2.731 (3)	171 (5)
C2—H2A···O4W^vii	0.99	2.35	3.324 (3)	167
C2—H2B···O6W	0.99	2.55	3.308 (4)	133
C3—H3A···O8W^viii	0.99	2.55	3.488 (4)	159
C6—H6A···O4W^ix	0.99	2.43	3.413 (3)	173
C6—H6B···O3W	0.99	2.60	3.365 (4)	134
C6—H6B···O6W^i	0.99	2.58	3.334 (3)	133
C10—H10B···O3^ii	0.99	2.27	3.150 (4)	148
C11—H11B···O5W^x	0.99	2.52	3.303 (4)	136
C11—H11B···O7W^x	0.99	2.58	3.516 (4)	158
C14—H14A···O9W^vi	0.99	2.45	3.260 (4)	139
C14—H14B···O3	0.99	2.29	3.169 (4)	148
C15—H15A···S3^v	0.99	2.84	3.609 (3)	135

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