Aqua­bis(1,10-phenanthroline-κ2N,N′)[2,4,6-tris­(4-sulfonatophenyl­amino)-1,3,5-triazin-1-ium-κO]nickel(II) dihydrate

Yu, Y.-F.; Wei, Y.-Q.; Wu, K.-C.

doi:10.1107/S1600536807033223

Aquabis(1,10-phenanthroline-κ²N,N′)[2,4,6-tris(4-sulfonatophenylamino)-1,3,5-triazin-1-ium-κO]nickel(II) dihydrate

In the title complex, [Ni(C₂₁H₁₆N₆O₉S₃)(C₁₂H₈N₂)₂(H₂O)]·2H₂O or [Ni(HTST)(phen)₂(H₂O)]·2H₂O, where H₃TST is 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine and phen is phenanthroline, the Ni^II ion is in a distorted octahedral coordination environment defined by four N atoms from two phen ligands, one O atom from an aqua ligand and one O atom from the SO₃ group of an HTST ligand. In the crystal structure, intermolecular N—H

O and O—H

O hydrogen bonds connect molecules to form a two-dimensional network.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033223/lh2447sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033223/lh2447Isup2.hkl Contains datablock I

CCDC reference: 657563

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.005 Å
R factor = 0.047
wR factor = 0.108
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.21 Ratio
PLAT223_ALERT_4_B Large Solvent/Anion  H     Ueq(max)/Ueq(min) ...       4.41 Ratio
PLAT245_ALERT_2_B U(iso) H19A    Smaller than U(eq) C19     by ...       0.05 AngSq

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT213_ALERT_2_C Atom C16     has ADP max/min Ratio .............       3.40 prola
PLAT213_ALERT_2_C Atom C19     has ADP max/min Ratio .............       3.20 prola
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.61 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C16
PLAT245_ALERT_2_C U(iso) H11     Smaller than U(eq) O11     by ...       0.03 AngSq
PLAT432_ALERT_2_C Short Inter X...Y Contact  O9     ..  C31     ..       2.96 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N3  -NI1 -O1  -S1     63.50  0.60   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            N4  -NI1 -N1  -C10  -146.50  0.60   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            N4  -NI1 -N1  -C10B   39.40  0.80   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         22
            O4  -NI1 -N2  -C11  -105.20  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         27
            O4  -NI1 -N2  -C10A   62.40  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         33
            O1  -NI1 -N3  -C20  -140.50  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         38
            O1  -NI1 -N3  -C20B   33.70  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         39
            N1  -NI1 -N4  -C21  -109.50  0.70   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         44
            N1  -NI1 -N4  -C20A   71.00  0.70   1.555   1.555   1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C45 H34 N10 Ni O10 S3
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.948
            Tmax scaled      0.948 Tmin scaled      0.860
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.06

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  19 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

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

Comment top

In the title complex (Fig. 1), the Ni^II atom is six-coordinated by four N atoms from two phen ligands, one O atom from an aqua ligand and one O atom from the SO₃ group of a HTST ligand. The Ni(II)(phen)₂O₂ unit of the complex has a cis arrangement, with a strong O—H···O H-bond involving the coordinated SO₃^- group and the aqua ligand giving additional stabilization to the coordination environment.

The HTST ligand exists in a negative divalent low-symmetry conformation form (Aakeroy et al., 2005), with two uncoordinated SO₃^- groups, and an H atom transferred to nitrogen atom N13 of the triazine ring. One phen group forms a weak intramolecular π-π stacking interaction (with a ring centroid separation 3.840 (3) Å) with the phenyl ring of the coordinated sulfophenyl group of the HTST ligand.

The two uncoordinated water molecules are hydrogen bonded to two uncoordinated SO₃ groups. In the crystal structure, water molecules, SO₃ groups and N—H groups form a hydrogen-bonded two-dimensional network.

Related literature top

For related literature, see: Aakeroy et al. (2005).

Experimental top

The title compound was synthesized by the hydrothermal method from a mixture of H₃TST^.7H₂O (0.072 g, 0.1 mmol), phen^.H₂O (0.059 g, 0.3 mmol), NiCl₂ (0.039 g, 0.3 mmol) and water (20.0 mL) in a 25.0 mL Teflon-lined stainless steel reactor. The solution was heated at 433 K for 67 h, and then the reactor was slowly cooled to room temperature to give blue crystals of the title complex.

Structure description top

For related literature, see: Aakeroy et al. (2005).

Computing details top

Data collection: CrystalClear (Rigaku Corporation, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXP97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure of the title complex, with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Aquabis(1,10-phenanthroline-κ²N,N')[2,4,6-τris(4-sulfonatophenylamino)-1,3,5-triazin-1-ium-κO]nickel(II) dihydrate top

Crystal data top

[Ni(C₂₁H₁₆N₆O₉S₃)(C₁₂H₈N₂)₂(H₂O)]·2H₂O	Z = 2
M_r = 1065.74	F(000) = 1100
Triclinic, P1	D_x = 1.620 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.256 (2) Å	Cell parameters from 5038 reflections
b = 11.684 (3) Å	θ = 2.2–27.5°
c = 24.086 (7) Å	µ = 0.67 mm⁻¹
α = 76.134 (7)°	T = 293 K
β = 84.875 (10)°	Prism, blue
γ = 75.718 (6)°	0.25 × 0.10 × 0.08 mm
V = 2185.0 (10) Å³

Data collection top

Rigaku Mercury70 (2x2 bin mode) diffractometer	9893 independent reflections
Radiation source: fine-focus sealed tube	7634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 14.6306 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
CCD_Profile_fitting scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku Corporation, 2000)	k = −15→15
T_min = 0.907, T_max = 1.000	l = −31→23
17176 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.042P)² + 1.2717P] where P = (F_o² + 2F_c²)/3
9893 reflections	(Δ/σ)_max = 0.001
668 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Ni(C₂₁H₁₆N₆O₉S₃)(C₁₂H₈N₂)₂(H₂O)]·2H₂O	γ = 75.718 (6)°
M_r = 1065.74	V = 2185.0 (10) Å³
Triclinic, P1	Z = 2
a = 8.256 (2) Å	Mo Kα radiation
b = 11.684 (3) Å	µ = 0.67 mm⁻¹
c = 24.086 (7) Å	T = 293 K
α = 76.134 (7)°	0.25 × 0.10 × 0.08 mm
β = 84.875 (10)°

Data collection top

Rigaku Mercury70 (2x2 bin mode) diffractometer	9893 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku Corporation, 2000)	7634 reflections with I > 2σ(I)
T_min = 0.907, T_max = 1.000	R_int = 0.025
17176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.36 e Å⁻³
9893 reflections	Δρ_min = −0.37 e Å⁻³
668 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	1.59674 (4)	−0.27469 (3)	0.887559 (13)	0.02613 (9)
S1	1.26211 (8)	−0.37669 (6)	0.88242 (3)	0.03091 (15)
S2	0.60698 (9)	−0.14127 (6)	0.24919 (3)	0.03524 (16)
S3	0.33563 (8)	0.42219 (5)	0.44922 (3)	0.02725 (14)
O1	1.4376 (2)	−0.39381 (15)	0.89659 (7)	0.0308 (4)
O2	1.2008 (3)	−0.48236 (19)	0.90877 (9)	0.0450 (5)
O3	1.1585 (2)	−0.26349 (18)	0.89380 (8)	0.0433 (5)
O4	1.3895 (3)	−0.1304 (2)	0.86597 (11)	0.0467 (6)
H2	1.370 (5)	−0.068 (4)	0.8408 (18)	0.074 (13)*
H22	1.294 (6)	−0.161 (4)	0.8753 (19)	0.096 (16)*
O5	0.7167 (3)	−0.0970 (2)	0.20325 (9)	0.0580 (6)
O6	0.4640 (3)	−0.04557 (19)	0.25793 (10)	0.0567 (6)
O7	0.5617 (3)	−0.24913 (18)	0.24324 (10)	0.0542 (6)
O8	0.4461 (2)	0.47574 (16)	0.40536 (8)	0.0411 (5)
O9	0.2036 (2)	0.38891 (17)	0.42546 (8)	0.0406 (5)
O10	0.2722 (2)	0.49828 (16)	0.48996 (8)	0.0407 (5)
O11	0.1494 (4)	−0.0270 (3)	0.31052 (11)	0.0586 (7)
H11	0.238 (4)	−0.029 (3)	0.2948 (14)	0.034 (9)*
H112	0.137 (8)	−0.097 (6)	0.311 (3)	0.15 (3)*
O12	0.2772 (4)	−0.2985 (3)	0.32023 (16)	0.0765 (8)
H122	0.350 (7)	−0.284 (5)	0.290 (2)	0.12 (2)*
N1	1.6612 (3)	−0.2990 (2)	0.80583 (9)	0.0378 (5)
N2	1.7821 (3)	−0.43427 (18)	0.90611 (9)	0.0298 (5)
N3	1.7329 (3)	−0.14640 (18)	0.88590 (9)	0.0291 (5)
N4	1.5618 (3)	−0.26009 (18)	0.97260 (9)	0.0288 (5)
N11	0.9046 (3)	−0.13966 (17)	0.51045 (8)	0.0257 (4)
N12	1.0119 (3)	−0.18043 (17)	0.60507 (9)	0.0280 (5)
N13	1.1280 (3)	−0.30553 (18)	0.54271 (9)	0.0245 (4)
N14	1.2348 (3)	−0.34576 (18)	0.63237 (9)	0.0287 (5)
H14A	1.3119	−0.3988	0.6200	0.034*
N15	0.8034 (3)	−0.01768 (17)	0.57616 (9)	0.0284 (5)
H15A	0.8079	−0.0143	0.6113	0.034*
N16	1.0174 (3)	−0.28450 (18)	0.45675 (9)	0.0300 (5)
H16A	1.0970	−0.3472	0.4554	0.036*
C10A	1.8304 (3)	−0.4807 (2)	0.85936 (13)	0.0352 (6)
C10B	1.7694 (4)	−0.4083 (3)	0.80575 (13)	0.0415 (7)
C10	1.6035 (5)	−0.2302 (3)	0.75616 (13)	0.0607 (10)
H10B	1.5282	−0.1560	0.7553	0.073*
C11	1.8331 (3)	−0.5018 (2)	0.95668 (13)	0.0392 (7)
H11B	1.8002	−0.4695	0.9888	0.047*
C12	1.9337 (4)	−0.6187 (3)	0.96427 (18)	0.0561 (10)
H12B	1.9650	−0.6636	1.0007	0.067*
C13	1.9848 (4)	−0.6657 (3)	0.9184 (2)	0.0661 (12)
H13B	2.0529	−0.7434	0.9229	0.079*
C14	1.9364 (4)	−0.5983 (3)	0.86341 (19)	0.0576 (10)
C15	1.9817 (5)	−0.6395 (5)	0.8118 (3)	0.0916 (17)
H15B	2.0525	−0.7156	0.8134	0.110*
C16	1.9258 (6)	−0.5726 (6)	0.7618 (3)	0.0989 (19)
H16B	1.9571	−0.6037	0.7293	0.119*
C17	1.8165 (5)	−0.4514 (4)	0.75576 (17)	0.0707 (12)
C18	1.7576 (7)	−0.3771 (6)	0.70484 (19)	0.0961 (18)
H18A	1.7886	−0.4022	0.6708	0.115*
C19	1.6550 (7)	−0.2682 (6)	0.70431 (15)	0.0906 (17)
C20B	1.7261 (3)	−0.1149 (2)	0.93718 (11)	0.0297 (6)
C20A	1.6363 (3)	−0.1765 (2)	0.98362 (11)	0.0288 (5)
C20	1.8099 (4)	−0.0880 (2)	0.84171 (13)	0.0386 (6)
C21	1.4793 (3)	−0.3184 (2)	1.01517 (12)	0.0362 (6)
H21A	1.4274	−0.3753	1.0079	0.043*
C22	1.4662 (4)	−0.2989 (3)	1.07029 (13)	0.0432 (7)
H22A	1.4080	−0.3427	1.0991	0.052*
C23	1.5394 (4)	−0.2150 (3)	1.08170 (13)	0.0440 (7)
H23A	1.5316	−0.2011	1.1184	0.053*
C24	1.6270 (3)	−0.1497 (2)	1.03773 (12)	0.0352 (6)
C25	1.7036 (4)	−0.0566 (3)	1.04464 (14)	0.0455 (8)
H25A	1.6973	−0.0370	1.0801	0.055*
C26	1.7846 (4)	0.0027 (3)	1.00037 (15)	0.0473 (8)
H26A	1.8320	0.0633	1.0060	0.057*
C27	1.8002 (3)	−0.0243 (2)	0.94508 (13)	0.0375 (6)
C28	1.8812 (4)	0.0350 (3)	0.89723 (16)	0.0502 (8)
H28A	1.9317	0.0959	0.9005	0.060*
C29	1.8867 (4)	0.0042 (3)	0.84600 (15)	0.0492 (8)
H29A	1.9405	0.0436	0.8143	0.059*
C31	1.0127 (3)	−0.2398 (2)	0.50303 (10)	0.0234 (5)
C32	1.1225 (3)	−0.2750 (2)	0.59416 (10)	0.0235 (5)
C33	0.9086 (3)	−0.1153 (2)	0.56200 (10)	0.0236 (5)
C41	1.2609 (3)	−0.3620 (2)	0.80735 (11)	0.0301 (6)
C42	1.1728 (4)	−0.2569 (3)	0.77264 (12)	0.0399 (7)
H42A	1.1199	−0.1918	0.7886	0.048*
C43	1.1617 (4)	−0.2467 (2)	0.71471 (12)	0.0396 (7)
H43A	1.1014	−0.1756	0.6920	0.047*
C44	1.2417 (3)	−0.3438 (2)	0.69070 (11)	0.0278 (5)
C45	1.3359 (3)	−0.4479 (2)	0.72549 (11)	0.0342 (6)
H45A	1.3944	−0.5116	0.7094	0.041*
C46	1.3430 (4)	−0.4572 (2)	0.78326 (12)	0.0370 (6)
H46A	1.4035	−0.5280	0.8062	0.044*
C51	0.6872 (3)	0.0800 (2)	0.54398 (11)	0.0258 (5)
C52	0.6232 (3)	0.1770 (2)	0.57027 (11)	0.0306 (6)
H52A	0.6543	0.1719	0.6071	0.037*
C53	0.5141 (3)	0.2803 (2)	0.54208 (11)	0.0293 (6)
H53A	0.4743	0.3452	0.5595	0.035*
C54	0.4643 (3)	0.2870 (2)	0.48802 (10)	0.0252 (5)
C55	0.5232 (3)	0.1893 (2)	0.46230 (11)	0.0293 (5)
H55A	0.4872	0.1932	0.4263	0.035*
C56	0.6350 (3)	0.0860 (2)	0.48978 (11)	0.0275 (5)
H56A	0.6748	0.0214	0.4722	0.033*
C61	0.9109 (3)	−0.2442 (2)	0.40948 (10)	0.0273 (5)
C62	0.8435 (3)	−0.1230 (2)	0.38574 (11)	0.0331 (6)
H62A	0.8617	−0.0627	0.4020	0.040*
C63	0.7488 (4)	−0.0929 (2)	0.33740 (11)	0.0343 (6)
H63A	0.7029	−0.0119	0.3213	0.041*
C64	0.7216 (3)	−0.1817 (2)	0.31291 (10)	0.0278 (5)
C65	0.7886 (3)	−0.3023 (2)	0.33721 (11)	0.0310 (6)
H65A	0.7696	−0.3625	0.3212	0.037*
C66	0.8835 (3)	−0.3333 (2)	0.38514 (11)	0.0318 (6)
H66A	0.9292	−0.4145	0.4012	0.038*
H19A	1.6158	−0.2151	0.6686	0.038*
H20A	1.8137	−0.1094	0.8054	0.038*
H13	1.189 (4)	−0.371 (3)	0.5364 (12)	0.034 (8)*
H12	0.298 (9)	−0.372 (7)	0.345 (3)	0.20 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.03295 (18)	0.02351 (16)	0.02262 (16)	−0.00547 (13)	−0.00518 (13)	−0.00608 (12)
S1	0.0311 (3)	0.0382 (3)	0.0242 (3)	−0.0095 (3)	−0.0061 (3)	−0.0051 (3)
S2	0.0428 (4)	0.0288 (3)	0.0301 (3)	−0.0016 (3)	−0.0131 (3)	−0.0017 (3)
S3	0.0292 (3)	0.0212 (3)	0.0247 (3)	0.0051 (2)	−0.0019 (2)	−0.0034 (2)
O1	0.0326 (10)	0.0302 (9)	0.0310 (10)	−0.0086 (8)	−0.0121 (8)	−0.0043 (8)
O2	0.0475 (12)	0.0554 (12)	0.0368 (11)	−0.0277 (10)	−0.0066 (9)	−0.0012 (10)
O3	0.0402 (11)	0.0496 (12)	0.0368 (11)	0.0017 (9)	−0.0022 (9)	−0.0156 (10)
O4	0.0508 (14)	0.0276 (10)	0.0560 (15)	−0.0020 (10)	−0.0159 (11)	−0.0006 (10)
O5	0.0652 (15)	0.0675 (15)	0.0315 (11)	−0.0143 (12)	−0.0048 (11)	0.0081 (11)
O6	0.0480 (13)	0.0483 (12)	0.0662 (16)	0.0125 (10)	−0.0243 (12)	−0.0149 (11)
O7	0.0777 (16)	0.0367 (11)	0.0521 (13)	−0.0137 (11)	−0.0308 (12)	−0.0067 (10)
O8	0.0426 (11)	0.0287 (9)	0.0397 (11)	0.0014 (8)	0.0069 (9)	0.0028 (8)
O9	0.0360 (11)	0.0431 (11)	0.0383 (11)	−0.0029 (9)	−0.0136 (9)	−0.0026 (9)
O10	0.0486 (12)	0.0286 (9)	0.0346 (11)	0.0142 (9)	−0.0038 (9)	−0.0106 (8)
O11	0.0592 (17)	0.0640 (18)	0.0458 (14)	0.0003 (14)	0.0020 (13)	−0.0159 (13)
O12	0.078 (2)	0.0666 (18)	0.083 (2)	−0.0167 (16)	0.0096 (18)	−0.0187 (17)
N1	0.0549 (15)	0.0425 (13)	0.0242 (11)	−0.0255 (12)	−0.0027 (11)	−0.0080 (10)
N2	0.0263 (11)	0.0285 (10)	0.0353 (12)	−0.0077 (9)	−0.0009 (9)	−0.0075 (9)
N3	0.0305 (11)	0.0268 (10)	0.0306 (11)	−0.0058 (9)	−0.0047 (9)	−0.0070 (9)
N4	0.0285 (11)	0.0298 (10)	0.0271 (11)	−0.0032 (9)	−0.0033 (9)	−0.0076 (9)
N11	0.0288 (11)	0.0223 (9)	0.0227 (10)	0.0024 (8)	−0.0046 (8)	−0.0060 (8)
N12	0.0310 (11)	0.0246 (10)	0.0227 (10)	0.0067 (9)	−0.0052 (9)	−0.0061 (8)
N13	0.0240 (11)	0.0206 (10)	0.0248 (10)	0.0053 (8)	−0.0032 (8)	−0.0074 (8)
N14	0.0295 (11)	0.0271 (10)	0.0242 (11)	0.0070 (9)	−0.0065 (9)	−0.0077 (9)
N15	0.0322 (11)	0.0244 (10)	0.0223 (10)	0.0083 (9)	−0.0047 (9)	−0.0071 (8)
N16	0.0316 (12)	0.0279 (10)	0.0259 (11)	0.0089 (9)	−0.0074 (9)	−0.0116 (9)
C10A	0.0270 (13)	0.0363 (14)	0.0493 (17)	−0.0106 (11)	0.0066 (12)	−0.0225 (13)
C10B	0.0414 (16)	0.0583 (18)	0.0403 (16)	−0.0276 (15)	0.0123 (13)	−0.0291 (15)
C10	0.095 (3)	0.067 (2)	0.0296 (16)	−0.045 (2)	−0.0148 (17)	0.0034 (16)
C11	0.0293 (14)	0.0375 (14)	0.0450 (17)	−0.0078 (12)	−0.0050 (13)	0.0030 (13)
C12	0.0335 (17)	0.0355 (16)	0.090 (3)	−0.0072 (14)	−0.0144 (18)	0.0070 (18)
C13	0.0287 (17)	0.0298 (16)	0.138 (4)	−0.0008 (13)	−0.018 (2)	−0.017 (2)
C14	0.0307 (16)	0.0501 (19)	0.106 (3)	−0.0114 (15)	0.0099 (18)	−0.047 (2)
C15	0.049 (2)	0.099 (4)	0.156 (5)	−0.010 (2)	0.016 (3)	−0.100 (4)
C16	0.065 (3)	0.153 (5)	0.121 (4)	−0.032 (3)	0.037 (3)	−0.119 (4)
C17	0.063 (2)	0.126 (4)	0.054 (2)	−0.049 (2)	0.0264 (19)	−0.061 (2)
C18	0.106 (4)	0.172 (6)	0.050 (3)	−0.079 (4)	0.030 (3)	−0.064 (3)
C19	0.133 (4)	0.145 (5)	0.0194 (16)	−0.091 (4)	−0.006 (2)	−0.003 (2)
C20B	0.0258 (13)	0.0246 (12)	0.0381 (15)	0.0007 (10)	−0.0089 (11)	−0.0098 (11)
C20A	0.0268 (13)	0.0282 (12)	0.0309 (13)	0.0028 (10)	−0.0082 (11)	−0.0127 (11)
C20	0.0382 (16)	0.0348 (14)	0.0406 (16)	−0.0086 (12)	−0.0038 (13)	−0.0034 (12)
C21	0.0353 (15)	0.0388 (14)	0.0341 (15)	−0.0087 (12)	0.0001 (12)	−0.0081 (12)
C22	0.0395 (16)	0.0505 (17)	0.0336 (15)	−0.0022 (14)	0.0011 (13)	−0.0076 (14)
C23	0.0406 (16)	0.0558 (18)	0.0306 (15)	0.0095 (14)	−0.0083 (13)	−0.0187 (14)
C24	0.0296 (14)	0.0381 (14)	0.0367 (15)	0.0082 (11)	−0.0129 (12)	−0.0186 (12)
C25	0.0439 (17)	0.0461 (17)	0.0499 (19)	0.0077 (14)	−0.0203 (15)	−0.0292 (15)
C26	0.0427 (17)	0.0383 (16)	0.068 (2)	0.0005 (14)	−0.0254 (16)	−0.0262 (16)
C27	0.0318 (14)	0.0278 (13)	0.0547 (18)	−0.0023 (11)	−0.0149 (13)	−0.0125 (13)
C28	0.0456 (18)	0.0327 (15)	0.076 (2)	−0.0146 (14)	−0.0168 (17)	−0.0075 (16)
C29	0.0454 (18)	0.0429 (16)	0.057 (2)	−0.0165 (14)	−0.0035 (16)	0.0008 (15)
C31	0.0244 (12)	0.0226 (11)	0.0216 (12)	−0.0024 (9)	−0.0031 (10)	−0.0039 (9)
C32	0.0244 (12)	0.0222 (11)	0.0214 (11)	−0.0014 (9)	−0.0034 (10)	−0.0036 (9)
C33	0.0250 (12)	0.0192 (10)	0.0232 (12)	0.0002 (9)	−0.0027 (10)	−0.0030 (9)
C41	0.0309 (14)	0.0333 (13)	0.0249 (13)	−0.0053 (11)	−0.0089 (11)	−0.0039 (11)
C42	0.0435 (16)	0.0392 (15)	0.0315 (14)	0.0074 (13)	−0.0091 (13)	−0.0125 (12)
C43	0.0480 (17)	0.0321 (14)	0.0298 (14)	0.0111 (12)	−0.0128 (13)	−0.0070 (12)
C44	0.0273 (13)	0.0297 (12)	0.0247 (12)	−0.0023 (10)	−0.0056 (10)	−0.0057 (10)
C45	0.0416 (16)	0.0260 (12)	0.0320 (14)	0.0032 (11)	−0.0116 (12)	−0.0081 (11)
C46	0.0462 (17)	0.0261 (12)	0.0337 (15)	0.0013 (12)	−0.0164 (13)	−0.0020 (11)
C51	0.0229 (12)	0.0210 (11)	0.0284 (13)	0.0031 (9)	−0.0022 (10)	−0.0038 (10)
C52	0.0351 (14)	0.0286 (12)	0.0236 (12)	0.0044 (11)	−0.0046 (11)	−0.0080 (10)
C53	0.0309 (13)	0.0248 (12)	0.0282 (13)	0.0029 (10)	0.0021 (11)	−0.0094 (10)
C54	0.0252 (12)	0.0201 (11)	0.0273 (12)	0.0003 (9)	−0.0015 (10)	−0.0051 (10)
C55	0.0348 (14)	0.0256 (12)	0.0250 (12)	0.0025 (10)	−0.0081 (11)	−0.0077 (10)
C56	0.0308 (13)	0.0210 (11)	0.0295 (13)	0.0020 (10)	−0.0050 (10)	−0.0100 (10)
C61	0.0279 (13)	0.0298 (12)	0.0200 (12)	0.0017 (10)	−0.0019 (10)	−0.0061 (10)
C62	0.0424 (16)	0.0249 (12)	0.0310 (14)	−0.0015 (11)	−0.0061 (12)	−0.0088 (11)
C63	0.0462 (16)	0.0201 (11)	0.0320 (14)	0.0003 (11)	−0.0100 (12)	−0.0022 (10)
C64	0.0307 (13)	0.0262 (12)	0.0237 (12)	−0.0012 (10)	−0.0050 (10)	−0.0041 (10)
C65	0.0378 (15)	0.0268 (12)	0.0298 (13)	−0.0046 (11)	−0.0056 (11)	−0.0104 (11)
C66	0.0374 (15)	0.0232 (12)	0.0301 (14)	0.0031 (11)	−0.0077 (11)	−0.0051 (10)

Geometric parameters (Å, º) top

Ni1—N1	2.061 (2)	C14—C15	1.425 (6)
Ni1—N3	2.075 (2)	C15—C16	1.321 (7)
Ni1—N2	2.082 (2)	C15—H15B	0.9300
Ni1—N4	2.085 (2)	C16—C17	1.461 (7)
Ni1—O4	2.087 (2)	C16—H16B	0.9300
Ni1—O1	2.1019 (18)	C17—C18	1.372 (7)
S1—O2	1.435 (2)	C18—C19	1.341 (7)
S1—O3	1.460 (2)	C18—H18A	0.9300
S1—O1	1.4723 (18)	C19—H19A	0.9625
S1—C41	1.776 (3)	C20B—C27	1.402 (4)
S2—O7	1.441 (2)	C20B—C20A	1.431 (4)
S2—O5	1.446 (2)	C20A—C24	1.403 (4)
S2—O6	1.451 (2)	C20—C29	1.405 (4)
S2—C64	1.779 (3)	C20—H20A	0.9604
S3—O9	1.447 (2)	C21—C22	1.391 (4)
S3—O10	1.4574 (19)	C21—H21A	0.9300
S3—O8	1.460 (2)	C22—C23	1.361 (4)
S3—C54	1.772 (2)	C22—H22A	0.9300
O4—H2	0.82 (4)	C23—C24	1.406 (4)
O4—H22	0.94 (5)	C23—H23A	0.9300
O11—H11	0.79 (3)	C24—C25	1.433 (4)
O11—H112	0.84 (6)	C25—C26	1.346 (5)
O12—H122	0.92 (6)	C25—H25A	0.9300
O12—H12	0.91 (8)	C26—C27	1.429 (4)
N1—C10	1.326 (4)	C26—H26A	0.9300
N1—C10B	1.366 (4)	C27—C28	1.402 (4)
N2—C11	1.323 (4)	C28—C29	1.360 (5)
N2—C10A	1.352 (3)	C28—H28A	0.9300
N3—C20	1.322 (3)	C29—H29A	0.9300
N3—C20B	1.364 (3)	C41—C46	1.378 (4)
N4—C21	1.322 (3)	C41—C42	1.383 (4)
N4—C20A	1.361 (3)	C42—C43	1.381 (4)
N11—C31	1.324 (3)	C42—H42A	0.9300
N11—C33	1.343 (3)	C43—C44	1.390 (3)
N12—C32	1.312 (3)	C43—H43A	0.9300
N12—C33	1.357 (3)	C44—C45	1.396 (3)
N13—C32	1.363 (3)	C45—C46	1.375 (4)
N13—C31	1.364 (3)	C45—H45A	0.9300
N13—H13	0.84 (3)	C46—H46A	0.9300
N14—C32	1.341 (3)	C51—C56	1.391 (3)
N14—C44	1.417 (3)	C51—C52	1.397 (3)
N14—H14A	0.8600	C52—C53	1.382 (3)
N15—C33	1.348 (3)	C52—H52A	0.9300
N15—C51	1.412 (3)	C53—C54	1.379 (4)
N15—H15A	0.8600	C53—H53A	0.9300
N16—C31	1.334 (3)	C54—C55	1.392 (3)
N16—C61	1.417 (3)	C55—C56	1.387 (3)
N16—H16A	0.8600	C55—H55A	0.9300
C10A—C10B	1.421 (4)	C56—H56A	0.9300
C10A—C14	1.422 (4)	C61—C66	1.383 (4)
C10B—C17	1.402 (4)	C61—C62	1.387 (3)
C10—C19	1.420 (6)	C62—C63	1.386 (4)
C10—H10B	0.9300	C62—H62A	0.9300
C11—C12	1.392 (4)	C63—C64	1.380 (4)
C11—H11B	0.9300	C63—H63A	0.9300
C12—C13	1.340 (6)	C64—C65	1.383 (3)
C12—H12B	0.9300	C65—C66	1.378 (4)
C13—C14	1.404 (6)	C65—H65A	0.9300
C13—H13B	0.9300	C66—H66A	0.9300

N1—Ni1—N3	97.20 (9)	C10—C19—H19A	119.4
N1—Ni1—N2	80.41 (9)	N3—C20B—C27	122.5 (3)
N3—Ni1—N2	101.02 (8)	N3—C20B—C20A	117.4 (2)
N1—Ni1—N4	173.02 (9)	C27—C20B—C20A	120.1 (2)
N3—Ni1—N4	80.27 (8)	N4—C20A—C24	122.6 (3)
N2—Ni1—N4	93.64 (8)	N4—C20A—C20B	117.2 (2)
N1—Ni1—O4	96.80 (10)	C24—C20A—C20B	120.2 (2)
N3—Ni1—O4	87.21 (9)	N3—C20—C29	122.3 (3)
N2—Ni1—O4	171.55 (9)	N3—C20—H20A	118.9
N4—Ni1—O4	89.60 (9)	C29—C20—H20A	118.9
N1—Ni1—O1	89.19 (8)	N4—C21—C22	123.2 (3)
N3—Ni1—O1	172.66 (8)	N4—C21—H21A	118.4
N2—Ni1—O1	83.55 (8)	C22—C21—H21A	118.4
N4—Ni1—O1	93.79 (8)	C23—C22—C21	119.3 (3)
O4—Ni1—O1	88.46 (9)	C23—C22—H22A	120.3
O2—S1—O3	114.59 (13)	C21—C22—H22A	120.3
O2—S1—O1	110.82 (11)	C22—C23—C24	119.6 (3)
O3—S1—O1	111.61 (11)	C22—C23—H23A	120.2
O2—S1—C41	106.65 (12)	C24—C23—H23A	120.2
O3—S1—C41	106.22 (12)	C20A—C24—C23	117.3 (3)
O1—S1—C41	106.39 (12)	C20A—C24—C25	118.6 (3)
O7—S2—O5	113.16 (15)	C23—C24—C25	124.1 (3)
O7—S2—O6	113.32 (15)	C26—C25—C24	120.8 (3)
O5—S2—O6	111.27 (14)	C26—C25—H25A	119.6
O7—S2—C64	106.78 (12)	C24—C25—H25A	119.6
O5—S2—C64	106.36 (13)	C25—C26—C27	122.2 (3)
O6—S2—C64	105.26 (13)	C25—C26—H26A	118.9
O9—S3—O10	112.51 (12)	C27—C26—H26A	118.9
O9—S3—O8	112.82 (13)	C28—C27—C20B	116.9 (3)
O10—S3—O8	111.72 (12)	C28—C27—C26	124.8 (3)
O9—S3—C54	107.53 (12)	C20B—C27—C26	118.2 (3)
O10—S3—C54	106.41 (11)	C29—C28—C27	120.5 (3)
O8—S3—C54	105.28 (11)	C29—C28—H28A	119.8
S1—O1—Ni1	133.23 (10)	C27—C28—H28A	119.8
Ni1—O4—H2	135 (3)	C28—C29—C20	119.0 (3)
Ni1—O4—H22	108 (3)	C28—C29—H29A	120.5
H2—O4—H22	110 (4)	C20—C29—H29A	120.5
H11—O11—H112	101 (5)	N11—C31—N16	123.1 (2)
H122—O12—H12	119 (6)	N11—C31—N13	122.1 (2)
C10—N1—C10B	118.1 (3)	N16—C31—N13	114.8 (2)
C10—N1—Ni1	129.6 (2)	N12—C32—N14	122.3 (2)
C10B—N1—Ni1	112.07 (18)	N12—C32—N13	120.8 (2)
C11—N2—C10A	118.5 (2)	N14—C32—N13	116.9 (2)
C11—N2—Ni1	128.72 (19)	N11—C33—N15	121.1 (2)
C10A—N2—Ni1	111.64 (18)	N11—C33—N12	126.9 (2)
C20—N3—C20B	118.8 (2)	N15—C33—N12	112.0 (2)
C20—N3—Ni1	128.46 (19)	C46—C41—C42	119.2 (2)
C20B—N3—Ni1	112.54 (17)	C46—C41—S1	120.23 (19)
C21—N4—C20A	117.9 (2)	C42—C41—S1	120.5 (2)
C21—N4—Ni1	129.58 (19)	C43—C42—C41	121.4 (3)
C20A—N4—Ni1	112.49 (17)	C43—C42—H42A	119.3
C31—N11—C33	114.4 (2)	C41—C42—H42A	119.3
C32—N12—C33	116.0 (2)	C42—C43—C44	119.3 (2)
C32—N13—C31	119.45 (19)	C42—C43—H43A	120.3
C32—N13—H13	122 (2)	C44—C43—H43A	120.3
C31—N13—H13	117 (2)	C43—C44—C45	119.1 (2)
C32—N14—C44	127.9 (2)	C43—C44—N14	124.6 (2)
C32—N14—H14A	116.0	C45—C44—N14	116.3 (2)
C44—N14—H14A	116.0	C46—C45—C44	120.7 (2)
C33—N15—C51	131.8 (2)	C46—C45—H45A	119.7
C33—N15—H15A	114.1	C44—C45—H45A	119.7
C51—N15—H15A	114.1	C45—C46—C41	120.3 (2)
C31—N16—C61	129.7 (2)	C45—C46—H46A	119.9
C31—N16—H16A	115.2	C41—C46—H46A	119.9
C61—N16—H16A	115.2	C56—C51—C52	119.5 (2)
N2—C10A—C10B	117.6 (2)	C56—C51—N15	125.4 (2)
N2—C10A—C14	121.6 (3)	C52—C51—N15	115.1 (2)
C10B—C10A—C14	120.9 (3)	C53—C52—C51	120.7 (2)
N1—C10B—C17	122.6 (3)	C53—C52—H52A	119.7
N1—C10B—C10A	117.3 (2)	C51—C52—H52A	119.7
C17—C10B—C10A	120.1 (3)	C54—C53—C52	119.9 (2)
N1—C10—C19	120.8 (4)	C54—C53—H53A	120.1
N1—C10—H10B	119.6	C52—C53—H53A	120.1
C19—C10—H10B	119.6	C53—C54—C55	119.8 (2)
N2—C11—C12	123.3 (3)	C53—C54—S3	120.62 (18)
N2—C11—H11B	118.4	C55—C54—S3	119.48 (19)
C12—C11—H11B	118.4	C56—C55—C54	120.8 (2)
C13—C12—C11	119.1 (3)	C56—C55—H55A	119.6
C13—C12—H12B	120.5	C54—C55—H55A	119.6
C11—C12—H12B	120.5	C55—C56—C51	119.4 (2)
C12—C13—C14	120.5 (3)	C55—C56—H56A	120.3
C12—C13—H13B	119.7	C51—C56—H56A	120.3
C14—C13—H13B	119.7	C66—C61—C62	120.2 (2)
C13—C14—C10A	117.0 (3)	C66—C61—N16	116.1 (2)
C13—C14—C15	125.3 (4)	C62—C61—N16	123.5 (2)
C10A—C14—C15	117.7 (4)	C63—C62—C61	119.0 (2)
C16—C15—C14	121.8 (4)	C63—C62—H62A	120.5
C16—C15—H15B	119.1	C61—C62—H62A	120.5
C14—C15—H15B	119.1	C64—C63—C62	120.9 (2)
C15—C16—C17	122.3 (4)	C64—C63—H63A	119.5
C15—C16—H16B	118.9	C62—C63—H63A	119.5
C17—C16—H16B	118.9	C63—C64—C65	119.5 (2)
C18—C17—C10B	118.0 (4)	C63—C64—S2	120.33 (18)
C18—C17—C16	124.7 (4)	C65—C64—S2	120.11 (19)
C10B—C17—C16	117.3 (4)	C66—C65—C64	120.1 (2)
C19—C18—C17	119.8 (4)	C66—C65—H65A	119.9
C19—C18—H18A	120.1	C64—C65—H65A	119.9
C17—C18—H18A	120.1	C65—C66—C61	120.2 (2)
C18—C19—C10	120.6 (4)	C65—C66—H66A	119.9
C18—C19—H19A	120.0	C61—C66—H66A	119.9

O2—S1—O1—Ni1	−167.03 (14)	C20B—N3—C20—C29	0.8 (4)
O3—S1—O1—Ni1	−38.02 (18)	Ni1—N3—C20—C29	174.7 (2)
C41—S1—O1—Ni1	77.42 (17)	C20A—N4—C21—C22	−0.4 (4)
N1—Ni1—O1—S1	−87.15 (16)	Ni1—N4—C21—C22	−179.9 (2)
N3—Ni1—O1—S1	63.5 (6)	N4—C21—C22—C23	0.8 (4)
N2—Ni1—O1—S1	−167.59 (16)	C21—C22—C23—C24	0.0 (4)
N4—Ni1—O1—S1	99.17 (15)	N4—C20A—C24—C23	1.4 (4)
O4—Ni1—O1—S1	9.67 (16)	C20B—C20A—C24—C23	−178.9 (2)
N3—Ni1—N1—C10	−78.3 (3)	N4—C20A—C24—C25	−177.4 (2)
N2—Ni1—N1—C10	−178.3 (3)	C20B—C20A—C24—C25	2.3 (4)
N4—Ni1—N1—C10	−146.5 (6)	C22—C23—C24—C20A	−1.0 (4)
O4—Ni1—N1—C10	9.8 (3)	C22—C23—C24—C25	177.8 (3)
O1—Ni1—N1—C10	98.1 (3)	C20A—C24—C25—C26	−0.8 (4)
N3—Ni1—N1—C10B	107.66 (19)	C23—C24—C25—C26	−179.6 (3)
N2—Ni1—N1—C10B	7.64 (18)	C24—C25—C26—C27	−0.7 (4)
N4—Ni1—N1—C10B	39.4 (8)	N3—C20B—C27—C28	0.9 (4)
O4—Ni1—N1—C10B	−164.31 (19)	C20A—C20B—C27—C28	−177.9 (2)
O1—Ni1—N1—C10B	−75.95 (19)	N3—C20B—C27—C26	179.4 (2)
N1—Ni1—N2—C11	−176.5 (2)	C20A—C20B—C27—C26	0.7 (4)
N3—Ni1—N2—C11	88.0 (2)	C25—C26—C27—C28	179.3 (3)
N4—Ni1—N2—C11	7.2 (2)	C25—C26—C27—C20B	0.8 (4)
O4—Ni1—N2—C11	−105.2 (7)	C20B—C27—C28—C29	−0.3 (4)
O1—Ni1—N2—C11	−86.2 (2)	C26—C27—C28—C29	−178.7 (3)
N1—Ni1—N2—C10A	−8.92 (17)	C27—C28—C29—C20	0.0 (5)
N3—Ni1—N2—C10A	−104.46 (18)	N3—C20—C29—C28	−0.3 (5)
N4—Ni1—N2—C10A	174.75 (17)	C33—N11—C31—N16	174.0 (2)
O4—Ni1—N2—C10A	62.4 (7)	C33—N11—C31—N13	−5.7 (3)
O1—Ni1—N2—C10A	81.35 (17)	C61—N16—C31—N11	−4.0 (4)
N1—Ni1—N3—C20	9.9 (2)	C61—N16—C31—N13	175.7 (2)
N2—Ni1—N3—C20	91.5 (2)	C32—N13—C31—N11	6.6 (3)
N4—Ni1—N3—C20	−176.7 (2)	C32—N13—C31—N16	−173.1 (2)
O4—Ni1—N3—C20	−86.6 (2)	C33—N12—C32—N14	178.5 (2)
O1—Ni1—N3—C20	−140.5 (5)	C33—N12—C32—N13	−1.4 (3)
N1—Ni1—N3—C20B	−175.90 (17)	C44—N14—C32—N12	9.1 (4)
N2—Ni1—N3—C20B	−94.33 (17)	C44—N14—C32—N13	−170.9 (2)
N4—Ni1—N3—C20B	−2.48 (16)	C31—N13—C32—N12	−2.7 (4)
O4—Ni1—N3—C20B	87.59 (18)	C31—N13—C32—N14	177.4 (2)
O1—Ni1—N3—C20B	33.7 (7)	C31—N11—C33—N15	−178.7 (2)
N1—Ni1—N4—C21	−109.5 (7)	C31—N11—C33—N12	1.3 (4)
N3—Ni1—N4—C21	−178.7 (2)	C51—N15—C33—N11	−6.6 (4)
N2—Ni1—N4—C21	−78.1 (2)	C51—N15—C33—N12	173.4 (2)
O4—Ni1—N4—C21	94.1 (2)	C32—N12—C33—N11	2.2 (4)
O1—Ni1—N4—C21	5.6 (2)	C32—N12—C33—N15	−177.8 (2)
N1—Ni1—N4—C20A	71.0 (7)	O2—S1—C41—C46	−54.7 (3)
N3—Ni1—N4—C20A	1.80 (16)	O3—S1—C41—C46	−177.3 (2)
N2—Ni1—N4—C20A	102.37 (17)	O1—S1—C41—C46	63.7 (2)
O4—Ni1—N4—C20A	−85.44 (17)	O2—S1—C41—C42	122.9 (2)
O1—Ni1—N4—C20A	−173.86 (16)	O3—S1—C41—C42	0.3 (3)
C11—N2—C10A—C10B	177.9 (2)	O1—S1—C41—C42	−118.7 (2)
Ni1—N2—C10A—C10B	8.9 (3)	C46—C41—C42—C43	1.8 (5)
C11—N2—C10A—C14	−1.3 (4)	S1—C41—C42—C43	−175.9 (2)
Ni1—N2—C10A—C14	−170.2 (2)	C41—C42—C43—C44	−0.4 (5)
C10—N1—C10B—C17	−2.2 (4)	C42—C43—C44—C45	−2.0 (4)
Ni1—N1—C10B—C17	172.6 (2)	C42—C43—C44—N14	177.7 (3)
C10—N1—C10B—C10A	179.8 (3)	C32—N14—C44—C43	−19.0 (4)
Ni1—N1—C10B—C10A	−5.3 (3)	C32—N14—C44—C45	160.7 (3)
N2—C10A—C10B—N1	−2.5 (4)	C43—C44—C45—C46	3.2 (4)
C14—C10A—C10B—N1	176.6 (2)	N14—C44—C45—C46	−176.5 (3)
N2—C10A—C10B—C17	179.5 (3)	C44—C45—C46—C41	−1.9 (4)
C14—C10A—C10B—C17	−1.4 (4)	C42—C41—C46—C45	−0.6 (4)
C10B—N1—C10—C19	−1.0 (5)	S1—C41—C46—C45	177.1 (2)
Ni1—N1—C10—C19	−174.8 (3)	C33—N15—C51—C56	11.6 (4)
C10A—N2—C11—C12	−0.3 (4)	C33—N15—C51—C52	−168.0 (3)
Ni1—N2—C11—C12	166.5 (2)	C56—C51—C52—C53	−2.6 (4)
N2—C11—C12—C13	1.2 (5)	N15—C51—C52—C53	177.1 (2)
C11—C12—C13—C14	−0.6 (5)	C51—C52—C53—C54	1.6 (4)
C12—C13—C14—C10A	−0.9 (5)	C52—C53—C54—C55	0.5 (4)
C12—C13—C14—C15	−179.3 (3)	C52—C53—C54—S3	−175.8 (2)
N2—C10A—C14—C13	1.8 (4)	O9—S3—C54—C53	−133.8 (2)
C10B—C10A—C14—C13	−177.3 (3)	O10—S3—C54—C53	−13.0 (2)
N2—C10A—C14—C15	−179.6 (3)	O8—S3—C54—C53	105.7 (2)
C10B—C10A—C14—C15	1.3 (4)	O9—S3—C54—C55	49.9 (2)
C13—C14—C15—C16	177.3 (4)	O10—S3—C54—C55	170.6 (2)
C10A—C14—C15—C16	−1.1 (6)	O8—S3—C54—C55	−70.7 (2)
C14—C15—C16—C17	1.1 (8)	C53—C54—C55—C56	−1.7 (4)
N1—C10B—C17—C18	3.5 (5)	S3—C54—C55—C56	174.7 (2)
C10A—C10B—C17—C18	−178.6 (3)	C54—C55—C56—C51	0.7 (4)
N1—C10B—C17—C16	−176.6 (3)	C52—C51—C56—C55	1.4 (4)
C10A—C10B—C17—C16	1.3 (5)	N15—C51—C56—C55	−178.2 (2)
C15—C16—C17—C18	178.7 (5)	C31—N16—C61—C66	−146.4 (3)
C15—C16—C17—C10B	−1.1 (7)	C31—N16—C61—C62	37.2 (4)
C10B—C17—C18—C19	−1.5 (7)	C66—C61—C62—C63	0.0 (4)
C16—C17—C18—C19	178.7 (4)	N16—C61—C62—C63	176.2 (2)
C17—C18—C19—C10	−1.6 (7)	C61—C62—C63—C64	−0.2 (4)
N1—C10—C19—C18	3.0 (6)	C62—C63—C64—C65	0.5 (4)
C20—N3—C20B—C27	−1.1 (4)	C62—C63—C64—S2	−177.4 (2)
Ni1—N3—C20B—C27	−175.98 (19)	O7—S2—C64—C63	−164.9 (2)
C20—N3—C20B—C20A	177.7 (2)	O5—S2—C64—C63	74.0 (2)
Ni1—N3—C20B—C20A	2.8 (3)	O6—S2—C64—C63	−44.1 (3)
C21—N4—C20A—C24	−0.7 (4)	O7—S2—C64—C65	17.2 (3)
Ni1—N4—C20A—C24	178.86 (19)	O5—S2—C64—C65	−103.9 (2)
C21—N4—C20A—C20B	179.6 (2)	O6—S2—C64—C65	137.9 (2)
Ni1—N4—C20A—C20B	−0.9 (3)	C63—C64—C65—C66	−0.8 (4)
N3—C20B—C20A—N4	−1.3 (3)	S2—C64—C65—C66	177.2 (2)
C27—C20B—C20A—N4	177.5 (2)	C64—C65—C66—C61	0.6 (4)
N3—C20B—C20A—C24	178.9 (2)	C62—C61—C66—C65	−0.2 (4)
C27—C20B—C20A—C24	−2.2 (4)	N16—C61—C66—C65	−176.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2···O5ⁱ	0.82 (4)	1.96 (4)	2.756 (3)	165 (4)
O4—H22···O3	0.94 (5)	1.78 (5)	2.691 (3)	162 (4)
O11—H11···O6	0.79 (3)	1.98 (3)	2.768 (4)	177 (3)
O11—H112···O12	0.84 (6)	2.32 (6)	3.045 (4)	144 (6)
O12—H122···O7	0.92 (6)	2.06 (6)	2.944 (4)	160 (5)
N14—H14A···O8ⁱ	0.86	2.08	2.887 (3)	156
N15—H15A···O11ⁱⁱ	0.86	2.13	2.974 (3)	166
N16—H16A···O10ⁱⁱⁱ	0.86	2.06	2.864 (3)	155
N13—H13···O10ⁱⁱⁱ	0.84 (3)	2.06 (3)	2.840 (3)	155 (3)
O12—H12···O8^iv	0.91 (8)	2.19 (8)	3.035 (4)	155 (7)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₂₁H₁₆N₆O₉S₃)(C₁₂H₈N₂)₂(H₂O)]·2H₂O
M_r	1065.74
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.256 (2), 11.684 (3), 24.086 (7)
α, β, γ (°)	76.134 (7), 84.875 (10), 75.718 (6)
V (Å³)	2185.0 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.25 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Mercury70 (2x2 bin mode)
Absorption correction	Multi-scan (CrystalClear; Rigaku Corporation, 2000)
T_min, T_max	0.907, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17176, 9893, 7634
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.108, 1.05
No. of reflections	9893
No. of parameters	668
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.37

Computer programs: CrystalClear (Rigaku Corporation, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXP97 (Sheldrick, 1997), SHELXL97.