catena-Poly[[[(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ⁴ N)nickel(II)]-μ-oxido-[dioxidotungstate(VI)]-μ-oxido] tetra­hydrate]

Abstract

In the title compound, {[NiWO₄(C₁₆H₃₆N₄)]·4H₂O}_n, the Ni^II ion lies on an inversion center and is octahedrally coordinated by four N atoms of the tetradentate macrocyclic 5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane (L) ligand in the equatorial plane and two O atoms of [WO₄]²⁻ anions in axial positions. Each [WO₄]²⁻ anion bridges two adjacent [NiL]²⁺ cations, forming a chain along [001]. The chains are further connected via N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding inter­actions, generating a three-dimensional structure.

Related literature  

For a related structure, see: Ou et al. (2011 ▶).

Experimental  

Crystal data  

• [NiWO₄(C₁₆H₃₆N₄)]·4H₂O

• M _r = 663.11

• Triclinic,

• a = 8.8402 (14) Å

• b = 11.7653 (18) Å

• c = 13.931 (2) Å

• α = 107.163 (2)°

• β = 102.529 (3)°

• γ = 104.984 (3)°

• V = 1268.1 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 5.32 mm⁻¹

• T = 173 K

• 0.31 × 0.11 × 0.02 mm

Data collection  

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.289, T _max = 0.901

• 7631 measured reflections

• 5397 independent reflections

• 4330 reflections with I > 2σ(I)

• R _int = 0.030

Refinement  

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.096

• S = 1.02

• 5397 reflections

• 304 parameters

• 13 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 2.33 e Å⁻³

• Δρ_min = −1.48 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2i	0.93	2.32	3.253 (7)	180
N2—H2C⋯O4W i	0.93	2.21	3.040 (8)	149
O4W—H4WB⋯O3W	0.85 (2)	2.12 (5)	2.720 (8)	128 (6)
O4W—H4WA⋯O3	0.86 (2)	2.05 (3)	2.900 (7)	168 (6)
O2W—H2WA⋯O1W ii	0.85 (2)	1.94 (2)	2.790 (8)	175 (7)
O3W—H3WA⋯O2iii	0.87 (2)	2.01 (5)	2.784 (7)	148 (8)
O1W—H1WA⋯O2	0.86 (2)	1.95 (2)	2.801 (7)	172 (8)
O2W—H2WB⋯O3	0.86 (2)	1.99 (3)	2.811 (7)	160 (8)
O3W—H3WB⋯O2W	0.86 (2)	2.08 (4)	2.834 (8)	145 (6)
O1W—H1WB⋯O2W	0.85 (2)	2.10 (4)	2.895 (9)	157 (7)
C16—H16A⋯O1iv	0.98	2.40	3.241 (9)	144

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Continuing our research (Ou et al., 2011), we now report the crystal structure of the title complex. The asymmetric unit of the title complex contains one cation [NiL]²⁺, one anion [WO₄]^2-, and four water molecules of hydration. Each Ni^II ion displays a distorted octahedral coordination geometry by coordination with four nitrogen atoms of L in in the equatorial plane, and two oxygen atoms of [WO₄]^2- anions in the axial positions. Each [WO₄]^2- anion bridges two adjacent [NiL]²⁺ cations to form a one-dimensional chain. The one-dimensional chains are further connected through O···O (2.720 (8)–2.900 (8) Å) and N···O (3.040 (8) and 3.253 (7) Å) hydrogen bonding interactions between the oxygen atoms of [WO₄]^2- anions, free water molecules and the secondary amine of [NiL]²⁺, forming a three-dimensional supramolecular structure (Tab. 2, Figs. 2, 3).

Experimental

A glass tube was charged with an aqueous solution of K₂WO₄ (0.033 g, 0.1 mmol) in water (20 ml), and a mixture of methanol and H₂O (1/1, 20 ml) was gently added as an upper layer. A solution of NiL (ClO₄)₂ (0.054 g, 0.1 mmol) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in methanol (20 ml) was added carefully as a third layer, and then the tube was sealed. After several weeks, yellow prism-shaped crystals were obtained.

Refinement

The H atoms bound to N and C atoms were positioned geometrically and refined using the riding model with N—H = 0.93 Å and C—H = 0.98 to 1.00 Å. The hydrogen atoms of the water molecules were located from a difference Fourier map and were constrained at distances O—H = 0.86 (2) Å. U_iso(H) were set to 1.5 × U_eq(methyl C) and 1.2 × U_eq(the rest of the parent atoms).

Figures

Fig. 1.

The molecular structure of the title complex, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Symmetry codes for the generated atoms: A: 2 - x, 2 - y, 1 - z; B: 2 - x, 2 - y, 2 - z.

Fig. 2.

A view of the hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen- bonding were omitted for clarity.

Fig. 3.

Hydrogen bonding (dashed lines) in the title compound. Symmetry codes for the generated atoms: A: 1 - x, 1 - y, 1 - z; B: -1 + x, y, z; C: - x, 1 - y, 1 - z.

Crystal data

[NiWO4(C16H36N4)]·4H2O	Z = 2
Mr = 663.11	F(000) = 668
Triclinic, P1	Dx = 1.737 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8402 (14) Å	Cell parameters from 3766 reflections
b = 11.7653 (18) Å	θ = 1.9–27.1°
c = 13.931 (2) Å	µ = 5.32 mm−1
α = 107.163 (2)°	T = 173 K
β = 102.529 (3)°	Prism, yellow
γ = 104.984 (3)°	0.31 × 0.11 × 0.02 mm
V = 1268.1 (3) Å3

Data collection

Bruker SMART CCD area-detector diffractometer	5397 independent reflections
Radiation source: fine-focus sealed tube	4330 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 27.1°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→4
Tmin = 0.289, Tmax = 0.901	k = −14→15
7631 measured reflections	l = −17→17

Refinement

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/3
5397 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 2.33 e Å−3
13 restraints	Δρmin = −1.48 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
W1	0.86432 (3)	0.90496 (2)	0.70182 (2)	0.01423 (9)
O4	0.9085 (5)	0.9844 (4)	0.8399 (3)	0.0187 (9)
O1	0.9900 (5)	0.9988 (4)	0.6505 (3)	0.0201 (10)
O3	0.6535 (5)	0.8719 (4)	0.6342 (4)	0.0231 (10)
O2	0.9049 (6)	0.7611 (4)	0.6806 (4)	0.0258 (11)
Ni1	1.0000	1.0000	1.0000	0.0130 (2)
Ni2	1.0000	1.0000	0.5000	0.0139 (2)
N1	0.9427 (7)	1.1622 (5)	1.0653 (4)	0.0170 (11)
H1C	0.9860	1.1842	1.1380	0.020*
N2	1.2351 (6)	1.1000 (5)	1.0097 (4)	0.0158 (11)
H2C	1.3028	1.1227	1.0785	0.019*
N4	0.7426 (6)	0.9212 (5)	0.4386 (4)	0.0183 (11)
H4D	0.7043	0.9048	0.4920	0.022*
N3	1.0343 (7)	0.8257 (5)	0.4733 (4)	0.0195 (12)
H3A	1.0258	0.8088	0.5334	0.023*
C6	1.0127 (9)	1.2828 (6)	1.0490 (5)	0.0219 (15)
C11	0.6783 (9)	0.7997 (7)	0.3458 (6)	0.0298 (17)
H11	0.7226	0.8148	0.2887	0.036*
C5	1.1979 (9)	1.3084 (6)	1.0670 (6)	0.0264 (16)
H5A	1.2466	1.3084	1.1380	0.032*
H5B	1.2477	1.3953	1.0694	0.032*
C9	1.2125 (8)	0.8541 (7)	0.4833 (6)	0.0271 (16)
H9A	1.2321	0.8652	0.4188	0.033*
H9B	1.2474	0.7833	0.4922	0.033*
C10	0.6896 (9)	1.0242 (7)	0.4200 (6)	0.0295 (17)
H10A	0.5698	1.0036	0.4095	0.035*
H10B	0.7109	1.0349	0.3558	0.035*
C14	0.9159 (9)	0.7086 (6)	0.3836 (6)	0.0266 (16)
C16	0.9464 (10)	0.7001 (7)	0.2778 (6)	0.0359 (19)
H16A	0.9446	0.7773	0.2649	0.054*
H16B	0.8597	0.6263	0.2204	0.054*
H16C	1.0543	0.6912	0.2805	0.054*
C13	0.7386 (9)	0.7023 (6)	0.3763 (6)	0.0313 (18)
H13A	0.6640	0.6175	0.3245	0.038*
H13B	0.7252	0.7078	0.4461	0.038*
C15	0.9397 (11)	0.5905 (7)	0.4055 (7)	0.041 (2)
H15A	0.8627	0.5129	0.3469	0.061*
H15B	0.9180	0.5911	0.4717	0.061*
H15C	1.0533	0.5934	0.4117	0.061*
C12	0.4873 (10)	0.7496 (8)	0.3017 (7)	0.045 (2)
H12A	0.4416	0.7344	0.3568	0.068*
H12B	0.4495	0.6701	0.2403	0.068*
H12C	0.4499	0.8125	0.2803	0.068*
C3	1.2531 (9)	1.2195 (6)	0.9881 (6)	0.0256 (16)
H3	1.1785	1.1969	0.9150	0.031*
C8	0.9959 (10)	1.3946 (6)	1.1322 (6)	0.0283 (16)
H8A	0.8787	1.3813	1.1227	0.042*
H8B	1.0477	1.4736	1.1233	0.042*
H8C	1.0506	1.4000	1.2034	0.042*
C7	0.9231 (9)	1.2735 (7)	0.9384 (6)	0.0298 (17)
H7A	0.9179	1.1950	0.8854	0.045*
H7B	0.9832	1.3464	0.9246	0.045*
H7C	0.8109	1.2731	0.9343	0.045*
C4	1.4286 (10)	1.2865 (8)	0.9937 (8)	0.051 (3)
H4A	1.5007	1.3220	1.0674	0.077*
H4B	1.4304	1.3550	0.9671	0.077*
H4C	1.4677	1.2257	0.9504	0.077*
C1	0.7623 (8)	1.1146 (6)	1.0442 (5)	0.0213 (14)
H1A	0.7047	1.1009	0.9702	0.026*
H1B	0.7301	1.1780	1.0919	0.026*
C2	1.2872 (8)	1.0076 (6)	0.9384 (5)	0.0188 (14)
H2A	1.4084	1.0407	0.9539	0.023*
H2B	1.2336	0.9936	0.8636	0.023*
O2W	0.3988 (7)	0.6388 (5)	0.5720 (5)	0.0422 (14)
H2WA	0.389 (10)	0.589 (5)	0.510 (3)	0.051*
H2WB	0.458 (9)	0.714 (3)	0.582 (5)	0.051*
O4W	0.5200 (7)	0.9166 (6)	0.8089 (4)	0.0441 (15)
H4WB	0.461 (7)	0.842 (3)	0.797 (4)	0.053*
H4WA	0.564 (9)	0.915 (6)	0.759 (5)	0.053*
O1W	0.6501 (8)	0.5326 (5)	0.6291 (5)	0.0447 (15)
H1WA	0.729 (5)	0.599 (5)	0.639 (7)	0.054*
H1WB	0.560 (4)	0.547 (7)	0.617 (7)	0.054*
O3W	0.2150 (7)	0.7401 (6)	0.6956 (5)	0.0504 (17)
H3WA	0.109 (3)	0.714 (8)	0.681 (5)	0.061*
H3WB	0.234 (7)	0.706 (8)	0.638 (3)	0.061*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
W1	0.01641 (14)	0.01438 (14)	0.01496 (14)	0.00471 (10)	0.00913 (10)	0.00725 (10)
O4	0.021 (2)	0.019 (2)	0.017 (2)	0.0070 (19)	0.0074 (19)	0.0073 (19)
O1	0.014 (2)	0.023 (2)	0.021 (3)	0.0006 (19)	0.0067 (19)	0.010 (2)
O3	0.015 (2)	0.028 (3)	0.022 (3)	0.003 (2)	0.007 (2)	0.004 (2)
O2	0.029 (3)	0.018 (2)	0.034 (3)	0.012 (2)	0.010 (2)	0.011 (2)
Ni1	0.0154 (6)	0.0136 (5)	0.0142 (6)	0.0060 (4)	0.0092 (5)	0.0070 (4)
Ni2	0.0161 (6)	0.0127 (5)	0.0161 (6)	0.0038 (4)	0.0092 (5)	0.0077 (4)
N1	0.027 (3)	0.016 (3)	0.019 (3)	0.011 (2)	0.016 (2)	0.012 (2)
N2	0.020 (3)	0.016 (3)	0.017 (3)	0.008 (2)	0.009 (2)	0.011 (2)
N4	0.019 (3)	0.021 (3)	0.018 (3)	0.006 (2)	0.008 (2)	0.010 (2)
N3	0.023 (3)	0.021 (3)	0.021 (3)	0.010 (2)	0.010 (2)	0.012 (2)
C6	0.039 (4)	0.015 (3)	0.021 (4)	0.016 (3)	0.017 (3)	0.010 (3)
C11	0.020 (4)	0.031 (4)	0.029 (4)	−0.001 (3)	0.007 (3)	0.008 (3)
C5	0.036 (4)	0.016 (3)	0.032 (4)	0.008 (3)	0.022 (3)	0.010 (3)
C9	0.024 (4)	0.038 (4)	0.030 (4)	0.020 (3)	0.013 (3)	0.017 (3)
C10	0.026 (4)	0.032 (4)	0.045 (5)	0.015 (3)	0.019 (4)	0.023 (4)
C14	0.042 (5)	0.015 (3)	0.024 (4)	0.007 (3)	0.020 (3)	0.007 (3)
C16	0.047 (5)	0.029 (4)	0.028 (4)	0.010 (4)	0.018 (4)	0.005 (3)
C13	0.042 (5)	0.013 (3)	0.029 (4)	−0.004 (3)	0.012 (4)	0.004 (3)
C15	0.059 (6)	0.018 (4)	0.046 (5)	0.013 (4)	0.024 (4)	0.010 (4)
C12	0.038 (5)	0.032 (5)	0.045 (5)	0.002 (4)	0.001 (4)	0.004 (4)
C3	0.028 (4)	0.017 (3)	0.041 (5)	0.009 (3)	0.024 (3)	0.015 (3)
C8	0.044 (5)	0.019 (4)	0.032 (4)	0.017 (3)	0.021 (4)	0.011 (3)
C7	0.044 (5)	0.032 (4)	0.027 (4)	0.021 (4)	0.016 (4)	0.020 (3)
C4	0.039 (5)	0.029 (5)	0.098 (8)	0.008 (4)	0.041 (5)	0.032 (5)
C1	0.024 (4)	0.021 (3)	0.025 (4)	0.012 (3)	0.013 (3)	0.010 (3)
C2	0.016 (3)	0.019 (3)	0.025 (4)	0.007 (3)	0.015 (3)	0.006 (3)
O2W	0.031 (3)	0.029 (3)	0.055 (4)	0.001 (3)	0.020 (3)	0.003 (3)
O4W	0.027 (3)	0.071 (4)	0.029 (3)	0.012 (3)	0.015 (3)	0.012 (3)
O1W	0.041 (3)	0.027 (3)	0.048 (4)	−0.003 (3)	0.000 (3)	0.011 (3)
O3W	0.032 (3)	0.044 (4)	0.060 (4)	0.007 (3)	0.025 (3)	−0.005 (3)

Geometric parameters (Å, º)

W1—O1	1.772 (4)	C10—H10A	0.9900
W1—O2	1.773 (4)	C10—H10B	0.9900
W1—O4	1.775 (4)	C14—C13	1.529 (10)
W1—O3	1.778 (4)	C14—C16	1.534 (9)
O4—Ni1	2.135 (4)	C14—C15	1.563 (9)
O1—Ni2	2.121 (4)	C16—H16A	0.9800
Ni1—N2	2.059 (5)	C16—H16B	0.9800
Ni1—N2i	2.059 (5)	C16—H16C	0.9800
Ni1—N1i	2.098 (5)	C13—H13A	0.9900
Ni1—N1	2.098 (5)	C13—H13B	0.9900
Ni1—O4i	2.135 (4)	C15—H15A	0.9800
Ni2—N3ii	2.087 (5)	C15—H15B	0.9800
Ni2—N3	2.087 (5)	C15—H15C	0.9800
Ni2—N4ii	2.089 (5)	C12—H12A	0.9800
Ni2—N4	2.089 (5)	C12—H12B	0.9800
Ni2—O1ii	2.121 (4)	C12—H12C	0.9800
N1—C1	1.477 (8)	C3—C4	1.521 (10)
N1—C6	1.498 (8)	C3—H3	1.0000
N1—H1C	0.9300	C8—H8A	0.9800
N2—C2	1.484 (7)	C8—H8B	0.9800
N2—C3	1.499 (8)	C8—H8C	0.9800
N2—H2C	0.9300	C7—H7A	0.9800
N4—C10	1.478 (8)	C7—H7B	0.9800
N4—C11	1.486 (8)	C7—H7C	0.9800
N4—H4D	0.9300	C4—H4A	0.9800
N3—C9	1.490 (8)	C4—H4B	0.9800
N3—C14	1.492 (8)	C4—H4C	0.9800
N3—H3A	0.9300	C1—C2i	1.498 (8)
C6—C7	1.530 (9)	C1—H1A	0.9900
C6—C5	1.535 (10)	C1—H1B	0.9900
C6—C8	1.539 (9)	C2—C1i	1.498 (8)
C11—C13	1.511 (10)	C2—H2A	0.9900
C11—C12	1.548 (10)	C2—H2B	0.9900
C11—H11	1.0000	O2W—H2WA	0.85 (2)
C5—C3	1.536 (9)	O2W—H2WB	0.86 (2)
C5—H5A	0.9900	O4W—H4WB	0.845 (19)
C5—H5B	0.9900	O4W—H4WA	0.86 (2)
C9—C10ii	1.526 (10)	O1W—H1WA	0.86 (2)
C9—H9A	0.9900	O1W—H1WB	0.85 (2)
C9—H9B	0.9900	O3W—H3WA	0.87 (2)
C10—C9ii	1.526 (10)	O3W—H3WB	0.863 (19)
O1—W1—O2	108.7 (2)	N3—C9—H9A	110.2
O1—W1—O4	110.9 (2)	C10ii—C9—H9A	110.2
O2—W1—O4	108.7 (2)	N3—C9—H9B	110.2
O1—W1—O3	108.9 (2)	C10ii—C9—H9B	110.2
O2—W1—O3	109.7 (2)	H9A—C9—H9B	108.5
O4—W1—O3	109.9 (2)	N4—C10—C9ii	108.0 (6)
W1—O4—Ni1	151.1 (2)	N4—C10—H10A	110.1
W1—O1—Ni2	137.9 (2)	C9ii—C10—H10A	110.1
N2—Ni1—N2i	180.000 (1)	N4—C10—H10B	110.1
N2—Ni1—N1i	85.46 (19)	C9ii—C10—H10B	110.1
N2i—Ni1—N1i	94.5 (2)	H10A—C10—H10B	108.4
N2—Ni1—N1	94.5 (2)	N3—C14—C13	109.8 (5)
N2i—Ni1—N1	85.46 (19)	N3—C14—C16	112.3 (6)
N1i—Ni1—N1	180.000 (3)	C13—C14—C16	110.8 (6)
N2—Ni1—O4	90.57 (18)	N3—C14—C15	108.7 (6)
N2i—Ni1—O4	89.43 (18)	C13—C14—C15	108.1 (6)
N1i—Ni1—O4	85.20 (18)	C16—C14—C15	106.9 (6)
N1—Ni1—O4	94.80 (18)	C14—C16—H16A	109.5
N2—Ni1—O4i	89.43 (18)	C14—C16—H16B	109.5
N2i—Ni1—O4i	90.57 (18)	H16A—C16—H16B	109.5
N1i—Ni1—O4i	94.80 (18)	C14—C16—H16C	109.5
N1—Ni1—O4i	85.20 (18)	H16A—C16—H16C	109.5
O4—Ni1—O4i	180.000 (2)	H16B—C16—H16C	109.5
N3ii—Ni2—N3	180.000 (2)	C11—C13—C14	118.9 (6)
N3ii—Ni2—N4ii	94.6 (2)	C11—C13—H13A	107.6
N3—Ni2—N4ii	85.4 (2)	C14—C13—H13A	107.6
N3ii—Ni2—N4	85.4 (2)	C11—C13—H13B	107.6
N3—Ni2—N4	94.6 (2)	C14—C13—H13B	107.6
N4ii—Ni2—N4	180.000 (1)	H13A—C13—H13B	107.0
N3ii—Ni2—O1ii	86.13 (19)	C14—C15—H15A	109.5
N3—Ni2—O1ii	93.87 (19)	C14—C15—H15B	109.5
N4ii—Ni2—O1ii	90.23 (18)	H15A—C15—H15B	109.5
N4—Ni2—O1ii	89.77 (18)	C14—C15—H15C	109.5
N3ii—Ni2—O1	93.87 (19)	H15A—C15—H15C	109.5
N3—Ni2—O1	86.13 (19)	H15B—C15—H15C	109.5
N4ii—Ni2—O1	89.77 (18)	C11—C12—H12A	109.5
N4—Ni2—O1	90.23 (18)	C11—C12—H12B	109.5
O1ii—Ni2—O1	180.000 (2)	H12A—C12—H12B	109.5
C1—N1—C6	116.7 (5)	C11—C12—H12C	109.5
C1—N1—Ni1	104.6 (4)	H12A—C12—H12C	109.5
C6—N1—Ni1	122.1 (4)	H12B—C12—H12C	109.5
C1—N1—H1C	103.7	N2—C3—C4	112.5 (6)
C6—N1—H1C	103.7	N2—C3—C5	109.4 (5)
Ni1—N1—H1C	103.7	C4—C3—C5	110.3 (6)
C2—N2—C3	113.8 (5)	N2—C3—H3	108.2
C2—N2—Ni1	105.4 (4)	C4—C3—H3	108.2
C3—N2—Ni1	115.3 (4)	C5—C3—H3	108.2
C2—N2—H2C	107.3	C6—C8—H8A	109.5
C3—N2—H2C	107.3	C6—C8—H8B	109.5
Ni1—N2—H2C	107.3	H8A—C8—H8B	109.5
C10—N4—C11	115.2 (5)	C6—C8—H8C	109.5
C10—N4—Ni2	104.7 (4)	H8A—C8—H8C	109.5
C11—N4—Ni2	114.5 (4)	H8B—C8—H8C	109.5
C10—N4—H4D	107.3	C6—C7—H7A	109.5
C11—N4—H4D	107.3	C6—C7—H7B	109.5
Ni2—N4—H4D	107.3	H7A—C7—H7B	109.5
C9—N3—C14	116.5 (5)	C6—C7—H7C	109.5
C9—N3—Ni2	104.7 (4)	H7A—C7—H7C	109.5
C14—N3—Ni2	121.3 (4)	H7B—C7—H7C	109.5
C9—N3—H3A	104.1	C3—C4—H4A	109.5
C14—N3—H3A	104.1	C3—C4—H4B	109.5
Ni2—N3—H3A	104.1	H4A—C4—H4B	109.5
N1—C6—C7	110.9 (6)	C3—C4—H4C	109.5
N1—C6—C5	107.7 (5)	H4A—C4—H4C	109.5
C7—C6—C5	111.8 (6)	H4B—C4—H4C	109.5
N1—C6—C8	110.2 (5)	N1—C1—C2i	109.7 (5)
C7—C6—C8	108.9 (5)	N1—C1—H1A	109.7
C5—C6—C8	107.4 (6)	C2i—C1—H1A	109.7
N4—C11—C13	109.7 (6)	N1—C1—H1B	109.7
N4—C11—C12	111.8 (6)	C2i—C1—H1B	109.7
C13—C11—C12	110.3 (6)	H1A—C1—H1B	108.2
N4—C11—H11	108.3	N2—C2—C1i	108.5 (5)
C13—C11—H11	108.3	N2—C2—H2A	110.0
C12—C11—H11	108.3	C1i—C2—H2A	110.0
C6—C5—C3	119.3 (6)	N2—C2—H2B	110.0
C6—C5—H5A	107.5	C1i—C2—H2B	110.0
C3—C5—H5A	107.5	H2A—C2—H2B	108.4
C6—C5—H5B	107.5	H2WA—O2W—H2WB	109 (3)
C3—C5—H5B	107.5	H4WB—O4W—H4WA	109 (3)
H5A—C5—H5B	107.0	H3WA—O3W—H3WB	107 (3)
N3—C9—C10ii	107.7 (5)
O1—W1—O4—Ni1	−113.9 (5)	N4ii—Ni2—N3—C14	−149.8 (5)
O2—W1—O4—Ni1	5.5 (6)	N4—Ni2—N3—C14	30.2 (5)
O3—W1—O4—Ni1	125.6 (5)	O1ii—Ni2—N3—C14	−59.9 (5)
O2—W1—O1—Ni2	73.4 (4)	O1—Ni2—N3—C14	120.1 (5)
O4—W1—O1—Ni2	−167.2 (3)	C1—N1—C6—C7	−53.1 (7)
O3—W1—O1—Ni2	−46.1 (4)	Ni1—N1—C6—C7	77.3 (6)
W1—O4—Ni1—N2	87.9 (5)	C1—N1—C6—C5	−175.7 (5)
W1—O4—Ni1—N2i	−92.1 (5)	Ni1—N1—C6—C5	−45.2 (7)
W1—O4—Ni1—N1i	2.5 (5)	C1—N1—C6—C8	67.5 (7)
W1—O4—Ni1—N1	−177.5 (5)	Ni1—N1—C6—C8	−162.1 (5)
W1—O1—Ni2—N3ii	117.7 (4)	C10—N4—C11—C13	−178.8 (5)
W1—O1—Ni2—N3	−62.3 (4)	Ni2—N4—C11—C13	59.7 (6)
W1—O1—Ni2—N4ii	−147.8 (4)	C10—N4—C11—C12	−56.2 (8)
W1—O1—Ni2—N4	32.2 (4)	Ni2—N4—C11—C12	−177.7 (5)
N2—Ni1—N1—C1	167.3 (4)	N1—C6—C5—C3	67.8 (7)
N2i—Ni1—N1—C1	−12.7 (4)	C7—C6—C5—C3	−54.3 (8)
O4—Ni1—N1—C1	76.4 (4)	C8—C6—C5—C3	−173.6 (6)
O4i—Ni1—N1—C1	−103.6 (4)	C14—N3—C9—C10ii	−179.4 (5)
N2—Ni1—N1—C6	32.0 (5)	Ni2—N3—C9—C10ii	43.7 (6)
N2i—Ni1—N1—C6	−148.0 (5)	C11—N4—C10—C9ii	−171.2 (5)
O4—Ni1—N1—C6	−58.9 (5)	Ni2—N4—C10—C9ii	−44.5 (6)
O4i—Ni1—N1—C6	121.1 (5)	C9—N3—C14—C13	−172.9 (5)
N1i—Ni1—N2—C2	16.8 (4)	Ni2—N3—C14—C13	−43.5 (7)
N1—Ni1—N2—C2	−163.2 (4)	C9—N3—C14—C16	−49.2 (8)
O4—Ni1—N2—C2	−68.4 (4)	Ni2—N3—C14—C16	80.2 (7)
O4i—Ni1—N2—C2	111.6 (4)	C9—N3—C14—C15	69.0 (7)
N1i—Ni1—N2—C3	143.2 (5)	Ni2—N3—C14—C15	−161.6 (5)
N1—Ni1—N2—C3	−36.8 (5)	N4—C11—C13—C14	−78.2 (8)
O4—Ni1—N2—C3	58.0 (4)	C12—C11—C13—C14	158.4 (6)
O4i—Ni1—N2—C3	−122.0 (4)	N3—C14—C13—C11	66.9 (8)
N3ii—Ni2—N4—C10	16.1 (4)	C16—C14—C13—C11	−57.8 (8)
N3—Ni2—N4—C10	−163.9 (4)	C15—C14—C13—C11	−174.6 (6)
O1ii—Ni2—N4—C10	−70.1 (4)	C2—N2—C3—C4	−56.5 (8)
O1—Ni2—N4—C10	109.9 (4)	Ni1—N2—C3—C4	−178.5 (5)
N3ii—Ni2—N4—C11	143.2 (5)	C2—N2—C3—C5	−179.3 (5)
N3—Ni2—N4—C11	−36.8 (5)	Ni1—N2—C3—C5	58.7 (7)
O1ii—Ni2—N4—C11	57.1 (4)	C6—C5—C3—N2	−77.9 (8)
O1—Ni2—N4—C11	−122.9 (4)	C6—C5—C3—C4	157.9 (6)
N4ii—Ni2—N3—C9	−15.4 (4)	C6—N1—C1—C2i	178.6 (5)
N4—Ni2—N3—C9	164.6 (4)	Ni1—N1—C1—C2i	40.5 (6)
O1ii—Ni2—N3—C9	74.5 (4)	C3—N2—C2—C1i	−170.8 (6)
O1—Ni2—N3—C9	−105.5 (4)	Ni1—N2—C2—C1i	−43.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2i	0.93	2.32	3.253 (7)	180
N2—H2C···O4Wi	0.93	2.21	3.040 (8)	149
O4W—H4WB···O3W	0.85 (2)	2.12 (5)	2.720 (8)	128 (6)
O4W—H4WA···O3	0.86 (2)	2.05 (3)	2.900 (7)	168 (6)
O2W—H2WA···O1Wiii	0.85 (2)	1.94 (2)	2.790 (8)	175 (7)
O3W—H3WA···O2iv	0.87 (2)	2.01 (5)	2.784 (7)	148 (8)
O1W—H1WA···O2	0.86 (2)	1.95 (2)	2.801 (7)	172 (8)
O2W—H2WB···O3	0.86 (2)	1.99 (3)	2.811 (7)	160 (8)
O3W—H3WB···O2W	0.86 (2)	2.08 (4)	2.834 (8)	145 (6)
O1W—H1WB···O2W	0.85 (2)	2.10 (4)	2.895 (9)	157 (7)
C16—H16A···O1ii	0.98	2.40	3.241 (9)	144

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