Synthesis, characterization and crystal structure of the new penta­hydrate of bis­(2,2′-bi­pyridine-κ²N,N′)(oxalato-κ²O¹,O²)nickel(II)

The reaction of NiCl₂, K₂C₂O₄·H₂O and 2,2′-bi­pyridine (bpy) in water–ethanol solution at 281 K yields light-purple needles of the new penta­hydrate of bis­(2,2′-bi­pyridine)­oxalato­nickel(II), [Ni(C₂O₄)(C₁₀H₈N₂)₂]·5H₂O or [Ni(ox)(bpy)₂]·5H₂O, while at room temperature, deep-pink prisms of the previously reported tetra­hydrate [Ni(ox)(bpy)₂]·4H₂O [Román, Luque, Guzmán-Miralles & Beitia (1995), Polyhedron, 14, 2863–2869] were gathered. The asymmetric unit in the crystal structure of the new penta­hydrate incorporates the discrete mol­ecular complex [Ni(ox)(bpy)₂] and five solvent water mol­ecules. Within the complex mol­ecule, all three ligands are bonded as chelates. The complex mol­ecules are involved in an extended system of hydrogen bonds with the solvent water mol­ecules. Additionally, π–π inter­actions also contribute to the stabilization of the extended structure. The dehydration of the penta­hydrate starts at 323 K and proceeds in at least two steps as determined by thermal analysis.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Bis(2,2'-bipyridine-κ²N,N')(oxalato-κ²O¹,O²)nickel(II) pentahydrate

Crystal data

[Ni(C2O4)(C10H8N2)2]·5H2O	F(000) = 1144
Mr = 549.18	Dx = 1.542 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.7474 (4) Å	Cell parameters from 4223 reflections
b = 22.7052 (9) Å	θ = 0.8–1.0°
c = 9.9647 (5) Å	µ = 0.88 mm^−1
β = 103.390 (4)°	T = 100 K
V = 2365.50 (18) Å^3	Needle, light purple
Z = 4	0.30 × 0.10 × 0.07 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer	5415 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4730 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 16.0655 pixels mm^-1	θmax = 27.5°, θmin = 4.2°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −29→29
Tmin = 0.779, Tmax = 1.000	l = −12→12
21922 measured 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 1.1619P] where P = (Fo^2 + 2Fc^2)/3
5415 reflections	(Δ/σ)max = 0.001
355 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. Elemental analysis was performed on CHNOS Elemental Analyzer vario MICRO instrument. Infrared spectra were recorded on a Perkin Elmer Spectrum 100 FT–IR Spectrophotometer with UATR accessory in the range of 4000–400 cm-1. The TG and DTA curves were recorded on a 2960 SDT V3.0 F instrument under the following conditions: sample weight = 5.7873 mg, heating rate = 2 °/min, nitrogen atmosphere, temperature range 20–700°C, aluminium crucibles. IR (in cm-1): 3285(m); 3105(w); 3088(w); 1718(w); 1641(s); 1601(m); 1595(m); 1573(m); 1566(m); 1489(w); 1470(m); 1438(m); 1421(m); 1309(w); 1284(m); 1248(w); 1224(w); 1168(w); 1155(w); 1119(w); 1100(w); 1072(w); 1043(w); 1022(w); 1016(w); 976(w); 903 (w); 863(w); 816(w); 763(m); 734(m); 649(m); 629(m); 549(m); 507(m); 461(m); 439(m); 415(m).

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
Ni1	0.345086 (18)	0.110379 (8)	0.70079 (2)	0.01229 (7)
C1	0.36811 (15)	0.23795 (7)	0.72976 (16)	0.0137 (3)
C2	0.34379 (16)	0.29781 (7)	0.70734 (17)	0.0185 (3)
H2	0.3859	0.3260	0.7728	0.022*
C3	0.25757 (17)	0.31585 (7)	0.58880 (18)	0.0208 (4)
H3	0.2393	0.3565	0.5723	0.025*
C4	0.19833 (16)	0.27409 (7)	0.49473 (18)	0.0204 (3)
H4	0.1400	0.2855	0.4118	0.024*
C5	0.22589 (15)	0.21518 (7)	0.52392 (17)	0.0169 (3)
H5	0.1844	0.1864	0.4597	0.020*
C6	0.45835 (14)	0.21456 (7)	0.85440 (16)	0.0135 (3)
C7	0.53731 (16)	0.25026 (7)	0.95159 (17)	0.0183 (3)
H7	0.5366	0.2918	0.9397	0.022*
C8	0.61699 (16)	0.22460 (7)	1.06586 (18)	0.0197 (3)
H8	0.6707	0.2483	1.1340	0.024*
C9	0.61720 (15)	0.16393 (7)	1.07940 (17)	0.0179 (3)
H9	0.6710	0.1453	1.1569	0.021*
C10	0.53734 (15)	0.13084 (7)	0.97768 (17)	0.0158 (3)
H10	0.5380	0.0892	0.9867	0.019*
C11	0.45342 (16)	0.07516 (7)	0.46851 (16)	0.0164 (3)
C12	0.54106 (17)	0.06554 (7)	0.38764 (18)	0.0216 (4)
H12	0.5137	0.0494	0.2976	0.026*
C13	0.66829 (18)	0.07965 (8)	0.43941 (19)	0.0240 (4)
H13	0.7290	0.0742	0.3847	0.029*
C14	0.70614 (17)	0.10188 (7)	0.57218 (19)	0.0222 (4)
H14	0.7932	0.1114	0.6106	0.027*
C15	0.61423 (16)	0.10999 (7)	0.64778 (18)	0.0189 (3)
H15	0.6403	0.1250	0.7390	0.023*
C16	0.31527 (16)	0.06224 (7)	0.42106 (17)	0.0174 (3)
C17	0.26045 (18)	0.03938 (7)	0.29108 (18)	0.0226 (4)
H17	0.3122	0.0310	0.2280	0.027*
C18	0.13049 (19)	0.02897 (8)	0.25457 (19)	0.0259 (4)
H18	0.0917	0.0133	0.1664	0.031*
C19	0.05756 (18)	0.04166 (8)	0.34862 (18)	0.0244 (4)
H19	−0.0322	0.0352	0.3260	0.029*
C20	0.11801 (16)	0.06401 (7)	0.47631 (18)	0.0210 (4)
H20	0.0678	0.0726	0.5407	0.025*
C21	0.28064 (15)	0.01334 (7)	0.84458 (16)	0.0160 (3)
C22	0.17847 (15)	0.06133 (7)	0.85287 (16)	0.0147 (3)
N1	0.30859 (12)	0.19701 (6)	0.63873 (14)	0.0137 (3)
N2	0.45918 (12)	0.15531 (6)	0.86708 (13)	0.0133 (3)
N3	0.49052 (13)	0.09766 (6)	0.59778 (14)	0.0156 (3)
N4	0.24424 (13)	0.07409 (6)	0.51318 (14)	0.0163 (3)
O1	0.37284 (10)	0.03031 (5)	0.79495 (12)	0.0161 (2)
O2	0.26399 (12)	−0.03711 (5)	0.88283 (15)	0.0296 (3)
O3	0.18687 (11)	0.10853 (5)	0.78563 (12)	0.0150 (2)
O4	0.09914 (12)	0.05107 (5)	0.92132 (13)	0.0223 (3)
O5W	0.81514 (12)	0.19349 (6)	0.83438 (14)	0.0246 (3)
H1O5	0.836 (2)	0.1682 (10)	0.897 (2)	0.029*
H2O5	0.826 (2)	0.2258 (11)	0.873 (2)	0.029*
O6W	0.85321 (14)	0.30956 (6)	0.90721 (16)	0.0297 (3)
H1O6	0.898 (2)	0.3122 (10)	0.989 (3)	0.036*
H2O6	0.899 (2)	0.3135 (11)	0.855 (3)	0.036*
O7W	0.01231 (14)	0.18470 (7)	0.22899 (15)	0.0292 (3)
H1O7	−0.014 (2)	0.1626 (11)	0.172 (2)	0.035*
H2O7	0.013 (2)	0.2179 (11)	0.195 (2)	0.035*
O8W	−0.00803 (13)	0.18857 (6)	0.67982 (13)	0.0227 (3)
H1O8	0.046 (2)	0.1663 (10)	0.708 (2)	0.027*
H2O8	−0.060 (2)	0.1872 (9)	0.730 (2)	0.027*
O9W	0.09388 (13)	−0.10459 (6)	0.98145 (14)	0.0225 (3)
H2O9	0.136 (2)	−0.0817 (10)	0.959 (2)	0.027*
H1O9	0.039 (2)	−0.0912 (10)	1.014 (2)	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01480 (11)	0.01073 (11)	0.01161 (11)	−0.00078 (7)	0.00363 (8)	−0.00061 (7)
C1	0.0154 (7)	0.0143 (7)	0.0133 (7)	−0.0004 (6)	0.0070 (6)	−0.0005 (6)
C2	0.0240 (8)	0.0137 (8)	0.0186 (9)	−0.0010 (6)	0.0065 (7)	−0.0012 (6)
C3	0.0270 (9)	0.0152 (8)	0.0220 (9)	0.0040 (6)	0.0089 (7)	0.0054 (7)
C4	0.0211 (8)	0.0215 (8)	0.0182 (8)	0.0024 (6)	0.0039 (7)	0.0071 (7)
C5	0.0185 (8)	0.0182 (8)	0.0139 (8)	−0.0016 (6)	0.0034 (6)	0.0017 (6)
C6	0.0147 (7)	0.0138 (7)	0.0132 (7)	−0.0004 (6)	0.0058 (6)	−0.0015 (6)
C7	0.0205 (8)	0.0136 (7)	0.0206 (8)	−0.0016 (6)	0.0046 (7)	−0.0036 (6)
C8	0.0184 (8)	0.0210 (8)	0.0182 (8)	−0.0014 (6)	0.0010 (6)	−0.0065 (7)
C9	0.0166 (8)	0.0224 (8)	0.0140 (8)	0.0035 (6)	0.0026 (6)	−0.0001 (6)
C10	0.0160 (7)	0.0151 (7)	0.0169 (8)	0.0028 (6)	0.0046 (6)	0.0008 (6)
C11	0.0256 (8)	0.0099 (7)	0.0151 (8)	−0.0004 (6)	0.0074 (6)	0.0008 (6)
C12	0.0330 (10)	0.0159 (8)	0.0183 (8)	0.0030 (7)	0.0110 (7)	0.0000 (6)
C13	0.0297 (9)	0.0197 (9)	0.0279 (10)	0.0033 (7)	0.0177 (8)	0.0021 (7)
C14	0.0211 (8)	0.0183 (8)	0.0296 (10)	−0.0013 (6)	0.0106 (7)	0.0011 (7)
C15	0.0222 (8)	0.0161 (8)	0.0189 (8)	−0.0013 (6)	0.0059 (7)	−0.0003 (6)
C16	0.0269 (9)	0.0105 (7)	0.0148 (8)	−0.0006 (6)	0.0046 (7)	0.0008 (6)
C17	0.0358 (10)	0.0168 (8)	0.0158 (8)	−0.0015 (7)	0.0070 (7)	−0.0007 (6)
C18	0.0374 (10)	0.0184 (8)	0.0173 (9)	−0.0049 (7)	−0.0031 (7)	0.0003 (7)
C19	0.0251 (9)	0.0216 (9)	0.0227 (9)	−0.0048 (7)	−0.0025 (7)	0.0011 (7)
C20	0.0224 (8)	0.0187 (8)	0.0210 (9)	−0.0031 (6)	0.0033 (7)	0.0006 (7)
C21	0.0171 (7)	0.0152 (7)	0.0147 (8)	−0.0008 (6)	0.0016 (6)	0.0001 (6)
C22	0.0161 (7)	0.0148 (7)	0.0127 (8)	−0.0027 (6)	0.0022 (6)	−0.0036 (6)
N1	0.0152 (6)	0.0135 (6)	0.0132 (7)	−0.0002 (5)	0.0046 (5)	0.0015 (5)
N2	0.0136 (6)	0.0131 (6)	0.0141 (7)	0.0004 (5)	0.0048 (5)	−0.0007 (5)
N3	0.0199 (7)	0.0124 (6)	0.0158 (7)	−0.0002 (5)	0.0065 (5)	0.0001 (5)
N4	0.0220 (7)	0.0117 (6)	0.0140 (7)	−0.0011 (5)	0.0020 (5)	−0.0004 (5)
O1	0.0177 (6)	0.0129 (5)	0.0187 (6)	0.0010 (4)	0.0064 (4)	−0.0002 (4)
O2	0.0264 (7)	0.0177 (6)	0.0474 (9)	0.0015 (5)	0.0143 (6)	0.0122 (6)
O3	0.0162 (5)	0.0126 (5)	0.0173 (6)	0.0006 (4)	0.0060 (4)	0.0003 (4)
O4	0.0241 (6)	0.0232 (6)	0.0234 (6)	−0.0021 (5)	0.0133 (5)	−0.0004 (5)
O5W	0.0265 (7)	0.0270 (7)	0.0194 (7)	0.0003 (5)	0.0036 (5)	0.0007 (6)
O6W	0.0327 (8)	0.0372 (8)	0.0202 (7)	0.0046 (6)	0.0079 (6)	−0.0021 (6)
O7W	0.0405 (8)	0.0245 (7)	0.0228 (7)	−0.0046 (6)	0.0079 (6)	−0.0031 (6)
O8W	0.0218 (7)	0.0269 (7)	0.0200 (7)	0.0067 (5)	0.0061 (5)	0.0030 (5)
O9W	0.0249 (7)	0.0191 (6)	0.0267 (7)	−0.0008 (5)	0.0127 (5)	0.0008 (5)

Geometric parameters (Å, º)

Ni1—O1	2.0359 (11)	C13—C14	1.386 (3)
Ni1—O3	2.0673 (12)	C13—H13	0.9500
Ni1—N1	2.0720 (13)	C14—C15	1.386 (2)
Ni1—N3	2.0793 (14)	C14—H14	0.9500
Ni1—N2	2.0854 (13)	C15—N3	1.337 (2)
Ni1—N4	2.1001 (13)	C15—H15	0.9500
C1—N1	1.352 (2)	C16—N4	1.350 (2)
C1—C2	1.392 (2)	C16—C17	1.393 (2)
C1—C6	1.486 (2)	C17—C18	1.380 (3)
C2—C3	1.384 (2)	C17—H17	0.9500
C2—H2	0.9500	C18—C19	1.384 (3)
C3—C4	1.381 (2)	C18—H18	0.9500
C3—H3	0.9500	C19—C20	1.384 (2)
C4—C5	1.386 (2)	C19—H19	0.9500
C4—H4	0.9500	C20—N4	1.340 (2)
C5—N1	1.341 (2)	C20—H20	0.9500
C5—H5	0.9500	C21—O2	1.233 (2)
C6—N2	1.351 (2)	C21—O1	1.266 (2)
C6—C7	1.391 (2)	C21—C22	1.563 (2)
C7—C8	1.385 (2)	C22—O4	1.231 (2)
C7—H7	0.9500	C22—O3	1.2781 (19)
C8—C9	1.384 (2)	O5W—H1O5	0.84 (2)
C8—H8	0.9500	O5W—H2O5	0.82 (2)
C9—C10	1.388 (2)	O6W—H1O6	0.85 (3)
C9—H9	0.9500	O6W—H2O6	0.80 (3)
C10—N2	1.342 (2)	O7W—H1O7	0.76 (2)
C10—H10	0.9500	O7W—H2O7	0.83 (3)
C11—N3	1.357 (2)	O8W—H1O8	0.77 (2)
C11—C12	1.391 (2)	O8W—H2O8	0.83 (2)
C11—C16	1.480 (2)	O9W—H2O9	0.76 (2)
C12—C13	1.383 (3)	O9W—H1O9	0.80 (2)
C12—H12	0.9500
O1—Ni1—O3	80.79 (4)	C11—C12—H12	120.3
O1—Ni1—N1	169.33 (5)	C12—C13—C14	119.13 (16)
O3—Ni1—N1	91.41 (5)	C12—C13—H13	120.4
O1—Ni1—N3	93.26 (5)	C14—C13—H13	120.4
O3—Ni1—N3	169.30 (5)	C13—C14—C15	118.58 (17)
N1—Ni1—N3	95.54 (5)	C13—C14—H14	120.7
O1—Ni1—N2	94.25 (5)	C15—C14—H14	120.7
O3—Ni1—N2	94.19 (5)	N3—C15—C14	122.82 (16)
N1—Ni1—N2	78.97 (5)	N3—C15—H15	118.6
N3—Ni1—N2	95.12 (5)	C14—C15—H15	118.6
O1—Ni1—N4	92.88 (5)	N4—C16—C17	121.50 (16)
O3—Ni1—N4	92.99 (5)	N4—C16—C11	115.27 (14)
N1—Ni1—N4	94.81 (5)	C17—C16—C11	123.23 (16)
N3—Ni1—N4	78.35 (5)	C18—C17—C16	119.56 (17)
N2—Ni1—N4	170.60 (5)	C18—C17—H17	120.2
N1—C1—C2	121.43 (14)	C16—C17—H17	120.2
N1—C1—C6	115.53 (13)	C17—C18—C19	118.89 (16)
C2—C1—C6	123.03 (14)	C17—C18—H18	120.6
C3—C2—C1	119.32 (15)	C19—C18—H18	120.6
C3—C2—H2	120.3	C20—C19—C18	118.68 (17)
C1—C2—H2	120.3	C20—C19—H19	120.7
C4—C3—C2	119.25 (15)	C18—C19—H19	120.7
C4—C3—H3	120.4	N4—C20—C19	122.98 (17)
C2—C3—H3	120.4	N4—C20—H20	118.5
C3—C4—C5	118.53 (15)	C19—C20—H20	118.5
C3—C4—H4	120.7	O2—C21—O1	125.89 (15)
C5—C4—H4	120.7	O2—C21—C22	118.51 (14)
N1—C5—C4	122.90 (15)	O1—C21—C22	115.58 (13)
N1—C5—H5	118.6	O4—C22—O3	126.24 (15)
C4—C5—H5	118.6	O4—C22—C21	118.85 (14)
N2—C6—C7	121.69 (14)	O3—C22—C21	114.90 (14)
N2—C6—C1	115.03 (13)	C5—N1—C1	118.56 (14)
C7—C6—C1	123.28 (14)	C5—N1—Ni1	126.09 (11)
C8—C7—C6	119.27 (15)	C1—N1—Ni1	115.15 (10)
C8—C7—H7	120.4	C10—N2—C6	118.59 (13)
C6—C7—H7	120.4	C10—N2—Ni1	126.25 (11)
C9—C8—C7	119.05 (15)	C6—N2—Ni1	115.01 (10)
C9—C8—H8	120.5	C15—N3—C11	118.74 (15)
C7—C8—H8	120.5	C15—N3—Ni1	125.69 (11)
C8—C9—C10	118.74 (15)	C11—N3—Ni1	115.57 (11)
C8—C9—H9	120.6	C20—N4—C16	118.39 (14)
C10—C9—H9	120.6	C20—N4—Ni1	126.29 (12)
N2—C10—C9	122.65 (15)	C16—N4—Ni1	115.28 (11)
N2—C10—H10	118.7	C21—O1—Ni1	114.05 (10)
C9—C10—H10	118.7	C22—O3—Ni1	113.33 (10)
N3—C11—C12	121.29 (15)	H1O5—O5W—H2O5	106 (2)
N3—C11—C16	115.50 (14)	H1O6—O6W—H2O6	109 (2)
C12—C11—C16	123.20 (15)	H1O7—O7W—H2O7	109 (2)
C13—C12—C11	119.41 (16)	H1O8—O8W—H2O8	108 (2)
C13—C12—H12	120.3	H2O9—O9W—H1O9	114 (2)
N1—C1—C2—C3	−0.5 (2)	O3—Ni1—N2—C10	92.16 (13)
C6—C1—C2—C3	−179.55 (15)	N1—Ni1—N2—C10	−177.22 (14)
C1—C2—C3—C4	−0.5 (3)	N3—Ni1—N2—C10	−82.56 (13)
C2—C3—C4—C5	1.1 (3)	N4—Ni1—N2—C10	−128.1 (3)
C3—C4—C5—N1	−0.8 (3)	O1—Ni1—N2—C6	−173.55 (11)
N1—C1—C6—N2	−6.5 (2)	O3—Ni1—N2—C6	−92.49 (11)
C2—C1—C6—N2	172.62 (15)	N1—Ni1—N2—C6	−1.88 (11)
N1—C1—C6—C7	173.22 (15)	N3—Ni1—N2—C6	92.79 (11)
C2—C1—C6—C7	−7.7 (2)	N4—Ni1—N2—C6	47.2 (4)
N2—C6—C7—C8	−1.4 (2)	C14—C15—N3—C11	1.3 (2)
C1—C6—C7—C8	178.96 (15)	C14—C15—N3—Ni1	−178.25 (12)
C6—C7—C8—C9	0.9 (3)	C12—C11—N3—C15	−0.8 (2)
C7—C8—C9—C10	0.0 (2)	C16—C11—N3—C15	179.53 (14)
C8—C9—C10—N2	−0.5 (3)	C12—C11—N3—Ni1	178.83 (12)
N3—C11—C12—C13	−0.6 (2)	C16—C11—N3—Ni1	−0.86 (17)
C16—C11—C12—C13	179.08 (15)	O1—Ni1—N3—C15	−86.83 (13)
C11—C12—C13—C14	1.4 (2)	O3—Ni1—N3—C15	−142.6 (2)
C12—C13—C14—C15	−0.9 (2)	N1—Ni1—N3—C15	87.11 (13)
C13—C14—C15—N3	−0.5 (3)	N2—Ni1—N3—C15	7.74 (14)
N3—C11—C16—N4	−0.5 (2)	N4—Ni1—N3—C15	−179.11 (14)
C12—C11—C16—N4	179.78 (14)	O1—Ni1—N3—C11	93.58 (11)
N3—C11—C16—C17	179.57 (15)	O3—Ni1—N3—C11	37.8 (3)
C12—C11—C16—C17	−0.1 (2)	N1—Ni1—N3—C11	−92.47 (11)
N4—C16—C17—C18	0.6 (2)	N2—Ni1—N3—C11	−171.85 (11)
C11—C16—C17—C18	−179.55 (15)	N4—Ni1—N3—C11	1.31 (11)
C16—C17—C18—C19	0.1 (3)	C19—C20—N4—C16	0.5 (2)
C17—C18—C19—C20	−0.4 (3)	C19—C20—N4—Ni1	177.82 (13)
C18—C19—C20—N4	0.1 (3)	C17—C16—N4—C20	−0.8 (2)
O2—C21—C22—O4	14.3 (2)	C11—C16—N4—C20	179.28 (14)
O1—C21—C22—O4	−167.41 (14)	C17—C16—N4—Ni1	−178.46 (12)
O2—C21—C22—O3	−165.80 (15)	C11—C16—N4—Ni1	1.65 (17)
O1—C21—C22—O3	12.5 (2)	O1—Ni1—N4—C20	88.23 (13)
C4—C5—N1—C1	−0.3 (2)	O3—Ni1—N4—C20	7.31 (13)
C4—C5—N1—Ni1	174.35 (13)	N1—Ni1—N4—C20	−84.35 (14)
C2—C1—N1—C5	0.9 (2)	N3—Ni1—N4—C20	−179.03 (14)
C6—C1—N1—C5	−179.98 (14)	N2—Ni1—N4—C20	−132.5 (3)
C2—C1—N1—Ni1	−174.29 (12)	O1—Ni1—N4—C16	−94.35 (11)
C6—C1—N1—Ni1	4.82 (17)	O3—Ni1—N4—C16	−175.27 (11)
O1—Ni1—N1—C5	−125.3 (2)	N1—Ni1—N4—C16	93.07 (11)
O3—Ni1—N1—C5	−82.55 (13)	N3—Ni1—N4—C16	−1.61 (11)
N3—Ni1—N1—C5	89.30 (14)	N2—Ni1—N4—C16	45.0 (4)
N2—Ni1—N1—C5	−176.54 (14)	O2—C21—O1—Ni1	165.63 (14)
N4—Ni1—N1—C5	10.57 (14)	C22—C21—O1—Ni1	−12.57 (16)
O1—Ni1—N1—C1	49.5 (3)	O3—Ni1—O1—C21	7.69 (10)
O3—Ni1—N1—C1	92.24 (11)	N1—Ni1—O1—C21	51.2 (3)
N3—Ni1—N1—C1	−95.91 (11)	N3—Ni1—O1—C21	−163.36 (11)
N2—Ni1—N1—C1	−1.75 (11)	N2—Ni1—O1—C21	101.25 (11)
N4—Ni1—N1—C1	−174.63 (11)	N4—Ni1—O1—C21	−84.88 (11)
C9—C10—N2—C6	0.0 (2)	O4—C22—O3—Ni1	174.34 (13)
C9—C10—N2—Ni1	175.21 (12)	C21—C22—O3—Ni1	−5.60 (16)
C7—C6—N2—C10	0.9 (2)	O1—Ni1—O3—C22	−0.40 (10)
C1—C6—N2—C10	−179.38 (14)	N1—Ni1—O3—C22	−173.08 (10)
C7—C6—N2—Ni1	−174.81 (12)	N3—Ni1—O3—C22	56.4 (3)
C1—C6—N2—Ni1	4.89 (17)	N2—Ni1—O3—C22	−94.04 (10)
O1—Ni1—N2—C10	11.10 (13)	N4—Ni1—O3—C22	92.03 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O8W^i	0.95	2.55	3.502 (2)	176
C5—H5···O7W	0.95	2.60	3.356 (2)	137
C9—H9···O2^ii	0.95	2.61	3.137 (2)	116
C10—H10···O1	0.95	2.65	3.1875 (19)	116
C10—H10···O2^ii	0.95	2.52	3.106 (2)	120
C12—H12···O1^iii	0.95	2.48	3.112 (2)	124
C15—H15···O5W	0.95	2.46	3.139 (2)	129
C20—H20···O3	0.95	2.61	3.164 (2)	118
O5W—H1O5···O9W^ii	0.84 (2)	1.92 (2)	2.7509 (19)	168 (2)
O5W—H2O5···O6W	0.82 (2)	1.94 (2)	2.739 (2)	162 (2)
O6W—H1O6···O8W^iv	0.85 (3)	1.94 (3)	2.780 (2)	174 (2)
O6W—H2O6···O7W^iv	0.80 (3)	1.94 (3)	2.739 (2)	175 (2)
O7W—H1O7···O9W^v	0.76 (2)	2.05 (3)	2.8107 (19)	177 (3)
O7W—H2O7···O8W^i	0.83 (3)	2.14 (3)	2.919 (2)	157 (2)
O8W—H1O8···O3	0.77 (2)	2.01 (2)	2.7890 (17)	178 (2)
O8W—H2O8···O5W^vi	0.83 (2)	1.88 (3)	2.711 (2)	173 (2)
O9W—H2O9···O2	0.76 (2)	1.99 (2)	2.7364 (19)	167 (2)
O9W—H1O9···O4^vii	0.80 (2)	1.97 (2)	2.7658 (18)	173 (2)

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