A half-salamo-based pyridine-containing ligand and its novel Ni^II com­plexes including different auxiliary ligands: syntheses, structures, fluorescence properties, DFT calculations and Hirshfeld surface analysis

Three novel multinuclear Ni^II com­plexes, namely, bis{μ-2-methoxy-6-[8-(pyri­din-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}bis[thiocyanatonickel(II)], [Ni₂(L)₂(NCS)₂], 1, bis{μ-2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}bis[azidonickel(II)], [Ni₂(L)₂(N₃)₂], 2, and catena-poly[[{2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}nickel(II)]-μ-dicyanamidato], [Ni(L)(dca)]_n, 3 {dca is dicyanamide, C₂N₃, and HL is 2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenol, C₁₆H₁₇N₃O₄}, with a half-salamo-based pyridine-containing HL ligand have been synthesized and characterized by FT–IR, UV–Vis absorption spectroscopy, X-ray crystallography, Hirshfeld surface analysis and density functional theory (DFT) calculations. The central Ni^II ions in com­plexes 1–3 are hosted in the half-salamo-based N₃O-donor cavity of the organic ligand. Com­plex 1 is a centrosymmetric dimer and two [Ni(L)(NCS)] units form a centrosymmetric dimeric structure, which is bridged by two phenolate O atoms. The two N atoms at the axial ends are provided by two NCS⁻ ligands. In com­plex 1, each Ni^II ion has a six-coordinated octahedral geometry. Com­plex 2 is similar to 1, but they differ in that the auxiliary NCS⁻ ligand is replaced by N₃⁻. However, com­plex 3 is a one-dimensional coordination polymer constructed from [Ni(L)(dca)] units, which are connected by the auxiliary bidentate dca ligand via N-donor atoms. As with com­plexes 1 and 2, the Ni^II ion in 3 has a six-coordinated octahedral geometry.

Computing details

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR2004 (Burla et al., 2007); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis{µ-2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}bis[thiocyanatonickel(II)] (1)

Crystal data

[Ni2(C16H16N3O4)2(NCS)2]	F(000) = 888
Mr = 862.21	Dx = 1.577 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.9403 (3) Å	Cell parameters from 5793 reflections
b = 11.5796 (3) Å	θ = 2.6–26.2°
c = 16.0806 (5) Å	µ = 1.22 mm^−1
β = 101.178 (1)°	T = 173 K
V = 1815.84 (9) Å^3	Block, green
Z = 2	0.12 × 0.12 × 0.09 mm

Data collection

Bruker D8 Venture diffractometer	2648 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
ω and φ scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
Tmin = 0.670, Tmax = 0.745	k = −13→14
20457 measured reflections	l = −19→19
3369 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.066	H-atom parameters constrained
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0697P)^2 + 5.615P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
3369 reflections	Δρmax = 1.49 e Å^−3
245 parameters	Δρmin = −0.84 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.42781 (6)	0.54958 (5)	0.41022 (4)	0.0373 (2)
S1	0.1111 (2)	0.4462 (3)	0.16042 (14)	0.1112 (9)
O1	0.3511 (5)	0.8103 (4)	0.3486 (3)	0.0736 (13)
O2	0.1442 (4)	0.6376 (4)	0.4565 (3)	0.0681 (12)
O3	0.4645 (3)	0.3962 (3)	0.46721 (19)	0.0373 (7)
O4	0.5335 (6)	0.1898 (4)	0.4185 (3)	0.0835 (15)
N1	0.6069 (4)	0.5415 (4)	0.3625 (3)	0.0457 (10)
N2	0.4404 (5)	0.7167 (4)	0.3577 (3)	0.0506 (11)
N3	0.2354 (4)	0.5457 (4)	0.4502 (3)	0.0458 (10)
N4	0.3205 (5)	0.4876 (4)	0.2973 (3)	0.0490 (11)
C1	0.6817 (6)	0.4473 (6)	0.3594 (3)	0.0545 (15)
H1	0.653564	0.375953	0.379732	0.065*
C2	0.8021 (7)	0.4523 (8)	0.3264 (4)	0.076 (2)
H2	0.855648	0.384660	0.324853	0.091*
C3	0.8423 (7)	0.5535 (9)	0.2966 (4)	0.084 (3)
H3	0.924007	0.557088	0.274311	0.101*
C4	0.7646 (7)	0.6505 (8)	0.2989 (4)	0.078 (2)
H4	0.791420	0.722112	0.278295	0.094*
C5	0.6448 (6)	0.6424 (6)	0.3322 (3)	0.0567 (15)
C6	0.5492 (7)	0.7359 (5)	0.3313 (4)	0.0600 (15)
H6	0.567825	0.810180	0.311184	0.072*
C7	0.2156 (7)	0.7740 (6)	0.3565 (5)	0.076 (2)
H7A	0.190058	0.704407	0.321173	0.092*
H7B	0.149311	0.835826	0.334711	0.092*
C8	0.2062 (7)	0.7474 (6)	0.4462 (4)	0.0685 (18)
H8A	0.299599	0.748607	0.481504	0.082*
H8B	0.152142	0.808740	0.467341	0.082*
C9	0.1754 (5)	0.4509 (5)	0.4587 (3)	0.0530 (14)
H9	0.084890	0.456265	0.469376	0.064*
C10	0.2293 (6)	0.3353 (5)	0.4539 (3)	0.0519 (14)
C11	0.3675 (6)	0.3139 (4)	0.4520 (3)	0.0444 (12)
C12	0.4017 (7)	0.2026 (5)	0.4310 (4)	0.0615 (16)
C13	0.3083 (11)	0.1126 (6)	0.4217 (4)	0.086 (3)
H13	0.335142	0.036876	0.408928	0.103*
C14	0.1756 (12)	0.1346 (7)	0.4311 (5)	0.102 (3)
H14	0.111778	0.072935	0.427660	0.123*
C15	0.1356 (8)	0.2438 (7)	0.4452 (4)	0.081 (2)
H15	0.043037	0.258231	0.449324	0.097*
C16	0.5722 (11)	0.0793 (7)	0.3902 (5)	0.111 (3)
H16A	0.508789	0.057636	0.337903	0.167*
H16B	0.568415	0.021176	0.433971	0.167*
H16C	0.665650	0.083553	0.379218	0.167*
C17	0.2336 (6)	0.4721 (5)	0.2417 (3)	0.0511 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0418 (4)	0.0401 (4)	0.0300 (3)	0.0009 (3)	0.0071 (2)	0.0012 (3)
S1	0.0560 (11)	0.190 (3)	0.0754 (13)	−0.0098 (14)	−0.0177 (9)	−0.0104 (15)
O1	0.090 (3)	0.051 (2)	0.083 (3)	0.010 (2)	0.027 (3)	0.019 (2)
O2	0.054 (2)	0.076 (3)	0.081 (3)	0.022 (2)	0.029 (2)	0.015 (2)
O3	0.0416 (18)	0.0339 (17)	0.0373 (17)	−0.0012 (14)	0.0104 (14)	−0.0046 (14)
O4	0.111 (4)	0.061 (3)	0.078 (3)	0.024 (3)	0.017 (3)	−0.024 (2)
N1	0.041 (2)	0.065 (3)	0.032 (2)	−0.001 (2)	0.0104 (17)	−0.003 (2)
N2	0.064 (3)	0.044 (2)	0.045 (2)	0.002 (2)	0.014 (2)	0.007 (2)
N3	0.037 (2)	0.063 (3)	0.041 (2)	0.010 (2)	0.0141 (18)	0.006 (2)
N4	0.051 (3)	0.064 (3)	0.030 (2)	−0.010 (2)	0.004 (2)	0.001 (2)
C1	0.049 (3)	0.082 (4)	0.034 (3)	0.012 (3)	0.011 (2)	−0.010 (3)
C2	0.054 (4)	0.128 (7)	0.047 (3)	0.017 (4)	0.014 (3)	−0.012 (4)
C3	0.049 (4)	0.153 (8)	0.056 (4)	−0.005 (5)	0.024 (3)	−0.019 (5)
C4	0.068 (4)	0.110 (6)	0.064 (4)	−0.035 (4)	0.031 (3)	−0.010 (4)
C5	0.055 (3)	0.079 (4)	0.039 (3)	−0.018 (3)	0.015 (2)	−0.003 (3)
C6	0.071 (4)	0.056 (4)	0.055 (3)	−0.018 (3)	0.019 (3)	0.003 (3)
C7	0.072 (4)	0.077 (5)	0.085 (5)	0.028 (4)	0.026 (4)	0.033 (4)
C8	0.072 (4)	0.062 (4)	0.075 (4)	0.027 (3)	0.024 (3)	0.010 (3)
C9	0.035 (3)	0.079 (4)	0.048 (3)	−0.011 (3)	0.015 (2)	0.000 (3)
C10	0.054 (3)	0.064 (4)	0.038 (3)	−0.022 (3)	0.011 (2)	−0.008 (3)
C11	0.066 (3)	0.038 (3)	0.029 (2)	−0.012 (2)	0.008 (2)	0.000 (2)
C12	0.088 (5)	0.054 (3)	0.040 (3)	0.000 (3)	0.007 (3)	−0.008 (3)
C13	0.149 (8)	0.053 (4)	0.050 (4)	−0.029 (5)	0.008 (4)	−0.013 (3)
C14	0.159 (9)	0.071 (5)	0.074 (5)	−0.065 (6)	0.015 (6)	−0.004 (4)
C15	0.082 (5)	0.099 (6)	0.062 (4)	−0.050 (4)	0.016 (3)	0.001 (4)
C16	0.190 (10)	0.065 (5)	0.079 (5)	0.048 (6)	0.026 (6)	−0.021 (4)
C17	0.046 (3)	0.070 (4)	0.041 (3)	0.000 (3)	0.016 (2)	−0.003 (3)

Geometric parameters (Å, º)

Ni1—O3	1.999 (3)	C3—C4	1.368 (11)
Ni1—O3^i	2.146 (3)	C4—H4	0.9500
Ni1—N1	2.073 (4)	C4—C5	1.400 (8)
Ni1—N2	2.125 (4)	C5—C6	1.438 (9)
Ni1—N3	2.133 (4)	C6—H6	0.9500
Ni1—N4	2.049 (4)	C7—H7A	0.9900
S1—C17	1.632 (6)	C7—H7B	0.9900
O1—N2	1.390 (6)	C7—C8	1.496 (9)
O1—C7	1.440 (8)	C8—H8A	0.9900
O2—N3	1.414 (6)	C8—H8B	0.9900
O2—C8	1.436 (8)	C9—H9	0.9500
O3—C11	1.344 (6)	C9—C10	1.449 (8)
O4—C12	1.372 (8)	C10—C11	1.402 (8)
O4—C16	1.436 (8)	C10—C15	1.400 (8)
N1—C1	1.327 (7)	C11—C12	1.392 (8)
N1—C5	1.348 (7)	C12—C13	1.384 (10)
N2—C6	1.256 (7)	C13—H13	0.9500
N3—C9	1.270 (7)	C13—C14	1.381 (12)
N4—C17	1.130 (7)	C14—H14	0.9500
C1—H1	0.9500	C14—C15	1.357 (12)
C1—C2	1.401 (9)	C15—H15	0.9500
C2—H2	0.9500	C16—H16A	0.9800
C2—C3	1.355 (11)	C16—H16B	0.9800
C3—H3	0.9500	C16—H16C	0.9800
O3—Ni1—O3^i	79.89 (13)	C4—C5—C6	123.7 (6)
O3—Ni1—N1	92.08 (16)	N2—C6—C5	118.3 (5)
O3—Ni1—N2	166.34 (16)	N2—C6—H6	120.8
O3—Ni1—N3	86.42 (15)	C5—C6—H6	120.8
O3—Ni1—N4	96.47 (16)	O1—C7—H7A	109.1
N1—Ni1—O3^i	92.40 (14)	O1—C7—H7B	109.1
N1—Ni1—N2	76.89 (18)	O1—C7—C8	112.3 (6)
N1—Ni1—N3	174.39 (17)	H7A—C7—H7B	107.9
N2—Ni1—O3^i	92.39 (15)	C8—C7—H7A	109.1
N2—Ni1—N3	105.32 (18)	C8—C7—H7B	109.1
N3—Ni1—O3^i	92.65 (15)	O2—C8—C7	113.7 (6)
N4—Ni1—O3^i	175.91 (15)	O2—C8—H8A	108.8
N4—Ni1—N1	89.59 (17)	O2—C8—H8B	108.8
N4—Ni1—N2	91.55 (18)	C7—C8—H8A	108.8
N4—Ni1—N3	85.21 (18)	C7—C8—H8B	108.8
N2—O1—C7	110.6 (4)	H8A—C8—H8B	107.7
N3—O2—C8	111.3 (4)	N3—C9—H9	116.3
Ni1—O3—Ni1^i	100.11 (13)	N3—C9—C10	127.3 (5)
C11—O3—Ni1^i	125.9 (3)	C10—C9—H9	116.3
C11—O3—Ni1	119.1 (3)	C11—C10—C9	122.6 (5)
C12—O4—C16	117.7 (7)	C15—C10—C9	117.3 (6)
C1—N1—Ni1	125.4 (4)	C15—C10—C11	120.0 (6)
C1—N1—C5	120.1 (5)	O3—C11—C10	122.8 (5)
C5—N1—Ni1	114.5 (4)	O3—C11—C12	120.1 (5)
O1—N2—Ni1	131.8 (3)	C12—C11—C10	117.1 (5)
C6—N2—Ni1	114.6 (4)	O4—C12—C11	114.9 (6)
C6—N2—O1	113.6 (5)	O4—C12—C13	122.8 (7)
O2—N3—Ni1	129.1 (3)	C13—C12—C11	122.3 (7)
C9—N3—Ni1	121.2 (4)	C12—C13—H13	120.5
C9—N3—O2	108.8 (4)	C14—C13—C12	118.9 (7)
C17—N4—Ni1	160.5 (5)	C14—C13—H13	120.5
N1—C1—H1	119.8	C13—C14—H14	119.7
N1—C1—C2	120.4 (6)	C15—C14—C13	120.5 (7)
C2—C1—H1	119.8	C15—C14—H14	119.7
C1—C2—H2	119.9	C10—C15—H15	119.6
C3—C2—C1	120.1 (7)	C14—C15—C10	120.7 (8)
C3—C2—H2	119.9	C14—C15—H15	119.6
C2—C3—H3	120.2	O4—C16—H16A	109.5
C2—C3—C4	119.6 (6)	O4—C16—H16B	109.5
C4—C3—H3	120.2	O4—C16—H16C	109.5
C3—C4—H4	120.6	H16A—C16—H16B	109.5
C3—C4—C5	118.8 (7)	H16A—C16—H16C	109.5
C5—C4—H4	120.6	H16B—C16—H16C	109.5
N1—C5—C4	120.9 (6)	N4—C17—S1	178.1 (6)
N1—C5—C6	115.2 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Bis{µ-2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}bis[azidonickel(II)] (2)

Crystal data

[Ni2(C16H16N3O4)2(N3)2]	F(000) = 856
Mr = 830.11	Dx = 1.608 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.6387 (4) Å	Cell parameters from 5276 reflections
b = 10.0171 (4) Å	θ = 5.1–74.3°
c = 14.7940 (6) Å	µ = 1.98 mm^−1
β = 96.348 (2)°	T = 173 K
V = 1714.20 (11) Å^3	Block
Z = 2	0.25 × 0.23 × 0.22 mm

Data collection

Bruker D8 Venture diffractometer	2893 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.050
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 74.3°, θmin = 5.1°
Tmin = 0.624, Tmax = 0.754	h = −14→14
10646 measured reflections	k = −12→8
3441 independent reflections	l = −13→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.175	w = 1/[σ^2(Fo^2) + (0.1022P)^2 + 1.4134P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3441 reflections	Δρmax = 1.66 e Å^−3
245 parameters	Δρmin = −0.87 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.37415 (4)	0.46255 (5)	0.44928 (3)	0.0254 (2)
O1	0.1664 (2)	0.6556 (3)	0.36789 (19)	0.0433 (6)
N1	0.4428 (2)	0.4369 (3)	0.32914 (18)	0.0286 (6)
C1	0.4043 (3)	0.5229 (4)	0.2631 (2)	0.0338 (7)
O2	0.2038 (2)	0.5426 (3)	0.59677 (19)	0.0428 (6)
N2	0.2661 (2)	0.5834 (3)	0.35839 (19)	0.0310 (6)
C2	0.4492 (4)	0.5263 (5)	0.1805 (2)	0.0448 (9)
H2	0.4235	0.5912	0.1360	0.054*
N3	0.3009 (2)	0.4672 (3)	0.57422 (18)	0.0308 (6)
O3	0.50989 (18)	0.3702 (2)	0.51820 (15)	0.0283 (5)
C3	0.5319 (4)	0.4338 (5)	0.1638 (3)	0.0532 (11)
H3	0.5643	0.4343	0.1076	0.064*
N4	0.2761 (2)	0.2905 (3)	0.41633 (19)	0.0334 (6)
O4	0.6290 (2)	0.1485 (3)	0.5024 (2)	0.0466 (7)
C4	0.5668 (3)	0.3414 (5)	0.2289 (3)	0.0497 (11)
H4	0.6206	0.2740	0.2171	0.060*
N5	0.1983 (2)	0.2607 (3)	0.4584 (2)	0.0334 (6)
C5	0.5232 (3)	0.3465 (4)	0.3127 (3)	0.0380 (8)
H5	0.5507	0.2850	0.3591	0.046*
C6	0.3054 (3)	0.6040 (4)	0.2822 (2)	0.0346 (7)
H6	0.2720	0.6686	0.2402	0.041*
N6	0.1220 (3)	0.2283 (4)	0.4983 (3)	0.0495 (8)
C7	0.1122 (3)	0.6059 (4)	0.4440 (3)	0.0442 (9)
H7A	0.1098	0.5072	0.4415	0.053*
H7B	0.0316	0.6388	0.4398	0.053*
C8	0.1762 (3)	0.6494 (4)	0.5339 (3)	0.0434 (9)
H8A	0.2487	0.6944	0.5220	0.052*
H8B	0.1282	0.7156	0.5624	0.052*
C9	0.3250 (3)	0.3787 (4)	0.6361 (2)	0.0369 (8)
H9	0.2822	0.3824	0.6871	0.044*
C10	0.4101 (3)	0.2741 (4)	0.6363 (2)	0.0368 (7)
C11	0.4935 (3)	0.2692 (3)	0.5740 (2)	0.0323 (7)
C12	0.5614 (3)	0.1519 (4)	0.5726 (3)	0.0417 (9)
C13	0.5552 (4)	0.0515 (4)	0.6354 (4)	0.0532 (12)
H13	0.6024	−0.0256	0.6337	0.064*
C14	0.4789 (4)	0.0638 (5)	0.7018 (3)	0.0587 (13)
H14	0.4775	−0.0029	0.7474	0.070*
C15	0.4067 (4)	0.1709 (5)	0.7014 (3)	0.0497 (10)
H15	0.3532	0.1764	0.7454	0.060*
C16	0.7052 (4)	0.0362 (4)	0.4985 (4)	0.0591 (13)
H16A	0.6600	−0.0465	0.4950	0.089*
H16B	0.7609	0.0347	0.5533	0.089*
H16C	0.7468	0.0438	0.4446	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0284 (3)	0.0272 (3)	0.0208 (3)	0.00154 (19)	0.0037 (2)	0.00201 (19)
O1	0.0320 (11)	0.0504 (16)	0.0477 (15)	0.0157 (11)	0.0060 (10)	0.0097 (12)
N1	0.0275 (11)	0.0358 (14)	0.0235 (12)	−0.0004 (11)	0.0070 (10)	−0.0025 (11)
C1	0.0355 (16)	0.0406 (19)	0.0245 (15)	−0.0059 (14)	0.0000 (12)	0.0000 (13)
O2	0.0476 (14)	0.0475 (16)	0.0372 (14)	0.0065 (12)	0.0227 (11)	0.0004 (11)
N2	0.0278 (12)	0.0331 (14)	0.0317 (14)	0.0032 (11)	0.0008 (10)	0.0018 (11)
C2	0.051 (2)	0.060 (3)	0.0237 (16)	−0.0112 (18)	0.0060 (15)	−0.0012 (16)
N3	0.0368 (14)	0.0338 (15)	0.0233 (13)	−0.0025 (11)	0.0097 (11)	−0.0034 (10)
O3	0.0308 (10)	0.0238 (10)	0.0293 (11)	−0.0018 (8)	−0.0010 (8)	0.0046 (8)
C3	0.052 (2)	0.076 (3)	0.036 (2)	−0.016 (2)	0.0204 (17)	−0.014 (2)
N4	0.0373 (13)	0.0338 (15)	0.0296 (13)	−0.0038 (12)	0.0056 (11)	−0.0008 (11)
O4	0.0392 (12)	0.0296 (13)	0.0705 (19)	0.0061 (10)	0.0038 (12)	0.0075 (13)
C4	0.0368 (17)	0.061 (3)	0.054 (2)	−0.0024 (17)	0.0186 (16)	−0.028 (2)
N5	0.0366 (13)	0.0270 (14)	0.0365 (14)	0.0011 (11)	0.0037 (12)	−0.0019 (11)
C5	0.0322 (15)	0.040 (2)	0.0424 (19)	−0.0002 (14)	0.0075 (13)	−0.0109 (16)
C6	0.0345 (15)	0.0417 (19)	0.0264 (15)	0.0017 (14)	−0.0016 (12)	0.0060 (14)
N6	0.0500 (17)	0.0426 (19)	0.061 (2)	−0.0070 (15)	0.0278 (16)	−0.0066 (16)
C7	0.0314 (15)	0.048 (2)	0.055 (2)	0.0066 (15)	0.0134 (15)	0.0041 (18)
C8	0.0480 (19)	0.037 (2)	0.049 (2)	0.0072 (15)	0.0204 (16)	−0.0037 (16)
C9	0.0467 (18)	0.0400 (19)	0.0250 (15)	−0.0134 (15)	0.0088 (13)	−0.0004 (14)
C10	0.0439 (17)	0.0370 (18)	0.0281 (16)	−0.0091 (15)	−0.0018 (13)	0.0076 (14)
C11	0.0344 (14)	0.0280 (16)	0.0318 (16)	−0.0070 (12)	−0.0085 (12)	0.0083 (13)
C12	0.0340 (16)	0.0317 (18)	0.057 (2)	−0.0020 (14)	−0.0070 (15)	0.0104 (16)
C13	0.043 (2)	0.037 (2)	0.075 (3)	−0.0048 (16)	−0.013 (2)	0.022 (2)
C14	0.064 (3)	0.053 (3)	0.055 (3)	−0.009 (2)	−0.013 (2)	0.032 (2)
C15	0.057 (2)	0.053 (2)	0.038 (2)	−0.0137 (19)	−0.0016 (17)	0.0162 (18)
C16	0.0387 (19)	0.034 (2)	0.101 (4)	0.0117 (16)	−0.005 (2)	0.003 (2)

Geometric parameters (Å, º)

Ni1—N1	2.044 (3)	C4—H4	0.9500
Ni1—N2	2.117 (3)	C4—C5	1.391 (5)
Ni1—N3	2.120 (3)	N5—N6	1.165 (4)
Ni1—O3	2.009 (2)	C5—H5	0.9500
Ni1—O3^i	2.172 (2)	C6—H6	0.9500
Ni1—N4	2.095 (3)	C7—H7A	0.9900
O1—N2	1.388 (3)	C7—H7B	0.9900
O1—C7	1.439 (5)	C7—C8	1.515 (6)
N1—C1	1.342 (4)	C8—H8A	0.9900
N1—C5	1.343 (4)	C8—H8B	0.9900
C1—C2	1.381 (5)	C9—H9	0.9500
C1—C6	1.462 (5)	C9—C10	1.442 (5)
O2—N3	1.429 (4)	C10—C11	1.411 (5)
O2—C8	1.431 (5)	C10—C15	1.417 (5)
N2—C6	1.279 (4)	C11—C12	1.418 (5)
C2—H2	0.9500	C12—C13	1.376 (6)
C2—C3	1.379 (7)	C13—H13	0.9500
N3—C9	1.283 (5)	C13—C14	1.400 (8)
O3—Ni1^i	2.172 (2)	C14—H14	0.9500
O3—C11	1.333 (4)	C14—C15	1.363 (7)
C3—H3	0.9500	C15—H15	0.9500
C3—C4	1.365 (7)	C16—H16A	0.9800
N4—N5	1.192 (4)	C16—H16B	0.9800
O4—C12	1.371 (5)	C16—H16C	0.9800
O4—C16	1.438 (4)
N1—Ni1—N2	77.38 (11)	N1—C5—H5	119.5
N1—Ni1—N3	174.01 (12)	C4—C5—H5	119.5
N1—Ni1—O3^i	89.79 (10)	C1—C6—H6	121.7
N1—Ni1—N4	87.11 (11)	N2—C6—C1	116.5 (3)
N2—Ni1—N3	105.87 (11)	N2—C6—H6	121.7
N2—Ni1—O3^i	90.58 (10)	O1—C7—H7A	109.2
N3—Ni1—O3^i	95.16 (10)	O1—C7—H7B	109.2
O3—Ni1—N1	91.27 (10)	O1—C7—C8	111.9 (3)
O3—Ni1—N2	164.67 (10)	H7A—C7—H7B	107.9
O3—Ni1—N3	86.39 (10)	C8—C7—H7A	109.2
O3—Ni1—O3^i	78.96 (9)	C8—C7—H7B	109.2
O3—Ni1—N4	96.70 (10)	O2—C8—C7	114.1 (3)
N4—Ni1—N2	93.03 (11)	O2—C8—H8A	108.7
N4—Ni1—N3	87.69 (11)	O2—C8—H8B	108.7
N4—Ni1—O3^i	174.62 (10)	C7—C8—H8A	108.7
N2—O1—C7	110.0 (3)	C7—C8—H8B	108.7
C1—N1—Ni1	114.9 (2)	H8A—C8—H8B	107.6
C1—N1—C5	119.0 (3)	N3—C9—H9	116.6
C5—N1—Ni1	126.1 (2)	N3—C9—C10	126.9 (3)
N1—C1—C2	122.1 (4)	C10—C9—H9	116.6
N1—C1—C6	115.0 (3)	C11—C10—C9	123.1 (3)
C2—C1—C6	122.7 (3)	C11—C10—C15	119.5 (4)
N3—O2—C8	111.7 (2)	C15—C10—C9	117.4 (3)
O1—N2—Ni1	132.7 (2)	O3—C11—C10	122.3 (3)
C6—N2—Ni1	114.0 (2)	O3—C11—C12	120.1 (3)
C6—N2—O1	112.9 (3)	C10—C11—C12	117.6 (3)
C1—C2—H2	120.6	O4—C12—C11	113.5 (3)
C3—C2—C1	118.8 (4)	O4—C12—C13	124.8 (4)
C3—C2—H2	120.6	C13—C12—C11	121.6 (4)
O2—N3—Ni1	128.3 (2)	C12—C13—H13	120.2
C9—N3—Ni1	122.0 (2)	C12—C13—C14	119.6 (4)
C9—N3—O2	108.3 (3)	C14—C13—H13	120.2
Ni1—O3—Ni1^i	101.04 (9)	C13—C14—H14	119.9
C11—O3—Ni1^i	125.20 (18)	C15—C14—C13	120.3 (4)
C11—O3—Ni1	120.37 (19)	C15—C14—H14	119.9
C2—C3—H3	120.4	C10—C15—H15	119.5
C4—C3—C2	119.2 (4)	C14—C15—C10	120.9 (4)
C4—C3—H3	120.4	C14—C15—H15	119.5
N5—N4—Ni1	120.7 (2)	O4—C16—H16A	109.5
C12—O4—C16	117.2 (3)	O4—C16—H16B	109.5
C3—C4—H4	120.2	O4—C16—H16C	109.5
C3—C4—C5	119.7 (4)	H16A—C16—H16B	109.5
C5—C4—H4	120.2	H16A—C16—H16C	109.5
N6—N5—N4	178.2 (4)	H16B—C16—H16C	109.5
N1—C5—C4	121.1 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

catena-Poly[[{2-methoxy-6-[8-(pyridin-2-yl)-3,6-dioxa-2,7-diazaocta-1,7-dien-1-yl]phenolato}nickel(II)]-µ-dicyanamidato] (3)

Crystal data

[Ni(C16H16N3O4)(C2N3)]	F(000) = 904
Mr = 439.08	Dx = 1.600 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.5255 (11) Å	Cell parameters from 1786 reflections
b = 17.0181 (16) Å	θ = 2.9–26.6°
c = 11.2611 (11) Å	µ = 1.11 mm^−1
β = 93.25 (1)°	T = 293 K
V = 1822.6 (3) Å^3	Block, black
Z = 4	0.13 × 0.12 × 0.11 mm

Data collection

Multiwire proportional diffractometer	Rint = 0.086
Graphite monochromator	θmax = 29.5°, θmin = 2.2°
phi and ω scans	h = −9→12
9546 measured reflections	k = −17→23
4320 independent reflections	l = −14→11
2651 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.077	H-atom parameters constrained
wR(F^2) = 0.179	w = 1/[σ^2(Fo^2) + (0.0579P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4320 reflections	Δρmax = 1.21 e Å^−3
263 parameters	Δρmin = −0.65 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.70181 (7)	0.66611 (4)	0.74134 (5)	0.0194 (2)
O1	0.4992 (3)	0.6488 (2)	0.7091 (3)	0.0243 (8)
O3	1.0274 (4)	0.7056 (2)	0.8147 (3)	0.0289 (9)
O4	0.2744 (4)	0.5879 (2)	0.5996 (3)	0.0317 (9)
O2	0.7542 (4)	0.6970 (2)	1.0192 (3)	0.0268 (8)
N1	0.6649 (4)	0.6680 (2)	0.9223 (3)	0.0196 (9)
N2	0.9188 (4)	0.6920 (2)	0.7289 (3)	0.0211 (9)
N6	0.7288 (4)	0.6583 (2)	0.5589 (3)	0.0211 (9)
N5	0.8289 (4)	0.2885 (3)	0.7765 (3)	0.0242 (10)
N3	0.7576 (5)	0.5474 (2)	0.7621 (3)	0.0244 (10)
N4	0.8972 (4)	0.4270 (2)	0.7962 (4)	0.0285 (10)
C10	0.9583 (5)	0.7022 (3)	0.6223 (4)	0.0245 (11)
H10	1.0483	0.7197	0.6079	0.029*
C2	0.2924 (5)	0.5741 (3)	0.7196 (4)	0.0239 (11)
C1	0.4153 (5)	0.6085 (3)	0.7743 (4)	0.0215 (11)
C11	0.8544 (6)	0.6850 (3)	0.5256 (4)	0.0233 (11)
C6	0.4414 (5)	0.5975 (3)	0.8978 (4)	0.0205 (11)
C7	0.5600 (5)	0.6311 (3)	0.9641 (4)	0.0219 (11)
H7	0.5615	0.6256	1.0463	0.026*
C17	0.8149 (5)	0.4883 (3)	0.7757 (4)	0.0180 (10)
C12	0.8849 (6)	0.6893 (3)	0.4059 (4)	0.0277 (12)
H12	0.9707	0.7091	0.3840	0.033*
C3	0.2009 (5)	0.5302 (3)	0.7848 (4)	0.0284 (12)
H3	0.1221	0.5068	0.7472	0.034*
C16	0.1602 (6)	0.5488 (3)	0.5376 (4)	0.0318 (13)
H16A	0.1605	0.5611	0.4544	0.048*
H16B	0.0733	0.5660	0.5682	0.048*
H16C	0.1699	0.4931	0.5485	0.048*
C13	0.7854 (6)	0.6638 (3)	0.3207 (4)	0.0295 (13)
H13	0.8030	0.6664	0.2404	0.035*
C18	0.8525 (5)	0.3545 (3)	0.7845 (4)	0.0212 (11)
C15	0.6338 (6)	0.6325 (3)	0.4763 (4)	0.0259 (12)
H15	0.5485	0.6130	0.4999	0.031*
C5	0.3434 (5)	0.5539 (3)	0.9633 (4)	0.0254 (12)
H5	0.3592	0.5478	1.0450	0.031*
C14	0.6588 (6)	0.6340 (3)	0.3564 (4)	0.0297 (13)
H14	0.5915	0.6153	0.3003	0.036*
C8	0.8729 (5)	0.7381 (3)	0.9782 (4)	0.0235 (11)
H8A	0.9157	0.7687	1.0433	0.028*
H8B	0.8412	0.7743	0.9158	0.028*
C4	0.2280 (6)	0.5213 (3)	0.9075 (4)	0.0287 (12)
H4	0.1658	0.4927	0.9513	0.034*
C9	0.9838 (6)	0.6831 (3)	0.9303 (4)	0.0269 (12)
H9A	1.0654	0.6823	0.9859	0.032*
H9B	0.9459	0.6302	0.9257	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0195 (4)	0.0163 (4)	0.0229 (4)	−0.0004 (3)	0.0058 (2)	0.0001 (3)
O1	0.0161 (19)	0.033 (2)	0.0240 (17)	−0.0059 (16)	0.0019 (14)	0.0040 (15)
O3	0.019 (2)	0.037 (2)	0.0309 (19)	−0.0044 (17)	0.0041 (15)	−0.0051 (16)
O4	0.026 (2)	0.040 (2)	0.0288 (19)	−0.0042 (18)	−0.0015 (15)	0.0032 (17)
O2	0.025 (2)	0.034 (2)	0.0221 (18)	−0.0056 (17)	0.0040 (14)	−0.0013 (16)
N1	0.016 (2)	0.023 (2)	0.020 (2)	−0.0011 (19)	0.0023 (16)	−0.0029 (17)
N2	0.017 (2)	0.022 (2)	0.025 (2)	−0.0010 (18)	0.0014 (16)	−0.0021 (18)
N6	0.026 (2)	0.015 (2)	0.023 (2)	0.0040 (19)	0.0090 (17)	0.0007 (17)
N5	0.024 (3)	0.023 (2)	0.026 (2)	0.000 (2)	0.0054 (17)	0.0057 (19)
N3	0.029 (3)	0.014 (2)	0.031 (2)	0.0012 (19)	0.0071 (18)	−0.0006 (18)
N4	0.022 (3)	0.017 (2)	0.047 (3)	−0.001 (2)	0.0070 (19)	−0.002 (2)
C10	0.023 (3)	0.017 (3)	0.033 (3)	−0.003 (2)	0.008 (2)	−0.001 (2)
C2	0.020 (3)	0.023 (3)	0.029 (3)	0.007 (2)	0.005 (2)	0.002 (2)
C1	0.020 (3)	0.017 (3)	0.029 (3)	−0.001 (2)	0.011 (2)	−0.002 (2)
C11	0.027 (3)	0.017 (3)	0.027 (3)	−0.001 (2)	0.012 (2)	0.001 (2)
C6	0.019 (3)	0.019 (3)	0.025 (3)	−0.004 (2)	0.007 (2)	−0.006 (2)
C7	0.028 (3)	0.021 (3)	0.018 (2)	0.005 (2)	0.006 (2)	0.001 (2)
C17	0.013 (3)	0.024 (3)	0.018 (2)	−0.008 (2)	0.0071 (18)	−0.003 (2)
C12	0.026 (3)	0.027 (3)	0.032 (3)	0.002 (2)	0.015 (2)	−0.003 (2)
C3	0.020 (3)	0.022 (3)	0.043 (3)	0.000 (2)	0.007 (2)	0.000 (2)
C16	0.028 (3)	0.037 (3)	0.030 (3)	0.000 (3)	−0.006 (2)	−0.009 (3)
C13	0.042 (4)	0.026 (3)	0.021 (3)	0.011 (3)	0.007 (2)	0.002 (2)
C18	0.016 (3)	0.024 (3)	0.024 (3)	0.003 (2)	0.0052 (19)	0.003 (2)
C15	0.025 (3)	0.023 (3)	0.031 (3)	0.007 (2)	0.007 (2)	0.002 (2)
C5	0.023 (3)	0.028 (3)	0.025 (3)	0.002 (2)	0.002 (2)	−0.003 (2)
C14	0.035 (3)	0.031 (3)	0.022 (3)	0.011 (3)	−0.002 (2)	0.003 (2)
C8	0.015 (3)	0.025 (3)	0.031 (3)	−0.008 (2)	0.005 (2)	−0.005 (2)
C4	0.030 (3)	0.026 (3)	0.032 (3)	0.000 (3)	0.010 (2)	0.003 (2)
C9	0.030 (3)	0.028 (3)	0.023 (3)	−0.001 (2)	0.000 (2)	0.000 (2)

Geometric parameters (Å, º)

Ni1—O1	1.966 (3)	C1—C6	1.410 (6)
Ni1—N1	2.088 (4)	C11—C12	1.396 (6)
Ni1—N2	2.126 (4)	C6—C7	1.437 (7)
Ni1—N6	2.089 (4)	C6—C5	1.430 (7)
Ni1—N5^i	2.112 (4)	C7—H7	0.9300
Ni1—N3	2.099 (4)	C12—H12	0.9300
O1—C1	1.309 (5)	C12—C13	1.380 (7)
O3—N2	1.394 (5)	C3—H3	0.9300
O3—C9	1.441 (6)	C3—C4	1.399 (7)
O4—C2	1.372 (5)	C16—H16A	0.9600
O4—C16	1.423 (6)	C16—H16B	0.9600
O2—N1	1.432 (5)	C16—H16C	0.9600
O2—C8	1.428 (6)	C13—H13	0.9300
N1—C7	1.291 (6)	C13—C14	1.388 (8)
N2—C10	1.290 (6)	C15—H15	0.9300
N6—C11	1.352 (6)	C15—C14	1.385 (6)
N6—C15	1.335 (6)	C5—H5	0.9300
N5—Ni1^ii	2.112 (4)	C5—C4	1.354 (7)
N5—C18	1.147 (6)	C14—H14	0.9300
N3—C17	1.150 (6)	C8—H8A	0.9700
N4—C17	1.318 (6)	C8—H8B	0.9700
N4—C18	1.309 (6)	C8—C9	1.532 (7)
C10—H10	0.9300	C4—H4	0.9300
C10—C11	1.460 (7)	C9—H9A	0.9700
C2—C1	1.419 (7)	C9—H9B	0.9700
C2—C3	1.389 (7)
O1—Ni1—N1	88.00 (14)	C5—C6—C7	117.1 (4)
O1—Ni1—N2	165.24 (14)	N1—C7—C6	127.3 (4)
O1—Ni1—N6	89.02 (15)	N1—C7—H7	116.4
O1—Ni1—N5^i	90.05 (15)	C6—C7—H7	116.4
O1—Ni1—N3	96.68 (16)	N3—C17—N4	171.3 (5)
N1—Ni1—N2	106.20 (15)	C11—C12—H12	120.6
N1—Ni1—N6	176.21 (16)	C13—C12—C11	118.8 (5)
N1—Ni1—N5^i	92.72 (15)	C13—C12—H12	120.6
N1—Ni1—N3	87.81 (15)	C2—C3—H3	120.2
N6—Ni1—N2	76.95 (16)	C2—C3—C4	119.6 (5)
N6—Ni1—N5^i	89.62 (14)	C4—C3—H3	120.2
N6—Ni1—N3	90.21 (14)	O4—C16—H16A	109.5
N5^i—Ni1—N2	85.36 (16)	O4—C16—H16B	109.5
N3—Ni1—N2	88.04 (16)	O4—C16—H16C	109.5
N3—Ni1—N5^i	173.27 (17)	H16A—C16—H16B	109.5
C1—O1—Ni1	126.7 (3)	H16A—C16—H16C	109.5
N2—O3—C9	109.9 (4)	H16B—C16—H16C	109.5
C2—O4—C16	116.9 (4)	C12—C13—H13	120.4
C8—O2—N1	111.7 (3)	C12—C13—C14	119.2 (5)
O2—N1—Ni1	128.6 (3)	C14—C13—H13	120.4
C7—N1—Ni1	121.6 (3)	N5—C18—N4	172.2 (6)
C7—N1—O2	109.2 (4)	N6—C15—H15	119.1
O3—N2—Ni1	132.5 (3)	N6—C15—C14	121.7 (5)
C10—N2—Ni1	115.2 (3)	C14—C15—H15	119.1
C10—N2—O3	112.2 (4)	C6—C5—H5	119.7
C11—N6—Ni1	114.3 (3)	C4—C5—C6	120.7 (4)
C15—N6—Ni1	126.1 (3)	C4—C5—H5	119.7
C15—N6—C11	119.5 (4)	C13—C14—H14	120.3
C18—N5—Ni1^ii	176.5 (4)	C15—C14—C13	119.3 (5)
C17—N3—Ni1	166.4 (4)	C15—C14—H14	120.3
C18—N4—C17	122.7 (4)	O2—C8—H8A	109.0
N2—C10—H10	121.7	O2—C8—H8B	109.0
N2—C10—C11	116.5 (5)	O2—C8—C9	112.9 (4)
C11—C10—H10	121.7	H8A—C8—H8B	107.8
O4—C2—C1	114.3 (4)	C9—C8—H8A	109.0
O4—C2—C3	124.4 (5)	C9—C8—H8B	109.0
C3—C2—C1	121.3 (4)	C3—C4—H4	119.6
O1—C1—C2	119.2 (4)	C5—C4—C3	120.9 (5)
O1—C1—C6	123.0 (4)	C5—C4—H4	119.6
C6—C1—C2	117.9 (4)	O3—C9—C8	113.3 (4)
N6—C11—C10	115.7 (4)	O3—C9—H9A	108.9
N6—C11—C12	121.4 (5)	O3—C9—H9B	108.9
C12—C11—C10	122.7 (5)	C8—C9—H9A	108.9
C1—C6—C7	123.3 (4)	C8—C9—H9B	108.9
C1—C6—C5	119.6 (4)	H9A—C9—H9B	107.7

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