Syntheses and structures of two new coordination polymers generated from a 4-amino­triazole-bridged organic ligand and Co^II salts

Organic ligands and counter-anions influence the coordination spheres of metal cations and hence the construction of coordination polymers (CPs). The specific bent geometries of five-membered heterocyclic triazole bridging organic ligands are capable of generating CPs with novel patterns not easily obtained using rigid linear ligands. A multidentate 4-amino­triazole-bridged organic ligand, namely 4-amino-3,5-bis­(4,3′-bipyridyl-5′-yl)-4H-1,2,4-triazole (L) has been pre­pared and used to synthesize two Co^II coordination polymers, namely poly[[[μ₂-4-amino-3,5-bis­(4,3′-bipyridyl-5′-yl)-4H-1,2,4-triazole-κ²N:N′]bis­(methanol-κO)cobalt(II)] bis­(perchlorate)], {[Co(C₂₂H₁₆N₈)₂(CH₃OH)₂](ClO₄)₂}_n, (I), and poly[[μ₃-4-amino-3,5-bis­(4,3′-bipyridyl-5′-yl)-4H-1,2,4-triazole-κ³N:N′:N′′]dichlorido­cobalt(II)], [CoCl₂(C₂₂H₁₆N₈)]_n, (II), using CoX₂ salts [X = ClO₄ for (I) and Cl for (II)] under solvothermal conditions. Single-crystal X-ray structure analysis revealed that they both feature two-dimensional networks. Cobalt is located on an inversion centre in (I) and in a general position in (II). In (I), L functions as a bidentate cis-conformation ligand linking Co^II ions, while it functions as a tridentate trans-conformation linker binding Co^II ions in (II). In addition, O—H...N and N—H...O hydrogen bonds and C—H...π inter­actions exist in (I), while N—H...Cl and π–π inter­actions exist in (II), and these weak inter­actions play an important role in aligning the two-dimensional nets of (I) and (II) in the solid state. As the compounds were synthesized under the same conditions, the significant structural variations between (I) and (II) are believed to be determined by the different sizes and coordination abilities of the counter-anions. IR spectroscopy and diffuse reflectance UV–Vis spectra were also used to investigate the title compounds.

Computing details

For both compounds, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXL2013 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).

(I) Poly[[[µ₂-4-amino-3,5-bis(4,3'-bipyridyl-5'-yl)-4H-1,2,4-triazole-κ²N:N']bis(methanol-κO)cobalt(II)] bis(perchlorate)]

Crystal data

[Co(C22H16N8)2(CH4O)2](ClO4)2	F(000) = 1138
Mr = 1106.77	Dx = 1.636 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.54931 (15) Å	Cell parameters from 5388 reflections
b = 16.1513 (2) Å	θ = 3.8–29.0°
c = 14.5715 (2) Å	µ = 0.58 mm^−1
β = 91.2561 (13)°	T = 100 K
V = 2246.89 (6) Å^3	Block, clear light pink
Z = 2	0.27 × 0.14 × 0.08 mm

Data collection

Rigaku Oxford Diffraction SuperNova Dual Source with an Eos detector diffractometer	4254 independent reflections
Radiation source: micro-focus sealed X-ray tube	3763 reflections with I > 2σ(I)
Detector resolution: 16.0793 pixels mm^-1	Rint = 0.021
ω scans	θmax = 25.7°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −11→9
Tmin = 0.943, Tmax = 1.000	k = −18→19
9168 measured reflections	l = −15→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0368P)^2 + 3.3466P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4254 reflections	Δρmax = 0.81 e Å^−3
341 parameters	Δρmin = −0.69 e Å^−3

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
C1	0.4765 (3)	0.64709 (14)	0.14002 (16)	0.0177 (5)
H1	0.4722	0.6778	0.0860	0.021*
C2	0.4897 (3)	0.68945 (15)	0.22179 (16)	0.0184 (5)
H2	0.4946	0.7470	0.2219	0.022*
C3	0.4956 (2)	0.64599 (14)	0.30452 (15)	0.0137 (5)
C4	0.4797 (3)	0.56043 (15)	0.29868 (16)	0.0177 (5)
H4	0.4768	0.5288	0.3519	0.021*
C5	0.4682 (3)	0.52258 (15)	0.21383 (16)	0.0168 (5)
H5	0.4592	0.4653	0.2121	0.020*
C6	0.5289 (2)	0.68845 (14)	0.39242 (15)	0.0136 (5)
C7	0.4945 (2)	0.77140 (14)	0.40707 (15)	0.0144 (5)
H7	0.4411	0.7985	0.3622	0.017*
C8	0.6082 (2)	0.77409 (14)	0.54674 (15)	0.0158 (5)
H8	0.6369	0.8033	0.5988	0.019*
C9	0.6450 (2)	0.69069 (14)	0.54042 (15)	0.0139 (5)
C10	0.6042 (2)	0.64769 (14)	0.46158 (15)	0.0142 (5)
H10	0.6272	0.5921	0.4551	0.017*
C11	0.7215 (2)	0.65106 (14)	0.61643 (15)	0.0134 (5)
C12	0.8571 (2)	0.56725 (13)	0.69452 (15)	0.0126 (5)
C13	0.9517 (2)	0.49882 (13)	0.71968 (15)	0.0119 (5)
C14	1.0501 (2)	0.50853 (14)	0.79092 (15)	0.0137 (5)
H14	1.0574	0.5600	0.8193	0.016*
C15	1.1245 (2)	0.37401 (14)	0.77834 (15)	0.0138 (5)
H15	1.1824	0.3313	0.7990	0.017*
C16	1.0316 (2)	0.35811 (14)	0.70507 (15)	0.0131 (5)
C17	0.9432 (2)	0.42243 (14)	0.67651 (15)	0.0132 (5)
H17	0.8787	0.4140	0.6286	0.016*
C18	1.0243 (2)	0.27572 (14)	0.65969 (14)	0.0127 (5)
C19	1.1375 (2)	0.22149 (15)	0.65998 (16)	0.0171 (5)
H19	1.2212	0.2362	0.6895	0.021*
C20	1.1256 (2)	0.14576 (14)	0.61641 (16)	0.0160 (5)
H20	1.2029	0.1107	0.6179	0.019*
C21	0.8997 (2)	0.17263 (14)	0.57188 (15)	0.0145 (5)
H21	0.8172	0.1566	0.5418	0.017*
C22	0.9031 (2)	0.24915 (14)	0.61391 (16)	0.0152 (5)
H22	0.8243	0.2830	0.6116	0.018*
C23	0.8191 (2)	0.50796 (14)	−0.04148 (16)	0.0145 (5)
H23A	0.8573	0.4531	−0.0371	0.022*
H23B	0.8919	0.5478	−0.0294	0.022*
H23C	0.7804	0.5166	−0.1021	0.022*
Cl1	0.74513 (7)	0.36325 (4)	0.40496 (4)	0.02741 (17)
Co1	0.5000	0.5000	0.0000	0.00883 (12)
N1	0.46942 (19)	0.56390 (12)	0.13334 (12)	0.0129 (4)
N2	0.5340 (2)	0.81414 (12)	0.48193 (13)	0.0173 (4)
N3	0.7098 (2)	0.67021 (12)	0.70338 (13)	0.0162 (4)
N4	0.7970 (2)	0.61649 (12)	0.75330 (13)	0.0152 (4)
N5	0.8124 (2)	0.58613 (12)	0.60718 (12)	0.0136 (4)
N6	0.8730 (2)	0.56344 (15)	0.52341 (13)	0.0254 (5)
H6A	0.8510	0.5067	0.5114	0.038*
H6B	0.9745	0.5770	0.5294	0.038*
N7	1.1344 (2)	0.44776 (12)	0.82042 (12)	0.0139 (4)
N8	1.0088 (2)	0.11967 (11)	0.57186 (12)	0.0116 (4)
O1	0.71051 (16)	0.51761 (9)	0.02488 (10)	0.0121 (3)
H1A	0.7533	0.5272	0.0804	0.018*
O2	0.7271 (3)	0.40534 (14)	0.49065 (15)	0.0507 (6)
O3	0.6700 (5)	0.4027 (2)	0.3360 (2)	0.1156 (16)
O4	0.6980 (2)	0.27976 (13)	0.41537 (16)	0.0455 (6)
O5	0.8885 (3)	0.35941 (19)	0.3867 (3)	0.0931 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0254 (13)	0.0157 (12)	0.0118 (11)	0.0048 (10)	−0.0015 (9)	0.0023 (9)
C2	0.0254 (13)	0.0153 (12)	0.0143 (11)	0.0049 (10)	−0.0021 (9)	0.0002 (9)
C3	0.0114 (11)	0.0172 (12)	0.0125 (11)	0.0025 (9)	−0.0022 (8)	−0.0017 (9)
C4	0.0245 (13)	0.0177 (12)	0.0108 (11)	−0.0024 (10)	−0.0020 (9)	0.0025 (9)
C5	0.0196 (12)	0.0144 (11)	0.0165 (12)	−0.0044 (10)	−0.0001 (9)	−0.0007 (9)
C6	0.0139 (11)	0.0155 (11)	0.0116 (11)	0.0000 (9)	0.0007 (9)	0.0009 (9)
C7	0.0157 (11)	0.0151 (11)	0.0124 (11)	0.0000 (9)	−0.0015 (9)	0.0013 (9)
C8	0.0181 (12)	0.0162 (12)	0.0129 (11)	−0.0009 (10)	−0.0016 (9)	−0.0029 (9)
C9	0.0133 (11)	0.0168 (11)	0.0115 (11)	0.0003 (9)	0.0001 (9)	0.0014 (9)
C10	0.0177 (12)	0.0116 (11)	0.0132 (11)	0.0026 (9)	−0.0017 (9)	−0.0013 (9)
C11	0.0147 (11)	0.0121 (11)	0.0132 (11)	−0.0012 (9)	−0.0011 (9)	−0.0014 (9)
C12	0.0132 (11)	0.0118 (11)	0.0127 (11)	−0.0037 (9)	−0.0025 (8)	0.0010 (9)
C13	0.0133 (11)	0.0133 (11)	0.0091 (10)	−0.0006 (9)	0.0002 (8)	0.0011 (8)
C14	0.0152 (11)	0.0129 (11)	0.0129 (11)	−0.0001 (9)	−0.0008 (9)	−0.0024 (9)
C15	0.0146 (11)	0.0139 (11)	0.0129 (11)	0.0018 (9)	−0.0016 (9)	−0.0002 (9)
C16	0.0132 (11)	0.0135 (11)	0.0125 (11)	−0.0016 (9)	0.0021 (8)	0.0001 (9)
C17	0.0135 (11)	0.0154 (11)	0.0107 (10)	−0.0017 (9)	−0.0012 (8)	0.0007 (9)
C18	0.0166 (11)	0.0131 (11)	0.0085 (10)	−0.0024 (9)	0.0011 (8)	0.0015 (8)
C19	0.0141 (11)	0.0187 (12)	0.0184 (12)	0.0002 (10)	−0.0037 (9)	−0.0021 (9)
C20	0.0133 (11)	0.0163 (12)	0.0182 (12)	0.0026 (9)	−0.0030 (9)	−0.0022 (9)
C21	0.0139 (11)	0.0150 (11)	0.0144 (11)	−0.0017 (9)	−0.0026 (9)	0.0007 (9)
C22	0.0127 (11)	0.0140 (11)	0.0190 (12)	0.0032 (9)	−0.0015 (9)	0.0000 (9)
C23	0.0125 (11)	0.0165 (11)	0.0145 (11)	−0.0008 (9)	−0.0011 (9)	0.0007 (9)
Cl1	0.0312 (4)	0.0297 (4)	0.0213 (3)	−0.0082 (3)	−0.0009 (3)	−0.0035 (3)
Co1	0.0092 (2)	0.0097 (2)	0.0075 (2)	−0.00041 (16)	−0.00208 (15)	0.00023 (15)
N1	0.0115 (9)	0.0156 (10)	0.0115 (9)	0.0012 (8)	−0.0015 (7)	−0.0017 (7)
N2	0.0215 (11)	0.0147 (10)	0.0155 (10)	0.0020 (8)	−0.0025 (8)	−0.0004 (8)
N3	0.0202 (10)	0.0155 (10)	0.0126 (10)	0.0038 (8)	−0.0047 (8)	−0.0012 (8)
N4	0.0194 (10)	0.0133 (10)	0.0126 (9)	0.0019 (8)	−0.0041 (8)	−0.0018 (8)
N5	0.0151 (10)	0.0163 (10)	0.0095 (9)	0.0027 (8)	−0.0010 (7)	−0.0014 (7)
N6	0.0271 (12)	0.0371 (13)	0.0122 (10)	0.0086 (10)	0.0043 (9)	−0.0051 (9)
N7	0.0146 (10)	0.0141 (10)	0.0129 (9)	0.0010 (8)	−0.0022 (7)	−0.0018 (7)
N8	0.0145 (10)	0.0119 (9)	0.0085 (9)	0.0006 (8)	0.0004 (7)	0.0011 (7)
O1	0.0105 (8)	0.0167 (8)	0.0090 (7)	−0.0015 (6)	−0.0029 (6)	0.0002 (6)
O2	0.0784 (19)	0.0419 (13)	0.0315 (12)	−0.0045 (13)	−0.0034 (12)	−0.0134 (10)
O3	0.209 (5)	0.079 (2)	0.0555 (19)	0.046 (3)	−0.070 (2)	−0.0026 (17)
O4	0.0493 (14)	0.0324 (12)	0.0553 (14)	−0.0161 (11)	0.0114 (11)	−0.0098 (10)
O5	0.0518 (18)	0.0667 (19)	0.163 (4)	−0.0254 (16)	0.055 (2)	−0.024 (2)

Geometric parameters (Å, º)

C1—N1	1.349 (3)	C16—C17	1.397 (3)
C1—C2	1.377 (3)	C16—C18	1.487 (3)
C1—H1	0.9300	C17—H17	0.9300
C2—C3	1.395 (3)	C18—C19	1.391 (3)
C2—H2	0.9300	C18—C22	1.391 (3)
C3—C4	1.393 (3)	C19—C20	1.382 (3)
C3—C6	1.481 (3)	C19—H19	0.9300
C4—C5	1.381 (3)	C20—N8	1.346 (3)
C4—H4	0.9300	C20—H20	0.9300
C5—N1	1.350 (3)	C21—N8	1.348 (3)
C5—H5	0.9300	C21—C22	1.379 (3)
C6—C10	1.391 (3)	C21—H21	0.9300
C6—C7	1.397 (3)	C22—H22	0.9300
C7—N2	1.338 (3)	C23—O1	1.442 (3)
C7—H7	0.9300	C23—H23A	0.9600
C8—N2	1.335 (3)	C23—H23B	0.9600
C8—C9	1.396 (3)	C23—H23C	0.9600
C8—H8	0.9300	Cl1—O3	1.378 (3)
C9—C10	1.391 (3)	Cl1—O5	1.402 (3)
C9—C11	1.461 (3)	Cl1—O4	1.431 (2)
C10—H10	0.9300	Cl1—O2	1.435 (2)
C11—N3	1.311 (3)	Co1—O1^i	2.0546 (15)
C11—N5	1.370 (3)	Co1—O1	2.0546 (15)
C12—N4	1.310 (3)	Co1—N8^ii	2.1991 (18)
C12—N5	1.368 (3)	Co1—N8^iii	2.1991 (18)
C12—C13	1.469 (3)	Co1—N1	2.2250 (18)
C13—C17	1.387 (3)	Co1—N1^i	2.2250 (18)
C13—C14	1.394 (3)	N3—N4	1.396 (3)
C14—N7	1.335 (3)	N5—N6	1.410 (3)
C14—H14	0.9300	N6—H6A	0.9559
C15—N7	1.342 (3)	N6—H6B	0.9953
C15—C16	1.397 (3)	N8—Co1^iv	2.1990 (18)
C15—H15	0.9300	O1—H1A	0.9121
N1—C1—C2	124.1 (2)	C18—C19—H19	120.0
N1—C1—H1	117.9	N8—C20—C19	123.9 (2)
C2—C1—H1	117.9	N8—C20—H20	118.0
C1—C2—C3	119.9 (2)	C19—C20—H20	118.0
C1—C2—H2	120.0	N8—C21—C22	123.9 (2)
C3—C2—H2	120.0	N8—C21—H21	118.1
C4—C3—C2	116.4 (2)	C22—C21—H21	118.1
C4—C3—C6	122.2 (2)	C21—C22—C18	120.0 (2)
C2—C3—C6	121.2 (2)	C21—C22—H22	120.0
C5—C4—C3	120.0 (2)	C18—C22—H22	120.0
C5—C4—H4	120.0	O1—C23—H23A	109.5
C3—C4—H4	120.0	O1—C23—H23B	109.5
N1—C5—C4	123.8 (2)	H23A—C23—H23B	109.5
N1—C5—H5	118.1	O1—C23—H23C	109.5
C4—C5—H5	118.1	H23A—C23—H23C	109.5
C10—C6—C7	117.6 (2)	H23B—C23—H23C	109.5
C10—C6—C3	120.3 (2)	O3—Cl1—O5	112.2 (3)
C7—C6—C3	122.0 (2)	O3—Cl1—O4	110.7 (2)
N2—C7—C6	123.8 (2)	O5—Cl1—O4	106.80 (16)
N2—C7—H7	118.1	O3—Cl1—O2	110.14 (19)
C6—C7—H7	118.1	O5—Cl1—O2	108.8 (2)
N2—C8—C9	123.5 (2)	O4—Cl1—O2	108.07 (14)
N2—C8—H8	118.3	O1^i—Co1—O1	180.0
C9—C8—H8	118.3	O1^i—Co1—N8^ii	89.40 (6)
C10—C9—C8	118.1 (2)	O1—Co1—N8^ii	90.60 (6)
C10—C9—C11	122.2 (2)	O1^i—Co1—N8^iii	90.60 (6)
C8—C9—C11	119.7 (2)	O1—Co1—N8^iii	89.40 (6)
C9—C10—C6	119.5 (2)	N8^ii—Co1—N8^iii	180.00 (9)
C9—C10—H10	120.2	O1^i—Co1—N1	94.11 (6)
C6—C10—H10	120.2	O1—Co1—N1	85.89 (6)
N3—C11—N5	110.1 (2)	N8^ii—Co1—N1	89.79 (7)
N3—C11—C9	125.3 (2)	N8^iii—Co1—N1	90.21 (7)
N5—C11—C9	124.63 (19)	O1^i—Co1—N1^i	85.89 (6)
N4—C12—N5	109.9 (2)	O1—Co1—N1^i	94.11 (6)
N4—C12—C13	124.7 (2)	N8^ii—Co1—N1^i	90.21 (7)
N5—C12—C13	125.3 (2)	N8^iii—Co1—N1^i	89.79 (7)
C17—C13—C14	118.0 (2)	N1—Co1—N1^i	180.0
C17—C13—C12	121.8 (2)	C1—N1—C5	115.54 (19)
C14—C13—C12	120.1 (2)	C1—N1—Co1	121.19 (15)
N7—C14—C13	123.3 (2)	C5—N1—Co1	122.23 (15)
N7—C14—H14	118.3	C8—N2—C7	117.5 (2)
C13—C14—H14	118.3	C11—N3—N4	107.12 (18)
N7—C15—C16	123.4 (2)	C12—N4—N3	107.54 (18)
N7—C15—H15	118.3	C12—N5—C11	105.32 (18)
C16—C15—H15	118.3	C12—N5—N6	128.48 (19)
C15—C16—C17	117.4 (2)	C11—N5—N6	123.83 (19)
C15—C16—C18	121.8 (2)	N5—N6—H6A	108.3
C17—C16—C18	120.7 (2)	N5—N6—H6B	106.4
C13—C17—C16	119.8 (2)	H6A—N6—H6B	115.9
C13—C17—H17	120.1	C14—N7—C15	118.0 (2)
C16—C17—H17	120.1	C20—N8—C21	115.71 (19)
C19—C18—C22	116.5 (2)	C20—N8—Co1^iv	121.84 (15)
C19—C18—C16	122.2 (2)	C21—N8—Co1^iv	122.42 (15)
C22—C18—C16	121.3 (2)	C23—O1—Co1	125.59 (13)
C20—C19—C18	120.0 (2)	C23—O1—H1A	107.4
C20—C19—H19	120.0	Co1—O1—H1A	126.7
N1—C1—C2—C3	−0.4 (4)	C17—C16—C18—C19	155.5 (2)
C1—C2—C3—C4	−3.4 (3)	C15—C16—C18—C22	154.8 (2)
C1—C2—C3—C6	171.6 (2)	C17—C16—C18—C22	−24.1 (3)
C2—C3—C4—C5	4.1 (3)	C22—C18—C19—C20	−0.1 (3)
C6—C3—C4—C5	−170.9 (2)	C16—C18—C19—C20	−179.7 (2)
C3—C4—C5—N1	−1.0 (4)	C18—C19—C20—N8	0.2 (4)
C4—C3—C6—C10	28.6 (3)	N8—C21—C22—C18	0.1 (3)
C2—C3—C6—C10	−146.2 (2)	C19—C18—C22—C21	0.0 (3)
C4—C3—C6—C7	−155.5 (2)	C16—C18—C22—C21	179.5 (2)
C2—C3—C6—C7	29.7 (3)	C2—C1—N1—C5	3.6 (4)
C10—C6—C7—N2	2.4 (3)	C2—C1—N1—Co1	−165.01 (19)
C3—C6—C7—N2	−173.6 (2)	C4—C5—N1—C1	−2.8 (3)
N2—C8—C9—C10	1.3 (3)	C4—C5—N1—Co1	165.58 (19)
N2—C8—C9—C11	−177.5 (2)	C9—C8—N2—C7	−0.5 (3)
C8—C9—C10—C6	−0.1 (3)	C6—C7—N2—C8	−1.4 (3)
C11—C9—C10—C6	178.6 (2)	N5—C11—N3—N4	0.5 (3)
C7—C6—C10—C9	−1.6 (3)	C9—C11—N3—N4	178.3 (2)
C3—C6—C10—C9	174.5 (2)	N5—C12—N4—N3	−0.2 (2)
C10—C9—C11—N3	−147.1 (2)	C13—C12—N4—N3	−176.9 (2)
C8—C9—C11—N3	31.6 (3)	C11—N3—N4—C12	−0.2 (2)
C10—C9—C11—N5	30.4 (3)	N4—C12—N5—C11	0.5 (3)
C8—C9—C11—N5	−150.9 (2)	C13—C12—N5—C11	177.1 (2)
N4—C12—C13—C17	137.4 (2)	N4—C12—N5—N6	163.3 (2)
N5—C12—C13—C17	−38.7 (3)	C13—C12—N5—N6	−20.1 (4)
N4—C12—C13—C14	−40.2 (3)	N3—C11—N5—C12	−0.6 (3)
N5—C12—C13—C14	143.7 (2)	C9—C11—N5—C12	−178.4 (2)
C17—C13—C14—N7	−1.2 (3)	N3—C11—N5—N6	−164.4 (2)
C12—C13—C14—N7	176.5 (2)	C9—C11—N5—N6	17.8 (3)
N7—C15—C16—C17	−1.6 (3)	C13—C14—N7—C15	0.8 (3)
N7—C15—C16—C18	179.5 (2)	C16—C15—N7—C14	0.6 (3)
C14—C13—C17—C16	0.1 (3)	C19—C20—N8—C21	−0.2 (3)
C12—C13—C17—C16	−177.5 (2)	C19—C20—N8—Co1^iv	177.86 (17)
C15—C16—C17—C13	1.1 (3)	C22—C21—N8—C20	0.0 (3)
C18—C16—C17—C13	−179.96 (19)	C22—C21—N8—Co1^iv	−178.00 (17)
C15—C16—C18—C19	−25.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N7^v	0.91	1.83	2.728 (2)	170
N6—H6B···O5^v	1.00	2.05	2.885 (4)	141
N6—H6A···O2	0.96	2.04	2.943 (3)	157

Symmetry code: (v) −x+2, −y+1, −z+1.

(II) Poly[[µ₃-4-amino-3,5-bis(4,3'-bipyridyl-5'-yl)-4H-1,2,4-triazole-κ³N:N':N'']dichloridocobalt(II)]

Crystal data

[CoCl2(C22H16N8)]	F(000) = 1060
Mr = 522.26	Dx = 1.636 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 20.4923 (5) Å	Cell parameters from 2414 reflections
b = 7.4278 (3) Å	θ = 6.5–71.0°
c = 13.9819 (4) Å	µ = 8.91 mm^−1
β = 94.891 (2)°	T = 101 K
V = 2120.49 (11) Å^3	Plate, clear light purple
Z = 4	0.21 × 0.13 × 0.08 mm

Data collection

Rigaku Oxford Diffraction SuperNova (Cu) X-ray Source diffractometer	3786 independent reflections
Radiation source: micro-focus sealed X-ray tube	3131 reflections with I > 2σ(I)
Detector resolution: 16.0793 pixels mm^-1	Rint = 0.024
ω scans	θmax = 67.1°, θmin = 4.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −19→24
Tmin = 0.408, Tmax = 1.000	k = −8→4
7172 measured reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0397P)^2 + 1.4405P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3786 reflections	Δρmax = 0.65 e Å^−3
299 parameters	Δρmin = −0.52 e Å^−3

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
C1	−0.16714 (13)	0.8344 (4)	0.1422 (2)	0.0322 (7)
H1	−0.2066	0.8689	0.1650	0.039*
C2	−0.11037 (13)	0.8624 (4)	0.2004 (2)	0.0321 (7)
H2	−0.1121	0.9143	0.2607	0.038*
C3	−0.05036 (13)	0.8125 (4)	0.1685 (2)	0.0283 (6)
C4	−0.05137 (13)	0.7435 (5)	0.0759 (2)	0.0326 (7)
H4	−0.0125	0.7145	0.0498	0.039*
C5	−0.11066 (14)	0.7184 (5)	0.0232 (2)	0.0333 (7)
H5	−0.1103	0.6695	−0.0380	0.040*
C6	0.01143 (13)	0.8274 (4)	0.2311 (2)	0.0276 (6)
C7	0.01360 (14)	0.7882 (4)	0.3283 (2)	0.0321 (7)
H7	−0.0253	0.7541	0.3529	0.038*
C8	0.12283 (13)	0.8479 (4)	0.3536 (2)	0.0299 (7)
H8	0.1607	0.8561	0.3950	0.036*
C9	0.12631 (13)	0.8904 (4)	0.2574 (2)	0.0253 (6)
C10	0.06998 (13)	0.8779 (4)	0.1952 (2)	0.0280 (7)
H10	0.0714	0.9031	0.1302	0.034*
C11	0.18541 (12)	0.9578 (4)	0.21637 (19)	0.0241 (6)
C12	0.28388 (12)	0.9815 (4)	0.17166 (19)	0.0253 (6)
C13	0.35190 (12)	0.9385 (4)	0.1528 (2)	0.0260 (6)
C14	0.36272 (14)	0.8978 (5)	0.0586 (2)	0.0376 (8)
H14	0.3272	0.8990	0.0126	0.045*
C15	0.47126 (14)	0.8591 (5)	0.0987 (2)	0.0408 (8)
H15	0.5126	0.8316	0.0802	0.049*
C16	0.46632 (13)	0.8987 (4)	0.1948 (2)	0.0289 (7)
C17	0.40396 (12)	0.9381 (4)	0.2222 (2)	0.0272 (6)
H17	0.3977	0.9637	0.2859	0.033*
C18	0.52583 (13)	0.8969 (4)	0.2632 (2)	0.0290 (7)
C19	0.58669 (13)	0.9364 (5)	0.2321 (2)	0.0396 (8)
H19	0.5900	0.9761	0.1696	0.048*
C20	0.64242 (14)	0.9167 (5)	0.2942 (2)	0.0395 (8)
H20	0.6827	0.9401	0.2708	0.047*
C21	0.58249 (14)	0.8382 (5)	0.4162 (2)	0.0378 (8)
H21	0.5803	0.8079	0.4804	0.045*
C22	0.52471 (14)	0.8512 (5)	0.3591 (2)	0.0356 (8)
H22	0.4850	0.8294	0.3847	0.043*
Cl1	−0.31474 (4)	0.67671 (15)	0.10573 (5)	0.0507 (3)
Cl2	−0.21707 (4)	0.43130 (13)	−0.08926 (7)	0.0597 (3)
Co1	−0.26176 (2)	0.68805 (7)	−0.03127 (3)	0.02810 (14)
N1	−0.16876 (11)	0.7602 (4)	0.05459 (17)	0.0293 (6)
N2	0.18280 (10)	1.0784 (4)	0.14814 (17)	0.0287 (6)
N3	0.24608 (10)	1.0949 (4)	0.11977 (16)	0.0278 (6)
N4	0.24817 (10)	0.8977 (3)	0.23471 (15)	0.0237 (5)
N5	0.27204 (12)	0.7672 (4)	0.3009 (2)	0.0394 (7)
H5A	0.2743	0.8128	0.3577	0.047*
H5B	0.2458	0.6761	0.2984	0.047*
N6	0.06733 (12)	0.7959 (4)	0.38932 (17)	0.0348 (6)
N7	0.42153 (13)	0.8573 (5)	0.03083 (19)	0.0476 (8)
N8	0.64183 (11)	0.8663 (4)	0.38543 (17)	0.0308 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0198 (14)	0.0380 (19)	0.0389 (17)	0.0007 (12)	0.0031 (12)	−0.0006 (15)
C2	0.0238 (14)	0.0396 (19)	0.0329 (16)	−0.0030 (13)	0.0034 (12)	−0.0063 (14)
C3	0.0214 (13)	0.0315 (17)	0.0316 (15)	−0.0045 (12)	0.0006 (11)	0.0056 (14)
C4	0.0181 (13)	0.050 (2)	0.0303 (15)	−0.0027 (13)	0.0040 (11)	−0.0007 (15)
C5	0.0260 (15)	0.048 (2)	0.0262 (15)	−0.0020 (14)	0.0014 (12)	−0.0003 (15)
C6	0.0205 (13)	0.0302 (17)	0.0319 (15)	−0.0053 (12)	0.0006 (11)	−0.0003 (13)
C7	0.0243 (14)	0.040 (2)	0.0322 (15)	−0.0080 (13)	0.0046 (12)	−0.0024 (15)
C8	0.0234 (14)	0.0366 (19)	0.0289 (15)	−0.0036 (12)	−0.0021 (11)	−0.0016 (14)
C9	0.0194 (13)	0.0272 (16)	0.0291 (14)	−0.0024 (11)	0.0008 (11)	−0.0007 (13)
C10	0.0221 (14)	0.0347 (18)	0.0268 (14)	−0.0030 (12)	0.0001 (11)	0.0019 (13)
C11	0.0186 (13)	0.0287 (16)	0.0244 (14)	−0.0016 (11)	−0.0013 (10)	−0.0014 (13)
C12	0.0168 (13)	0.0325 (17)	0.0258 (14)	0.0004 (11)	−0.0031 (10)	−0.0006 (13)
C13	0.0177 (13)	0.0298 (17)	0.0303 (15)	0.0005 (11)	0.0006 (11)	0.0006 (13)
C14	0.0245 (14)	0.056 (2)	0.0316 (16)	0.0039 (14)	−0.0022 (12)	−0.0053 (16)
C15	0.0227 (15)	0.062 (2)	0.0387 (18)	0.0086 (15)	0.0065 (13)	−0.0062 (17)
C16	0.0195 (13)	0.0333 (18)	0.0336 (15)	0.0028 (12)	0.0010 (11)	0.0042 (14)
C17	0.0194 (13)	0.0333 (17)	0.0285 (14)	0.0011 (12)	0.0006 (11)	0.0041 (14)
C18	0.0180 (13)	0.0330 (17)	0.0359 (16)	0.0050 (12)	0.0021 (11)	0.0012 (14)
C19	0.0217 (14)	0.063 (2)	0.0343 (16)	−0.0009 (15)	0.0011 (12)	0.0117 (17)
C20	0.0191 (14)	0.060 (2)	0.0394 (18)	−0.0001 (14)	0.0033 (12)	0.0049 (17)
C21	0.0244 (15)	0.058 (2)	0.0313 (16)	0.0008 (14)	0.0024 (12)	0.0032 (16)
C22	0.0197 (14)	0.052 (2)	0.0357 (17)	0.0003 (13)	0.0046 (12)	0.0034 (15)
Cl1	0.0297 (4)	0.0945 (8)	0.0277 (4)	−0.0141 (4)	0.0014 (3)	0.0097 (4)
Cl2	0.0475 (5)	0.0466 (6)	0.0792 (7)	0.0143 (4)	−0.0288 (4)	−0.0244 (5)
Co1	0.0212 (2)	0.0352 (3)	0.0276 (2)	−0.0008 (2)	0.00065 (17)	0.0044 (2)
N1	0.0211 (11)	0.0349 (15)	0.0314 (13)	−0.0028 (10)	−0.0009 (9)	0.0036 (12)
N2	0.0138 (10)	0.0387 (15)	0.0331 (13)	−0.0009 (10)	−0.0004 (9)	0.0036 (12)
N3	0.0135 (10)	0.0395 (16)	0.0300 (12)	−0.0012 (10)	0.0000 (9)	0.0028 (12)
N4	0.0183 (11)	0.0279 (14)	0.0243 (11)	−0.0004 (9)	−0.0015 (9)	0.0029 (10)
N5	0.0348 (14)	0.0422 (17)	0.0407 (15)	0.0059 (13)	0.0000 (11)	0.0166 (14)
N6	0.0311 (13)	0.0447 (17)	0.0288 (13)	−0.0067 (12)	0.0026 (10)	−0.0011 (12)
N7	0.0314 (14)	0.078 (2)	0.0332 (14)	0.0094 (14)	0.0020 (11)	−0.0117 (15)
N8	0.0197 (11)	0.0391 (16)	0.0333 (13)	0.0028 (10)	−0.0002 (10)	0.0004 (12)

Geometric parameters (Å, º)

C1—N1	1.341 (4)	C14—H14	0.9300
C1—C2	1.377 (4)	C15—N7	1.332 (4)
C1—H1	0.9300	C15—C16	1.387 (4)
C2—C3	1.394 (4)	C15—H15	0.9300
C2—H2	0.9300	C16—C17	1.396 (4)
C3—C4	1.391 (4)	C16—C18	1.485 (4)
C3—C6	1.481 (4)	C17—H17	0.9300
C4—C5	1.379 (4)	C18—C22	1.386 (4)
C4—H4	0.9300	C18—C19	1.387 (4)
C5—N1	1.340 (4)	C19—C20	1.383 (4)
C5—H5	0.9300	C19—H19	0.9300
C6—C7	1.387 (4)	C20—N8	1.331 (4)
C6—C10	1.391 (4)	C20—H20	0.9300
C7—N6	1.335 (4)	C21—N8	1.341 (4)
C7—H7	0.9300	C21—C22	1.374 (4)
C8—N6	1.338 (4)	C21—H21	0.9300
C8—C9	1.389 (4)	C22—H22	0.9300
C8—H8	0.9300	Cl1—Co1	2.2825 (9)
C9—C10	1.388 (4)	Cl2—Co1	2.2935 (10)
C9—C11	1.472 (4)	Co1—N3^i	2.074 (2)
C10—H10	0.9300	Co1—N1	2.229 (2)
C11—N2	1.306 (4)	Co1—N8^ii	2.243 (2)
C11—N4	1.365 (3)	N2—N3	1.394 (3)
C12—N3	1.319 (3)	N3—Co1^i	2.074 (2)
C12—N4	1.345 (3)	N4—N5	1.399 (3)
C12—C13	1.476 (3)	N5—H5A	0.8620
C13—C17	1.380 (4)	N5—H5B	0.8622
C13—C14	1.387 (4)	N8—Co1^iii	2.243 (2)
C14—N7	1.332 (4)
N1—C1—C2	123.8 (3)	C17—C16—C18	123.1 (3)
N1—C1—H1	118.1	C13—C17—C16	118.6 (3)
C2—C1—H1	118.1	C13—C17—H17	120.7
C1—C2—C3	119.6 (3)	C16—C17—H17	120.7
C1—C2—H2	120.2	C22—C18—C19	116.4 (3)
C3—C2—H2	120.2	C22—C18—C16	123.1 (3)
C4—C3—C2	116.9 (3)	C19—C18—C16	120.5 (3)
C4—C3—C6	121.5 (3)	C20—C19—C18	119.8 (3)
C2—C3—C6	121.6 (3)	C20—C19—H19	120.1
C5—C4—C3	119.3 (3)	C18—C19—H19	120.1
C5—C4—H4	120.3	N8—C20—C19	123.9 (3)
C3—C4—H4	120.3	N8—C20—H20	118.1
N1—C5—C4	124.1 (3)	C19—C20—H20	118.1
N1—C5—H5	118.0	N8—C21—C22	124.2 (3)
C4—C5—H5	118.0	N8—C21—H21	117.9
C7—C6—C10	117.0 (3)	C22—C21—H21	117.9
C7—C6—C3	121.2 (2)	C21—C22—C18	119.7 (3)
C10—C6—C3	121.8 (3)	C21—C22—H22	120.2
N6—C7—C6	124.9 (3)	C18—C22—H22	120.2
N6—C7—H7	117.5	N3^i—Co1—N1	88.03 (9)
C6—C7—H7	117.5	N3^i—Co1—N8^ii	90.27 (9)
N6—C8—C9	122.9 (3)	N1—Co1—N8^ii	176.05 (10)
N6—C8—H8	118.6	N3^i—Co1—Cl1	129.67 (8)
C9—C8—H8	118.6	N1—Co1—Cl1	90.16 (7)
C10—C9—C8	118.9 (3)	N8^ii—Co1—Cl1	88.18 (7)
C10—C9—C11	116.5 (2)	N3^i—Co1—Cl2	110.41 (7)
C8—C9—C11	124.5 (2)	N1—Co1—Cl2	92.37 (7)
C9—C10—C6	119.2 (3)	N8^ii—Co1—Cl2	91.56 (7)
C9—C10—H10	120.4	Cl1—Co1—Cl2	119.92 (5)
C6—C10—H10	120.4	C5—N1—C1	116.2 (2)
N2—C11—N4	109.9 (2)	C5—N1—Co1	120.7 (2)
N2—C11—C9	122.3 (2)	C1—N1—Co1	122.96 (18)
N4—C11—C9	127.5 (3)	C11—N2—N3	106.7 (2)
N3—C12—N4	109.2 (2)	C12—N3—N2	107.7 (2)
N3—C12—C13	124.0 (3)	C12—N3—Co1^i	135.32 (18)
N4—C12—C13	126.3 (3)	N2—N3—Co1^i	115.68 (18)
C17—C13—C14	119.4 (3)	C12—N4—C11	106.4 (2)
C17—C13—C12	124.1 (3)	C12—N4—N5	125.1 (2)
C14—C13—C12	116.5 (2)	C11—N4—N5	128.4 (2)
N7—C14—C13	123.2 (3)	N4—N5—H5A	109.0
N7—C14—H14	118.4	N4—N5—H5B	109.6
C13—C14—H14	118.4	H5A—N5—H5B	109.2
N7—C15—C16	125.3 (3)	C7—N6—C8	117.1 (3)
N7—C15—H15	117.4	C14—N7—C15	116.5 (3)
C16—C15—H15	117.4	C20—N8—C21	115.8 (3)
C15—C16—C17	117.0 (3)	C20—N8—Co1^iii	117.96 (18)
C15—C16—C18	119.9 (3)	C21—N8—Co1^iii	126.0 (2)
N1—C1—C2—C3	0.1 (5)	C15—C16—C18—C19	29.0 (5)
C1—C2—C3—C4	2.9 (5)	C17—C16—C18—C19	−151.3 (3)
C1—C2—C3—C6	−175.4 (3)	C22—C18—C19—C20	4.5 (5)
C2—C3—C4—C5	−3.6 (5)	C16—C18—C19—C20	−173.5 (3)
C6—C3—C4—C5	174.7 (3)	C18—C19—C20—N8	−2.2 (6)
C3—C4—C5—N1	1.5 (5)	N8—C21—C22—C18	−0.3 (6)
C4—C3—C6—C7	−140.2 (3)	C19—C18—C22—C21	−3.3 (5)
C2—C3—C6—C7	38.0 (5)	C16—C18—C22—C21	174.6 (3)
C4—C3—C6—C10	38.6 (5)	C4—C5—N1—C1	1.6 (5)
C2—C3—C6—C10	−143.2 (3)	C4—C5—N1—Co1	−173.8 (3)
C10—C6—C7—N6	0.2 (5)	C2—C1—N1—C5	−2.3 (5)
C3—C6—C7—N6	179.0 (3)	C2—C1—N1—Co1	172.9 (2)
N6—C8—C9—C10	−0.2 (5)	N4—C11—N2—N3	1.1 (3)
N6—C8—C9—C11	176.4 (3)	C9—C11—N2—N3	−173.5 (3)
C8—C9—C10—C6	1.5 (5)	N4—C12—N3—N2	−2.3 (3)
C11—C9—C10—C6	−175.5 (3)	C13—C12—N3—N2	170.1 (3)
C7—C6—C10—C9	−1.4 (5)	N4—C12—N3—Co1^i	163.6 (2)
C3—C6—C10—C9	179.7 (3)	C13—C12—N3—Co1^i	−24.0 (5)
C10—C9—C11—N2	33.5 (4)	C11—N2—N3—C12	0.7 (3)
C8—C9—C11—N2	−143.2 (3)	C11—N2—N3—Co1^i	−168.36 (18)
C10—C9—C11—N4	−140.1 (3)	N3—C12—N4—C11	3.0 (3)
C8—C9—C11—N4	43.2 (5)	C13—C12—N4—C11	−169.2 (3)
N3—C12—C13—C17	131.7 (3)	N3—C12—N4—N5	179.5 (3)
N4—C12—C13—C17	−57.2 (5)	C13—C12—N4—N5	7.3 (4)
N3—C12—C13—C14	−47.7 (4)	N2—C11—N4—C12	−2.5 (3)
N4—C12—C13—C14	123.4 (3)	C9—C11—N4—C12	171.7 (3)
C17—C13—C14—N7	0.2 (5)	N2—C11—N4—N5	−178.9 (3)
C12—C13—C14—N7	179.7 (3)	C9—C11—N4—N5	−4.6 (5)
N7—C15—C16—C17	0.6 (6)	C6—C7—N6—C8	1.0 (5)
N7—C15—C16—C18	−179.7 (3)	C9—C8—N6—C7	−1.0 (5)
C14—C13—C17—C16	0.7 (5)	C13—C14—N7—C15	−0.7 (6)
C12—C13—C17—C16	−178.7 (3)	C16—C15—N7—C14	0.3 (6)
C15—C16—C17—C13	−1.1 (5)	C19—C20—N8—C21	−1.4 (5)
C18—C16—C17—C13	179.2 (3)	C19—C20—N8—Co1^iii	173.1 (3)
C15—C16—C18—C22	−148.9 (3)	C22—C21—N8—C20	2.7 (5)
C17—C16—C18—C22	30.8 (5)	C22—C21—N8—Co1^iii	−171.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···Cl1^iv	0.86	2.86	3.396 (3)	122

Symmetry code: (iv) −x, y+1/2, −z+1/2.