Crystal structure of tetra-aqua-bis(3,5-di-amino-4H-1,2,4-triazol-1-ium)cobalt(II) bis-[bis-(pyridine-2,6-di-carboxyl-ato)cobaltate(II)] dihydrate.

The asymmetric unit of the title compound, [Co(C2H6N5)2(H2O)4][Co(C7H3NO4)2]2·2H2O, features 1.5 Co(II) ions (one anionic complex and one half cationic complex) and one water mol-ecule. In the cationic complex, the Co(II) atom is located on an inversion centre and is coordinated by two triazolium cations and four water mol-ecules, adopting an octa-hedral geometry where the N atoms of the two triazolium cations occupy the axial positions and the O atoms of the four water mol-ecules the equatorial positions. The two triazole ligands are parallel offset (with a distance of 1.38 Å between their planes). In the anionic complex, the Co(II) ion is six-coordinated by two N and four O atoms of the two pyridine-2,6-di-carboxyl-ate anions, exhibiting a slightly distorted octa-hedral coordination geometry in which the mean plane of the two pyridine-2,6-di-carboxyl-ate anions are almost perpendicular to each other, making a dihedral angle of 85.87 (2)°. In the crystal, mol-ecules are linked into a three-dimensional network via C-H⋯O, C-H⋯N, O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For the different coordination modes of transition metal–dipicolinate complexes, see: Håkansson et al. (1993 ▸); Okabe & Oya (2000 ▸); Aghajani et al. (2009 ▸). For crystal structures of related complexes, see: Yousuf et al. (2011a ▸,b ▸); Aghabozorg et al. (2009 ▸); Ramos Silva et al. (2008 ▸); Wang et al. (2004 ▸); MacDonald et al. (2004 ▸). For studies on proton transfer from carb­oxy­lic acids to both heterocyclic and substituted amine N atoms, see: Aghabozorg et al. (2008 ▸); Moghimi et al. (2002 ▸, 2005 ▸, 2007 ▸); Pasdar et al. (2011 ▸); Tabatabaee et al. (2009 ▸).

Experimental

Crystal data

[Co(C2H6N5)2(H2O)4][Co(C7H3NO4)2]2·2H2O

M = 1145.54

Monoclinic,

a = 7.1499 (2) Å

b = 10.8807 (2) Å

c = 26.6877 (6) Å

β = 90.649 (1)°

V = 2076.06 (8) Å3

Z = 2

Mo Kα radiation

μ = 1.29 mm−1

T = 100 K

0.43 × 0.28 × 0.28 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.607, T max = 0.718

35534 measured reflections

9081 independent reflections

8203 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.068

S = 1.05

9081 reflections

370 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick 2008 ▸); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015010014/zl2619sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010014/zl2619Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015010014/zl2619fig1.tif

The mol­ecular structure of the title compound with atom labels and 50% probability displacement ellipsoids. Atoms with suffix A were generated by the symmetry operation −x, −y, −z.

Click here for additional data file.

. DOI: 10.1107/S2056989015010014/zl2619fig2.tif

Crystal packing of the title compound, showing the three-dimensional network. H atoms not involved in the inter­molecular inter­actions (dashed lines) have been omitted for clarity.

CCDC reference: 1402526

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Co(C2H6N5)2(H2O)4][Co(C7H3NO4)2]2·2H2O	F(000) = 1166
Mr = 1145.54	Dx = 1.833 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1499 (2) Å	Cell parameters from 9904 reflections
b = 10.8807 (2) Å	θ = 2.4–35.0°
c = 26.6877 (6) Å	µ = 1.29 mm−1
β = 90.649 (1)°	T = 100 K
V = 2076.06 (8) Å3	Block, purple
Z = 2	0.43 × 0.28 × 0.28 mm

Bruker SMART APEXII CCD area-detector diffractometer	9081 independent reflections
Radiation source: fine-focus sealed tube	8203 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 35.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→11
Tmin = 0.607, Tmax = 0.718	k = −17→17
35534 measured reflections	l = −42→41

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068	w = 1/[σ2(Fo2) + (0.0314P)2 + 1.0292P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
9081 reflections	Δρmax = 0.56 e Å−3
370 parameters	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
Co1	0.55162 (2)	0.25891 (2)	0.13399 (2)	0.00894 (3)
Co2	0.0000	0.0000	0.0000	0.00821 (4)
O1	0.82104 (10)	0.26153 (6)	0.09788 (3)	0.01282 (12)
O2	0.27767 (10)	0.33471 (6)	0.14695 (3)	0.01253 (12)
O3	0.65732 (11)	0.31798 (7)	0.20566 (3)	0.01412 (12)
O4	0.46908 (10)	0.11281 (6)	0.07992 (2)	0.01164 (11)
O5	0.98594 (10)	0.35876 (7)	0.03895 (3)	0.01370 (12)
O6	0.11089 (10)	0.50933 (6)	0.13722 (3)	0.01255 (12)
O7	0.79218 (12)	0.24719 (7)	0.27668 (3)	0.01834 (14)
O8	0.44182 (11)	−0.09334 (7)	0.07506 (3)	0.01482 (13)
N1	0.54987 (11)	0.41617 (7)	0.09324 (3)	0.00998 (12)
N2	0.59941 (11)	0.09926 (7)	0.17147 (3)	0.00943 (12)
N3	−0.00429 (11)	−0.02963 (7)	0.08158 (3)	0.01012 (12)
N4	0.03927 (11)	0.07247 (7)	0.11156 (3)	0.01056 (12)
N5	0.08642 (11)	−0.08746 (7)	0.15824 (3)	0.01057 (12)
N6	0.13643 (13)	0.11292 (8)	0.19445 (3)	0.01373 (14)
N7	−0.00180 (14)	−0.24234 (8)	0.09908 (3)	0.01487 (15)
C1	0.85009 (12)	0.34939 (8)	0.06704 (3)	0.01023 (14)
C2	0.69856 (12)	0.44549 (8)	0.06584 (3)	0.01026 (14)
C3	0.70679 (14)	0.55422 (9)	0.03875 (4)	0.01333 (15)
H3A	0.8119	0.5733	0.0187	0.016*
C4	0.55548 (15)	0.63436 (9)	0.04196 (4)	0.01642 (17)
H4A	0.5576	0.7105	0.0246	0.020*
C5	0.40079 (14)	0.60293 (9)	0.07070 (4)	0.01499 (16)
H5A	0.2967	0.6568	0.0730	0.018*
C6	0.40236 (13)	0.49099 (8)	0.09586 (3)	0.01047 (14)
C7	0.24820 (12)	0.44216 (8)	0.12908 (3)	0.00996 (13)
C8	0.71223 (13)	0.23375 (9)	0.23540 (3)	0.01208 (15)
C9	0.67492 (13)	0.10389 (8)	0.21746 (3)	0.01040 (14)
C10	0.71742 (14)	−0.00249 (9)	0.24395 (3)	0.01303 (15)
H10A	0.7708	0.0016	0.2767	0.016*
C11	0.67989 (14)	−0.11541 (9)	0.22139 (4)	0.01395 (15)
H11A	0.7070	−0.1896	0.2388	0.017*
C12	0.60241 (13)	−0.11954 (8)	0.17318 (3)	0.01207 (15)
H12A	0.5762	−0.1957	0.1572	0.014*
C13	0.56501 (12)	−0.00872 (8)	0.14938 (3)	0.00955 (13)
C14	0.48503 (12)	0.00302 (8)	0.09707 (3)	0.00989 (14)
C15	0.09005 (12)	0.03737 (8)	0.15732 (3)	0.01009 (14)
C16	0.02562 (12)	−0.12445 (8)	0.11143 (3)	0.00985 (13)
O1W	0.81160 (12)	0.54803 (8)	0.20623 (3)	0.01822 (14)
O2W	0.16935 (10)	0.15580 (6)	0.01259 (3)	0.01110 (11)
O3W	−0.23235 (10)	0.11122 (7)	0.00395 (3)	0.01179 (11)
H1N4	−0.017 (2)	0.1420 (17)	0.1043 (6)	0.024 (4)*
H1N5	0.124 (3)	−0.1360 (19)	0.1831 (7)	0.037 (5)*
H1N6	0.147 (2)	0.1885 (17)	0.1873 (7)	0.026 (4)*
H2N6	0.151 (3)	0.0852 (17)	0.2268 (7)	0.030 (5)*
H1N7	−0.047 (3)	−0.2572 (17)	0.0707 (8)	0.030 (5)*
H2N7	0.024 (2)	−0.2988 (17)	0.1167 (6)	0.023 (4)*
H1W1	0.753 (3)	0.482 (2)	0.2054 (8)	0.043 (6)*
H2W1	0.899 (3)	0.5365 (19)	0.1887 (8)	0.038 (5)*
H1W2	0.113 (3)	0.2197 (18)	0.0235 (7)	0.030 (5)*
H2W2	0.261 (3)	0.1440 (18)	0.0306 (7)	0.032 (5)*
H1W3	−0.295 (3)	0.1150 (18)	0.0282 (7)	0.035 (5)*
H2W3	−0.308 (3)	0.1054 (18)	−0.0198 (7)	0.033 (5)*

	U11	U22	U33	U12	U13	U23
Co1	0.01044 (5)	0.00761 (5)	0.00876 (5)	0.00044 (4)	0.00033 (4)	0.00075 (4)
Co2	0.00864 (7)	0.00831 (7)	0.00767 (7)	0.00067 (5)	−0.00032 (5)	0.00030 (5)
O1	0.0124 (3)	0.0111 (3)	0.0150 (3)	0.0025 (2)	0.0028 (2)	0.0036 (2)
O2	0.0126 (3)	0.0105 (3)	0.0145 (3)	0.0007 (2)	0.0027 (2)	0.0029 (2)
O3	0.0188 (3)	0.0109 (3)	0.0126 (3)	−0.0005 (2)	−0.0018 (2)	−0.0012 (2)
O4	0.0143 (3)	0.0100 (3)	0.0106 (3)	0.0002 (2)	−0.0021 (2)	0.0011 (2)
O5	0.0120 (3)	0.0122 (3)	0.0170 (3)	0.0011 (2)	0.0051 (2)	0.0012 (2)
O6	0.0118 (3)	0.0128 (3)	0.0132 (3)	0.0027 (2)	0.0025 (2)	0.0001 (2)
O7	0.0262 (4)	0.0160 (3)	0.0126 (3)	−0.0015 (3)	−0.0069 (3)	−0.0036 (2)
O8	0.0184 (3)	0.0113 (3)	0.0146 (3)	0.0006 (2)	−0.0057 (2)	−0.0035 (2)
N1	0.0101 (3)	0.0093 (3)	0.0105 (3)	0.0005 (2)	0.0017 (2)	0.0006 (2)
N2	0.0102 (3)	0.0097 (3)	0.0084 (3)	−0.0006 (2)	−0.0005 (2)	−0.0002 (2)
N3	0.0127 (3)	0.0083 (3)	0.0093 (3)	0.0014 (2)	−0.0004 (2)	0.0004 (2)
N4	0.0143 (3)	0.0086 (3)	0.0088 (3)	0.0013 (2)	−0.0007 (2)	0.0005 (2)
N5	0.0129 (3)	0.0102 (3)	0.0086 (3)	0.0006 (2)	−0.0010 (2)	0.0019 (2)
N6	0.0190 (4)	0.0125 (3)	0.0097 (3)	−0.0029 (3)	−0.0009 (3)	−0.0002 (2)
N7	0.0210 (4)	0.0088 (3)	0.0147 (3)	0.0004 (3)	−0.0025 (3)	0.0008 (3)
C1	0.0099 (3)	0.0093 (3)	0.0116 (3)	0.0001 (3)	0.0004 (3)	−0.0006 (3)
C2	0.0103 (3)	0.0090 (3)	0.0115 (3)	0.0007 (3)	0.0017 (3)	0.0006 (3)
C3	0.0135 (4)	0.0095 (3)	0.0170 (4)	0.0003 (3)	0.0046 (3)	0.0027 (3)
C4	0.0166 (4)	0.0112 (4)	0.0216 (4)	0.0031 (3)	0.0070 (3)	0.0059 (3)
C5	0.0146 (4)	0.0107 (4)	0.0198 (4)	0.0032 (3)	0.0058 (3)	0.0040 (3)
C6	0.0107 (3)	0.0097 (3)	0.0111 (3)	0.0014 (3)	0.0018 (3)	0.0006 (3)
C7	0.0104 (3)	0.0104 (3)	0.0091 (3)	−0.0003 (3)	0.0007 (3)	−0.0002 (3)
C8	0.0133 (4)	0.0122 (4)	0.0108 (3)	−0.0013 (3)	0.0000 (3)	−0.0027 (3)
C9	0.0116 (3)	0.0115 (3)	0.0081 (3)	−0.0011 (3)	−0.0007 (3)	−0.0006 (3)
C10	0.0155 (4)	0.0137 (4)	0.0099 (3)	−0.0011 (3)	−0.0022 (3)	0.0015 (3)
C11	0.0172 (4)	0.0117 (4)	0.0129 (4)	−0.0004 (3)	−0.0024 (3)	0.0037 (3)
C12	0.0143 (4)	0.0094 (3)	0.0125 (3)	−0.0012 (3)	−0.0022 (3)	0.0011 (3)
C13	0.0101 (3)	0.0094 (3)	0.0091 (3)	−0.0010 (3)	−0.0009 (3)	0.0000 (3)
C14	0.0097 (3)	0.0100 (3)	0.0100 (3)	0.0002 (3)	−0.0008 (3)	−0.0006 (3)
C15	0.0103 (3)	0.0110 (3)	0.0090 (3)	0.0005 (3)	0.0008 (3)	0.0012 (3)
C16	0.0101 (3)	0.0098 (3)	0.0097 (3)	0.0010 (3)	0.0006 (3)	0.0010 (3)
O1W	0.0221 (4)	0.0180 (3)	0.0146 (3)	−0.0055 (3)	0.0041 (3)	−0.0028 (3)
O2W	0.0109 (3)	0.0105 (3)	0.0118 (3)	0.0005 (2)	−0.0007 (2)	0.0000 (2)
O3W	0.0110 (3)	0.0155 (3)	0.0088 (3)	0.0026 (2)	−0.0005 (2)	−0.0011 (2)

Co1—N1	2.0275 (8)	N6—C15	1.3269 (12)
Co1—N2	2.0315 (8)	N6—H1N6	0.848 (19)
Co1—O3	2.1471 (7)	N6—H2N6	0.921 (18)
Co1—O2	2.1567 (7)	N7—C16	1.3383 (12)
Co1—O1	2.1640 (7)	N7—H1N7	0.84 (2)
Co1—O4	2.2223 (7)	N7—H2N7	0.795 (18)
Co2—O3W	2.0590 (7)	C1—C2	1.5058 (13)
Co2—O3Wi	2.0590 (7)	C2—C3	1.3880 (13)
Co2—O2Wi	2.1080 (7)	C3—C4	1.3929 (14)
Co2—O2W	2.1080 (7)	C3—H3A	0.9500
Co2—N3i	2.2015 (7)	C4—C5	1.3957 (13)
Co2—N3	2.2016 (7)	C4—H4A	0.9500
O1—C1	1.2800 (11)	C5—C6	1.3908 (13)
O2—C7	1.2792 (11)	C5—H5A	0.9500
O3—C8	1.2715 (12)	C6—C7	1.5183 (12)
O4—C14	1.2840 (11)	C8—C9	1.5146 (13)
O5—C1	1.2378 (11)	C9—C10	1.3881 (13)
O6—C7	1.2451 (11)	C10—C11	1.3928 (14)
O7—C8	1.2440 (11)	C10—H10A	0.9500
O8—C14	1.2392 (11)	C11—C12	1.3959 (13)
N1—C6	1.3347 (12)	C11—H11A	0.9500
N1—C2	1.3358 (11)	C12—C13	1.3873 (12)
N2—C13	1.3361 (11)	C12—H12A	0.9500
N2—C9	1.3363 (11)	C13—C14	1.5080 (12)
N3—C16	1.3194 (11)	O1W—H1W1	0.83 (2)
N3—N4	1.4020 (11)	O1W—H2W1	0.79 (2)
N4—C15	1.3261 (11)	O2W—H1W2	0.86 (2)
N4—H1N4	0.877 (18)	O2W—H2W2	0.817 (19)
N5—C15	1.3587 (12)	O3W—H1W3	0.79 (2)
N5—C16	1.3781 (12)	O3W—H2W3	0.830 (19)
N5—H1N5	0.89 (2)
N1—Co1—N2	170.32 (3)	O5—C1—O1	125.80 (9)
N1—Co1—O3	103.02 (3)	O5—C1—C2	119.95 (8)
N2—Co1—O3	76.22 (3)	O1—C1—C2	114.23 (8)
N1—Co1—O2	76.30 (3)	N1—C2—C3	121.83 (8)
N2—Co1—O2	113.33 (3)	N1—C2—C1	113.54 (8)
O3—Co1—O2	93.09 (3)	C3—C2—C1	124.62 (8)
N1—Co1—O1	75.53 (3)	C2—C3—C4	117.64 (8)
N2—Co1—O1	94.87 (3)	C2—C3—H3A	121.2
O3—Co1—O1	94.97 (3)	C4—C3—H3A	121.2
O2—Co1—O1	151.77 (3)	C3—C4—C5	120.09 (9)
N1—Co1—O4	104.80 (3)	C3—C4—H4A	120.0
N2—Co1—O4	75.52 (3)	C5—C4—H4A	120.0
O3—Co1—O4	151.74 (3)	C6—C5—C4	118.54 (9)
O2—Co1—O4	98.20 (3)	C6—C5—H5A	120.7
O1—Co1—O4	87.21 (3)	C4—C5—H5A	120.7
O3W—Co2—O3Wi	180.0	N1—C6—C5	120.72 (8)
O3W—Co2—O2Wi	91.06 (3)	N1—C6—C7	113.36 (8)
O3Wi—Co2—O2Wi	88.94 (3)	C5—C6—C7	125.90 (8)
O3W—Co2—O2W	88.94 (3)	O6—C7—O2	126.75 (8)
O3Wi—Co2—O2W	91.06 (3)	O6—C7—C6	118.39 (8)
O2Wi—Co2—O2W	180.0	O2—C7—C6	114.83 (8)
O3W—Co2—N3i	89.13 (3)	O7—C8—O3	127.12 (9)
O3Wi—Co2—N3i	90.87 (3)	O7—C8—C9	117.84 (8)
O2Wi—Co2—N3i	88.54 (3)	O3—C8—C9	115.04 (8)
O2W—Co2—N3i	91.46 (3)	N2—C9—C10	121.34 (8)
O3W—Co2—N3	90.87 (3)	N2—C9—C8	113.16 (8)
O3Wi—Co2—N3	89.13 (3)	C10—C9—C8	125.47 (8)
O2Wi—Co2—N3	91.46 (3)	C9—C10—C11	118.39 (8)
O2W—Co2—N3	88.54 (3)	C9—C10—H10A	120.8
N3i—Co2—N3	180.0	C11—C10—H10A	120.8
C1—O1—Co1	116.61 (6)	C10—C11—C12	119.95 (8)
C7—O2—Co1	115.83 (6)	C10—C11—H11A	120.0
C8—O3—Co1	116.32 (6)	C12—C11—H11A	120.0
C14—O4—Co1	114.34 (6)	C13—C12—C11	117.80 (8)
C6—N1—C2	121.15 (8)	C13—C12—H12A	121.1
C6—N1—Co1	119.12 (6)	C11—C12—H12A	121.1
C2—N1—Co1	119.68 (6)	N2—C13—C12	121.93 (8)
C13—N2—C9	120.58 (8)	N2—C13—C14	113.57 (7)
C13—N2—Co1	120.38 (6)	C12—C13—C14	124.50 (8)
C9—N2—Co1	118.95 (6)	O8—C14—O4	126.69 (8)
C16—N3—N4	103.98 (7)	O8—C14—C13	117.20 (8)
C16—N3—Co2	135.05 (6)	O4—C14—C13	116.11 (8)
N4—N3—Co2	116.28 (5)	N4—C15—N6	124.95 (9)
C15—N4—N3	110.73 (7)	N4—C15—N5	107.43 (8)
C15—N4—H1N4	124.9 (11)	N6—C15—N5	127.62 (8)
N3—N4—H1N4	117.3 (11)	N3—C16—N7	125.34 (8)
C15—N5—C16	106.34 (7)	N3—C16—N5	111.49 (8)
C15—N5—H1N5	127.1 (13)	N7—C16—N5	123.16 (8)
C16—N5—H1N5	126.4 (13)	H1W1—O1W—H2W1	104 (2)
C15—N6—H1N6	117.0 (12)	Co2—O2W—H1W2	115.8 (13)
C15—N6—H2N6	121.6 (12)	Co2—O2W—H2W2	115.0 (14)
H1N6—N6—H2N6	121.3 (17)	H1W2—O2W—H2W2	107.6 (18)
C16—N7—H1N7	117.6 (13)	Co2—O3W—H1W3	122.4 (14)
C16—N7—H2N7	124.3 (13)	Co2—O3W—H2W3	115.8 (13)
H1N7—N7—H2N7	118.2 (18)	H1W3—O3W—H2W3	104.9 (18)
C16—N3—N4—C15	−0.82 (10)	C13—N2—C9—C8	177.27 (8)
Co2—N3—N4—C15	−160.26 (6)	Co1—N2—C9—C8	0.78 (10)
Co1—O1—C1—O5	−171.62 (7)	O7—C8—C9—N2	−176.02 (9)
Co1—O1—C1—C2	7.05 (10)	O3—C8—C9—N2	3.74 (12)
C6—N1—C2—C3	−0.26 (14)	O7—C8—C9—C10	2.07 (14)
Co1—N1—C2—C3	−177.65 (7)	O3—C8—C9—C10	−178.16 (9)
C6—N1—C2—C1	−179.43 (8)	N2—C9—C10—C11	0.15 (14)
Co1—N1—C2—C1	3.18 (10)	C8—C9—C10—C11	−177.80 (9)
O5—C1—C2—N1	172.01 (8)	C9—C10—C11—C12	0.38 (14)
O1—C1—C2—N1	−6.75 (12)	C10—C11—C12—C13	−0.15 (14)
O5—C1—C2—C3	−7.13 (14)	C9—N2—C13—C12	1.16 (13)
O1—C1—C2—C3	174.11 (9)	Co1—N2—C13—C12	177.60 (7)
N1—C2—C3—C4	1.55 (15)	C9—N2—C13—C14	−178.31 (8)
C1—C2—C3—C4	−179.38 (9)	Co1—N2—C13—C14	−1.88 (10)
C2—C3—C4—C5	−1.50 (16)	C11—C12—C13—N2	−0.62 (14)
C3—C4—C5—C6	0.24 (16)	C11—C12—C13—C14	178.80 (9)
C2—N1—C6—C5	−1.10 (14)	Co1—O4—C14—O8	177.20 (8)
Co1—N1—C6—C5	176.31 (7)	Co1—O4—C14—C13	−2.90 (10)
C2—N1—C6—C7	−179.62 (8)	N2—C13—C14—O8	−176.90 (8)
Co1—N1—C6—C7	−2.21 (10)	C12—C13—C14—O8	3.64 (14)
C4—C5—C6—N1	1.09 (15)	N2—C13—C14—O4	3.20 (12)
C4—C5—C6—C7	179.41 (9)	C12—C13—C14—O4	−176.26 (9)
Co1—O2—C7—O6	−170.41 (8)	N3—N4—C15—N6	−178.78 (9)
Co1—O2—C7—C6	7.75 (10)	N3—N4—C15—N5	1.67 (10)
N1—C6—C7—O6	174.41 (8)	C16—N5—C15—N4	−1.82 (10)
C5—C6—C7—O6	−4.03 (14)	C16—N5—C15—N6	178.65 (9)
N1—C6—C7—O2	−3.91 (11)	N4—N3—C16—N7	178.47 (9)
C5—C6—C7—O2	177.65 (9)	Co2—N3—C16—N7	−27.99 (15)
Co1—O3—C8—O7	173.50 (9)	N4—N3—C16—N5	−0.36 (10)
Co1—O3—C8—C9	−6.24 (10)	Co2—N3—C16—N5	153.18 (7)
C13—N2—C9—C10	−0.92 (13)	C15—N5—C16—N3	1.37 (10)
Co1—N2—C9—C10	−177.40 (7)	C15—N5—C16—N7	−177.50 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···O1ii	0.88 (2)	1.74 (2)	2.6044 (12)	165 (2)
N5—H1N5···O7iii	0.89 (2)	1.77 (2)	2.6402 (12)	169 (2)
N6—H1N6···O2	0.84 (2)	2.15 (2)	2.9117 (12)	151.1 (19)
N6—H2N6···O1Wiii	0.92 (2)	1.85 (2)	2.7645 (12)	173.6 (19)
N7—H2N7···O6iv	0.80 (2)	2.24 (2)	2.9956 (13)	158.4 (18)
O1W—H1W1···O3	0.83 (2)	1.90 (2)	2.7354 (13)	171 (3)
O1W—H2W1···O6v	0.79 (2)	2.09 (2)	2.8711 (12)	175 (2)
O2W—H1W2···O5ii	0.86 (2)	1.80 (2)	2.6666 (11)	173 (2)
O2W—H2W2···O4	0.82 (2)	2.00 (2)	2.8206 (11)	175 (2)
O3W—H1W3···O4ii	0.79 (2)	2.19 (2)	2.9602 (11)	163 (2)
O3W—H2W3···O8i	0.83 (2)	1.76 (2)	2.5795 (11)	173 (2)
C3—H3A···O5vi	0.95	2.25	3.1816 (13)	167
C5—H5A···N7vii	0.95	2.50	3.4265 (15)	164
C10—H10A···O6iii	0.95	2.44	3.3898 (13)	177

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N4H1N4O1i	0.88(2)	1.74(2)	2.6044(12)	165(2)
N5H1N5O7ii	0.89(2)	1.77(2)	2.6402(12)	169(2)
N6H1N6O2	0.84(2)	2.15(2)	2.9117(12)	151.1(19)
N6H2N6O1W ii	0.92(2)	1.85(2)	2.7645(12)	173.6(19)
N7H2N7O6iii	0.80(2)	2.24(2)	2.9956(13)	158.4(18)
O1WH1W1O3	0.83(2)	1.90(2)	2.7354(13)	171(3)
O1WH2W1O6iv	0.79(2)	2.09(2)	2.8711(12)	175(2)
O2WH1W2O5i	0.86(2)	1.80(2)	2.6666(11)	173(2)
O2WH2W2O4	0.82(2)	2.00(2)	2.8206(11)	175(2)
O3WH1W3O4i	0.79(2)	2.19(2)	2.9602(11)	163(2)
O3WH2W3O8v	0.83(2)	1.76(2)	2.5795(11)	173(2)
C3H3AO5vi	0.95	2.25	3.1816(13)	167
C5H5AN7vii	0.95	2.50	3.4265(15)	164
C10H10AO6ii	0.95	2.44	3.3898(13)	177

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .