Triaqua­(N2,N4-di-2-pyridylpyrimidine-2,4-diamine)cobalt(II) fumarate

Yang, M.

doi:10.1107/S1600536808032613

metal-organic compounds

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Volume 64| Part 11| November 2008| Page m1406

doi:10.1107/S1600536808032613

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Triaqua(N²,N⁴-di-2-pyridylpyrimidine-2,4-diamine)cobalt(II) fumarate

Ming-hua Yang ^a ^*

^aDepartment of Chemistry, Lishui University, Lishui 323000, People's Republic of China
^*Correspondence e-mail: zjlsxyhx@126.com

(Received 18 September 2008; accepted 9 October 2008; online 15 October 2008)

The Co atom in the title compound, [Co(C₁₄H₁₂N₆)(H₂O)₃]C₄H₂O₄, has a mer-CoN₃O₃ octahedral coordination arising from the tridentate N²,N⁴-di-2-pyridylpyrimidine-2,4-diamine (tpda) ligand and three coordinated water molecules. The asymmetric unit contains two fumarate half-anions, both completed by inversion symmetry. A network of N—H⋯O and O—H⋯O hydrogen bonds leads to a three-dimensional network in the crystal structure.

Related literature

For a related structure, see: Fang et al. (2005 ). For background, see: Sheu et al. (1996 ); Peng et al. (2000 ).

Experimental

Crystal data

[Co(C₁₄H₁₂N₆)(H₂O)₃]C₄H₂O₄
M_r = 491.33
Monoclinic, P 2₁ /n
a = 9.3239 (3) Å
b = 17.1115 (6) Å
c = 13.1395 (5) Å
β = 96.224 (1)°
V = 2084.00 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 298 (2) K
0.29 × 0.25 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.785, T_max = 0.858
10365 measured reflections
3746 independent reflections
3363 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.078
S = 0.86
3746 reflections
307 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.0989 (13)
Co1—O2	2.0905 (13)
Co1—O3	2.0396 (13)
Co1—N1	2.0790 (15)
Co1—N3	2.0624 (14)
Co1—N5	2.0803 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2D⋯O4ⁱ	0.836 (10)	1.943 (14)	2.7396 (19)	159 (2)
O2—H2C⋯O6ⁱⁱ	0.841 (10)	1.898 (10)	2.7374 (18)	176 (3)
O3—H3C⋯O7ⁱⁱ	0.840 (9)	1.858 (11)	2.6929 (18)	172 (3)
O3—H3D⋯O5ⁱⁱⁱ	0.832 (10)	1.734 (11)	2.559 (2)	171 (2)
O1—H1D⋯O6^iv	0.829 (10)	1.930 (13)	2.7374 (19)	165 (3)
O1—H1C⋯O4ⁱⁱⁱ	0.832 (10)	2.001 (13)	2.8143 (19)	166 (2)
N4—H4A⋯O5^v	0.86	1.93	2.782 (2)	169
N2—H2⋯O7^vi	0.86	2.28	3.002 (2)	141
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) x, y, z-1; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x+1, y, z-1.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808032613/hb2798sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032613/hb2798Isup2.hkl

checkCIF report

Comment top

Transition metal complexes with polypyridylamine ligands, possessing diverse structures and unusual optical and electromagnetic properties (Sheu et al.,1996), have aroused great interest among researchers. The tri-pyridyldiamine ligand can exhibit donor as well as acceptor properties and can act as a chelating ligand (Peng et al., 2000). In this paper, we report the synthesis and crystal structure of the title compound, (I), (Fig. 1).

The Co atom in (I) has an octahedral coordination formed by the N,N,N-tridentate tpda ligand and three coordinated water molecules. The tpda ligand is tri-coordinated, with the peripheral N1 and N5 atoms in the axial positions [N1—Co1—N5 = 174.48 (6)°] and the central N3 atom in the equatorial plane of the bipyramid. The remaining two equatorial positions are occupied by water molecules (Table 1). The three pyridine rings of the tpda ligand are not coplanar: the dihedral angles between the planes of the central pyridine ring and two peripheral rings are 18.5 (4) and 26.4 (2)° respectively.

The H atoms of both NH groups of the tpda ligand and coordinated water molecules are involved in hydrogen bonds with O atoms of carboxylate groups of fumarate which link the complex molecules to form an infinite three-dimensional network (Table 2, Fig. 2).

The molcular configuration of (I) is similar to that of [2,6-bis(2-pyridylamino)pyridine]dinitrato cadmium monohydrate (Fang et al., 2005).

Related literature top

For a related structure, see: Fang et al. (2005). For background, see: Sheu et al. (1996); Peng et al. (2000).

Experimental top

Tpda (0.025 g, 0.07 mmol), Co(NO₃)2 (0.026 g, 0.1 mmol), fumaric acid (0.023 g, 0.09 mmol) and NaOH (0.041 g, 0.1 mmol) were mixed in acetonitrile, and the mixture was heated for six hours under reflux with stirring. The resultant was then filtered to give a solution which was infiltrated by diethyl ether in a closed vessel, one week later some pink blocks of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids for the non-hydrogen atoms. Symmetry codes: (i) 1-x, 1-y, -z; (ii) 1-x, -y, 2-z.
	Fig. 2. The packing diagram of (I), viewed along the a axis; hydrogen bonds are shown as dashed lines.

Triaqua(N²,N⁴-di-2-pyridylpyrimidine-2,4-diamine)cobalt(II) fumarate top

Crystal data top

[Co(C₁₄H₁₂N₆)(H₂O)₃]C₄H₂O₄	F(000) = 1012
M_r = 491.33	D_x = 1.566 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3746 reflections
a = 9.3239 (3) Å	θ = 2.0–25.2°
b = 17.1115 (6) Å	µ = 0.88 mm⁻¹
c = 13.1395 (5) Å	T = 298 K
β = 96.224 (1)°	Block, pink
V = 2084.00 (13) Å³	0.29 × 0.25 × 0.18 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	3746 independent reflections
Radiation source: fine-focus sealed tube	3363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 25.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→8
T_min = 0.785, T_max = 0.858	k = −18→20
10365 measured reflections	l = −15→15

Refinement top

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.86	w = 1/[σ²(F_o²) + (0.06P)² + 0.982P] where P = (F_o² + 2F_c²)/3
3746 reflections	(Δ/σ)_max = 0.001
307 parameters	Δρ_max = 0.28 e Å⁻³
9 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Co(C₁₄H₁₂N₆)(H₂O)₃]C₄H₂O₄	V = 2084.00 (13) Å³
M_r = 491.33	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.3239 (3) Å	µ = 0.88 mm⁻¹
b = 17.1115 (6) Å	T = 298 K
c = 13.1395 (5) Å	0.29 × 0.25 × 0.18 mm
β = 96.224 (1)°

Data collection top

Bruker APEX CCD diffractometer	3746 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3363 reflections with I > 2σ(I)
T_min = 0.785, T_max = 0.858	R_int = 0.014
10365 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	9 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.86	Δρ_max = 0.28 e Å⁻³
3746 reflections	Δρ_min = −0.33 e Å⁻³
307 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.89198 (2)	0.212482 (12)	0.174122 (15)	0.02637 (9)
N1	1.07828 (17)	0.25958 (9)	0.12520 (12)	0.0386 (3)
N2	1.12613 (18)	0.14671 (9)	0.03083 (12)	0.0428 (4)
H2	1.1513	0.1318	−0.0272	0.051*
N3	0.96644 (15)	0.10180 (8)	0.14666 (11)	0.0311 (3)
N4	0.81107 (18)	0.04503 (9)	0.25721 (12)	0.0418 (4)
H4A	0.8147	0.0119	0.3066	0.050*
N5	0.69822 (17)	0.16405 (10)	0.20828 (12)	0.0411 (4)
N6	1.1419 (2)	0.01872 (10)	0.08085 (15)	0.0527 (4)
O1	0.80120 (15)	0.22962 (8)	0.02251 (10)	0.0413 (3)
O2	0.98217 (16)	0.20786 (7)	0.32677 (10)	0.0404 (3)
O3	0.82120 (18)	0.31928 (8)	0.21618 (11)	0.0515 (4)
O4	0.31016 (15)	0.62641 (8)	0.05353 (10)	0.0449 (3)
O5	0.2958 (2)	0.57346 (11)	−0.09942 (12)	0.0843 (7)
O6	0.56949 (16)	0.15459 (8)	0.92018 (12)	0.0521 (4)
O7	0.35145 (14)	0.10201 (8)	0.89469 (10)	0.0432 (3)
C1	1.1139 (3)	0.33447 (13)	0.14869 (18)	0.0572 (6)
H1A	1.0742	0.3578	0.2031	0.069*
C2	1.2052 (3)	0.37778 (15)	0.0965 (2)	0.0756 (8)
H2A	1.2276	0.4291	0.1152	0.091*
C3	1.2637 (3)	0.34310 (15)	0.0147 (2)	0.0701 (7)
H3A	1.3229	0.3718	−0.0241	0.084*
C4	1.2337 (3)	0.26690 (14)	−0.00838 (18)	0.0548 (5)
H4	1.2728	0.2426	−0.0624	0.066*
C5	1.1431 (2)	0.22600 (11)	0.05069 (14)	0.0389 (4)
C6	1.0754 (2)	0.08795 (10)	0.08910 (14)	0.0356 (4)
C7	1.0969 (2)	−0.04032 (12)	0.13765 (18)	0.0523 (5)
H7	1.1423	−0.0886	0.1355	0.063*
C8	0.9887 (2)	−0.03233 (11)	0.19754 (15)	0.0425 (4)
H8	0.9600	−0.0737	0.2365	0.051*
C9	0.9231 (2)	0.03917 (10)	0.19853 (13)	0.0348 (4)
C10	0.6933 (2)	0.09433 (12)	0.25191 (15)	0.0423 (4)
C11	0.5709 (3)	0.06721 (17)	0.2948 (2)	0.0669 (7)
H11	0.5709	0.0186	0.3263	0.080*
C12	0.4505 (3)	0.1148 (2)	0.2887 (3)	0.0845 (9)
H12	0.3688	0.0992	0.3180	0.101*
C13	0.4526 (3)	0.1857 (2)	0.2388 (2)	0.0773 (8)
H13	0.3714	0.2176	0.2317	0.093*
C14	0.5759 (2)	0.20770 (15)	0.2004 (2)	0.0587 (6)
H14	0.5766	0.2555	0.1667	0.070*
C15	0.4580 (2)	0.51840 (11)	0.02931 (13)	0.0376 (4)
H15	0.4687	0.5068	0.0989	0.045*
C16	0.3459 (2)	0.57780 (10)	−0.00850 (14)	0.0362 (4)
C17	0.5353 (2)	0.03277 (11)	0.99689 (14)	0.0372 (4)
H17	0.6254	0.0371	1.0344	0.045*
C18	0.4805 (2)	0.10121 (10)	0.93323 (13)	0.0353 (4)
H1C	0.782 (3)	0.2754 (7)	0.005 (2)	0.080*
H1D	0.733 (2)	0.2009 (12)	0.001 (2)	0.080*
H3D	0.785 (3)	0.3513 (12)	0.1732 (13)	0.080*
H3C	0.827 (3)	0.3404 (14)	0.2742 (9)	0.080*
H2C	1.007 (3)	0.2514 (8)	0.353 (2)	0.080*
H2D	1.044 (2)	0.1753 (10)	0.350 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02877 (14)	0.02434 (14)	0.02585 (14)	0.00162 (8)	0.00225 (9)	−0.00098 (8)
N1	0.0415 (9)	0.0367 (8)	0.0378 (8)	−0.0084 (7)	0.0053 (7)	−0.0034 (6)
N2	0.0500 (10)	0.0384 (9)	0.0432 (9)	−0.0037 (7)	0.0204 (7)	−0.0032 (7)
N3	0.0336 (8)	0.0285 (7)	0.0315 (7)	−0.0020 (6)	0.0049 (6)	−0.0015 (6)
N4	0.0486 (9)	0.0378 (8)	0.0410 (9)	−0.0051 (7)	0.0139 (7)	0.0064 (7)
N5	0.0344 (8)	0.0476 (9)	0.0419 (9)	0.0019 (7)	0.0063 (7)	−0.0009 (7)
N6	0.0538 (11)	0.0425 (10)	0.0641 (11)	0.0088 (8)	0.0162 (9)	−0.0029 (8)
O1	0.0443 (8)	0.0391 (7)	0.0381 (7)	−0.0007 (6)	−0.0059 (6)	0.0020 (6)
O2	0.0501 (8)	0.0356 (7)	0.0338 (7)	0.0059 (6)	−0.0036 (6)	−0.0028 (5)
O3	0.0763 (10)	0.0389 (8)	0.0367 (7)	0.0209 (7)	−0.0056 (7)	−0.0068 (6)
O4	0.0464 (8)	0.0398 (7)	0.0477 (8)	0.0067 (6)	0.0009 (6)	−0.0092 (6)
O5	0.1314 (17)	0.0680 (11)	0.0454 (9)	0.0625 (12)	−0.0268 (10)	−0.0174 (8)
O6	0.0531 (8)	0.0400 (8)	0.0595 (9)	−0.0146 (7)	−0.0111 (7)	0.0168 (6)
O7	0.0394 (7)	0.0431 (7)	0.0461 (7)	0.0006 (6)	0.0008 (6)	0.0109 (6)
C1	0.0691 (15)	0.0468 (12)	0.0583 (13)	−0.0196 (11)	0.0183 (11)	−0.0138 (10)
C2	0.097 (2)	0.0503 (14)	0.0836 (18)	−0.0367 (14)	0.0304 (16)	−0.0141 (13)
C3	0.0840 (18)	0.0588 (15)	0.0724 (16)	−0.0314 (14)	0.0309 (14)	−0.0004 (12)
C4	0.0608 (14)	0.0522 (12)	0.0550 (13)	−0.0138 (11)	0.0225 (11)	−0.0006 (10)
C5	0.0384 (10)	0.0400 (10)	0.0384 (10)	−0.0056 (8)	0.0051 (8)	0.0000 (8)
C6	0.0361 (9)	0.0350 (9)	0.0362 (9)	−0.0015 (7)	0.0062 (7)	−0.0028 (7)
C7	0.0587 (13)	0.0326 (10)	0.0659 (14)	0.0109 (9)	0.0079 (11)	0.0020 (9)
C8	0.0549 (12)	0.0283 (9)	0.0450 (10)	0.0014 (8)	0.0083 (9)	0.0069 (8)
C9	0.0400 (9)	0.0329 (9)	0.0313 (8)	−0.0043 (7)	0.0034 (7)	−0.0007 (7)
C10	0.0396 (10)	0.0512 (12)	0.0371 (10)	−0.0055 (9)	0.0090 (8)	−0.0025 (8)
C11	0.0558 (14)	0.0774 (17)	0.0714 (15)	−0.0124 (13)	0.0249 (12)	0.0100 (13)
C12	0.0458 (14)	0.122 (3)	0.091 (2)	−0.0025 (16)	0.0318 (14)	0.0096 (19)
C13	0.0408 (13)	0.106 (2)	0.087 (2)	0.0129 (14)	0.0168 (13)	0.0048 (18)
C14	0.0410 (12)	0.0697 (16)	0.0651 (15)	0.0102 (10)	0.0054 (10)	0.0038 (11)
C15	0.0460 (10)	0.0327 (9)	0.0335 (9)	0.0025 (8)	0.0009 (7)	0.0030 (7)
C16	0.0419 (10)	0.0295 (9)	0.0362 (9)	0.0008 (7)	−0.0006 (8)	−0.0026 (7)
C17	0.0382 (10)	0.0358 (9)	0.0364 (9)	−0.0010 (7)	−0.0016 (7)	0.0053 (7)
C18	0.0420 (10)	0.0329 (9)	0.0308 (8)	−0.0017 (8)	0.0027 (7)	0.0020 (7)

Geometric parameters (Å, º) top

Co1—O1	2.0989 (13)	O6—C18	1.258 (2)
Co1—O2	2.0905 (13)	O7—C18	1.254 (2)
Co1—O3	2.0396 (13)	C1—C2	1.369 (3)
Co1—N1	2.0790 (15)	C1—H1A	0.9300
Co1—N3	2.0624 (14)	C2—C3	1.390 (4)
Co1—N5	2.0803 (16)	C2—H2A	0.9300
N1—C5	1.335 (2)	C3—C4	1.361 (3)
N1—C1	1.351 (3)	C3—H3A	0.9300
N2—C6	1.378 (2)	C4—C5	1.396 (3)
N2—C5	1.387 (2)	C4—H4	0.9300
N2—H2	0.8600	C7—C8	1.352 (3)
N3—C6	1.352 (2)	C7—H7	0.9300
N3—C9	1.355 (2)	C8—C9	1.368 (3)
N4—C9	1.368 (2)	C8—H8	0.9300
N4—C10	1.381 (3)	C10—C11	1.405 (3)
N4—H4A	0.8600	C11—C12	1.381 (4)
N5—C10	1.327 (3)	C11—H11	0.9300
N5—C14	1.358 (3)	C12—C13	1.380 (4)
N6—C6	1.347 (2)	C12—H12	0.9300
N6—C7	1.350 (3)	C13—C14	1.358 (4)
O1—H1C	0.832 (10)	C13—H13	0.9300
O1—H1D	0.829 (10)	C14—H14	0.9300
O2—H2C	0.841 (10)	C15—C15ⁱ	1.317 (4)
O2—H2D	0.836 (10)	C15—C16	1.503 (3)
O3—H3D	0.832 (10)	C15—H15	0.9300
O3—H3C	0.840 (9)	C17—C17ⁱⁱ	1.308 (4)
O4—C16	1.235 (2)	C17—C18	1.497 (2)
O5—C16	1.237 (2)	C17—H17	0.9300

O3—Co1—N3	174.38 (6)	C4—C3—H3A	120.2
O3—Co1—N1	92.41 (7)	C2—C3—H3A	120.2
N3—Co1—N1	89.63 (6)	C3—C4—C5	118.6 (2)
O3—Co1—N5	89.11 (7)	C3—C4—H4	120.7
N3—Co1—N5	89.35 (6)	C5—C4—H4	120.7
N1—Co1—N5	174.48 (6)	N1—C5—N2	120.50 (17)
O3—Co1—O2	83.24 (5)	N1—C5—C4	122.78 (19)
N3—Co1—O2	91.44 (5)	N2—C5—C4	116.69 (18)
N1—Co1—O2	92.79 (6)	N6—C6—N3	125.42 (17)
N5—Co1—O2	92.66 (6)	N6—C6—N2	114.11 (16)
O3—Co1—O1	91.31 (6)	N3—C6—N2	120.46 (16)
N3—Co1—O1	94.07 (6)	N6—C7—C8	122.84 (19)
N1—Co1—O1	85.23 (6)	N6—C7—H7	118.6
N5—Co1—O1	89.44 (6)	C8—C7—H7	118.6
O2—Co1—O1	174.13 (5)	C7—C8—C9	117.28 (18)
C5—N1—C1	117.16 (17)	C7—C8—H8	121.4
C5—N1—Co1	121.31 (12)	C9—C8—H8	121.4
C1—N1—Co1	119.33 (14)	N3—C9—N4	120.86 (16)
C6—N2—C5	130.39 (16)	N3—C9—C8	123.00 (17)
C6—N2—H2	114.8	N4—C9—C8	116.13 (16)
C5—N2—H2	114.8	N5—C10—N4	120.42 (17)
C6—N3—C9	115.20 (15)	N5—C10—C11	122.6 (2)
C6—N3—Co1	123.13 (11)	N4—C10—C11	117.0 (2)
C9—N3—Co1	120.93 (11)	C12—C11—C10	118.2 (3)
C9—N4—C10	131.96 (16)	C12—C11—H11	120.9
C9—N4—H4A	114.0	C10—C11—H11	120.9
C10—N4—H4A	114.0	C13—C12—C11	119.5 (2)
C10—N5—C14	117.34 (18)	C13—C12—H12	120.3
C10—N5—Co1	121.56 (13)	C11—C12—H12	120.3
C14—N5—Co1	120.41 (15)	C14—C13—C12	118.4 (3)
C6—N6—C7	116.15 (17)	C14—C13—H13	120.8
Co1—O1—H1C	117 (2)	C12—C13—H13	120.8
Co1—O1—H1D	118 (2)	N5—C14—C13	123.9 (2)
H1C—O1—H1D	109.1 (16)	N5—C14—H14	118.1
Co1—O2—H2C	114.8 (18)	C13—C14—H14	118.1
Co1—O2—H2D	124.7 (19)	C15ⁱ—C15—C16	124.5 (2)
H2C—O2—H2D	106.8 (15)	C15ⁱ—C15—H15	117.8
Co1—O3—H3D	121.7 (17)	C16—C15—H15	117.8
Co1—O3—H3C	129.8 (17)	O4—C16—O5	125.24 (18)
H3D—O3—H3C	108.4 (15)	O4—C16—C15	117.70 (16)
N1—C1—C2	123.4 (2)	O5—C16—C15	117.05 (16)
N1—C1—H1A	118.3	C17ⁱⁱ—C17—C18	124.2 (2)
C2—C1—H1A	118.3	C17ⁱⁱ—C17—H17	117.9
C1—C2—C3	118.3 (2)	C18—C17—H17	117.9
C1—C2—H2A	120.8	O7—C18—O6	123.72 (17)
C3—C2—H2A	120.8	O7—C18—C17	119.26 (16)
C4—C3—C2	119.5 (2)	O6—C18—C17	117.01 (16)

O3—Co1—N1—C5	−151.20 (15)	C3—C4—C5—N2	−174.2 (2)
N3—Co1—N1—C5	34.03 (15)	C7—N6—C6—N3	−1.9 (3)
O2—Co1—N1—C5	125.45 (15)	C7—N6—C6—N2	179.18 (18)
O1—Co1—N1—C5	−60.08 (15)	C9—N3—C6—N6	−0.5 (3)
O3—Co1—N1—C1	11.43 (17)	Co1—N3—C6—N6	169.80 (15)
N3—Co1—N1—C1	−163.33 (17)	C9—N3—C6—N2	178.32 (16)
O2—Co1—N1—C1	−71.91 (17)	Co1—N3—C6—N2	−11.4 (2)
O1—Co1—N1—C1	102.55 (17)	C5—N2—C6—N6	−144.6 (2)
N1—Co1—N3—C6	−15.88 (14)	C5—N2—C6—N3	36.5 (3)
N5—Co1—N3—C6	158.70 (14)	C6—N6—C7—C8	1.9 (3)
O2—Co1—N3—C6	−108.66 (14)	N6—C7—C8—C9	0.5 (3)
O1—Co1—N3—C6	69.31 (14)	C6—N3—C9—N4	−178.14 (16)
N1—Co1—N3—C9	153.86 (14)	Co1—N3—C9—N4	11.3 (2)
N5—Co1—N3—C9	−31.56 (14)	C6—N3—C9—C8	3.1 (3)
O2—Co1—N3—C9	61.08 (14)	Co1—N3—C9—C8	−167.37 (15)
O1—Co1—N3—C9	−120.95 (13)	C10—N4—C9—N3	26.2 (3)
O3—Co1—N5—C10	−141.78 (15)	C10—N4—C9—C8	−155.0 (2)
N3—Co1—N5—C10	32.82 (15)	C7—C8—C9—N3	−3.2 (3)
O2—Co1—N5—C10	−58.59 (15)	C7—C8—C9—N4	178.03 (18)
O1—Co1—N5—C10	126.90 (15)	C14—N5—C10—N4	176.3 (2)
O3—Co1—N5—C14	28.44 (17)	Co1—N5—C10—N4	−13.2 (2)
N3—Co1—N5—C14	−156.96 (17)	C14—N5—C10—C11	−4.0 (3)
O2—Co1—N5—C14	111.63 (17)	Co1—N5—C10—C11	166.54 (18)
O1—Co1—N5—C14	−62.88 (17)	C9—N4—C10—N5	−25.1 (3)
C5—N1—C1—C2	3.8 (4)	C9—N4—C10—C11	155.2 (2)
Co1—N1—C1—C2	−159.5 (2)	N5—C10—C11—C12	1.5 (4)
N1—C1—C2—C3	0.4 (5)	N4—C10—C11—C12	−178.8 (2)
C1—C2—C3—C4	−2.7 (5)	C10—C11—C12—C13	1.8 (5)
C2—C3—C4—C5	0.7 (4)	C11—C12—C13—C14	−2.5 (5)
C1—N1—C5—N2	171.9 (2)	C10—N5—C14—C13	3.3 (4)
Co1—N1—C5—N2	−25.1 (2)	Co1—N5—C14—C13	−167.3 (2)
C1—N1—C5—C4	−6.0 (3)	C12—C13—C14—N5	−0.1 (5)
Co1—N1—C5—C4	157.03 (17)	C15ⁱ—C15—C16—O4	−155.6 (2)
C6—N2—C5—N1	−15.7 (3)	C15ⁱ—C15—C16—O5	25.1 (4)
C6—N2—C5—C4	162.4 (2)	C17ⁱⁱ—C17—C18—O7	11.0 (3)
C3—C4—C5—N1	3.8 (4)	C17ⁱⁱ—C17—C18—O6	−167.7 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2D···O4ⁱⁱⁱ	0.84 (1)	1.94 (1)	2.7396 (19)	159 (2)
O2—H2C···O6^iv	0.84 (1)	1.90 (1)	2.7374 (18)	176 (3)
O3—H3C···O7^iv	0.84 (1)	1.86 (1)	2.6929 (18)	172 (3)
O3—H3D···O5ⁱ	0.83 (1)	1.73 (1)	2.559 (2)	171 (2)
O1—H1D···O6^v	0.83 (1)	1.93 (1)	2.7374 (19)	165 (3)
O1—H1C···O4ⁱ	0.83 (1)	2.00 (1)	2.8143 (19)	166 (2)
N4—H4A···O5^vi	0.86	1.93	2.782 (2)	169
N2—H2···O7^vii	0.86	2.28	3.002 (2)	141

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₄H₁₂N₆)(H₂O)₃]C₄H₂O₄
M_r	491.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.3239 (3), 17.1115 (6), 13.1395 (5)
β (°)	96.224 (1)
V (Å³)	2084.00 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.29 × 0.25 × 0.18

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.785, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	10365, 3746, 3363
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.078, 0.86
No. of reflections	3746
No. of parameters	307
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.33

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1	2.0989 (13)	Co1—N1	2.0790 (15)
Co1—O2	2.0905 (13)	Co1—N3	2.0624 (14)
Co1—O3	2.0396 (13)	Co1—N5	2.0803 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2D···O4ⁱ	0.836 (10)	1.943 (14)	2.7396 (19)	159 (2)
O2—H2C···O6ⁱⁱ	0.841 (10)	1.898 (10)	2.7374 (18)	176 (3)
O3—H3C···O7ⁱⁱ	0.840 (9)	1.858 (11)	2.6929 (18)	172 (3)
O3—H3D···O5ⁱⁱⁱ	0.832 (10)	1.734 (11)	2.559 (2)	171 (2)
O1—H1D···O6^iv	0.829 (10)	1.930 (13)	2.7374 (19)	165 (3)
O1—H1C···O4ⁱⁱⁱ	0.832 (10)	2.001 (13)	2.8143 (19)	166 (2)
N4—H4A···O5^v	0.86	1.93	2.782 (2)	169
N2—H2···O7^vi	0.86	2.28	3.002 (2)	141

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

Acknowledgements

The authors are grateful to the Natural Science Foundation of Zhejiang Province (grant No. Y407081) for financial support.

References

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