Aqua­(dicyanamido-κN1)(2,9-dimethyl-1,10-phenanthroline-κ2N,N′)(nitrato-κ2O,O′)cobalt(II)–2,9-dimethyl-1,10-phenanthroline–water (2/1/2)

Cui, F.-H.; Zhao, P.-Z.

doi:10.1107/S1600536811035148

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Pages m1341-m1342

https://doi.org/10.1107/S1600536811035148

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Aqua(dicyanamido-κN¹)(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)(nitrato-κ²O,O′)cobalt(II)–2,9-dimethyl-1,10-phenanthroline–water (2/1/2)

Feng-Hua Cui ^a,^b and Pei-Zheng Zhao ^a ^*

^aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China, and ^bDepartment of Engineering and Technology, Xinxiang Vocational and Technical College, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: pz_zhao@hotmail.com

(Received 6 July 2011; accepted 27 August 2011; online 14 September 2011)

In the title compound, 2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O, the Co^II ion is coordinated by a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand, a bidentate nitrate anion, a water molecule and a monodentate dicyanamide group in a distorted octahedral geometry. One uncoordinated dmphen molecule is situated on a crystallographic twofold axis and the asymmetric unit is completed by one water molecule. In the crystal, molecules form a one-dimensional framework in the [001] direction through O—H⋯N and O—H⋯O hydrogen bonds. The crystal packing is further stabilized by π–π stacking interactions between the dmphen rings of neighboring molecules, with a centroid–centroid separation of 3.5641 (8) Å and a partially overlapped arrangement of parallel dmphen rings with a distance of 3.407 (2) Å.

Related literature

For background to metal–phenanthroline complexes, see: Naing et al. (1995 ); Wang et al. (1996 ); Wall et al. (1999 ). For related Co(II)–phenanthroline structures, see: Ding et al. (2006 ); Xuan & Zhao (2007 ); Zhao et al. (2008 ).

Experimental

Crystal data

2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O
M_r = 1070.82
Monoclinic, C 2/c
a = 17.993 (6) Å
b = 11.770 (4) Å
c = 23.428 (7) Å
β = 106.981 (4)°
V = 4745 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 291 K
0.34 × 0.18 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.781, T_max = 0.917
17592 measured reflections
4400 independent reflections
2862 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.196
S = 1.04
4400 reflections
328 parameters
36 restraints
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1W⋯O5ⁱ	0.85	2.57	3.111 (9)	123
O4—H2W⋯N7	0.85	1.97	2.810 (6)	167
O5—H4W⋯N5ⁱⁱ	0.85	2.25	2.830 (15)	126
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811035148/bh2369sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035148/bh2369Isup2.hkl

checkCIF report

Comment top

Metal-phenanthroline complexes and their derivatives have attracted much attention because of their peculiar features (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). Some Co(II)-phenanthroline complexes have been synthesized and structures were determined (Ding et al., 2006; Xuan & Zhao, 2007; Zhao et al., 2008). Recently, we obtained the title cobalt(II) complex, by reacting 2,9-dimethyl-1,10-phenanthroline, NaN(CN)₂ and Co(NO₃)₂ in an ethanol/water mixture. The structure of the title compound, 2[Co(C₁₄H₁₂N₂)N(CN)₂NO₃H₂O]^.C₁₄H₁₂N₂^.2H₂O is described below.

Each Co^II ion is six-coordinated by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, two O atoms from a nitrate anion, one O atom from a water molecule and one N from a dicyanamide anion. The water and N3/C15/N4/C16/N5 ligands occupy the axial positions, with a N3—Co1—O4 bond angle of 171.71 (16)°. The Co^II ion locates in the center, and CoO₃N₃ unit forms a distorted octahedral geometry. The uncoordinated dmphen molecule is placed on a crystallographic twofold axis (Fig. 1).

In the crystal structure, molecules are linked into a one-dimensional framework by O—H···N and O—H···O hydrogen bonds (Fig. 2). A partially overlapped arrangement of neighboring parallel Co1A-dmphen and Co1B-dmphen [symmetry code: (A) -x + 1, y, -z + 1/2; (B) -x + 1, -y + 1, -z + 1] rings with distance of 3.4065 (20) Å is observed. The shorter face-to-face separation clearly indicates the existence of π-π stacking between the dmphen rings. Uncoordinated N7A-dmphen and N7B-dmphen rings are also parallel with distance of 10.4286 (19) Å. In addition, the distance between the ring centroids Cg (C4A···C7A/C11A/C12A) and Cg (C17A···C20A/C22A/N7A) is 3.5641 (8) Å (Fig. 3). This value is close to the van der Waals thickness of the π-π stacking between nearly parallel dmphen (N7A-dmphen with Co1A-dmphen and Co1B-dmphen with N7B-dmphen) rings [dihedral angle: 3.4 (1)°].

Related literature top

For background to metal–phenanthroline complexes, see: Naing et al. (1995); Wang et al. (1996); Wall et al. (1999). For related Co(II)–phenanthroline structures, see: Ding et al. (2006); Xuan & Zhao (2007); Zhao et al. (2008).

Experimental top

NaN(CN)₂ (0.0892 g, 1 mmol) was dissolved in distilled water (10 ml) and Co(NO₃)₂.6H₂O (0.1456 g, 0.5 mmol) was added. This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C₁₄H₁₂N₂.0.5H₂O, 0.1088 g, 0.5 mmol) in ethanol (10 ml). The mixture was stirred at 323 K and then refluxed for 5 h, cooled to room temperature and filtered. Pink single crystals appeared over a period of 8 days by slow evaporation at room temperature.

Structure description top

For background to metal–phenanthroline complexes, see: Naing et al. (1995); Wang et al. (1996); Wall et al. (1999). For related Co(II)–phenanthroline structures, see: Ding et al. (2006); Xuan & Zhao (2007); Zhao et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids. [Symmetry code: (A) -x + 1, y, -z + 1/2].
	Fig. 2. The hydrogen-bonding motifs in the crystal structure. Dashed lines indicate the hydrogen bonds.
	Fig. 3. The π-π interaction between the dmphen rings of neighboring molecules in the crystal structure [Symmetry codes: (A) -x + 1, y, -z + 1/2; (B) -x + 1, -y + 1, -z + 1; (C) x, -y + 1, z + 1/2].

Aqua(dicyanamido-κN¹)(2,9-dimethyl-1,10-phenanthroline- κ²N,N')(nitrato-κ²O,O')cobalt(II)– 2,9-dimethyl-1,10-phenanthroline–water (2/1/2) top

Crystal data top

2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O	F(000) = 2208
M_r = 1070.82	D_x = 1.499 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2628 reflections
a = 17.993 (6) Å	θ = 2.4–21.2°
b = 11.770 (4) Å	µ = 0.77 mm⁻¹
c = 23.428 (7) Å	T = 291 K
β = 106.981 (4)°	Block, pink
V = 4745 (3) Å³	0.34 × 0.18 × 0.11 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	4400 independent reflections
Radiation source: fine-focus sealed tube	2862 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.070
φ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −21→21
T_min = 0.781, T_max = 0.917	k = −13→14
17592 measured reflections	l = −28→28

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.196	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1026P)² + 4.8562P] where P = (F_o² + 2F_c²)/3
4400 reflections	(Δ/σ)_max < 0.001
328 parameters	Δρ_max = 1.06 e Å⁻³
36 restraints	Δρ_min = −0.58 e Å⁻³
0 constraints

Crystal data top

2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O	V = 4745 (3) Å³
M_r = 1070.82	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.993 (6) Å	µ = 0.77 mm⁻¹
b = 11.770 (4) Å	T = 291 K
c = 23.428 (7) Å	0.34 × 0.18 × 0.11 mm
β = 106.981 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4400 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2862 reflections with I > 2σ(I)
T_min = 0.781, T_max = 0.917	R_int = 0.070
17592 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	36 restraints
wR(F²) = 0.196	H-atom parameters constrained
S = 1.04	Δρ_max = 1.06 e Å⁻³
4400 reflections	Δρ_min = −0.58 e Å⁻³
328 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.42687 (4)	0.19148 (5)	0.38145 (3)	0.0453 (3)
O1	0.3472 (2)	0.0602 (3)	0.32847 (17)	0.0706 (10)
O2	0.3720 (3)	−0.1178 (3)	0.3477 (2)	0.1070 (17)
O3	0.4528 (2)	0.0107 (3)	0.39358 (17)	0.0648 (10)
O4	0.4792 (3)	0.1851 (3)	0.31525 (17)	0.0672 (11)
H1W	0.4450	0.1747	0.2819	0.101*
H2W	0.5124	0.2344	0.3124	0.101*
O5	0.5612 (6)	−0.0066 (7)	0.2802 (4)	0.233 (5)
H3W	0.5731	0.0572	0.2975	0.350*
H4W	0.5602	−0.0359	0.3132	0.350*
N1	0.5202 (2)	0.2867 (3)	0.43700 (16)	0.0443 (9)
N2	0.3892 (2)	0.3599 (3)	0.35623 (16)	0.0434 (9)
N3	0.3653 (3)	0.1776 (4)	0.4424 (2)	0.0694 (13)
N4	0.2925 (4)	0.1214 (6)	0.5087 (3)	0.114 (2)
N5	0.3362 (7)	0.1052 (7)	0.6164 (4)	0.172 (4)
N6	0.3906 (3)	−0.0181 (4)	0.3558 (2)	0.0667 (12)
N7	0.5696 (2)	0.3653 (4)	0.29332 (18)	0.0534 (10)
C1	0.5844 (3)	0.2489 (5)	0.4772 (2)	0.0568 (13)
C2	0.6423 (3)	0.3248 (7)	0.5087 (3)	0.0753 (18)
H2	0.6866	0.2966	0.5363	0.090*
C3	0.6345 (3)	0.4380 (6)	0.4995 (3)	0.0701 (16)
H3	0.6737	0.4871	0.5200	0.084*
C4	0.5662 (3)	0.4812 (5)	0.4582 (2)	0.0582 (14)
C5	0.5522 (4)	0.5994 (5)	0.4464 (3)	0.0696 (16)
H5	0.5887	0.6522	0.4669	0.084*
C6	0.4872 (4)	0.6351 (5)	0.4062 (3)	0.0694 (16)
H6	0.4793	0.7125	0.3991	0.083*
C7	0.4299 (3)	0.5567 (4)	0.3738 (2)	0.0534 (13)
C8	0.3608 (4)	0.5883 (4)	0.3314 (3)	0.0639 (15)
H8	0.3504	0.6647	0.3226	0.077*
C9	0.3089 (3)	0.5090 (5)	0.3029 (3)	0.0651 (15)
H9	0.2633	0.5308	0.2745	0.078*
C10	0.3242 (3)	0.3931 (4)	0.3164 (2)	0.0504 (12)
C11	0.4419 (3)	0.4398 (4)	0.38500 (19)	0.0433 (11)
C12	0.5111 (3)	0.4015 (4)	0.4278 (2)	0.0455 (11)
C13	0.5937 (4)	0.1235 (5)	0.4881 (3)	0.0800 (18)
H13A	0.5582	0.0983	0.5091	0.120*
H13B	0.6460	0.1073	0.5115	0.120*
H13C	0.5827	0.0844	0.4505	0.120*
C14	0.2674 (3)	0.3042 (5)	0.2860 (3)	0.0705 (16)
H14A	0.2920	0.2521	0.2658	0.106*
H14B	0.2240	0.3394	0.2576	0.106*
H14C	0.2495	0.2638	0.3151	0.106*
C15	0.3341 (4)	0.1530 (5)	0.4758 (3)	0.0691 (16)
C16	0.3184 (6)	0.1179 (7)	0.5646 (5)	0.110 (3)
C17	0.6397 (4)	0.3631 (7)	0.3335 (3)	0.0808 (18)
C18	0.6784 (4)	0.4641 (8)	0.3554 (3)	0.099 (2)
H18	0.7274	0.4612	0.3830	0.118*
C19	0.6457 (5)	0.5651 (8)	0.3371 (3)	0.101 (2)
H19	0.6712	0.6315	0.3534	0.121*
C20	0.5729 (5)	0.5711 (6)	0.2933 (3)	0.0904 (19)
C21	0.5337 (5)	0.6744 (6)	0.2707 (4)	0.105 (3)
H21	0.5565	0.7433	0.2856	0.127*
C22	0.5374 (3)	0.4659 (4)	0.2729 (2)	0.0542 (13)
C23	0.6749 (4)	0.2515 (8)	0.3539 (3)	0.111 (3)
H23A	0.6522	0.1949	0.3245	0.167*
H23B	0.6655	0.2320	0.3910	0.167*
H23C	0.7299	0.2550	0.3595	0.167*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0533 (5)	0.0302 (4)	0.0530 (4)	−0.0039 (3)	0.0165 (3)	−0.0007 (3)
O1	0.075 (3)	0.048 (2)	0.079 (3)	−0.002 (2)	0.007 (2)	0.0021 (19)
O2	0.133 (4)	0.035 (2)	0.144 (4)	−0.020 (2)	0.026 (3)	−0.015 (2)
O3	0.070 (3)	0.043 (2)	0.078 (2)	−0.0033 (18)	0.017 (2)	0.0042 (17)
O4	0.104 (3)	0.041 (2)	0.071 (2)	−0.0056 (19)	0.048 (2)	−0.0030 (16)
O5	0.371 (15)	0.145 (7)	0.204 (9)	−0.066 (8)	0.118 (9)	−0.001 (6)
N1	0.047 (2)	0.040 (2)	0.047 (2)	−0.0035 (17)	0.0147 (18)	0.0012 (16)
N2	0.047 (2)	0.035 (2)	0.051 (2)	−0.0026 (18)	0.0189 (19)	−0.0007 (17)
N3	0.078 (3)	0.060 (3)	0.082 (3)	−0.016 (2)	0.041 (3)	−0.010 (2)
N4	0.129 (5)	0.110 (5)	0.136 (5)	−0.022 (4)	0.092 (5)	−0.001 (4)
N5	0.295 (11)	0.124 (7)	0.147 (7)	−0.022 (7)	0.141 (8)	−0.015 (5)
N6	0.084 (4)	0.032 (3)	0.082 (3)	−0.010 (2)	0.022 (3)	−0.004 (2)
N7	0.043 (2)	0.062 (3)	0.058 (2)	−0.001 (2)	0.020 (2)	−0.004 (2)
C1	0.054 (3)	0.064 (3)	0.051 (3)	−0.004 (3)	0.014 (2)	0.001 (3)
C2	0.049 (3)	0.112 (6)	0.059 (3)	−0.008 (3)	0.007 (3)	−0.003 (3)
C3	0.055 (3)	0.078 (4)	0.075 (4)	−0.022 (3)	0.017 (3)	−0.017 (3)
C4	0.060 (3)	0.057 (3)	0.064 (3)	−0.023 (3)	0.028 (3)	−0.017 (3)
C5	0.082 (4)	0.050 (3)	0.083 (4)	−0.032 (3)	0.034 (4)	−0.026 (3)
C6	0.097 (5)	0.037 (3)	0.087 (4)	−0.015 (3)	0.048 (4)	−0.013 (3)
C7	0.071 (4)	0.030 (2)	0.069 (3)	−0.001 (2)	0.036 (3)	−0.006 (2)
C8	0.085 (4)	0.034 (3)	0.081 (4)	0.015 (3)	0.037 (3)	0.009 (3)
C9	0.066 (4)	0.054 (3)	0.076 (4)	0.016 (3)	0.021 (3)	0.008 (3)
C10	0.057 (3)	0.042 (3)	0.053 (3)	0.006 (2)	0.017 (2)	0.002 (2)
C11	0.052 (3)	0.034 (2)	0.050 (3)	−0.005 (2)	0.023 (2)	−0.0062 (19)
C12	0.050 (3)	0.041 (3)	0.052 (3)	−0.009 (2)	0.025 (2)	−0.007 (2)
C13	0.078 (4)	0.073 (4)	0.078 (4)	0.012 (3)	0.007 (3)	0.021 (3)
C14	0.061 (4)	0.066 (4)	0.074 (4)	−0.002 (3)	0.003 (3)	−0.001 (3)
C15	0.079 (4)	0.045 (3)	0.098 (4)	−0.009 (3)	0.049 (4)	−0.010 (3)
C16	0.160 (6)	0.081 (5)	0.128 (6)	−0.018 (4)	0.105 (6)	−0.018 (5)
C17	0.054 (4)	0.130 (6)	0.065 (3)	−0.010 (4)	0.028 (3)	−0.011 (4)
C18	0.066 (4)	0.145 (6)	0.088 (4)	−0.038 (4)	0.028 (3)	−0.032 (4)
C19	0.096 (5)	0.118 (5)	0.106 (5)	−0.066 (4)	0.057 (4)	−0.047 (4)
C20	0.114 (5)	0.072 (4)	0.112 (5)	−0.040 (4)	0.075 (4)	−0.027 (3)
C21	0.152 (7)	0.053 (3)	0.139 (7)	−0.025 (4)	0.085 (5)	−0.023 (4)
C22	0.061 (3)	0.046 (3)	0.071 (3)	−0.014 (2)	0.043 (3)	−0.012 (2)
C23	0.073 (5)	0.174 (8)	0.084 (5)	0.046 (5)	0.019 (4)	0.030 (5)

Geometric parameters (Å, º) top

Co1—O4	2.037 (4)	C5—H5	0.9300
Co1—N3	2.053 (5)	C6—C7	1.425 (8)
Co1—N1	2.120 (4)	C6—H6	0.9300
Co1—N2	2.122 (4)	C7—C8	1.397 (7)
Co1—O3	2.180 (4)	C7—C11	1.405 (7)
Co1—O1	2.224 (4)	C8—C9	1.350 (8)
O1—N6	1.256 (6)	C8—H8	0.9300
O2—N6	1.220 (5)	C9—C10	1.408 (7)
O3—N6	1.253 (6)	C9—H9	0.9300
O4—H1W	0.8501	C10—C14	1.491 (7)
O4—H2W	0.8500	C11—C12	1.425 (7)
O5—H3W	0.8500	C13—H13A	0.9600
O5—H4W	0.8501	C13—H13B	0.9600
N1—C1	1.336 (6)	C13—H13C	0.9600
N1—C12	1.371 (6)	C14—H14A	0.9600
N2—C10	1.325 (6)	C14—H14B	0.9600
N2—C11	1.366 (6)	C14—H14C	0.9600
N3—C15	1.126 (7)	C17—C18	1.398 (10)
N4—C16	1.256 (11)	C17—C23	1.476 (11)
N4—C15	1.276 (8)	C18—C19	1.339 (11)
N5—C16	1.172 (11)	C18—H18	0.9300
N7—C17	1.336 (7)	C19—C20	1.410 (11)
N7—C22	1.344 (7)	C19—H19	0.9300
C1—C2	1.406 (8)	C20—C22	1.411 (8)
C1—C13	1.499 (8)	C20—C21	1.427 (10)
C2—C3	1.349 (9)	C21—C21ⁱ	1.314 (17)
C2—H2	0.9300	C21—H21	0.9300
C3—C4	1.419 (8)	C22—C22ⁱ	1.455 (11)
C3—H3	0.9300	C23—H23A	0.9600
C4—C12	1.398 (7)	C23—H23B	0.9600
C4—C5	1.426 (8)	C23—H23C	0.9600
C5—C6	1.337 (9)

O4—Co1—N3	171.71 (16)	C9—C8—C7	120.8 (5)
O4—Co1—N1	91.57 (16)	C9—C8—H8	119.6
N3—Co1—N1	96.13 (17)	C7—C8—H8	119.6
O4—Co1—N2	90.19 (14)	C8—C9—C10	119.8 (5)
N3—Co1—N2	94.27 (17)	C8—C9—H9	120.1
N1—Co1—N2	78.95 (14)	C10—C9—H9	120.1
O4—Co1—O3	86.23 (14)	N2—C10—C9	121.2 (5)
N3—Co1—O3	88.30 (17)	N2—C10—C14	118.1 (4)
N1—Co1—O3	109.58 (15)	C9—C10—C14	120.7 (5)
N2—Co1—O3	170.81 (15)	N2—C11—C7	122.4 (4)
O4—Co1—O1	85.13 (16)	N2—C11—C12	117.9 (4)
N3—Co1—O1	86.69 (17)	C7—C11—C12	119.7 (4)
N1—Co1—O1	167.45 (15)	N1—C12—C4	123.1 (5)
N2—Co1—O1	113.10 (14)	N1—C12—C11	117.5 (4)
O3—Co1—O1	58.18 (14)	C4—C12—C11	119.3 (5)
N6—O1—Co1	91.2 (3)	C1—C13—H13A	109.5
N6—O3—Co1	93.4 (3)	C1—C13—H13B	109.5
Co1—O4—H1W	109.6	H13A—C13—H13B	109.5
Co1—O4—H2W	121.9	C1—C13—H13C	109.5
H1W—O4—H2W	111.2	H13A—C13—H13C	109.5
H3W—O5—H4W	89.8	H13B—C13—H13C	109.5
C1—N1—C12	118.6 (4)	C10—C14—H14A	109.5
C1—N1—Co1	128.6 (3)	C10—C14—H14B	109.5
C12—N1—Co1	112.8 (3)	H14A—C14—H14B	109.5
C10—N2—C11	119.2 (4)	C10—C14—H14C	109.5
C10—N2—Co1	128.1 (3)	H14A—C14—H14C	109.5
C11—N2—Co1	112.8 (3)	H14B—C14—H14C	109.5
C15—N3—Co1	169.5 (5)	N3—C15—N4	173.6 (8)
C16—N4—C15	122.4 (8)	N5—C16—N4	172.3 (10)
O2—N6—O3	121.2 (5)	N7—C17—C18	120.5 (7)
O2—N6—O1	121.6 (5)	N7—C17—C23	118.3 (7)
O3—N6—O1	117.1 (4)	C18—C17—C23	121.2 (7)
C17—N7—C22	119.3 (5)	C19—C18—C17	120.9 (7)
N1—C1—C2	120.9 (5)	C19—C18—H18	119.6
N1—C1—C13	118.5 (5)	C17—C18—H18	119.6
C2—C1—C13	120.6 (5)	C18—C19—C20	120.3 (7)
C3—C2—C1	121.1 (6)	C18—C19—H19	119.8
C3—C2—H2	119.4	C20—C19—H19	119.8
C1—C2—H2	119.4	C19—C20—C22	115.8 (7)
C2—C3—C4	119.4 (5)	C19—C20—C21	124.5 (7)
C2—C3—H3	120.3	C22—C20—C21	119.7 (7)
C4—C3—H3	120.3	C21ⁱ—C21—C20	121.6 (4)
C12—C4—C3	116.8 (5)	C21ⁱ—C21—H21	119.2
C12—C4—C5	119.8 (5)	C20—C21—H21	119.2
C3—C4—C5	123.4 (5)	N7—C22—C20	123.2 (6)
C6—C5—C4	120.8 (5)	N7—C22—C22ⁱ	118.2 (3)
C6—C5—H5	119.6	C20—C22—C22ⁱ	118.7 (4)
C4—C5—H5	119.6	C17—C23—H23A	109.5
C5—C6—C7	121.3 (5)	C17—C23—H23B	109.5
C5—C6—H6	119.4	H23A—C23—H23B	109.5
C7—C6—H6	119.4	C17—C23—H23C	109.5
C8—C7—C11	116.7 (5)	H23A—C23—H23C	109.5
C8—C7—C6	124.2 (5)	H23B—C23—H23C	109.5
C11—C7—C6	119.1 (5)

O4—Co1—O1—N6	90.4 (3)	C5—C6—C7—C8	179.8 (5)
N3—Co1—O1—N6	−88.2 (3)	C5—C6—C7—C11	0.5 (8)
N1—Co1—O1—N6	15.2 (8)	C11—C7—C8—C9	−0.1 (8)
N2—Co1—O1—N6	178.5 (3)	C6—C7—C8—C9	−179.5 (5)
O3—Co1—O1—N6	1.8 (3)	C7—C8—C9—C10	0.5 (8)
O4—Co1—O3—N6	−88.4 (3)	C11—N2—C10—C9	0.6 (7)
N3—Co1—O3—N6	85.3 (3)	Co1—N2—C10—C9	−177.4 (4)
N1—Co1—O3—N6	−178.8 (3)	C11—N2—C10—C14	−179.6 (4)
O1—Co1—O3—N6	−1.8 (3)	Co1—N2—C10—C14	2.4 (7)
O4—Co1—N1—C1	−90.8 (4)	C8—C9—C10—N2	−0.8 (8)
N3—Co1—N1—C1	86.1 (4)	C8—C9—C10—C14	179.3 (5)
N2—Co1—N1—C1	179.3 (4)	C10—N2—C11—C7	−0.1 (6)
O3—Co1—N1—C1	−4.3 (4)	Co1—N2—C11—C7	178.2 (3)
O1—Co1—N1—C1	−16.3 (9)	C10—N2—C11—C12	179.8 (4)
O4—Co1—N1—C12	87.9 (3)	Co1—N2—C11—C12	−1.9 (5)
N3—Co1—N1—C12	−95.2 (3)	C8—C7—C11—N2	−0.1 (7)
N2—Co1—N1—C12	−2.0 (3)	C6—C7—C11—N2	179.3 (4)
O3—Co1—N1—C12	174.4 (3)	C8—C7—C11—C12	180.0 (4)
O1—Co1—N1—C12	162.4 (6)	C6—C7—C11—C12	−0.6 (7)
O4—Co1—N2—C10	88.7 (4)	C1—N1—C12—C4	0.4 (7)
N3—Co1—N2—C10	−84.3 (4)	Co1—N1—C12—C4	−178.4 (4)
N1—Co1—N2—C10	−179.8 (4)	C1—N1—C12—C11	−179.5 (4)
O1—Co1—N2—C10	3.9 (4)	Co1—N1—C12—C11	1.7 (5)
O4—Co1—N2—C11	−89.4 (3)	C3—C4—C12—N1	1.1 (7)
N3—Co1—N2—C11	97.5 (3)	C5—C4—C12—N1	−179.5 (4)
N1—Co1—N2—C11	2.1 (3)	C3—C4—C12—C11	−179.0 (4)
O1—Co1—N2—C11	−174.2 (3)	C5—C4—C12—C11	0.4 (7)
N1—Co1—N3—C15	−113 (3)	N2—C11—C12—N1	0.2 (6)
N2—Co1—N3—C15	167 (3)	C7—C11—C12—N1	−179.9 (4)
O3—Co1—N3—C15	−4 (3)	N2—C11—C12—C4	−179.7 (4)
O1—Co1—N3—C15	55 (3)	C7—C11—C12—C4	0.2 (6)
Co1—O3—N6—O2	−174.5 (5)	C22—N7—C17—C18	1.8 (8)
Co1—O3—N6—O1	3.1 (5)	C22—N7—C17—C23	−178.1 (5)
Co1—O1—N6—O2	174.5 (5)	N7—C17—C18—C19	0.8 (10)
Co1—O1—N6—O3	−3.0 (5)	C23—C17—C18—C19	−179.3 (6)
C12—N1—C1—C2	−1.2 (7)	C17—C18—C19—C20	−2.9 (11)
Co1—N1—C1—C2	177.4 (4)	C18—C19—C20—C22	2.4 (10)
C12—N1—C1—C13	178.9 (4)	C18—C19—C20—C21	−179.6 (7)
Co1—N1—C1—C13	−2.5 (7)	C19—C20—C21—C21ⁱ	179.3 (9)
N1—C1—C2—C3	0.4 (9)	C22—C20—C21—C21ⁱ	−2.8 (14)
C13—C1—C2—C3	−179.8 (6)	C17—N7—C22—C20	−2.2 (7)
C1—C2—C3—C4	1.2 (9)	C17—N7—C22—C22ⁱ	177.2 (5)
C2—C3—C4—C12	−1.9 (8)	C19—C20—C22—N7	0.1 (8)
C2—C3—C4—C5	178.8 (5)	C21—C20—C22—N7	−177.9 (6)
C12—C4—C5—C6	−0.5 (8)	C19—C20—C22—C22ⁱ	−179.3 (6)
C3—C4—C5—C6	178.8 (5)	C21—C20—C22—C22ⁱ	2.6 (9)
C4—C5—C6—C7	0.1 (9)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1W···O5ⁱ	0.85	2.57	3.111 (9)	123
O4—H2W···N7	0.85	1.97	2.810 (6)	167
O5—H3W···O4	0.85	2.39	2.941 (11)	123
O5—H4W···N5ⁱⁱ	0.85	2.25	2.830 (15)	126

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

Experimental details

Crystal data
Chemical formula	2[Co(C₂N₃)(NO₃)(C₁₄H₁₂N₂)(H₂O)]·C₁₄H₁₂N₂·2H₂O
M_r	1070.82
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	291
a, b, c (Å)	17.993 (6), 11.770 (4), 23.428 (7)
β (°)	106.981 (4)
V (Å³)	4745 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.34 × 0.18 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.781, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	17592, 4400, 2862
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.196, 1.04
No. of reflections	4400
No. of parameters	328
No. of restraints	36
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.58

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1W···O5ⁱ	0.85	2.57	3.111 (9)	122.8
O4—H2W···N7	0.85	1.97	2.810 (6)	167.3
O5—H4W···N5ⁱⁱ	0.85	2.25	2.830 (15)	125.5

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

Acknowledgements

Financial support from the National Natural Science Foundation of Henan Educational Committee (2011 A150018) is gratefully acknowledged.

References

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