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Acta Cryst. (2007). E63, m1986    [ doi:10.1107/S1600536807030279 ]

catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')(nitrato-[kappa]2O,O')cobalt(II)]-[mu]-dicyanamido-[kappa]2N1:N5]

Y.-Y. Wang and T.-F. Liu

Abstract top

The title compound, [Co(C2N3)(NO3)(C14H12N2)]n, exhibits a zigzag chain structure. The CoII atom has a slightly distorted octahedral geometry formed by two N atoms of a 2,9-dimethyl-1,10-phenanthroline ligand, two N atoms from two different dicyanamide ligands and two O atoms of a nitrate anion. A one-dimensional chain is formed through the dicyanamides, which act as end-to-end bridging ligands. The chains are linked into a three-dimensional network via weak C-H...O hydrogen bonds.

Comment top

Due to the stabilization of relatively strong magnetic coupling, multi-dimensional coordination polymers consisting of transition metal ions and dicyanamide ligand are currently being studied (Batten & Murray, 2003). Although the addition of ancillary ligands (e.g. pyridine, pyrazine, pyrimidine, 2,2'-bipyrimidine, 4,4'-bipyridine and 2,2'-bipyridine, etc.) into these binary systems frequently alters the bridging mode of the dicyanamide ligand from µ-1,3 to µ-1,5 and therefore leads to a paramagnetic behavior, a wide variety of molecular architectures subsequently obtained conduce to establish a better understanding of the relationship between structure and magnetic behavior (Burčák et al., 2004; Potočňák et al., 2002; Vangdal et al., 2002; Wu et al., 2003). Here we describe the structure of an end-to-end dicyanamide-bridged cobalt(II) complex, (I), incorporating 2,9-dimethyl-1,10-phenanthroline (dmphen) as an ancillay ligand.

The structure of compound (I) consists of well isolated chains of CoII atoms bridged by end-to-end dicyanamide ligands (Fig.1). In the chain structure, each CoII atom is coordinated by one dmphen ligand, one nitrate anion and two dicyanamide ligands in an octahedral geometry. The Co—N bond distances are in the range of 2.069 (2) to 2.123 (2)Å (Table 1). The nitrate ion binds in a bidentate fashion and the distances of Co—O are 2.1466 (17) and 2.2268 (18) Å. The shortest Co···Co distance is 7.169 (7)Å in the chain and 7.348 (2)Å between the chains.

An N1—O1···Cg(aryl ring) interaction is observed [Cg is the centroid of the ring C5, C6, C7, C8, C9 and C10 at 1/2 − x, 1/2 + y, 1/2 − z) with O1···Cg = 3.296 Å. No significant π–π interaction between the dmphen rings is observed (the shortest centroid-to-centroid distance is 4.364 Å). The weak C—H···O hydrogen bonds link the chains into a three-dimensional structure (Fig. 2, Table 2).

Related literature top

For general background, see: Batten & Murray (2003); Burčák et al. (2004); Potočňák et al. (2002); Vangdal et al. (2002); Wu et al. (2003).

Experimental top

Co(NO3)2·6H2O (0.073 g, 0.25 mmol) and sodium dicyanamide (0.022 g, 0.25 mmol) were dissolved in water (10 ml). A methanol solution (10 ml) of dmphen (0.052 g, 0.25 mmol) was added with continuous stirring. The resulting solution was filtrated and allowed to slowly evaporate at room temperature. After one month, red single crystals suitable for X-ray diffraction appeared. The crystals were collected, washed with water and dried in air (0.059 g, yield 60%). IR (KBr, cm−1): 2318 (ms), 2293 (ms), 2269 (ms), 2247 (m), 2211 (s), 2180 (s).

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic rings, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl groups.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the CoII coordination. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1/2 − x, 1/2 + y, 1/2 − z; (ii) 1/2 − x, −1/2 + y, 1/2 − z.]
[Figure 2] Fig. 2. Hydrogen bonds (dashed lines) between neighboring chains create a three-dimensional structure.
catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ2N,N')(nitrato- κ2O,O')cobalt(II)]-µ-dicyanamido-κ2N1:N5] top
Crystal data top
[Co(C2N3)(NO3)(C14H12N2)]F000 = 804
Mr = 395.25Dx = 1.583 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 16421 reflections
a = 7.3481 (15) Åθ = 3.4–27.5º
b = 13.925 (3) ŵ = 1.07 mm−1
c = 16.531 (3) ÅT = 153 (2) K
β = 101.42 (3)ºBlock, red
V = 1658.0 (6) Å30.20 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker KappaCCD area-detector
diffractometer		3784 independent reflections
Radiation source: sealed tube2450 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 153(2) Kθmax = 27.5º
ω scansθmin = 3.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.815, Tmax = 0.901k = −18→18
7407 measured reflectionsl = −21→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0613P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
3784 reflectionsΔρmax = 0.44 e Å−3
237 parametersΔρmin = −0.32 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(C2N3)(NO3)(C14H12N2)]V = 1658.0 (6) Å3
Mr = 395.25Z = 4
Monoclinic, P21/nMo Kα
a = 7.3481 (15) ŵ = 1.07 mm−1
b = 13.925 (3) ÅT = 153 (2) K
c = 16.531 (3) Å0.20 × 0.15 × 0.10 mm
β = 101.42 (3)º
Data collection top
Bruker KappaCCD area-detector
diffractometer		3784 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2450 reflections with I > 2σ(I)
Tmin = 0.815, Tmax = 0.901Rint = 0.022
7407 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033237 parameters
wR(F2) = 0.098H-atom parameters constrained
S = 0.94Δρmax = 0.44 e Å−3
3784 reflectionsΔρmin = −0.32 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.17457 (4)0.86364 (2)0.203521 (18)0.03941 (12)
C10.5626 (4)0.9754 (2)0.1736 (2)0.0718 (8)
H1A0.57900.94780.22780.108*
H1B0.47171.02570.16840.108*
H1C0.67851.00130.16530.108*
C20.4981 (3)0.8998 (2)0.11066 (16)0.0550 (6)
C30.5930 (4)0.8817 (2)0.0460 (2)0.0689 (8)
H30.69730.91780.04190.083*
C40.5327 (4)0.8119 (2)−0.01033 (18)0.0710 (9)
H40.59740.7997−0.05220.085*
C50.3748 (4)0.75839 (19)−0.00591 (15)0.0564 (7)
C60.2852 (3)0.77972 (16)0.05976 (13)0.0432 (5)
C70.3025 (5)0.6845 (2)−0.06323 (16)0.0685 (9)
H70.36400.6690−0.10550.082*
C80.1478 (5)0.63745 (19)−0.05684 (16)0.0683 (9)
H80.10210.5905−0.09560.082*
C90.0506 (4)0.65740 (17)0.00819 (15)0.0544 (7)
C100.1201 (3)0.72828 (15)0.06690 (13)0.0422 (5)
C11−0.1105 (4)0.60941 (19)0.01902 (18)0.0640 (8)
H11−0.16470.5638−0.01940.077*
C12−0.1875 (4)0.62898 (18)0.08485 (19)0.0644 (8)
H12−0.29180.59510.09270.077*
C13−0.1113 (3)0.69973 (17)0.14120 (15)0.0498 (6)
C14−0.1931 (4)0.7203 (2)0.21529 (18)0.0675 (8)
H14A−0.20270.78840.22190.101*
H14B−0.11480.69360.26350.101*
H14C−0.31440.69190.20810.101*
C150.0563 (3)1.05722 (17)0.12152 (13)0.0429 (5)
C160.1296 (4)1.20845 (18)0.16598 (16)0.0506 (6)
N10.1251 (3)0.97749 (16)0.32013 (12)0.0586 (6)
N20.0411 (3)0.97627 (14)0.12771 (12)0.0497 (5)
N30.0722 (4)1.14768 (15)0.10658 (14)0.0778 (8)
N40.1824 (3)1.26809 (16)0.21111 (13)0.0608 (6)
N50.3482 (3)0.84869 (13)0.11715 (12)0.0433 (5)
N60.0384 (2)0.74995 (12)0.13134 (11)0.0398 (4)
O10.0919 (3)1.03262 (17)0.37294 (13)0.0953 (8)
O20.0128 (3)0.91132 (14)0.29068 (11)0.0593 (5)
O30.2731 (3)0.98178 (13)0.29219 (11)0.0595 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0450 (2)0.03348 (18)0.03892 (18)−0.00008 (14)0.00622 (13)−0.00058 (13)
C10.0499 (17)0.0674 (19)0.098 (2)−0.0148 (14)0.0133 (16)−0.0054 (17)
C20.0438 (15)0.0568 (15)0.0646 (16)0.0035 (12)0.0112 (13)0.0095 (13)
C30.0508 (17)0.079 (2)0.082 (2)0.0055 (15)0.0261 (15)0.0217 (17)
C40.076 (2)0.084 (2)0.0608 (18)0.0249 (18)0.0327 (16)0.0142 (16)
C50.0659 (17)0.0580 (16)0.0472 (14)0.0186 (14)0.0160 (13)0.0087 (12)
C60.0515 (14)0.0397 (12)0.0372 (12)0.0117 (11)0.0063 (11)0.0031 (10)
C70.105 (3)0.0627 (19)0.0404 (14)0.0280 (18)0.0199 (16)−0.0004 (13)
C80.111 (3)0.0458 (16)0.0421 (14)0.0168 (17)−0.0005 (16)−0.0048 (12)
C90.077 (2)0.0366 (13)0.0416 (13)0.0102 (12)−0.0073 (13)0.0002 (10)
C100.0514 (14)0.0315 (11)0.0399 (12)0.0059 (10)−0.0004 (10)0.0000 (9)
C110.079 (2)0.0379 (14)0.0621 (17)−0.0032 (14)−0.0180 (16)−0.0042 (12)
C120.0582 (17)0.0427 (15)0.084 (2)−0.0113 (13)−0.0060 (16)0.0039 (14)
C130.0478 (15)0.0369 (13)0.0602 (15)−0.0010 (11)0.0001 (12)0.0078 (11)
C140.0626 (18)0.0605 (18)0.084 (2)−0.0099 (14)0.0253 (16)0.0085 (15)
C150.0458 (14)0.0410 (14)0.0391 (12)−0.0005 (10)0.0018 (10)0.0000 (10)
C160.0627 (16)0.0350 (13)0.0492 (14)−0.0038 (12)−0.0003 (12)0.0057 (11)
N10.0713 (17)0.0570 (14)0.0440 (12)0.0149 (12)0.0030 (12)−0.0053 (10)
N20.0554 (13)0.0367 (12)0.0545 (12)0.0012 (9)0.0051 (10)0.0024 (9)
N30.128 (2)0.0393 (13)0.0535 (14)−0.0122 (13)−0.0121 (15)0.0048 (11)
N40.0799 (17)0.0452 (13)0.0506 (12)−0.0086 (11)−0.0034 (12)0.0024 (10)
N50.0407 (11)0.0412 (11)0.0475 (11)0.0039 (9)0.0077 (9)0.0024 (9)
N60.0428 (11)0.0325 (10)0.0419 (10)0.0005 (8)0.0033 (9)0.0017 (8)
O10.1099 (19)0.0995 (18)0.0737 (14)0.0292 (14)0.0117 (13)−0.0411 (13)
O20.0649 (12)0.0634 (12)0.0513 (10)−0.0039 (10)0.0160 (9)−0.0018 (9)
O30.0559 (11)0.0576 (12)0.0617 (11)0.0011 (9)0.0039 (10)−0.0098 (8)
Geometric parameters (Å, °) top
Co—N4i2.069 (2)C8—C91.431 (4)
Co—N52.105 (2)C8—H80.9300
Co—N62.1116 (18)C9—C111.402 (4)
Co—N22.123 (2)C9—C101.407 (3)
Co—O22.1466 (17)C10—N61.357 (3)
Co—O32.2268 (18)C11—C121.350 (4)
C1—C21.490 (4)C11—H110.9300
C1—H1A0.9600C12—C131.395 (4)
C1—H1B0.9600C12—H120.9300
C1—H1C0.9600C13—N61.340 (3)
C2—N51.333 (3)C13—C141.495 (3)
C2—C31.409 (4)C14—H14A0.9600
C3—C41.359 (4)C14—H14B0.9600
C3—H30.9300C14—H14C0.9600
C4—C51.393 (4)C15—N21.139 (3)
C4—H40.9300C15—N31.293 (3)
C5—C61.408 (3)C16—N41.132 (3)
C5—C71.428 (4)C16—N31.302 (3)
C6—N51.365 (3)N1—O11.223 (3)
C6—C101.433 (3)N1—O31.264 (3)
C7—C81.334 (4)N1—O21.268 (3)
C7—H70.9300N4—Coii2.069 (2)
N4i—Co—N596.01 (8)C7—C8—H8119.2
N4i—Co—N691.33 (8)C9—C8—H8119.2
N5—Co—N679.97 (7)C11—C9—C10116.5 (2)
N4i—Co—N2172.30 (8)C11—C9—C8124.3 (3)
N5—Co—N286.78 (8)C10—C9—C8119.2 (3)
N6—Co—N296.23 (8)N6—C10—C9122.7 (2)
N4i—Co—O290.87 (8)N6—C10—C6117.84 (19)
N5—Co—O2167.53 (7)C9—C10—C6119.4 (2)
N6—Co—O2110.34 (7)C12—C11—C9120.4 (2)
N2—Co—O285.14 (7)C12—C11—H11119.8
N4i—Co—O388.35 (8)C9—C11—H11119.8
N5—Co—O3110.97 (7)C11—C12—C13120.3 (3)
N6—Co—O3169.04 (7)C11—C12—H12119.9
N2—Co—O383.96 (8)C13—C12—H12119.9
O2—Co—O358.71 (7)N6—C13—C12121.2 (2)
C2—C1—H1A109.5N6—C13—C14118.2 (2)
C2—C1—H1B109.5C12—C13—C14120.6 (2)
H1A—C1—H1B109.5C13—C14—H14A109.5
C2—C1—H1C109.5C13—C14—H14B109.5
H1A—C1—H1C109.5H14A—C14—H14B109.5
H1B—C1—H1C109.5C13—C14—H14C109.5
N5—C2—C3120.4 (3)H14A—C14—H14C109.5
N5—C2—C1118.3 (2)H14B—C14—H14C109.5
C3—C2—C1121.3 (2)N2—C15—N3174.2 (3)
C4—C3—C2120.3 (3)N4—C16—N3172.5 (3)
C4—C3—H3119.9O1—N1—O3122.6 (3)
C2—C3—H3119.9O1—N1—O2121.6 (2)
C3—C4—C5120.6 (3)O3—N1—O2115.82 (19)
C3—C4—H4119.7C15—N2—Co137.9 (2)
C5—C4—H4119.7C15—N3—C16121.1 (2)
C4—C5—C6116.7 (3)C16—N4—Coii169.3 (2)
C4—C5—C7123.7 (3)C2—N5—C6119.5 (2)
C6—C5—C7119.6 (3)C2—N5—Co128.54 (17)
N5—C6—C5122.5 (2)C6—N5—Co111.90 (15)
N5—C6—C10118.09 (19)C13—N6—C10118.8 (2)
C5—C6—C10119.4 (2)C13—N6—Co129.13 (16)
C8—C7—C5120.8 (3)C10—N6—Co112.11 (14)
C8—C7—H7119.6N1—O2—Co94.46 (14)
C5—C7—H7119.6N1—O3—Co90.83 (14)
C7—C8—C9121.6 (3)
N5—C2—C3—C4−0.1 (4)N2—Co—N5—C281.6 (2)
C1—C2—C3—C4179.4 (3)O2—Co—N5—C231.9 (5)
C2—C3—C4—C51.1 (4)O3—Co—N5—C2−0.7 (2)
C3—C4—C5—C6−0.9 (4)N4i—Co—N5—C692.44 (16)
C3—C4—C5—C7179.5 (3)N6—Co—N5—C62.15 (14)
C4—C5—C6—N5−0.4 (4)N2—Co—N5—C6−94.76 (16)
C7—C5—C6—N5179.3 (2)O2—Co—N5—C6−144.4 (3)
C4—C5—C6—C10179.0 (2)O3—Co—N5—C6−177.03 (14)
C7—C5—C6—C10−1.4 (3)C12—C13—N6—C10−2.6 (3)
C4—C5—C7—C8−178.3 (3)C14—C13—N6—C10176.3 (2)
C6—C5—C7—C82.1 (4)C12—C13—N6—Co177.26 (18)
C5—C7—C8—C9−1.3 (4)C14—C13—N6—Co−3.8 (3)
C7—C8—C9—C11−178.9 (3)C9—C10—N6—C132.3 (3)
C7—C8—C9—C10−0.1 (4)C6—C10—N6—C13−177.1 (2)
C11—C9—C10—N60.3 (3)C9—C10—N6—Co−177.60 (17)
C8—C9—C10—N6−178.6 (2)C6—C10—N6—Co3.1 (2)
C11—C9—C10—C6179.6 (2)N4i—Co—N6—C1381.5 (2)
C8—C9—C10—C60.8 (3)N5—Co—N6—C13177.3 (2)
N5—C6—C10—N6−1.3 (3)N2—Co—N6—C13−97.05 (19)
C5—C6—C10—N6179.4 (2)O2—Co—N6—C13−9.9 (2)
N5—C6—C10—C9179.4 (2)O3—Co—N6—C13−6.7 (5)
C5—C6—C10—C90.0 (3)N4i—Co—N6—C10−98.67 (15)
C10—C9—C11—C12−2.6 (4)N5—Co—N6—C10−2.80 (15)
C8—C9—C11—C12176.2 (3)N2—Co—N6—C1082.81 (16)
C9—C11—C12—C132.4 (4)O2—Co—N6—C10169.91 (14)
C11—C12—C13—N60.3 (4)O3—Co—N6—C10173.2 (3)
C11—C12—C13—C14−178.6 (3)O1—N1—O2—Co176.7 (2)
N5—Co—N2—C15−89.6 (3)O3—N1—O2—Co−4.1 (2)
N6—Co—N2—C15−169.1 (3)N4i—Co—O2—N190.02 (15)
O2—Co—N2—C1580.9 (3)N5—Co—O2—N1−33.6 (4)
O3—Co—N2—C1521.9 (3)N6—Co—O2—N1−178.24 (13)
C3—C2—N5—C6−1.2 (4)N2—Co—O2—N1−83.39 (15)
C1—C2—N5—C6179.3 (2)O3—Co—O2—N12.48 (13)
C3—C2—N5—Co−177.25 (19)O1—N1—O3—Co−176.8 (2)
C1—C2—N5—Co3.2 (3)O2—N1—O3—Co4.0 (2)
C5—C6—N5—C21.4 (3)N4i—Co—O3—N1−94.50 (14)
C10—C6—N5—C2−177.9 (2)N5—Co—O3—N1169.70 (13)
C5—C6—N5—Co178.11 (18)N6—Co—O3—N1−6.0 (4)
C10—C6—N5—Co−1.2 (2)N2—Co—O3—N185.49 (14)
N4i—Co—N5—C2−91.2 (2)O2—Co—O3—N1−2.48 (13)
N6—Co—N5—C2178.5 (2)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14A···O20.962.453.190 (4)133
C12—H12···O1iii0.932.543.455 (4)169
C7—H7···O2iv0.932.483.388 (3)167
Symmetry codes: (iii) −x−1/2, y−1/2, −z+1/2; (iv) x+1/2, −y+3/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Co—N4i2.069 (2)Co—N22.123 (2)
Co—N52.105 (2)Co—O22.1466 (17)
Co—N62.1116 (18)Co—O32.2268 (18)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14A···O20.962.453.190 (4)133
C12—H12···O1ii0.932.543.455 (4)169
C7—H7···O2iii0.932.483.388 (3)167
Symmetry codes: (ii) −x−1/2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2.
Acknowledgements top

The authors acknowledge support from the Natural Science Foundation of China (NSFC) (grant No. 20401003) and the Excellent Young Scholars Research Fund of the Beijing Institute of Technology (grant No. 000Y07–26).

references
References top

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