Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030279/hy2068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030279/hy2068Isup2.hkl |
CCDC reference: 654815
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).
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.
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).
For general background, see: Batten & Murray (2003); Burčák et al. (2004); Potočňák et al. (2002); Vangdal et al. (2002); Wu et al. (2003).
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.
[Co(C2N3)(NO3)(C14H12N2)] | F(000) = 804 |
Mr = 395.25 | Dx = 1.583 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 16421 reflections |
a = 7.3481 (15) Å | θ = 3.4–27.5° |
b = 13.925 (3) Å | µ = 1.07 mm−1 |
c = 16.531 (3) Å | T = 153 K |
β = 101.42 (3)° | Block, red |
V = 1658.0 (6) Å3 | 0.20 × 0.15 × 0.10 mm |
Z = 4 |
Bruker KappaCCD area-detector diffractometer | 3784 independent reflections |
Radiation source: sealed tube | 2450 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 27.5°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.815, Tmax = 0.901 | k = −18→18 |
7407 measured reflections | l = −21→21 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
3784 reflections | (Δ/σ)max < 0.001 |
237 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Co(C2N3)(NO3)(C14H12N2)] | V = 1658.0 (6) Å3 |
Mr = 395.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.3481 (15) Å | µ = 1.07 mm−1 |
b = 13.925 (3) Å | T = 153 K |
c = 16.531 (3) Å | 0.20 × 0.15 × 0.10 mm |
β = 101.42 (3)° |
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 = 0.901 | Rint = 0.022 |
7407 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.44 e Å−3 |
3784 reflections | Δρmin = −0.32 e Å−3 |
237 parameters |
x | y | z | Uiso*/Ueq | ||
Co | 0.17457 (4) | 0.86364 (2) | 0.203521 (18) | 0.03941 (12) | |
C1 | 0.5626 (4) | 0.9754 (2) | 0.1736 (2) | 0.0718 (8) | |
H1A | 0.5790 | 0.9478 | 0.2278 | 0.108* | |
H1B | 0.4717 | 1.0257 | 0.1684 | 0.108* | |
H1C | 0.6785 | 1.0013 | 0.1653 | 0.108* | |
C2 | 0.4981 (3) | 0.8998 (2) | 0.11066 (16) | 0.0550 (6) | |
C3 | 0.5930 (4) | 0.8817 (2) | 0.0460 (2) | 0.0689 (8) | |
H3 | 0.6973 | 0.9178 | 0.0419 | 0.083* | |
C4 | 0.5327 (4) | 0.8119 (2) | −0.01033 (18) | 0.0710 (9) | |
H4 | 0.5974 | 0.7997 | −0.0522 | 0.085* | |
C5 | 0.3748 (4) | 0.75839 (19) | −0.00591 (15) | 0.0564 (7) | |
C6 | 0.2852 (3) | 0.77972 (16) | 0.05976 (13) | 0.0432 (5) | |
C7 | 0.3025 (5) | 0.6845 (2) | −0.06323 (16) | 0.0685 (9) | |
H7 | 0.3640 | 0.6690 | −0.1055 | 0.082* | |
C8 | 0.1478 (5) | 0.63745 (19) | −0.05684 (16) | 0.0683 (9) | |
H8 | 0.1021 | 0.5905 | −0.0956 | 0.082* | |
C9 | 0.0506 (4) | 0.65740 (17) | 0.00819 (15) | 0.0544 (7) | |
C10 | 0.1201 (3) | 0.72828 (15) | 0.06690 (13) | 0.0422 (5) | |
C11 | −0.1105 (4) | 0.60941 (19) | 0.01902 (18) | 0.0640 (8) | |
H11 | −0.1647 | 0.5638 | −0.0194 | 0.077* | |
C12 | −0.1875 (4) | 0.62898 (18) | 0.08485 (19) | 0.0644 (8) | |
H12 | −0.2918 | 0.5951 | 0.0927 | 0.077* | |
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 | −0.2027 | 0.7884 | 0.2219 | 0.101* | |
H14B | −0.1148 | 0.6936 | 0.2635 | 0.101* | |
H14C | −0.3144 | 0.6919 | 0.2081 | 0.101* | |
C15 | 0.0563 (3) | 1.05722 (17) | 0.12152 (13) | 0.0429 (5) | |
C16 | 0.1296 (4) | 1.20845 (18) | 0.16598 (16) | 0.0506 (6) | |
N1 | 0.1251 (3) | 0.97749 (16) | 0.32013 (12) | 0.0586 (6) | |
N2 | 0.0411 (3) | 0.97627 (14) | 0.12771 (12) | 0.0497 (5) | |
N3 | 0.0722 (4) | 1.14768 (15) | 0.10658 (14) | 0.0778 (8) | |
N4 | 0.1824 (3) | 1.26809 (16) | 0.21111 (13) | 0.0608 (6) | |
N5 | 0.3482 (3) | 0.84869 (13) | 0.11715 (12) | 0.0433 (5) | |
N6 | 0.0384 (2) | 0.74995 (12) | 0.13134 (11) | 0.0398 (4) | |
O1 | 0.0919 (3) | 1.03262 (17) | 0.37294 (13) | 0.0953 (8) | |
O2 | 0.0128 (3) | 0.91132 (14) | 0.29068 (11) | 0.0593 (5) | |
O3 | 0.2731 (3) | 0.98178 (13) | 0.29219 (11) | 0.0595 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0450 (2) | 0.03348 (18) | 0.03892 (18) | −0.00008 (14) | 0.00622 (13) | −0.00058 (13) |
C1 | 0.0499 (17) | 0.0674 (19) | 0.098 (2) | −0.0148 (14) | 0.0133 (16) | −0.0054 (17) |
C2 | 0.0438 (15) | 0.0568 (15) | 0.0646 (16) | 0.0035 (12) | 0.0112 (13) | 0.0095 (13) |
C3 | 0.0508 (17) | 0.079 (2) | 0.082 (2) | 0.0055 (15) | 0.0261 (15) | 0.0217 (17) |
C4 | 0.076 (2) | 0.084 (2) | 0.0608 (18) | 0.0249 (18) | 0.0327 (16) | 0.0142 (16) |
C5 | 0.0659 (17) | 0.0580 (16) | 0.0472 (14) | 0.0186 (14) | 0.0160 (13) | 0.0087 (12) |
C6 | 0.0515 (14) | 0.0397 (12) | 0.0372 (12) | 0.0117 (11) | 0.0063 (11) | 0.0031 (10) |
C7 | 0.105 (3) | 0.0627 (19) | 0.0404 (14) | 0.0280 (18) | 0.0199 (16) | −0.0004 (13) |
C8 | 0.111 (3) | 0.0458 (16) | 0.0421 (14) | 0.0168 (17) | −0.0005 (16) | −0.0048 (12) |
C9 | 0.077 (2) | 0.0366 (13) | 0.0416 (13) | 0.0102 (12) | −0.0073 (13) | 0.0002 (10) |
C10 | 0.0514 (14) | 0.0315 (11) | 0.0399 (12) | 0.0059 (10) | −0.0004 (10) | 0.0000 (9) |
C11 | 0.079 (2) | 0.0379 (14) | 0.0621 (17) | −0.0032 (14) | −0.0180 (16) | −0.0042 (12) |
C12 | 0.0582 (17) | 0.0427 (15) | 0.084 (2) | −0.0113 (13) | −0.0060 (16) | 0.0039 (14) |
C13 | 0.0478 (15) | 0.0369 (13) | 0.0602 (15) | −0.0010 (11) | 0.0001 (12) | 0.0078 (11) |
C14 | 0.0626 (18) | 0.0605 (18) | 0.084 (2) | −0.0099 (14) | 0.0253 (16) | 0.0085 (15) |
C15 | 0.0458 (14) | 0.0410 (14) | 0.0391 (12) | −0.0005 (10) | 0.0018 (10) | 0.0000 (10) |
C16 | 0.0627 (16) | 0.0350 (13) | 0.0492 (14) | −0.0038 (12) | −0.0003 (12) | 0.0057 (11) |
N1 | 0.0713 (17) | 0.0570 (14) | 0.0440 (12) | 0.0149 (12) | 0.0030 (12) | −0.0053 (10) |
N2 | 0.0554 (13) | 0.0367 (12) | 0.0545 (12) | 0.0012 (9) | 0.0051 (10) | 0.0024 (9) |
N3 | 0.128 (2) | 0.0393 (13) | 0.0535 (14) | −0.0122 (13) | −0.0121 (15) | 0.0048 (11) |
N4 | 0.0799 (17) | 0.0452 (13) | 0.0506 (12) | −0.0086 (11) | −0.0034 (12) | 0.0024 (10) |
N5 | 0.0407 (11) | 0.0412 (11) | 0.0475 (11) | 0.0039 (9) | 0.0077 (9) | 0.0024 (9) |
N6 | 0.0428 (11) | 0.0325 (10) | 0.0419 (10) | 0.0005 (8) | 0.0033 (9) | 0.0017 (8) |
O1 | 0.1099 (19) | 0.0995 (18) | 0.0737 (14) | 0.0292 (14) | 0.0117 (13) | −0.0411 (13) |
O2 | 0.0649 (12) | 0.0634 (12) | 0.0513 (10) | −0.0039 (10) | 0.0160 (9) | −0.0018 (9) |
O3 | 0.0559 (11) | 0.0576 (12) | 0.0617 (11) | 0.0011 (9) | 0.0039 (10) | −0.0098 (8) |
Co—N4i | 2.069 (2) | C8—C9 | 1.431 (4) |
Co—N5 | 2.105 (2) | C8—H8 | 0.9300 |
Co—N6 | 2.1116 (18) | C9—C11 | 1.402 (4) |
Co—N2 | 2.123 (2) | C9—C10 | 1.407 (3) |
Co—O2 | 2.1466 (17) | C10—N6 | 1.357 (3) |
Co—O3 | 2.2268 (18) | C11—C12 | 1.350 (4) |
C1—C2 | 1.490 (4) | C11—H11 | 0.9300 |
C1—H1A | 0.9600 | C12—C13 | 1.395 (4) |
C1—H1B | 0.9600 | C12—H12 | 0.9300 |
C1—H1C | 0.9600 | C13—N6 | 1.340 (3) |
C2—N5 | 1.333 (3) | C13—C14 | 1.495 (3) |
C2—C3 | 1.409 (4) | C14—H14A | 0.9600 |
C3—C4 | 1.359 (4) | C14—H14B | 0.9600 |
C3—H3 | 0.9300 | C14—H14C | 0.9600 |
C4—C5 | 1.393 (4) | C15—N2 | 1.139 (3) |
C4—H4 | 0.9300 | C15—N3 | 1.293 (3) |
C5—C6 | 1.408 (3) | C16—N4 | 1.132 (3) |
C5—C7 | 1.428 (4) | C16—N3 | 1.302 (3) |
C6—N5 | 1.365 (3) | N1—O1 | 1.223 (3) |
C6—C10 | 1.433 (3) | N1—O3 | 1.264 (3) |
C7—C8 | 1.334 (4) | N1—O2 | 1.268 (3) |
C7—H7 | 0.9300 | N4—Coii | 2.069 (2) |
N4i—Co—N5 | 96.01 (8) | C7—C8—H8 | 119.2 |
N4i—Co—N6 | 91.33 (8) | C9—C8—H8 | 119.2 |
N5—Co—N6 | 79.97 (7) | C11—C9—C10 | 116.5 (2) |
N4i—Co—N2 | 172.30 (8) | C11—C9—C8 | 124.3 (3) |
N5—Co—N2 | 86.78 (8) | C10—C9—C8 | 119.2 (3) |
N6—Co—N2 | 96.23 (8) | N6—C10—C9 | 122.7 (2) |
N4i—Co—O2 | 90.87 (8) | N6—C10—C6 | 117.84 (19) |
N5—Co—O2 | 167.53 (7) | C9—C10—C6 | 119.4 (2) |
N6—Co—O2 | 110.34 (7) | C12—C11—C9 | 120.4 (2) |
N2—Co—O2 | 85.14 (7) | C12—C11—H11 | 119.8 |
N4i—Co—O3 | 88.35 (8) | C9—C11—H11 | 119.8 |
N5—Co—O3 | 110.97 (7) | C11—C12—C13 | 120.3 (3) |
N6—Co—O3 | 169.04 (7) | C11—C12—H12 | 119.9 |
N2—Co—O3 | 83.96 (8) | C13—C12—H12 | 119.9 |
O2—Co—O3 | 58.71 (7) | N6—C13—C12 | 121.2 (2) |
C2—C1—H1A | 109.5 | N6—C13—C14 | 118.2 (2) |
C2—C1—H1B | 109.5 | C12—C13—C14 | 120.6 (2) |
H1A—C1—H1B | 109.5 | C13—C14—H14A | 109.5 |
C2—C1—H1C | 109.5 | C13—C14—H14B | 109.5 |
H1A—C1—H1C | 109.5 | H14A—C14—H14B | 109.5 |
H1B—C1—H1C | 109.5 | C13—C14—H14C | 109.5 |
N5—C2—C3 | 120.4 (3) | H14A—C14—H14C | 109.5 |
N5—C2—C1 | 118.3 (2) | H14B—C14—H14C | 109.5 |
C3—C2—C1 | 121.3 (2) | N2—C15—N3 | 174.2 (3) |
C4—C3—C2 | 120.3 (3) | N4—C16—N3 | 172.5 (3) |
C4—C3—H3 | 119.9 | O1—N1—O3 | 122.6 (3) |
C2—C3—H3 | 119.9 | O1—N1—O2 | 121.6 (2) |
C3—C4—C5 | 120.6 (3) | O3—N1—O2 | 115.82 (19) |
C3—C4—H4 | 119.7 | C15—N2—Co | 137.9 (2) |
C5—C4—H4 | 119.7 | C15—N3—C16 | 121.1 (2) |
C4—C5—C6 | 116.7 (3) | C16—N4—Coii | 169.3 (2) |
C4—C5—C7 | 123.7 (3) | C2—N5—C6 | 119.5 (2) |
C6—C5—C7 | 119.6 (3) | C2—N5—Co | 128.54 (17) |
N5—C6—C5 | 122.5 (2) | C6—N5—Co | 111.90 (15) |
N5—C6—C10 | 118.09 (19) | C13—N6—C10 | 118.8 (2) |
C5—C6—C10 | 119.4 (2) | C13—N6—Co | 129.13 (16) |
C8—C7—C5 | 120.8 (3) | C10—N6—Co | 112.11 (14) |
C8—C7—H7 | 119.6 | N1—O2—Co | 94.46 (14) |
C5—C7—H7 | 119.6 | N1—O3—Co | 90.83 (14) |
C7—C8—C9 | 121.6 (3) | ||
N5—C2—C3—C4 | −0.1 (4) | N2—Co—N5—C2 | 81.6 (2) |
C1—C2—C3—C4 | 179.4 (3) | O2—Co—N5—C2 | 31.9 (5) |
C2—C3—C4—C5 | 1.1 (4) | O3—Co—N5—C2 | −0.7 (2) |
C3—C4—C5—C6 | −0.9 (4) | N4i—Co—N5—C6 | 92.44 (16) |
C3—C4—C5—C7 | 179.5 (3) | N6—Co—N5—C6 | 2.15 (14) |
C4—C5—C6—N5 | −0.4 (4) | N2—Co—N5—C6 | −94.76 (16) |
C7—C5—C6—N5 | 179.3 (2) | O2—Co—N5—C6 | −144.4 (3) |
C4—C5—C6—C10 | 179.0 (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—C10 | 176.3 (2) |
C6—C5—C7—C8 | 2.1 (4) | C12—C13—N6—Co | 177.26 (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—C13 | 2.3 (3) |
C7—C8—C9—C10 | −0.1 (4) | C6—C10—N6—C13 | −177.1 (2) |
C11—C9—C10—N6 | 0.3 (3) | C9—C10—N6—Co | −177.60 (17) |
C8—C9—C10—N6 | −178.6 (2) | C6—C10—N6—Co | 3.1 (2) |
C11—C9—C10—C6 | 179.6 (2) | N4i—Co—N6—C13 | 81.5 (2) |
C8—C9—C10—C6 | 0.8 (3) | N5—Co—N6—C13 | 177.3 (2) |
N5—C6—C10—N6 | −1.3 (3) | N2—Co—N6—C13 | −97.05 (19) |
C5—C6—C10—N6 | 179.4 (2) | O2—Co—N6—C13 | −9.9 (2) |
N5—C6—C10—C9 | 179.4 (2) | O3—Co—N6—C13 | −6.7 (5) |
C5—C6—C10—C9 | 0.0 (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—C12 | 176.2 (3) | N2—Co—N6—C10 | 82.81 (16) |
C9—C11—C12—C13 | 2.4 (4) | O2—Co—N6—C10 | 169.91 (14) |
C11—C12—C13—N6 | 0.3 (4) | O3—Co—N6—C10 | 173.2 (3) |
C11—C12—C13—C14 | −178.6 (3) | O1—N1—O2—Co | 176.7 (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—N1 | 90.02 (15) |
O2—Co—N2—C15 | 80.9 (3) | N5—Co—O2—N1 | −33.6 (4) |
O3—Co—N2—C15 | 21.9 (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—C6 | 179.3 (2) | O3—Co—O2—N1 | 2.48 (13) |
C3—C2—N5—Co | −177.25 (19) | O1—N1—O3—Co | −176.8 (2) |
C1—C2—N5—Co | 3.2 (3) | O2—N1—O3—Co | 4.0 (2) |
C5—C6—N5—C2 | 1.4 (3) | N4i—Co—O3—N1 | −94.50 (14) |
C10—C6—N5—C2 | −177.9 (2) | N5—Co—O3—N1 | 169.70 (13) |
C5—C6—N5—Co | 178.11 (18) | N6—Co—O3—N1 | −6.0 (4) |
C10—C6—N5—Co | −1.2 (2) | N2—Co—O3—N1 | 85.49 (14) |
N4i—Co—N5—C2 | −91.2 (2) | O2—Co—O3—N1 | −2.48 (13) |
N6—Co—N5—C2 | 178.5 (2) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14A···O2 | 0.96 | 2.45 | 3.190 (4) | 133 |
C12—H12···O1iii | 0.93 | 2.54 | 3.455 (4) | 169 |
C7—H7···O2iv | 0.93 | 2.48 | 3.388 (3) | 167 |
Symmetry codes: (iii) −x−1/2, y−1/2, −z+1/2; (iv) x+1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C2N3)(NO3)(C14H12N2)] |
Mr | 395.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 153 |
a, b, c (Å) | 7.3481 (15), 13.925 (3), 16.531 (3) |
β (°) | 101.42 (3) |
V (Å3) | 1658.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.07 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker KappaCCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.815, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7407, 3784, 2450 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.098, 0.94 |
No. of reflections | 3784 |
No. of parameters | 237 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.32 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), SHELXTL.
Co—N4i | 2.069 (2) | Co—N2 | 2.123 (2) |
Co—N5 | 2.105 (2) | Co—O2 | 2.1466 (17) |
Co—N6 | 2.1116 (18) | Co—O3 | 2.2268 (18) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14A···O2 | 0.96 | 2.45 | 3.190 (4) | 133 |
C12—H12···O1ii | 0.93 | 2.54 | 3.455 (4) | 169 |
C7—H7···O2iii | 0.93 | 2.48 | 3.388 (3) | 167 |
Symmetry codes: (ii) −x−1/2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
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).