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Acta Cryst. (2004). C60, m520-m522
https://doi.org/10.1107/S0108270104020657
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catena-Poly­[[bis­(quinoxaline-[kappa]N)cobalt(II)]-di-[mu]-dicyan­amido-[kappa]2N1:N5] and catena-poly­[[bis(quinoxaline-[kappa]N)copper(II)]-di-[mu]-dicyan­amido-[kappa]2N1:N5]

J. Luo, B.-S. Liu, X.-G. Zhou, L.-H. Weng, Y.-R. Li and H.-X. Wu
Two new complexes, [Co(C2N3)2(C8H6N2)2], (I), and [Cu(C2N3)2(C8H6N2)2], (II), are reported. They are essentially isomorphous. Complex (I) displays distorted octahedral geometry, with the Co atom coordinated by four dicyan­amide nitrile N atoms [Co-N = 2.098 (3) and 2.104 (3) Å] in the basal plane, along with two monodentate quinoxaline N atoms [Co-N = 2.257 (2) Å] in the apical positions. In complex (II), the Cu atom is surrounded by four dicyan­amide nitrile N atoms [Cu-N = 2.003 (3) and 2.005 (3) Å] in the equatorial plane and two monodentate quinoxaline N atoms [Cu-N = 2.479 (3) Å] in the axial sites, to form a distorted tetragonal-bipyramidal geometry. The metal atoms reside on twofold axes of rotation. Neighbouring metal atoms are connected via double dicyan­amide bridges to form one-dimensional infinite chains. Adjacent chains are then linked by [pi]-[pi] stacking interactions of the quinoxaline mol­ecules, resulting in the formation of a three-dimensional structure.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104020657/sq1171sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020657/sq1171Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020657/sq1171IIsup3.hkl
Contains datablock II

CCDC references: 254909; 254910

Comment top

Dicyanamide coordination polymers have attracted considerable interest because of their novel structural characteristics (Manson et al., 1998; Batten et al., 1999) and fascinating magnetic properties (Manson et al., 1999; Batten et al., 1998). Previous results indicate that the introduction of N-containing conjugated rigid co-ligands, such as pyridine (Luo et al., 2002), 2,2'-bipyridine (Vangdal et al., 2002), 4,4'-bipyridine (Jensen et al., 2002), pyrimidine (Manson et al., 2003), 2,2'-bipyrimidine (Triki et al., 2001) and pyrazine (Jensen et al., 2001) to binary transition metal dicyanamide systems can not only modify the structures, but also adjust the magnetic properties. For example, the binary complex [Mn(C2N3)2] shows a rutile-like structure and weak ferromagnetic ordering below 16 K, while the corresponding pyrazine (pyz) adduct α-[Mn(C2N3)2(pyz)] displays an interpenetrating three-dimensional α-Po-related network structure and behaves as an ordered antiferromagnet at temperatures below 2.7 K (Jensen et al., 2001). To the best of our knowledge, no dicyanamide complex with quinoxaline as co-ligand has been reported to date. In order to gain insight into the influence of the nature of co-ligands on the structure and properties of dicyanamide-type complexes, we report here the syntheses and crystal structures of two new complexes, (I) and (II). \sch

In (I) (Fig. 1), the CoII ion is coordinated to four dicyanamide anions and two quinoxaline ligands to give a distorted octahedral geometry, in which the basal plane is formed by four nitrile N atoms (atoms N3, N3i, N5ii and N5iii) of the dicyanamide anions and the apical positions are occupied by two N atoms (N1 and N1i) from two monodentate quinoxaline molecules [symmetry codes: (i) -x, y, 1/2 - z; (ii) x, y - 1, z; (iii) -x, y - 1, 1/2 - z]. The CoII ions are linked by double dicyanamide anion bridges to form a one-dimensional infinite chain, and π–π stacking interactions between quinoxaline ligands in adjacent chains result in the formation of a three-dimensional structure (Fig. 2).

In (II), the CuII ion is in essentially the same coordination environment as the Co, with the only notable difference being the Jahn-Teller distortion of the former. As observed in (I), the CuII ions are joined by double dicyanamide anion bridges to form a one-dimensional chain, and a similar three-dimensional structure (Fig. 3) is also generated via quinoxaline π–π interactions between adjacent chains.

In (I), the Co—N(quinoxaline) distances [2.257 (2) Å] are slightly longer than the Co—N(dicyanamide) distances [2.098 (3)–2.104 (3) Å; Table 1]. These values are similar to the corresponding distances observed in other cobalt dicyanamide complexes (Jensen et al., 2002, 2001).

In (II), the axial Cu—N(quinoxaline) distances [2.479 (3) Å] are obviously longer than the basal Cu—N(dicyanamide) distances [2.003 (3)–2.005 (3) Å; Table 2]. This situation is quite different from that found in [Cu(C2N3)2(ampym)2] (ampym is 2-aminopyrimidine) and [Cu(C2N3)2(pm)]n(CH3CN)n (pm is pyrimidine) (van Albada et al., 2000; Riggio et al., 2001), in which the Cu atoms are coordinated by the N atoms of the neutral rigid co-ligands in the basal plane, and the apical sites are totally occupied by dicyanamide nitrile N atoms.

In (I), the N—Co—N angles (two neighbouring N atoms) are in the range 86.76 (14)–93.83 (9)°. Analogous to (I), the corresponding N—Cu—N angles in (II) are in the range 86.84 (9)–93.72 (10)°, indicating that the distortion of geometry in (I) and (II) is not serious.

In both complexes, the bond distances and angles of the quinoxaline ring [1.299 (4)–1.420 (4) Å and 114.9 (3)–123.4 (3)°] are in the normal ranges observed in phenazine-containing complexes (Kutasi et al., 2002). Each dicyanamide is almost planar. Two different bond distances and angles are found: C≡N triple-bond distances [1.140 (4)–1.148 (3) Å] and C—N single-bond distances [1.300 (4)–1.301 (4) Å], together with C—N—C angles [119.9 (2)–120.2 (2)°] and N—C—N angles [173.7 (3)–175.6 (3)°]. These values are in good agreement with those found in other dicyanamide complexes (Luo et al., 2002; Vangdal et al., 2002; Manson et al., 2003).

Experimental top

An aqueous solution (4 ml) of quinoxaline (0.30 mmol, 39.05 mg) was added to an aqueous solution (4 ml) of cobalt nitrate (0.30 mmol, 87.31 mg) and stirred for 2 min. To the mixed solution was added dropwise an aqueous solution (2 ml) of sodium dicyanamide (0.30 mmol, 26.71 mg). An orange precipitate was immediately formed and the mixture was then warmed slowly until the precipitate had dissolved. One week later, orange block crystals of (I) were isolated in 57% yield. Analysis, calculated for C20H12N10Co: C 53.22, H 2.68, N 31.03%; found: C 53.53, H 2.97, N 31.37%. Complex (II) was prepared by a similar manner in 21% yield. Analysis, calculated for C20H12N10Cu: C 52.69, H 2.65, N 30.72%; ound C 52.94, H 2.87, N 30.95%.

Refinement top

In both cases, all H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C). Please check amended text.

Structure description top

Dicyanamide coordination polymers have attracted considerable interest because of their novel structural characteristics (Manson et al., 1998; Batten et al., 1999) and fascinating magnetic properties (Manson et al., 1999; Batten et al., 1998). Previous results indicate that the introduction of N-containing conjugated rigid co-ligands, such as pyridine (Luo et al., 2002), 2,2'-bipyridine (Vangdal et al., 2002), 4,4'-bipyridine (Jensen et al., 2002), pyrimidine (Manson et al., 2003), 2,2'-bipyrimidine (Triki et al., 2001) and pyrazine (Jensen et al., 2001) to binary transition metal dicyanamide systems can not only modify the structures, but also adjust the magnetic properties. For example, the binary complex [Mn(C2N3)2] shows a rutile-like structure and weak ferromagnetic ordering below 16 K, while the corresponding pyrazine (pyz) adduct α-[Mn(C2N3)2(pyz)] displays an interpenetrating three-dimensional α-Po-related network structure and behaves as an ordered antiferromagnet at temperatures below 2.7 K (Jensen et al., 2001). To the best of our knowledge, no dicyanamide complex with quinoxaline as co-ligand has been reported to date. In order to gain insight into the influence of the nature of co-ligands on the structure and properties of dicyanamide-type complexes, we report here the syntheses and crystal structures of two new complexes, (I) and (II). \sch

In (I) (Fig. 1), the CoII ion is coordinated to four dicyanamide anions and two quinoxaline ligands to give a distorted octahedral geometry, in which the basal plane is formed by four nitrile N atoms (atoms N3, N3i, N5ii and N5iii) of the dicyanamide anions and the apical positions are occupied by two N atoms (N1 and N1i) from two monodentate quinoxaline molecules [symmetry codes: (i) -x, y, 1/2 - z; (ii) x, y - 1, z; (iii) -x, y - 1, 1/2 - z]. The CoII ions are linked by double dicyanamide anion bridges to form a one-dimensional infinite chain, and π–π stacking interactions between quinoxaline ligands in adjacent chains result in the formation of a three-dimensional structure (Fig. 2).

In (II), the CuII ion is in essentially the same coordination environment as the Co, with the only notable difference being the Jahn-Teller distortion of the former. As observed in (I), the CuII ions are joined by double dicyanamide anion bridges to form a one-dimensional chain, and a similar three-dimensional structure (Fig. 3) is also generated via quinoxaline π–π interactions between adjacent chains.

In (I), the Co—N(quinoxaline) distances [2.257 (2) Å] are slightly longer than the Co—N(dicyanamide) distances [2.098 (3)–2.104 (3) Å; Table 1]. These values are similar to the corresponding distances observed in other cobalt dicyanamide complexes (Jensen et al., 2002, 2001).

In (II), the axial Cu—N(quinoxaline) distances [2.479 (3) Å] are obviously longer than the basal Cu—N(dicyanamide) distances [2.003 (3)–2.005 (3) Å; Table 2]. This situation is quite different from that found in [Cu(C2N3)2(ampym)2] (ampym is 2-aminopyrimidine) and [Cu(C2N3)2(pm)]n(CH3CN)n (pm is pyrimidine) (van Albada et al., 2000; Riggio et al., 2001), in which the Cu atoms are coordinated by the N atoms of the neutral rigid co-ligands in the basal plane, and the apical sites are totally occupied by dicyanamide nitrile N atoms.

In (I), the N—Co—N angles (two neighbouring N atoms) are in the range 86.76 (14)–93.83 (9)°. Analogous to (I), the corresponding N—Cu—N angles in (II) are in the range 86.84 (9)–93.72 (10)°, indicating that the distortion of geometry in (I) and (II) is not serious.

In both complexes, the bond distances and angles of the quinoxaline ring [1.299 (4)–1.420 (4) Å and 114.9 (3)–123.4 (3)°] are in the normal ranges observed in phenazine-containing complexes (Kutasi et al., 2002). Each dicyanamide is almost planar. Two different bond distances and angles are found: C≡N triple-bond distances [1.140 (4)–1.148 (3) Å] and C—N single-bond distances [1.300 (4)–1.301 (4) Å], together with C—N—C angles [119.9 (2)–120.2 (2)°] and N—C—N angles [173.7 (3)–175.6 (3)°]. These values are in good agreement with those found in other dicyanamide complexes (Luo et al., 2002; Vangdal et al., 2002; Manson et al., 2003).

Computing details top

For both compounds, data collection: SMART APEX (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the one-dimensional chain in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. [Symmetry codes: (i) -x, y, 1/2 - z; (ii) x, y - 1, z; (iii) -x, y - 1, 1/2 - z]. Compound (II) is essentially isostructural.
[Figure 2] Fig. 2. The three-dimensional network formed via quinoxaline π–π interactions, viewed along the b axis.
[Figure 3] Fig. 3. A view along the c axis, emphasizing the quinoxaline π–π interactions.
(I) catena-Poly[[bis(quinoxaline-κN)cobalt(II)]-di-(µ-dicyanamide-κ2N1:N5)] top
Crystal data top
[Co(C2N3)2(C8H6N2)2]F(000) = 916
Mr = 451.33Dx = 1.598 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 17.598 (5) ÅCell parameters from 932 reflections
b = 7.374 (2) Åθ = 2.4–27.1°
c = 14.771 (4) ŵ = 0.95 mm−1
β = 101.894 (4)°T = 293 K
V = 1875.7 (9) Å3Block, orange
Z = 40.10 × 0.05 × 0.02 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2036 independent reflections
Radiation source: fine-focus sealed tube1546 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
Detector resolution: 0 pixels mm-1θmax = 27.0°, θmin = 2.4°
φ and ω scansh = −17→22
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −9→9
Tmin = 0.911, Tmax = 0.981l = −18→12
4491 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0435P)2 + 1.4128P]
where P = (Fo2 + 2Fc2)/3
2036 reflections(Δ/σ)max < 0.001
141 parametersΔρmax = 0.35 e Å−3
0 restraintsΔρmin = −0.23 e Å−3
Crystal data top
[Co(C2N3)2(C8H6N2)2]V = 1875.7 (9) Å3
Mr = 451.33Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.598 (5) ŵ = 0.95 mm−1
b = 7.374 (2) ÅT = 293 K
c = 14.771 (4) Å0.10 × 0.05 × 0.02 mm
β = 101.894 (4)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2036 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1546 reflections with I > 2σ(I)
Tmin = 0.911, Tmax = 0.981Rint = 0.040
4491 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.07Δρmax = 0.35 e Å−3
2036 reflectionsΔρmin = −0.23 e Å−3
141 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
xyzUiso*/Ueq
Co10.00000.38345 (7)0.25000.02737 (18)
N10.11641 (13)0.3799 (3)0.20844 (15)0.0311 (5)
N20.24990 (16)0.3720 (4)0.12992 (18)0.0495 (7)
N3−0.03195 (15)0.5902 (3)0.15201 (17)0.0375 (6)
N4−0.04773 (16)0.8840 (3)0.07377 (15)0.0406 (6)
N5−0.03493 (15)1.1778 (3)0.15142 (17)0.0365 (6)
C10.18943 (16)0.3834 (4)0.26355 (18)0.0311 (6)
C20.19989 (18)0.3909 (4)0.36035 (19)0.0373 (7)
H20.15700.39090.38800.045*
C30.27270 (19)0.3981 (5)0.4137 (2)0.0458 (8)
H30.27890.40580.47760.055*
C40.33830 (19)0.3944 (5)0.3743 (2)0.0539 (9)
H40.38760.39810.41200.065*
C50.3302 (2)0.3853 (5)0.2810 (2)0.0543 (9)
H50.37410.38220.25510.065*
C60.25588 (18)0.3805 (4)0.2230 (2)0.0387 (7)
C70.1796 (2)0.3667 (5)0.0804 (2)0.0474 (8)
H70.17310.35930.01640.057*
C80.11320 (18)0.3718 (4)0.1191 (2)0.0394 (7)
H80.06470.36920.07950.047*
C9−0.03907 (16)0.7321 (4)0.11942 (18)0.0285 (7)
C10−0.04069 (17)1.0374 (4)0.11826 (19)0.0300 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0331 (3)0.0181 (3)0.0310 (3)0.0000.0066 (2)0.000
N10.0344 (13)0.0280 (12)0.0313 (12)−0.0025 (11)0.0078 (10)−0.0005 (10)
N20.0457 (17)0.067 (2)0.0403 (15)−0.0120 (16)0.0186 (12)−0.0055 (15)
N30.0463 (16)0.0265 (14)0.0397 (14)−0.0002 (11)0.0085 (12)0.0023 (11)
N40.0679 (18)0.0242 (12)0.0271 (12)−0.0025 (13)0.0038 (11)0.0005 (11)
N50.0440 (16)0.0263 (13)0.0392 (15)−0.0044 (11)0.0084 (12)−0.0041 (11)
C10.0341 (15)0.0256 (14)0.0343 (14)−0.0027 (13)0.0088 (11)−0.0009 (13)
C20.0376 (16)0.0392 (17)0.0360 (16)−0.0010 (15)0.0093 (12)−0.0030 (14)
C30.0418 (18)0.058 (2)0.0353 (16)0.0020 (17)0.0028 (13)−0.0032 (16)
C40.0317 (17)0.079 (3)0.0487 (19)−0.0043 (19)0.0016 (14)−0.009 (2)
C50.0331 (17)0.080 (3)0.053 (2)−0.004 (2)0.0164 (15)−0.010 (2)
C60.0384 (16)0.0411 (17)0.0384 (16)−0.0061 (16)0.0121 (13)−0.0032 (16)
C70.053 (2)0.063 (2)0.0292 (15)−0.0110 (19)0.0139 (14)−0.0011 (17)
C80.0418 (17)0.0421 (18)0.0339 (15)−0.0081 (16)0.0072 (13)−0.0015 (15)
C90.0332 (17)0.0280 (15)0.0240 (15)−0.0002 (12)0.0051 (12)−0.0060 (12)
C100.0324 (17)0.0305 (16)0.0266 (16)0.0002 (12)0.0052 (13)0.0046 (12)
Geometric parameters (Å, º) top
Co1—N3i2.098 (3)N5—Co1iv2.104 (3)
Co1—N32.098 (3)C1—C21.405 (4)
Co1—N5ii2.104 (3)C1—C61.420 (4)
Co1—N5iii2.104 (3)C2—C31.360 (4)
Co1—N1i2.257 (2)C2—H20.9300
Co1—N12.257 (2)C3—C41.396 (5)
N1—C81.311 (4)C3—H30.9300
N1—C11.372 (3)C4—C51.357 (5)
N2—C71.302 (4)C4—H40.9300
N2—C61.359 (4)C5—C61.408 (4)
N3—C91.148 (3)C5—H50.9300
N4—C91.300 (4)C7—C81.403 (5)
N4—C101.301 (4)C7—H70.9300
N5—C101.141 (4)C8—H80.9300
N3i—Co1—N386.76 (14)C2—C1—C6118.9 (3)
N3i—Co1—N5ii178.59 (11)C3—C2—C1120.1 (3)
N3—Co1—N5ii92.73 (10)C3—C2—H2120.0
N3i—Co1—N5iii92.73 (10)C1—C2—H2120.0
N3—Co1—N5iii178.59 (11)C2—C3—C4121.3 (3)
N5ii—Co1—N5iii87.81 (14)C2—C3—H3119.3
N3i—Co1—N1i87.13 (9)C4—C3—H3119.3
N3—Co1—N1i93.83 (9)C5—C4—C3120.1 (3)
N5ii—Co1—N1i91.60 (9)C5—C4—H4120.0
N5iii—Co1—N1i87.46 (9)C3—C4—H4120.0
N3i—Co1—N193.83 (9)C4—C5—C6120.6 (3)
N3—Co1—N187.13 (9)C4—C5—H5119.7
N5ii—Co1—N187.46 (9)C6—C5—H5119.7
N5iii—Co1—N191.60 (9)N2—C6—C5119.0 (3)
N1i—Co1—N1178.69 (13)N2—C6—C1121.9 (3)
C8—N1—C1116.0 (2)C5—C6—C1119.0 (3)
C8—N1—Co1114.92 (19)N2—C7—C8123.0 (3)
C1—N1—Co1129.04 (17)N2—C7—H7118.5
C7—N2—C6115.9 (3)C8—C7—H7118.5
C9—N3—Co1160.5 (2)N1—C8—C7123.0 (3)
C9—N4—C10119.9 (2)N1—C8—H8118.5
C10—N5—Co1iv159.8 (2)C7—C8—H8118.5
N1—C1—C2121.0 (2)N3—C9—N4173.7 (3)
N1—C1—C6120.1 (2)N5—C10—N4175.2 (3)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1, −z+1/2; (iv) x, y+1, z.
(II) catena-poly[[bis(quinoxaline-κN)copper(II)]-di-(µ-dicyanamide-κ2N1:N5)] top
Crystal data top
[Cu(C2N3)2(C8H6N2)2]F(000) = 924
Mr = 455.94Dx = 1.600 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 18.205 (4) ÅCell parameters from 775 reflections
b = 7.2185 (16) Åθ = 2.8–20.7°
c = 14.766 (3) ŵ = 1.19 mm−1
β = 102.730 (4)°T = 293 K
V = 1892.7 (7) Å3Block, green
Z = 40.10 × 0.10 × 0.05 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1843 independent reflections
Radiation source: fine-focus sealed tube1328 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 0 pixels mm-1θmax = 26.0°, θmin = 2.3°
φ and ω scansh = −16→22
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −8→8
Tmin = 0.891, Tmax = 0.943l = −18→18
4189 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0355P)2 + 0.8836P]
where P = (Fo2 + 2Fc2)/3
1843 reflections(Δ/σ)max < 0.001
141 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
[Cu(C2N3)2(C8H6N2)2]V = 1892.7 (7) Å3
Mr = 455.94Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.205 (4) ŵ = 1.19 mm−1
b = 7.2185 (16) ÅT = 293 K
c = 14.766 (3) Å0.10 × 0.10 × 0.05 mm
β = 102.730 (4)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1843 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1328 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.943Rint = 0.037
4189 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å−3
1843 reflectionsΔρmin = −0.22 e Å−3
141 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
xyzUiso*/Ueq
Cu10.00000.38666 (6)0.25000.0417 (2)
N10.12330 (14)0.3819 (3)0.20479 (16)0.0445 (6)
N20.25147 (17)0.3724 (4)0.12576 (18)0.0609 (8)
N3−0.03098 (15)0.5876 (3)0.15554 (18)0.0487 (7)
N4−0.04521 (16)0.8871 (3)0.07737 (16)0.0524 (7)
N5−0.03213 (15)1.1869 (4)0.15542 (17)0.0476 (7)
C10.19513 (17)0.3825 (4)0.25919 (19)0.0397 (7)
C20.20550 (18)0.3885 (4)0.35657 (19)0.0497 (8)
H20.16410.38920.38390.060*
C30.27632 (19)0.3932 (5)0.4102 (2)0.0566 (9)
H30.28310.39850.47450.068*
C40.3390 (2)0.3902 (5)0.3707 (2)0.0623 (10)
H40.38700.39340.40880.075*
C50.3307 (2)0.3826 (5)0.2774 (2)0.0613 (10)
H50.37300.37970.25170.074*
C60.25879 (18)0.3790 (4)0.2196 (2)0.0463 (8)
C70.1829 (2)0.3693 (5)0.0764 (2)0.0612 (10)
H70.17570.36250.01220.073*
C80.11951 (19)0.3756 (4)0.1152 (2)0.0516 (8)
H80.07220.37540.07530.062*
C9−0.03709 (16)0.7317 (4)0.12296 (19)0.0374 (7)
C10−0.03790 (16)1.0439 (4)0.12180 (19)0.0374 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0598 (4)0.0257 (3)0.0368 (3)0.0000.0046 (2)0.000
N10.0568 (17)0.0410 (15)0.0354 (13)−0.0041 (13)0.0098 (12)−0.0036 (11)
N20.068 (2)0.076 (2)0.0426 (15)−0.0121 (17)0.0192 (15)−0.0045 (15)
N30.0617 (18)0.0347 (16)0.0474 (15)0.0000 (12)0.0070 (13)0.0007 (12)
N40.086 (2)0.0349 (15)0.0322 (13)−0.0042 (14)0.0037 (13)0.0015 (12)
N50.0611 (19)0.0340 (15)0.0472 (16)−0.0039 (13)0.0109 (13)−0.0027 (12)
C10.0502 (19)0.0297 (16)0.0381 (15)0.0002 (15)0.0075 (14)−0.0026 (13)
C20.051 (2)0.059 (2)0.0396 (17)0.0018 (17)0.0116 (15)−0.0050 (16)
C30.060 (2)0.068 (2)0.0388 (17)0.0009 (19)0.0034 (16)−0.0046 (17)
C40.047 (2)0.077 (3)0.060 (2)−0.0013 (19)0.0046 (17)−0.010 (2)
C50.051 (2)0.078 (3)0.059 (2)−0.005 (2)0.0190 (18)−0.014 (2)
C60.057 (2)0.0408 (18)0.0428 (17)−0.0056 (17)0.0150 (15)−0.0021 (15)
C70.077 (3)0.071 (3)0.0370 (17)−0.015 (2)0.0159 (18)−0.0042 (17)
C80.060 (2)0.049 (2)0.0425 (17)−0.0084 (17)0.0048 (16)−0.0055 (15)
C90.0399 (19)0.0390 (18)0.0318 (16)−0.0038 (14)0.0047 (13)−0.0063 (13)
C100.0412 (19)0.0392 (17)0.0304 (16)−0.0013 (14)0.0049 (14)0.0078 (13)
Geometric parameters (Å, º) top
Cu1—N3i2.005 (3)N5—Cu1iv2.003 (3)
Cu1—N32.005 (3)C1—C21.409 (4)
Cu1—N5ii2.003 (3)C1—C61.409 (4)
Cu1—N5iii2.003 (3)C2—C31.357 (4)
Cu1—N1i2.479 (3)C2—H20.9300
Cu1—N12.479 (3)C3—C41.391 (5)
N1—C81.311 (4)C3—H30.9300
N1—C11.376 (4)C4—C51.355 (4)
N2—C71.299 (4)C4—H40.9300
N2—C61.363 (4)C5—C61.397 (4)
N3—C91.141 (4)C5—H50.9300
N4—C91.300 (4)C7—C81.397 (5)
N4—C101.300 (4)C7—H70.9300
N5—C101.140 (4)C8—H80.9300
N3i—Cu1—N387.33 (14)C6—C1—C2119.1 (3)
N5ii—Cu1—N3i179.37 (11)C3—C2—C1119.5 (3)
N5ii—Cu1—N392.39 (10)C3—C2—H2120.2
N5iii—Cu1—N3i92.39 (10)C1—C2—H2120.2
N5iii—Cu1—N3179.37 (11)C2—C3—C4121.1 (3)
N5ii—Cu1—N5iii87.90 (15)C2—C3—H3119.4
N3i—Cu1—N1i87.44 (10)C4—C3—H3119.4
N3—Cu1—N1i93.72 (10)C5—C4—C3120.6 (3)
N5ii—Cu1—N1i92.01 (9)C5—C4—H4119.7
N5iii—Cu1—N1i86.84 (9)C3—C4—H4119.7
N3i—Cu1—N193.72 (10)C4—C5—C6120.1 (3)
N3—Cu1—N187.44 (10)C4—C5—H5120.0
N5ii—Cu1—N186.84 (9)C6—C5—H5120.0
N5iii—Cu1—N192.01 (9)N2—C6—C5119.3 (3)
N1—Cu1—N1i178.40 (11)N2—C6—C1121.2 (3)
C8—N1—C1114.9 (3)C5—C6—C1119.5 (3)
C8—N1—Cu1115.0 (2)N2—C7—C8123.2 (3)
C1—N1—Cu1130.04 (18)N2—C7—H7118.4
C7—N2—C6115.9 (3)C8—C7—H7118.4
C9—N3—Cu1159.9 (2)N1—C8—C7123.4 (3)
C9—N4—C10120.2 (2)N1—C8—H8118.3
C10—N5—Cu1iv160.1 (2)C7—C8—H8118.3
N1—C1—C2119.5 (3)N3—C9—N4173.9 (3)
N1—C1—C6121.4 (2)N5—C10—N4175.6 (3)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1, −z+1/2; (iv) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Co(C2N3)2(C8H6N2)2][Cu(C2N3)2(C8H6N2)2]
Mr451.33455.94
Crystal system, space groupMonoclinic, C2/cMonoclinic, C2/c
Temperature (K)293293
a, b, c (Å)17.598 (5), 7.374 (2), 14.771 (4)18.205 (4), 7.2185 (16), 14.766 (3)
β (°) 101.894 (4) 102.730 (4)
V (Å3)1875.7 (9)1892.7 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm−1)0.951.19
Crystal size (mm)0.10 × 0.05 × 0.020.10 × 0.10 × 0.05
Data collection
DiffractometerBruker SMART APEX CCD area-detectorBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)		Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.911, 0.9810.891, 0.943
No. of measured, independent and
observed [I > 2σ(I)] reflections		4491, 2036, 1546 4189, 1843, 1328
Rint0.0400.037
(sin θ/λ)max (Å−1)0.6390.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.105, 1.07 0.041, 0.098, 1.03
No. of reflections20361843
No. of parameters141141
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.35, −0.230.27, −0.22

Computer programs: SMART APEX (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Co1—N3i2.098 (3)Co1—N12.257 (2)
Co1—N5ii2.104 (3)
N3i—Co1—N386.76 (14)N3—Co1—N187.13 (9)
N3—Co1—N5ii92.73 (10)N5ii—Co1—N187.46 (9)
N3—Co1—N5iii178.59 (11)N5iii—Co1—N191.60 (9)
N5ii—Co1—N5iii87.81 (14)N1i—Co1—N1178.69 (13)
N3—Co1—N1i93.83 (9)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1, −z+1/2.
Selected geometric parameters (Å, º) for (II) top
Cu1—N3i2.005 (3)Cu1—N12.479 (3)
Cu1—N5ii2.003 (3)
N3i—Cu1—N387.33 (14)N3—Cu1—N187.44 (10)
N5ii—Cu1—N392.39 (10)N5ii—Cu1—N186.84 (9)
N5iii—Cu1—N3179.37 (11)N5iii—Cu1—N192.01 (9)
N5ii—Cu1—N5iii87.90 (15)N1—Cu1—N1i178.40 (11)
N3—Cu1—N1i93.72 (10)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, y−1, z; (iii) −x, y−1, −z+1/2.
 

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