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Acta Cryst. (2009). E65, m386    [ doi:10.1107/S160053680900796X ]

catena-Poly[[(dimethylformamide-[kappa]O)copper(II)]-bis([mu]-4-nitrophenylcyanamido-[kappa]2N1:N3)\]

H. Chiniforoshan, S. Jalilpour, B. Shirinfar and H. R. Khavasi

Abstract top

In the title compound, [Cu(C7H4N3O2)2(C3H7NO)], the CuII atom is five-coordinated in a distorted square-pyramidal geometry, with the N atoms in equatorial positions and the dimethylformamide O atom in an axial position. The dihedral angle between adjacent benzene rings is 70.33 (12)°.

Comment top

Phenylcyanamide ligands are used in the construction of transition metal coordination complexes. The study of coordination polymeric materials holds great interest. The phenylcyanamide can function as bridging ligand and can coordinate to two different metallic centers by means of the nitrile and amine nitrogen (µ1,3 bonding mode), forming di- and polynuclear complexes (Brader et al., 1990; Crutchley et al., 2001; Ainscough et al., 1991; Escuer et al., 2004). It can modify the solubility and crystallinety of resulting compounds and there is the different coordination in complexes. We are attempting to construct conductive inorganic polymer chains that are cross-linked by cyanamide groups to a coordination complex. Coordination polymers also hold promise as novel materials because of their magnetic properties (Grosshenny et al., 1996). More recently various aromatic cyanamide complexes have been studied by x-ray crystallography.

In the molecule of the title compound, (I), (Fig. 1) the selected bond lengths and angles are listed in Table 1. In this molecule, the {Cu(4—NO2-pcyd)2(DMF)}n one-dimensional chain coordination polymer bridged by 4-NO2-phenylcyanamide. Each copper atom has a distored square pyramidal geometry, that nitrogen atoms are in equatorial position and oxygen atom from DMF molecule is in axial position (Table 1.). The dihedral angle between adjacent phenyl rings in the polymeric chain is 70.33 (12)°.

Related literature top

The phenylcyanamide can function as bridging ligand and cancoordinate to two different metallic centers by means of the nitrile and amine nitrogen (µ1,3 bonding mode), forming di- and polynuclear complexes, see: Ainscough et al. (1991); Brader et al. (1990); Crutchley (2001); Escuer et al. (2004). For the magnetic properties of coordination polymers, see: Grosshenny et al. (1996). For the preparation of 4-NO2-phenylcyanamide used in the synthesis, see: Crutchley & Naklicki (1989);

Experimental top

The 4-NO2-phenylcyanamide (Crutchley et al.,1989) (0.163 gr, 0.5 mmol) dissolved in methanol (30 ml) was added slowly to a solution of copper(II) acetate monohydrate (0.998 gr, 1 mmol) in methanol (30 ml). The mixture was stirred for 4 h. The solid filtered and crystals suitable for X-ray structure determination were obtained by dissolving in DMF then diffused by n-Hexane, after 1 week.

Refinement top

All of the H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic and aldehyde H atoms and with C—H = 0.93 Å for methyl H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of (I) with 30% probability displacement ellipsoids. Symmetry code (i): x, -y - 3/2, z - 1/2.
catena-Poly[[(dimethylformamide-κO)copper(II)]- bis(µ-4-nitrophenylcyanamido-κ2N1:N3)] top
Crystal data top
[Cu(C7H4N3O2)2(C3H7NO)]F(000) = 940
Mr = 460.91Dx = 1.668 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1359 reflections
a = 21.5103 (12) Åθ = 3.0–29.3°
b = 8.7883 (5) ŵ = 1.24 mm−1
c = 9.9195 (5) ÅT = 120 K
β = 101.746 (4)°Prism, violet
V = 1835.91 (17) Å30.5 × 0.23 × 0.15 mm
Z = 4
Data collection top
Stoe IPDS-II
diffractometer		4496 reflections with I > 2σ(I)
rotation method scansRint = 0.050
Absorption correction: numerical
shape of crystal determined optically		θmax = 29.3°, θmin = 3.0°
Tmin = 0.720, Tmax = 0.832h = −29→24
13057 measured reflectionsk = −10→12
4874 independent reflectionsl = −13→13
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033 w = 1/[σ2(Fo2) + (0.051P)2 + 0.8628P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091(Δ/σ)max = 0.017
S = 1.08Δρmax = 0.99 e Å−3
4874 reflectionsΔρmin = −0.91 e Å−3
273 parameters
Crystal data top
[Cu(C7H4N3O2)2(C3H7NO)]V = 1835.91 (17) Å3
Mr = 460.91Z = 4
Monoclinic, P21/cMo Kα radiation
a = 21.5103 (12) ŵ = 1.24 mm−1
b = 8.7883 (5) ÅT = 120 K
c = 9.9195 (5) Å0.5 × 0.23 × 0.15 mm
β = 101.746 (4)°
Data collection top
Stoe IPDS-II
diffractometer		4874 independent reflections
Absorption correction: numerical
shape of crystal determined optically		4496 reflections with I > 2σ(I)
Tmin = 0.720, Tmax = 0.832Rint = 0.050
13057 measured reflectionsθmax = 29.3°
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.99 e Å−3
S = 1.08Δρmin = −0.91 e Å−3
4874 reflectionsAbsolute structure: ?
273 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.18470 (7)−0.78476 (17)0.48486 (14)0.0134 (3)
C20.11109 (7)−0.85879 (17)0.61210 (15)0.0134 (3)
C30.06225 (7)−0.77637 (19)0.52815 (15)0.0170 (3)
H30.0717−0.71320.45990.02*
C4−0.00005 (7)−0.78755 (19)0.54535 (16)0.0187 (3)
H4−0.0323−0.73270.48930.022*
C5−0.01325 (7)−0.8821 (2)0.64786 (16)0.0179 (3)
C60.03397 (8)−0.96827 (18)0.73088 (16)0.0177 (3)
H60.0239−1.03250.79780.021*
C70.09602 (7)−0.95722 (17)0.71271 (15)0.0155 (3)
H70.1278−1.0150.76710.019*
C80.31962 (7)−0.74093 (18)1.03158 (14)0.0140 (3)
C90.39374 (7)−0.82569 (17)0.90993 (15)0.0142 (3)
C100.41040 (7)−0.94717 (18)0.83254 (15)0.0156 (3)
H100.3799−1.01780.79320.019*
C110.47252 (7)−0.96186 (19)0.81480 (15)0.0179 (3)
H110.4839−1.04190.76340.021*
C120.51748 (8)−0.8551 (2)0.87497 (16)0.0186 (3)
C130.50288 (7)−0.7369 (2)0.95631 (16)0.0192 (3)
H130.534−0.66880.99820.023*
C140.44059 (7)−0.72297 (19)0.97349 (15)0.0170 (3)
H140.4299−0.64481.02770.02*
C150.23643 (8)−1.18081 (18)0.70530 (16)0.0164 (3)
H150.2162−1.14690.61870.02*
C160.27640 (9)−1.3914 (2)0.85538 (18)0.0239 (3)
H16A0.2471−1.45440.89140.029*
H16B0.2907−1.31010.91870.029*
H16C0.3121−1.45140.84310.029*
C170.22428 (9)−1.4360 (2)0.61151 (18)0.0242 (3)
H17C0.195−1.50730.63750.029*
H17B0.2605−1.48960.59280.029*
H17A0.2038−1.3820.53050.029*
N10.19773 (6)−0.73209 (16)0.38708 (13)0.0159 (2)
N20.17467 (6)−0.84608 (14)0.59891 (13)0.0133 (2)
N3−0.07813 (7)−0.8905 (2)0.67009 (16)0.0245 (3)
N40.30602 (6)−0.68183 (17)1.12639 (13)0.0169 (3)
N50.32972 (6)−0.80866 (16)0.92140 (12)0.0136 (2)
N60.58231 (7)−0.8682 (2)0.85134 (15)0.0249 (3)
N70.24485 (6)−1.32833 (16)0.72334 (14)0.0166 (3)
Cu10.252435 (8)−0.842098 (19)0.763487 (17)0.01030 (7)
O1−0.11924 (6)−0.8137 (2)0.59671 (16)0.0360 (3)
O2−0.08874 (8)−0.9731 (2)0.7622 (2)0.0497 (5)
O30.61904 (7)−0.7620 (2)0.88752 (16)0.0380 (4)
O40.59667 (7)−0.9839 (2)0.79478 (16)0.0379 (4)
O50.25389 (6)−1.08324 (13)0.79693 (11)0.0182 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0091 (6)0.0152 (6)0.0141 (6)−0.0002 (5)−0.0015 (5)−0.0010 (5)
C20.0118 (6)0.0143 (6)0.0137 (6)−0.0026 (5)0.0017 (5)−0.0023 (5)
C30.0150 (7)0.0208 (7)0.0146 (6)0.0011 (5)0.0017 (5)0.0014 (5)
C40.0131 (7)0.0228 (8)0.0189 (6)0.0024 (6)0.0005 (5)−0.0020 (6)
C50.0116 (6)0.0208 (7)0.0219 (7)−0.0027 (6)0.0047 (5)−0.0059 (6)
C60.0162 (7)0.0176 (7)0.0204 (7)−0.0046 (5)0.0062 (5)−0.0007 (5)
C70.0139 (6)0.0158 (6)0.0163 (6)−0.0025 (5)0.0019 (5)0.0004 (5)
C80.0089 (6)0.0183 (7)0.0135 (6)−0.0012 (5)−0.0009 (5)0.0010 (5)
C90.0115 (6)0.0182 (7)0.0125 (6)0.0023 (5)0.0015 (5)0.0023 (5)
C100.0134 (6)0.0177 (7)0.0145 (6)0.0020 (5)0.0005 (5)−0.0002 (5)
C110.0163 (7)0.0224 (7)0.0147 (6)0.0060 (6)0.0029 (5)0.0012 (5)
C120.0116 (6)0.0271 (8)0.0173 (7)0.0029 (6)0.0035 (5)0.0051 (6)
C130.0133 (6)0.0246 (8)0.0190 (7)−0.0025 (6)0.0019 (5)0.0015 (6)
C140.0144 (7)0.0204 (7)0.0159 (6)0.0002 (5)0.0025 (5)−0.0024 (5)
C150.0183 (7)0.0142 (7)0.0169 (6)−0.0004 (5)0.0039 (5)0.0002 (5)
C160.0293 (8)0.0163 (7)0.0251 (8)0.0047 (6)0.0031 (6)0.0053 (6)
C170.0303 (9)0.0170 (7)0.0265 (8)−0.0018 (6)0.0089 (7)−0.0079 (6)
N10.0104 (5)0.0230 (7)0.0139 (5)−0.0003 (5)0.0014 (4)0.0018 (5)
N20.0100 (5)0.0181 (6)0.0110 (5)−0.0018 (4)0.0006 (4)0.0006 (4)
N30.0151 (6)0.0283 (8)0.0312 (7)−0.0031 (6)0.0074 (5)−0.0066 (6)
N40.0105 (5)0.0263 (7)0.0130 (5)−0.0018 (5)−0.0001 (4)−0.0031 (5)
N50.0093 (5)0.0191 (6)0.0119 (5)0.0002 (4)0.0007 (4)−0.0023 (4)
N60.0147 (6)0.0396 (9)0.0211 (6)0.0052 (6)0.0049 (5)0.0051 (6)
N70.0183 (6)0.0130 (6)0.0186 (6)−0.0008 (4)0.0039 (5)−0.0012 (4)
Cu10.00955 (10)0.01191 (10)0.00912 (10)−0.00041 (6)0.00118 (6)−0.00033 (5)
O10.0144 (6)0.0544 (10)0.0386 (8)0.0052 (6)0.0040 (5)−0.0007 (7)
O20.0246 (7)0.0595 (11)0.0711 (12)0.0005 (7)0.0246 (8)0.0261 (10)
O30.0161 (6)0.0527 (10)0.0463 (8)−0.0059 (6)0.0087 (6)−0.0026 (7)
O40.0244 (7)0.0487 (9)0.0443 (8)0.0094 (7)0.0154 (6)−0.0049 (7)
O50.0248 (6)0.0119 (5)0.0169 (5)−0.0014 (4)0.0017 (4)−0.0005 (4)
Geometric parameters (Å, °) top
C1—N11.160 (2)C13—C141.390 (2)
C1—N21.3099 (18)C13—H130.93
C2—C31.402 (2)C14—H140.93
C2—N21.4046 (19)C15—O51.250 (2)
C2—C71.408 (2)C15—N71.316 (2)
C3—C41.388 (2)C15—H150.93
C3—H30.93C16—N71.457 (2)
C4—C51.387 (2)C16—H16A0.96
C4—H40.93C16—H16B0.96
C5—C61.394 (2)C16—H16C0.96
C5—N31.458 (2)C17—N71.457 (2)
C6—C71.386 (2)C17—H17C0.96
C6—H60.93C17—H17B0.96
C7—H70.93C17—H17A0.96
C8—N41.163 (2)N1—Cu1i1.9748 (13)
C8—N51.3010 (19)N2—Cu12.0862 (13)
C9—C141.403 (2)N3—O21.224 (2)
C9—C101.403 (2)N3—O11.227 (2)
C9—N51.4126 (19)N4—Cu1ii1.9648 (13)
C10—C111.389 (2)N5—Cu12.0599 (12)
C10—H100.93N6—O31.229 (2)
C11—C121.392 (2)N6—O41.230 (2)
C11—H110.93Cu1—N4i1.9648 (13)
C12—C131.390 (2)Cu1—N1ii1.9748 (13)
C12—N61.465 (2)Cu1—O52.1443 (12)
N1—C1—N2175.56 (15)N7—C16—H16A109.5
C3—C2—N2121.98 (13)N7—C16—H16B109.5
C3—C2—C7119.06 (14)H16A—C16—H16B109.5
N2—C2—C7118.96 (13)N7—C16—H16C109.5
C4—C3—C2121.05 (14)H16A—C16—H16C109.5
C4—C3—H3119.5H16B—C16—H16C109.5
C2—C3—H3119.5N7—C17—H17C109.5
C5—C4—C3118.64 (14)N7—C17—H17B109.5
C5—C4—H4120.7H17C—C17—H17B109.5
C3—C4—H4120.7N7—C17—H17A109.5
C4—C5—C6121.70 (14)H17C—C17—H17A109.5
C4—C5—N3119.07 (15)H17B—C17—H17A109.5
C6—C5—N3119.22 (15)C1—N1—Cu1i158.01 (12)
C7—C6—C5119.36 (14)C1—N2—C2116.60 (12)
C7—C6—H6120.3C1—N2—Cu1114.97 (10)
C5—C6—H6120.3C2—N2—Cu1124.69 (9)
C6—C7—C2120.15 (14)O2—N3—O1123.22 (16)
C6—C7—H7119.9O2—N3—C5118.16 (16)
C2—C7—H7119.9O1—N3—C5118.63 (16)
N4—C8—N5175.15 (15)C8—N4—Cu1ii152.54 (13)
C14—C9—C10119.68 (14)C8—N5—C9116.64 (12)
C14—C9—N5121.22 (13)C8—N5—Cu1117.20 (10)
C10—C9—N5119.09 (14)C9—N5—Cu1124.94 (9)
C11—C10—C9119.96 (15)O3—N6—O4123.70 (16)
C11—C10—H10120O3—N6—C12118.03 (16)
C9—C10—H10120O4—N6—C12118.26 (16)
C10—C11—C12119.05 (14)C15—N7—C17121.62 (15)
C10—C11—H11120.5C15—N7—C16121.55 (14)
C12—C11—H11120.5C17—N7—C16116.82 (14)
C13—C12—C11122.23 (14)N4i—Cu1—N1ii154.42 (6)
C13—C12—N6119.11 (15)N4i—Cu1—N590.85 (5)
C11—C12—N6118.65 (15)N1ii—Cu1—N588.36 (5)
C14—C13—C12118.31 (15)N4i—Cu1—N287.13 (5)
C14—C13—H13120.8N1ii—Cu1—N290.41 (5)
C12—C13—H13120.8N5—Cu1—N2172.66 (5)
C13—C14—C9120.69 (14)N4i—Cu1—O5102.75 (5)
C13—C14—H14119.7N1ii—Cu1—O5102.83 (5)
C9—C14—H14119.7N5—Cu1—O592.25 (5)
O5—C15—N7124.33 (15)N2—Cu1—O595.08 (5)
O5—C15—H15117.8C15—O5—Cu1124.92 (11)
N7—C15—H15117.8
N2—C2—C3—C4−178.27 (14)C14—C9—N5—C8−27.7 (2)
C7—C2—C3—C41.7 (2)C10—C9—N5—C8152.76 (14)
C2—C3—C4—C50.1 (2)C14—C9—N5—Cu1139.25 (12)
C3—C4—C5—C6−1.6 (2)C10—C9—N5—Cu1−40.26 (19)
C3—C4—C5—N3177.78 (15)C13—C12—N6—O3−10.4 (2)
C4—C5—C6—C71.3 (2)C11—C12—N6—O3169.52 (16)
N3—C5—C6—C7−178.12 (14)C13—C12—N6—O4170.58 (16)
C5—C6—C7—C20.6 (2)C11—C12—N6—O4−9.5 (2)
C3—C2—C7—C6−2.0 (2)O5—C15—N7—C17−178.97 (15)
N2—C2—C7—C6177.94 (14)O5—C15—N7—C16−0.3 (3)
C14—C9—C10—C11−2.5 (2)C8—N5—Cu1—N4i147.21 (12)
N5—C9—C10—C11177.06 (13)C9—N5—Cu1—N4i−19.70 (13)
C9—C10—C11—C120.2 (2)C8—N5—Cu1—N1ii−7.22 (12)
C10—C11—C12—C132.2 (2)C9—N5—Cu1—N1ii−174.13 (13)
C10—C11—C12—N6−177.70 (14)C8—N5—Cu1—O5−110.00 (12)
C11—C12—C13—C14−2.2 (2)C9—N5—Cu1—O583.09 (13)
N6—C12—C13—C14177.69 (14)C1—N2—Cu1—N4i−21.30 (11)
C12—C13—C14—C9−0.1 (2)C2—N2—Cu1—N4i−178.68 (12)
C10—C9—C14—C132.5 (2)C1—N2—Cu1—N1ii133.23 (11)
N5—C9—C14—C13−177.06 (14)C2—N2—Cu1—N1ii−24.15 (12)
C3—C2—N2—C1−16.4 (2)C1—N2—Cu1—O5−123.85 (11)
C7—C2—N2—C1163.60 (14)C2—N2—Cu1—O578.76 (12)
C3—C2—N2—Cu1140.62 (12)N7—C15—O5—Cu1171.10 (11)
C7—C2—N2—Cu1−39.34 (18)N4i—Cu1—O5—C15−57.95 (14)
C4—C5—N3—O2−179.12 (18)N1ii—Cu1—O5—C15121.84 (13)
C6—C5—N3—O20.3 (3)N5—Cu1—O5—C15−149.33 (13)
C4—C5—N3—O10.3 (2)N2—Cu1—O5—C1530.25 (13)
C6—C5—N3—O1179.73 (16)
Symmetry codes: (i) x, −y−3/2, z−1/2; (ii) x, −y−3/2, z+1/2.
Table 1
Selected geometric parameters (Å, °) top
N2—Cu12.0862 (13)Cu1—N1ii1.9748 (13)
N5—Cu12.0599 (12)Cu1—O52.1443 (12)
Cu1—N4i1.9648 (13)
N4i—Cu1—N1ii154.42 (6)N4i—Cu1—O5102.75 (5)
N4i—Cu1—N590.85 (5)N1ii—Cu1—O5102.83 (5)
N1ii—Cu1—N290.41 (5)N5—Cu1—O592.25 (5)
N5—Cu1—N2172.66 (5)N2—Cu1—O595.08 (5)
Symmetry codes: (i) x, −y−3/2, z−1/2; (ii) x, −y−3/2, z+1/2.
Acknowledgements top

The authors acknowledge financial support from Isfahan University of Technology.

references
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