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Acta Cryst. (2007). E63, m1416    [ doi:10.1107/S1600536807018570 ]

Bis[1,3-bis(benzimidazol-2-yl)propane-[kappa]2N,N']copper(II) dinitrate methanol disolvate

B. Hu, M. Wang, X.-Y. Wang, X.-G. Song and C.-G. Wang

Abstract top

In the title compound, [Cu(C17H16N4)2](NO3)2·2C2H5OH, the CuII ion lies on a crystallographic twofold rotation axis and is in a distorted square-planar coordination geometry formed by four N atoms from two 1,3-bis(benzimidazol-2-yl)propane ligands. The N-Cu-N angles range from 90.25 (7) to 144.89 (11)°. In the crystal structure, a two-dimensional framework is formed by a combination of N-H...O and O-H...O hydrogen bonds.

Comment top

Interest in bis(2-benzimidazolyl)alkanes is widespread, due to their wide-ranging antiviral activity (Roderick et al., 1972). Herein, we report the crystal structure of the title compound (I). In the cation (Fig. 1), the CuII ion lies on a crystallogrphic twofold axis. Hence, the CuII ion is coordinated by four N atoms (N1, N3, N1a, N3a [symmety code: (a) 1/2 - x, 3/2 - y, z]) from two dbz ligangs. The bond anlges listed in Table 1 indicate a distorted square-planar coordination geomtry.

In the crystal structure, molecules are linked by N—Hbenzimidazole···Onitrate and O—Hmethanol···O nitrate hydrogen bonds, forming a two-dimensional framework structure perpendicular to the ab plane (Table 2, Fig. 2).

Related literature top

For related literature, see: Albada et al. (1995); Roderick et al. (1972); Wang & Joullie (1957), Allen et al. (1987); Sun et al. (2004).

Experimental top

The ligand 1,3-bis(2-benzimidazolyl)propane (dbz) was synthesized from reported literature earlier (van Albada et al., 1995; Wang

& Joullie, 1957). The title compound was prepared according to the following procedure: The ligand (0.28 g, 1 mmol) in 10 ml me thanol was added slowly to a Cu(NO3)2.2H2O (0.12 g, 0.5 mmol) solution of 10 ml me thanol. The mixture was stirred for 1 h. After filtration, the brownish solution was allowed to stand at room temperature. Green block-shaped crystals of (I) were obtained after three weeks.

Refinement top

H atoms bonded to O and N atoms were located in difference maps and then included in the refinement with bond-length restraints of O–H = 0.82 Å and N–H = 0.78 Å, with Uiso(H)= 1.2Ueq (O) and the Uiso(H) of the N—H atoms refined. H atoms bonded to C atoms were placed in calculated positions and included in the riding-model approximation, with C–H = 0.97—0.98 Å and U iso(H) = 1.2Ueq(C of methylene and aromatic) or 1.5U eq(C of methyl).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. The H atoms, anion and solvent molecules are not shown. [symmetry code: (a) 1/2 - x, 3/2 - y, z]
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of hydrogen-bonded (dashed lines) two-dimensional layers.
Bis[1,3-bis(benzimidazol-2-yl)propane-κ2N,N']copper(II) dinitrate methanol solvate top
Crystal data top
[Cu(C17H16N4)2](NO3)2·2C2H6OF(000) = 1676
Mr = 804.32Dx = 1.441 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 5026 reflections
a = 14.4793 (10) Åθ = 2.3–25.4°
b = 17.8978 (13) ŵ = 0.66 mm−1
c = 14.3078 (10) ÅT = 297 K
V = 3707.8 (5) Å3Block, green
Z = 40.45 × 0.32 × 0.20 mm
Data collection top
Bruker APEX CCD
diffractometer		3394 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
graphiteθmax = 28.0°, θmin = 1.8°
φ and ω scansh = −19→18
23966 measured reflectionsk = −21→23
4453 independent reflectionsl = −17→18
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0635P)2 + 1.4161P]
where P = (Fo2 + 2Fc2)/3
4453 reflections(Δ/σ)max = 0.001
261 parametersΔρmax = 0.48 e Å−3
1 restraintΔρmin = −0.25 e Å−3
Crystal data top
[Cu(C17H16N4)2](NO3)2·2C2H6OV = 3707.8 (5) Å3
Mr = 804.32Z = 4
Orthorhombic, PccnMo Kα radiation
a = 14.4793 (10) ŵ = 0.66 mm−1
b = 17.8978 (13) ÅT = 297 K
c = 14.3078 (10) Å0.45 × 0.32 × 0.20 mm
Data collection top
Bruker APEX CCD
diffractometer		3394 reflections with I > 2σ(I)
23966 measured reflectionsRint = 0.042
4453 independent reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130Δρmax = 0.48 e Å−3
S = 1.07Δρmin = −0.25 e Å−3
4453 reflectionsAbsolute structure: ?
261 parametersFlack parameter: ?
1 restraintRogers 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.

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
H4N0.293 (2)0.4833 (17)0.041 (2)0.048 (8)*
H2N−0.077 (2)0.6948 (16)0.111 (2)0.048 (8)*
Cu10.25000.75000.06676 (3)0.03171 (13)
N10.11849 (13)0.74057 (10)0.10902 (14)0.0352 (4)
N30.27403 (13)0.64615 (10)0.02440 (14)0.0342 (4)
C10.07694 (16)0.79298 (12)0.16863 (16)0.0368 (5)
C20.1142 (2)0.85029 (14)0.22291 (17)0.0449 (6)
H20.17730.86010.22280.054*
C30.0542 (2)0.89193 (15)0.2768 (2)0.0554 (7)
H30.07740.93100.31270.067*
C4−0.0399 (2)0.87695 (17)0.2789 (2)0.0619 (8)
H4−0.07820.90620.31620.074*
C5−0.0778 (2)0.82015 (17)0.2275 (2)0.0562 (7)
H5−0.14070.80980.22940.067*
C6−0.01757 (17)0.77856 (15)0.17211 (18)0.0430 (6)
C70.04996 (16)0.69688 (13)0.07935 (16)0.0371 (5)
C80.05757 (17)0.62941 (14)0.01904 (18)0.0434 (6)
H8A0.10470.6377−0.02800.052*
H8B−0.00070.6213−0.01290.052*
C90.08211 (18)0.55980 (13)0.07567 (19)0.0465 (6)
H9A0.08570.51730.03380.056*
H9B0.03310.55010.12030.056*
C100.17360 (16)0.56732 (13)0.12819 (17)0.0405 (5)
H10A0.16980.60850.17210.049*
H10B0.18560.52200.16330.049*
C110.25044 (16)0.58083 (13)0.06119 (16)0.0371 (5)
C120.36087 (17)0.55352 (13)−0.03919 (17)0.0396 (5)
C130.4271 (2)0.52029 (15)−0.09541 (19)0.0516 (7)
H130.43760.4690−0.09400.062*
C140.4766 (2)0.56670 (17)−0.1534 (2)0.0568 (7)
H140.52190.5465−0.19180.068*
C150.4603 (2)0.64322 (17)−0.1558 (2)0.0543 (7)
H150.49510.6729−0.19590.065*
C160.39374 (18)0.67644 (14)−0.10034 (18)0.0465 (6)
H160.38250.7275−0.10300.056*
C170.34427 (16)0.63005 (13)−0.04022 (16)0.0363 (5)
C180.1719 (4)0.1726 (3)0.0359 (4)0.1238 (19)
H18A0.16750.21850.07050.186*
H18B0.11100.15400.02320.186*
H18C0.20350.1816−0.02210.186*
N2−0.03139 (15)0.71824 (13)0.11500 (16)0.0444 (5)
N40.30001 (15)0.52477 (12)0.02574 (16)0.0423 (5)
N50.81550 (16)0.58786 (18)0.1762 (2)0.0654 (7)
O10.7826 (3)0.53217 (18)0.2119 (3)0.1170 (11)
O20.81605 (17)0.64741 (15)0.2217 (2)0.0854 (7)
O30.84823 (19)0.58743 (19)0.0982 (2)0.1039 (10)
O40.2211 (2)0.11977 (14)0.08836 (19)0.0816 (7)
H4A0.216 (4)0.122 (3)0.1451 (8)0.122*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0331 (2)0.0260 (2)0.0361 (2)−0.00241 (15)0.0000.000
N10.0356 (10)0.0323 (10)0.0376 (10)−0.0013 (8)0.0028 (8)0.0005 (8)
N30.0372 (10)0.0273 (9)0.0380 (10)−0.0017 (7)0.0034 (8)−0.0023 (8)
C10.0435 (13)0.0311 (12)0.0357 (12)0.0029 (9)0.0047 (9)0.0073 (9)
C20.0571 (16)0.0381 (13)0.0395 (13)−0.0006 (11)0.0073 (11)0.0030 (11)
C30.084 (2)0.0397 (14)0.0424 (15)0.0062 (14)0.0068 (14)0.0015 (11)
C40.075 (2)0.0527 (17)0.0581 (18)0.0256 (15)0.0183 (15)0.0057 (14)
C50.0488 (15)0.0561 (17)0.0636 (18)0.0159 (13)0.0125 (13)0.0094 (14)
C60.0441 (14)0.0407 (13)0.0441 (14)0.0063 (11)0.0030 (10)0.0098 (11)
C70.0365 (12)0.0381 (12)0.0367 (12)−0.0029 (10)−0.0020 (9)0.0079 (10)
C80.0415 (13)0.0463 (14)0.0425 (14)−0.0091 (11)−0.0029 (10)−0.0071 (11)
C90.0459 (14)0.0346 (13)0.0589 (16)−0.0109 (11)0.0082 (11)−0.0028 (11)
C100.0464 (14)0.0302 (12)0.0448 (14)−0.0018 (10)0.0081 (10)0.0029 (10)
C110.0404 (12)0.0317 (11)0.0391 (12)−0.0022 (10)−0.0016 (10)−0.0015 (9)
C120.0442 (13)0.0341 (12)0.0407 (13)−0.0009 (10)0.0020 (10)−0.0012 (10)
C130.0596 (17)0.0414 (14)0.0540 (16)0.0069 (12)0.0091 (13)−0.0075 (12)
C140.0592 (17)0.0622 (18)0.0491 (16)0.0052 (14)0.0167 (13)−0.0060 (14)
C150.0610 (17)0.0585 (17)0.0434 (14)−0.0055 (14)0.0155 (13)0.0019 (13)
C160.0572 (16)0.0381 (13)0.0441 (14)−0.0047 (11)0.0067 (12)0.0026 (11)
C170.0391 (12)0.0349 (12)0.0348 (12)−0.0031 (10)0.0006 (9)−0.0024 (9)
C180.140 (5)0.074 (3)0.158 (5)0.013 (3)0.034 (4)0.030 (3)
N20.0335 (12)0.0476 (12)0.0521 (13)−0.0011 (10)−0.0017 (9)0.0090 (11)
N40.0517 (13)0.0253 (10)0.0498 (12)−0.0002 (9)0.0078 (10)−0.0003 (9)
N50.0395 (13)0.0756 (19)0.081 (2)−0.0106 (13)−0.0033 (13)0.0111 (16)
O10.133 (3)0.084 (2)0.134 (3)−0.032 (2)0.020 (2)0.025 (2)
O20.0706 (16)0.0768 (17)0.109 (2)−0.0088 (13)0.0124 (14)0.0026 (16)
O30.0819 (18)0.147 (3)0.0829 (19)−0.0447 (18)0.0125 (15)−0.0126 (18)
O40.114 (2)0.0473 (13)0.0834 (17)0.0018 (13)0.0006 (16)−0.0110 (13)
Geometric parameters (Å, °) top
Cu1—N31.9857 (18)C9—H9B0.9700
Cu1—N3i1.9857 (18)C10—C111.488 (3)
Cu1—N12.0049 (19)C10—H10A0.9700
Cu1—N1i2.0049 (19)C10—H10B0.9700
N1—C71.333 (3)C11—N41.334 (3)
N1—C11.403 (3)C12—N41.380 (3)
N3—C111.327 (3)C12—C131.386 (4)
N3—C171.404 (3)C12—C171.391 (3)
C1—C61.393 (3)C13—C141.375 (4)
C1—C21.395 (3)C13—H130.9300
C2—C31.380 (4)C14—C151.390 (4)
C2—H20.9300C14—H140.9300
C3—C41.390 (5)C15—C161.382 (4)
C3—H30.9300C15—H150.9300
C4—C51.369 (5)C16—C171.394 (3)
C4—H40.9300C16—H160.9300
C5—C61.393 (4)C18—O41.403 (5)
C5—H50.9300C18—H18A0.9600
C6—N21.369 (4)C18—H18B0.9600
C7—N21.339 (3)C18—H18C0.9600
C7—C81.488 (3)N2—H2N0.78 (3)
C8—C91.528 (4)N4—H4N0.78 (3)
C8—H8A0.9700N5—O31.213 (4)
C8—H8B0.9700N5—O11.217 (4)
C9—C101.529 (4)N5—O21.249 (4)
C9—H9A0.9700O4—H4A0.816 (10)
N3—Cu1—N3i144.46 (12)H9A—C9—H9B107.8
N3—Cu1—N1100.35 (7)C11—C10—C9110.2 (2)
N3i—Cu1—N190.25 (7)C11—C10—H10A109.6
N3—Cu1—N1i90.25 (7)C9—C10—H10A109.6
N3i—Cu1—N1i100.35 (7)C11—C10—H10B109.6
N1—Cu1—N1i144.89 (11)C9—C10—H10B109.6
C7—N1—C1105.46 (19)H10A—C10—H10B108.1
C7—N1—Cu1131.33 (16)N3—C11—N4111.9 (2)
C1—N1—Cu1122.29 (15)N3—C11—C10126.2 (2)
C11—N3—C17105.48 (19)N4—C11—C10121.7 (2)
C11—N3—Cu1131.19 (16)N4—C12—C13132.3 (2)
C17—N3—Cu1121.32 (15)N4—C12—C17105.3 (2)
C6—C1—C2119.8 (2)C13—C12—C17122.4 (2)
C6—C1—N1108.6 (2)C14—C13—C12116.8 (2)
C2—C1—N1131.6 (2)C14—C13—H13121.6
C3—C2—C1117.7 (3)C12—C13—H13121.6
C3—C2—H2121.2C13—C14—C15121.4 (3)
C1—C2—H2121.2C13—C14—H14119.3
C2—C3—C4121.7 (3)C15—C14—H14119.3
C2—C3—H3119.2C16—C15—C14121.9 (3)
C4—C3—H3119.2C16—C15—H15119.1
C5—C4—C3121.6 (3)C14—C15—H15119.1
C5—C4—H4119.2C15—C16—C17117.1 (2)
C3—C4—H4119.2C15—C16—H16121.4
C4—C5—C6116.9 (3)C17—C16—H16121.4
C4—C5—H5121.6C12—C17—C16120.3 (2)
C6—C5—H5121.6C12—C17—N3108.7 (2)
N2—C6—C5132.0 (3)C16—C17—N3131.0 (2)
N2—C6—C1105.6 (2)O4—C18—H18A109.5
C5—C6—C1122.4 (3)O4—C18—H18B109.5
N1—C7—N2111.5 (2)H18A—C18—H18B109.5
N1—C7—C8127.3 (2)O4—C18—H18C109.5
N2—C7—C8121.2 (2)H18A—C18—H18C109.5
C7—C8—C9111.8 (2)H18B—C18—H18C109.5
C7—C8—H8A109.3C7—N2—C6108.9 (2)
C9—C8—H8A109.3C7—N2—H2N124 (2)
C7—C8—H8B109.3C6—N2—H2N126 (2)
C9—C8—H8B109.3C11—N4—C12108.6 (2)
H8A—C8—H8B107.9C11—N4—H4N123 (2)
C8—C9—C10112.97 (19)C12—N4—H4N128 (2)
C8—C9—H9A109.0O3—N5—O1122.3 (4)
C10—C9—H9A109.0O3—N5—O2118.9 (3)
C8—C9—H9B109.0O1—N5—O2118.9 (3)
C10—C9—H9B109.0C18—O4—H4A117 (4)
N3—Cu1—N1—C7−30.8 (2)N2—C7—C8—C9−93.1 (3)
N3i—Cu1—N1—C7115.1 (2)C7—C8—C9—C10−59.3 (3)
N1i—Cu1—N1—C7−136.3 (2)C8—C9—C10—C11−59.8 (3)
N3—Cu1—N1—C1161.87 (17)C17—N3—C11—N40.3 (3)
N3i—Cu1—N1—C1−52.24 (18)Cu1—N3—C11—N4−163.27 (17)
N1i—Cu1—N1—C156.35 (16)C17—N3—C11—C10−174.9 (2)
N3i—Cu1—N3—C11−146.5 (2)Cu1—N3—C11—C1021.5 (4)
N1—Cu1—N3—C11−41.2 (2)C9—C10—C11—N382.5 (3)
N1i—Cu1—N3—C11105.1 (2)C9—C10—C11—N4−92.3 (3)
N3i—Cu1—N3—C1752.10 (16)N4—C12—C13—C14180.0 (3)
N1—Cu1—N3—C17157.37 (17)C17—C12—C13—C14−0.1 (4)
N1i—Cu1—N3—C17−56.28 (18)C12—C13—C14—C15−0.5 (5)
C7—N1—C1—C6−0.3 (2)C13—C14—C15—C160.0 (5)
Cu1—N1—C1—C6169.84 (15)C14—C15—C16—C171.1 (4)
C7—N1—C1—C2176.9 (2)N4—C12—C17—C16−178.9 (2)
Cu1—N1—C1—C2−13.0 (3)C13—C12—C17—C161.2 (4)
C6—C1—C2—C3−1.5 (3)N4—C12—C17—N30.3 (3)
N1—C1—C2—C3−178.5 (2)C13—C12—C17—N3−179.7 (2)
C1—C2—C3—C41.2 (4)C15—C16—C17—C12−1.6 (4)
C2—C3—C4—C5−0.1 (4)C15—C16—C17—N3179.4 (3)
C3—C4—C5—C6−0.7 (4)C11—N3—C17—C12−0.4 (3)
C4—C5—C6—N2178.3 (3)Cu1—N3—C17—C12165.21 (16)
C4—C5—C6—C10.3 (4)C11—N3—C17—C16178.7 (3)
C2—C1—C6—N2−177.6 (2)Cu1—N3—C17—C16−15.7 (4)
N1—C1—C6—N20.0 (3)N1—C7—N2—C6−0.6 (3)
C2—C1—C6—C50.8 (4)C8—C7—N2—C6176.1 (2)
N1—C1—C6—C5178.4 (2)C5—C6—N2—C7−177.8 (3)
C1—N1—C7—N20.6 (3)C1—C6—N2—C70.4 (3)
Cu1—N1—C7—N2−168.34 (16)N3—C11—N4—C12−0.1 (3)
C1—N1—C7—C8−175.9 (2)C10—C11—N4—C12175.4 (2)
Cu1—N1—C7—C815.1 (4)C13—C12—N4—C11179.8 (3)
N1—C7—C8—C983.1 (3)C17—C12—N4—C11−0.1 (3)
Symmetry codes: (i) −x+1/2, −y+3/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O2ii0.82 (1)2.01 (2)2.814 (4)167 (5)
O4—H4A···O1ii0.82 (1)2.60 (4)3.261 (5)139 (5)
N2—H2N···O3iii0.78 (3)2.21 (3)2.929 (4)152 (3)
N2—H2N···O2iii0.78 (3)2.37 (3)2.969 (3)134 (3)
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, y, z.
Table 1
Selected geometric parameters (°) top
N3—Cu1—N3i144.46 (12)N3—Cu1—N1i90.25 (7)
N3—Cu1—N1100.35 (7)N1—Cu1—N1i144.89 (11)
Symmetry codes: (i) −x+1/2, −y+3/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O2ii0.82 (1)2.01 (2)2.814 (4)167 (5)
O4—H4A···O1ii0.82 (1)2.60 (4)3.261 (5)139 (5)
N2—H2N···O3iii0.78 (3)2.21 (3)2.929 (4)152 (3)
N2—H2N···O2iii0.78 (3)2.37 (3)2.969 (3)134 (3)
Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) x−1, y, z.
Acknowledgements top

This work is supported by the Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology (No. RCT2004011).

references
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