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Acta Cryst. (2007). E63, m1678-m1679    [ doi:10.1107/S160053680702288X ]

cis-[N-(4-Chlorobenzyl)iminodiacetato-[kappa]3N,O,O']bis(1H-imidazole-[kappa]N3)copper(II)

M. P. Brandi-Blanco, M. M. de Benavides-Giménez, J. M. González-Pérez and D. Choquesillo-Lazarte

Abstract top

In the title compound, [Cu(C11H10ClNO4)(C3H4N)2], the CuII atom is in a square-pyramidal coordination geometry, with the two imidazole ligands in cis positions and the N-(4-chlorobenzyl)iminodiacetate ligand occupying the apical and two cis-basal positions. In the crystal structure, molecules are linked into sheets by N-H...O hydrogen bonds.

Comment top

The molecular structure of (I) (Fig. 1) is centrosymmetric. The Cu(II) atom exhibits a square pyramidal coordination geometry, with a τ parameter of 0.27 (Addison et al., 1984), built by a N-(p-chlorobenzyl)iminodiacetato ligand in a fac-tridentate conformation and two cis imidazole ligands. In the dianionic ligand, the two five-membered chelate rings lie nearly perpendicular (dihedral angle 72.1 (1)°).

In the crystal, centrosymmetric pairs of molecules are H-bonded by two N—H···O interactions involving parallel Him (N23) ligands which are weakly π,π-stacked (Fig. 2). Additional N—H···O interactions connect pairs of molecules generating sheets (Fig. 3).

Related literature top

In addition to the related dinuclear iminodiacetate derivative (Nguyen-Huy et al., 1990), it is known that a closely related N-(benzyl)iminodiacetate(2-) derivative also exists, and is a Him solvate as well, with Him referring to the imidazole molecule (Polyakova et al., 2001).

For related literature, see: Addison et al. (1984).

Experimental top

The new ternary complex [CuII(C11H10ClNO4)(C3H4N)2] was obtained by reaction of a mixture having Cu2CO3(OH)2/H2L/Him 1 mmol/2 mmol/20 mmol (H2L, N-(p-chlorobenzyl)iminodiacetic acid; Him, imidazole) in water (200 ml); with Him in a large excess. The resulting solution was filtered on a crystallization device which was covered with a plastic film to control the evaporation. After multiple days, prismatic blue crystals were collected and used for X-ray diffraction studies.

Refinement top

The amine (imidazole) H atoms were located in the difference map and refined as riding, with N—H = 0.86 Å and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and treated as riding with C—H = 0.95–0.99 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as spheres of arbitrary radii.
[Figure 2] Fig. 2. A pair of centrosymmetric molecules of (I) built by N—H···O and π,π-interactions (dashed lines). Symmetry code (i): -x, -y, -z.
[Figure 3] Fig. 3. A view of part of the crystal structure of (I), showing the formation of a sheet. The hydrogen bonds and π,π stacking interactions are shown as dashed lines and for the sake of clarity the H atoms bonded to C atoms have been omitted..
cis-[N-(4-Chlorobenzyl)iminodiacetato-κ3N,O,O']bis(1H-imidazole- κN3)copper(II) top
Crystal data top
[Cu(C11H10ClNO4)(C3H4N)2]F(000) = 932
Mr = 455.35Dx = 1.599 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9904 reflections
a = 10.2028 (5) Åθ = 2.3–27.8°
b = 13.4280 (6) ŵ = 1.33 mm−1
c = 13.9113 (7) ÅT = 298 K
β = 97.119 (1)°Prism, blue
V = 1891.20 (16) Å30.49 × 0.32 × 0.15 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4437 independent reflections
Radiation source: fine-focus sealed tube4043 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −13→13
Tmin = 0.562, Tmax = 0.825k = −17→17
21629 measured reflectionsl = −18→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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0462P)2 + 0.8491P]
where P = (Fo2 + 2Fc2)/3
4437 reflections(Δ/σ)max = 0.001
253 parametersΔρmax = 0.55 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Cu(C11H10ClNO4)(C3H4N)2]V = 1891.20 (16) Å3
Mr = 455.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.2028 (5) ŵ = 1.33 mm−1
b = 13.4280 (6) ÅT = 298 K
c = 13.9113 (7) Å0.49 × 0.32 × 0.15 mm
β = 97.119 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		4437 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		4043 reflections with I > 2σ(I)
Tmin = 0.562, Tmax = 0.825Rint = 0.024
21629 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.086Δρmax = 0.55 e Å−3
S = 1.05Δρmin = −0.47 e Å−3
4437 reflectionsAbsolute structure: ?
253 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.

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
Cu10.245284 (19)0.061386 (15)0.202469 (15)0.02673 (8)
N10.42366 (14)0.13906 (11)0.21938 (11)0.0286 (3)
C20.39633 (19)0.24419 (13)0.19177 (15)0.0357 (4)
H2A0.47710.27510.17640.043*
H2B0.36800.27950.24640.043*
C30.28983 (18)0.25385 (14)0.10470 (14)0.0334 (4)
O40.20768 (13)0.18265 (10)0.09352 (10)0.0367 (3)
O50.28859 (16)0.33030 (12)0.05607 (13)0.0534 (4)
C60.49925 (17)0.09147 (13)0.14677 (14)0.0309 (4)
H6A0.59310.09760.16820.037*
H6B0.48060.12610.08540.037*
C70.46428 (17)−0.01813 (13)0.13216 (13)0.0294 (3)
O80.34874 (12)−0.04288 (9)0.14890 (10)0.0340 (3)
O90.54492 (13)−0.07508 (10)0.10158 (11)0.0390 (3)
C100.4993 (2)0.13779 (15)0.31940 (14)0.0382 (4)
H10A0.57130.18520.32190.046*
H10B0.44130.15910.36560.046*
C110.55438 (19)0.03720 (15)0.34877 (14)0.0354 (4)
C120.4757 (2)−0.03648 (16)0.38096 (15)0.0391 (4)
H120.3882−0.02240.38820.047*
C130.5256 (2)−0.13117 (17)0.40257 (15)0.0429 (5)
H130.4726−0.18080.42400.052*
C140.6554 (2)−0.14963 (16)0.39155 (16)0.0452 (5)
Cl140.71813 (8)−0.26918 (5)0.41465 (7)0.0785 (2)
C150.7374 (2)−0.0771 (2)0.3637 (2)0.0544 (6)
H150.8257−0.09090.35890.065*
C160.6863 (2)0.01688 (18)0.34306 (17)0.0478 (5)
H160.74120.06710.32510.057*
N210.08104 (14)−0.01447 (12)0.15999 (11)0.0313 (3)
C220.06850 (19)−0.08136 (14)0.09012 (14)0.0342 (4)
H220.1385−0.10740.06120.041*
N23−0.05788 (16)−0.10680 (13)0.06625 (12)0.0385 (4)
H23−0.0938−0.14000.01780.046*
C24−0.1310 (2)−0.05290 (18)0.12264 (19)0.0507 (6)
H24−0.2223−0.05440.12150.061*
C25−0.0452 (2)0.00305 (19)0.18050 (17)0.0484 (5)
H25−0.06780.04700.22740.058*
N310.16465 (15)0.12642 (12)0.31048 (11)0.0333 (3)
C320.1159 (2)0.21764 (15)0.30966 (15)0.0382 (4)
H320.13430.26720.26660.046*
N330.03733 (18)0.22961 (13)0.37816 (13)0.0432 (4)
H330.00690.28720.39120.052*
C340.0349 (2)0.14175 (17)0.42734 (16)0.0463 (5)
H34−0.01180.12830.47920.056*
C350.1139 (2)0.07826 (15)0.38561 (15)0.0393 (4)
H350.13140.01270.40450.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02382 (12)0.02576 (13)0.03157 (13)−0.00142 (7)0.00726 (8)−0.00333 (8)
N10.0274 (7)0.0249 (7)0.0333 (7)−0.0021 (5)0.0031 (6)−0.0019 (6)
C20.0360 (10)0.0241 (8)0.0469 (10)−0.0043 (7)0.0046 (8)−0.0022 (8)
C30.0313 (9)0.0308 (9)0.0398 (9)0.0016 (7)0.0114 (7)0.0025 (7)
O40.0364 (7)0.0343 (7)0.0383 (7)−0.0045 (5)−0.0003 (5)0.0031 (6)
O50.0478 (9)0.0449 (9)0.0683 (10)−0.0006 (7)0.0098 (8)0.0252 (8)
C60.0265 (8)0.0296 (9)0.0377 (9)−0.0038 (7)0.0082 (7)−0.0015 (7)
C70.0255 (8)0.0314 (9)0.0316 (8)−0.0010 (7)0.0049 (7)−0.0008 (7)
O80.0254 (6)0.0296 (6)0.0486 (8)−0.0038 (5)0.0113 (5)−0.0092 (5)
O90.0299 (7)0.0339 (7)0.0560 (9)0.0008 (5)0.0167 (6)−0.0054 (6)
C100.0384 (10)0.0348 (10)0.0393 (10)−0.0033 (8)−0.0035 (8)−0.0060 (8)
C110.0330 (9)0.0404 (10)0.0314 (9)−0.0022 (8)−0.0017 (7)−0.0025 (8)
C120.0287 (9)0.0492 (11)0.0391 (10)−0.0023 (8)0.0026 (8)0.0010 (9)
C130.0398 (11)0.0451 (11)0.0428 (11)−0.0094 (9)0.0007 (8)0.0053 (9)
C140.0470 (12)0.0425 (11)0.0456 (11)0.0057 (9)0.0037 (9)0.0062 (9)
Cl140.0848 (5)0.0506 (4)0.1031 (6)0.0214 (3)0.0231 (4)0.0204 (4)
C150.0358 (11)0.0629 (15)0.0663 (15)0.0110 (10)0.0133 (10)0.0200 (12)
C160.0341 (10)0.0507 (13)0.0582 (13)−0.0046 (9)0.0043 (9)0.0146 (10)
N210.0252 (7)0.0338 (8)0.0356 (8)−0.0022 (6)0.0065 (6)−0.0010 (6)
C220.0328 (9)0.0332 (9)0.0370 (9)−0.0026 (7)0.0057 (7)−0.0010 (7)
N230.0357 (8)0.0392 (9)0.0388 (8)−0.0086 (7)−0.0023 (7)0.0000 (7)
C240.0264 (10)0.0654 (15)0.0606 (14)−0.0069 (9)0.0062 (9)−0.0075 (11)
C250.0275 (10)0.0648 (15)0.0548 (13)−0.0037 (9)0.0123 (9)−0.0177 (11)
N310.0355 (8)0.0315 (8)0.0344 (8)0.0009 (6)0.0104 (6)−0.0024 (6)
C320.0446 (11)0.0333 (10)0.0388 (10)0.0050 (8)0.0130 (8)0.0007 (8)
N330.0490 (10)0.0373 (9)0.0459 (9)0.0095 (8)0.0169 (8)−0.0047 (7)
C340.0542 (13)0.0482 (12)0.0403 (11)0.0032 (10)0.0214 (9)−0.0007 (9)
C350.0469 (11)0.0328 (10)0.0402 (10)0.0028 (8)0.0138 (9)0.0026 (8)
Geometric parameters (Å, °) top
Cu1—O81.9556 (13)C13—C141.374 (3)
Cu1—N211.9874 (15)C13—H130.9300
Cu1—N312.0009 (15)C14—C151.370 (3)
Cu1—N12.0855 (14)C14—Cl141.743 (2)
Cu1—O42.2252 (13)C15—C161.382 (3)
N1—C21.480 (2)C15—H150.9300
N1—C61.489 (2)C16—H160.9300
N1—C101.505 (2)N21—C221.318 (2)
C2—C31.529 (3)N21—C251.373 (2)
C2—H2A0.9700C22—N231.335 (2)
C2—H2B0.9700C22—H220.9300
C3—O51.229 (2)N23—C241.357 (3)
C3—O41.268 (2)N23—H230.8528
C6—C71.522 (2)C24—C251.343 (3)
C6—H6A0.9700C24—H240.9300
C6—H6B0.9700C25—H250.9300
C7—O91.237 (2)N31—C321.322 (2)
C7—O81.274 (2)N31—C351.383 (2)
C10—C111.500 (3)C32—N331.329 (3)
C10—H10A0.9700C32—H320.9300
C10—H10B0.9700N33—C341.366 (3)
C11—C121.383 (3)N33—H330.8605
C11—C161.386 (3)C34—C351.353 (3)
C12—C131.389 (3)C34—H340.9300
C12—H120.9300C35—H350.9300
O8—Cu1—N2189.70 (6)C11—C12—C13120.84 (19)
O8—Cu1—N31152.89 (6)C11—C12—H12119.6
N21—Cu1—N3192.12 (6)C13—C12—H12119.6
O8—Cu1—N184.05 (5)C14—C13—C12118.28 (19)
N21—Cu1—N1169.05 (6)C14—C13—H13120.9
N31—Cu1—N197.54 (6)C12—C13—H13120.9
O8—Cu1—O4108.66 (6)C15—C14—C13122.3 (2)
N21—Cu1—O496.01 (6)C15—C14—Cl14118.91 (18)
N31—Cu1—O498.04 (6)C13—C14—Cl14118.83 (18)
N1—Cu1—O477.60 (5)C14—C15—C16118.7 (2)
C2—N1—C6109.27 (14)C14—C15—H15120.7
C2—N1—C10108.01 (14)C16—C15—H15120.7
C6—N1—C10111.90 (14)C15—C16—C11120.8 (2)
C2—N1—Cu1108.30 (11)C15—C16—H16119.6
C6—N1—Cu1103.12 (10)C11—C16—H16119.6
C10—N1—Cu1116.03 (11)C22—N21—C25105.20 (16)
N1—C2—C3112.27 (15)C22—N21—Cu1124.73 (13)
N1—C2—H2A109.2C25—N21—Cu1128.92 (14)
C3—C2—H2A109.2N21—C22—N23111.10 (17)
N1—C2—H2B109.2N21—C22—H22124.4
C3—C2—H2B109.2N23—C22—H22124.4
H2A—C2—H2B107.9C22—N23—C24107.64 (17)
O5—C3—O4126.93 (19)C22—N23—H23129.6
O5—C3—C2117.70 (17)C24—N23—H23121.6
O4—C3—C2115.28 (16)C25—C24—N23106.28 (19)
C3—O4—Cu1114.37 (12)C25—C24—H24126.9
N1—C6—C7111.90 (14)N23—C24—H24126.9
N1—C6—H6A109.2C24—C25—N21109.77 (19)
C7—C6—H6A109.2C24—C25—H25125.1
N1—C6—H6B109.2N21—C25—H25125.1
C7—C6—H6B109.2C32—N31—C35105.33 (16)
H6A—C6—H6B107.9C32—N31—Cu1125.97 (13)
O9—C7—O8124.87 (17)C35—N31—Cu1126.20 (13)
O9—C7—C6119.27 (15)N31—C32—N33111.45 (18)
O8—C7—C6115.78 (15)N31—C32—H32124.3
C7—O8—Cu1116.00 (11)N33—C32—H32124.3
C11—C10—N1113.20 (15)C32—N33—C34107.75 (17)
C11—C10—H10A108.9C32—N33—H33121.7
N1—C10—H10A108.9C34—N33—H33129.8
C11—C10—H10B108.9C35—C34—N33106.30 (18)
N1—C10—H10B108.9C35—C34—H34126.9
H10A—C10—H10B107.8N33—C34—H34126.9
C12—C11—C16119.00 (19)C34—C35—N31109.17 (18)
C12—C11—C10121.28 (18)C34—C35—H35125.4
C16—C11—C10119.72 (19)N31—C35—H35125.4
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N23—H23···O4i0.851.902.733 (2)164
N33—H33···O9ii0.861.932.779 (2)169
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O81.9556 (13)Cu1—N12.0855 (14)
Cu1—N211.9874 (15)Cu1—O42.2252 (13)
Cu1—N312.0009 (15)
O8—Cu1—N2189.70 (6)N31—Cu1—N197.54 (6)
O8—Cu1—N31152.89 (6)O8—Cu1—O4108.66 (6)
N21—Cu1—N3192.12 (6)N21—Cu1—O496.01 (6)
O8—Cu1—N184.05 (5)N31—Cu1—O498.04 (6)
N21—Cu1—N1169.05 (6)N1—Cu1—O477.60 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N23—H23···O4i0.851.902.733 (2)164
N33—H33···O9ii0.861.932.779 (2)169
Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z+1/2.
Acknowledgements top

Financial support from ERDF-EC, MEC Spain (project CTQ2006–15329-C02–02/BQU) is gratefully acknowledged. DCh-L thanks CSIC-EU for an I3P postdoctoral research contract.

references
References top

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Westrip, S. P. (2007). publCIF. In preparation.