Diaqua­bis(ethyl­enediamine)copper(II) bis­(4-nitro­benzoate)

Harrison, W.T.A.; Slawin, A.M.Z.; Sharma, R.P.; Sharma, B.; Bhama, S.

doi:10.1107/S1600536806052901

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 63| Part 1| January 2007| Pages m178-m180

https://doi.org/10.1107/S1600536806052901

Diaquabis(ethylenediamine)copper(II) bis(4-nitrobenzoate)

William T. A. Harrison,^a ^* Alexandra M. Z. Slawin,^b Raj Pal Sharma,^c ^* Bhavna Sharma ^c and Shekar Bhama ^c

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, and ^cPanjab University, Department of Chemistry, Chandigarh 160 014, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk, rpsharma@yahoo.co.in

(Received 27 October 2006; accepted 6 December 2006; online 13 December 2006)

In the title compound, [Cu(C₂H₈N₂)₂(H₂O)₂](C₇H₄NO₄)₂, the component complex cations and organic anions interact by way of N—H⋯O and O—H⋯O hydrogen bonds, leading to a layered structure. The Cu atom has site symmetry $[\overline{1}]$ .

Comment

The title compound, (I), was prepared as part of our ongoing studies of second-sphere hydrogen-bonding interactions in compounds containing cationic metal complexes and organic counter-anions (Sharma, Bala et al., 2006 ; Sharma, Sharma et al., 2006 ).

The geometrical parameters for the component species in (I) fall within their expected ranges (Allen et al., 1987 ). The well known [Cu(C₂N₂H₈)₂(H₂O)₂]²⁺ complex cation in (I) is built up from a central copper(II) ion (site symmetry $[\overline{1}]$ ) chelated by two ethylenediamine molecules to form an approximate CuN₄ square. The Jahn–Teller distorted copper coordination is completed by two trans water molecules (Table 1). The Cu—N and Cu—O bond lengths in (I) are very similar to the equivalent values observed for the same complex cation in its bis(naphthalene-2-sulfonate) (Sharma et al., 2005 ) and bis(4-fluorobenzoate) (Liu et al., 2004 ) salts.

The 4-nitrobenzoate anion in (I) is almost planar, the dihedral angles between the mean plane of the C3–C8 benzene ring and the planes of its attached C9/O2/O3 carboxylate and N3/O4/O5 nitro groups being 2.14 (17) and 1.9 (2)°, respectively. The carboxylate C—O bond lengths are almost equal, suggesting charge delocalization.

As well as electrostatic forces, the component species in (I) interact by way of O—H⋯O and N—H⋯O hydrogen bonds (Table 2). Firstly, adjacent complex cations are linked into chains propagating along [100] by way of translation-related pairs of N1—H1⋯O1ⁱ bonds (see Table 2 for symmetry code). A bridging carboxylate atom O3 also helps to consolidate the chains (Fig. 2). Then, adjacent cations and anions form a distinctive bridged chain propagating along [010] (Fig. 3), where each carboxylate group in the chain accepts no fewer than four hydrogen bonds from its two adjoining cations. Combining these hydrogen-bonding motifs results in (001) sheets of tightly bound cations and anions. It is notable that the nitro O atoms do not serve as acceptors for any of the hydrogen bonds.

Figure 1
View of the molecular structure of (I)

, showing 50% probability displacement ellipsoids (arbitrary spheres for the H atoms). [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]

Figure 2
Detail of (I)

, showing part of a [100] chain arising from hydrogen-bonding interactions (dashed lines). C-bound H atoms have been omitted. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 2 − x, 1 − y, 1 − z; (iii) 1 + x, y, z; (iv) 1 + x, 1 + y, z.]

Figure 3
Detail of (I)

, showing part of a [010] chain arising from hydrogen-bonding interactions (dashed lines). C-bound H atoms have been omitted. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 1 + y, z; (iii) 1 − x, 2 − y, 1 − z; (iv) x, 1 + y, z.]

Experimental

Compound (I) was prepared by taking a suspension of [Cu(H₂O)₆](C₇H₄NO₄)₂ [obtained by reacting basic copper(II) carbonate with p-nitrobenzoic acid in water] and adding a methanol solution of ethylenediamine dropwise until a slight excess of a 1:2 Cu–en stoichiometry was achieved, resulting in a deep-blue solution, which was allowed to evaporate at room temperature to obtain purple crystals of (I) after a few days. Crystals were filtered off and dried in air.

Crystal data

[Cu(C₂H₈N₂)₂(H₂O)₂](C₇H₄NO₄)₂
M_r = 552.00
Triclinic, $[P \overline 1]$
a = 6.0019 (5) Å
b = 7.1230 (4) Å
c = 15.370 (2) Å
α = 95.48 (2)°
β = 98.43 (2)°
γ = 114.26 (2)°
V = 583.69 (15) Å³
Z = 1
D_x = 1.570 Mg m⁻³
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 93 (2) K
Cube, purple
0.10 × 0.10 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer
φ and ω scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.856, T_max = 1.000 (expected range = 0.774–0.905)
3754 measured reflections
2005 independent reflections
1930 reflections with I > 2σ(I)
R_int = 0.015
θ_max = 25.3°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.077
S = 1.08
2005 reflections
160 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0337P)² + 0.5044P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.0146 (18)
Cu1—N2	2.0272 (19)
Cu1—O1	2.5369 (17)
C9—O2	1.256 (3)
C9—O3	1.261 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.92	2.11	3.018 (2)	170
N1—H2⋯O3	0.92	2.20	3.081 (2)	161
N2—H3⋯O3ⁱⁱ	0.92	2.24	3.037 (3)	145
N2—H4⋯O2ⁱⁱⁱ	0.92	2.07	2.960 (2)	162
O1—H5⋯O3^iv	0.89	1.88	2.754 (2)	166
O1—H6⋯O2	0.86	1.93	2.767 (2)	164
Symmetry codes: (i) x-1, y, z; (ii) x+1, y+1, z; (iii) x, y+1, z; (iv) -x+1, -y, -z+1.

The O-bound H atoms were located in a difference map and refined as riding in their as-found relative positions with U_iso(H) = 1.2U_eq(O). The C- and N-bound H atoms were geometrically placed (C—H = 0.95–0.99 Å, N—H = 0.92 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N).

Data collection: CrystalClear (Rigaku, 2004 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806052901/cf2072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806052901/cf2072Isup2.hkl

Computing details top

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Diaquabis(ethylenediamine)copper(II) bis(4-nitrobenzoate) top

Crystal data top

[Cu(C₂H₈N₂)₂(H₂O)₂](C₇H₄NO₄)₂	Z = 1
M_r = 552.00	F(000) = 287
Triclinic, P1	D_x = 1.570 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0019 (5) Å	Cell parameters from 2340 reflections
b = 7.1230 (4) Å	θ = 2.7–28.2°
c = 15.370 (2) Å	µ = 1.00 mm⁻¹
α = 95.48 (2)°	T = 93 K
β = 98.43 (2)°	Cube, purple
γ = 114.26 (2)°	0.10 × 0.10 × 0.10 mm
V = 583.69 (15) Å³

Data collection top

Rigaku Mercury CCD diffractometer	2005 independent reflections
Radiation source: rotating anode	1930 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.015
Detector resolution: 0.83 pixels mm^-1	θ_max = 25.3°, θ_min = 2.7°
φ and ω scans	h = −5→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −6→8
T_min = 0.856, T_max = 1.000	l = −18→18
3754 measured reflections

Refinement top

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0337P)² + 0.5044P] where P = (F_o² + 2F_c²)/3
2005 reflections	(Δ/σ)_max = 0.002
160 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.01301 (14)
C1	0.3527 (4)	0.4877 (4)	0.66944 (15)	0.0177 (5)
H1A	0.2872	0.4000	0.7143	0.021*
H1B	0.2922	0.5978	0.6710	0.021*
C2	0.6352 (4)	0.5864 (4)	0.69053 (15)	0.0177 (5)
H2A	0.6998	0.6899	0.7465	0.021*
H2B	0.6960	0.4780	0.6983	0.021*
N1	0.2647 (3)	0.3572 (3)	0.57892 (12)	0.0131 (4)
H1	0.1061	0.3396	0.5551	0.016*
H2	0.2599	0.2274	0.5826	0.016*
N2	0.7230 (3)	0.6905 (3)	0.61493 (12)	0.0138 (4)
H3	0.8861	0.7141	0.6160	0.017*
H4	0.7145	0.8170	0.6191	0.017*
O1	0.7238 (3)	0.2674 (2)	0.51837 (10)	0.0158 (4)
H5	0.7064	0.1756	0.4710	0.019*
H6	0.6952	0.1896	0.5589	0.019*
C3	0.4867 (4)	0.1037 (3)	0.78913 (14)	0.0139 (5)
C4	0.7093 (5)	0.2037 (5)	0.85044 (17)	0.0297 (6)
H4A	0.8620	0.2341	0.8313	0.036*
C5	0.7131 (5)	0.2603 (5)	0.93950 (17)	0.0354 (7)
H5A	0.8666	0.3270	0.9818	0.042*
C6	0.4916 (4)	0.2183 (3)	0.96539 (15)	0.0167 (5)
C7	0.2672 (5)	0.1185 (5)	0.90654 (17)	0.0350 (7)
H7	0.1152	0.0891	0.9262	0.042*
C8	0.2663 (5)	0.0614 (5)	0.81761 (17)	0.0330 (7)
H8	0.1120	−0.0078	0.7759	0.040*
C9	0.4873 (4)	0.0454 (3)	0.69155 (14)	0.0136 (5)
N3	0.4942 (4)	0.2855 (3)	1.05959 (13)	0.0222 (5)
O2	0.6956 (3)	0.0885 (2)	0.67087 (10)	0.0171 (4)
O3	0.2795 (3)	−0.0400 (2)	0.63757 (10)	0.0183 (4)
O4	0.6929 (4)	0.3750 (4)	1.11118 (13)	0.0516 (6)
O5	0.2963 (4)	0.2486 (4)	1.08147 (13)	0.0499 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0109 (2)	0.0139 (2)	0.0121 (2)	0.00344 (16)	0.00238 (15)	0.00153 (15)
C1	0.0215 (13)	0.0168 (13)	0.0140 (11)	0.0066 (10)	0.0070 (10)	0.0020 (9)
C2	0.0204 (13)	0.0176 (13)	0.0124 (11)	0.0065 (10)	0.0012 (10)	0.0017 (9)
N1	0.0124 (9)	0.0120 (10)	0.0152 (9)	0.0059 (8)	0.0019 (8)	0.0018 (7)
N2	0.0111 (9)	0.0127 (10)	0.0172 (10)	0.0048 (8)	0.0037 (8)	0.0017 (8)
O1	0.0175 (8)	0.0155 (8)	0.0158 (8)	0.0080 (7)	0.0046 (7)	0.0032 (6)
C3	0.0172 (12)	0.0093 (12)	0.0164 (11)	0.0067 (9)	0.0034 (9)	0.0025 (9)
C4	0.0155 (13)	0.0513 (18)	0.0181 (13)	0.0107 (12)	0.0046 (10)	0.0028 (12)
C5	0.0165 (14)	0.0567 (19)	0.0168 (13)	0.0039 (13)	−0.0026 (11)	−0.0018 (12)
C6	0.0261 (13)	0.0135 (12)	0.0118 (11)	0.0096 (10)	0.0050 (10)	0.0015 (9)
C7	0.0181 (14)	0.063 (2)	0.0184 (13)	0.0124 (13)	0.0080 (11)	−0.0036 (13)
C8	0.0153 (13)	0.0508 (18)	0.0197 (13)	0.0038 (12)	0.0034 (11)	−0.0050 (12)
C9	0.0191 (12)	0.0086 (11)	0.0152 (11)	0.0073 (9)	0.0047 (10)	0.0037 (9)
N3	0.0327 (13)	0.0195 (11)	0.0138 (10)	0.0106 (10)	0.0052 (10)	0.0020 (8)
O2	0.0167 (8)	0.0188 (9)	0.0183 (8)	0.0086 (7)	0.0075 (7)	0.0038 (7)
O3	0.0162 (9)	0.0215 (9)	0.0135 (8)	0.0054 (7)	0.0027 (7)	−0.0005 (6)
O4	0.0385 (13)	0.0721 (16)	0.0171 (10)	0.0033 (11)	0.0003 (10)	−0.0118 (10)
O5	0.0417 (13)	0.0851 (18)	0.0219 (11)	0.0273 (12)	0.0131 (10)	−0.0052 (11)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	2.0146 (18)	O1—H6	0.8625
Cu1—N1	2.0146 (18)	C3—C8	1.378 (3)
Cu1—N2	2.0272 (19)	C3—C4	1.379 (3)
Cu1—N2ⁱ	2.0272 (19)	C3—C9	1.519 (3)
Cu1—O1	2.5369 (17)	C4—C5	1.384 (4)
Cu1—O1ⁱ	2.5369 (17)	C4—H4A	0.950
C1—N1	1.488 (3)	C5—C6	1.366 (4)
C1—C2	1.513 (3)	C5—H5A	0.950
C1—H1A	0.990	C6—C7	1.368 (4)
C1—H1B	0.990	C6—N3	1.477 (3)
C2—N2	1.483 (3)	C7—C8	1.387 (4)
C2—H2A	0.990	C7—H7	0.950
C2—H2B	0.990	C8—H8	0.950
N1—H1	0.920	C9—O2	1.256 (3)
N1—H2	0.920	C9—O3	1.261 (3)
N2—H3	0.920	N3—O4	1.208 (3)
N2—H4	0.920	N3—O5	1.212 (3)
O1—H5	0.8941

N1ⁱ—Cu1—N1	180.0	H1—N1—H2	108.3
N1ⁱ—Cu1—N2	95.08 (7)	C2—N2—Cu1	107.93 (14)
N1—Cu1—N2	84.92 (7)	C2—N2—H3	110.1
N1ⁱ—Cu1—N2ⁱ	84.92 (7)	Cu1—N2—H3	110.1
N1—Cu1—N2ⁱ	95.08 (7)	C2—N2—H4	110.1
N2—Cu1—N2ⁱ	180.0	Cu1—N2—H4	110.1
O1—Cu1—N1	92.58 (7)	H3—N2—H4	108.4
O1—Cu1—N2	89.44 (7)	H5—O1—H6	101.3
O1—Cu1—N1ⁱ	87.42 (7)	C8—C3—C4	119.0 (2)
O1—Cu1—N2ⁱ	90.56 (7)	C8—C3—C9	121.0 (2)
O1ⁱ—Cu1—N1ⁱ	92.58 (7)	C4—C3—C9	119.9 (2)
O1ⁱ—Cu1—N2ⁱ	89.44 (7)	C3—C4—C5	120.9 (2)
O1ⁱ—Cu1—N1	87.42 (7)	C3—C4—H4A	119.6
O1ⁱ—Cu1—N2	90.56 (7)	C5—C4—H4A	119.6
O1—Cu1—O1ⁱ	180.0	C6—C5—C4	118.6 (2)
N1—C1—C2	108.30 (18)	C6—C5—H5A	120.7
N1—C1—H1A	110.0	C4—C5—H5A	120.7
C2—C1—H1A	110.0	C5—C6—C7	122.1 (2)
N1—C1—H1B	110.0	C5—C6—N3	119.1 (2)
C2—C1—H1B	110.0	C7—C6—N3	118.8 (2)
H1A—C1—H1B	108.4	C6—C7—C8	118.6 (2)
N2—C2—C1	107.83 (18)	C6—C7—H7	120.7
N2—C2—H2A	110.1	C8—C7—H7	120.7
C1—C2—H2A	110.1	C3—C8—C7	120.8 (2)
N2—C2—H2B	110.1	C3—C8—H8	119.6
C1—C2—H2B	110.1	C7—C8—H8	119.6
H2A—C2—H2B	108.5	O2—C9—O3	125.2 (2)
C1—N1—Cu1	109.03 (13)	O2—C9—C3	117.2 (2)
C1—N1—H1	109.9	O3—C9—C3	117.57 (19)
Cu1—N1—H1	109.9	O4—N3—O5	123.0 (2)
C1—N1—H2	109.9	O4—N3—C6	118.6 (2)
Cu1—N1—H2	109.9	O5—N3—C6	118.4 (2)

N1—C1—C2—N2	51.7 (2)	N3—C6—C7—C8	178.1 (2)
C2—C1—N1—Cu1	−36.6 (2)	C4—C3—C8—C7	0.2 (4)
N2—Cu1—N1—C1	11.08 (14)	C9—C3—C8—C7	−178.8 (3)
N2ⁱ—Cu1—N1—C1	−168.92 (14)	C6—C7—C8—C3	0.1 (5)
C1—C2—N2—Cu1	−41.2 (2)	C8—C3—C9—O2	−179.8 (2)
N1ⁱ—Cu1—N2—C2	−163.03 (14)	C4—C3—C9—O2	1.3 (3)
N1—Cu1—N2—C2	16.97 (14)	C8—C3—C9—O3	1.1 (3)
C8—C3—C4—C5	0.3 (4)	C4—C3—C9—O3	−177.8 (2)
C9—C3—C4—C5	179.3 (2)	C5—C6—N3—O4	−0.3 (4)
C3—C4—C5—C6	−1.1 (4)	C7—C6—N3—O4	−179.4 (3)
C4—C5—C6—C7	1.4 (4)	C5—C6—N3—O5	179.4 (3)
C4—C5—C6—N3	−177.6 (2)	C7—C6—N3—O5	0.4 (4)
C5—C6—C7—C8	−0.9 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	0.92	2.11	3.018 (2)	170
N1—H2···O3	0.92	2.20	3.081 (2)	161
N2—H3···O3ⁱⁱⁱ	0.92	2.24	3.037 (3)	145
N2—H4···O2^iv	0.92	2.07	2.960 (2)	162
O1—H5···O3^v	0.89	1.88	2.754 (2)	166
O1—H6···O2	0.86	1.93	2.767 (2)	164

Symmetry codes: (ii) x−1, y, z; (iii) x+1, y+1, z; (iv) x, y+1, z; (v) −x+1, −y, −z+1.

Acknowledgements

The authors gratefully acknowledge the financial support of UGC vide grant No. F.12-38/2003(SR).

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