Bis(1-carbamimidoyl-2-ethyl­isourea)copper(II) dinitrate

Meenongwa, A.; Chaveerach, U.; Pakawatchai, C.

doi:10.1107/S1600536809041932

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1389-m1390

https://doi.org/10.1107/S1600536809041932

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Bis(1-carbamimidoyl-2-ethylisourea)copper(II) dinitrate

Atittaya Meenongwa,^a Unchulee Chaveerach ^a ^* and Chaveng Pakawatchai ^b

^aDepartment of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand, and ^bDepartment of Chemistry, Prince of Songkla University, Hatyai 90112, Thailand
^*Correspondence e-mail: sunchul@kku.ac.th

(Received 1 October 2009; accepted 13 October 2009; online 17 October 2009)

The copper(II) complex, [Cu(C₄H₁₀N₄O)₂](NO₃)₂ or [Cu(L^1e)₂](NO₃)₂, where L^1e is 1-carbamimidoyl-2-ethylisourea, was obtained from a 1:2 molar ratio of copper(II) nitrate hemipentahydrate with 2-cyanoguanidine in ethanol. The crystal structure consists of the centrosymmetric [Cu(L^1e)₂]²⁺ cation and two NO₃⁻ counter-anions. The cation exhibits four-coordinate bonding of the two N,N-bidentate ligands and the Cu^II atom through the N-donor atoms, yielding a square-planar CuN₄ geometry. Intermolecular N—H⋯O hydrogen bonds link between the cation and and counter-anion, forming a two-dimentional layered structure extending parallel to ( $[\overline3]$ 01).

Related literature

For a copper(II) complex containg the same N,N-bidentate 1-carbamimidoyl-2-ethylisourea ligand but with the charge balance provided by two chloride and perchlorate anions, see: Begley et al. (1986 ); Meenongwa et al. (2009 ).

Experimental

Crystal data

[Cu(C₄H₁₀N₄O)₂](NO₃)₂
M_r = 447.89
Monoclinic, P 2₁ /n
a = 5.2547 (6) Å
b = 14.0087 (15) Å
c = 12.1511 (13) Å
β = 96.982 (2)°
V = 887.83 (17) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 293 K
0.26 × 0.16 × 0.11 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.793, T_max = 1.00
11998 measured reflections
2206 independent reflections
1810 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.102
S = 1.05
2206 reflections
125 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—N1	1.932 (4)
Cu1—N1ⁱ	1.932 (4)
Cu1—N2	1.967 (4)
Cu1—N2ⁱ	1.967 (4)

N1—Cu1—N1ⁱ	180.0
N1—Cu1—N2	88.33 (19)
N1ⁱ—Cu1—N2	91.67 (19)
N1—Cu1—N2ⁱ	91.67 (19)
N1ⁱ—Cu1—N2ⁱ	88.33 (19)
N2—Cu1—N2ⁱ	179.999 (1)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱⁱ	0.86	2.05	2.904 (7)	170
N2—H2⋯O2ⁱⁱⁱ	0.86	2.18	3.009 (6)	163
N3—H3⋯O4	0.86	2.14	2.979 (6)	165
N4—H45⋯O3	0.86	2.06	2.917 (7)	171
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004 ) and publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809041932/ds2008sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809041932/ds2008Isup2.hkl

checkCIF report

Comment top

Herein, we report the structure of [Cu(L¹^e)₂](NO₃)₂, which was obtained from the similar procedure as previously reported by Meenongwa et al. (2009), but using copper(II) nitrate hemipentahydrate. Structural determination on the title complex reveals a centrosymmetric [Cu(L¹^e)₂]²⁺ cation and two NO₃^- counteranions. Fig. 1 shows the [Cu(L¹^e)₂]²⁺ moiety. The square-planar CuN₄ geometry is yielded by the coordination of the two N,N-bidentate ligands (Table 1) with Cu— N bond distances of 1.9313 (16) - 1.9650 (17) Å. Moreover, NO₃^- anions also contact to the neighboring cationic units by various hydrogen bonds of the type N—H···O (nitrate) to give a two dimentional layered structure (Fig. 2) as observed in the previuos [Cu(L¹^e)₂](ClO₄)₂ complex.

Related literature top

Experimental top

The initial product of the title complex was obtained from the reaction of 2-cyanoguanidine (0.1682 g, 2 mmol, Aldrich, 99%) with copper(II) nitrate hemipentahydrate (0.2325 g, 1 mmol, Sigma-Aldrich, 98%). The reaction was carried out in ethanol under refluxing condition for 24 h. The reddish-pink precipitate thus formed was isolated by filtration. The red block shaped single crystals were grown by slow vapor phase diffusion of methanol-ethanol solution of this products into toluene medium at room temperature for a week.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004) and publCIF (Westrip, 2009).

Figures top

	Fig. 1. View of the title copper(II) complex, showing the atom numbering of the cationic [Cu(L¹^e)₂]²⁺ moiety of [Cu(L¹^e)₂](NO₃)₂. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal structure of [Cu(L¹^e)₂](NO₃)₂ showing the linking of [Cu(L¹^e)₂]²⁺cation and NO₃^- counteranion along b axis. Hydrogen bonds are presented as a dashed lines.

Bis(1-carbamimidoyl-2-ethylisourea)copper(II) dinitrate top

Crystal data top

[Cu(C₄H₁₀N₄O)₂](NO₃)₂	F(000) = 462
M_r = 447.89	D_x = 1.675 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4098 reflections
a = 5.2547 (6) Å	θ = 2.9–27.1°
b = 14.0087 (15) Å	µ = 1.29 mm⁻¹
c = 12.1511 (13) Å	T = 293 K
β = 96.982 (2)°	Block, red
V = 887.83 (17) Å³	0.26 × 0.16 × 0.11 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area detector diffractometer	2206 independent reflections
Radiation source: fine-focus sealed tube	1810 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Frames each covering 0.3 ° in ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −7→7
T_min = 0.793, T_max = 1.00	k = −18→18
11998 measured reflections	l = −16→16

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) = 0.102	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0621P)² + 0.2477P] where P = (F_o² + 2F_c²)/3
2206 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.73 e Å⁻³
3 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Cu(C₄H₁₀N₄O)₂](NO₃)₂	V = 887.83 (17) Å³
M_r = 447.89	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.2547 (6) Å	µ = 1.29 mm⁻¹
b = 14.0087 (15) Å	T = 293 K
c = 12.1511 (13) Å	0.26 × 0.16 × 0.11 mm
β = 96.982 (2)°

Data collection top

Bruker SMART APEX CCD area detector diffractometer	2206 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1810 reflections with I > 2σ(I)
T_min = 0.793, T_max = 1.00	R_int = 0.028
11998 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.05	Δρ_max = 0.73 e Å⁻³
2206 reflections	Δρ_min = −0.27 e Å⁻³
125 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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.5000	0.0000	0.0348 (3)
N1	0.3075 (8)	0.5323 (3)	0.0966 (4)	0.0406 (10)
H1	0.3311	0.5925	0.1070	0.049*
N2	0.0819 (9)	0.3645 (3)	0.0282 (4)	0.0434 (11)
H2	−0.0240	0.3241	−0.0050	0.052*
N3	0.4651 (8)	0.3829 (3)	0.1454 (4)	0.0408 (10)
H3	0.5879	0.3520	0.1829	0.049*
O1	0.3213 (8)	0.2382 (3)	0.1101 (4)	0.0516 (11)
N4	0.6968 (10)	0.5138 (3)	0.2062 (5)	0.0541 (14)
H44	0.7222	0.5744	0.2107	0.065*
H45	0.8084	0.4751	0.2391	0.065*
C1	0.4823 (10)	0.4794 (4)	0.1477 (5)	0.0378 (11)
C3	0.1450 (12)	0.1670 (3)	0.0590 (5)	0.0506 (14)
H31	0.1250	0.1730	−0.0211	0.061*
H32	−0.0219	0.1733	0.0847	0.061*
C2	0.2729 (9)	0.3293 (4)	0.0898 (4)	0.0383 (11)
N5	0.9978 (9)	0.2854 (3)	0.3317 (4)	0.0479 (11)
O2	1.1439 (11)	0.2388 (4)	0.3966 (5)	0.090 (2)
C4	0.2662 (17)	0.0734 (4)	0.0945 (7)	0.075 (2)
H41	0.4291	0.0681	0.0668	0.113*
H43	0.1567	0.0222	0.0654	0.113*
H42	0.2904	0.0700	0.1740	0.113*
O4	0.8192 (10)	0.2461 (4)	0.2742 (4)	0.0705 (14)
O3	1.0295 (12)	0.3715 (3)	0.3254 (5)	0.0863 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0290 (5)	0.0239 (5)	0.0475 (6)	0.0021 (3)	−0.0123 (3)	0.0011 (3)
N1	0.034 (2)	0.0256 (19)	0.057 (3)	0.0008 (17)	−0.0160 (19)	−0.0010 (18)
N2	0.038 (2)	0.0252 (19)	0.061 (3)	−0.0003 (17)	−0.0196 (19)	−0.0003 (18)
N3	0.032 (2)	0.029 (2)	0.055 (3)	0.0029 (16)	−0.0159 (18)	0.0043 (18)
O1	0.048 (2)	0.0249 (17)	0.075 (3)	0.0016 (15)	−0.0226 (19)	0.0038 (17)
N4	0.041 (3)	0.035 (2)	0.077 (4)	−0.0022 (18)	−0.029 (3)	0.002 (2)
C1	0.032 (2)	0.031 (2)	0.047 (3)	−0.0008 (18)	−0.008 (2)	−0.0002 (19)
C3	0.053 (3)	0.027 (2)	0.066 (4)	−0.001 (2)	−0.017 (3)	−0.001 (2)
C2	0.035 (2)	0.027 (2)	0.050 (3)	0.0019 (18)	−0.008 (2)	0.0025 (19)
N5	0.049 (3)	0.035 (2)	0.056 (3)	0.0082 (19)	−0.011 (2)	0.005 (2)
O2	0.090 (4)	0.043 (3)	0.119 (5)	0.006 (3)	−0.064 (3)	0.012 (3)
C4	0.084 (5)	0.031 (3)	0.103 (6)	0.004 (3)	−0.026 (4)	0.002 (3)
O4	0.057 (3)	0.059 (3)	0.086 (3)	−0.001 (2)	−0.029 (2)	0.000 (2)
O3	0.102 (4)	0.032 (2)	0.117 (5)	0.004 (2)	−0.023 (3)	0.015 (3)

Geometric parameters (Å, º) top

Cu1—N1	1.932 (4)	N4—C1	1.347 (7)
Cu1—N1ⁱ	1.932 (4)	N4—H44	0.8600
Cu1—N2	1.967 (4)	N4—H45	0.8600
Cu1—N2ⁱ	1.967 (4)	C3—C4	1.498 (8)
N1—C1	1.281 (7)	C3—H31	0.9700
N1—H1	0.8600	C3—H32	0.9700
N2—C2	1.276 (6)	N5—O3	1.221 (6)
N2—H2	0.8600	N5—O2	1.221 (6)
N3—C1	1.355 (7)	N5—O4	1.230 (6)
N3—C2	1.369 (6)	C4—H41	0.9600
N3—H3	0.8600	C4—H43	0.9600
O1—C2	1.319 (6)	C4—H42	0.9600
O1—C3	1.449 (6)

N1—Cu1—N1ⁱ	180.0	N1—C1—N3	121.7 (5)
N1—Cu1—N2	88.33 (19)	N4—C1—N3	114.7 (5)
N1ⁱ—Cu1—N2	91.67 (19)	O1—C3—C4	104.6 (5)
N1—Cu1—N2ⁱ	91.67 (19)	O1—C3—H31	110.8
N1ⁱ—Cu1—N2ⁱ	88.33 (19)	C4—C3—H31	110.8
N2—Cu1—N2ⁱ	179.999 (1)	O1—C3—H32	110.8
C1—N1—Cu1	131.1 (4)	C4—C3—H32	110.8
C1—N1—H1	114.5	H31—C3—H32	108.9
Cu1—N1—H1	114.5	N2—C2—O1	127.1 (5)
C2—N2—Cu1	128.0 (4)	N2—C2—N3	123.9 (4)
C2—N2—H2	116.0	O1—C2—N3	108.9 (4)
Cu1—N2—H2	116.0	O3—N5—O2	119.3 (6)
C1—N3—C2	126.9 (4)	O3—N5—O4	120.5 (5)
C1—N3—H3	116.6	O2—N5—O4	120.3 (5)
C2—N3—H3	116.6	C3—C4—H41	109.5
C2—O1—C3	119.2 (4)	C3—C4—H43	109.5
C1—N4—H44	120.0	H41—C4—H43	109.5
C1—N4—H45	120.0	C3—C4—H42	109.5
H44—N4—H45	120.0	H41—C4—H42	109.5
N1—C1—N4	123.7 (5)	H43—C4—H42	109.5

N2—Cu1—N1—C1	3.1 (6)	C2—O1—C3—C4	176.9 (6)
N2ⁱ—Cu1—N1—C1	−176.9 (6)	Cu1—N2—C2—O1	178.1 (4)
N1—Cu1—N2—C2	0.4 (5)	Cu1—N2—C2—N3	−2.6 (9)
N1ⁱ—Cu1—N2—C2	−179.6 (5)	C3—O1—C2—N2	0.1 (9)
Cu1—N1—C1—N4	174.9 (5)	C3—O1—C2—N3	−179.3 (5)
Cu1—N1—C1—N3	−4.2 (9)	C1—N3—C2—N2	2.1 (10)
C2—N3—C1—N1	1.3 (10)	C1—N3—C2—O1	−178.5 (5)
C2—N3—C1—N4	−177.9 (6)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.86	2.05	2.904 (7)	170
N2—H2···O2ⁱⁱⁱ	0.86	2.18	3.009 (6)	163
N3—H3···O4	0.86	2.14	2.979 (6)	165
N4—H45···O3	0.86	2.06	2.917 (7)	171

Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−3/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₄H₁₀N₄O)₂](NO₃)₂
M_r	447.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.2547 (6), 14.0087 (15), 12.1511 (13)
β (°)	96.982 (2)
V (Å³)	887.83 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.26 × 0.16 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.793, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	11998, 2206, 1810
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.102, 1.05
No. of reflections	2206
No. of parameters	125
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.27

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top

Cu1—N1	1.932 (4)	Cu1—N2	1.967 (4)
Cu1—N1ⁱ	1.932 (4)	Cu1—N2ⁱ	1.967 (4)

N1—Cu1—N1ⁱ	180.0	N1—Cu1—N2ⁱ	91.67 (19)
N1—Cu1—N2	88.33 (19)	N1ⁱ—Cu1—N2ⁱ	88.33 (19)
N1ⁱ—Cu1—N2	91.67 (19)	N2—Cu1—N2ⁱ	179.999 (1)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.86	2.05	2.904 (7)	169.8
N2—H2···O2ⁱⁱⁱ	0.86	2.18	3.009 (6)	162.5
N3—H3···O4	0.86	2.14	2.979 (6)	164.9
N4—H45···O3	0.86	2.06	2.917 (7)	171.3

Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−3/2, −y+1/2, z−1/2.

Acknowledgements

We gratefully thank the Thailand Research Fund (TRF), Khon Kaen University, the Center of Excellence for Innovation in Chemistry (PERCH-CIC) and the Development and Promotion of Science and Technology talent project (DPST) for financial support.

References

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