{2-[(3-Amino­propyl)­amino­propyl­imino­methyl]­imidazol­ato-N,N',N'',N'''}­(methanol-O)­copper(II) per­chlorate

In the title compound, [Cu(C₁₀H₁₈N₅)(CH₄O)]ClO₄, four N atoms from the deprotonated ligand derived from bis(3-amino­propyl)­amine and 2-imidazole­carbox­aldehyde are coordinated to the Cu atom. The four N atoms occupy equatorial positions with Cu-N bond distances ranging from 1.998 (2) to 2.046 (3) Å. The methanol O atom occupies one axial position with a Cu-O bond distance of 2.295 (2) Å.

S1. Comment

A good strategy to prepare heteronuclear complexes is that of using metal complexes as ligands. Among the precursors that have been commonly used to prepare heteronuclear complexes the mononuclear complexes containing imidazole ligands (Dominques-Vera et al., 1996) deserve special attention. In basic medium, these precursors can coordinate to another metal ion or metal complex leading to a heteronuclear complex (Dominques-Vera et al., 1998). In this paper, we report the synthesis of a new mononuclear copper(II) complex, (I), containing an imidazole ligand, which may be used as a precursor in the preparation of homo- and heteronuclear complexes.

The structure consists of a mononuclear complex cation and a perchlorate anion. Although the amine:aldehyde ratio was 1:2, the ligand is formed by condensation of only one aldehyde molecule with one amine molecule. The ligand contains two imidazole, two amine and one imino N atoms. In the title compound, the ligand coordinates by four of its five N atoms in its deprotonated form leaving the deprotonated N2 atom uncoordinated. The tetradentate behaviour of the ligand results in the formation of one five- and two six-membered chelate rings around the Cu atom. The four N atoms of the coordination plane are almost coplanar with deviations from the least-squares plane < 0.006 Å. The Cu atom deviates by 0.203 (1) Å from the basal plane towards the O atom of the coordinated methanol molecule at 2.295 (2) Å. The nearest atom in the direction of the sixth coordination position is N2(1 − x,-y,1 − z) at 3.738 (3) Å. The five-membered chelate ring and the imidazole ring are planar, the six-membered rings adopt chair conformations. The complex cations and anions are connected by hydrogen bonds involving the methanol O—H, the three amino H atoms, the deprotonated N2 of the imidazole ring, and O1 and O2 of the perchlorate ion.

S2. Experimental

2-Imidazolecarboxaldehyde (2 mmol) was reacted with bis(3-aminopropyl)amine (1 mmol) in 50 ml of methanol. To the yellow solution, Cu(ClO₄)·6H₂O (1 mmol) was added with continuous stirring. The resulting blue solution was allowed to stand at room temperature for one day, upon which blue needle-like crystals of the compound were obtained.

S3. Refinement

The H5 atom of the methanol molecule was refined in a riding model with an O—H bond length of 0.85 Å and all other H-atom coordinates were constrained using the SHELXL97 default N—H and C—H distances.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); data reduction: TEXSAN PROCESS (Molecular Structure Corporation, 1993b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

{2-[(3-aminopropyl)aminopropyliminomethyl]imidazolato-N, N', N'', N'''}- (methanol-O)copper(II) perchlorate.

Crystal data

[Cu(C10H18N5)(CH4O)]ClO4	F(000) = 836
Mr = 403.33	Dx = 1.590 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.488 (3) Å	Cell parameters from 25 reflections
b = 12.475 (5) Å	θ = 6.4–10.1°
c = 18.176 (6) Å	µ = 1.49 mm^−1
β = 97.15 (3)°	T = 193 K
V = 1684.7 (11) Å^3	Needle, blue
Z = 4	0.45 × 0.30 × 0.30 mm

Data collection

Rigaku AFC 7S diffractometer	3122 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
Graphite monochromator	θmax = 26.5°, θmin = 2.7°
2θ/ω scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.565, Tmax = 0.640	l = −22→22
3676 measured reflections	3 standard reflections every 200 reflections
3501 independent reflections	intensity decay: −0.1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: difference Fourier map
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 2.3975P] where P = (Fo^2 + 2Fc^2)/3
3501 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.70 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu	0.28951 (4)	0.15313 (3)	0.408792 (18)	0.02844 (13)
Cl	0.64242 (11)	0.16484 (7)	0.15727 (4)	0.0410 (2)
O1	0.4630 (4)	0.1600 (2)	0.11883 (16)	0.0595 (8)
O2	0.6417 (5)	0.1233 (4)	0.22867 (17)	0.0885 (12)
O3	0.7025 (7)	0.2693 (4)	0.1593 (4)	0.164 (3)
O4	0.7582 (5)	0.1006 (5)	0.1207 (2)	0.1248 (19)
O5	0.0315 (3)	0.24613 (18)	0.42281 (13)	0.0408 (5)
H5	−0.0449	0.1966	0.4263	0.049*
N1	0.2976 (3)	0.0671 (2)	0.50190 (13)	0.0313 (5)
N2	0.2200 (3)	−0.0905 (2)	0.55052 (15)	0.0361 (6)
N3	0.1486 (3)	0.0217 (2)	0.36674 (14)	0.0331 (5)
N4	0.3138 (4)	0.2136 (2)	0.30639 (14)	0.0376 (6)
H41	0.4135	0.1832	0.2927	0.045*
N5	0.4710 (3)	0.2559 (2)	0.46126 (15)	0.0348 (5)
H51	0.5789	0.2233	0.4641	0.042*
H52	0.4447	0.2621	0.5080	0.042*
C1	0.3628 (4)	0.0663 (3)	0.57553 (16)	0.0349 (6)
H1	0.4297	0.1219	0.6019	0.042*
C2	0.3141 (4)	−0.0299 (3)	0.60454 (17)	0.0376 (7)
H2	0.3420	−0.0509	0.6549	0.045*
C3	0.2147 (4)	−0.0280 (2)	0.49006 (16)	0.0312 (6)
C4	0.1328 (4)	−0.0503 (2)	0.41575 (17)	0.0341 (6)
H4	0.0699	−0.1153	0.4036	0.041*
C5	0.0608 (4)	0.0034 (3)	0.29100 (17)	0.0428 (8)
H5A	−0.0660	0.0275	0.2872	0.051*
H5B	0.0610	−0.0743	0.2798	0.051*
C6	0.1565 (5)	0.0633 (3)	0.23499 (18)	0.0478 (9)
H6A	0.0937	0.0493	0.1847	0.057*
H6B	0.2806	0.0352	0.2368	0.057*
C7	0.1649 (5)	0.1833 (3)	0.24795 (18)	0.0464 (8)
H7A	0.1825	0.2199	0.2010	0.056*
H7B	0.0491	0.2080	0.2629	0.056*
C8	0.3449 (5)	0.3308 (3)	0.3039 (2)	0.0488 (9)
H8A	0.2405	0.3684	0.3204	0.059*
H8B	0.3532	0.3523	0.2520	0.059*
C9	0.5152 (5)	0.3658 (3)	0.3522 (2)	0.0501 (9)
H9A	0.6146	0.3169	0.3436	0.060*
H9B	0.5481	0.4388	0.3372	0.060*
C10	0.4963 (5)	0.3666 (3)	0.4340 (2)	0.0422 (7)
H10A	0.6055	0.3985	0.4619	0.051*
H10B	0.3918	0.4113	0.4427	0.051*
C11	0.0275 (6)	0.3265 (4)	0.4787 (3)	0.0766 (15)
H11A	−0.0939	0.3569	0.4757	0.115*
H11B	0.1134	0.3834	0.4710	0.115*
H11C	0.0601	0.2943	0.5277	0.115*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0287 (2)	0.0305 (2)	0.0258 (2)	0.00042 (13)	0.00220 (13)	0.00113 (13)
Cl	0.0368 (4)	0.0508 (5)	0.0348 (4)	−0.0015 (3)	0.0016 (3)	0.0138 (3)
O1	0.0416 (14)	0.082 (2)	0.0520 (16)	−0.0041 (13)	−0.0068 (12)	0.0200 (14)
O2	0.069 (2)	0.154 (4)	0.0421 (16)	0.022 (2)	0.0056 (14)	0.040 (2)
O3	0.116 (4)	0.077 (3)	0.271 (7)	−0.046 (3)	−0.086 (4)	0.075 (4)
O4	0.066 (2)	0.229 (6)	0.081 (3)	0.033 (3)	0.017 (2)	−0.039 (3)
O5	0.0341 (11)	0.0379 (12)	0.0520 (14)	0.0004 (9)	0.0109 (10)	−0.0001 (10)
N1	0.0317 (12)	0.0318 (12)	0.0301 (12)	−0.0008 (10)	0.0022 (10)	0.0002 (10)
N2	0.0311 (12)	0.0358 (14)	0.0420 (14)	0.0037 (10)	0.0073 (11)	0.0096 (11)
N3	0.0283 (12)	0.0370 (13)	0.0326 (13)	0.0036 (10)	−0.0015 (10)	−0.0031 (10)
N4	0.0355 (13)	0.0465 (15)	0.0309 (13)	0.0036 (12)	0.0049 (10)	0.0060 (11)
N5	0.0331 (13)	0.0336 (13)	0.0373 (14)	−0.0016 (10)	0.0032 (10)	0.0016 (11)
C1	0.0360 (15)	0.0398 (16)	0.0285 (14)	−0.0003 (13)	0.0021 (12)	−0.0005 (12)
C2	0.0350 (15)	0.0455 (18)	0.0327 (15)	0.0070 (13)	0.0054 (12)	0.0080 (13)
C3	0.0246 (13)	0.0345 (15)	0.0344 (15)	0.0034 (11)	0.0037 (11)	0.0020 (12)
C4	0.0269 (13)	0.0337 (15)	0.0412 (16)	−0.0002 (12)	0.0015 (12)	−0.0043 (13)
C5	0.0381 (17)	0.053 (2)	0.0342 (16)	−0.0004 (15)	−0.0066 (13)	−0.0086 (14)
C6	0.0397 (17)	0.073 (3)	0.0296 (16)	0.0035 (17)	0.0006 (13)	−0.0096 (16)
C7	0.0437 (18)	0.064 (2)	0.0298 (16)	0.0064 (16)	−0.0007 (13)	0.0067 (15)
C8	0.057 (2)	0.047 (2)	0.0426 (19)	0.0017 (16)	0.0072 (16)	0.0146 (15)
C9	0.053 (2)	0.0439 (19)	0.055 (2)	−0.0077 (16)	0.0146 (17)	0.0123 (16)
C10	0.0417 (18)	0.0322 (16)	0.052 (2)	−0.0032 (13)	0.0045 (15)	0.0040 (14)
C11	0.054 (2)	0.068 (3)	0.114 (4)	−0.007 (2)	0.035 (3)	−0.039 (3)

Geometric parameters (Å, º)

Cu—N1	1.998 (2)	C1—H1	0.9500
Cu—N5	2.020 (3)	C2—H2	0.9500
Cu—N4	2.037 (3)	C3—C4	1.439 (4)
Cu—N3	2.046 (3)	C4—H4	0.9500
Cu—O5	2.295 (2)	C5—C6	1.513 (5)
Cl—O3	1.378 (4)	C5—H5A	0.9900
Cl—O2	1.398 (3)	C5—H5B	0.9900
Cl—O4	1.407 (4)	C6—C7	1.516 (6)
Cl—O1	1.436 (3)	C6—H6A	0.9900
O5—C11	1.431 (5)	C6—H6B	0.9900
O5—H5	0.8500	C7—H7A	0.9900
N1—C3	1.345 (4)	C7—H7B	0.9899
N1—C1	1.366 (4)	C8—C9	1.520 (6)
N2—C3	1.344 (4)	C8—H8A	0.9900
N2—C2	1.364 (4)	C8—H8B	0.9899
N3—C4	1.281 (4)	C9—C10	1.510 (5)
N3—C5	1.468 (4)	C9—H9A	0.9900
N4—C8	1.482 (5)	C9—H9B	0.9900
N4—C7	1.490 (4)	C10—H10A	0.9900
N4—H41	0.9000	C10—H10B	0.9900
N5—C10	1.487 (4)	C11—H11A	0.9800
N5—H51	0.9000	C11—H11B	0.9800
N5—H52	0.9000	C11—H11C	0.9799
C1—C2	1.378 (5)
N1—Cu—N5	89.61 (11)	N1—C3—C4	117.1 (3)
N1—Cu—N4	167.36 (11)	N3—C4—C3	116.9 (3)
N5—Cu—N4	93.73 (11)	N3—C4—H4	121.6
N1—Cu—N3	81.15 (10)	C3—C4—H4	121.6
N5—Cu—N3	166.12 (10)	N3—C5—C6	111.1 (3)
N4—Cu—N3	93.20 (11)	N3—C5—H5A	109.4
N1—Cu—O5	96.58 (10)	C6—C5—H5A	109.4
N5—Cu—O5	98.80 (10)	N3—C5—H5B	109.4
N4—Cu—O5	94.95 (10)	C6—C5—H5B	109.4
N3—Cu—O5	92.57 (9)	H5A—C5—H5B	108.0
O3—Cl—O2	111.4 (3)	C5—C6—C7	113.4 (3)
O3—Cl—O4	109.5 (4)	C5—C6—H6A	108.9
O2—Cl—O4	107.5 (3)	C7—C6—H6A	108.9
O3—Cl—O1	109.6 (2)	C5—C6—H6B	108.9
O2—Cl—O1	108.96 (19)	C7—C6—H6B	108.9
O4—Cl—O1	109.9 (2)	H6A—C6—H6B	107.7
C11—O5—Cu	121.7 (2)	N4—C7—C6	112.0 (3)
C11—O5—H5	112.5	N4—C7—H7A	109.2
Cu—O5—H5	103.0	C6—C7—H7A	109.2
C3—N1—C1	104.6 (2)	N4—C7—H7B	109.2
C3—N1—Cu	111.94 (19)	C6—C7—H7B	109.2
C1—N1—Cu	143.5 (2)	H7A—C7—H7B	107.9
C3—N2—C2	103.1 (3)	N4—C8—C9	113.0 (3)
C4—N3—C5	118.3 (3)	N4—C8—H8A	109.0
C4—N3—Cu	113.0 (2)	C9—C8—H8A	109.0
C5—N3—Cu	128.7 (2)	N4—C8—H8B	109.0
C8—N4—C7	109.6 (3)	C9—C8—H8B	109.0
C8—N4—Cu	115.2 (2)	H8A—C8—H8B	107.8
C7—N4—Cu	114.4 (2)	C10—C9—C8	113.3 (3)
C8—N4—H41	105.6	C10—C9—H9A	108.9
C7—N4—H41	105.6	C8—C9—H9A	108.9
Cu—N4—H41	105.6	C10—C9—H9B	108.9
C10—N5—Cu	122.6 (2)	C8—C9—H9B	108.9
C10—N5—H51	106.7	H9A—C9—H9B	107.7
Cu—N5—H51	106.7	N5—C10—C9	110.7 (3)
C10—N5—H52	106.7	N5—C10—H10A	109.5
Cu—N5—H52	106.7	C9—C10—H10A	109.5
H51—N5—H52	106.6	N5—C10—H10B	109.5
N1—C1—C2	107.6 (3)	C9—C10—H10B	109.5
N1—C1—H1	126.2	H10A—C10—H10B	108.1
C2—C1—H1	126.2	O5—C11—H11A	109.5
N2—C2—C1	110.2 (3)	O5—C11—H11B	109.5
N2—C2—H2	124.9	H11A—C11—H11B	109.5
C1—C2—H2	124.9	O5—C11—H11C	109.5
N2—C3—N1	114.5 (3)	H11A—C11—H11C	109.5
N2—C3—C4	128.4 (3)	H11B—C11—H11C	109.5
N1—Cu—O5—C11	70.3 (3)	N4—Cu—N5—C10	32.0 (3)
N5—Cu—O5—C11	−20.3 (3)	N3—Cu—N5—C10	151.8 (4)
N4—Cu—O5—C11	−114.8 (3)	O5—Cu—N5—C10	−63.6 (3)
N3—Cu—O5—C11	151.7 (3)	C3—N1—C1—C2	−0.5 (3)
N5—Cu—N1—C3	−168.5 (2)	Cu—N1—C1—C2	−177.3 (3)
N4—Cu—N1—C3	−63.0 (5)	C3—N2—C2—C1	−0.2 (3)
N3—Cu—N1—C3	1.09 (19)	N1—C1—C2—N2	0.4 (4)
O5—Cu—N1—C3	92.7 (2)	C2—N2—C3—N1	−0.2 (3)
N5—Cu—N1—C1	8.2 (4)	C2—N2—C3—C4	179.8 (3)
N4—Cu—N1—C1	113.6 (5)	C1—N1—C3—N2	0.4 (3)
N3—Cu—N1—C1	177.8 (4)	Cu—N1—C3—N2	178.38 (19)
O5—Cu—N1—C1	−90.6 (4)	C1—N1—C3—C4	−179.5 (3)
N1—Cu—N3—C4	−0.4 (2)	Cu—N1—C3—C4	−1.6 (3)
N5—Cu—N3—C4	48.3 (5)	C5—N3—C4—C3	−177.7 (3)
N4—Cu—N3—C4	168.2 (2)	Cu—N3—C4—C3	−0.3 (3)
O5—Cu—N3—C4	−96.7 (2)	N2—C3—C4—N3	−178.7 (3)
N1—Cu—N3—C5	176.6 (3)	N1—C3—C4—N3	1.3 (4)
N5—Cu—N3—C5	−134.6 (4)	C4—N3—C5—C6	−153.7 (3)
N4—Cu—N3—C5	−14.7 (3)	Cu—N3—C5—C6	29.4 (4)
O5—Cu—N3—C5	80.4 (3)	N3—C5—C6—C7	−58.5 (4)
N1—Cu—N4—C8	−140.1 (4)	C8—N4—C7—C6	166.0 (3)
N5—Cu—N4—C8	−35.1 (2)	Cu—N4—C7—C6	−62.8 (3)
N3—Cu—N4—C8	156.9 (2)	C5—C6—C7—N4	81.3 (4)
O5—Cu—N4—C8	64.1 (2)	C7—N4—C8—C9	−169.8 (3)
N1—Cu—N4—C7	91.5 (5)	Cu—N4—C8—C9	59.4 (4)
N5—Cu—N4—C7	−163.4 (2)	N4—C8—C9—C10	−75.4 (4)
N3—Cu—N4—C7	28.6 (2)	Cu—N5—C10—C9	−48.8 (4)
O5—Cu—N4—C7	−64.3 (2)	C8—C9—C10—N5	66.2 (4)
N1—Cu—N5—C10	−160.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···N2^i	0.85	1.95	2.789 (4)	171
N4—H41···O2	0.90	2.31	3.188 (5)	166
N5—H51···N2^ii	0.90	2.28	3.127 (4)	158
N5—H52···O1^iii	0.90	2.22	3.057 (4)	154

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