[Bis(3-amino­propyl-κN)(2-furylmeth­yl)amine-κN]dichloridocopper(II)

In the title complex, [CuCl₂(C₁₁H₂₁N₃O)], the five-coordinate Cu atom has a distorted square-pyramidal configuration. The crystal packing is stabilized by inter­molecular N—H...Cl hydrogen-bonding inter­actions. The furan ring is disordered over two position, with site occupancy factors of ca. 0.6 and 0.4.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.027
• wR factor = 0.076
• Data-to-parameter ratio = 15.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT432_ALERT_2_A Short Inter X...Y Contact  C9'    ..  C9'     ..       2.89 Ang.

Author Response: The short inter contact is owing to the disorder of the furan ring, which should be omitted.

Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT301_ALERT_3_C Main Residue  Disorder .........................      22.00 Perc.
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2C    ...          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         17

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Polyamines with pendant arm have received much attention because of their strong coordination ability with transition metal ions and interesting biochemical properties (Kurisaki et al., 2005; Kang et al., 1995; Jee et al., 2003; Zhu et al., 1996). Up to the present, many linear and cyclic polyamine complexes with branched chain have been made in order to search for their potential uses. In order to search for new complexes of polyamine with pendant arms, we report the synthesis and crystal structure of the title complex, dichloro[N,N'-bis(3-aminopropyl-κN,κN') -2-furanmethylamine-κN]copper(II), (I).

In the structure of (I), the copper atom is coordinated with three N atoms and two chloride anions (Fig. 1). The equatorial positions are occupied by three nitrogen atoms and one chloride in which the Cu—N and Cu—Cl bond lengths fall in the range 1.9930 (16)–2.3810 (5) Å. The deviation of the Cu atom from the N₃Cl basal plane is 0.3536 (2) Å. One Cl atom occupies the axial position with the elongated Cu—Cl distance of 2.5163 (6) Å. Intermolecular N—H···Cl hydrogen bonds play an important role in stabilizing the crystal packing.

Related literature

For related literature, see: Jee et al. (2003); Kang et al. (1995); Kurisaki et al. (2005); Zhang et al. (2006); Zhu et al. (1996).

S2. Experimental

All the solvents and chemicals were of analytical grade and used without further purification. Furanmethylamine and acrylonitrile were purified by distillation. N,N'-bis(3-aminopropyl) -2-furanmethylamine was prepared by a similar method to that described in the literature (Zhang et al., 2006). The title complex was synthesized by the following procedure: a methanol solution (10 ml) of CuCl₂ (0.134 g, 1 mmol) was added to a methanol solution (10 ml) of [N,N'-bis(3-aminopropyl) -2-furanmethylamine (0.22 g, 1 mmol). The mixture was stirred at ambient temperature for about one day and then filtered. A methanol solution (5 ml) of NaClO₄(0.142 g, 1 mmol) was added to the filtrate and the stirring was continued for 2 h. Blue crystals suitable for the X-ray diffraction were obtained by slow diffusion of diethyl ether into the mother solution over one month.

S3. Refinement

Furan was disordered and major to minor of occupancy was 0.61 (1): 0.39 (1). H atoms bonded to C atoms of CH₂ and furan were placed in calculated positions, with C—H distances 0.97Å (for CH₂) and 0.93Å (for furan), and included in the refinement in the riding-model approximation with U_iso(H) = 1.2 U_eq(C). Other H atoms bonded to N atoms were located in a difference map and refined with distance restraints of N—H = 0.90 Å, and with U_iso(H) = 1.2 U_eq(N).

Computing details

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

Figures

Fig. 1. A view of the title complex cation, showing the labeling of the non-H atoms and 30% probability ellipsoids.

[Bis(3-aminopropyl-κN)(2-furylmethyl)amine-κN]dichloridocopper(II)

Crystal data

[CuCl2(C11H21N3O)]	Z = 2
Mr = 345.75	F(000) = 358
Triclinic, P1	Dx = 1.575 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7493 (4) Å	Cell parameters from 4753 reflections
b = 9.7335 (5) Å	θ = 2.2–28.3°
c = 11.9658 (6) Å	µ = 1.86 mm^−1
α = 94.358 (1)°	T = 298 K
β = 104.696 (1)°	Block, blue
γ = 104.181 (1)°	0.30 × 0.20 × 0.16 mm
V = 729.16 (7) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3156 independent reflections
Radiation source: fine-focus sealed tube	2934 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
phi and ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→8
Tmin = 0.584, Tmax = 0.756	k = −12→12
7493 measured reflections	l = −15→15

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.076	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.1388P] where P = (Fo^2 + 2Fc^2)/3
3156 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.25 e Å^−3
17 restraints	Δρmin = −0.38 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	Occ. (<1)
Cu1	0.31362 (3)	0.24158 (2)	0.095524 (17)	0.03385 (9)
C1	0.4985 (3)	0.1845 (3)	0.33945 (18)	0.0492 (5)
H1A	0.5099	0.1986	0.4222	0.059*
H1B	0.6378	0.2288	0.3305	0.059*
C2	0.4441 (4)	0.0255 (3)	0.2990 (2)	0.0576 (6)
H2A	0.2972	−0.0180	0.2965	0.069*
H2B	0.5335	−0.0164	0.3553	0.069*
C3	0.4735 (4)	−0.0094 (3)	0.1794 (2)	0.0562 (5)
H3A	0.6173	0.0391	0.1793	0.067*
H3B	0.4526	−0.1117	0.1616	0.067*
C4	0.4435 (3)	0.4152 (2)	0.33239 (17)	0.0473 (5)
H4A	0.5840	0.4458	0.3208	0.057*
H4B	0.4625	0.4211	0.4159	0.057*
C5	0.3204 (4)	0.5202 (2)	0.2869 (2)	0.0543 (6)
H5A	0.1728	0.4818	0.2854	0.065*
H5B	0.3771	0.6094	0.3407	0.065*
C6	0.3291 (4)	0.5515 (2)	0.1663 (2)	0.0518 (5)
H6A	0.2587	0.6255	0.1456	0.062*
H6B	0.4764	0.5866	0.1661	0.062*
C7	0.1299 (3)	0.2061 (2)	0.29461 (16)	0.0369 (4)
H7A	0.0799	0.1042	0.2661	0.044*
H7B	0.0333	0.2517	0.2468	0.044*
C8	0.119 (3)	0.2299 (16)	0.4226 (12)	0.040 (3)	0.608 (12)
C11	0.1618 (14)	0.1877 (10)	0.6011 (8)	0.0581 (17)	0.608 (12)
H11	0.1950	0.1457	0.6682	0.070*	0.608 (12)
C10	0.0701 (12)	0.2934 (8)	0.5932 (6)	0.0441 (13)	0.608 (12)
H10	0.0318	0.3398	0.6518	0.053*	0.608 (12)
O1	0.2010 (11)	0.1482 (5)	0.5006 (5)	0.0572 (15)	0.608 (12)
C9	0.0425 (18)	0.3213 (12)	0.4752 (8)	0.0432 (17)	0.608 (12)
H9	−0.0174	0.3903	0.4419	0.052*	0.608 (12)
C8'	0.115 (5)	0.222 (2)	0.4068 (19)	0.038 (4)	0.392 (12)
C10'	0.103 (2)	0.2105 (17)	0.5948 (12)	0.068 (4)	0.392 (12)
H10'	0.1185	0.1813	0.6680	0.082*	0.392 (12)
C11'	0.053 (2)	0.3265 (15)	0.5613 (12)	0.060 (3)	0.392 (12)
H11'	0.0185	0.3920	0.6083	0.072*	0.392 (12)
C9'	0.1286 (19)	0.1389 (8)	0.4902 (12)	0.059 (3)	0.392 (12)
H9'	0.1510	0.0486	0.4826	0.071*	0.392 (12)
O1'	0.059 (2)	0.3387 (14)	0.4501 (11)	0.055 (3)	0.392 (12)
Cl1	0.12864 (9)	0.17685 (6)	−0.10687 (4)	0.05026 (14)
Cl2	0.70195 (8)	0.33846 (7)	0.10934 (5)	0.05553 (15)
N1	0.3464 (2)	0.26238 (17)	0.27872 (13)	0.0351 (3)
N2	0.3189 (3)	0.03707 (18)	0.08969 (15)	0.0450 (4)
H2D	0.1882	−0.0145	0.0892	0.054*
H2C	0.3373	0.0105	0.0202	0.054*
N3	0.2241 (3)	0.42131 (17)	0.07939 (14)	0.0407 (4)
H3C	0.2356	0.4457	0.0098	0.049*
H3D	0.0846	0.3991	0.0750	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03157 (13)	0.03896 (14)	0.03096 (13)	0.00929 (9)	0.00983 (9)	0.00263 (9)
C1	0.0379 (10)	0.0731 (14)	0.0370 (10)	0.0214 (10)	0.0055 (8)	0.0078 (9)
C2	0.0583 (14)	0.0710 (15)	0.0585 (13)	0.0382 (12)	0.0180 (11)	0.0277 (11)
C3	0.0566 (13)	0.0565 (13)	0.0687 (14)	0.0320 (11)	0.0236 (11)	0.0143 (11)
C4	0.0433 (11)	0.0508 (11)	0.0347 (9)	−0.0030 (9)	0.0074 (8)	−0.0070 (8)
C5	0.0671 (15)	0.0392 (10)	0.0519 (12)	0.0039 (10)	0.0235 (11)	−0.0096 (9)
C6	0.0603 (13)	0.0369 (10)	0.0560 (13)	0.0068 (9)	0.0200 (11)	0.0029 (9)
C7	0.0328 (9)	0.0401 (9)	0.0356 (9)	0.0082 (7)	0.0092 (7)	−0.0001 (7)
C8	0.038 (4)	0.056 (5)	0.027 (3)	0.008 (3)	0.016 (3)	0.004 (3)
C11	0.074 (4)	0.082 (3)	0.042 (2)	0.044 (3)	0.031 (3)	0.022 (2)
C10	0.047 (2)	0.056 (3)	0.034 (3)	0.016 (2)	0.018 (2)	0.003 (2)
O1	0.078 (4)	0.081 (2)	0.0387 (19)	0.052 (2)	0.029 (2)	0.0234 (17)
C9	0.045 (3)	0.049 (3)	0.043 (4)	0.019 (2)	0.020 (3)	0.010 (2)
C8'	0.033 (5)	0.042 (5)	0.039 (7)	0.015 (4)	0.006 (5)	0.006 (4)
C10'	0.078 (7)	0.098 (8)	0.040 (4)	0.027 (6)	0.034 (5)	0.008 (5)
C11'	0.055 (5)	0.078 (6)	0.045 (6)	0.006 (4)	0.027 (4)	−0.001 (4)
C9'	0.060 (6)	0.071 (5)	0.057 (5)	0.025 (4)	0.026 (4)	0.021 (4)
O1'	0.057 (3)	0.063 (5)	0.050 (5)	0.011 (3)	0.032 (3)	−0.003 (3)
Cl1	0.0550 (3)	0.0574 (3)	0.0319 (2)	0.0085 (2)	0.0095 (2)	−0.0003 (2)
Cl2	0.0330 (2)	0.0742 (4)	0.0657 (3)	0.0146 (2)	0.0198 (2)	0.0286 (3)
N1	0.0299 (7)	0.0420 (8)	0.0309 (7)	0.0085 (6)	0.0068 (6)	0.0007 (6)
N2	0.0489 (10)	0.0448 (9)	0.0465 (9)	0.0172 (8)	0.0196 (8)	0.0024 (7)
N3	0.0400 (9)	0.0413 (8)	0.0410 (8)	0.0116 (7)	0.0117 (7)	0.0055 (7)

Geometric parameters (Å, º)

Cu1—N3	1.9930 (16)	C7—C8'	1.372 (19)
Cu1—N2	1.9959 (17)	C7—N1	1.495 (2)
Cu1—N1	2.1353 (15)	C7—C8	1.555 (12)
Cu1—Cl1	2.3810 (5)	C7—H7A	0.9700
Cu1—Cl2	2.5163 (6)	C7—H7B	0.9700
C1—N1	1.497 (3)	C8—C9	1.326 (9)
C1—C2	1.511 (3)	C8—O1	1.370 (11)
C1—H1A	0.9700	C11—C10	1.322 (6)
C1—H1B	0.9700	C11—O1	1.343 (8)
C2—C3	1.518 (3)	C11—H11	0.9300
C2—H2A	0.9700	C10—C9	1.433 (7)
C2—H2B	0.9700	C10—H10	0.9300
C3—N2	1.477 (3)	C9—H9	0.9300
C3—H3A	0.9700	C8'—C9'	1.331 (9)
C3—H3B	0.9700	C8'—O1'	1.385 (15)
C4—N1	1.490 (2)	C10'—C11'	1.317 (8)
C4—C5	1.517 (3)	C10'—C9'	1.455 (9)
C4—H4A	0.9700	C10'—H10'	0.9300
C4—H4B	0.9700	C11'—O1'	1.353 (11)
C5—C6	1.509 (3)	C11'—H11'	0.9300
C5—H5A	0.9700	C9'—H9'	0.9300
C5—H5B	0.9700	N2—H2D	0.9000
C6—N3	1.475 (3)	N2—H2C	0.9000
C6—H6A	0.9700	N3—H3C	0.9000
C6—H6B	0.9700	N3—H3D	0.9000
N3—Cu1—N2	164.28 (7)	C8—C7—H7A	108.5
N3—Cu1—N1	92.82 (6)	C8'—C7—H7B	108.8
N2—Cu1—N1	91.68 (7)	N1—C7—H7B	108.5
N3—Cu1—Cl1	84.66 (5)	C8—C7—H7B	108.5
N2—Cu1—Cl1	85.11 (5)	H7A—C7—H7B	107.5
N1—Cu1—Cl1	155.99 (4)	C9—C8—O1	109.9 (9)
N3—Cu1—Cl2	99.22 (5)	C9—C8—C7	130.9 (9)
N2—Cu1—Cl2	95.14 (5)	O1—C8—C7	119.1 (9)
N1—Cu1—Cl2	97.20 (4)	C10—C11—O1	111.9 (8)
Cl1—Cu1—Cl2	106.78 (2)	C10—C11—H11	124.1
N1—C1—C2	116.70 (17)	O1—C11—H11	124.1
N1—C1—H1A	108.1	C11—C10—C9	105.4 (8)
C2—C1—H1A	108.1	C11—C10—H10	127.3
N1—C1—H1B	108.1	C9—C10—H10	127.3
C2—C1—H1B	108.1	C11—O1—C8	105.9 (7)
H1A—C1—H1B	107.3	C8—C9—C10	106.7 (8)
C1—C2—C3	113.1 (2)	C8—C9—H9	126.6
C1—C2—H2A	109.0	C10—C9—H9	126.6
C3—C2—H2A	109.0	C9'—C8'—C7	133.0 (16)
C1—C2—H2B	109.0	C9'—C8'—O1'	106.0 (14)
C3—C2—H2B	109.0	C7—C8'—O1'	120.8 (10)
H2A—C2—H2B	107.8	C11'—C10'—C9'	103.5 (11)
N2—C3—C2	109.90 (18)	C11'—C10'—H10'	128.2
N2—C3—H3A	109.7	C9'—C10'—H10'	128.2
C2—C3—H3A	109.7	C10'—C11'—O1'	111.8 (13)
N2—C3—H3B	109.7	C10'—C11'—H11'	124.1
C2—C3—H3B	109.7	O1'—C11'—H11'	124.1
H3A—C3—H3B	108.2	C8'—C9'—C10'	109.9 (13)
N1—C4—C5	116.33 (17)	C8'—C9'—H9'	125.1
N1—C4—H4A	108.2	C10'—C9'—H9'	125.1
C5—C4—H4A	108.2	C11'—O1'—C8'	108.4 (12)
N1—C4—H4B	108.2	C4—N1—C7	111.55 (15)
C5—C4—H4B	108.2	C4—N1—C1	104.91 (15)
H4A—C4—H4B	107.4	C7—N1—C1	111.46 (15)
C6—C5—C4	113.80 (19)	C4—N1—Cu1	109.90 (12)
C6—C5—H5A	108.8	C7—N1—Cu1	107.77 (10)
C4—C5—H5A	108.8	C1—N1—Cu1	111.28 (12)
C6—C5—H5B	108.8	C3—N2—Cu1	121.57 (15)
C4—C5—H5B	108.8	C3—N2—H2D	106.9
H5A—C5—H5B	107.7	Cu1—N2—H2D	106.9
N3—C6—C5	110.68 (17)	C3—N2—H2C	106.9
N3—C6—H6A	109.5	Cu1—N2—H2C	106.9
C5—C6—H6A	109.5	H2D—N2—H2C	106.7
N3—C6—H6B	109.5	C6—N3—Cu1	121.74 (14)
C5—C6—H6B	109.5	C6—N3—H3C	106.9
H6A—C6—H6B	108.1	Cu1—N3—H3C	106.9
C8'—C7—N1	116.5 (13)	C6—N3—H3D	106.9
N1—C7—C8	114.9 (8)	Cu1—N3—H3D	106.9
C8'—C7—H7A	106.6	H3C—N3—H3D	106.7
N1—C7—H7A	108.5
N1—C1—C2—C3	71.7 (3)	C8—C7—N1—C1	64.8 (5)
C1—C2—C3—N2	−65.9 (3)	C8'—C7—N1—Cu1	−174.3 (7)
N1—C4—C5—C6	−73.3 (2)	C8—C7—N1—Cu1	−172.9 (5)
C4—C5—C6—N3	64.4 (3)	C2—C1—N1—C4	−177.78 (18)
N1—C7—C8—C9	105.3 (19)	C2—C1—N1—C7	61.4 (2)
N1—C7—C8—O1	−73.6 (15)	C2—C1—N1—Cu1	−59.0 (2)
O1—C11—C10—C9	1.8 (10)	N3—Cu1—N1—C4	−39.90 (13)
C10—C11—O1—C8	−3.1 (13)	N2—Cu1—N1—C4	155.16 (13)
C9—C8—O1—C11	3.3 (17)	Cl1—Cu1—N1—C4	−123.10 (13)
C7—C8—O1—C11	−177.6 (12)	Cl2—Cu1—N1—C4	59.76 (13)
O1—C8—C9—C10	−2.2 (18)	N3—Cu1—N1—C7	81.85 (12)
C7—C8—C9—C10	178.8 (16)	N2—Cu1—N1—C7	−83.09 (12)
C11—C10—C9—C8	0.3 (14)	Cl1—Cu1—N1—C7	−1.35 (19)
N1—C7—C8'—C9'	−92 (3)	Cl2—Cu1—N1—C7	−178.49 (11)
N1—C7—C8'—O1'	95 (2)	N3—Cu1—N1—C1	−155.67 (13)
C9'—C10'—C11'—O1'	−4.0 (17)	N2—Cu1—N1—C1	39.40 (14)
C7—C8'—C9'—C10'	179 (3)	Cl1—Cu1—N1—C1	121.14 (14)
O1'—C8'—C9'—C10'	−6 (3)	Cl2—Cu1—N1—C1	−56.00 (13)
C11'—C10'—C9'—C8'	6 (2)	C2—C3—N2—Cu1	59.8 (2)
C10'—C11'—O1'—C8'	0 (2)	N3—Cu1—N2—C3	−150.6 (2)
C9'—C8'—O1'—C11'	4 (3)	N1—Cu1—N2—C3	−44.01 (16)
C7—C8'—O1'—C11'	179 (2)	Cl1—Cu1—N2—C3	159.83 (16)
C5—C4—N1—C7	−58.9 (2)	Cl2—Cu1—N2—C3	53.38 (16)
C5—C4—N1—C1	−179.74 (17)	C5—C6—N3—Cu1	−56.2 (2)
C5—C4—N1—Cu1	60.5 (2)	N2—Cu1—N3—C6	148.3 (2)
C8'—C7—N1—C4	−53.6 (8)	N1—Cu1—N3—C6	41.86 (16)
C8—C7—N1—C4	−52.1 (5)	Cl1—Cu1—N3—C6	−162.08 (15)
C8'—C7—N1—C1	63.3 (8)	Cl2—Cu1—N3—C6	−55.91 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.97	2.46	3.098 (6)	124
C7—H7B···Cl2^i	0.97	2.77	3.732 (2)	170
N3—H3D···Cl2^i	0.90	2.65	3.5345 (18)	168
N3—H3C···Cl2^ii	0.90	2.64	3.4086 (17)	144
N2—H2D···Cl1^iii	0.90	2.40	3.2865 (19)	170

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