Di-μ-iodido-bis­[(N-morpholino-2-pyridyl­methanimine-κ²N,N′)copper(I)] acetonitrile solvate

In the crystal structure of the title compound, [Cu₂I₂(C₁₀H₁₃N₃O)₂]·CH₃CN, the Schiff base chelates the Cu^I atom, which is linked to two I atoms in a tetra­hedral geometry; the covalent Cu—I bond is only marginally shorter than the dative Cu—I bond. The dinuclear mol­ecule lies about a centre of inversion and the solvent mol­ecule on a twofold rotation axis.

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.030
• wR factor = 0.080
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found





Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  I1     -   Cu1     ..      28.80 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  I1     -   Cu1_a   ..      32.41 su

Alert level C
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C11
PLAT410_ALERT_2_C Short Intra H...H Contact  H6     ..  H7B     ..       1.97 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C2 H3 N

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (1)       0.94

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

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

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S1. Comment

Copper(I) iodide forms a large number of adducts with Schiff bases. However, there are no structural studies on the morpholine-2-pyridyl-methanimine. In the title compound, the Schiff base chelates to the copper(I) atom, which is linked to two iodine atoms in a tetrahedral geometry; the covalent Cu–I bond is only marginally shorter than the dative Cu–I bond (Table 1) in the crystal structure of (C₁₀H₁₃N₃O)₂(CuI)₂^.CH₃CN. The dinuclear molecule lies about a center-of-inversion whereas the solvent molecule lies on a twofold rotation axis.

Related literature

For the synthesis of the Schiff base ligand, see Wiley et al. (1959). There are only two reports of metal adducts (not crystallographic studies): see Nasser-Eddine et al. (2004) for the copper(I) bromide adduct, and Nikolcheva et al. (2003) for the platinum(II) dichloride adduct.

S2. Experimental

Copper(I) iodide (1 mmol) and morpholine-2-pyridylmethanimine (1 mmol) were dissolved in acetonitrile under a nitrogen atmosphere. The solvent was partially removed and diethyl ether vapor diffused into the concentrated solution. Orange crystals were obtained in 90% yield. Calc. for C₂₀H₂₆Cu₂I₂N₆O₂:C 31.47, H 3.43, N 11.01%. Found: C 31.45, H 3.40, N 11.06%.

S3. Refinement

The carbon-bound hydrogen atoms were placed at calculated positions (C–H 0.93 – 0.99 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2 – 1.5 U_eq(C). The methyl group of the acetonitrile molecule is disordered over two equally occupied sites. The final difference Fourier map had a large peak/hole in the vicinity of the iodine atom.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

Fig. 1. Thermal ellipsoid plot of (C10H13N3O)2(CuI)2^.CH3CN drawn at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius. Symmetry code (i): 1 – x, 1 – y, 1 – z.

Di-µ-iodido-bis[(N-morpholino-2-pyridylmethanimine-κ²N,N')copper(I)] acetonitrile solvate

Crystal data

[Cu2I2(C10H13N3O)2]·C2H3N	F(000) = 1560
Mr = 804.40	Dx = 1.893 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8192 reflections
a = 16.0206 (2) Å	θ = 2.4–27.5°
b = 10.2820 (1) Å	µ = 3.73 mm^−1
c = 17.2086 (1) Å	T = 200 K
β = 95.329 (1)°	Polyhedron, orange
V = 2822.41 (5) Å^3	0.24 × 0.18 × 0.05 mm
Z = 4

Data collection

Bruker SMART area-detector diffractometer	3247 independent reflections
Radiation source: fine-focus sealed tube	2897 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
Tmin = 0.468, Tmax = 0.836	k = −13→13
13511 measured reflections	l = −22→22

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 6.1582P] where P = (Fo^2 + 2Fc^2)/3
3247 reflections	(Δ/σ)max = 0.001
161 parameters	Δρmax = 1.01 e Å^−3
0 restraints	Δρmin = −1.03 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.55574 (2)	0.41824 (4)	0.48182 (2)	0.03299 (11)
I1	0.600440 (12)	0.60525 (2)	0.576912 (13)	0.03845 (9)
O1	0.69807 (18)	0.6939 (3)	0.24161 (16)	0.0525 (7)
N1	0.59867 (15)	0.2310 (2)	0.50200 (15)	0.0302 (5)
N2	0.64685 (15)	0.4059 (2)	0.39882 (14)	0.0274 (5)
N3	0.67489 (16)	0.5071 (2)	0.35742 (15)	0.0309 (5)
N4	0.5000	0.9807 (8)	0.2500	0.135 (4)
C1	0.5713 (2)	0.1401 (3)	0.5497 (2)	0.0395 (7)
H1	0.5306	0.1643	0.5838	0.047*
C2	0.5995 (2)	0.0129 (3)	0.5513 (2)	0.0433 (8)
H2	0.5778	−0.0489	0.5853	0.052*
C3	0.6595 (2)	−0.0229 (3)	0.5030 (2)	0.0421 (8)
H3	0.6803	−0.1094	0.5034	0.051*
C4	0.6886 (2)	0.0692 (3)	0.45417 (19)	0.0348 (7)
H4	0.7303	0.0470	0.4207	0.042*
C5	0.65638 (17)	0.1957 (3)	0.45415 (16)	0.0271 (6)
C6	0.68527 (18)	0.2951 (3)	0.40212 (17)	0.0278 (6)
H6	0.7307	0.2789	0.3717	0.033*
C7	0.7327 (2)	0.4817 (3)	0.29850 (18)	0.0342 (6)
H7A	0.7036	0.4332	0.2542	0.041*
H7B	0.7803	0.4284	0.3211	0.041*
C8	0.7643 (2)	0.6107 (3)	0.2703 (2)	0.0456 (8)
H8A	0.7979	0.6544	0.3139	0.055*
H8B	0.8014	0.5946	0.2284	0.055*
C9	0.6470 (3)	0.7216 (4)	0.3030 (3)	0.0560 (10)
H9A	0.6020	0.7828	0.2839	0.067*
H9B	0.6814	0.7639	0.3466	0.067*
C10	0.6084 (2)	0.5989 (3)	0.3320 (2)	0.0453 (9)
H10A	0.5752	0.6197	0.3761	0.054*
H10B	0.5704	0.5597	0.2897	0.054*
C11	0.5000	1.0891 (7)	0.2500	0.0634 (17)
C12	0.5000	1.2277 (6)	0.2500	0.0564 (14)
H12A	0.4421	1.2595	0.2474	0.085*	0.50
H12B	0.5267	1.2595	0.2047	0.085*	0.50
H12C	0.5311	1.2595	0.2980	0.085*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0308 (2)	0.02673 (19)	0.0425 (2)	0.00814 (14)	0.00937 (16)	−0.00119 (15)
I1	0.03060 (13)	0.03548 (13)	0.04833 (15)	0.00547 (8)	−0.00136 (9)	−0.01112 (8)
O1	0.0623 (16)	0.0444 (14)	0.0523 (15)	−0.0009 (12)	0.0136 (13)	0.0198 (12)
N1	0.0269 (12)	0.0278 (12)	0.0356 (13)	0.0044 (9)	0.0018 (10)	0.0041 (10)
N2	0.0281 (12)	0.0240 (11)	0.0303 (12)	0.0011 (9)	0.0040 (10)	0.0011 (9)
N3	0.0345 (13)	0.0273 (12)	0.0317 (12)	0.0028 (10)	0.0077 (10)	0.0042 (10)
N4	0.110 (6)	0.059 (5)	0.239 (12)	0.000	0.024 (7)	0.000
C1	0.0387 (17)	0.0377 (17)	0.0425 (18)	0.0016 (14)	0.0058 (14)	0.0101 (14)
C2	0.0465 (19)	0.0343 (17)	0.0476 (19)	−0.0028 (14)	−0.0036 (15)	0.0134 (15)
C3	0.0484 (19)	0.0254 (15)	0.0499 (19)	0.0067 (14)	−0.0098 (15)	0.0039 (13)
C4	0.0342 (16)	0.0285 (14)	0.0403 (17)	0.0102 (12)	−0.0027 (13)	−0.0026 (12)
C5	0.0261 (13)	0.0239 (13)	0.0300 (14)	0.0041 (10)	−0.0039 (11)	−0.0025 (10)
C6	0.0278 (13)	0.0258 (13)	0.0299 (14)	0.0032 (11)	0.0036 (11)	−0.0049 (11)
C7	0.0384 (16)	0.0348 (16)	0.0306 (15)	0.0002 (13)	0.0103 (12)	−0.0009 (12)
C8	0.049 (2)	0.046 (2)	0.0441 (19)	−0.0056 (15)	0.0149 (16)	0.0072 (15)
C9	0.064 (2)	0.0336 (18)	0.073 (3)	0.0077 (17)	0.020 (2)	0.0157 (18)
C10	0.0424 (19)	0.0364 (18)	0.059 (2)	0.0099 (14)	0.0142 (17)	0.0162 (15)
C11	0.044 (3)	0.056 (4)	0.091 (5)	0.000	0.015 (3)	0.000
C12	0.064 (4)	0.055 (3)	0.052 (3)	0.000	0.013 (3)	0.000

Geometric parameters (Å, º)

Cu1—N1	2.063 (2)	C3—H3	0.9500
Cu1—N2	2.139 (2)	C4—C5	1.399 (4)
Cu1—Cu1^i	2.5719 (7)	C4—H4	0.9500
Cu1—I1	2.5827 (4)	C5—C6	1.462 (4)
Cu1—I1^i	2.6211 (4)	C6—H6	0.9500
I1—Cu1^i	2.6211 (4)	C7—C8	1.516 (4)
O1—C8	1.415 (5)	C7—H7A	0.9900
O1—C9	1.423 (5)	C7—H7B	0.9900
N1—C5	1.344 (4)	C8—H8A	0.9900
N1—C1	1.345 (4)	C8—H8B	0.9900
N2—C6	1.293 (4)	C9—C10	1.510 (5)
N2—N3	1.361 (3)	C9—H9A	0.9900
N3—C7	1.459 (4)	C9—H9B	0.9900
N3—C10	1.459 (4)	C10—H10A	0.9900
N4—C11	1.114 (9)	C10—H10B	0.9900
C1—C2	1.383 (5)	C11—C12	1.425 (9)
C1—H1	0.9500	C12—H12A	0.9800
C2—C3	1.378 (5)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C3—C4	1.376 (5)
N1—Cu1—N2	79.59 (9)	C4—C5—C6	120.8 (3)
N1—Cu1—Cu1^i	142.87 (8)	N2—C6—C5	117.8 (3)
N2—Cu1—Cu1^i	137.20 (7)	N2—C6—H6	121.1
N1—Cu1—I1	121.31 (7)	C5—C6—H6	121.1
N2—Cu1—I1	107.53 (7)	N3—C7—C8	108.6 (3)
Cu1^i—Cu1—I1	61.128 (16)	N3—C7—H7A	110.0
N1—Cu1—I1^i	105.69 (7)	C8—C7—H7A	110.0
N2—Cu1—I1^i	115.04 (7)	N3—C7—H7B	110.0
Cu1^i—Cu1—I1^i	59.638 (16)	C8—C7—H7B	110.0
I1—Cu1—I1^i	120.766 (14)	H7A—C7—H7B	108.4
Cu1—I1—Cu1^i	59.234 (14)	O1—C8—C7	112.2 (3)
C8—O1—C9	109.0 (3)	O1—C8—H8A	109.2
C5—N1—C1	117.9 (3)	C7—C8—H8A	109.2
C5—N1—Cu1	112.77 (19)	O1—C8—H8B	109.2
C1—N1—Cu1	129.0 (2)	C7—C8—H8B	109.2
C6—N2—N3	121.2 (3)	H8A—C8—H8B	107.9
C6—N2—Cu1	112.01 (19)	O1—C9—C10	111.1 (3)
N3—N2—Cu1	125.65 (18)	O1—C9—H9A	109.4
N2—N3—C7	119.2 (2)	C10—C9—H9A	109.4
N2—N3—C10	112.6 (2)	O1—C9—H9B	109.4
C7—N3—C10	113.6 (3)	C10—C9—H9B	109.4
N1—C1—C2	123.1 (3)	H9A—C9—H9B	108.0
N1—C1—H1	118.5	N3—C10—C9	109.2 (3)
C2—C1—H1	118.5	N3—C10—H10A	109.8
C3—C2—C1	119.0 (3)	C9—C10—H10A	109.8
C3—C2—H2	120.5	N3—C10—H10B	109.8
C1—C2—H2	120.5	C9—C10—H10B	109.8
C4—C3—C2	118.7 (3)	H10A—C10—H10B	108.3
C4—C3—H3	120.7	N4—C11—C12	180.000 (3)
C2—C3—H3	120.7	C11—C12—H12A	109.5
C3—C4—C5	119.6 (3)	C11—C12—H12B	109.5
C3—C4—H4	120.2	H12A—C12—H12B	109.5
C5—C4—H4	120.2	C11—C12—H12C	109.5
N1—C5—C4	121.7 (3)	H12A—C12—H12C	109.5
N1—C5—C6	117.4 (2)	H12B—C12—H12C	109.5
N1—Cu1—I1—Cu1^i	−136.91 (9)	C5—N1—C1—C2	−0.2 (5)
N2—Cu1—I1—Cu1^i	134.79 (7)	Cu1—N1—C1—C2	172.5 (3)
I1^i—Cu1—I1—Cu1^i	0.0	N1—C1—C2—C3	1.1 (5)
N2—Cu1—N1—C5	−2.1 (2)	C1—C2—C3—C4	−0.7 (5)
Cu1^i—Cu1—N1—C5	171.24 (14)	C2—C3—C4—C5	−0.5 (5)
I1—Cu1—N1—C5	−106.40 (19)	C1—N1—C5—C4	−1.1 (4)
I1^i—Cu1—N1—C5	111.17 (19)	Cu1—N1—C5—C4	−174.9 (2)
N2—Cu1—N1—C1	−175.1 (3)	C1—N1—C5—C6	179.5 (3)
Cu1^i—Cu1—N1—C1	−1.8 (4)	Cu1—N1—C5—C6	5.7 (3)
I1—Cu1—N1—C1	80.6 (3)	C3—C4—C5—N1	1.5 (5)
I1^i—Cu1—N1—C1	−61.8 (3)	C3—C4—C5—C6	−179.2 (3)
N1—Cu1—N2—C6	−2.0 (2)	N3—N2—C6—C5	173.9 (2)
Cu1^i—Cu1—N2—C6	−176.06 (16)	Cu1—N2—C6—C5	5.5 (3)
I1—Cu1—N2—C6	117.78 (19)	N1—C5—C6—N2	−7.8 (4)
I1^i—Cu1—N2—C6	−104.5 (2)	C4—C5—C6—N2	172.8 (3)
N1—Cu1—N2—N3	−169.6 (2)	N2—N3—C7—C8	−171.4 (3)
Cu1^i—Cu1—N2—N3	16.3 (3)	C10—N3—C7—C8	52.2 (4)
I1—Cu1—N2—N3	−49.9 (2)	C9—O1—C8—C7	61.5 (4)
I1^i—Cu1—N2—N3	87.8 (2)	N3—C7—C8—O1	−56.1 (4)
C6—N2—N3—C7	18.0 (4)	C8—O1—C9—C10	−61.5 (4)
Cu1—N2—N3—C7	−175.4 (2)	N2—N3—C10—C9	167.4 (3)
C6—N2—N3—C10	154.8 (3)	C7—N3—C10—C9	−53.2 (4)
Cu1—N2—N3—C10	−38.6 (4)	O1—C9—C10—N3	57.0 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.