A redetermination of bis(N-methyl­ethyl­enedi­amine-κ²N,N′)­bis­(perchlorato-κO)copper(II)

In the title compound, [Cu(ClO₄)₂(C₃H₁₀N₂)₂], the Cu atom is located at a center of symmetry. Despite asymmetric introduction of N-methyl groups into the ethyl­enedi­amine moieties, a second-order Jahn–Teller effect produces a typical semi-coordination trans-[CuN₄(O₂)] environment with long axial Cu—O bonds of 2.569 (2) Å. The Cu—N bond distances are 2.004 (2) and 2.057 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.024
• wR factor = 0.068
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low    U(eq) as Compared to Neighbors ....        Cl1

Alert level C
PLAT128_ALERT_4_C Non-standard setting of Space group P21/c   ....    P21/a
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O4       =       9.05 su
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ....         O4

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[Cu(ClO4)2(C3H10N2)2]	F(000) = 422.0
Mr = 410.71	Dx = 1.787 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2yab	Cell parameters from 25 reflections
a = 8.436 (3) Å	θ = 10.1–15.0°
b = 11.857 (4) Å	µ = 1.82 mm^−1
c = 8.352 (3) Å	T = 297 K
β = 113.96 (3)°	Prismatic, blue
V = 763.4 (5) Å^3	0.40 × 0.30 × 0.30 mm
Z = 2

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.008
ω–2θ scans	θmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −10→4
Tmin = 0.524, Tmax = 0.579	k = 0→15
2072 measured reflections	l = −9→10
1749 independent reflections	3 standard reflections every 150 reflections
1538 reflections with I > 2σ(I)	intensity decay: 0.2%

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0348P)^2 + 0.3309P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max = 0.002
S = 1.08	Δρmax = 0.33 e Å^−3
1538 reflections	Δρmin = −0.29 e Å^−3
98 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Cu1	1.0000	0.0000	1.0000	0.0275 (1)
Cl1	0.73426 (6)	−0.07774 (4)	1.21713 (7)	0.0386 (1)
O1	0.8766 (3)	−0.1037 (2)	1.3773 (3)	0.0841 (7)
O2	0.7048 (4)	0.0395 (2)	1.2088 (4)	0.0930 (8)
O3	0.5861 (2)	−0.1389 (2)	1.2088 (3)	0.0620 (5)
O4	0.7800 (2)	−0.1125 (2)	1.0767 (2)	0.0558 (4)
N1	1.1792 (2)	−0.1188 (1)	1.1155 (2)	0.0375 (4)
N2	1.1113 (2)	0.0813 (1)	1.2374 (2)	0.0342 (3)
C1	1.2620 (3)	−0.0962 (2)	1.3064 (3)	0.0426 (5)
C2	1.2840 (3)	0.0286 (2)	1.3290 (3)	0.0423 (5)
C3	1.1224 (4)	0.2051 (2)	1.2403 (3)	0.0538 (6)
H1	1.1256	−0.1909	1.0950	0.0444*
H2	1.2647	−0.1168	1.0688	0.0444*
H3	1.1895	−0.1233	1.3612	0.0512*
H4	1.3713	−0.1329	1.3573	0.0512*
H5	1.3612	0.0547	1.2807	0.0512*
H6	1.3297	0.0472	1.4509	0.0512*
H7	1.0443	0.0616	1.3020	0.0415*
H8	1.1702	0.2320	1.3572	0.0658*
H9	1.1945	0.2289	1.1829	0.0658*
H10	1.0097	0.2370	1.1796	0.0658*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0281 (2)	0.0271 (2)	0.0255 (2)	0.0012 (1)	0.0092 (1)	−0.0008 (1)
Cl1	0.0434 (3)	0.0384 (3)	0.0437 (3)	−0.0084 (2)	0.0276 (2)	−0.0067 (2)
O1	0.058 (1)	0.144 (2)	0.048 (1)	−0.003 (1)	0.0189 (9)	−0.002 (1)
O2	0.133 (2)	0.0392 (10)	0.140 (2)	0.000 (1)	0.089 (2)	−0.010 (1)
O3	0.0506 (9)	0.066 (1)	0.087 (1)	−0.0160 (8)	0.0456 (10)	−0.0089 (10)
O4	0.072 (1)	0.0622 (10)	0.0532 (9)	−0.0143 (8)	0.0455 (9)	−0.0130 (8)
N1	0.0347 (8)	0.0325 (8)	0.0421 (9)	0.0037 (6)	0.0124 (7)	0.0026 (7)
N2	0.0339 (8)	0.0401 (8)	0.0303 (7)	−0.0030 (7)	0.0147 (6)	−0.0050 (6)
C1	0.0321 (9)	0.059 (1)	0.035 (1)	0.0077 (9)	0.0113 (8)	0.0137 (9)
C2	0.0305 (9)	0.063 (1)	0.0306 (9)	−0.0041 (9)	0.0092 (8)	−0.0052 (9)
C3	0.067 (2)	0.044 (1)	0.050 (1)	−0.008 (1)	0.023 (1)	−0.0152 (10)

Geometric parameters (Å, º)

Cu1—O4	2.569 (2)	N2—C3	1.470 (3)
Cu1—N1	2.004 (2)	N2—H7	0.955
Cu1—N2	2.057 (2)	C1—C2	1.493 (3)
Cl1—O1	1.422 (2)	C1—H3	0.956
Cl1—O2	1.409 (2)	C1—H4	0.950
Cl1—O3	1.421 (2)	C2—H5	0.948
Cl1—O4	1.435 (2)	C2—H6	0.956
N1—C1	1.482 (3)	C3—H8	0.948
N1—H1	0.950	C3—H9	0.957
N1—H2	0.950	C3—H10	0.955
N2—C2	1.481 (3)
N1—Cu1—O4^i	90.28 (7)	Cu1—N2—H7	106.7
N1—Cu1—O4	89.72 (7)	C2—N2—C3	111.7 (2)
N2—Cu1—O4^i	84.49 (7)	C2—N2—H7	106.8
N2—Cu1—O4	95.51 (7)	C3—N2—H7	106.4
N1—Cu1—N1^i	180.0	N1—C1—C2	107.2 (2)
N1—Cu1—N2	84.58 (7)	N1—C1—H3	109.9
N1—Cu1—N2^i	95.42 (7)	N1—C1—H4	110.3
N2—Cu1—N2^i	180.0	C2—C1—H3	110.1
O1—Cl1—O2	108.9 (2)	C2—C1—H4	110.4
O1—Cl1—O3	109.0 (1)	H3—C1—H4	109.0
O1—Cl1—O4	107.6 (1)	N2—C2—C1	107.9 (2)
O2—Cl1—O3	111.5 (2)	N2—C2—H5	110.1
O2—Cl1—O4	110.1 (2)	N2—C2—H6	109.9
O3—Cl1—O4	109.6 (1)	C1—C2—H5	110.0
Cu1—N1—C1	108.9 (1)	C1—C2—H6	109.8
Cu1—N1—H1	109.6	H5—C2—H6	109.1
Cu1—N1—H2	109.6	N2—C3—H8	110.5
C1—N1—H1	109.8	N2—C3—H9	109.7
C1—N1—H2	109.4	N2—C3—H10	110.1
H1—N1—H2	109.5	H8—C3—H9	109.0
Cu1—N2—C2	105.6 (1)	H8—C3—H10	109.2
Cu1—N2—C3	119.0 (1)	H9—C3—H10	108.4
Cu1—N1—C1—C2	−39.1 (2)	N1—Cu1—N2^i—C3^i	35.5 (2)
Cu1—N1^i—C1^i—C2^i	39.1 (2)	N1—C1—C2—N2	56.2 (2)
Cu1—N2—C2—C1	−44.5 (2)	N2—Cu1—N1—C1	11.6 (1)
Cu1—N2^i—C2^i—C1^i	44.5 (2)	N2—Cu1—N1^i—C1^i	168.4 (1)
N1—Cu1—N2—C2	18.1 (1)	C1—C2—N2—C3	−175.3 (2)
N1—Cu1—N2—C3	144.5 (2)	C1—C2—N2—C3	−175.3 (2)
N1—Cu1—N2^i—C2^i	161.9 (1)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.95	3.01	3.250 (3)	96
N2—H7···O1	0.96	2.64	3.460 (3)	144
N2—H7···O2	0.96	2.66	3.376 (4)	132
N2—H7···O4	0.96	3.06	3.442 (2)	106
N1—H2···O3^ii	0.95	2.49	3.206 (2)	132
N1—H1···O3^iii	0.95	2.31	3.158 (2)	148
N1—H1···O4^iii	0.95	2.70	3.347 (2)	126

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