Aqua-di-μ₂-chloro-bis­(diethyl­enetri­amine)­dicopper(II) dichloride

Reaction of CuCl₂(H₂O)₂ with diethyl­enetri­amine (henceforth dien) in a 1:1 ratio has led to the formation of a non-centrosymmetric di-μ-chloro bibridged binuclear Cu^II species in which a water mol­ecule is coordinated axially to one of the Cu^II ions. [Cu₂Cl₂(C₄H₁₃N₃)₂(H₂O)] contains dinuclear [(dien)₂Cu₂Cl₂(H₂O)]²⁺ cations and chloride ions. Both Cu^II ions in the dimer have a primary coordination sphere that is approximately planar, consisting of one dien mol­ecule and one chloride ion. These monomeric units are linked via semicoordinate Cu—Cl bonds to form dinuclear units. One Cu^II ion has a 4+1 coordination geometry while the second expands to a 4+2 geometry by the incorporation of a water mol­ecule. The dinuclear cation has crystallographic reflection symmetry, the mirror plane containing the central Cu₂Cl₂ unit and the central N atom of each dien ligand.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.041
• wR factor = 0.116
• Data-to-parameter ratio = 22.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.50
         From the CIF: _reflns_number_total               2243
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         2405
         Completeness (_total/calc)             93.26%
          Alert C: < 95% complete

PLAT_030  Alert C Refined Extinction parameter within range ....       3.00 Sigma

PLAT_162  Alert C Missing or Zero su (esd) on y-coordinate for .       CL1

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.891
          Tmax scaled      0.767 Tmin scaled      0.431


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

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Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: XS in SHELXTL (Bruker, 1998); program(s) used to refine structure: XL in SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: XCIF in SHELXTL.

(I)

Crystal data

[Cu2Cl2(C4H13N3)2(H2O)]	F(000) = 502
Mr = 493.24	Dx = 1.624 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
a = 6.7155 (8) Å	Cell parameters from 34 reflections
b = 14.6106 (11) Å	θ = 5.9–15.0°
c = 10.3011 (8) Å	µ = 2.65 mm^−1
β = 95.333 (10)°	T = 293 K
V = 1006.34 (16) Å^3	Parallelepiped, blue
Z = 2	0.3 × 0.25 × 0.1 mm

Data collection

Four-circle diffractometer	1948 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
ω scans	h = −1→8
Absorption correction: empirical (using intensity measurements) (XEMP; Siemens, 1990)	k = −1→18
Tmin = 0.484, Tmax = 0.861	l = −13→13
3012 measured reflections	3 standard reflections every 100 reflections
2243 independent reflections	intensity decay: <3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0743P)^2 + 0.9546P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2243 reflections	Δρmax = 0.75 e Å^−3
102 parameters	Δρmin = −0.57 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (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
Cu1	0.39424 (14)	0.7500	1.06341 (9)	0.0318 (4)
Cu2	0.57159 (14)	0.7500	1.40987 (10)	0.0328 (4)
Cl2	0.7211 (3)	0.7500	1.1425 (2)	0.0587 (8)
Cl3	0.2609 (3)	0.7500	1.3003 (2)	0.0453 (6)
N1	0.3840 (12)	0.6159 (5)	1.0301 (6)	0.0605 (19)
H1A	0.4657	0.6014	0.9686	0.073*
H1B	0.4258	0.5854	1.1036	0.073*
C2	0.1794 (19)	0.5893 (10)	0.9864 (10)	0.105 (5)
H2A	0.1040	0.5796	1.0611	0.127*
H2B	0.1797	0.5326	0.9375	0.127*
C3	0.0844 (14)	0.6634 (11)	0.9024 (9)	0.103 (5)
H3A	0.1453	0.6666	0.8207	0.124*
H3B	−0.0574	0.6515	0.8833	0.124*
N4	0.1159 (12)	0.7500	0.9754 (8)	0.072 (4)
H4	0.0306	0.7500	1.0391	0.086*
N11	0.5938 (8)	0.6144 (4)	1.4370 (5)	0.0414 (12)
H11A	0.5306	0.5980	1.5067	0.050*
H11B	0.5357	0.5849	1.3666	0.050*
C12	0.8066 (12)	0.5891 (6)	1.4578 (8)	0.058 (2)
H12A	0.8610	0.5807	1.3746	0.070*
H12B	0.8215	0.5321	1.5060	0.070*
C13	0.9168 (10)	0.6647 (7)	1.5336 (7)	0.054 (2)
H13A	0.8761	0.6676	1.6214	0.065*
H13B	1.0599	0.6541	1.5389	0.065*
N14	0.8664 (4)	0.7500	1.46409 (17)	0.0383 (17)
H14	0.9310	0.7500	1.3903	0.046*
O	0.4490 (4)	0.7500	1.64280 (17)	0.070 (2)
H0A	0.4831	0.7099	1.6939	0.084*
Cl1	0.5645 (4)	0.5562	1.75621 (17)	0.0761 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0276 (6)	0.0407 (6)	0.0269 (5)	0.000	0.0020 (4)	0.000
Cu2	0.0281 (6)	0.0332 (6)	0.0359 (6)	0.000	−0.0029 (4)	0.000
Cl2	0.0262 (10)	0.112 (3)	0.0381 (12)	0.000	0.0046 (8)	0.000
Cl3	0.0243 (9)	0.0834 (18)	0.0285 (9)	0.000	0.0041 (7)	0.000
N1	0.097 (5)	0.049 (4)	0.038 (3)	−0.022 (4)	0.019 (3)	−0.005 (3)
C2	0.121 (10)	0.134 (11)	0.065 (6)	−0.093 (9)	0.031 (7)	−0.031 (7)
C3	0.055 (5)	0.209 (15)	0.046 (4)	−0.064 (7)	0.003 (4)	−0.026 (7)
N4	0.026 (4)	0.161 (13)	0.028 (4)	0.000	0.003 (3)	0.000
N11	0.050 (3)	0.037 (3)	0.036 (3)	0.003 (2)	0.003 (2)	−0.001 (2)
C12	0.059 (4)	0.054 (5)	0.062 (5)	0.026 (4)	0.012 (4)	0.007 (4)
C13	0.035 (3)	0.079 (6)	0.047 (4)	0.015 (4)	−0.001 (3)	0.014 (4)
N14	0.028 (3)	0.059 (5)	0.028 (3)	0.000	0.007 (3)	0.000
O	0.094 (7)	0.061 (5)	0.055 (5)	0.000	0.008 (5)	0.000
Cl1	0.150 (2)	0.0428 (11)	0.0393 (9)	−0.0209 (13)	0.0271 (12)	−0.0037 (8)

Geometric parameters (Å, º)

Cu1—N1	1.989 (7)	C3—N4	1.477 (14)
Cu1—N1^i	1.990 (7)	C3—H3A	0.9700
Cu1—N4	2.000 (8)	C3—H3B	0.9700
Cu1—Cl2	2.269 (2)	N4—C3^i	1.477 (14)
Cu1—Cl3	2.676 (2)	N4—H4	0.9100
Cu2—N11^i	2.005 (6)	N11—C12	1.472 (9)
Cu2—N11	2.005 (6)	N11—H11A	0.9000
Cu2—N14	2.006 (3)	N11—H11B	0.9000
Cu2—Cl3	2.278 (2)	C12—C13	1.507 (13)
Cu2—O	2.608 (2)	C12—H12A	0.9700
Cu2—Cl2	3.018 (2)	C12—H12B	0.9700
N1—C2	1.459 (13)	C13—N14	1.461 (8)
N1—H1A	0.9000	C13—H13A	0.9700
N1—H1B	0.9000	C13—H13B	0.9700
C2—C3	1.49 (2)	N14—C13^i	1.461 (8)
C2—H2A	0.9700	N14—H14	0.9100
C2—H2B	0.9700	O—H0A	0.8064
N1—Cu1—N1^i	160.1 (4)	N4—C3—H3B	110.3
N1—Cu1—N4	84.6 (2)	C2—C3—H3B	110.3
N1^i—Cu1—N4	84.6 (2)	H3A—C3—H3B	108.6
N1—Cu1—Cl2	94.5 (2)	C3—N4—C3^i	117.9 (12)
N1^i—Cu1—Cl2	94.5 (2)	C3—N4—Cu1	108.3 (6)
N4—Cu1—Cl2	174.1 (2)	C3^i—N4—Cu1	108.3 (6)
N1—Cu1—Cl3	98.53 (18)	C3—N4—H4	107.3
N1^i—Cu1—Cl3	98.53 (18)	C3^i—N4—H4	107.3
N4—Cu1—Cl3	92.0 (2)	Cu1—N4—H4	107.3
Cl2—Cu1—Cl3	93.84 (8)	C12—N11—Cu2	109.1 (5)
N11^i—Cu2—N11	162.6 (3)	C12—N11—H11A	109.9
N11^i—Cu2—N14	84.40 (17)	Cu2—N11—H11A	109.9
N11—Cu2—N14	84.40 (17)	C12—N11—H11B	109.9
N11^i—Cu2—Cl3	97.00 (17)	Cu2—N11—H11B	109.9
N11—Cu2—Cl3	97.00 (17)	H11A—N11—H11B	108.3
N14—Cu2—Cl3	166.53 (9)	N11—C12—C13	108.3 (6)
Cu2—Cl3—Cu1	94.77 (7)	N11—C12—H12A	110.0
Cu2—Cl2—Cu1	86.27 (7)	C13—C12—H12A	110.0
C2—N1—Cu1	109.4 (8)	N11—C12—H12B	110.0
C2—N1—H1A	109.8	C13—C12—H12B	110.0
Cu1—N1—H1A	109.8	H12A—C12—H12B	108.4
C2—N1—H1B	109.8	N14—C13—C12	106.9 (5)
Cu1—N1—H1B	109.8	N14—C13—H13A	110.3
H1A—N1—H1B	108.2	C12—C13—H13A	110.3
N1—C2—C3	109.0 (8)	N14—C13—H13B	110.3
N1—C2—H2A	109.9	C12—C13—H13B	110.3
C3—C2—H2A	109.9	H13A—C13—H13B	108.6
N1—C2—H2B	109.9	C13^i—N14—C13	117.0 (7)
C3—C2—H2B	109.9	C13^i—N14—Cu2	108.3 (3)
H2A—C2—H2B	108.3	C13—N14—Cu2	108.3 (3)
N4—C3—C2	107.1 (7)	C13^i—N14—H14	107.6
N4—C3—H3A	110.3	C13—N14—H14	107.6
C2—C3—H3A	110.3	Cu2—N14—H14	107.6

Symmetry code: (i) x, −y+3/2, z.