The unexpected fixation of CO2 employing a CuIBr(bpy)2 complex

Kickelbick, G.

doi:10.1107/S1600536801015276

The unexpected fixation of CO₂ employing a Cu^IBr(bpy)₂ complex

The attempt to crystallize Cu^IBr(bpy)₂, where bpy is bipyridine, from an acetonitrile solution in a glove-box led unexpectedly to a dimeric carbonato-bridged Cu^II precipitate, viz. μ-carbonato-bis[bis(bipyridine)copper(II)] dibromide diacetonitrile monohydrate, [Cu₂(C₁₀H₈N₂)₄(CO₃)]Br₂·2CH₃CN·H₂O. The μ₂-carbonato ligand is probably the result of an oxidation of traces of CO₂ by Cu^I. The resulting structure contains two square-pyramidally coordinated Cu^II atoms bridged by a CO₃²⁻ unit.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015276/wn6050sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015276/wn6050Isup2.hkl Contains datablock I

CCDC reference: 175341

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.012 Å
R factor = 0.047
wR factor = 0.110
Data-to-parameter ratio = 8.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



THETM_01  Alert A The value of sine(theta_max)/wavelength is less than 0.550
          Calculated sin(theta_max)/wavelength =    0.5001

Author response: The measured dataset had a low scattering intensity in the high theta range, therefore we employed a high resolution limit of 1.0 \%A and used this modified dataset for the refinement!


 Alert Level C:



CHEMW_01  Alert C The difference between the given and expected weight for
          compound is greater 1 mass unit. Check that all hydrogen
          atoms have been taken into account.

REFNR_01  Alert C Ratio of reflections to parameters is < 10 for a
          centrosymmetric structure
          sine(theta)/lambda                0.5001
          Proportion of unique data used    1.0000
          Ratio reflections to parameters   8.2267

RINTA_01  Alert C The value of Rint is greater than 0.10
          Rint given   0.149

PLAT_030  Alert C Refined Extinction parameter within range ....       2.50 Sigma

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C45 H38 Br2 Cu2 N10 O4
          Atom count from _chemical_formula_moiety:C45 H40 Br2 Cu2 N10 O4


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 4 Alert Level C = Please check

Comment top

The fixation of atmospheric CO₂ by copper complexes is a widely known phenomenon (Van Albada et al., 2000; Sertucha et al., 1999; Escuer et al., 1997; Kitajima et al., 1993). However, it is still not easy to predict whether fixation will occur or not. The crystals studied in this report were obtained from a reaction in an argon-filled glove-box where CO₂ should not usually be present. Currently, we do not know the source of the CO₂. Either there were small impurities in the argon atmosphere or the chemicals, such as the acetonitrile, were carriers of CO₂ impurities. A possible explanation for the reaction is an oxidation of traces of CO₂ by Cu^I resulting in CO₃^2- ions. In addition, H₂O was also found in the structure; therefore, probably traces of Cu(OH)₂ were also present in the acetonitrile solution. This has been described already in the literature as promoting CO₂ fixation (Kruger et al., 1995; Kitajima et al., 1991; Menif et al., 1991).

In the title complex, (I), each copper has a square-pyramidal environment with a basal plane formed by three N atoms of the two chelating bipyridine ligands and the O atom of the bridging carbonato group (Fig. 1). The axial position is occupied by the remaining N atom of the bipyridine ligand. The same structural motif was also obtained by the recrystallization of a hexanuclear (µ₂-hydroxo)(µ₂-carbonato)copper(II) bipyridine complex (Kruger et al., 1995). However, in this related compound, the counter-ion is PF₆^- and the structure crystallized in space group P1. Additionally, the latter structure shows disorder over two sites of the bridging carbonate ligand, which seems to be a reasonably common phenomenon in bridged carbonate structures but was not observed in the current structure (Einstein & Willis, 1981; Palmer & van Eldik, 1983). Cu—O distances [Cu1—O62 1.944 (4) Å, Cu2—O63 1.928 (4) Å] are similar to those in other (µ₂-carbonato)copper complexes (Kruger et al., 1995). The Cu1···Cu2 separation is 5.339 Å, with the non-coordinated carbonate O atom sitting almost centrally between the two Cu atoms (Cu1—O61 2.808 Å and Cu2—O62 2.779 Å). The µ₂-carbonato ligand shows an internal asymmetry with three different C—O bond lengths [C60—O61 1.245 (8) Å, C60—O62 1.293 (8) Å and C60—O63 1.311 (8) Å]. These bond lengths also reveal the different bonding modes of the carbonato O atoms; two atoms are coordinated to the copper centers, which reduces the electron density on these atoms and leads to a lower C—O bond order with a longer bond, while the third O atom shows obviously no, or only a small, interaction with the copper centers resulting in a shorter C—O bond distance. Bipyridyl–bipyridyl π-stacking interactions in the crystal lattice may be a reason for the crystallization of this compound (Fig. 2).

Experimental top

0.57 g (4.0 mmol) CuBr and 1.25 g (8.0 mmol) bipyridine were placed in a 50 ml round-bottomed flask in a glove-box containing an argon atmosphere. 10 ml of acetonitrile were slowly added with stirring. The mixture was heated for a short time until all of the solid completely dissolved. The maroon solution was cooled to room temperature and was allowed to stand for one week. The solvent was evaporated and green crystals were isolated.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The structure of (I) showing displacement ellipsoids at the 50% probability level. For clarity, H atoms have been omitted. The asymmetric unit also contains (not shown) two molecules of acetonitrile, one molecule of water and two bromide counter-ions.
	Fig. 2. Projection of the structure of (I) along [100], showing displacement ellipsoids at the 50% probability level. For clarity, H atoms have been omitted.

(I) top

Crystal data top

[Cu₂(C₁₀H₈N₂)₄(CO₃)]Br₂·2CH₃CN·H₂O	F(000) = 2152
M_r = 1071.77	D_x = 1.579 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.0977 (2) Å	Cell parameters from 5127 reflections
b = 23.7744 (2) Å	θ = 2.3–24.3°
c = 17.1024 (1) Å	µ = 2.78 mm⁻¹
β = 94.347 (1)°	T = 293 K
V = 4499.34 (9) Å³	Irregular, green
Z = 4	0.16 × 0.14 × 0.14 mm

Data collection top

Siemens SMART diffractometer with CCD area detector	4681 independent reflections
Radiation source: fine-focus sealed tube	4013 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.149
ω scans	θ_max = 20.8°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.665, T_max = 0.697	k = 0→23
10354 measured reflections	l = 0→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0245P)² + 20.6621P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.001
4681 reflections	Δρ_max = 1.02 e Å⁻³
569 parameters	Δρ_min = −0.56 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00015 (6)

Crystal data top

[Cu₂(C₁₀H₈N₂)₄(CO₃)]Br₂·2CH₃CN·H₂O	V = 4499.34 (9) Å³
M_r = 1071.77	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.0977 (2) Å	µ = 2.78 mm⁻¹
b = 23.7744 (2) Å	T = 293 K
c = 17.1024 (1) Å	0.16 × 0.14 × 0.14 mm
β = 94.347 (1)°

Data collection top

Siemens SMART diffractometer with CCD area detector	4681 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4013 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.697	R_int = 0.149
10354 measured reflections	θ_max = 20.8°

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0245P)² + 20.6621P] where P = (F_o² + 2F_c²)/3
4681 reflections	Δρ_max = 1.02 e Å⁻³
569 parameters	Δρ_min = −0.56 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.84485 (7)	0.81670 (3)	0.43039 (4)	0.0327 (3)
N1	0.8511 (5)	0.8820 (2)	0.3537 (3)	0.0373 (15)
Br1	0.07263 (10)	0.43466 (4)	0.62217 (5)	0.0731 (3)
Cu2	0.50038 (7)	0.70377 (3)	0.26131 (4)	0.0301 (2)
Br2	0.42833 (8)	0.95427 (3)	0.28040 (5)	0.0572 (3)
C2	0.7538 (7)	0.9085 (3)	0.3216 (4)	0.045 (2)
H2A	0.6785	0.8965	0.3354	0.054*
C3	0.7570 (8)	0.9527 (3)	0.2692 (4)	0.057 (2)
H3A	0.6869	0.9698	0.2476	0.068*
C4	0.8708 (9)	0.9700 (4)	0.2508 (5)	0.058 (2)
H4A	0.8781	1.0001	0.2167	0.069*
C5	0.9723 (8)	0.9434 (3)	0.2822 (4)	0.050 (2)
H5A	1.0482	0.9548	0.2689	0.060*
C6	0.9611 (7)	0.8986 (3)	0.3347 (4)	0.0391 (19)
C7	1.0651 (6)	0.8670 (3)	0.3699 (4)	0.0398 (19)
C8	1.1848 (7)	0.8767 (4)	0.3530 (5)	0.055 (2)
H8A	1.2029	0.9054	0.3190	0.066*
C9	1.2747 (8)	0.8437 (4)	0.3868 (5)	0.065 (3)
H9A	1.3541	0.8491	0.3746	0.078*
C10	1.2479 (7)	0.8021 (4)	0.4390 (5)	0.062 (2)
H10A	1.3082	0.7795	0.4630	0.074*
C11	1.1276 (7)	0.7952 (4)	0.4544 (5)	0.052 (2)
H11A	1.1084	0.7675	0.4898	0.062*
N12	1.0396 (5)	0.8262 (3)	0.4212 (3)	0.0408 (15)
N13	0.8303 (5)	0.8658 (2)	0.5267 (3)	0.0359 (14)
C14	0.8255 (7)	0.9219 (3)	0.5293 (4)	0.049 (2)
H14A	0.8327	0.9418	0.4831	0.059*
C15	0.8104 (8)	0.9519 (3)	0.5972 (5)	0.061 (2)
H15A	0.8065	0.9910	0.5965	0.073*
C16	0.8015 (8)	0.9228 (3)	0.6649 (5)	0.057 (2)
H16A	0.7904	0.9417	0.7113	0.068*
C17	0.8091 (6)	0.8647 (3)	0.6641 (4)	0.0412 (19)
H17A	0.8043	0.8445	0.7103	0.049*
C18	0.8238 (6)	0.8370 (3)	0.5948 (4)	0.0324 (17)
C19	0.8327 (6)	0.7752 (3)	0.5868 (4)	0.0312 (17)
C20	0.8314 (6)	0.7380 (3)	0.6490 (4)	0.0377 (18)
H20A	0.8229	0.7512	0.6995	0.045*
C21	0.8426 (7)	0.6817 (3)	0.6355 (4)	0.045 (2)
H21A	0.8418	0.6563	0.6769	0.054*
C22	0.8550 (7)	0.6626 (3)	0.5608 (4)	0.046 (2)
H22A	0.8644	0.6245	0.5510	0.055*
C23	0.8531 (6)	0.7014 (3)	0.5008 (4)	0.0374 (18)
H23A	0.8594	0.6885	0.4499	0.045*
N24	0.8425 (4)	0.7565 (2)	0.5128 (3)	0.0301 (13)
N25	0.3203 (5)	0.7086 (3)	0.2758 (3)	0.0427 (16)
C26	0.2440 (7)	0.7463 (4)	0.2430 (5)	0.056 (2)
H26A	0.2735	0.7735	0.2104	0.067*
C27	0.1211 (8)	0.7467 (5)	0.2557 (6)	0.078 (3)
H27A	0.0692	0.7734	0.2320	0.094*
C28	0.0797 (8)	0.7065 (5)	0.3042 (6)	0.079 (3)
H28A	−0.0016	0.7057	0.3139	0.095*
C29	0.1588 (8)	0.6669 (4)	0.3390 (5)	0.068 (3)
H29A	0.1311	0.6399	0.3726	0.081*
C30	0.2791 (7)	0.6682 (4)	0.3230 (4)	0.048 (2)
C31	0.3712 (7)	0.6273 (3)	0.3524 (4)	0.042 (2)
C32	0.3460 (9)	0.5777 (4)	0.3906 (5)	0.065 (3)
H32A	0.2676	0.5699	0.4032	0.078*
C33	0.4376 (12)	0.5400 (4)	0.4097 (5)	0.074 (3)
H33A	0.4212	0.5063	0.4342	0.089*
C34	0.5529 (10)	0.5525 (3)	0.3925 (4)	0.065 (3)
H34A	0.6161	0.5277	0.4052	0.078*
C35	0.5731 (8)	0.6032 (3)	0.3556 (4)	0.0427 (19)
H35A	0.6517	0.6123	0.3449	0.051*
N36	0.4853 (5)	0.6390 (2)	0.3351 (3)	0.0349 (14)
N37	0.4918 (5)	0.6506 (2)	0.1537 (3)	0.0333 (14)
C38	0.4829 (7)	0.5953 (3)	0.1462 (4)	0.046 (2)
H38A	0.4709	0.5740	0.1906	0.055*
C39	0.4905 (8)	0.5678 (3)	0.0764 (5)	0.059 (2)
H39A	0.4811	0.5289	0.0732	0.070*
C40	0.5124 (8)	0.5988 (3)	0.0113 (5)	0.055 (2)
H40A	0.5190	0.5811	−0.0367	0.065*
C41	0.5245 (6)	0.6561 (3)	0.0177 (4)	0.0394 (18)
H41A	0.5406	0.6777	−0.0257	0.047*
C42	0.5125 (5)	0.6813 (3)	0.0900 (4)	0.0280 (16)
C43	0.5189 (5)	0.7434 (3)	0.1012 (4)	0.0291 (16)
C44	0.5366 (6)	0.7808 (3)	0.0418 (4)	0.0347 (17)
H44A	0.5459	0.7678	−0.0087	0.042*
C45	0.5405 (7)	0.8374 (3)	0.0574 (4)	0.044 (2)
H45A	0.5528	0.8629	0.0175	0.053*
C46	0.5260 (7)	0.8567 (3)	0.1325 (4)	0.046 (2)
H46A	0.5272	0.8950	0.1439	0.055*
C47	0.5099 (6)	0.8177 (3)	0.1891 (4)	0.0391 (18)
H47A	0.5013	0.8301	0.2399	0.047*
N48	0.5059 (5)	0.7626 (2)	0.1750 (3)	0.0301 (13)
C60	0.6989 (6)	0.7512 (3)	0.3344 (4)	0.0278 (16)
O61	0.6196 (4)	0.7778 (2)	0.3665 (3)	0.0395 (12)
O62	0.8128 (4)	0.76267 (19)	0.3460 (2)	0.0371 (12)
O63	0.6725 (4)	0.71026 (18)	0.2849 (2)	0.0325 (11)
C102	0.8523 (11)	0.1174 (6)	0.3569 (8)	0.142 (6)
H10B	0.9342	0.1245	0.3454	0.171*
H10C	0.8156	0.1519	0.3723	0.171*
H10D	0.8077	0.1026	0.3112	0.171*
C101	0.8512 (10)	0.0783 (5)	0.4181 (7)	0.095 (4)
N100	0.8547 (12)	0.0494 (5)	0.4703 (7)	0.137 (4)
N103	0.2028 (10)	0.8144 (5)	0.0675 (7)	0.128 (4)
C104	0.1948 (9)	0.8581 (5)	0.0839 (5)	0.065 (3)
C105	0.1878 (11)	0.9153 (4)	0.1074 (7)	0.109 (4)
H10E	0.1615	0.9172	0.1595	0.130*
H10F	0.1311	0.9349	0.0719	0.130*
H10G	0.2660	0.9325	0.1065	0.130*
O110	0.1553 (6)	0.4851 (3)	0.4541 (4)	0.0798 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0362 (5)	0.0423 (5)	0.0193 (5)	−0.0102 (4)	0.0000 (4)	0.0004 (4)
N1	0.040 (4)	0.042 (4)	0.031 (3)	−0.014 (3)	0.005 (3)	−0.004 (3)
Br1	0.0967 (8)	0.0682 (6)	0.0551 (6)	−0.0036 (6)	0.0112 (5)	0.0080 (5)
Cu2	0.0276 (5)	0.0374 (5)	0.0253 (5)	−0.0016 (4)	0.0008 (4)	0.0045 (4)
Br2	0.0736 (6)	0.0457 (5)	0.0543 (5)	−0.0041 (4)	0.0187 (4)	−0.0056 (4)
C2	0.053 (5)	0.054 (5)	0.028 (4)	−0.009 (4)	0.003 (4)	−0.001 (4)
C3	0.073 (7)	0.053 (5)	0.042 (5)	0.003 (5)	−0.009 (4)	0.007 (4)
C4	0.082 (7)	0.054 (5)	0.037 (5)	−0.008 (5)	0.005 (5)	0.011 (4)
C5	0.064 (6)	0.049 (5)	0.037 (5)	−0.017 (5)	0.008 (4)	0.000 (4)
C6	0.048 (5)	0.046 (5)	0.023 (4)	−0.014 (4)	0.004 (4)	−0.003 (4)
C7	0.037 (5)	0.054 (5)	0.029 (4)	−0.019 (4)	0.005 (4)	−0.005 (4)
C8	0.051 (6)	0.072 (6)	0.044 (5)	−0.022 (5)	0.009 (4)	0.000 (4)
C9	0.042 (5)	0.098 (7)	0.054 (6)	−0.015 (5)	0.002 (5)	−0.002 (6)
C10	0.040 (6)	0.082 (7)	0.059 (6)	−0.008 (5)	−0.020 (4)	0.007 (5)
C11	0.043 (5)	0.068 (6)	0.045 (5)	−0.015 (5)	0.001 (4)	0.003 (4)
N12	0.034 (4)	0.051 (4)	0.037 (4)	−0.010 (3)	−0.006 (3)	0.005 (3)
N13	0.039 (4)	0.037 (4)	0.032 (4)	−0.005 (3)	0.003 (3)	−0.003 (3)
C14	0.065 (6)	0.048 (6)	0.034 (5)	−0.010 (4)	0.003 (4)	0.001 (4)
C15	0.095 (7)	0.041 (5)	0.046 (6)	−0.016 (5)	−0.002 (5)	−0.012 (5)
C16	0.082 (7)	0.055 (6)	0.033 (5)	−0.017 (5)	0.008 (4)	−0.014 (4)
C17	0.046 (5)	0.051 (5)	0.026 (4)	−0.012 (4)	0.000 (3)	0.000 (4)
C18	0.031 (4)	0.046 (5)	0.021 (4)	−0.011 (3)	0.001 (3)	0.001 (4)
C19	0.025 (4)	0.046 (5)	0.022 (4)	−0.004 (3)	−0.001 (3)	0.002 (4)
C20	0.035 (4)	0.056 (5)	0.023 (4)	0.000 (4)	0.003 (3)	0.002 (4)
C21	0.050 (5)	0.048 (5)	0.038 (5)	0.005 (4)	0.003 (4)	0.017 (4)
C22	0.049 (5)	0.042 (5)	0.047 (5)	0.005 (4)	0.002 (4)	−0.002 (4)
C23	0.042 (5)	0.051 (5)	0.019 (4)	0.002 (4)	−0.004 (3)	−0.004 (4)
N24	0.026 (3)	0.040 (4)	0.025 (4)	−0.004 (3)	0.002 (2)	0.000 (3)
N25	0.027 (3)	0.064 (4)	0.036 (4)	0.007 (3)	−0.003 (3)	−0.006 (3)
C26	0.039 (5)	0.079 (6)	0.050 (5)	0.002 (5)	−0.003 (4)	−0.008 (5)
C27	0.044 (6)	0.120 (9)	0.068 (7)	0.015 (6)	−0.005 (5)	−0.028 (7)
C28	0.034 (5)	0.145 (10)	0.058 (6)	0.001 (7)	0.007 (5)	−0.036 (7)
C29	0.051 (6)	0.114 (8)	0.040 (5)	−0.029 (6)	0.013 (5)	−0.016 (5)
C30	0.041 (5)	0.073 (6)	0.031 (4)	−0.022 (5)	0.010 (4)	−0.005 (4)
C31	0.052 (5)	0.053 (5)	0.022 (4)	−0.022 (4)	0.009 (4)	−0.003 (4)
C32	0.088 (7)	0.070 (7)	0.037 (5)	−0.044 (6)	0.014 (5)	0.000 (5)
C33	0.151 (11)	0.040 (6)	0.032 (5)	−0.028 (7)	0.007 (6)	0.004 (4)
C34	0.121 (9)	0.043 (6)	0.031 (5)	0.001 (6)	0.015 (5)	0.003 (4)
C35	0.065 (6)	0.040 (5)	0.024 (4)	0.002 (4)	0.010 (4)	−0.002 (4)
N36	0.041 (4)	0.039 (4)	0.025 (3)	−0.004 (3)	0.003 (3)	0.001 (3)
N37	0.039 (3)	0.032 (4)	0.029 (4)	−0.003 (3)	−0.001 (3)	−0.005 (3)
C38	0.062 (5)	0.043 (5)	0.033 (5)	−0.004 (4)	0.000 (4)	0.000 (4)
C39	0.094 (7)	0.035 (5)	0.047 (6)	−0.007 (5)	0.004 (5)	−0.001 (5)
C40	0.079 (6)	0.049 (5)	0.034 (5)	0.006 (5)	−0.006 (4)	−0.010 (4)
C41	0.049 (5)	0.046 (5)	0.021 (4)	0.006 (4)	−0.005 (3)	−0.001 (4)
C42	0.024 (4)	0.037 (4)	0.023 (4)	0.001 (3)	−0.002 (3)	0.001 (3)
C43	0.022 (4)	0.039 (4)	0.026 (4)	0.001 (3)	0.000 (3)	0.001 (4)
C44	0.034 (4)	0.048 (5)	0.021 (4)	0.002 (4)	−0.003 (3)	0.002 (4)
C45	0.056 (5)	0.044 (5)	0.032 (5)	−0.001 (4)	0.000 (4)	0.012 (4)
C46	0.065 (5)	0.030 (4)	0.041 (5)	0.001 (4)	0.002 (4)	0.004 (4)
C47	0.047 (5)	0.036 (5)	0.034 (4)	0.002 (4)	0.003 (4)	−0.006 (4)
N48	0.034 (3)	0.035 (4)	0.021 (3)	0.003 (3)	−0.002 (3)	0.003 (3)
C60	0.030 (5)	0.037 (4)	0.017 (4)	−0.006 (4)	−0.001 (3)	0.007 (3)
O61	0.042 (3)	0.050 (3)	0.027 (3)	0.005 (3)	0.006 (2)	−0.006 (2)
O62	0.038 (3)	0.051 (3)	0.022 (3)	−0.012 (2)	0.001 (2)	−0.003 (2)
O63	0.029 (3)	0.040 (3)	0.028 (3)	−0.003 (2)	0.003 (2)	−0.003 (2)
C102	0.113 (10)	0.176 (14)	0.132 (11)	−0.017 (10)	−0.026 (9)	0.094 (11)
C101	0.098 (9)	0.102 (9)	0.085 (9)	0.002 (7)	0.005 (7)	0.023 (7)
N100	0.210 (13)	0.098 (8)	0.104 (9)	−0.002 (8)	0.019 (8)	0.030 (7)
N103	0.126 (9)	0.095 (8)	0.153 (10)	0.004 (7)	−0.061 (7)	−0.034 (8)
C104	0.073 (7)	0.061 (7)	0.059 (6)	0.007 (6)	−0.014 (5)	−0.003 (5)
C105	0.147 (11)	0.078 (8)	0.100 (9)	0.023 (8)	0.003 (8)	0.008 (7)
O110	0.080 (4)	0.093 (5)	0.070 (4)	−0.018 (4)	0.026 (3)	0.000 (4)

Geometric parameters (Å, º) top

Cu1—O62	1.944 (4)	C23—N24	1.333 (9)
Cu1—N24	2.011 (5)	N25—C26	1.328 (10)
Cu1—N13	2.035 (5)	N25—C30	1.355 (9)
Cu1—N1	2.036 (6)	C26—C27	1.398 (12)
Cu1—N12	2.191 (6)	C27—C28	1.366 (14)
N1—C2	1.333 (9)	C28—C29	1.391 (13)
N1—C6	1.346 (9)	C29—C30	1.384 (11)
Cu2—O63	1.928 (4)	C30—C31	1.471 (11)
Cu2—N36	2.005 (5)	C31—N36	1.351 (9)
Cu2—N25	2.036 (6)	C31—C32	1.388 (11)
Cu2—N48	2.037 (5)	C32—C33	1.375 (13)
Cu2—N37	2.229 (5)	C33—C34	1.367 (13)
C2—C3	1.382 (10)	C34—C35	1.385 (11)
C3—C4	1.387 (11)	C35—N36	1.322 (9)
C4—C5	1.366 (11)	N37—C38	1.325 (9)
C5—C6	1.404 (10)	N37—C42	1.345 (8)
C6—C7	1.468 (10)	C38—C39	1.369 (10)
C7—N12	1.352 (9)	C39—C40	1.373 (11)
C7—C8	1.400 (10)	C40—C41	1.373 (10)
C8—C9	1.362 (12)	C41—C42	1.390 (9)
C9—C10	1.379 (12)	C42—C43	1.490 (9)
C10—C11	1.390 (11)	C43—N48	1.359 (8)
C11—N12	1.318 (9)	C43—C44	1.376 (9)
N13—C14	1.335 (9)	C44—C45	1.372 (10)
N13—C18	1.357 (8)	C45—C46	1.385 (10)
C14—C15	1.384 (10)	C46—C47	1.362 (9)
C15—C16	1.359 (11)	C47—N48	1.333 (8)
C16—C17	1.383 (10)	C60—O61	1.244 (7)
C17—C18	1.376 (9)	C60—O62	1.294 (7)
C18—C19	1.479 (10)	C60—O63	1.310 (8)
C19—N24	1.353 (8)	C102—C101	1.400 (15)
C19—C20	1.385 (9)	C101—N100	1.125 (13)
C20—C21	1.365 (10)	N103—C104	1.082 (12)
C21—C22	1.372 (10)	C104—C105	1.422 (14)
C22—C23	1.378 (10)

O62—Cu1—N24	92.2 (2)	C20—C21—C22	119.8 (7)
O62—Cu1—N13	163.4 (2)	C21—C22—C23	118.5 (7)
N24—Cu1—N13	80.5 (2)	N24—C23—C22	122.5 (6)
O62—Cu1—N1	92.2 (2)	C23—N24—C19	118.9 (6)
N24—Cu1—N1	175.5 (2)	C23—N24—Cu1	125.8 (4)
N13—Cu1—N1	95.3 (2)	C19—N24—Cu1	115.3 (4)
O62—Cu1—N12	98.1 (2)	C26—N25—C30	119.8 (7)
N24—Cu1—N12	100.9 (2)	C26—N25—Cu2	125.9 (5)
N13—Cu1—N12	98.0 (2)	C30—N25—Cu2	114.3 (5)
N1—Cu1—N12	78.1 (2)	N25—C26—C27	122.5 (9)
C2—N1—C6	118.8 (6)	C28—C27—C26	117.8 (10)
C2—N1—Cu1	124.1 (5)	C27—C28—C29	120.2 (9)
C6—N1—Cu1	117.1 (5)	C30—C29—C28	119.2 (9)
O63—Cu2—N36	93.4 (2)	N25—C30—C29	120.5 (8)
O63—Cu2—N25	159.4 (2)	N25—C30—C31	114.5 (6)
N36—Cu2—N25	80.6 (2)	C29—C30—C31	125.0 (8)
O63—Cu2—N48	90.73 (19)	N36—C31—C32	120.3 (8)
N36—Cu2—N48	172.3 (2)	N36—C31—C30	115.3 (6)
N25—Cu2—N48	97.7 (2)	C32—C31—C30	124.2 (8)
O63—Cu2—N37	101.39 (19)	C33—C32—C31	119.5 (8)
N36—Cu2—N37	94.8 (2)	C34—C33—C32	119.7 (8)
N25—Cu2—N37	98.7 (2)	C33—C34—C35	118.3 (9)
N48—Cu2—N37	78.0 (2)	N36—C35—C34	122.7 (8)
N1—C2—C3	124.5 (7)	C35—N36—C31	119.5 (6)
C2—C3—C4	116.3 (8)	C35—N36—Cu2	124.6 (5)
C5—C4—C3	120.6 (8)	C31—N36—Cu2	114.9 (5)
C4—C5—C6	119.5 (8)	C38—N37—C42	118.5 (6)
N1—C6—C5	120.2 (7)	C38—N37—Cu2	129.9 (5)
N1—C6—C7	116.7 (6)	C42—N37—Cu2	111.2 (4)
C5—C6—C7	123.0 (7)	N37—C38—C39	123.3 (7)
N12—C7—C8	120.0 (7)	C38—C39—C40	118.5 (7)
N12—C7—C6	115.9 (6)	C39—C40—C41	119.4 (7)
C8—C7—C6	124.1 (7)	C40—C41—C42	118.9 (7)
C9—C8—C7	119.6 (8)	N37—C42—C41	121.4 (6)
C8—C9—C10	120.0 (8)	N37—C42—C43	116.3 (6)
C9—C10—C11	117.7 (8)	C41—C42—C43	122.4 (6)
N12—C11—C10	122.9 (8)	N48—C43—C44	120.0 (6)
C11—N12—C7	119.8 (6)	N48—C43—C42	116.4 (6)
C11—N12—Cu1	127.9 (5)	C44—C43—C42	123.6 (6)
C7—N12—Cu1	112.1 (5)	C45—C44—C43	119.6 (6)
C14—N13—C18	118.0 (6)	C44—C45—C46	120.1 (7)
C14—N13—Cu1	127.2 (5)	C47—C46—C45	117.7 (7)
C18—N13—Cu1	114.7 (4)	N48—C47—C46	123.1 (7)
N13—C14—C15	123.5 (7)	C47—N48—C43	119.5 (6)
C16—C15—C14	118.2 (8)	C47—N48—Cu2	123.1 (5)
C15—C16—C17	119.5 (7)	C43—N48—Cu2	117.0 (4)
C18—C17—C16	119.8 (7)	O61—C60—O62	122.8 (6)
N13—C18—C17	121.0 (6)	O61—C60—O63	122.2 (6)
N13—C18—C19	114.4 (6)	O62—C60—O63	115.1 (6)
C17—C18—C19	124.6 (6)	C60—O62—Cu1	112.0 (4)
N24—C19—C20	120.9 (6)	C60—O63—Cu2	111.4 (4)
N24—C19—C18	115.1 (6)	N100—C101—C102	175.4 (15)
C20—C19—C18	124.0 (6)	N103—C104—C105	178.0 (12)
C21—C20—C19	119.4 (7)

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₀H₈N₂)₄(CO₃)]Br₂·2CH₃CN·H₂O
M_r	1071.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.0977 (2), 23.7744 (2), 17.1024 (1)
β (°)	94.347 (1)
V (Å³)	4499.34 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.78
Crystal size (mm)	0.16 × 0.14 × 0.14

Data collection
Diffractometer	Siemens SMART diffractometer with CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.665, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	10354, 4681, 4013
R_int	0.149
θ_max (°)	20.8
(sin θ/λ)_max (Å⁻¹)	0.500

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.110, 1.17
No. of reflections	4681
No. of parameters	569
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0245P)² + 20.6621P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.56

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXL97.

Selected geometric parameters (Å, º) top

Cu1—O62	1.944 (4)	Cu2—O63	1.928 (4)
Cu1—N24	2.011 (5)	Cu2—N36	2.005 (5)
Cu1—N13	2.035 (5)	Cu2—N25	2.036 (6)
Cu1—N1	2.036 (6)	Cu2—N48	2.037 (5)
Cu1—N12	2.191 (6)	Cu2—N37	2.229 (5)

O62—Cu1—N24	92.2 (2)	N36—Cu2—N25	80.6 (2)
O62—Cu1—N13	163.4 (2)	O63—Cu2—N48	90.73 (19)
N24—Cu1—N13	80.5 (2)	N36—Cu2—N48	172.3 (2)
O62—Cu1—N1	92.2 (2)	N25—Cu2—N48	97.7 (2)
N24—Cu1—N1	175.5 (2)	O63—Cu2—N37	101.39 (19)
N13—Cu1—N1	95.3 (2)	N36—Cu2—N37	94.8 (2)
O62—Cu1—N12	98.1 (2)	N25—Cu2—N37	98.7 (2)
N24—Cu1—N12	100.9 (2)	N48—Cu2—N37	78.0 (2)
N13—Cu1—N12	98.0 (2)	O61—C60—O62	122.8 (6)
N1—Cu1—N12	78.1 (2)	O61—C60—O63	122.2 (6)
O63—Cu2—N36	93.4 (2)	O62—C60—O63	115.1 (6)
O63—Cu2—N25	159.4 (2)

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