Bis[1,3-bis­(benzimidazol-2-yl)-2-oxapropane]copper(II)–picrate–dimethyl­formamide (1/2/4)

Yun, R.; Ying, W.; Qi, B.; Fan, X.; Wu, H.

doi:10.1107/S1600536808036829

Bis[1,3-bis(benzimidazol-2-yl)-2-oxapropane]copper(II)–picrate–dimethylformamide (1/2/4)

R. Yun, W. Ying, B. Qi, X. Fan and H. Wu

In the title compound, [Cu(C₁₆H₁₄N₄O)₂](C₆H₂N₃O₇)₂·4C₃H₇NO, the Cu^II ion is located on a crystallographic inversion center and is coordinated in a distorted octahedral environment by four N atoms and two O atoms forming two long Cu—O bonds. One of the unique dimethylformamide solvent molecules is disordered over two sites with occupancies of 0.715 (6) and 0.285 (6). The crystal structure is stabilized by intermolecular N—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808036829/lh2715sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536808036829/lh2715Isup2.hkl Contains datablock I

CCDC reference: 711800

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.008 Å
Disorder in solvent or counterion
R factor = 0.075
wR factor = 0.232
Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N7
PLAT413_ALERT_2_B Short Inter XH3 .. XHn     H12    ..  H26D    ..       2.01 Ang.

Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.61 Ratio
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.00 Sigma
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT234_ALERT_4_C Large Hirshfeld Difference C3     --  C4      ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C4     --  C5      ..       0.12  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference O2     --  N5      ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference O5     --  N6      ..       0.13  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference N7     --  C21     ..       0.13  Ang.
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C28
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C27
PLAT736_ALERT_1_C H...A   Calc     1.92(6), Rep     1.92(2) ......       3.00 su-Ra
              H4N  -O9      1.555   2.666

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         18
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT302_ALERT_4_G Anion/Solvent Disorder .........................      33.00 Perc.
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            O1  -CU  -O1  -C9      8.00  0.00   2.566   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            O1  -CU  -O1  -C8     16.00  0.00   2.566   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            N1  -CU  -N1  -C7      4.00  0.00   2.566   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            N1  -CU  -N1  -C1     15.00  0.00   2.566   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         21
            N3  -CU  -N3  -C10    15.00  0.00   2.566   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         26
            N3  -CU  -N3  -C16     3.00  0.00   2.566   1.555   1.555   1.555

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

   5 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
   2 ALERT type 3 Indicator that the structure quality may be low
  15 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The asymmetric unit of the title compound consists of half of a di[1,3-bis(benzimidazol-2-yl)-2-oxopropane] copper(II) cation (Fig.1), one picrate anion and two molecules of DMF. The Cu^II ion is six-coordinated with a N₄O₂ ligand set. The obb (1,3-bis(benzimidazol-2-yl)-2-oxopropane) ligand acts as a tridentate donor. The coordination geometry of the Cu^II may be best described as distorted octahedral. This geometry is assumed by the Cu^II to relieve the steric crowding. The equatorial plane is occupied by four N atoms of two benzimidazolyl groups. The axial positions are occuppied two O atoms. The crystal structure is stabilized by intermolecular N-H···O hydrogen bonds.

Related literature top

For the analagous Zn(II) diperchlorate complex, see: Zhou & Yang (2006).

Experimental top

To a stirred solution of 1,3-bis(benzimidazol-2-yl)-2-oxopropane (0.139 g, 0.5 mmol) in hot MeOH (15 ml) was added Cu(C₆H₂N₃O₇)₂ (0.130 g, 0.25 mmol) in MeOH (5 ml). A green crystalline product formed rapidly. The precipitate was filtered off, washed with MeOH and absolute Et₂O, and dried in vacuo. The dried precipitate was dissolved in DMF resulting in a green solution. The green crystals suitable for X-ray diffraction studies were obtained by ether diffusion into DMF after three days at room temperature. Yield, 0.106 g (66%). (found: C, 49.23; H, 4.37; N,18.58. Calcd. for C56H60N18O20Cu: C, 49.14; H, 4.42; N, 18.42)

Computing details top

Data collection: RAPID-AUTO (Rigaku/MSC, 2004); cell refinement: RAPID-AUTO (Rigaku/MSC, 2004); data reduction: RAPID-AUTO (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The cation of the title compound showing displacement ellipsoids at the 30% probability level [symmetry code: (a) -x, -y+1, -x+1].

Bis[1,3-bis(benzimidazol-2-yl)-2-oxapropane]copper(II)–picrate–dimethylformamide (1/2/4) top

Crystal data top

[Cu(C₁₆H₁₄N₄O)₂](C₆H₂N₃O₇)₂·4C₃H₇NO	Z = 1
M_r = 1368.77	F(000) = 711
Triclinic, P1	D_x = 1.506 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9656 (7) Å	Cell parameters from 5605 reflections
b = 12.6028 (12) Å	θ = 3.0–25.5°
c = 13.4100 (9) Å	µ = 0.46 mm⁻¹
α = 65.746 (2)°	T = 293 K
β = 88.629 (2)°	Block, green
γ = 65.187 (2)°	0.28 × 0.21 × 0.11 mm
V = 1508.8 (2) Å³

Data collection top

Rigaku R-AXIS Spider diffractometer	5605 independent reflections
Radiation source: fine-focus sealed tube	3363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
ϕ and ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.883, T_max = 0.952	k = −15→15
12429 measured reflections	l = −16→15

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)] = 0.075	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.232	w = 1/[σ²(F_o²) + (0.1327P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
5605 reflections	Δρ_max = 0.78 e Å⁻³
457 parameters	Δρ_min = −1.09 e Å⁻³
18 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (3)

Crystal data top

[Cu(C₁₆H₁₄N₄O)₂](C₆H₂N₃O₇)₂·4C₃H₇NO	γ = 65.187 (2)°
M_r = 1368.77	V = 1508.8 (2) Å³
Triclinic, P1	Z = 1
a = 10.9656 (7) Å	Mo Kα radiation
b = 12.6028 (12) Å	µ = 0.46 mm⁻¹
c = 13.4100 (9) Å	T = 293 K
α = 65.746 (2)°	0.28 × 0.21 × 0.11 mm
β = 88.629 (2)°

Data collection top

Rigaku R-AXIS Spider diffractometer	5605 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3363 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.952	R_int = 0.078
12429 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	18 restraints
wR(F²) = 0.232	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.78 e Å⁻³
5605 reflections	Δρ_min = −1.09 e Å⁻³
457 parameters

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	Occ. (<1)
Cu	0.0000	0.5000	0.5000	0.0414 (3)
O1	0.1409 (3)	0.5704 (3)	0.5882 (2)	0.0445 (8)
O2	−0.1106 (4)	0.1849 (4)	0.7815 (3)	0.0747 (12)
O3	−0.0335 (4)	−0.0186 (5)	0.8206 (3)	0.0701 (11)
O4	0.4289 (4)	−0.3097 (4)	1.0041 (3)	0.0651 (11)
O5	0.4919 (4)	−0.2964 (4)	1.1479 (3)	0.0816 (14)
O6	0.4312 (3)	−0.0496 (4)	1.1048 (3)	0.0577 (10)
O7	0.3068 (6)	0.1965 (6)	1.0630 (6)	0.151 (3)
O8	0.1451 (5)	0.3258 (4)	0.9307 (4)	0.0838 (13)
N1	0.1462 (3)	0.3364 (4)	0.6167 (3)	0.0418 (9)
N2	0.3339 (4)	0.2162 (4)	0.7450 (3)	0.0440 (10)
N3	0.1426 (3)	0.5132 (4)	0.4093 (3)	0.0434 (10)
N4	0.3198 (4)	0.5527 (5)	0.3577 (3)	0.0493 (10)
N5	−0.0233 (4)	0.0710 (6)	0.8286 (3)	0.0577 (12)
N6	0.4176 (4)	−0.2487 (5)	1.0584 (3)	0.0574 (12)
N7	0.2262 (4)	0.2166 (5)	0.9921 (3)	0.0593 (12)
C1	0.1934 (4)	0.2071 (5)	0.6375 (4)	0.0431 (11)
C2	0.1446 (5)	0.1495 (5)	0.5898 (4)	0.0488 (12)
H2	0.0674	0.1994	0.5343	0.059*
C3	0.2141 (5)	0.0169 (6)	0.6273 (4)	0.0561 (13)
H3	0.1823	−0.0239	0.5980	0.067*
C4	0.3320 (5)	−0.0576 (6)	0.7088 (4)	0.0586 (14)
H4	0.3773	−0.1471	0.7319	0.070*
C5	0.3832 (5)	−0.0029 (5)	0.7558 (4)	0.0490 (12)
H5	0.4619	−0.0528	0.8098	0.059*
C6	0.3118 (4)	0.1294 (5)	0.7189 (3)	0.0436 (11)
C7	0.2347 (4)	0.3364 (5)	0.6822 (4)	0.0433 (12)
C8	0.2230 (4)	0.4562 (5)	0.6871 (4)	0.0468 (12)
H8A	0.1828	0.4627	0.7508	0.056*
H8B	0.3134	0.4503	0.6965	0.056*
C9	0.2173 (4)	0.6123 (5)	0.5063 (4)	0.0481 (12)
H9A	0.3083	0.5841	0.5424	0.058*
H9B	0.1733	0.7067	0.4674	0.058*
C10	0.2273 (4)	0.5579 (5)	0.4249 (4)	0.0464 (12)
C11	0.2956 (4)	0.5003 (5)	0.2916 (4)	0.0498 (13)
C12	0.3633 (5)	0.4699 (6)	0.2106 (4)	0.0596 (15)
H12	0.4351	0.4895	0.1874	0.072*
C13	0.3170 (5)	0.4088 (7)	0.1670 (5)	0.0686 (17)
H13	0.3598	0.3854	0.1134	0.082*
C14	0.2084 (5)	0.3810 (6)	0.2004 (4)	0.0662 (16)
H14	0.1808	0.3396	0.1687	0.079*
C15	0.1411 (5)	0.4134 (6)	0.2791 (4)	0.0564 (14)
H15	0.0686	0.3947	0.3014	0.068*
C16	0.1863 (4)	0.4754 (5)	0.3240 (4)	0.0444 (11)
C17	0.0969 (4)	0.0407 (5)	0.8985 (4)	0.0480 (12)
C18	0.2005 (5)	−0.0854 (5)	0.9460 (4)	0.0496 (13)
H18	0.1943	−0.1493	0.9315	0.060*
C19	0.3118 (4)	−0.1151 (5)	1.0143 (4)	0.0496 (13)
C20	0.3311 (4)	−0.0229 (5)	1.0410 (3)	0.0456 (12)
C21	0.2194 (5)	0.1088 (5)	0.9812 (4)	0.0472 (12)
C22	0.1076 (4)	0.1381 (5)	0.9134 (4)	0.0488 (13)
H22	0.0392	0.2234	0.8776	0.059*
O9	0.5277 (3)	0.3378 (4)	0.6011 (3)	0.0581 (10)
N8	0.5913 (4)	0.1433 (4)	0.6002 (3)	0.0551 (12)
C23	0.6860 (5)	0.0045 (5)	0.6489 (4)	0.0723 (18)
H23A	0.7387	−0.0147	0.5950	0.087*
H23B	0.6355	−0.0454	0.6710	0.087*
H23C	0.7461	−0.0176	0.7128	0.087*
C24	0.4876 (5)	0.1923 (6)	0.5051 (4)	0.0651 (16)
H24A	0.4192	0.2779	0.4908	0.078*
H24B	0.4459	0.1350	0.5211	0.078*
H24C	0.5295	0.1961	0.4408	0.078*
C25	0.6028 (5)	0.2181 (5)	0.6400 (4)	0.0551 (14)
H25	0.6710	0.1799	0.7010	0.066*
O10	0.1119 (11)	0.8119 (10)	0.6125 (7)	0.161 (4)	0.715 (6)
N9	0.1418 (5)	0.6993 (7)	0.7922 (6)	0.068 (2)	0.715 (6)
C26	0.2883 (6)	0.6379 (9)	0.7915 (9)	0.095 (4)	0.715 (6)
H26A	0.3044	0.6737	0.7170	0.143*	0.715 (6)
H26B	0.3205	0.5457	0.8187	0.143*	0.715 (6)
H26C	0.3360	0.6541	0.8384	0.143*	0.715 (6)
C27	0.0966 (8)	0.6585 (9)	0.8996 (6)	0.081 (3)	0.715 (6)
H27A	−0.0009	0.7062	0.8888	0.122*	0.715 (6)
H27B	0.1386	0.6758	0.9493	0.122*	0.715 (6)
H27C	0.1225	0.5670	0.9309	0.122*	0.715 (6)
C28	0.0578 (8)	0.7873 (8)	0.6984 (6)	0.071 (3)	0.715 (6)
H28A	−0.0359	0.8292	0.6950	0.085*	0.715 (6)
O10A	0.3069 (17)	0.6919 (19)	0.6726 (13)	0.100*	0.285 (6)
N9A	0.1822 (19)	0.667 (3)	0.8055 (15)	0.100*	0.285 (6)
C26A	0.303 (2)	0.552 (2)	0.8825 (17)	0.100*	0.285 (6)
H26D	0.3777	0.5331	0.8430	0.150*	0.285 (6)
H26E	0.2838	0.4784	0.9143	0.150*	0.285 (6)
H26F	0.3281	0.5688	0.9406	0.150*	0.285 (6)
C27A	0.0588 (19)	0.700 (3)	0.8533 (19)	0.100*	0.285 (6)
H27D	−0.0151	0.7755	0.7973	0.150*	0.285 (6)
H27E	0.0739	0.7182	0.9135	0.150*	0.285 (6)
H27F	0.0364	0.6282	0.8806	0.150*	0.285 (6)
C28A	0.1935 (19)	0.729 (2)	0.7029 (14)	0.100*	0.285 (6)
H28B	0.1175	0.8016	0.6525	0.120*	0.285 (6)
H2N	0.400 (4)	0.199 (6)	0.792 (4)	0.08 (2)*
H4N	0.374 (5)	0.587 (5)	0.357 (4)	0.069 (18)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0295 (4)	0.0509 (6)	0.0466 (5)	−0.0148 (4)	0.0089 (3)	−0.0273 (4)
O1	0.0332 (15)	0.051 (2)	0.0461 (17)	−0.0136 (15)	0.0083 (14)	−0.0237 (16)
O2	0.045 (2)	0.073 (3)	0.077 (3)	−0.011 (2)	−0.0100 (19)	−0.021 (2)
O3	0.058 (2)	0.081 (3)	0.070 (2)	−0.029 (2)	−0.0037 (19)	−0.033 (2)
O4	0.063 (2)	0.059 (3)	0.068 (2)	−0.0146 (19)	0.0012 (18)	−0.037 (2)
O5	0.081 (3)	0.064 (3)	0.064 (2)	−0.002 (2)	−0.032 (2)	−0.026 (2)
O6	0.0501 (19)	0.060 (2)	0.0532 (19)	−0.0160 (17)	−0.0023 (16)	−0.0245 (18)
O7	0.136 (5)	0.082 (4)	0.197 (6)	0.010 (3)	−0.097 (5)	−0.082 (4)
O8	0.084 (3)	0.059 (3)	0.088 (3)	−0.019 (2)	−0.011 (2)	−0.026 (2)
N1	0.0338 (18)	0.051 (3)	0.047 (2)	−0.0186 (18)	0.0123 (17)	−0.027 (2)
N2	0.0352 (19)	0.054 (3)	0.044 (2)	−0.0163 (19)	0.0124 (18)	−0.027 (2)
N3	0.0315 (17)	0.054 (3)	0.045 (2)	−0.0156 (18)	0.0086 (16)	−0.027 (2)
N4	0.0325 (19)	0.058 (3)	0.059 (2)	−0.019 (2)	0.0144 (19)	−0.028 (2)
N5	0.041 (2)	0.080 (4)	0.047 (2)	−0.023 (2)	0.0048 (19)	−0.027 (3)
N6	0.052 (2)	0.059 (3)	0.057 (2)	−0.015 (2)	0.007 (2)	−0.032 (2)
N7	0.051 (2)	0.063 (3)	0.048 (2)	−0.007 (2)	−0.002 (2)	−0.030 (2)
C1	0.037 (2)	0.055 (3)	0.045 (2)	−0.021 (2)	0.015 (2)	−0.029 (2)
C2	0.043 (2)	0.058 (3)	0.048 (3)	−0.022 (2)	0.012 (2)	−0.026 (3)
C3	0.061 (3)	0.063 (4)	0.053 (3)	−0.030 (3)	0.018 (3)	−0.033 (3)
C4	0.067 (3)	0.054 (4)	0.059 (3)	−0.026 (3)	0.025 (3)	−0.030 (3)
C5	0.045 (2)	0.058 (3)	0.042 (2)	−0.015 (2)	0.009 (2)	−0.028 (2)
C6	0.037 (2)	0.048 (3)	0.041 (2)	−0.013 (2)	0.013 (2)	−0.022 (2)
C7	0.0260 (19)	0.061 (3)	0.042 (2)	−0.012 (2)	0.0078 (18)	−0.030 (2)
C8	0.039 (2)	0.058 (3)	0.044 (2)	−0.017 (2)	0.002 (2)	−0.027 (2)
C9	0.035 (2)	0.059 (3)	0.053 (3)	−0.021 (2)	0.010 (2)	−0.028 (3)
C10	0.031 (2)	0.058 (3)	0.053 (3)	−0.017 (2)	0.009 (2)	−0.030 (2)
C11	0.036 (2)	0.057 (3)	0.049 (3)	−0.011 (2)	0.009 (2)	−0.027 (3)
C12	0.043 (3)	0.073 (4)	0.062 (3)	−0.021 (3)	0.021 (2)	−0.036 (3)
C13	0.048 (3)	0.096 (5)	0.075 (3)	−0.024 (3)	0.027 (3)	−0.059 (4)
C14	0.057 (3)	0.085 (5)	0.070 (3)	−0.026 (3)	0.021 (3)	−0.052 (3)
C15	0.041 (2)	0.070 (4)	0.062 (3)	−0.021 (3)	0.014 (2)	−0.038 (3)
C16	0.031 (2)	0.053 (3)	0.047 (2)	−0.012 (2)	0.0093 (19)	−0.027 (2)
C17	0.038 (2)	0.059 (3)	0.043 (2)	−0.018 (2)	0.008 (2)	−0.023 (2)
C18	0.046 (3)	0.064 (4)	0.041 (2)	−0.027 (3)	0.014 (2)	−0.023 (2)
C19	0.040 (2)	0.057 (3)	0.043 (2)	−0.010 (2)	0.005 (2)	−0.026 (2)
C20	0.041 (2)	0.052 (3)	0.033 (2)	−0.013 (2)	0.008 (2)	−0.017 (2)
C21	0.047 (3)	0.052 (3)	0.043 (2)	−0.017 (2)	0.016 (2)	−0.027 (2)
C22	0.036 (2)	0.058 (3)	0.041 (2)	−0.010 (2)	0.007 (2)	−0.022 (2)
O9	0.0464 (18)	0.070 (3)	0.062 (2)	−0.0275 (19)	0.0155 (17)	−0.032 (2)
N8	0.038 (2)	0.067 (3)	0.052 (2)	−0.014 (2)	0.0108 (18)	−0.028 (2)
C23	0.055 (3)	0.072 (4)	0.070 (3)	−0.009 (3)	0.013 (3)	−0.034 (3)
C24	0.056 (3)	0.077 (4)	0.053 (3)	−0.018 (3)	0.003 (3)	−0.032 (3)
C25	0.038 (2)	0.079 (4)	0.055 (3)	−0.027 (3)	0.015 (2)	−0.035 (3)
O10	0.230 (12)	0.138 (9)	0.169 (9)	−0.105 (9)	0.009 (9)	−0.091 (8)
N9	0.016 (3)	0.079 (5)	0.137 (7)	−0.012 (3)	0.021 (3)	−0.082 (5)
C26	0.025 (3)	0.086 (7)	0.202 (13)	−0.011 (4)	0.008 (5)	−0.102 (9)
C27	0.082 (6)	0.054 (6)	0.077 (6)	−0.025 (5)	−0.019 (5)	−0.006 (5)
C28	0.087 (6)	0.078 (7)	0.079 (6)	−0.055 (6)	0.027 (5)	−0.046 (6)

Geometric parameters (Å, º) top

Cu—N3	1.979 (3)	C13—C14	1.392 (8)
Cu—N3ⁱ	1.979 (3)	C13—H13	0.9300
Cu—N1	1.992 (4)	C14—C15	1.375 (6)
Cu—N1ⁱ	1.992 (4)	C14—H14	0.9300
Cu—O1ⁱ	2.583 (3)	C15—C16	1.395 (7)
Cu—O1	2.583 (3)	C15—H15	0.9300
O1—C9	1.427 (5)	C17—C22	1.373 (7)
O1—C8	1.429 (5)	C17—C18	1.382 (7)
O2—N5	1.227 (6)	C18—C19	1.363 (6)
O3—N5	1.227 (6)	C18—H18	0.9300
O4—N6	1.230 (5)	C19—C20	1.440 (7)
O5—N6	1.228 (5)	C20—C21	1.465 (7)
O6—C20	1.244 (5)	C21—C22	1.366 (6)
O7—N7	1.185 (5)	C22—H22	0.9300
O8—N7	1.199 (6)	O9—C25	1.248 (6)
N1—C7	1.324 (5)	N8—C25	1.306 (6)
N1—C1	1.387 (6)	N8—C23	1.461 (6)
N2—C7	1.342 (6)	N8—C24	1.461 (5)
N2—C6	1.386 (6)	C23—H23A	0.9600
N2—H2N	0.87 (5)	C23—H23B	0.9600
N3—C10	1.329 (6)	C23—H23C	0.9600
N3—C16	1.413 (5)	C24—H24A	0.9600
N4—C10	1.339 (6)	C24—H24B	0.9600
N4—C11	1.389 (6)	C24—H24C	0.9600
N4—H4N	0.87 (5)	C25—H25	0.9300
N5—C17	1.451 (6)	O10—C28	1.266 (7)
N6—C19	1.451 (6)	N9—C28	1.309 (7)
N7—C21	1.456 (7)	N9—C26	1.463 (6)
C1—C2	1.395 (6)	N9—C27	1.468 (6)
C1—C6	1.399 (6)	C26—H26A	0.9600
C2—C3	1.373 (8)	C26—H26B	0.9600
C2—H2	0.9300	C26—H26C	0.9600
C3—C4	1.397 (7)	C27—H27A	0.9600
C3—H3	0.9300	C27—H27B	0.9600
C4—C5	1.374 (7)	C27—H27C	0.9600
C4—H4	0.9300	C28—H28A	0.9300
C5—C6	1.372 (7)	O10A—C28A	1.255 (8)
C5—H5	0.9300	N9A—C28A	1.309 (7)
C7—C8	1.490 (7)	N9A—C27A	1.456 (7)
C8—H8A	0.9700	N9A—C26A	1.466 (7)
C8—H8B	0.9700	C26A—H26D	0.9600
C9—C10	1.489 (6)	C26A—H26E	0.9600
C9—H9A	0.9700	C26A—H26F	0.9600
C9—H9B	0.9700	C27A—H27D	0.9600
C11—C16	1.380 (7)	C27A—H27E	0.9600
C11—C12	1.394 (6)	C27A—H27F	0.9600
C12—C13	1.381 (8)	C28A—H28B	0.9300
C12—H12	0.9300

N3—Cu—N3ⁱ	180	C14—C13—H13	118.8
N3—Cu—N1	87.55 (15)	C15—C14—C13	121.4 (5)
N3ⁱ—Cu—N1	92.45 (15)	C15—C14—H14	119.3
N3—Cu—N1ⁱ	92.45 (15)	C13—C14—H14	119.3
N3ⁱ—Cu—N1ⁱ	87.55 (15)	C14—C15—C16	117.1 (5)
N1—Cu—N1ⁱ	180	C14—C15—H15	121.5
N3—Cu—O1ⁱ	106.54 (12)	C16—C15—H15	121.5
N3ⁱ—Cu—O1ⁱ	73.46 (12)	C11—C16—C15	120.9 (4)
N1—Cu—O1ⁱ	106.14 (13)	C11—C16—N3	109.3 (4)
N1ⁱ—Cu—O1ⁱ	73.86 (13)	C15—C16—N3	129.7 (4)
N3—Cu—O1	73.46 (12)	C22—C17—C18	121.3 (4)
N3ⁱ—Cu—O1	106.54 (12)	C22—C17—N5	119.6 (5)
N1—Cu—O1	73.86 (13)	C18—C17—N5	119.1 (5)
N1ⁱ—Cu—O1	106.14 (13)	C19—C18—C17	119.2 (5)
O1ⁱ—Cu—O1	180	C19—C18—H18	120.4
C9—O1—C8	114.0 (3)	C17—C18—H18	120.4
C9—O1—Cu	105.0 (2)	C18—C19—C20	124.5 (5)
C8—O1—Cu	104.8 (3)	C18—C19—N6	115.8 (5)
C7—N1—C1	105.4 (4)	C20—C19—N6	119.7 (4)
C7—N1—Cu	122.5 (3)	O6—C20—C19	124.9 (4)
C1—N1—Cu	131.4 (3)	O6—C20—C21	123.4 (5)
C7—N2—C6	108.1 (4)	C19—C20—C21	111.7 (4)
C7—N2—H2N	124 (4)	C22—C21—N7	117.0 (5)
C6—N2—H2N	128 (4)	C22—C21—C20	123.6 (5)
C10—N3—C16	104.3 (4)	N7—C21—C20	119.4 (4)
C10—N3—Cu	123.2 (3)	C21—C22—C17	119.5 (5)
C16—N3—Cu	132.4 (3)	C21—C22—H22	120.3
C10—N4—C11	107.3 (4)	C17—C22—H22	120.3
C10—N4—H4N	120 (4)	C25—N8—C23	120.4 (4)
C11—N4—H4N	133 (4)	C25—N8—C24	122.9 (4)
O2—N5—O3	123.3 (4)	C23—N8—C24	116.7 (4)
O2—N5—C17	118.3 (5)	N8—C23—H23A	109.5
O3—N5—C17	118.4 (5)	N8—C23—H23B	109.5
O5—N6—O4	122.7 (4)	H23A—C23—H23B	109.5
O5—N6—C19	119.1 (4)	N8—C23—H23C	109.5
O4—N6—C19	118.2 (4)	H23A—C23—H23C	109.5
O7—N7—O8	120.8 (6)	H23B—C23—H23C	109.5
O7—N7—C21	120.5 (5)	N8—C24—H24A	109.5
O8—N7—C21	118.7 (4)	N8—C24—H24B	109.5
N1—C1—C2	131.0 (4)	H24A—C24—H24B	109.5
N1—C1—C6	109.6 (4)	N8—C24—H24C	109.5
C2—C1—C6	119.4 (5)	H24A—C24—H24C	109.5
C3—C2—C1	118.0 (4)	H24B—C24—H24C	109.5
C3—C2—H2	121.0	O9—C25—N8	124.0 (4)
C1—C2—H2	121.0	O9—C25—H25	118.0
C2—C3—C4	121.0 (5)	N8—C25—H25	118.0
C2—C3—H3	119.5	C28—N9—C26	119.1 (6)
C4—C3—H3	119.5	C28—N9—C27	123.2 (5)
C5—C4—C3	122.1 (5)	C26—N9—C27	117.7 (6)
C5—C4—H4	118.9	N9—C26—H26A	109.5
C3—C4—H4	118.9	N9—C26—H26B	109.5
C6—C5—C4	116.4 (4)	H26A—C26—H26B	109.5
C6—C5—H5	121.8	N9—C26—H26C	109.5
C4—C5—H5	121.8	H26A—C26—H26C	109.5
C5—C6—N2	132.3 (4)	H26B—C26—H26C	109.5
C5—C6—C1	123.1 (5)	N9—C27—H27A	109.5
N2—C6—C1	104.6 (4)	N9—C27—H27B	109.5
N1—C7—N2	112.3 (5)	H27A—C27—H27B	109.5
N1—C7—C8	123.6 (4)	N9—C27—H27C	109.5
N2—C7—C8	124.1 (4)	H27A—C27—H27C	109.5
O1—C8—C7	111.3 (3)	H27B—C27—H27C	109.5
O1—C8—H8A	109.4	O10—C28—N9	116.0 (7)
C7—C8—H8A	109.4	O10—C28—H28A	122.0
O1—C8—H8B	109.4	N9—C28—H28A	122.0
C7—C8—H8B	109.4	C28A—N9A—C27A	126.2 (9)
H8A—C8—H8B	108.0	C28A—N9A—C26A	118.7 (8)
O1—C9—C10	111.0 (4)	C27A—N9A—C26A	115.1 (8)
O1—C9—H9A	109.4	N9A—C26A—H26D	109.5
C10—C9—H9A	109.4	N9A—C26A—H26E	109.5
O1—C9—H9B	109.4	H26D—C26A—H26E	109.5
C10—C9—H9B	109.4	N9A—C26A—H26F	109.5
H9A—C9—H9B	108.0	H26D—C26A—H26F	109.5
N3—C10—N4	113.2 (4)	H26E—C26A—H26F	109.5
N3—C10—C9	123.3 (4)	N9A—C27A—H27D	109.5
N4—C10—C9	123.5 (4)	N9A—C27A—H27E	109.5
C16—C11—N4	106.0 (4)	H27D—C27A—H27E	109.5
C16—C11—C12	122.6 (5)	N9A—C27A—H27F	109.5
N4—C11—C12	131.4 (5)	H27D—C27A—H27F	109.5
C13—C12—C11	115.7 (5)	H27E—C27A—H27F	109.5
C13—C12—H12	122.2	O10A—C28A—N9A	120.0 (10)
C11—C12—H12	122.2	O10A—C28A—H28B	120.0
C12—C13—C14	122.3 (5)	N9A—C28A—H28B	120.0
C12—C13—H13	118.8

N3—Cu—O1—C9	15.0 (3)	C16—N3—C10—N4	0.2 (6)
N3ⁱ—Cu—O1—C9	−165.0 (3)	Cu—N3—C10—N4	177.0 (3)
N1—Cu—O1—C9	107.2 (3)	C16—N3—C10—C9	178.4 (4)
N1ⁱ—Cu—O1—C9	−72.8 (3)	Cu—N3—C10—C9	−4.8 (7)
O1ⁱ—Cu—O1—C9	−79 (100)	C11—N4—C10—N3	0.0 (6)
N3—Cu—O1—C8	−105.5 (3)	C11—N4—C10—C9	−178.1 (5)
N3ⁱ—Cu—O1—C8	74.5 (3)	O1—C9—C10—N3	19.8 (7)
N1—Cu—O1—C8	−13.2 (2)	O1—C9—C10—N4	−162.2 (4)
N1ⁱ—Cu—O1—C8	166.8 (2)	C10—N4—C11—C16	−0.3 (5)
O1ⁱ—Cu—O1—C8	161 (100)	C10—N4—C11—C12	−177.8 (6)
N3—Cu—N1—C7	76.3 (3)	C16—C11—C12—C13	−2.1 (8)
N3ⁱ—Cu—N1—C7	−103.7 (3)	N4—C11—C12—C13	175.1 (5)
N1ⁱ—Cu—N1—C7	−42 (100)	C11—C12—C13—C14	0.9 (9)
O1ⁱ—Cu—N1—C7	−177.2 (3)	C12—C13—C14—C15	0.1 (10)
O1—Cu—N1—C7	2.8 (3)	C13—C14—C15—C16	0.0 (9)
N3—Cu—N1—C1	−92.3 (4)	N4—C11—C16—C15	−175.4 (4)
N3ⁱ—Cu—N1—C1	87.7 (4)	C12—C11—C16—C15	2.4 (8)
N1ⁱ—Cu—N1—C1	149 (100)	N4—C11—C16—N3	0.4 (6)
O1ⁱ—Cu—N1—C1	14.2 (4)	C12—C11—C16—N3	178.2 (5)
O1—Cu—N1—C1	−165.8 (4)	C14—C15—C16—C11	−1.2 (8)
N3ⁱ—Cu—N3—C10	153 (100)	C14—C15—C16—N3	−176.1 (5)
N1—Cu—N3—C10	−79.7 (4)	C10—N3—C16—C11	−0.4 (5)
N1ⁱ—Cu—N3—C10	100.3 (4)	Cu—N3—C16—C11	−176.8 (3)
O1ⁱ—Cu—N3—C10	174.2 (4)	C10—N3—C16—C15	175.0 (5)
O1—Cu—N3—C10	−5.8 (4)	Cu—N3—C16—C15	−1.4 (8)
N3ⁱ—Cu—N3—C16	−31 (100)	O2—N5—C17—C22	2.5 (7)
N1—Cu—N3—C16	96.1 (4)	O3—N5—C17—C22	−176.7 (4)
N1ⁱ—Cu—N3—C16	−83.9 (4)	O2—N5—C17—C18	−175.6 (4)
O1ⁱ—Cu—N3—C16	−10.0 (4)	O3—N5—C17—C18	5.3 (6)
O1—Cu—N3—C16	170.0 (4)	C22—C17—C18—C19	3.9 (7)
C7—N1—C1—C2	−177.3 (4)	N5—C17—C18—C19	−178.1 (4)
Cu—N1—C1—C2	−7.2 (7)	C17—C18—C19—C20	−0.5 (7)
C7—N1—C1—C6	1.0 (5)	C17—C18—C19—N6	−178.4 (4)
Cu—N1—C1—C6	171.1 (3)	O5—N6—C19—C18	−152.7 (5)
N1—C1—C2—C3	179.6 (4)	O4—N6—C19—C18	27.1 (7)
C6—C1—C2—C3	1.5 (6)	O5—N6—C19—C20	29.3 (7)
C1—C2—C3—C4	−1.5 (7)	O4—N6—C19—C20	−150.9 (4)
C2—C3—C4—C5	0.6 (7)	C18—C19—C20—O6	178.7 (4)
C3—C4—C5—C6	0.3 (7)	N6—C19—C20—O6	−3.5 (7)
C4—C5—C6—N2	−178.4 (4)	C18—C19—C20—C21	−2.9 (6)
C4—C5—C6—C1	−0.4 (7)	N6—C19—C20—C21	174.9 (4)
C7—N2—C6—C5	178.2 (5)	O7—N7—C21—C22	167.0 (6)
C7—N2—C6—C1	−0.2 (4)	O8—N7—C21—C22	−10.0 (7)
N1—C1—C6—C5	−179.0 (4)	O7—N7—C21—C20	−13.8 (8)
C2—C1—C6—C5	−0.6 (7)	O8—N7—C21—C20	169.2 (4)
N1—C1—C6—N2	−0.5 (5)	O6—C20—C21—C22	−178.2 (4)
C2—C1—C6—N2	178.0 (4)	C19—C20—C21—C22	3.3 (6)
C1—N1—C7—N2	−1.1 (5)	O6—C20—C21—N7	2.6 (6)
Cu—N1—C7—N2	−172.3 (3)	C19—C20—C21—N7	−175.8 (4)
C1—N1—C7—C8	−179.9 (4)	N7—C21—C22—C17	178.8 (4)
Cu—N1—C7—C8	8.9 (6)	C20—C21—C22—C17	−0.3 (7)
C6—N2—C7—N1	0.8 (5)	C18—C17—C22—C21	−3.5 (7)
C6—N2—C7—C8	179.6 (4)	N5—C17—C22—C21	178.5 (4)
C9—O1—C8—C7	−94.6 (4)	C23—N8—C25—O9	178.3 (5)
Cu—O1—C8—C7	19.7 (4)	C24—N8—C25—O9	−0.3 (7)
N1—C7—C8—O1	−21.8 (6)	C26—N9—C28—O10	0.4 (13)
N2—C7—C8—O1	159.6 (4)	C27—N9—C28—O10	−179.7 (9)
C8—O1—C9—C10	94.0 (4)	C27A—N9A—C28A—O10A	178 (3)
Cu—O1—C9—C10	−20.2 (4)	C26A—N9A—C28A—O10A	−1 (5)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O6ⁱⁱ	0.87 (5)	1.95 (4)	2.709 (5)	145 (6)
N2—H2N···O5ⁱⁱ	0.87 (5)	2.41 (5)	3.104 (6)	138 (6)
N4—H4N···O9ⁱⁱⁱ	0.87 (5)	1.92 (2)	2.753 (6)	162 (5)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₆H₁₄N₄O)₂](C₆H₂N₃O₇)₂·4C₃H₇NO
M_r	1368.77
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.9656 (7), 12.6028 (12), 13.4100 (9)
α, β, γ (°)	65.746 (2), 88.629 (2), 65.187 (2)
V (Å³)	1508.8 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.28 × 0.21 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS Spider diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.883, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	12429, 5605, 3363
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.232, 1.02
No. of reflections	5605
No. of parameters	457
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.78, −1.09

Computer programs: RAPID-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu—N3	1.979 (3)	Cu—O1	2.583 (3)
Cu—N1	1.992 (4)

N3—Cu—N3ⁱ	180	N1—Cu—O1ⁱ	106.14 (13)
N3—Cu—N1	87.55 (15)	N3—Cu—O1	73.46 (12)
N3—Cu—N1ⁱ	92.45 (15)	N1—Cu—O1	73.86 (13)
N1—Cu—N1ⁱ	180	O1ⁱ—Cu—O1	180
N3—Cu—O1ⁱ	106.54 (12)