Tetra­kis(μ-4-azido­benzoato-κ2O:O′)bis­[(N,N-dimethyl­formamide-κO)copper(II)]

Wang, A.

doi:10.1107/S1600536811050999

Tetrakis(μ-4-azidobenzoato-κ²O:O′)bis[(N,N-dimethylformamide-κO)copper(II)]

The binuclear title compound, [Cu₂(C₇H₄N₃O₂)₄(C₃H₇NO)₂], is a discrete metal–organic compound having a paddle-wheel-type structure. The Cu

Cu distance is 2.6366 (5) Å and an inversion center is located at the mid-point of this bond. The Cu^II cation is coordinated by four carboxylate O atoms from four 4-azidobenzoate ligands, and one O atom from a dimethylformamide molecule, forming an overall distorted octahedral geometry when the Cu

Cu bond is also considered.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811050999/bh2402sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811050999/bh2402Isup2.hkl Contains datablock I

CCDC reference: 861691

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.033
wR factor = 0.091
Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N4     --  N5      ..        7.3 su

Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         29
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C16
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C17
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          80 Perc.
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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

Comment top

The title compound, tetrakis(4-azidobenzoato)bis[(N,N-dimethylformamide)copper(II)], crystallizes in the monoclinic form with centrosymmetric space group P2₁/c. The asymmetric unit contains one copper atom, two 4-azidobenzoate ligands, and one DMF molecule. The Cu atom has a coordination number of six and is coordinated by four carboxylate O atoms from four 4-azidobenzoate ligands and one O atom from DMF molecule. The Cu—Cu bond length is 2.6366 (5) Å. The main structural feature of the title compound is the presence of the well known paddle-wheel unit (Del Sesto et al., 2000; Li et al., 2011) constructed by the asymmetric unit via the inversion symmetry. The azido groups of the ligands are not coordinated and the axial positions of the octahedral coordination polyhedra are occupied by two DMF molecules, to generate the 0D compound.

Related literature top

For similar complexes displaying a paddle-wheel structure, see: Del Sesto et al. (2000); Li et al. (2011). For the synthesis of 4-azidobenzoic acid, see: Sato et al. (2010).

Experimental top

4-Azidobenzoic acid was prepared from 4-aminoisophthalic acid by diazotization followed by azidation with sodium azide (Sato et al., 2010). A mixture of Cu(NO₃)₂3 H₂O (0.130 g, 0.5 mmol) 4-azidobenzoic acid (0.085 g,0.5 mmol) and DMF (5 ml) was sealed in a 20 ml stainless steel reactor with Teflon liner and heated at 393 K for 4 days. Blue crystals of the title complex were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalClear (Rigaku, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A molecular drawing of the title complex, showing 30% probability displacement ellipsoids. All H atoms were omitted for clarity. Unlabeled atoms are generated by symmetry -x, 1-y, 1-z.

Tetrakis(µ-4-azidobenzoato-κ²O:O')bis[(N,N- dimethylformamide-κO)copper(II)] top

Crystal data top

[Cu₂(C₇H₄N₃O₂)₄(C₃H₇NO)₂]	F(000) = 940
M_r = 921.80	D_x = 1.529 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4783 reflections
a = 11.9209 (8) Å	θ = 3.1–25°
b = 17.9387 (10) Å	µ = 1.14 mm⁻¹
c = 9.3680 (5) Å	T = 293 K
β = 91.277 (5)°	Block, blue
V = 2002.8 (2) Å³	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection top

Rigaku Mercury70 diffractometer	3496 independent reflections
Radiation source: fine-focus sealed tube	3141 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.0°, θ_min = 2.5°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	k = −19→21
T_min = 0.805, T_max = 0.805	l = −11→11
12312 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0482P)² + 0.7327P] where P = (F_o² + 2F_c²)/3
3496 reflections	(Δ/σ)_max = 0.001
271 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³
0 constraints

Crystal data top

[Cu₂(C₇H₄N₃O₂)₄(C₃H₇NO)₂]	V = 2002.8 (2) Å³
M_r = 921.80	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.9209 (8) Å	µ = 1.14 mm⁻¹
b = 17.9387 (10) Å	T = 293 K
c = 9.3680 (5) Å	0.2 × 0.2 × 0.2 mm
β = 91.277 (5)°

Data collection top

Rigaku Mercury70 diffractometer	3496 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2002)	3141 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.805	R_int = 0.031
12312 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.02	Δρ_max = 0.33 e Å⁻³
3496 reflections	Δρ_min = −0.31 e Å⁻³
271 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.05068 (2)	0.451211 (14)	0.58459 (3)	0.03461 (12)
O1	0.16267 (14)	0.44589 (9)	0.43570 (18)	0.0472 (4)
O5	0.12483 (14)	0.36844 (9)	0.72800 (17)	0.0470 (4)
O3	0.04281 (13)	0.62087 (9)	0.52445 (18)	0.0461 (4)
O2	0.07599 (14)	0.52740 (10)	0.28944 (17)	0.0467 (4)
O4	0.12931 (15)	0.53807 (9)	0.66805 (19)	0.0497 (4)
N7	0.1214 (2)	0.31119 (12)	0.9451 (2)	0.0567 (6)
N1	0.4690 (2)	0.4056 (2)	−0.1016 (3)	0.0854 (9)
N2	0.4467 (3)	0.4246 (2)	−0.2269 (4)	0.1045 (11)
N6	0.4782 (4)	0.8193 (3)	1.0817 (4)	0.1397 (18)
N3	0.4367 (4)	0.4395 (3)	−0.3436 (4)	0.155 (2)
N4	0.3389 (3)	0.84292 (18)	0.9011 (3)	0.0855 (9)
N5	0.4106 (3)	0.8267 (2)	0.9946 (3)	0.0987 (12)
C4	0.3881 (2)	0.42884 (18)	−0.0005 (3)	0.0584 (7)
C7	0.15287 (19)	0.48163 (13)	0.3208 (2)	0.0398 (5)
C15	0.0863 (2)	0.35912 (14)	0.8475 (3)	0.0484 (6)
H15A	0.0259	0.3892	0.8714	0.058*
C1	0.2378 (2)	0.46654 (13)	0.2094 (3)	0.0414 (5)
C8	0.17273 (19)	0.66528 (13)	0.6976 (2)	0.0409 (5)
C2	0.2172 (2)	0.48554 (14)	0.0677 (2)	0.0460 (6)
H2A	0.1524	0.5118	0.0430	0.055*
C6	0.3359 (2)	0.42912 (18)	0.2440 (3)	0.0595 (7)
H6A	0.3512	0.4159	0.3384	0.071*
C13	0.1512 (2)	0.73877 (15)	0.6624 (3)	0.0539 (6)
H13A	0.0985	0.7498	0.5907	0.065*
C3	0.2911 (2)	0.46609 (15)	−0.0371 (3)	0.0512 (6)
H3A	0.2753	0.4781	−0.1320	0.061*
C9	0.2511 (2)	0.65078 (16)	0.8053 (3)	0.0556 (7)
H9A	0.2661	0.6016	0.8308	0.067*
C14	0.11051 (19)	0.60338 (13)	0.6237 (2)	0.0397 (5)
C10	0.3073 (2)	0.70738 (18)	0.8752 (3)	0.0603 (7)
H10A	0.3596	0.6966	0.9475	0.072*
C12	0.2067 (3)	0.79604 (16)	0.7321 (3)	0.0635 (8)
H12B	0.1908	0.8453	0.7081	0.076*
C11	0.2856 (2)	0.78027 (17)	0.8373 (3)	0.0576 (7)
C17	0.0706 (3)	0.3082 (2)	1.0850 (3)	0.0822 (11)
H17A	0.0097	0.3432	1.0881	0.123*
H17B	0.1258	0.3207	1.1572	0.123*
H17C	0.0428	0.2588	1.1018	0.123*
C16	0.2150 (3)	0.26297 (19)	0.9201 (4)	0.0807 (10)
H16A	0.2407	0.2704	0.8248	0.121*
H16B	0.1923	0.2120	0.9315	0.121*
H16C	0.2746	0.2742	0.9873	0.121*
C5	0.4114 (2)	0.4111 (2)	0.1403 (3)	0.0717 (9)
H5A	0.4781	0.3871	0.1652	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04444 (19)	0.02783 (19)	0.03131 (18)	0.00240 (10)	−0.00460 (12)	0.00345 (10)
O1	0.0503 (10)	0.0503 (11)	0.0409 (9)	0.0099 (7)	0.0020 (7)	0.0104 (8)
O5	0.0606 (10)	0.0393 (10)	0.0408 (9)	0.0062 (8)	−0.0076 (7)	0.0085 (8)
O3	0.0538 (10)	0.0364 (10)	0.0474 (9)	−0.0021 (7)	−0.0126 (8)	0.0021 (8)
O2	0.0541 (10)	0.0447 (10)	0.0416 (9)	0.0133 (8)	0.0052 (7)	0.0058 (8)
O4	0.0648 (11)	0.0328 (10)	0.0507 (10)	−0.0040 (8)	−0.0167 (8)	0.0013 (8)
N7	0.0779 (15)	0.0430 (13)	0.0485 (12)	−0.0044 (11)	−0.0166 (11)	0.0141 (10)
N1	0.0804 (18)	0.112 (3)	0.0643 (18)	0.0276 (17)	0.0221 (14)	−0.0009 (17)
N2	0.088 (2)	0.157 (3)	0.069 (2)	0.035 (2)	0.0240 (17)	−0.016 (2)
N6	0.135 (3)	0.192 (5)	0.091 (3)	−0.087 (3)	−0.021 (2)	−0.024 (3)
N3	0.131 (3)	0.272 (7)	0.061 (2)	0.059 (3)	0.026 (2)	−0.009 (3)
N4	0.094 (2)	0.088 (2)	0.0738 (18)	−0.0434 (17)	0.0006 (16)	−0.0252 (16)
N5	0.105 (2)	0.124 (3)	0.0677 (19)	−0.068 (2)	0.0097 (18)	−0.0299 (19)
C4	0.0564 (16)	0.0638 (19)	0.0553 (16)	0.0072 (14)	0.0110 (13)	−0.0019 (14)
C7	0.0454 (13)	0.0319 (13)	0.0421 (13)	0.0001 (10)	−0.0022 (10)	−0.0011 (10)
C15	0.0594 (15)	0.0403 (15)	0.0450 (14)	−0.0014 (11)	−0.0108 (11)	0.0081 (11)
C1	0.0471 (13)	0.0353 (13)	0.0418 (13)	0.0009 (10)	0.0004 (10)	0.0003 (10)
C8	0.0455 (12)	0.0370 (13)	0.0403 (12)	−0.0018 (10)	0.0023 (10)	−0.0048 (10)
C2	0.0527 (14)	0.0416 (14)	0.0437 (13)	0.0080 (11)	−0.0016 (10)	0.0015 (11)
C6	0.0550 (16)	0.076 (2)	0.0476 (15)	0.0150 (14)	−0.0009 (12)	0.0108 (14)
C13	0.0583 (15)	0.0437 (16)	0.0593 (16)	0.0019 (12)	−0.0070 (12)	−0.0032 (13)
C3	0.0627 (16)	0.0511 (16)	0.0398 (14)	−0.0009 (13)	−0.0006 (11)	−0.0011 (12)
C9	0.0623 (16)	0.0483 (16)	0.0557 (16)	−0.0008 (13)	−0.0105 (12)	−0.0027 (13)
C14	0.0473 (13)	0.0348 (13)	0.0370 (12)	−0.0003 (10)	0.0025 (10)	−0.0008 (10)
C10	0.0559 (16)	0.073 (2)	0.0517 (16)	−0.0075 (14)	−0.0087 (12)	−0.0109 (15)
C12	0.0780 (19)	0.0398 (16)	0.0725 (19)	−0.0082 (14)	−0.0040 (15)	−0.0064 (14)
C11	0.0612 (16)	0.0577 (18)	0.0543 (16)	−0.0193 (14)	0.0113 (13)	−0.0180 (14)
C17	0.124 (3)	0.076 (2)	0.0466 (17)	−0.021 (2)	−0.0081 (17)	0.0223 (15)
C16	0.098 (2)	0.059 (2)	0.084 (2)	0.0146 (18)	−0.0344 (19)	0.0090 (18)
C5	0.0555 (17)	0.097 (3)	0.0628 (18)	0.0284 (16)	0.0050 (14)	0.0108 (18)

Geometric parameters (Å, º) top

Cu1—O1	1.9545 (17)	C1—C2	1.387 (3)
Cu1—O4	1.9711 (17)	C1—C6	1.382 (4)
Cu1—O2ⁱ	1.9747 (16)	C8—C13	1.382 (4)
Cu1—O3ⁱ	1.9765 (16)	C8—C9	1.384 (3)
Cu1—O5	2.1767 (16)	C8—C14	1.496 (3)
Cu1—Cu1ⁱ	2.6363 (5)	C2—C3	1.379 (3)
O1—C7	1.256 (3)	C2—H2A	0.9300
O5—C15	1.231 (3)	C6—C5	1.377 (4)
O3—C14	1.258 (3)	C6—H6A	0.9300
O3—Cu1ⁱ	1.9765 (16)	C13—C12	1.379 (4)
O2—C7	1.260 (3)	C13—H13A	0.9300
O2—Cu1ⁱ	1.9747 (16)	C3—H3A	0.9300
O4—C14	1.261 (3)	C9—C10	1.375 (4)
N7—C15	1.316 (3)	C9—H9A	0.9300
N7—C16	1.436 (4)	C10—C11	1.378 (4)
N7—C17	1.456 (4)	C10—H10A	0.9300
N1—N2	1.245 (4)	C12—C11	1.376 (4)
N1—C4	1.429 (3)	C12—H12B	0.9300
N2—N3	1.130 (5)	C17—H17A	0.9600
N6—N5	1.142 (5)	C17—H17B	0.9600
N4—N5	1.245 (5)	C17—H17C	0.9600
N4—C11	1.417 (4)	C16—H16A	0.9600
C4—C3	1.373 (4)	C16—H16B	0.9600
C4—C5	1.379 (4)	C16—H16C	0.9600
C7—C1	1.495 (3)	C5—H5A	0.9300
C15—H15A	0.9300

O1—Cu1—O4	89.73 (8)	C3—C2—C1	121.1 (2)
O1—Cu1—O2ⁱ	168.40 (7)	C3—C2—H2A	119.4
O4—Cu1—O2ⁱ	88.43 (8)	C1—C2—H2A	119.4
O1—Cu1—O3ⁱ	89.17 (7)	C5—C6—C1	120.8 (3)
O4—Cu1—O3ⁱ	168.48 (7)	C5—C6—H6A	119.6
O2ⁱ—Cu1—O3ⁱ	90.35 (7)	C1—C6—H6A	119.6
O1—Cu1—O5	97.62 (6)	C12—C13—C8	120.9 (3)
O4—Cu1—O5	96.40 (7)	C12—C13—H13A	119.6
O2ⁱ—Cu1—O5	93.97 (7)	C8—C13—H13A	119.6
O3ⁱ—Cu1—O5	95.12 (7)	C4—C3—C2	119.6 (2)
O1—Cu1—Cu1ⁱ	85.10 (5)	C4—C3—H3A	120.2
O4—Cu1—Cu1ⁱ	85.48 (5)	C2—C3—H3A	120.2
O2ⁱ—Cu1—Cu1ⁱ	83.34 (5)	C10—C9—C8	121.5 (3)
O3ⁱ—Cu1—Cu1ⁱ	83.00 (5)	C10—C9—H9A	119.2
O5—Cu1—Cu1ⁱ	176.69 (5)	C8—C9—H9A	119.2
C7—O1—Cu1	122.33 (15)	O3—C14—O4	125.6 (2)
C15—O5—Cu1	119.94 (16)	O3—C14—C8	117.4 (2)
C14—O3—Cu1ⁱ	124.34 (15)	O4—C14—C8	117.0 (2)
C7—O2—Cu1ⁱ	123.31 (15)	C9—C10—C11	119.4 (3)
C14—O4—Cu1	121.62 (15)	C9—C10—H10A	120.3
C15—N7—C16	121.1 (3)	C11—C10—H10A	120.3
C15—N7—C17	121.1 (3)	C11—C12—C13	120.0 (3)
C16—N7—C17	117.7 (3)	C11—C12—H12B	120.0
N2—N1—C4	114.4 (3)	C13—C12—H12B	120.0
N3—N2—N1	173.3 (4)	C12—C11—C10	120.1 (3)
N5—N4—C11	114.0 (3)	C12—C11—N4	115.6 (3)
N6—N5—N4	173.3 (4)	C10—C11—N4	124.3 (3)
C3—C4—C5	120.1 (2)	N7—C17—H17A	109.5
C3—C4—N1	123.6 (3)	N7—C17—H17B	109.5
C5—C4—N1	116.2 (3)	H17A—C17—H17B	109.5
O1—C7—O2	125.8 (2)	N7—C17—H17C	109.5
O1—C7—C1	117.0 (2)	H17A—C17—H17C	109.5
O2—C7—C1	117.1 (2)	H17B—C17—H17C	109.5
O5—C15—N7	126.9 (3)	N7—C16—H16A	109.5
O5—C15—H15A	116.5	N7—C16—H16B	109.5
N7—C15—H15A	116.5	H16A—C16—H16B	109.5
C2—C1—C6	118.4 (2)	N7—C16—H16C	109.5
C2—C1—C7	121.0 (2)	H16A—C16—H16C	109.5
C6—C1—C7	120.5 (2)	H16B—C16—H16C	109.5
C13—C8—C9	118.2 (2)	C4—C5—C6	120.0 (3)
C13—C8—C14	120.7 (2)	C4—C5—H5A	120.0
C9—C8—C14	121.1 (2)	C6—C5—H5A	120.0

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₇H₄N₃O₂)₄(C₃H₇NO)₂]
M_r	921.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.9209 (8), 17.9387 (10), 9.3680 (5)
β (°)	91.277 (5)
V (Å³)	2002.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury70 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2002)
T_min, T_max	0.805, 0.805
No. of measured, independent and observed [I > 2σ(I)] reflections	12312, 3496, 3141
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.091, 1.02
No. of reflections	3496
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: CrystalClear (Rigaku, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

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Tetra­kis(μ-4-azido­benzoato-κ2O:O′)bis­[(N,N-dimethyl­formamide-κO)copper(II)]

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Tetrakis(μ-4-azidobenzoato-κ²O:O′)bis[(N,N-dimethylformamide-κO)copper(II)]