Crystal structure, Hirshfeld surface analysis and DFT studies of tetra­kis­(μ-3-nitro­benzoato-κ²O¹:O^1′)bis­[(N,N-di­methyl­formamide-κO)copper(II)] di­methyl­formamide disolvate

The title compound, [Cu₂(C₇H₄NO₄)₄(C₃H₇NO)₂]·(C₃H₇NO)₂, is a binuclear copper(II) complex located on an inversion center midway between the two copper(II) cations. The asymmetric unit consists of one Cu^II cation, two 3-nitro­benzoato ligands, and two di­methyl­formamide (DMF) mol­ecules, one of which coordinates to the Cu^II cation and one is a solvate mol­ecule. The carboxyl­ate groups of the ligands bridge two Cu^II cations, completing a distorted octa­hedral O₅Cu coordination environment.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.043
• wR factor = 0.120
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         N1 Check
PLAT244_ALERT_4_C Low    'Solvent' Ueq as Compared to Neighbors of         N4 Check
PLAT260_ALERT_2_C Large Average Ueq of Residue Including       O10      0.113 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.344 Check
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1       (II)      .       2.11 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         65 Note

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

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

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Computing details

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Tetrakis(µ-3-nitrobenzoato-κ²O¹:O^1')bis[(N,N-dimethylformamide-κO)copper(II)] dimethylformamide disolvate

Crystal data

[Cu2(C7H4NO4)4(C3H7NO)2]·2C3H7NO	F(000) = 1116
Mr = 1083.91	Dx = 1.505 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 11.5657 (4) Å	Cell parameters from 5941 reflections
b = 10.4851 (3) Å	θ = 4.2–75.5°
c = 19.7258 (5) Å	µ = 1.84 mm^−1
β = 91.581 (3)°	T = 293 K
V = 2391.19 (12) Å^3	Plate, blue
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection

Xcalibur, Ruby diffractometer	4940 independent reflections
Radiation source: Enhance (Cu) X-ray Source	4016 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 10.2576 pixels mm^-1	θmax = 76.2°, θmin = 3.8°
wσcans	h = −14→14
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	k = −13→12
Tmin = 0.366, Tmax = 1.000	l = −24→16
17186 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0582P)^2 + 0.9153P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4940 reflections	Δρmax = 0.38 e Å^−3
320 parameters	Δρmin = −0.65 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Cu1	0.52536 (3)	0.37834 (3)	0.48912 (2)	0.03259 (12)
O1	0.67889 (15)	0.43281 (17)	0.52255 (9)	0.0438 (4)
O2	0.63778 (15)	0.63846 (16)	0.54126 (9)	0.0442 (4)
O3	0.48321 (16)	0.35248 (16)	0.58396 (8)	0.0447 (4)
O4	0.43655 (16)	0.55704 (16)	0.60163 (8)	0.0438 (4)
O5	0.57752 (17)	0.18687 (16)	0.46685 (9)	0.0474 (4)
O6	0.2420 (2)	0.6543 (3)	0.81319 (13)	0.0853 (8)
O7	0.2426 (3)	0.5167 (3)	0.89371 (12)	0.0977 (10)
O8	1.1930 (2)	0.3843 (3)	0.60860 (15)	0.0927 (9)
O9	1.0475 (2)	0.2614 (3)	0.59089 (17)	0.1004 (10)
N1	0.7192 (2)	0.0413 (2)	0.45278 (11)	0.0533 (6)
N2	0.2717 (2)	0.5527 (3)	0.83778 (12)	0.0612 (7)
N3	1.0906 (2)	0.3660 (3)	0.59792 (14)	0.0659 (8)
C1	0.4512 (2)	0.4433 (2)	0.62026 (11)	0.0376 (5)
C2	0.4313 (2)	0.4157 (2)	0.69403 (11)	0.0376 (5)
C3	0.4849 (3)	0.3128 (3)	0.72534 (13)	0.0509 (7)
H3	0.5305	0.2581	0.7004	0.061*
C4	0.4709 (3)	0.2912 (3)	0.79400 (15)	0.0614 (8)
H4	0.5092	0.2233	0.8150	0.074*
C5	0.4012 (3)	0.3685 (3)	0.83118 (13)	0.0543 (7)
H5	0.3909	0.3534	0.8771	0.065*
C6	0.3469 (2)	0.4689 (3)	0.79880 (12)	0.0445 (6)
C7	0.3616 (2)	0.4953 (2)	0.73090 (12)	0.0411 (6)
H7	0.3253	0.5651	0.7105	0.049*
C8	0.7049 (2)	0.5442 (2)	0.54082 (11)	0.0373 (5)
C9	0.8275 (2)	0.5637 (2)	0.56579 (12)	0.0398 (5)
C10	0.8687 (3)	0.6832 (3)	0.58268 (15)	0.0547 (7)
H10	0.8197	0.7534	0.5794	0.066*
C11	0.9830 (3)	0.6997 (3)	0.60457 (18)	0.0701 (9)
H11	1.0098	0.7807	0.6161	0.084*
C12	1.0562 (3)	0.5977 (3)	0.60927 (17)	0.0654 (9)
H12	1.1332	0.6084	0.6231	0.078*
C13	1.0132 (2)	0.4784 (3)	0.59303 (14)	0.0504 (7)
C14	0.9006 (2)	0.4592 (3)	0.57205 (12)	0.0449 (6)
H14	0.8736	0.3776	0.5622	0.054*
C15	0.6799 (3)	0.1556 (3)	0.46790 (13)	0.0482 (6)
H15	0.7341	0.2174	0.4803	0.058*
C16	0.6410 (4)	−0.0611 (3)	0.4369 (2)	0.0850 (12)
H16A	0.6331	−0.1143	0.4761	0.128*
H16B	0.6707	−0.1107	0.4004	0.128*
H16C	0.5668	−0.0268	0.4236	0.128*
C17	0.8432 (3)	0.0129 (4)	0.4595 (2)	0.0837 (12)
H17A	0.8833	0.0858	0.4779	0.126*
H17B	0.8726	−0.0069	0.4157	0.126*
H17C	0.8548	−0.0587	0.4892	0.126*
O10	1.0396 (3)	0.4379 (4)	0.7733 (2)	0.1376 (14)
N4	0.8658 (3)	0.5366 (3)	0.76200 (16)	0.0773 (8)
C18	0.9808 (5)	0.5333 (5)	0.7716 (2)	0.0941 (13)
H18	1.0188	0.6109	0.7774	0.113*
C19	0.8031 (6)	0.4220 (6)	0.7556 (3)	0.145 (2)
H19A	0.8554	0.3532	0.7469	0.217*
H19B	0.7477	0.4292	0.7187	0.217*
H19C	0.7636	0.4056	0.7968	0.217*
C20	0.8067 (5)	0.6575 (5)	0.7589 (2)	0.1113 (16)
H20A	0.7587	0.6661	0.7976	0.167*
H20B	0.7594	0.6616	0.7182	0.167*
H20C	0.8624	0.7253	0.7589	0.167*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0397 (2)	0.02672 (19)	0.03118 (18)	0.00108 (14)	−0.00230 (14)	−0.00110 (12)
O1	0.0408 (10)	0.0382 (9)	0.0517 (10)	0.0001 (8)	−0.0074 (8)	−0.0067 (8)
O2	0.0428 (10)	0.0384 (10)	0.0511 (10)	0.0009 (8)	−0.0070 (8)	−0.0056 (8)
O3	0.0604 (12)	0.0393 (10)	0.0346 (8)	0.0024 (8)	0.0043 (8)	0.0023 (7)
O4	0.0626 (12)	0.0360 (9)	0.0328 (8)	−0.0022 (8)	0.0026 (8)	0.0038 (7)
O5	0.0572 (12)	0.0315 (9)	0.0533 (10)	0.0070 (8)	0.0008 (9)	−0.0047 (8)
O6	0.108 (2)	0.0639 (15)	0.0859 (17)	0.0257 (15)	0.0341 (15)	0.0078 (13)
O7	0.125 (2)	0.122 (2)	0.0477 (13)	0.0305 (19)	0.0330 (14)	0.0112 (14)
O8	0.0399 (13)	0.133 (3)	0.105 (2)	0.0118 (14)	−0.0095 (13)	0.0151 (17)
O9	0.0694 (17)	0.0748 (18)	0.156 (3)	0.0204 (15)	−0.0189 (17)	−0.0202 (19)
N1	0.0728 (17)	0.0353 (12)	0.0528 (13)	0.0130 (11)	0.0181 (12)	0.0010 (10)
N2	0.0669 (17)	0.0692 (18)	0.0480 (13)	0.0005 (14)	0.0093 (12)	−0.0031 (13)
N3	0.0449 (16)	0.089 (2)	0.0635 (16)	0.0140 (15)	−0.0027 (12)	0.0034 (15)
C1	0.0405 (13)	0.0390 (13)	0.0330 (11)	−0.0051 (11)	−0.0030 (9)	0.0045 (10)
C2	0.0425 (14)	0.0361 (12)	0.0339 (11)	−0.0029 (11)	−0.0014 (10)	0.0042 (9)
C3	0.0568 (17)	0.0503 (16)	0.0456 (14)	0.0095 (14)	0.0034 (12)	0.0074 (12)
C4	0.074 (2)	0.062 (2)	0.0476 (15)	0.0153 (17)	−0.0003 (14)	0.0188 (14)
C5	0.0636 (19)	0.0632 (19)	0.0359 (13)	0.0016 (15)	0.0001 (12)	0.0138 (12)
C6	0.0498 (15)	0.0479 (15)	0.0361 (12)	−0.0027 (12)	0.0035 (11)	0.0015 (11)
C7	0.0435 (14)	0.0391 (14)	0.0404 (12)	−0.0016 (11)	−0.0025 (10)	0.0076 (10)
C8	0.0409 (13)	0.0399 (13)	0.0310 (11)	−0.0013 (11)	−0.0013 (9)	0.0010 (9)
C9	0.0402 (14)	0.0434 (14)	0.0357 (11)	−0.0029 (11)	−0.0014 (10)	−0.0003 (10)
C10	0.0547 (17)	0.0478 (16)	0.0610 (17)	−0.0100 (14)	−0.0097 (14)	0.0025 (13)
C11	0.065 (2)	0.059 (2)	0.085 (2)	−0.0241 (17)	−0.0192 (18)	0.0027 (17)
C12	0.0466 (18)	0.081 (2)	0.0672 (19)	−0.0181 (17)	−0.0165 (15)	0.0062 (17)
C13	0.0398 (14)	0.0673 (19)	0.0438 (13)	0.0021 (14)	−0.0017 (11)	0.0014 (13)
C14	0.0411 (14)	0.0527 (16)	0.0409 (13)	−0.0042 (12)	−0.0018 (11)	−0.0046 (11)
C15	0.0596 (18)	0.0360 (14)	0.0494 (14)	0.0068 (13)	0.0075 (13)	−0.0021 (11)
C16	0.110 (3)	0.0401 (18)	0.107 (3)	0.0039 (19)	0.027 (2)	−0.0158 (19)
C17	0.085 (3)	0.072 (2)	0.096 (3)	0.034 (2)	0.034 (2)	0.008 (2)
O10	0.140 (3)	0.109 (3)	0.163 (4)	0.049 (3)	−0.008 (3)	0.016 (3)
N4	0.086 (2)	0.072 (2)	0.0730 (19)	−0.0017 (18)	0.0054 (16)	0.0005 (16)
C18	0.107 (4)	0.085 (3)	0.090 (3)	0.008 (3)	0.004 (3)	0.006 (2)
C19	0.179 (6)	0.133 (5)	0.122 (4)	−0.071 (5)	0.000 (4)	−0.009 (4)
C20	0.117 (4)	0.120 (4)	0.097 (3)	0.040 (3)	0.014 (3)	0.009 (3)

Geometric parameters (Å, º)

Cu1—O1	1.9620 (17)	C6—C7	1.383 (3)
Cu1—O3	1.9650 (16)	C7—H7	0.9300
Cu1—O2^i	1.9719 (18)	C8—C9	1.502 (3)
Cu1—O4^i	1.9751 (16)	C9—C10	1.378 (4)
Cu1—O5	2.1453 (17)	C9—C14	1.387 (4)
Cu1—Cu1^i	2.6554 (6)	C10—C11	1.390 (4)
O1—C8	1.257 (3)	C10—H10	0.9300
O2—C8	1.257 (3)	C11—C12	1.365 (5)
O2—Cu1^i	1.9718 (18)	C11—H11	0.9300
O3—C1	1.254 (3)	C12—C13	1.381 (4)
O4—C1	1.258 (3)	C12—H12	0.9300
O4—Cu1^i	1.9751 (16)	C13—C14	1.371 (4)
O5—C15	1.229 (3)	C14—H14	0.9300
O6—N2	1.216 (3)	C15—H15	0.9300
O7—N2	1.222 (3)	C16—H16A	0.9600
O8—N3	1.213 (3)	C16—H16B	0.9600
O9—N3	1.211 (4)	C16—H16C	0.9600
N1—C15	1.318 (3)	C17—H17A	0.9600
N1—C16	1.432 (4)	C17—H17B	0.9600
N1—C17	1.467 (4)	C17—H17C	0.9600
N2—C6	1.469 (4)	O10—C18	1.209 (5)
N3—C13	1.481 (4)	N4—C18	1.339 (6)
C1—C2	1.508 (3)	N4—C19	1.407 (6)
C2—C3	1.381 (4)	N4—C20	1.441 (5)
C2—C7	1.381 (3)	C18—H18	0.9300
C3—C4	1.387 (4)	C19—H19A	0.9600
C3—H3	0.9300	C19—H19B	0.9600
C4—C5	1.370 (4)	C19—H19C	0.9600
C4—H4	0.9300	C20—H20A	0.9600
C5—C6	1.374 (4)	C20—H20B	0.9600
C5—H5	0.9300	C20—H20C	0.9600
O1—Cu1—O3	88.06 (8)	O1—C8—C9	115.9 (2)
O1—Cu1—O2^i	167.89 (7)	C10—C9—C14	119.4 (2)
O3—Cu1—O2^i	90.95 (8)	C10—C9—C8	121.3 (2)
O1—Cu1—O4^i	88.98 (8)	C14—C9—C8	119.3 (2)
O3—Cu1—O4^i	167.85 (7)	C9—C10—C11	120.5 (3)
O2^i—Cu1—O4^i	89.47 (8)	C9—C10—H10	119.7
O1—Cu1—O5	94.83 (7)	C11—C10—H10	119.7
O3—Cu1—O5	98.30 (7)	C12—C11—C10	120.4 (3)
O2^i—Cu1—O5	97.26 (7)	C12—C11—H11	119.8
O4^i—Cu1—O5	93.69 (7)	C10—C11—H11	119.8
O1—Cu1—Cu1^i	82.41 (5)	C11—C12—C13	118.4 (3)
O3—Cu1—Cu1^i	85.24 (5)	C11—C12—H12	120.8
O2^i—Cu1—Cu1^i	85.48 (5)	C13—C12—H12	120.8
O4^i—Cu1—Cu1^i	82.68 (5)	C14—C13—C12	122.4 (3)
O5—Cu1—Cu1^i	175.46 (6)	C14—C13—N3	118.0 (3)
C8—O1—Cu1	125.04 (17)	C12—C13—N3	119.5 (3)
C8—O2—Cu1^i	120.92 (16)	C13—C14—C9	118.9 (3)
C1—O3—Cu1	121.59 (15)	C13—C14—H14	120.6
C1—O4—Cu1^i	123.95 (16)	C9—C14—H14	120.6
C15—O5—Cu1	121.53 (18)	O5—C15—N1	125.2 (3)
C15—N1—C16	120.8 (3)	O5—C15—H15	117.4
C15—N1—C17	120.4 (3)	N1—C15—H15	117.4
C16—N1—C17	118.5 (3)	N1—C16—H16A	109.5
O6—N2—O7	123.3 (3)	N1—C16—H16B	109.5
O6—N2—C6	118.7 (2)	H16A—C16—H16B	109.5
O7—N2—C6	118.0 (3)	N1—C16—H16C	109.5
O9—N3—O8	124.1 (3)	H16A—C16—H16C	109.5
O9—N3—C13	117.9 (3)	H16B—C16—H16C	109.5
O8—N3—C13	118.1 (3)	N1—C17—H17A	109.5
O3—C1—O4	126.4 (2)	N1—C17—H17B	109.5
O3—C1—C2	117.4 (2)	H17A—C17—H17B	109.5
O4—C1—C2	116.2 (2)	N1—C17—H17C	109.5
C3—C2—C7	119.8 (2)	H17A—C17—H17C	109.5
C3—C2—C1	120.2 (2)	H17B—C17—H17C	109.5
C7—C2—C1	119.9 (2)	C18—N4—C19	119.9 (4)
C2—C3—C4	120.1 (3)	C18—N4—C20	119.8 (4)
C2—C3—H3	120.0	C19—N4—C20	120.3 (4)
C4—C3—H3	120.0	O10—C18—N4	125.5 (5)
C5—C4—C3	120.8 (3)	O10—C18—H18	117.3
C5—C4—H4	119.6	N4—C18—H18	117.3
C3—C4—H4	119.6	N4—C19—H19A	109.5
C4—C5—C6	118.2 (2)	N4—C19—H19B	109.5
C4—C5—H5	120.9	H19A—C19—H19B	109.5
C6—C5—H5	120.9	N4—C19—H19C	109.5
C5—C6—C7	122.5 (3)	H19A—C19—H19C	109.5
C5—C6—N2	119.0 (2)	H19B—C19—H19C	109.5
C7—C6—N2	118.5 (2)	N4—C20—H20A	109.5
C2—C7—C6	118.6 (2)	N4—C20—H20B	109.5
C2—C7—H7	120.7	H20A—C20—H20B	109.5
C6—C7—H7	120.7	N4—C20—H20C	109.5
O2—C8—O1	126.1 (2)	H20A—C20—H20C	109.5
O2—C8—C9	118.0 (2)	H20B—C20—H20C	109.5
Cu1—O3—C1—O4	3.6 (4)	Cu1—O1—C8—C9	179.02 (15)
Cu1—O3—C1—C2	−174.57 (15)	O2—C8—C9—C10	−6.0 (4)
Cu1^i—O4—C1—O3	−5.6 (4)	O1—C8—C9—C10	175.3 (2)
Cu1^i—O4—C1—C2	172.56 (15)	O2—C8—C9—C14	173.9 (2)
O3—C1—C2—C3	23.2 (4)	O1—C8—C9—C14	−4.8 (3)
O4—C1—C2—C3	−155.2 (3)	C14—C9—C10—C11	1.2 (4)
O3—C1—C2—C7	−158.5 (2)	C8—C9—C10—C11	−178.9 (3)
O4—C1—C2—C7	23.1 (3)	C9—C10—C11—C12	0.4 (5)
C7—C2—C3—C4	−1.4 (4)	C10—C11—C12—C13	−1.2 (5)
C1—C2—C3—C4	176.9 (3)	C11—C12—C13—C14	0.5 (5)
C2—C3—C4—C5	2.0 (5)	C11—C12—C13—N3	−179.8 (3)
C3—C4—C5—C6	−0.8 (5)	O9—N3—C13—C14	−8.5 (4)
C4—C5—C6—C7	−1.0 (4)	O8—N3—C13—C14	171.4 (3)
C4—C5—C6—N2	179.9 (3)	O9—N3—C13—C12	171.8 (3)
O6—N2—C6—C5	165.9 (3)	O8—N3—C13—C12	−8.4 (4)
O7—N2—C6—C5	−13.7 (4)	C12—C13—C14—C9	1.1 (4)
O6—N2—C6—C7	−13.2 (4)	N3—C13—C14—C9	−178.7 (2)
O7—N2—C6—C7	167.2 (3)	C10—C9—C14—C13	−1.9 (4)
C3—C2—C7—C6	−0.4 (4)	C8—C9—C14—C13	178.2 (2)
C1—C2—C7—C6	−178.7 (2)	Cu1—O5—C15—N1	−177.7 (2)
C5—C6—C7—C2	1.6 (4)	C16—N1—C15—O5	−3.6 (4)
N2—C6—C7—C2	−179.3 (2)	C17—N1—C15—O5	−176.6 (3)
Cu1^i—O2—C8—O1	−0.5 (3)	C19—N4—C18—O10	2.5 (7)
Cu1^i—O2—C8—C9	−178.98 (15)	C20—N4—C18—O10	−178.0 (4)
Cu1—O1—C8—O2	0.5 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4^ii	0.93	2.47	3.360 (4)	161
C15—H15···O1	0.93	2.50	3.100 (4)	123
C16—H16C···O5	0.96	2.40	2.770 (4)	102
C19—H19A···O10	0.96	2.35	2.753 (8)	104
C20—H20C···O10^iii	0.96	2.59	3.503 (7)	160

Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2.