First heterobimetallic Ag^I–Co^III coordination compound with both bridging and terminal –NO₂ coordination modes: synthesis, characterization, structural and computational studies of (PPh₃)₂Ag^I–(μ-κ²O,O′:κN-NO₂)–Co^III(DMGH)₂(κN-NO₂)

An unusual heterobimetallic bis­(tri­phenyl­phosphane)(NO₂)Ag^I–Co^III(di­methyl­glyoximate)(NO₂) coordination compound with both bridging and terminal –NO₂ (nitro) coordination modes has been isolated and characterized from the reaction of [CoCl(DMGH)₂(PPh₃)] (DMGH₂ is di­methyl­glyoxime or N,N′-di­­hydroxy­butane-2,3-di­imine) with excess AgNO₂. In the title compound, namely bis­(di­methyl­glyoximato-1κ²O,O′)(μ-nitro-1κN:2κ²O,O′)(nitro-1κN)bis­(tri­phenyl­phosphane-2κP)cobalt(III)silver(I), [AgCo(C₄H₇N₂O₂)₂(NO₂)₂(C₁₈H₁₅P)₂], one of the ambidentate –NO₂ ligands, in a bridging mode, chelates the Ag^I atom in an isobidentate κ²O,O′-manner and its N atom is coordinated to the Co^III atom. The other –NO₂ ligand is terminally κN-coordinated to the Co^III atom. The structure has been fully characterized by X-ray crystallography and spectroscopic methods. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been used to study the ground-state electronic structure and elucidate the origin of the electronic transitions, respectively.

Computing details

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Bis(dimethylglyoximato-1κ²O,O')(µ-nitro-1κN:2κ²O,O')(nitro-1κN)bis(triphenylphosphane-2κP)cobalt(III)silver(I

Crystal data

[AgCo(C4H7N2O2)2(NO2)2(C18H15P)2]	Dx = 1.545 Mg m^−3
Mr = 1013.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 3350 reflections
a = 17.9885 (5) Å	θ = 3.9–29.5°
b = 16.7765 (5) Å	µ = 0.96 mm^−1
c = 14.4364 (4) Å	T = 150 K
V = 4356.7 (2) Å^3	Needle, light-brown
Z = 4	0.35 × 0.10 × 0.08 mm
F(000) = 2072

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer	4272 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3277 reflections with I > 2σ(I)
Detector resolution: 10.3795 pixels mm^-1	Rint = 0.029
ω scan	θmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −20→22
Tmin = 0.914, Tmax = 1.000	k = −15→20
11476 measured reflections	l = −12→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 2.8869P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
4272 reflections	Δρmax = 0.45 e Å^−3
284 parameters	Δρmin = −0.44 e Å^−3

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
C18	0.17463 (14)	−0.13986 (14)	0.83883 (16)	0.0199 (5)
H18A	0.199193	−0.152039	0.783940	0.024*
C16	0.08044 (14)	−0.11074 (14)	0.61587 (16)	0.0195 (5)
H16A	0.035848	−0.110608	0.648466	0.023*
C6	0.27460 (13)	0.03899 (15)	0.77943 (16)	0.0189 (5)
H6A	0.280848	−0.012006	0.803461	0.023*
C12	0.20585 (14)	−0.06507 (14)	0.59682 (16)	0.0198 (5)
H12A	0.245946	−0.034354	0.616309	0.024*
C10	0.19524 (13)	0.14238 (14)	0.71844 (15)	0.0169 (5)
H10A	0.148174	0.160754	0.702484	0.020*
C9	0.25627 (14)	0.19229 (14)	0.70905 (17)	0.0204 (5)
H9A	0.250256	0.243434	0.685350	0.024*
C15	0.08731 (15)	−0.15744 (15)	0.53750 (17)	0.0243 (6)
H15A	0.047569	−0.188711	0.518067	0.029*
C13	0.21228 (15)	−0.11213 (15)	0.51798 (16)	0.0245 (6)
H13A	0.256850	−0.112771	0.485354	0.029*
C19	0.17818 (14)	−0.19223 (15)	0.91299 (17)	0.0233 (6)
H19A	0.205409	−0.239131	0.907749	0.028*
C22	0.09856 (14)	−0.05167 (14)	0.92936 (16)	0.0199 (5)
H22A	0.072035	−0.004356	0.935238	0.024*
C21	0.10219 (15)	−0.10414 (15)	1.00282 (16)	0.0229 (6)
H21A	0.078220	−0.091934	1.058106	0.027*
C11	0.13949 (13)	−0.06371 (13)	0.64683 (15)	0.0151 (5)
C8	0.32609 (14)	0.16587 (15)	0.73501 (16)	0.0216 (5)
H8A	0.367025	0.199241	0.728327	0.026*
C7	0.33532 (13)	0.08988 (15)	0.77092 (16)	0.0207 (5)
H7A	0.382228	0.072850	0.789393	0.025*
C17	0.13471 (12)	−0.06950 (13)	0.84597 (15)	0.0137 (5)
C20	0.14143 (15)	−0.17506 (15)	0.99469 (16)	0.0237 (6)
H20A	0.142993	−0.210786	1.043909	0.028*
C14	0.15355 (15)	−0.15786 (15)	0.48751 (17)	0.0240 (6)
H14A	0.158067	−0.188619	0.434211	0.029*
Co1	0.000000	0.34778 (2)	0.750000	0.01217 (11)
O4	0.12916 (9)	0.34598 (10)	0.63551 (12)	0.0226 (4)
O3	0.15207 (9)	0.35230 (10)	0.80376 (12)	0.0226 (4)
H3	0.145277	0.354729	0.741141	0.034*
N3	0.08150 (11)	0.35120 (11)	0.83323 (13)	0.0164 (4)
N4	0.05425 (11)	0.34878 (11)	0.63768 (13)	0.0175 (4)
C4	0.01555 (14)	0.35613 (14)	0.56268 (16)	0.0201 (5)
C3	0.04929 (17)	0.36449 (17)	0.46905 (17)	0.0327 (7)
H3A	0.102142	0.357522	0.473370	0.049*
H3B	0.038569	0.416568	0.444931	0.049*
H3C	0.028907	0.324789	0.428451	0.049*
C2	0.06497 (14)	0.35940 (14)	0.92011 (16)	0.0199 (5)
C1	0.12136 (16)	0.37434 (16)	0.99388 (17)	0.0303 (6)
H1A	0.169117	0.382876	0.965920	0.045*
H1B	0.123803	0.329045	1.034409	0.045*
H1C	0.107428	0.420698	1.028783	0.045*
N1	0.000000	0.46485 (17)	0.750000	0.0173 (6)
O1	0.00512 (10)	0.50137 (10)	0.67629 (12)	0.0272 (4)
Ag1	0.000000	0.05667 (2)	0.750000	0.01334 (8)
P1	0.12400 (3)	−0.00101 (3)	0.74891 (4)	0.01308 (13)
C5	0.20390 (13)	0.06500 (13)	0.75155 (14)	0.0143 (5)
N2	0.000000	0.23136 (16)	0.750000	0.0136 (6)
O2	−0.00540 (9)	0.19336 (9)	0.67646 (11)	0.0195 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C18	0.0204 (13)	0.0196 (13)	0.0196 (12)	0.0025 (10)	0.0016 (10)	−0.0002 (10)
C16	0.0167 (12)	0.0198 (12)	0.0221 (12)	0.0010 (10)	0.0018 (10)	−0.0007 (10)
C6	0.0181 (12)	0.0202 (13)	0.0183 (11)	0.0032 (10)	−0.0006 (10)	−0.0017 (10)
C12	0.0184 (13)	0.0233 (13)	0.0177 (12)	0.0005 (10)	−0.0006 (10)	−0.0009 (10)
C10	0.0160 (12)	0.0186 (12)	0.0160 (11)	0.0007 (10)	−0.0013 (10)	−0.0016 (10)
C9	0.0243 (14)	0.0161 (12)	0.0208 (12)	−0.0018 (10)	0.0012 (11)	−0.0005 (10)
C15	0.0255 (14)	0.0221 (14)	0.0254 (13)	−0.0009 (11)	−0.0027 (11)	−0.0048 (11)
C13	0.0225 (14)	0.0296 (14)	0.0213 (13)	0.0035 (11)	0.0052 (11)	−0.0026 (11)
C19	0.0289 (15)	0.0167 (13)	0.0242 (13)	0.0052 (11)	−0.0043 (11)	0.0018 (11)
C22	0.0237 (14)	0.0182 (13)	0.0179 (12)	0.0002 (10)	−0.0009 (10)	−0.0031 (10)
C21	0.0292 (15)	0.0257 (14)	0.0137 (11)	−0.0046 (12)	−0.0002 (10)	−0.0027 (11)
C11	0.0194 (12)	0.0129 (12)	0.0129 (11)	0.0031 (9)	−0.0014 (10)	0.0019 (9)
C8	0.0193 (13)	0.0228 (13)	0.0227 (13)	−0.0061 (10)	0.0021 (10)	−0.0077 (11)
C7	0.0119 (12)	0.0283 (14)	0.0220 (12)	0.0029 (10)	−0.0039 (10)	−0.0080 (11)
C17	0.0151 (12)	0.0118 (11)	0.0142 (11)	−0.0028 (9)	−0.0009 (9)	0.0006 (9)
C20	0.0342 (16)	0.0206 (13)	0.0163 (12)	−0.0059 (12)	−0.0077 (11)	0.0042 (11)
C14	0.0308 (15)	0.0229 (14)	0.0182 (12)	0.0081 (11)	−0.0014 (11)	−0.0059 (11)
Co1	0.0117 (2)	0.0114 (2)	0.0134 (2)	0.000	0.00000 (17)	0.000
O4	0.0137 (9)	0.0257 (10)	0.0284 (9)	0.0001 (7)	0.0067 (7)	0.0009 (8)
O3	0.0117 (9)	0.0292 (10)	0.0268 (9)	−0.0013 (7)	−0.0023 (7)	−0.0012 (8)
N3	0.0133 (10)	0.0140 (10)	0.0219 (11)	−0.0006 (8)	−0.0018 (8)	−0.0006 (8)
N4	0.0178 (10)	0.0136 (10)	0.0210 (10)	0.0008 (8)	0.0036 (9)	0.0018 (8)
C4	0.0296 (15)	0.0147 (12)	0.0160 (12)	0.0020 (10)	0.0012 (11)	0.0034 (10)
C3	0.0414 (17)	0.0365 (16)	0.0200 (13)	0.0081 (14)	0.0052 (12)	0.0080 (12)
C2	0.0275 (14)	0.0153 (12)	0.0171 (12)	−0.0002 (10)	−0.0035 (10)	0.0000 (10)
C1	0.0368 (17)	0.0313 (15)	0.0226 (13)	−0.0033 (13)	−0.0107 (12)	−0.0027 (12)
N1	0.0122 (14)	0.0185 (14)	0.0212 (15)	0.000	−0.0036 (12)	0.000
O1	0.0374 (11)	0.0179 (9)	0.0262 (9)	0.0020 (8)	−0.0003 (8)	0.0060 (8)
Ag1	0.01213 (13)	0.01171 (13)	0.01616 (13)	0.000	0.00087 (10)	0.000
P1	0.0130 (3)	0.0131 (3)	0.0132 (3)	0.0008 (2)	0.0003 (2)	0.0003 (2)
C5	0.0145 (12)	0.0166 (11)	0.0117 (10)	−0.0009 (9)	0.0009 (9)	−0.0041 (10)
N2	0.0086 (13)	0.0156 (13)	0.0165 (14)	0.000	0.0006 (11)	0.000
O2	0.0268 (10)	0.0152 (8)	0.0165 (8)	0.0008 (7)	−0.0022 (7)	−0.0038 (7)

Geometric parameters (Å, º)

C18—C17	1.385 (3)	C17—P1	1.822 (2)
C18—C19	1.386 (3)	C20—H20A	0.9300
C18—H18A	0.9300	C14—H14A	0.9300
C16—C15	1.382 (3)	Co1—N4^i	1.8927 (19)
C16—C11	1.397 (3)	Co1—N3^i	1.8965 (19)
C16—H16A	0.9300	Co1—N1	1.964 (3)
C6—C7	1.392 (3)	Co1—N2	1.953 (3)
C6—C5	1.404 (3)	Co1—N3	1.8965 (19)
C6—H6A	0.9300	Co1—N4	1.8927 (19)
C12—C13	1.390 (3)	O4—N4	1.349 (2)
C12—C11	1.395 (3)	O3—N3	1.339 (2)
C12—H12A	0.9300	O3—H3	0.9132
C10—C9	1.387 (3)	N3—C2	1.296 (3)
C10—C5	1.392 (3)	N4—C4	1.293 (3)
C10—H10A	0.9300	C4—C2^i	1.471 (3)
C9—C8	1.384 (3)	C4—C3	1.488 (3)
C9—H9A	0.9300	C3—H3A	0.9600
C15—C14	1.393 (4)	C3—H3B	0.9600
C15—H15A	0.9300	C3—H3C	0.9600
C13—C14	1.378 (4)	C2—C1	1.492 (3)
C13—H13A	0.9300	C1—H1A	0.9600
C19—C20	1.382 (4)	C1—H1B	0.9600
C19—H19A	0.9300	C1—H1C	0.9600
C22—C21	1.380 (3)	N1—O1	1.231 (2)
C22—C17	1.401 (3)	N1—O1^i	1.231 (2)
C22—H22A	0.9300	Ag1—P1	2.4315 (6)
C21—C20	1.388 (4)	Ag1—P1^i	2.4315 (6)
C21—H21A	0.9300	Ag1—O2^i	2.5288 (16)
C11—P1	1.832 (2)	Ag1—O2	2.5288 (16)
C8—C7	1.386 (4)	P1—C5	1.815 (2)
C8—H8A	0.9300	N2—O2^i	1.242 (2)
C7—H7A	0.9300	N2—O2	1.242 (2)
C17—C18—C19	120.4 (2)	N4—Co1—N2	90.51 (6)
C17—C18—H18A	119.8	N4^i—Co1—N2	90.51 (6)
C19—C18—H18A	119.8	N3—Co1—N2	91.73 (6)
C15—C16—C11	121.0 (2)	N3^i—Co1—N2	91.74 (6)
C15—C16—H16A	119.5	N4—Co1—N1	89.49 (6)
C11—C16—H16A	119.5	N4^i—Co1—N1	89.49 (6)
C7—C6—C5	119.7 (2)	N3—Co1—N1	88.27 (6)
C7—C6—H6A	120.2	N3^i—Co1—N1	88.26 (6)
C5—C6—H6A	120.2	N2—Co1—N1	180.0
C13—C12—C11	120.3 (2)	N3—O3—H3	100.9
C13—C12—H12A	119.9	C2—N3—O3	121.57 (19)
C11—C12—H12A	119.9	C2—N3—Co1	116.03 (16)
C9—C10—C5	120.5 (2)	O3—N3—Co1	122.14 (14)
C9—C10—H10A	119.7	C4—N4—O4	121.5 (2)
C5—C10—H10A	119.7	C4—N4—Co1	116.14 (17)
C8—C9—C10	119.9 (2)	O4—N4—Co1	122.33 (15)
C8—C9—H9A	120.1	N4—C4—C2^i	113.1 (2)
C10—C9—H9A	120.1	N4—C4—C3	123.4 (2)
C16—C15—C14	120.2 (2)	C2^i—C4—C3	123.5 (2)
C16—C15—H15A	119.9	C4—C3—H3A	109.5
C14—C15—H15A	119.9	C4—C3—H3B	109.5
C14—C13—C12	120.9 (2)	H3A—C3—H3B	109.5
C14—C13—H13A	119.5	C4—C3—H3C	109.5
C12—C13—H13A	119.5	H3A—C3—H3C	109.5
C20—C19—C18	120.3 (2)	H3B—C3—H3C	109.5
C20—C19—H19A	119.8	N3—C2—C4^i	112.7 (2)
C18—C19—H19A	119.8	N3—C2—C1	123.5 (2)
C21—C22—C17	120.2 (2)	C4^i—C2—C1	123.7 (2)
C21—C22—H22A	119.9	C2—C1—H1A	109.5
C17—C22—H22A	119.9	C2—C1—H1B	109.5
C22—C21—C20	120.4 (2)	H1A—C1—H1B	109.5
C22—C21—H21A	119.8	C2—C1—H1C	109.5
C20—C21—H21A	119.8	H1A—C1—H1C	109.5
C12—C11—C16	118.4 (2)	H1B—C1—H1C	109.5
C12—C11—P1	123.77 (18)	O1—N1—O1^i	120.3 (3)
C16—C11—P1	117.78 (17)	O1—N1—Co1	119.85 (14)
C9—C8—C7	120.3 (2)	O1^i—N1—Co1	119.85 (14)
C9—C8—H8A	119.8	P1—Ag1—P1^i	133.10 (3)
C7—C8—H8A	119.8	P1—Ag1—O2^i	109.17 (4)
C8—C7—C6	120.2 (2)	P1^i—Ag1—O2^i	113.16 (4)
C8—C7—H7A	119.9	P1—Ag1—O2	113.17 (4)
C6—C7—H7A	119.9	P1^i—Ag1—O2	109.17 (4)
C18—C17—C22	119.1 (2)	O2^i—Ag1—O2	49.86 (7)
C18—C17—P1	122.33 (17)	C5—P1—C17	106.55 (10)
C22—C17—P1	118.50 (17)	C5—P1—C11	104.29 (10)
C19—C20—C21	119.6 (2)	C17—P1—C11	103.91 (10)
C19—C20—H20A	120.2	C5—P1—Ag1	118.92 (8)
C21—C20—H20A	120.2	C17—P1—Ag1	110.06 (8)
C13—C14—C15	119.2 (2)	C11—P1—Ag1	111.92 (8)
C13—C14—H14A	120.4	C10—C5—C6	119.3 (2)
C15—C14—H14A	120.4	C10—C5—P1	118.24 (17)
N4—Co1—N4^i	178.99 (12)	C6—C5—P1	122.27 (18)
N4^i—Co1—N3	81.69 (8)	O2^i—N2—O2	118.2 (3)
N4—Co1—N3	98.27 (8)	O2^i—N2—Co1	120.88 (13)
N4—Co1—N3^i	81.70 (8)	O2—N2—Co1	120.88 (13)
N4^i—Co1—N3^i	98.27 (8)	N2—O2—Ag1	95.95 (14)
N3—Co1—N3^i	176.53 (11)
C5—C10—C9—C8	−1.7 (3)	N2—Co1—N4—O4	−87.32 (16)
C11—C16—C15—C14	−0.5 (4)	N1—Co1—N4—O4	92.68 (16)
C11—C12—C13—C14	0.3 (4)	O4—N4—C4—C2^i	−179.0 (2)
C17—C18—C19—C20	0.5 (4)	Co1—N4—C4—C2^i	−2.1 (3)
C17—C22—C21—C20	−0.2 (4)	O4—N4—C4—C3	−1.9 (4)
C13—C12—C11—C16	0.2 (3)	Co1—N4—C4—C3	175.0 (2)
C13—C12—C11—P1	−177.58 (18)	O3—N3—C2—C4^i	−179.80 (19)
C15—C16—C11—C12	−0.1 (3)	Co1—N3—C2—C4^i	5.9 (3)
C15—C16—C11—P1	177.80 (19)	O3—N3—C2—C1	2.9 (3)
C10—C9—C8—C7	−0.4 (4)	Co1—N3—C2—C1	−171.38 (19)
C9—C8—C7—C6	1.3 (3)	C18—C17—P1—C5	−87.1 (2)
C5—C6—C7—C8	−0.1 (3)	C22—C17—P1—C5	95.68 (19)
C19—C18—C17—C22	0.6 (4)	C18—C17—P1—C11	22.7 (2)
C19—C18—C17—P1	−176.67 (19)	C22—C17—P1—C11	−154.51 (18)
C21—C22—C17—C18	−0.7 (3)	C18—C17—P1—Ag1	142.72 (18)
C21—C22—C17—P1	176.64 (18)	C22—C17—P1—Ag1	−34.5 (2)
C18—C19—C20—C21	−1.4 (4)	C12—C11—P1—C5	9.8 (2)
C22—C21—C20—C19	1.2 (4)	C16—C11—P1—C5	−168.03 (17)
C12—C13—C14—C15	−0.9 (4)	C12—C11—P1—C17	−101.7 (2)
C16—C15—C14—C13	1.0 (4)	C16—C11—P1—C17	80.50 (19)
N4—Co1—N3—C2	173.30 (17)	C12—C11—P1—Ag1	139.59 (18)
N4^i—Co1—N3—C2	−5.67 (17)	C16—C11—P1—Ag1	−38.22 (19)
N2—Co1—N3—C2	−95.93 (16)	C9—C10—C5—C6	2.9 (3)
N1—Co1—N3—C2	84.07 (16)	C9—C10—C5—P1	−172.63 (18)
N4—Co1—N3—O3	−0.93 (18)	C7—C6—C5—C10	−2.0 (3)
N4^i—Co1—N3—O3	−179.90 (18)	C7—C6—C5—P1	173.33 (17)
N2—Co1—N3—O3	89.84 (16)	C17—P1—C5—C10	−149.69 (17)
N1—Co1—N3—O3	−90.16 (16)	C11—P1—C5—C10	100.77 (18)
N3—Co1—N4—C4	−172.33 (17)	Ag1—P1—C5—C10	−24.7 (2)
N3^i—Co1—N4—C4	4.17 (17)	C17—P1—C5—C6	34.9 (2)
N2—Co1—N4—C4	95.84 (17)	C11—P1—C5—C6	−74.6 (2)
N1—Co1—N4—C4	−84.16 (17)	Ag1—P1—C5—C6	159.89 (16)
N3—Co1—N4—O4	4.51 (18)	O2^i—N2—O2—Ag1	−0.002 (1)
N3^i—Co1—N4—O4	−178.99 (18)	Co1—N2—O2—Ag1	180.000 (1)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4	0.91	1.56	2.466 (2)	171
O3—H3···N4	0.91	2.22	2.975 (3)	140
C3—H3B···O1^ii	0.96	2.36	3.229 (3)	150
C6—H6A···O3^iii	0.93	2.58	3.417 (3)	150
C7—H7A···O1^iv	0.93	2.56	3.481 (3)	169

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