(2,2′-Bipyridyl-κ²N,N′)(succinamidato-κN)silver(I)

In the mol­ecular title complex, [Ag(C₄H₄NO₂)(C₁₀H₈N₂)], the Ag atom adopts a distorted T-shaped AgN₃ coordination. Aromatic π–π stacking inter­actions [centroid–centroid separation = 3.8393 (17) Å] lead to centrosymmetric dimers of mol­ecules in the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.084
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.91
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ag1    -   N3      ..       5.26 su

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.909
            Tmax scaled      0.791 Tmin scaled      0.641
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ag1         (9)       0.86

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

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

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S1. Comment

Most homoleptic silver coordination complexes form polymeric structures, many of which exhibit poor solubility, such as silver carboxylates (Tolochko et al., 1998; Whitcomb and Rajeswaran, 2006a; Jaber et al., 1996), silver cyclic amidates (Whitcomb and Rajeswaran 2006b; Whitcomb and Rajeswaran, 2006c), and silver thiolates (Fijolek et al., 1997; Voicu et al., 2001). The connecting groups of these polymeric structures can be disrupted by incorporating argentophilic neutral-donor ligands into the complex, especially triarylphosphines (Oldham and Sandford, 1977; Othman et al., 2003; Whitcomb and Rajeswaran, 2006b). In our investigations to manipulate the solid-state structure of silver complexes, we now consider the effect of weaker argentophilic N donor atoms in the ligand 2,2'-dipyridyl (dipy, C₁₀H₈N₂). We report here the crystal structure of the title silver complex, (I).

The new structure is a simple molecular complex of both ligands, having the composition AgSI-dipy (SI = succinimide anion, C₄H₄NO₂^-), which are additionally held together by π-π stacking interactions between dipy rings with centroid separations of 3.8393 (17) Å. The molecular structure of (I) is shown in Fig. 1, and the packing diagram of the π-π -bonded dimers is given in Fig 2. In order to achieve this structure, the dipy ligand both depolymerized and dehydrated the starting {[AgSI]₂.H₂O} complex.

The structures of three complexes of silver cyclic amides can now be compared: the title complex, the starting {[AgSI]₂.H₂O} complex (Whitcomb and Rajeswaran, 2006c), and the related bis-triphenylphosphine silver phthalimide (Whitcomb and Rajeswaran, 2006b). The starting {[AgSI]₂.H₂O} complex exhibits the shortest Ag—N bond lengths at 2.077 (3) and 2.095 (3) Å, while the phthalimide complex has a single Ag—N at 2.223 (3) Å. The Ag—N bonds of the title complex (Table 1) span the normal range with a tendency to the high side.

Related literature

For related literature, see: Fijolek et al. (1997); Jaber et al. (1996); Oldham & Sandford (1977); Othman et al. (2003); Tolochko et al. (1998); Voicu et al. (2001); Whitcomb & Rajeswaran (2006a,b,c).

S2. Experimental

Silver succinate hydrate (Whitcomb and Rajeswaran, 2006c) (0.40 g) was reacted with 0.40 g bipyridyl in 20 ml EtOH. The thick dispersion completely cleared with mild heating. Slow cooling yielded colourless rods of (I). M.P. 454 K (sharp). Analysis: calc. for C₁₄H₁₂N₃O₂Ag: C = 46.43, H =3.34, N =11.60%, found C = 46.15, H =3.15, N =11.31%.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001) and Materials Studio (Accelrys, 2002); software used to prepare material for publication: publCIF.

Figures

	Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids for non-hydrogen atoms.
	Fig. 2. Packing diagram for (I).

(2,2'-Bipyidyl-κ²N,N')(succinamidato-κN)silver

Crystal data

[Ag(C4H4NO2)(C10H8N2)]	F(000) = 720
Mr = 362.14	Dx = 1.856 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8777 reflections
a = 12.0853 (3) Å	θ = 1.0–27.5°
b = 7.4188 (2) Å	µ = 1.56 mm^−1
c = 14.6724 (4) Å	T = 293 K
β = 99.924 (1)°	Rod, colorless
V = 1295.82 (6) Å^3	0.5 × 0.25 × 0.15 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2967 independent reflections
Radiation source: fine-focus sealed tube	2176 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
Detector resolution: 9 pixels mm^-1	θmax = 27.5°, θmin = 4.1°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SORTAV; Blessing 1995)	k = −7→9
Tmin = 0.706, Tmax = 0.871	l = −16→19
14369 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0421P)^2] where P = (Fo^2 + 2Fc^2)/3
2967 reflections	(Δ/σ)max = 0.002
181 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.98 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Ag1	0.180684 (16)	0.19961 (3)	1.040989 (15)	0.04664 (12)
O1	0.4046 (2)	0.3033 (3)	0.96269 (17)	0.0641 (7)
O2	0.36059 (15)	0.0042 (3)	1.22380 (13)	0.0497 (5)
N1	0.35406 (18)	0.1646 (3)	1.08880 (16)	0.0374 (6)
N2	−0.00208 (19)	0.2619 (3)	1.01848 (16)	0.0348 (5)
N3	0.09929 (18)	0.1201 (4)	0.88357 (16)	0.0403 (6)
C1	0.4306 (3)	0.2259 (4)	1.0372 (2)	0.0413 (7)
C2	0.5483 (3)	0.1835 (4)	1.0839 (2)	0.0448 (8)
H2A	0.5902	0.2931	1.1019	0.054*
H2B	0.5876	0.1140	1.0434	0.054*
C3	0.5330 (2)	0.0749 (4)	1.1676 (2)	0.0438 (7)
H3A	0.5720	0.1305	1.2239	0.053*
H3B	0.5607	−0.0470	1.1637	0.053*
C4	0.4069 (2)	0.0756 (4)	1.16514 (19)	0.0351 (6)
C5	−0.0482 (3)	0.3534 (4)	1.0814 (2)	0.0413 (7)
H5	−0.0037	0.3801	1.1380	0.050*
C6	−0.1581 (2)	0.4094 (4)	1.0658 (2)	0.0438 (7)
H6	−0.1871	0.4721	1.1113	0.053*
C7	−0.2248 (2)	0.3717 (5)	0.9821 (2)	0.0454 (7)
H7	−0.2993	0.4093	0.9699	0.054*
C8	−0.1789 (2)	0.2764 (4)	0.9162 (2)	0.0429 (7)
H8	−0.2224	0.2486	0.8593	0.051*
C9	−0.0668 (2)	0.2231 (4)	0.93656 (19)	0.0322 (6)
C10	−0.0127 (2)	0.1233 (4)	0.86720 (18)	0.0334 (6)
C11	−0.0747 (2)	0.0387 (4)	0.79043 (19)	0.0408 (7)
H11	−0.1528	0.0412	0.7802	0.049*
C12	−0.0174 (3)	−0.0496 (4)	0.7294 (2)	0.0468 (7)
H12	−0.0569	−0.1067	0.6774	0.056*
C13	0.0980 (3)	−0.0524 (4)	0.7463 (2)	0.0493 (8)
H13	0.1380	−0.1107	0.7061	0.059*
C14	0.1524 (2)	0.0329 (4)	0.8237 (2)	0.0474 (8)
H14	0.2305	0.0304	0.8355	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.03268 (15)	0.05414 (19)	0.04831 (18)	−0.00169 (10)	−0.00653 (10)	0.00760 (11)
O1	0.0784 (17)	0.0724 (17)	0.0437 (15)	0.0069 (12)	0.0170 (12)	0.0134 (12)
O2	0.0411 (11)	0.0646 (14)	0.0435 (12)	−0.0047 (11)	0.0074 (9)	0.0113 (11)
N1	0.0327 (12)	0.0456 (14)	0.0330 (13)	0.0016 (10)	0.0030 (10)	−0.0013 (11)
N2	0.0362 (12)	0.0354 (12)	0.0316 (13)	−0.0028 (10)	0.0028 (10)	0.0039 (10)
N3	0.0335 (12)	0.0463 (14)	0.0391 (14)	0.0004 (11)	0.0010 (10)	0.0017 (12)
C1	0.0476 (17)	0.0403 (17)	0.0384 (17)	0.0021 (14)	0.0139 (14)	−0.0046 (14)
C2	0.0398 (16)	0.0470 (19)	0.0507 (19)	−0.0045 (13)	0.0167 (14)	−0.0099 (14)
C3	0.0307 (14)	0.0497 (19)	0.0491 (18)	0.0007 (13)	0.0018 (12)	−0.0019 (14)
C4	0.0325 (13)	0.0357 (15)	0.0354 (15)	0.0010 (12)	0.0010 (11)	−0.0065 (13)
C5	0.0504 (18)	0.0396 (16)	0.0337 (16)	−0.0040 (14)	0.0061 (13)	0.0054 (13)
C6	0.0482 (17)	0.0409 (17)	0.0450 (18)	−0.0005 (14)	0.0159 (14)	0.0011 (14)
C7	0.0356 (15)	0.0464 (18)	0.056 (2)	0.0046 (14)	0.0129 (14)	0.0055 (16)
C8	0.0351 (15)	0.0493 (19)	0.0422 (17)	−0.0020 (13)	0.0007 (12)	0.0043 (15)
C9	0.0319 (14)	0.0297 (14)	0.0341 (15)	−0.0020 (11)	0.0030 (11)	0.0062 (12)
C10	0.0348 (14)	0.0317 (14)	0.0328 (15)	−0.0025 (12)	0.0031 (11)	0.0076 (12)
C11	0.0382 (15)	0.0427 (16)	0.0386 (16)	−0.0032 (13)	−0.0013 (12)	0.0033 (14)
C12	0.0576 (18)	0.0435 (18)	0.0364 (16)	−0.0037 (15)	0.0001 (13)	−0.0045 (14)
C13	0.0620 (19)	0.0455 (18)	0.0427 (18)	0.0083 (15)	0.0150 (15)	−0.0016 (14)
C14	0.0390 (16)	0.059 (2)	0.0446 (18)	0.0069 (14)	0.0085 (13)	0.0020 (15)

Geometric parameters (Å, º)

Ag1—N1	2.108 (2)	C5—C6	1.372 (4)
Ag1—N2	2.225 (2)	C5—H5	0.9300
Ag1—N3	2.422 (2)	C6—C7	1.377 (4)
O1—C1	1.227 (4)	C6—H6	0.9300
O2—C4	1.225 (3)	C7—C8	1.388 (5)
N1—C4	1.361 (4)	C7—H7	0.9300
N1—C1	1.369 (4)	C8—C9	1.393 (4)
N2—C5	1.342 (4)	C8—H8	0.9300
N2—C9	1.347 (3)	C9—C10	1.497 (4)
N3—C10	1.333 (3)	C10—C11	1.390 (4)
N3—C14	1.341 (4)	C11—C12	1.387 (4)
C1—C2	1.502 (4)	C11—H11	0.9300
C2—C3	1.507 (4)	C12—C13	1.374 (4)
C2—H2A	0.9700	C12—H12	0.9300
C2—H2B	0.9700	C13—C14	1.366 (4)
C3—C4	1.518 (3)	C13—H13	0.9300
C3—H3A	0.9700	C14—H14	0.9300
C3—H3B	0.9700
N1—Ag1—N2	168.37 (9)	N2—C5—C6	122.9 (3)
N1—Ag1—N3	120.30 (8)	N2—C5—H5	118.5
N2—Ag1—N3	71.30 (8)	C6—C5—H5	118.5
C4—N1—C1	110.5 (2)	C5—C6—C7	119.2 (3)
C4—N1—Ag1	129.19 (18)	C5—C6—H6	120.4
C1—N1—Ag1	120.15 (19)	C7—C6—H6	120.4
C5—N2—C9	118.4 (2)	C6—C7—C8	118.8 (3)
C5—N2—Ag1	121.49 (19)	C6—C7—H7	120.6
C9—N2—Ag1	119.80 (18)	C8—C7—H7	120.6
C10—N3—C14	118.5 (3)	C7—C8—C9	119.1 (3)
C10—N3—Ag1	113.59 (17)	C7—C8—H8	120.5
C14—N3—Ag1	125.51 (18)	C9—C8—H8	120.5
O1—C1—N1	123.7 (3)	N2—C9—C8	121.6 (3)
O1—C1—C2	125.5 (3)	N2—C9—C10	117.2 (2)
N1—C1—C2	110.8 (3)	C8—C9—C10	121.2 (3)
C1—C2—C3	104.1 (2)	N3—C10—C11	121.7 (3)
C1—C2—H2A	110.9	N3—C10—C9	115.8 (2)
C3—C2—H2A	110.9	C11—C10—C9	122.5 (2)
C1—C2—H2B	110.9	C12—C11—C10	118.5 (3)
C3—C2—H2B	110.9	C12—C11—H11	120.8
H2A—C2—H2B	109.0	C10—C11—H11	120.8
C2—C3—C4	104.0 (2)	C13—C12—C11	119.7 (3)
C2—C3—H3A	111.0	C13—C12—H12	120.2
C4—C3—H3A	111.0	C11—C12—H12	120.2
C2—C3—H3B	111.0	C14—C13—C12	118.1 (3)
C4—C3—H3B	111.0	C14—C13—H13	121.0
H3A—C3—H3B	109.0	C12—C13—H13	121.0
O2—C4—N1	125.6 (2)	N3—C14—C13	123.5 (3)
O2—C4—C3	124.0 (3)	N3—C14—H14	118.2
N1—C4—C3	110.3 (2)	C13—C14—H14	118.2
N2—Ag1—N1—C4	57.8 (5)	Ag1—N2—C5—C6	173.4 (2)
N3—Ag1—N1—C4	−127.1 (2)	N2—C5—C6—C7	−0.3 (4)
N2—Ag1—N1—C1	−126.9 (4)	C5—C6—C7—C8	0.6 (4)
N3—Ag1—N1—C1	48.2 (2)	C6—C7—C8—C9	−0.4 (5)
N1—Ag1—N2—C5	4.4 (5)	C5—N2—C9—C8	0.3 (4)
N3—Ag1—N2—C5	−171.1 (2)	Ag1—N2—C9—C8	−173.3 (2)
N1—Ag1—N2—C9	177.9 (4)	C5—N2—C9—C10	179.1 (2)
N3—Ag1—N2—C9	2.36 (19)	Ag1—N2—C9—C10	5.4 (3)
N1—Ag1—N3—C10	170.39 (19)	C7—C8—C9—N2	−0.1 (4)
N2—Ag1—N3—C10	−10.66 (19)	C7—C8—C9—C10	−178.8 (3)
N1—Ag1—N3—C14	8.5 (3)	C14—N3—C10—C11	0.2 (4)
N2—Ag1—N3—C14	−172.5 (3)	Ag1—N3—C10—C11	−163.0 (2)
C4—N1—C1—O1	176.5 (3)	C14—N3—C10—C9	−179.9 (2)
Ag1—N1—C1—O1	0.4 (4)	Ag1—N3—C10—C9	16.8 (3)
C4—N1—C1—C2	−2.9 (3)	N2—C9—C10—N3	−15.5 (4)
Ag1—N1—C1—C2	−179.00 (18)	C8—C9—C10—N3	163.2 (3)
O1—C1—C2—C3	−175.1 (3)	N2—C9—C10—C11	164.4 (3)
N1—C1—C2—C3	4.2 (3)	C8—C9—C10—C11	−16.9 (4)
C1—C2—C3—C4	−3.8 (3)	N3—C10—C11—C12	−0.6 (4)
C1—N1—C4—O2	−179.2 (3)	C9—C10—C11—C12	179.6 (3)
Ag1—N1—C4—O2	−3.6 (4)	C10—C11—C12—C13	0.4 (4)
C1—N1—C4—C3	0.3 (3)	C11—C12—C13—C14	0.1 (5)
Ag1—N1—C4—C3	175.92 (19)	C10—N3—C14—C13	0.3 (5)
C2—C3—C4—O2	−178.1 (3)	Ag1—N3—C14—C13	161.4 (2)
C2—C3—C4—N1	2.4 (3)	C12—C13—C14—N3	−0.5 (5)
C9—N2—C5—C6	−0.2 (4)