Synthesis, structure and spectroscopic properties of a novel compound bis(benzylamino)silver(I) benzylcarbamate

A novel silver-containing compound, bis(benzylamino)silver(I) benzylcarbamate, with an unusual molecular structure is easily synthesized by the reaction of benzylammonium benzylcarbamate and silver oxide. It crystallizes in the triclinic crystal system with the space group with a = 5.2006 (5), b = 14.6298 (15), c = 14.7246 (15) Å, α = 68.729 (2), β = 83.507 (2), γ = 85.412 (2)° and Z = 2. In the crystal, one Ag atom coordinates with the two amino groups in two benzylamine molecules, and there are no silver–silver and silver–oxygen interactions. The carboxylate groups take part in balancing the electric charge and forming hydrogen bonds. Both the compound and the starting material benzylammonium benzylcarbamate exhibit room-temperature solid-state emissions with the peaks at 300 and 406 nm, respectively.

Computing details

Data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL.

(I)

Crystal data

C22H26AgN3O2	Z = 2
Mr = 472.33	F(000) = 484
Triclinic, P1	Dx = 1.514 Mg m^−3
a = 5.2006 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.6298 (15) Å	Cell parameters from 328 reflections
c = 14.7246 (15) Å	θ = 2.5–26.0°
α = 68.729 (2)°	µ = 0.99 mm^−1
β = 83.507 (2)°	T = 293 K
γ = 85.412 (2)°	Block, colourless
V = 1036.37 (18) Å^3	0.32 × 0.28 × 0.26 mm

Data collection

Bruker diffractometer	4009 independent reflections
Radiation source: fine-focus sealed tube	3622 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Semisphere scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan SADABS	h = −6→5
Tmin = 0.741, Tmax = 0.782	k = −17→16
6094 measured reflections	l = −18→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 0.2277P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
4009 reflections	Δρmax = 0.33 e Å^−3
254 parameters	Δρmin = −0.51 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0129 (11)

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	0.53362 (3)	0.873586 (12)	0.034393 (13)	0.04639 (9)
C1	0.1886 (4)	0.80409 (18)	−0.09264 (18)	0.0475 (5)
H1A	0.0677	0.8262	−0.1426	0.057*
H1B	0.1020	0.7581	−0.0339	0.057*
C2	0.4212 (5)	0.75304 (17)	−0.12702 (17)	0.0462 (5)
C3	0.5345 (6)	0.7933 (2)	−0.2216 (2)	0.0594 (7)
H3	0.4632	0.8511	−0.2644	0.071*
C4	0.7522 (6)	0.7489 (3)	−0.2537 (3)	0.0741 (9)
H4	0.8270	0.7770	−0.3175	0.089*
C5	0.8568 (6)	0.6642 (3)	−0.1918 (3)	0.0804 (10)
H5	1.0030	0.6342	−0.2133	0.096*
C6	0.7476 (7)	0.6233 (2)	−0.0984 (3)	0.0844 (11)
H6	0.8197	0.5653	−0.0564	0.101*
C7	0.5290 (6)	0.6676 (2)	−0.0653 (2)	0.0652 (7)
H7	0.4559	0.6393	−0.0013	0.078*
C8	0.9235 (5)	0.75033 (17)	0.19255 (18)	0.0478 (5)
H8A	1.0005	0.7503	0.2496	0.057*
H8B	1.0617	0.7389	0.1473	0.057*
C9	0.7383 (4)	0.66834 (16)	0.22339 (16)	0.0429 (5)
C10	0.7522 (5)	0.60312 (19)	0.17517 (19)	0.0550 (6)
H10	0.8791	0.6092	0.1237	0.066*
C11	0.5795 (6)	0.5284 (2)	0.2022 (2)	0.0629 (7)
H11	0.5909	0.4849	0.1687	0.075*
C12	0.3928 (5)	0.51837 (19)	0.2778 (2)	0.0613 (7)
H12	0.2765	0.4684	0.2959	0.074*
C13	0.3778 (5)	0.5821 (2)	0.3268 (2)	0.0646 (7)
H13	0.2518	0.5752	0.3787	0.078*
C14	0.5484 (5)	0.6568 (2)	0.2999 (2)	0.0561 (6)
H14	0.5356	0.7000	0.3337	0.067*
C15	1.0662 (5)	0.2159 (2)	0.56050 (19)	0.0591 (7)
H15	1.1947	0.1949	0.6036	0.071*
C16	1.0397 (6)	0.3139 (2)	0.5046 (2)	0.0688 (8)
H16	1.1494	0.3583	0.5104	0.083*
C17	0.8519 (6)	0.3464 (2)	0.4403 (2)	0.0678 (8)
H17	0.8315	0.4128	0.4031	0.081*
C18	0.6956 (6)	0.2800 (3)	0.4316 (2)	0.0736 (9)
H18	0.5701	0.3012	0.3873	0.088*
C19	0.7216 (5)	0.1818 (2)	0.4878 (2)	0.0634 (7)
H19	0.6131	0.1376	0.4811	0.076*
C20	0.9076 (4)	0.1481 (2)	0.55430 (16)	0.0482 (6)
C21	0.9360 (5)	0.04127 (19)	0.61706 (17)	0.0522 (6)
H21A	0.7875	0.0078	0.6120	0.063*
H21B	1.0891	0.0127	0.5917	0.063*
C22	0.7457 (4)	0.03002 (15)	0.78199 (16)	0.0380 (5)
N1	0.2648 (4)	0.88914 (13)	−0.07174 (13)	0.0408 (4)
H1C	0.1180	0.9174	−0.0535	0.049*
H1D	0.3304	0.9325	−0.1289	0.049*
N2	0.7950 (4)	0.84740 (13)	0.14526 (14)	0.0421 (4)
H2A	0.9216	0.8903	0.1189	0.050*
H2B	0.7071	0.8643	0.1935	0.050*
N3	0.9570 (4)	0.02365 (15)	0.71937 (13)	0.0466 (5)
H3A	1.1067	0.0087	0.7416	0.056*
O1	0.5253 (3)	0.04092 (13)	0.75078 (12)	0.0485 (4)
O2	0.7879 (3)	0.02260 (11)	0.86767 (11)	0.0427 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ag1	0.04028 (12)	0.04843 (13)	0.05196 (13)	−0.00295 (7)	−0.01089 (8)	−0.01752 (9)
C1	0.0422 (13)	0.0505 (13)	0.0529 (13)	−0.0076 (10)	−0.0076 (10)	−0.0202 (11)
C2	0.0457 (13)	0.0481 (13)	0.0520 (13)	−0.0058 (10)	−0.0114 (10)	−0.0237 (11)
C3	0.0634 (17)	0.0626 (16)	0.0565 (15)	0.0000 (13)	−0.0048 (13)	−0.0271 (13)
C4	0.0660 (19)	0.092 (2)	0.082 (2)	−0.0063 (17)	0.0049 (16)	−0.0550 (19)
C5	0.0607 (19)	0.090 (2)	0.123 (3)	0.0092 (17)	−0.021 (2)	−0.076 (2)
C6	0.090 (2)	0.0589 (18)	0.118 (3)	0.0236 (17)	−0.051 (2)	−0.0405 (19)
C7	0.0736 (19)	0.0557 (16)	0.0671 (17)	0.0033 (14)	−0.0224 (15)	−0.0194 (14)
C8	0.0394 (12)	0.0503 (13)	0.0541 (14)	−0.0004 (10)	−0.0124 (10)	−0.0170 (11)
C9	0.0383 (12)	0.0437 (12)	0.0446 (12)	0.0037 (9)	−0.0138 (10)	−0.0114 (10)
C10	0.0589 (16)	0.0533 (15)	0.0533 (14)	−0.0044 (12)	−0.0027 (12)	−0.0199 (12)
C11	0.0725 (19)	0.0494 (15)	0.0709 (18)	−0.0042 (13)	−0.0139 (15)	−0.0240 (13)
C12	0.0535 (16)	0.0459 (14)	0.0745 (18)	−0.0083 (12)	−0.0150 (14)	−0.0056 (13)
C13	0.0504 (15)	0.0660 (18)	0.0691 (18)	−0.0071 (13)	0.0057 (13)	−0.0164 (14)
C14	0.0517 (15)	0.0584 (16)	0.0608 (16)	−0.0029 (12)	−0.0037 (12)	−0.0244 (13)
C15	0.0509 (15)	0.0737 (18)	0.0482 (14)	−0.0044 (13)	−0.0109 (11)	−0.0141 (13)
C16	0.0680 (19)	0.076 (2)	0.0597 (17)	−0.0122 (15)	−0.0023 (14)	−0.0203 (15)
C17	0.0609 (18)	0.0726 (19)	0.0554 (16)	0.0053 (15)	0.0036 (13)	−0.0097 (14)
C18	0.0538 (17)	0.093 (2)	0.0601 (17)	0.0114 (16)	−0.0175 (13)	−0.0103 (16)
C19	0.0461 (14)	0.086 (2)	0.0589 (16)	−0.0034 (14)	−0.0118 (12)	−0.0244 (15)
C20	0.0380 (12)	0.0698 (16)	0.0353 (11)	0.0021 (11)	0.0007 (9)	−0.0189 (11)
C21	0.0477 (14)	0.0657 (16)	0.0452 (13)	0.0019 (12)	−0.0011 (11)	−0.0239 (12)
C22	0.0315 (11)	0.0367 (11)	0.0444 (12)	−0.0021 (8)	−0.0026 (9)	−0.0128 (9)
N1	0.0351 (9)	0.0420 (10)	0.0435 (10)	−0.0008 (8)	−0.0033 (8)	−0.0135 (8)
N2	0.0378 (10)	0.0424 (10)	0.0497 (11)	−0.0046 (8)	−0.0054 (8)	−0.0198 (8)
N3	0.0321 (9)	0.0639 (12)	0.0397 (10)	0.0034 (9)	−0.0036 (8)	−0.0145 (9)
O1	0.0299 (8)	0.0635 (10)	0.0544 (9)	−0.0016 (7)	−0.0067 (7)	−0.0232 (8)
O2	0.0350 (8)	0.0537 (9)	0.0405 (8)	−0.0037 (7)	−0.0031 (6)	−0.0179 (7)

Geometric parameters (Å, º)

Ag1—N2	2.1504 (19)	C12—H12	0.9300
Ag1—N1	2.1527 (18)	C13—C14	1.378 (4)
C1—N1	1.478 (3)	C13—H13	0.9300
C1—C2	1.506 (3)	C14—H14	0.9300
C1—H1A	0.9700	C15—C20	1.373 (4)
C1—H1B	0.9700	C15—C16	1.375 (4)
C2—C7	1.371 (4)	C15—H15	0.9300
C2—C3	1.382 (4)	C16—C17	1.373 (4)
C3—C4	1.382 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.364 (5)
C4—C5	1.359 (5)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.378 (4)
C5—C6	1.361 (5)	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.387 (3)
C6—C7	1.391 (5)	C19—H19	0.9300
C6—H6	0.9300	C20—C21	1.505 (4)
C7—H7	0.9300	C21—N3	1.449 (3)
C8—N2	1.478 (3)	C21—H21A	0.9700
C8—C9	1.504 (3)	C21—H21B	0.9700
C8—H8A	0.9700	C22—O1	1.260 (3)
C8—H8B	0.9700	C22—O2	1.269 (3)
C9—C10	1.374 (4)	C22—N3	1.372 (3)
C9—C14	1.382 (3)	N1—H1C	0.9000
C10—C11	1.386 (4)	N1—H1D	0.9000
C10—H10	0.9300	N2—H2A	0.9000
C11—C12	1.366 (4)	N2—H2B	0.9000
C11—H11	0.9300	N3—H3A	0.8600
C12—C13	1.364 (4)
N2—Ag1—N1	175.96 (7)	C13—C14—C9	120.9 (3)
N1—C1—C2	111.10 (18)	C13—C14—H14	119.6
N1—C1—H1A	109.4	C9—C14—H14	119.6
C2—C1—H1A	109.4	C20—C15—C16	121.6 (3)
N1—C1—H1B	109.4	C20—C15—H15	119.2
C2—C1—H1B	109.4	C16—C15—H15	119.2
H1A—C1—H1B	108.0	C17—C16—C15	120.2 (3)
C7—C2—C3	118.6 (3)	C17—C16—H16	119.9
C7—C2—C1	121.3 (2)	C15—C16—H16	119.9
C3—C2—C1	120.1 (2)	C18—C17—C16	119.1 (3)
C4—C3—C2	121.0 (3)	C18—C17—H17	120.5
C4—C3—H3	119.5	C16—C17—H17	120.5
C2—C3—H3	119.5	C17—C18—C19	120.7 (3)
C5—C4—C3	119.8 (3)	C17—C18—H18	119.7
C5—C4—H4	120.1	C19—C18—H18	119.7
C3—C4—H4	120.1	C18—C19—C20	120.9 (3)
C4—C5—C6	120.1 (3)	C18—C19—H19	119.6
C4—C5—H5	120.0	C20—C19—H19	119.6
C6—C5—H5	120.0	C15—C20—C19	117.5 (3)
C5—C6—C7	120.5 (3)	C15—C20—C21	121.1 (2)
C5—C6—H6	119.7	C19—C20—C21	121.4 (3)
C7—C6—H6	119.7	N3—C21—C20	114.1 (2)
C2—C7—C6	120.0 (3)	N3—C21—H21A	108.7
C2—C7—H7	120.0	C20—C21—H21A	108.7
C6—C7—H7	120.0	N3—C21—H21B	108.7
N2—C8—C9	112.28 (18)	C20—C21—H21B	108.7
N2—C8—H8A	109.1	H21A—C21—H21B	107.6
C9—C8—H8A	109.1	O1—C22—O2	125.1 (2)
N2—C8—H8B	109.1	O1—C22—N3	117.7 (2)
C9—C8—H8B	109.1	O2—C22—N3	117.16 (19)
H8A—C8—H8B	107.9	C1—N1—Ag1	121.93 (14)
C10—C9—C14	118.1 (2)	C1—N1—H1C	106.8
C10—C9—C8	120.6 (2)	Ag1—N1—H1C	106.8
C14—C9—C8	121.3 (2)	C1—N1—H1D	106.8
C9—C10—C11	120.9 (3)	Ag1—N1—H1D	106.8
C9—C10—H10	119.6	H1C—N1—H1D	106.7
C11—C10—H10	119.6	C8—N2—Ag1	122.49 (14)
C12—C11—C10	120.2 (3)	C8—N2—H2A	106.7
C12—C11—H11	119.9	Ag1—N2—H2A	106.7
C10—C11—H11	119.9	C8—N2—H2B	106.7
C13—C12—C11	119.6 (3)	Ag1—N2—H2B	106.7
C13—C12—H12	120.2	H2A—N2—H2B	106.6
C11—C12—H12	120.2	C22—N3—C21	122.13 (19)
C12—C13—C14	120.4 (3)	C22—N3—H3A	118.9
C12—C13—H13	119.8	C21—N3—H3A	118.9
C14—C13—H13	119.8
N1—C1—C2—C7	101.7 (3)	C8—C9—C14—C13	179.2 (2)
N1—C1—C2—C3	−76.7 (3)	C20—C15—C16—C17	−0.2 (4)
C7—C2—C3—C4	−0.2 (4)	C15—C16—C17—C18	−1.1 (4)
C1—C2—C3—C4	178.2 (2)	C16—C17—C18—C19	1.3 (5)
C2—C3—C4—C5	0.3 (5)	C17—C18—C19—C20	−0.2 (5)
C3—C4—C5—C6	−0.1 (5)	C16—C15—C20—C19	1.3 (4)
C4—C5—C6—C7	−0.1 (5)	C16—C15—C20—C21	−179.0 (2)
C3—C2—C7—C6	0.0 (4)	C18—C19—C20—C15	−1.0 (4)
C1—C2—C7—C6	−178.5 (3)	C18—C19—C20—C21	179.2 (3)
C5—C6—C7—C2	0.2 (5)	C15—C20—C21—N3	47.1 (3)
N2—C8—C9—C10	109.3 (2)	C19—C20—C21—N3	−133.2 (2)
N2—C8—C9—C14	−70.1 (3)	C2—C1—N1—Ag1	−58.7 (2)
C14—C9—C10—C11	0.4 (4)	N2—Ag1—N1—C1	−23.4 (10)
C8—C9—C10—C11	−179.0 (2)	C9—C8—N2—Ag1	−46.1 (3)
C9—C10—C11—C12	−0.2 (4)	N1—Ag1—N2—C8	29.8 (10)
C10—C11—C12—C13	−0.2 (4)	O1—C22—N3—C21	7.9 (3)
C11—C12—C13—C14	0.5 (4)	O2—C22—N3—C21	−173.4 (2)
C12—C13—C14—C9	−0.3 (4)	C20—C21—N3—C22	77.1 (3)
C10—C9—C14—C13	−0.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1^i	0.86	2.29	3.087 (2)	154
N2—H2B···O1^ii	0.90	2.10	2.931 (2)	154
N2—H2A···O2^iii	0.90	2.12	2.943 (2)	151
N1—H1D···O1^iv	0.90	2.12	3.011 (2)	171
N1—H1C···O2^v	0.90	2.32	3.037 (2)	136

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