A luminescent Cu₂I₂P₂S₂-type binuclear com­plex and its fluorescence sensing for pyridine

Luminescent Cu^I com­plexes are an important class of coordination com­pounds due to their relative abundance, low cost and ability to display excellent luminescence. The title Cu₂I₂P₂S₂-type binuclear com­plex, di-μ-iodido-bis­[(thio­urea-κS)(tri­phenyl­phosphine-κP)copper(I)], [Cu₂I₂(CH₄N₂S)₂(C₁₈H₁₅P)₂], con­ven­tionally abbreviated as Cu₂I₂TPP₂TU₂, where TPP and TU represent tri­phenyl­phosphine and thio­urea, respectively, is described. In this com­plex, each Cu^I atom adopts a CuI₂PS four-coordination mode and pairs of atoms are connected to each other by two μ₂-I ligands to form a centrosymmetric binuclear cluster. It was also found that the paper-based film of this com­plex exhibited obvious luminescence light-up sensing for pyridine and 4-methyl­pyri­dine.

Computing details

Di-µ-iodido-bis[(thiourea-κS)(triphenylphosphine-κP)copper(I)]

Crystal data

[Cu2I2(CH4N2S)2(C18H15P)2]	Z = 1
Mr = 1057.66	F(000) = 520
Triclinic, P1	Dx = 1.747 Mg m^−3
a = 8.7405 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3363 (9) Å	Cell parameters from 9860 reflections
c = 14.3558 (13) Å	θ = 2.4–27.1°
α = 89.212 (4)°	µ = 2.81 mm^−1
β = 72.987 (4)°	T = 170 K
γ = 64.826 (3)°	Block, colourless
V = 1005.50 (16) Å^3	0.49 × 0.29 × 0.23 mm

Data collection

Bruker APEXII CCD diffractometer	3709 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.052
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 26.0°, θmin = 2.4°
Tmin = 0.423, Tmax = 0.746	h = −9→10
17531 measured reflections	k = −11→11
3947 independent reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 4.5581P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3947 reflections	Δρmax = 2.32 e Å^−3
230 parameters	Δρmin = −1.76 e Å^−3
6 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	Occ. (<1)
I1	1.89594 (4)	−1.67987 (4)	0.53274 (2)	0.03301 (12)
Cu1	2.14519 (7)	−1.60348 (7)	0.41096 (4)	0.02722 (15)
S1A	2.3792 (4)	−1.8210 (4)	0.4361 (3)	0.0269 (9)	0.579 (15)
P1	2.12866 (14)	−1.62692 (12)	0.25878 (7)	0.0191 (2)
N2A	2.7090 (10)	−1.9137 (9)	0.4251 (6)	0.0269 (9)	0.579 (15)
H2AA	2.802733	−1.894665	0.413626	0.032*	0.579 (15)
H2AB	2.717488	−2.008669	0.438245	0.032*	0.579 (15)
N1A	2.5694 (9)	−1.6568 (8)	0.4005 (7)	0.0269 (9)	0.579 (15)
H1AA	2.671431	−1.679966	0.354259	0.032*	0.579 (15)
H1AB	2.480732	−1.595508	0.379292	0.032*	0.579 (15)
C13	2.3362 (6)	−1.6591 (5)	0.1645 (3)	0.0219 (8)
C19A	2.5542 (11)	−1.7988 (9)	0.4227 (8)	0.0269 (9)	0.579 (15)
C1	2.0928 (6)	−1.7995 (5)	0.2332 (3)	0.0212 (8)
C6	2.1924 (6)	−1.9419 (5)	0.2644 (3)	0.0268 (9)
H6	2.277435	−1.946584	0.294528	0.032*
C7	1.9588 (6)	−1.4609 (5)	0.2233 (3)	0.0214 (8)
C12	1.9797 (6)	−1.4258 (5)	0.1265 (3)	0.0250 (9)
H12	2.085452	−1.491225	0.075253	0.030*
C2	1.9682 (7)	−1.7954 (6)	0.1899 (4)	0.0337 (11)
H2	1.900144	−1.699698	0.167849	0.040*
C8	1.8019 (6)	−1.3644 (6)	0.2966 (3)	0.0319 (10)
H8	1.786686	−1.386451	0.362664	0.038*
C14	2.4228 (6)	−1.7786 (6)	0.0837 (3)	0.0284 (9)
H14	2.371505	−1.846827	0.074776	0.034*
C18	2.4141 (6)	−1.5605 (6)	0.1755 (4)	0.0296 (10)
H18	2.357487	−1.479575	0.230142	0.035*
C5	2.1671 (7)	−2.0770 (6)	0.2514 (3)	0.0322 (10)
H5	2.237676	−2.174324	0.270900	0.039*
C4	2.0408 (8)	−2.0701 (6)	0.2104 (4)	0.0388 (12)
H4	2.021077	−2.161495	0.204143	0.047*
C17	2.5740 (7)	−1.5791 (6)	0.1074 (4)	0.0354 (11)
H17	2.625099	−1.509871	0.114788	0.043*
C10	1.6897 (7)	−1.2014 (6)	0.1795 (4)	0.0383 (12)
H10	1.598134	−1.112909	0.164460	0.046*
C16	2.6582 (7)	−1.6994 (6)	0.0288 (4)	0.0368 (11)
H16	2.768594	−1.714044	−0.017190	0.044*
C11	1.8462 (7)	−1.2956 (6)	0.1054 (4)	0.0325 (10)
H11	1.861817	−1.270655	0.039865	0.039*
C3	1.9424 (8)	−1.9309 (7)	0.1785 (4)	0.0419 (13)
H3	1.857192	−1.927253	0.148762	0.050*
C15	2.5825 (7)	−1.7973 (6)	0.0171 (4)	0.0363 (11)
H15	2.640540	−1.878729	−0.037348	0.044*
C9	1.6669 (7)	−1.2361 (6)	0.2747 (4)	0.0414 (13)
H9	1.559164	−1.172396	0.325239	0.050*
S1B	2.4207 (13)	−1.7895 (11)	0.4153 (6)	0.067 (2)	0.421 (15)
C19B	2.589 (2)	−1.7827 (19)	0.4257 (15)	0.067 (2)	0.421 (15)
N2B	2.723 (2)	−1.906 (2)	0.4477 (12)	0.067 (2)	0.421 (15)
H2BA	2.788908	−1.871994	0.470306	0.080*	0.421 (15)
H2BB	2.681590	−1.958857	0.493506	0.080*	0.421 (15)
N1B	2.583 (2)	−1.6260 (17)	0.4327 (11)	0.067 (2)	0.421 (15)
H1BA	2.548541	−1.574358	0.382895	0.080*	0.421 (15)
H1BB	2.693817	−1.636700	0.427860	0.080*	0.421 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0382 (2)	0.02971 (18)	0.02997 (18)	−0.01769 (14)	−0.00495 (13)	0.00112 (12)
Cu1	0.0290 (3)	0.0319 (3)	0.0219 (3)	−0.0123 (2)	−0.0112 (2)	0.0015 (2)
S1A	0.0208 (12)	0.0247 (12)	0.0410 (15)	−0.0115 (8)	−0.0157 (9)	0.0070 (8)
P1	0.0200 (5)	0.0186 (5)	0.0181 (5)	−0.0076 (4)	−0.0063 (4)	0.0001 (4)
N2A	0.0208 (12)	0.0247 (12)	0.0410 (15)	−0.0115 (8)	−0.0157 (9)	0.0070 (8)
N1A	0.0208 (12)	0.0247 (12)	0.0410 (15)	−0.0115 (8)	−0.0157 (9)	0.0070 (8)
C13	0.022 (2)	0.0209 (19)	0.0211 (19)	−0.0070 (16)	−0.0076 (16)	0.0035 (16)
C19A	0.0208 (12)	0.0247 (12)	0.0410 (15)	−0.0115 (8)	−0.0157 (9)	0.0070 (8)
C1	0.024 (2)	0.0196 (19)	0.0196 (19)	−0.0105 (17)	−0.0043 (16)	−0.0008 (15)
C6	0.030 (2)	0.024 (2)	0.025 (2)	−0.0106 (18)	−0.0080 (18)	0.0015 (17)
C7	0.022 (2)	0.0198 (19)	0.023 (2)	−0.0092 (17)	−0.0088 (17)	0.0011 (16)
C12	0.028 (2)	0.023 (2)	0.025 (2)	−0.0110 (18)	−0.0089 (18)	−0.0004 (16)
C2	0.038 (3)	0.029 (2)	0.044 (3)	−0.018 (2)	−0.023 (2)	0.008 (2)
C8	0.028 (2)	0.034 (2)	0.025 (2)	−0.006 (2)	−0.0074 (19)	−0.0004 (19)
C14	0.031 (2)	0.029 (2)	0.026 (2)	−0.0142 (19)	−0.0073 (19)	−0.0005 (18)
C18	0.029 (2)	0.028 (2)	0.033 (2)	−0.0129 (19)	−0.0090 (19)	0.0016 (19)
C5	0.042 (3)	0.022 (2)	0.028 (2)	−0.013 (2)	−0.005 (2)	0.0025 (17)
C4	0.050 (3)	0.032 (3)	0.040 (3)	−0.029 (2)	−0.005 (2)	0.000 (2)
C17	0.033 (3)	0.039 (3)	0.045 (3)	−0.022 (2)	−0.016 (2)	0.013 (2)
C10	0.034 (3)	0.029 (2)	0.047 (3)	−0.003 (2)	−0.023 (2)	0.004 (2)
C16	0.027 (2)	0.043 (3)	0.035 (3)	−0.016 (2)	−0.003 (2)	0.009 (2)
C11	0.038 (3)	0.033 (2)	0.033 (2)	−0.016 (2)	−0.021 (2)	0.009 (2)
C3	0.048 (3)	0.043 (3)	0.056 (3)	−0.031 (3)	−0.029 (3)	0.009 (3)
C15	0.033 (3)	0.040 (3)	0.026 (2)	−0.014 (2)	0.001 (2)	−0.004 (2)
C9	0.029 (3)	0.038 (3)	0.039 (3)	0.002 (2)	−0.011 (2)	−0.004 (2)
S1B	0.061 (4)	0.065 (3)	0.049 (3)	0.004 (3)	−0.032 (2)	−0.010 (2)
C19B	0.061 (4)	0.065 (3)	0.049 (3)	0.004 (3)	−0.032 (2)	−0.010 (2)
N2B	0.061 (4)	0.065 (3)	0.049 (3)	0.004 (3)	−0.032 (2)	−0.010 (2)
N1B	0.061 (4)	0.065 (3)	0.049 (3)	0.004 (3)	−0.032 (2)	−0.010 (2)

Geometric parameters (Å, º)

I1—Cu1^i	2.6192 (7)	C8—H8	0.9500
I1—Cu1	2.7147 (7)	C8—C9	1.390 (7)
Cu1—Cu1^i	2.9794 (11)	C14—H14	0.9500
Cu1—S1A	2.306 (3)	C14—C15	1.382 (7)
Cu1—P1	2.2509 (12)	C18—H18	0.9500
Cu1—S1B	2.313 (6)	C18—C17	1.392 (7)
S1A—C19A	1.586 (7)	C5—H5	0.9500
P1—C13	1.823 (4)	C5—C4	1.374 (8)
P1—C1	1.828 (4)	C4—H4	0.9500
P1—C7	1.824 (4)	C4—C3	1.379 (8)
N2A—H2AA	0.8800	C17—H17	0.9500
N2A—H2AB	0.8800	C17—C16	1.387 (8)
N2A—C19A	1.332 (9)	C10—H10	0.9500
N1A—H1AA	0.8814	C10—C11	1.388 (7)
N1A—H1AB	0.8815	C10—C9	1.377 (8)
N1A—C19A	1.411 (9)	C16—H16	0.9500
C13—C14	1.402 (6)	C16—C15	1.373 (8)
C13—C18	1.391 (6)	C11—H11	0.9500
C1—C6	1.398 (6)	C3—H3	0.9500
C1—C2	1.391 (7)	C15—H15	0.9500
C6—H6	0.9500	C9—H9	0.9500
C6—C5	1.393 (7)	S1B—C19B	1.545 (12)
C7—C12	1.401 (6)	C19B—N2B	1.365 (14)
C7—C8	1.390 (6)	C19B—N1B	1.448 (15)
C12—H12	0.9500	N2B—H2BA	0.8996
C12—C11	1.386 (7)	N2B—H2BB	0.8988
C2—H2	0.9500	N1B—H1BA	0.9101
C2—C3	1.395 (7)	N1B—H1BB	0.9101
Cu1^i—I1—Cu1	67.89 (2)	C3—C2—H2	119.7
I1^i—Cu1—I1	112.11 (2)	C7—C8—H8	119.6
I1^i—Cu1—Cu1^i	57.58 (2)	C7—C8—C9	120.9 (4)
I1—Cu1—Cu1^i	54.53 (2)	C9—C8—H8	119.6
S1A—Cu1—I1^i	117.28 (8)	C13—C14—H14	119.9
S1A—Cu1—I1	93.22 (9)	C15—C14—C13	120.2 (5)
S1A—Cu1—Cu1^i	117.01 (11)	C15—C14—H14	119.9
P1—Cu1—I1^i	113.05 (3)	C13—C18—H18	119.6
P1—Cu1—I1	106.81 (4)	C13—C18—C17	120.8 (4)
P1—Cu1—Cu1^i	127.42 (4)	C17—C18—H18	119.6
P1—Cu1—S1A	112.28 (11)	C6—C5—H5	119.8
P1—Cu1—S1B	109.21 (15)	C4—C5—C6	120.3 (5)
S1B—Cu1—I1	107.3 (4)	C4—C5—H5	119.8
S1B—Cu1—Cu1^i	123.05 (16)	C5—C4—H4	119.9
C19A—S1A—Cu1	115.1 (3)	C5—C4—C3	120.2 (5)
C13—P1—Cu1	111.75 (15)	C3—C4—H4	119.9
C13—P1—C1	104.43 (19)	C18—C17—H17	120.3
C13—P1—C7	103.78 (19)	C16—C17—C18	119.5 (5)
C1—P1—Cu1	112.80 (14)	C16—C17—H17	120.3
C7—P1—Cu1	118.44 (14)	C11—C10—H10	120.0
C7—P1—C1	104.3 (2)	C9—C10—H10	120.0
H2AA—N2A—H2AB	120.0	C9—C10—C11	120.1 (4)
C19A—N2A—H2AA	120.0	C17—C16—H16	119.9
C19A—N2A—H2AB	120.0	C15—C16—C17	120.2 (5)
H1AA—N1A—H1AB	109.3	C15—C16—H16	119.9
C19A—N1A—H1AA	109.5	C12—C11—C10	120.3 (4)
C19A—N1A—H1AB	108.8	C12—C11—H11	119.8
C14—C13—P1	124.0 (3)	C10—C11—H11	119.8
C18—C13—P1	117.3 (3)	C2—C3—H3	120.0
C18—C13—C14	118.6 (4)	C4—C3—C2	120.0 (5)
N2A—C19A—S1A	124.8 (6)	C4—C3—H3	120.0
N2A—C19A—N1A	110.9 (7)	C14—C15—H15	119.7
N1A—C19A—S1A	124.2 (6)	C16—C15—C14	120.7 (5)
C6—C1—P1	116.7 (3)	C16—C15—H15	119.7
C2—C1—P1	124.5 (3)	C8—C9—H9	120.1
C2—C1—C6	118.8 (4)	C10—C9—C8	119.8 (5)
C1—C6—H6	119.9	C10—C9—H9	120.1
C5—C6—C1	120.2 (4)	C19B—S1B—Cu1	135.4 (7)
C5—C6—H6	119.9	N2B—C19B—S1B	124.5 (13)
C12—C7—P1	123.3 (3)	N2B—C19B—N1B	117.8 (13)
C8—C7—P1	117.9 (3)	N1B—C19B—S1B	116.4 (10)
C8—C7—C12	118.8 (4)	C19B—N2B—H2BA	111.4
C7—C12—H12	120.0	C19B—N2B—H2BB	112.1
C11—C12—C7	120.0 (4)	H2BA—N2B—H2BB	107.6
C11—C12—H12	120.0	C19B—N1B—H1BA	109.3
C1—C2—H2	119.7	C19B—N1B—H1BB	109.1
C1—C2—C3	120.5 (5)	H1BA—N1B—H1BB	109.5
Cu1—S1A—C19A—N2A	−173.7 (8)	C1—P1—C13—C18	−169.1 (3)
Cu1—S1A—C19A—N1A	2.1 (11)	C1—P1—C7—C12	−83.3 (4)
Cu1—P1—C13—C14	131.6 (3)	C1—P1—C7—C8	97.2 (4)
Cu1—P1—C13—C18	−46.8 (4)	C1—C6—C5—C4	−1.9 (7)
Cu1—P1—C1—C6	−42.9 (4)	C1—C2—C3—C4	0.1 (9)
Cu1—P1—C1—C2	133.7 (4)	C6—C1—C2—C3	0.4 (7)
Cu1—P1—C7—C12	150.3 (3)	C6—C5—C4—C3	2.4 (8)
Cu1—P1—C7—C8	−29.2 (4)	C7—P1—C13—C14	−99.6 (4)
Cu1—S1B—C19B—N2B	165.0 (13)	C7—P1—C13—C18	81.9 (4)
Cu1—S1B—C19B—N1B	−2 (2)	C7—P1—C1—C6	−172.8 (3)
P1—C13—C14—C15	−178.2 (4)	C7—P1—C1—C2	3.8 (4)
P1—C13—C18—C17	179.0 (4)	C7—C12—C11—C10	−1.4 (7)
P1—C1—C6—C5	177.3 (3)	C7—C8—C9—C10	−1.4 (9)
P1—C1—C2—C3	−176.1 (4)	C12—C7—C8—C9	0.6 (7)
P1—C7—C12—C11	−178.7 (4)	C2—C1—C6—C5	0.4 (7)
P1—C7—C8—C9	−179.9 (4)	C8—C7—C12—C11	0.8 (7)
C13—P1—C1—C6	78.6 (4)	C14—C13—C18—C17	0.5 (7)
C13—P1—C1—C2	−104.8 (4)	C18—C13—C14—C15	0.2 (7)
C13—P1—C7—C12	25.8 (4)	C18—C17—C16—C15	1.3 (8)
C13—P1—C7—C8	−153.7 (4)	C5—C4—C3—C2	−1.5 (9)
C13—C14—C15—C16	−0.2 (8)	C17—C16—C15—C14	−0.6 (8)
C13—C18—C17—C16	−1.3 (7)	C11—C10—C9—C8	0.8 (9)
C1—P1—C13—C14	9.4 (4)	C9—C10—C11—C12	0.6 (8)

Symmetry code: (i) −x+4, −y−3, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···I1^ii	0.86	2.93	3.7738 (4)	166
N2—H2A···S1A^iii	0.86	2.76	3.3753 (3)	129
N2—H2B···I1^iv	0.86	2.91	3.7094 (4)	153

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