Synthesis, characterization and crystal structures of the bidentate Schiff base N,N′-bis­(2-nitro­cinnamaldehyde)­ethyl­enedi­amine and its complex with CuNCS and tri­phenyl­phosphane

Reaction of copper(I) thio­cyanate and tri­phenyl­phosphane with the bidentate Schiff base N,N′-bis­(trans-2-nitro­cinnamaldehyde)­ethyl­enedi­amine {Nca₂en, (1); systematic name (1E,1′E,2E,2′E)-N,N′-(ethane-1,2-di­yl)bis­[3-(2-nitro­phen­yl)prop-2-en-1-imine]}, C₂₀H₁₈N₄O₄, in a 1:1:1 molar ratio in aceto­nitrile resulted in the formation of the complex {(1E,1′E,2E,2′E)-N,N′-(ethane-1,2-di­yl)bis­[3-(2-nitro­phen­yl)prop-2-en-1-imine]-κ²N,N′}(thio­cyanato-κN)(tri­phenyl­phosphane-κP)copper(I)], [Cu(NCS)(C₂₀H₁₈N₄O₄)(C₁₈H₁₅P)] or [Cu(NCS)(Nca₂en)(PPh₃)], (2). The Schiff base and copper(I) complex have been characterized by elemental analyses, IR, electronic and ¹H NMR spectroscopy, and X-ray crystallography [from synchrotron data for (1)]. The mol­ecule of (1) lies on a crystallographic inversion centre, with a trans conformation for the ethyl­enedi­amine unit, and displays significant twists from coplanarity of its nitro group, aromatic ring, conjugated chain and especially ethyl­enedi­amine segments. It acts as a bidentate ligand coordinating via the imine N atoms to the Cu^I atom in complex (2), in which the ethyl­enedi­amine unit necessarily adopts a somewhat flattened gauche conformation, resulting in a rather bowed shape overall for the ligand. The NCS⁻ ligand is coordinated through its N atom. The geometry around the Cu^I atom is distorted tetra­hedral, with a small N—Cu—N bite angle of 81.56 (12)° and an enlarged opposite angle of 117.29 (9)° for SCN—Cu—P. Comparisons are made with the analogous Schiff base having no nitro substituents and with metal complexes of both ligands.

Computing details

Data collection: APEX2 (Bruker, 2006) for (1); SMART (Bruker, 2006) for (2). Cell refinement: APEX2 (Bruker, 2006) for (1); SAINT (Bruker, 2006) for (2). Data reduction: APEX2 (Bruker, 2006) for (1); SAINT (Bruker, 2006) for (2). For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2012). Software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015) and local programs for (1); SHELXL2014 (Sheldrick, 2015) and local programs for (2).

(1) (E,E)-N,N'-Bis[(E)-3-(2-nitrophenyl)prop-2-en-1-ylidene]ethane-1,2-diamine

Crystal data

C20H18N4O4	F(000) = 396
Mr = 378.38	Dx = 1.425 Mg m^−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.6727 Å
a = 11.441 (7) Å	Cell parameters from 667 reflections
b = 3.781 (2) Å	θ = 3.8–24.9°
c = 20.553 (12) Å	µ = 0.10 mm^−1
β = 97.444 (10)°	T = 120 K
V = 881.6 (9) Å^3	Plate, colourless
Z = 2	0.10 × 0.08 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer	2804 reflections with I > 2σ(I)
Radiation source: Daresbury SRS station 9.8	Rint = 0.042
thin–slice ω scans	θmax = 24.9°, θmin = 3.8°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008a)	h = −14→14
Tmin = 0.90, Tmax = 1.00	k = −4→4
8304 measured reflections	l = −25→25
3085 independent 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.125	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0714P)^2] where P = (Fo^2 + 2Fc^2)/3
3085 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.19 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. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq
C1	0.9926 (2)	0.5701 (7)	0.53409 (11)	0.0227 (6)
H1A	1.0109	0.3807	0.5671	0.027*
H1B	1.0479	0.7686	0.5456	0.027*
C2	0.8147 (2)	0.5585 (6)	0.57802 (11)	0.0216 (5)
H2	0.8516	0.3868	0.6076	0.026*
C3	0.6941 (2)	0.6670 (6)	0.58311 (11)	0.0216 (5)
H3	0.6570	0.8293	0.5517	0.026*
C4	0.6331 (2)	0.5488 (6)	0.62995 (11)	0.0207 (6)
H4	0.6704	0.3840	0.6608	0.025*
C5	0.5119 (2)	0.6585 (6)	0.63654 (11)	0.0205 (6)
C6	0.4326 (2)	0.7507 (6)	0.58151 (11)	0.0230 (6)
H6	0.4586	0.7426	0.5395	0.028*
C7	0.3179 (2)	0.8534 (7)	0.58595 (12)	0.0249 (6)
H7	0.2672	0.9197	0.5476	0.030*
C8	0.2772 (2)	0.8591 (7)	0.64661 (11)	0.0248 (6)
H8	0.1985	0.9302	0.6499	0.030*
C9	0.3508 (2)	0.7616 (7)	0.70205 (12)	0.0241 (6)
H9	0.3229	0.7601	0.7436	0.029*
C10	0.4660 (2)	0.6657 (6)	0.69655 (11)	0.0209 (6)
N1	0.87125 (19)	0.6910 (6)	0.53446 (9)	0.0219 (5)
N2	0.5416 (2)	0.5838 (6)	0.75785 (10)	0.0263 (5)
O1	0.49714 (18)	0.4252 (6)	0.80087 (8)	0.0371 (5)
O2	0.64449 (17)	0.6823 (6)	0.76401 (8)	0.0362 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0171 (13)	0.0241 (13)	0.0275 (13)	0.0013 (11)	0.0055 (11)	0.0015 (10)
C2	0.0213 (13)	0.0208 (13)	0.0223 (12)	0.0015 (11)	0.0017 (11)	−0.0025 (10)
C3	0.0207 (14)	0.0212 (13)	0.0228 (11)	0.0016 (11)	0.0027 (10)	−0.0005 (10)
C4	0.0186 (14)	0.0210 (13)	0.0218 (12)	0.0007 (11)	0.0006 (10)	−0.0017 (10)
C5	0.0209 (14)	0.0168 (13)	0.0244 (12)	−0.0023 (11)	0.0054 (11)	−0.0011 (9)
C6	0.0232 (14)	0.0232 (14)	0.0233 (12)	−0.0018 (11)	0.0053 (12)	−0.0005 (10)
C7	0.0205 (14)	0.0270 (14)	0.0267 (12)	−0.0007 (13)	0.0016 (11)	0.0021 (11)
C8	0.0156 (13)	0.0262 (15)	0.0332 (13)	0.0016 (11)	0.0054 (11)	−0.0003 (11)
C9	0.0203 (14)	0.0288 (14)	0.0245 (12)	−0.0045 (12)	0.0084 (11)	−0.0008 (11)
C10	0.0203 (14)	0.0206 (14)	0.0213 (11)	−0.0027 (11)	0.0010 (11)	−0.0006 (10)
N1	0.0176 (11)	0.0247 (11)	0.0241 (10)	0.0012 (9)	0.0053 (9)	−0.0012 (9)
N2	0.0209 (12)	0.0350 (13)	0.0238 (11)	0.0026 (10)	0.0061 (10)	−0.0022 (9)
O1	0.0322 (12)	0.0533 (13)	0.0270 (9)	0.0045 (11)	0.0087 (9)	0.0126 (9)
O2	0.0169 (10)	0.0620 (14)	0.0295 (9)	−0.0023 (10)	0.0018 (8)	−0.0076 (9)

Geometric parameters (Å, º)

C1—C1^i	1.528 (5)	C5—C10	1.402 (3)
C1—H1A	0.990	C6—H6	0.950
C1—H1B	0.990	C6—C7	1.383 (4)
C1—N1	1.463 (3)	C7—H7	0.950
C2—H2	0.950	C7—C8	1.386 (3)
C2—C3	1.456 (4)	C8—H8	0.950
C2—N1	1.273 (3)	C8—C9	1.376 (4)
C3—H3	0.950	C9—H9	0.950
C3—C4	1.337 (3)	C9—C10	1.386 (4)
C4—H4	0.950	C10—N2	1.466 (3)
C4—C5	1.471 (3)	N2—O1	1.232 (3)
C5—C6	1.399 (3)	N2—O2	1.225 (3)
C1^i—C1—H1A	109.8	C5—C6—C7	122.5 (2)
C1^i—C1—H1B	109.8	H6—C6—C7	118.7
C1^i—C1—N1	109.3 (2)	C6—C7—H7	120.1
H1A—C1—H1B	108.3	C6—C7—C8	119.7 (2)
H1A—C1—N1	109.8	H7—C7—C8	120.1
H1B—C1—N1	109.8	C7—C8—H8	120.0
H2—C2—C3	119.6	C7—C8—C9	120.0 (3)
H2—C2—N1	119.6	H8—C8—C9	120.0
C3—C2—N1	120.8 (2)	C8—C9—H9	120.4
C2—C3—H3	118.5	C8—C9—C10	119.3 (2)
C2—C3—C4	123.0 (2)	H9—C9—C10	120.4
H3—C3—C4	118.5	C5—C10—C9	123.0 (2)
C3—C4—H4	118.0	C5—C10—N2	120.4 (2)
C3—C4—C5	123.9 (2)	C9—C10—N2	116.5 (2)
H4—C4—C5	118.0	C1—N1—C2	116.7 (2)
C4—C5—C6	121.1 (2)	C10—N2—O1	117.8 (2)
C4—C5—C10	123.5 (2)	C10—N2—O2	118.5 (2)
C6—C5—C10	115.4 (2)	O1—N2—O2	123.7 (2)
C5—C6—H6	118.7
N1—C2—C3—C4	−176.6 (2)	C4—C5—C10—C9	−178.4 (2)
C2—C3—C4—C5	179.1 (2)	C4—C5—C10—N2	4.1 (4)
C3—C4—C5—C6	30.9 (4)	C6—C5—C10—C9	−0.9 (4)
C3—C4—C5—C10	−151.6 (2)	C6—C5—C10—N2	−178.3 (2)
C4—C5—C6—C7	179.7 (2)	C3—C2—N1—C1	178.9 (2)
C10—C5—C6—C7	2.0 (4)	C1^i—C1—N1—C2	125.2 (3)
C5—C6—C7—C8	−1.5 (4)	C5—C10—N2—O1	−144.7 (2)
C6—C7—C8—C9	−0.2 (4)	C5—C10—N2—O2	36.7 (3)
C7—C8—C9—C10	1.4 (4)	C9—C10—N2—O1	37.7 (3)
C8—C9—C10—C5	−0.8 (4)	C9—C10—N2—O2	−140.9 (2)
C8—C9—C10—N2	176.7 (2)	N1^i—C1^i—C1—N1	180

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2	0.95	2.45	2.788 (3)	101
C4—H4···O2^ii	0.95	2.57	3.422 (3)	149
C7—H7···N1^iii	0.95	2.61	3.519 (4)	160
C8—H8···O1^iv	0.95	2.57	3.458 (4)	155
C9—H9···O1	0.95	2.52	2.769 (3)	95

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

(2) {(1E,1'E,2E,2'E)-N,N'-(Ethane-1,2-diyl)bis[3-(2-nitrophenyl)prop-2-en-1-imine]-κ²N,N'}(thiocyanato-κN)(triphenylphosphane-κP)copper(I)]

Crystal data

[Cu(NCS)(C20H18N4O4)(C18H15P)]	Z = 2
Mr = 762.27	F(000) = 788
Triclinic, P1	Dx = 1.399 Mg m^−3
a = 9.1038 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.8186 (12) Å	Cell parameters from 5264 reflections
c = 15.2972 (14) Å	θ = 2.3–26.3°
α = 104.7831 (14)°	µ = 0.75 mm^−1
β = 102.6778 (14)°	T = 150 K
γ = 91.3000 (14)°	Block, orange
V = 1809.0 (3) Å^3	0.34 × 0.30 × 0.30 mm

Data collection

Bruker SMART 1K CCD diffractometer	6786 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.025
thin–slice ω scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→11
Tmin = 0.75, Tmax = 0.81	k = −17→17
14710 measured reflections	l = −19→19
7308 independent 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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 1.35	w = 1/[σ^2(Fo^2) + (0.0213P)^2 + 4.1072P] where P = (Fo^2 + 2Fc^2)/3
7308 reflections	(Δ/σ)max < 0.001
460 parameters	Δρmax = 0.76 e Å^−3
0 restraints	Δρmin = −0.65 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
Cu1	0.43497 (5)	0.33281 (3)	0.31978 (3)	0.01539 (12)
N1	1.1164 (4)	0.1899 (3)	0.6447 (3)	0.0363 (9)
O1	1.0179 (4)	0.2216 (3)	0.6828 (2)	0.0429 (8)
O2	1.2495 (5)	0.1992 (4)	0.6860 (3)	0.0940 (19)
N2	0.4633 (4)	0.3011 (2)	0.4500 (2)	0.0206 (7)
O3	0.2966 (4)	0.8025 (2)	0.2733 (2)	0.0371 (7)
O4	0.1522 (4)	0.8761 (2)	0.1817 (3)	0.0429 (8)
N3	0.3104 (3)	0.4428 (2)	0.3803 (2)	0.0177 (6)
N4	0.2166 (4)	0.8030 (3)	0.1977 (3)	0.0306 (8)
C1	1.0814 (5)	0.1430 (3)	0.5439 (3)	0.0248 (8)
C2	1.1994 (5)	0.0993 (3)	0.5090 (3)	0.0311 (9)
H2	1.2956	0.1016	0.5495	0.037*
C3	1.1776 (5)	0.0526 (3)	0.4158 (3)	0.0342 (10)
H3	1.2576	0.0215	0.3916	0.041*
C4	1.0375 (5)	0.0515 (3)	0.3578 (3)	0.0351 (10)
H4	1.0210	0.0195	0.2932	0.042*
C5	0.9209 (5)	0.0968 (3)	0.3930 (3)	0.0290 (9)
H5	0.8260	0.0958	0.3516	0.035*
C6	0.9384 (4)	0.1440 (3)	0.4876 (3)	0.0241 (8)
C7	0.8048 (4)	0.1859 (3)	0.5189 (3)	0.0241 (8)
H7	0.7916	0.1806	0.5774	0.029*
C8	0.7016 (4)	0.2309 (3)	0.4697 (3)	0.0234 (8)
H8	0.7172	0.2410	0.4132	0.028*
C9	0.5667 (4)	0.2648 (3)	0.4997 (3)	0.0230 (8)
H9	0.5550	0.2597	0.5586	0.028*
C10	0.3289 (4)	0.3330 (3)	0.4839 (3)	0.0250 (8)
H10A	0.3443	0.3328	0.5500	0.030*
H10B	0.2402	0.2858	0.4475	0.030*
C11	0.3008 (5)	0.4383 (3)	0.4740 (3)	0.0244 (8)
H11A	0.1995	0.4550	0.4839	0.029*
H11B	0.3771	0.4878	0.5213	0.029*
C12	0.2507 (4)	0.5137 (3)	0.3497 (3)	0.0211 (8)
H12	0.1976	0.5593	0.3867	0.025*
C13	0.2612 (4)	0.5268 (3)	0.2607 (3)	0.0224 (8)
H13	0.3127	0.4804	0.2233	0.027*
C14	0.2011 (4)	0.6016 (3)	0.2294 (3)	0.0228 (8)
H14	0.1545	0.6487	0.2695	0.027*
C15	0.2005 (4)	0.6177 (3)	0.1380 (3)	0.0227 (8)
C16	0.1887 (4)	0.5350 (3)	0.0609 (3)	0.0275 (9)
H16	0.1907	0.4694	0.0698	0.033*
C17	0.1742 (5)	0.5464 (3)	−0.0282 (3)	0.0303 (9)
H17	0.1672	0.4891	−0.0792	0.036*
C18	0.1698 (5)	0.6411 (4)	−0.0425 (3)	0.0338 (10)
H18	0.1583	0.6486	−0.1036	0.041*
C19	0.1820 (5)	0.7246 (3)	0.0312 (3)	0.0325 (10)
H19	0.1798	0.7899	0.0216	0.039*
C20	0.1974 (4)	0.7119 (3)	0.1196 (3)	0.0254 (8)
P1	0.31569 (10)	0.21748 (6)	0.19398 (6)	0.01374 (19)
C21	0.3989 (4)	0.0974 (3)	0.1825 (2)	0.0152 (7)
C22	0.4603 (4)	0.0721 (3)	0.2646 (3)	0.0204 (8)
H22	0.4588	0.1177	0.3225	0.025*
C23	0.5239 (4)	−0.0185 (3)	0.2633 (3)	0.0268 (9)
H23	0.5651	−0.0348	0.3199	0.032*
C24	0.5267 (4)	−0.0849 (3)	0.1791 (3)	0.0281 (9)
H24	0.5708	−0.1467	0.1779	0.034*
C25	0.4658 (4)	−0.0616 (3)	0.0971 (3)	0.0249 (8)
H25	0.4668	−0.1078	0.0394	0.030*
C26	0.4026 (4)	0.0294 (3)	0.0985 (3)	0.0193 (7)
H26	0.3617	0.0452	0.0416	0.023*
C27	0.3137 (4)	0.2494 (3)	0.0845 (2)	0.0165 (7)
C28	0.4350 (4)	0.3106 (3)	0.0812 (3)	0.0224 (8)
H28	0.5170	0.3320	0.1341	0.027*
C29	0.4374 (4)	0.3407 (3)	0.0016 (3)	0.0259 (8)
H29	0.5204	0.3831	0.0006	0.031*
C30	0.3196 (4)	0.3093 (3)	−0.0762 (3)	0.0254 (8)
H30	0.3213	0.3300	−0.1307	0.030*
C31	0.1996 (4)	0.2479 (3)	−0.0743 (3)	0.0256 (8)
H31	0.1193	0.2251	−0.1280	0.031*
C32	0.1955 (4)	0.2192 (3)	0.0058 (3)	0.0213 (8)
H32	0.1109	0.1784	0.0069	0.026*
C33	0.1166 (4)	0.1808 (3)	0.1830 (2)	0.0155 (7)
C34	0.0477 (4)	0.0854 (3)	0.1332 (3)	0.0203 (8)
H34	0.1052	0.0361	0.1039	0.024*
C35	−0.1039 (4)	0.0623 (3)	0.1264 (3)	0.0261 (9)
H35	−0.1498	−0.0029	0.0929	0.031*
C36	−0.1894 (5)	0.1347 (3)	0.1684 (3)	0.0303 (9)
H36	−0.2941	0.1196	0.1622	0.036*
C37	−0.1212 (4)	0.2277 (3)	0.2188 (3)	0.0255 (8)
H37	−0.1785	0.2763	0.2491	0.031*
C38	0.0300 (4)	0.2514 (3)	0.2260 (3)	0.0199 (8)
H38	0.0754	0.3165	0.2606	0.024*
N5	0.6208 (4)	0.4041 (2)	0.3132 (2)	0.0232 (7)
C39	0.7137 (4)	0.4576 (3)	0.3062 (3)	0.0245 (8)
S1	0.84730 (16)	0.53232 (11)	0.29704 (10)	0.0519 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0173 (2)	0.0141 (2)	0.0127 (2)	0.00109 (16)	0.00241 (16)	0.00084 (16)
N1	0.039 (2)	0.036 (2)	0.0279 (19)	0.0180 (17)	−0.0045 (17)	0.0070 (16)
O1	0.0356 (18)	0.061 (2)	0.0277 (17)	0.0044 (16)	0.0083 (14)	0.0030 (15)
O2	0.062 (3)	0.140 (5)	0.047 (2)	0.061 (3)	−0.017 (2)	−0.013 (3)
N2	0.0249 (16)	0.0189 (15)	0.0177 (15)	0.0019 (13)	0.0046 (13)	0.0047 (12)
O3	0.0451 (19)	0.0303 (16)	0.0408 (19)	0.0021 (14)	0.0158 (16)	0.0134 (14)
O4	0.0435 (19)	0.0250 (16)	0.071 (2)	0.0142 (14)	0.0235 (17)	0.0219 (16)
N3	0.0194 (15)	0.0146 (14)	0.0187 (15)	0.0028 (12)	0.0056 (12)	0.0025 (12)
N4	0.0294 (19)	0.0238 (18)	0.049 (2)	0.0043 (15)	0.0212 (18)	0.0174 (16)
C1	0.029 (2)	0.0224 (19)	0.026 (2)	0.0082 (16)	0.0051 (17)	0.0117 (16)
C2	0.030 (2)	0.031 (2)	0.038 (2)	0.0086 (18)	0.0086 (19)	0.0176 (19)
C3	0.041 (3)	0.035 (2)	0.041 (3)	0.017 (2)	0.025 (2)	0.020 (2)
C4	0.052 (3)	0.039 (2)	0.022 (2)	0.014 (2)	0.019 (2)	0.0135 (19)
C5	0.033 (2)	0.037 (2)	0.022 (2)	0.0062 (18)	0.0069 (17)	0.0161 (18)
C6	0.030 (2)	0.0219 (19)	0.025 (2)	0.0037 (16)	0.0072 (17)	0.0139 (16)
C7	0.028 (2)	0.026 (2)	0.0189 (19)	0.0023 (16)	0.0053 (16)	0.0071 (16)
C8	0.025 (2)	0.026 (2)	0.0177 (18)	0.0013 (16)	0.0007 (15)	0.0067 (15)
C9	0.030 (2)	0.0215 (19)	0.0175 (18)	0.0010 (16)	0.0047 (16)	0.0067 (15)
C10	0.028 (2)	0.031 (2)	0.0198 (19)	0.0021 (17)	0.0085 (16)	0.0106 (16)
C11	0.028 (2)	0.028 (2)	0.0181 (19)	0.0069 (17)	0.0101 (16)	0.0036 (16)
C12	0.0225 (19)	0.0156 (17)	0.0227 (19)	0.0000 (15)	0.0071 (15)	−0.0010 (14)
C13	0.0226 (19)	0.0203 (19)	0.027 (2)	0.0065 (15)	0.0094 (16)	0.0069 (15)
C14	0.0203 (19)	0.0177 (18)	0.032 (2)	0.0037 (15)	0.0094 (16)	0.0068 (16)
C15	0.0173 (18)	0.025 (2)	0.030 (2)	0.0062 (15)	0.0073 (16)	0.0128 (16)
C16	0.023 (2)	0.026 (2)	0.037 (2)	0.0080 (16)	0.0078 (18)	0.0148 (18)
C17	0.026 (2)	0.036 (2)	0.030 (2)	0.0058 (18)	0.0046 (18)	0.0122 (19)
C18	0.027 (2)	0.050 (3)	0.034 (2)	0.012 (2)	0.0094 (19)	0.024 (2)
C19	0.026 (2)	0.035 (2)	0.049 (3)	0.0113 (18)	0.013 (2)	0.027 (2)
C20	0.0186 (19)	0.024 (2)	0.039 (2)	0.0076 (16)	0.0103 (17)	0.0142 (17)
P1	0.0133 (4)	0.0131 (4)	0.0143 (4)	0.0019 (3)	0.0034 (3)	0.0025 (3)
C21	0.0091 (15)	0.0145 (16)	0.0218 (18)	0.0012 (13)	0.0048 (14)	0.0034 (14)
C22	0.0216 (18)	0.0207 (18)	0.0185 (18)	0.0034 (15)	0.0047 (15)	0.0041 (15)
C23	0.027 (2)	0.026 (2)	0.029 (2)	0.0074 (17)	0.0001 (17)	0.0146 (17)
C24	0.026 (2)	0.0162 (18)	0.044 (3)	0.0082 (16)	0.0129 (19)	0.0075 (17)
C25	0.028 (2)	0.0206 (19)	0.027 (2)	0.0019 (16)	0.0169 (17)	−0.0016 (16)
C26	0.0183 (18)	0.0206 (18)	0.0191 (18)	0.0035 (14)	0.0062 (15)	0.0036 (14)
C27	0.0178 (17)	0.0181 (17)	0.0138 (17)	0.0051 (14)	0.0049 (14)	0.0031 (14)
C28	0.0219 (19)	0.026 (2)	0.0174 (18)	0.0015 (16)	0.0031 (15)	0.0046 (15)
C29	0.024 (2)	0.028 (2)	0.030 (2)	0.0008 (16)	0.0127 (17)	0.0101 (17)
C30	0.030 (2)	0.030 (2)	0.0212 (19)	0.0132 (17)	0.0126 (17)	0.0109 (16)
C31	0.023 (2)	0.035 (2)	0.0173 (19)	0.0056 (17)	0.0020 (16)	0.0065 (16)
C32	0.0185 (18)	0.0231 (19)	0.0218 (19)	0.0020 (15)	0.0036 (15)	0.0060 (15)
C33	0.0140 (16)	0.0172 (17)	0.0166 (17)	0.0007 (14)	0.0028 (14)	0.0076 (14)
C34	0.0181 (18)	0.0226 (19)	0.0211 (19)	0.0032 (15)	0.0058 (15)	0.0059 (15)
C35	0.023 (2)	0.028 (2)	0.023 (2)	−0.0063 (16)	−0.0011 (16)	0.0062 (16)
C36	0.0188 (19)	0.037 (2)	0.041 (3)	0.0043 (17)	0.0090 (18)	0.019 (2)
C37	0.0221 (19)	0.029 (2)	0.029 (2)	0.0092 (16)	0.0111 (17)	0.0095 (17)
C38	0.0185 (18)	0.0181 (18)	0.0250 (19)	0.0040 (14)	0.0078 (15)	0.0067 (15)
N5	0.0208 (16)	0.0238 (17)	0.0216 (17)	−0.0042 (14)	0.0055 (13)	−0.0001 (13)
C39	0.024 (2)	0.028 (2)	0.0189 (19)	0.0036 (17)	0.0079 (16)	−0.0015 (16)
S1	0.0490 (8)	0.0519 (8)	0.0543 (8)	−0.0218 (6)	0.0266 (7)	0.0030 (6)

Geometric parameters (Å, º)

Cu1—N2	2.109 (3)	C17—H17	0.950
Cu1—N3	2.067 (3)	C17—C18	1.380 (6)
Cu1—P1	2.2049 (10)	C18—H18	0.950
Cu1—N5	1.973 (3)	C18—C19	1.374 (6)
N1—O1	1.205 (5)	C19—H19	0.950
N1—O2	1.225 (5)	C19—C20	1.386 (6)
N1—C1	1.471 (5)	P1—C21	1.824 (3)
N2—C9	1.272 (5)	P1—C27	1.834 (4)
N2—C10	1.465 (5)	P1—C33	1.831 (3)
O3—N4	1.225 (5)	C21—C22	1.391 (5)
O4—N4	1.230 (4)	C21—C26	1.393 (5)
N3—C11	1.471 (5)	C22—H22	0.950
N3—C12	1.273 (5)	C22—C23	1.389 (5)
N4—C20	1.474 (5)	C23—H23	0.950
C1—C2	1.386 (6)	C23—C24	1.383 (6)
C1—C6	1.398 (5)	C24—H24	0.950
C2—H2	0.950	C24—C25	1.376 (6)
C2—C3	1.374 (6)	C25—H25	0.950
C3—H3	0.950	C25—C26	1.391 (5)
C3—C4	1.383 (6)	C26—H26	0.950
C4—H4	0.950	C27—C28	1.393 (5)
C4—C5	1.385 (6)	C27—C32	1.391 (5)
C5—H5	0.950	C28—H28	0.950
C5—C6	1.399 (6)	C28—C29	1.389 (5)
C6—C7	1.479 (5)	C29—H29	0.950
C7—H7	0.950	C29—C30	1.383 (6)
C7—C8	1.338 (5)	C30—H30	0.950
C8—H8	0.950	C30—C31	1.378 (6)
C8—C9	1.449 (5)	C31—H31	0.950
C9—H9	0.950	C31—C32	1.388 (5)
C10—H10A	0.990	C32—H32	0.950
C10—H10B	0.990	C33—C34	1.397 (5)
C10—C11	1.522 (5)	C33—C38	1.393 (5)
C11—H11A	0.990	C34—H34	0.950
C11—H11B	0.990	C34—C35	1.385 (5)
C12—H12	0.950	C35—H35	0.950
C12—C13	1.442 (5)	C35—C36	1.395 (6)
C13—H13	0.950	C36—H36	0.950
C13—C14	1.326 (5)	C36—C37	1.371 (6)
C14—H14	0.950	C37—H37	0.950
C14—C15	1.470 (5)	C37—C38	1.382 (5)
C15—C16	1.400 (6)	C38—H38	0.950
C15—C20	1.399 (5)	N5—C39	1.151 (5)
C16—H16	0.950	C39—S1	1.629 (4)
C16—C17	1.390 (6)
N2—Cu1—N3	81.56 (12)	C16—C17—C18	120.0 (4)
N2—Cu1—P1	118.76 (9)	H17—C17—C18	120.0
N2—Cu1—N5	110.10 (13)	C17—C18—H18	119.8
N3—Cu1—P1	117.58 (9)	C17—C18—C19	120.4 (4)
N3—Cu1—N5	105.80 (12)	H18—C18—C19	119.8
P1—Cu1—N5	117.29 (9)	C18—C19—H19	120.6
O1—N1—O2	122.5 (4)	C18—C19—C20	118.8 (4)
O1—N1—C1	120.5 (4)	H19—C19—C20	120.6
O2—N1—C1	116.9 (4)	N4—C20—C15	119.2 (4)
Cu1—N2—C9	134.3 (3)	N4—C20—C19	117.6 (4)
Cu1—N2—C10	106.0 (2)	C15—C20—C19	123.2 (4)
C9—N2—C10	119.7 (3)	Cu1—P1—C21	112.49 (11)
Cu1—N3—C11	112.5 (2)	Cu1—P1—C27	114.52 (12)
Cu1—N3—C12	129.1 (3)	Cu1—P1—C33	118.05 (12)
C11—N3—C12	118.2 (3)	C21—P1—C27	105.11 (16)
O3—N4—O4	124.0 (4)	C21—P1—C33	102.08 (15)
O3—N4—C20	118.9 (3)	C27—P1—C33	103.01 (16)
O4—N4—C20	117.1 (4)	P1—C21—C22	116.6 (3)
N1—C1—C2	115.7 (4)	P1—C21—C26	125.0 (3)
N1—C1—C6	121.6 (4)	C22—C21—C26	118.3 (3)
C2—C1—C6	122.6 (4)	C21—C22—H22	119.4
C1—C2—H2	119.9	C21—C22—C23	121.1 (3)
C1—C2—C3	120.2 (4)	H22—C22—C23	119.4
H2—C2—C3	119.9	C22—C23—H23	120.2
C2—C3—H3	120.5	C22—C23—C24	119.6 (4)
C2—C3—C4	119.0 (4)	H23—C23—C24	120.2
H3—C3—C4	120.5	C23—C24—H24	119.9
C3—C4—H4	119.7	C23—C24—C25	120.2 (3)
C3—C4—C5	120.5 (4)	H24—C24—C25	119.9
H4—C4—C5	119.7	C24—C25—H25	119.9
C4—C5—H5	118.9	C24—C25—C26	120.1 (3)
C4—C5—C6	122.1 (4)	H25—C25—C26	119.9
H5—C5—C6	118.9	C21—C26—C25	120.6 (3)
C1—C6—C5	115.6 (4)	C21—C26—H26	119.7
C1—C6—C7	126.5 (4)	C25—C26—H26	119.7
C5—C6—C7	117.9 (4)	P1—C27—C28	118.0 (3)
C6—C7—H7	118.0	P1—C27—C32	123.8 (3)
C6—C7—C8	124.0 (4)	C28—C27—C32	118.2 (3)
H7—C7—C8	118.0	C27—C28—H28	119.6
C7—C8—H8	118.8	C27—C28—C29	120.8 (3)
C7—C8—C9	122.4 (4)	H28—C28—C29	119.6
H8—C8—C9	118.8	C28—C29—H29	119.9
N2—C9—C8	122.4 (3)	C28—C29—C30	120.2 (4)
N2—C9—H9	118.8	H29—C29—C30	119.9
C8—C9—H9	118.8	C29—C30—H30	120.2
N2—C10—H10A	109.9	C29—C30—C31	119.6 (4)
N2—C10—H10B	109.9	H30—C30—C31	120.2
N2—C10—C11	109.1 (3)	C30—C31—H31	119.9
H10A—C10—H10B	108.3	C30—C31—C32	120.3 (4)
H10A—C10—C11	109.9	H31—C31—C32	119.9
H10B—C10—C11	109.9	C27—C32—C31	120.9 (4)
N3—C11—C10	109.3 (3)	C27—C32—H32	119.6
N3—C11—H11A	109.8	C31—C32—H32	119.6
N3—C11—H11B	109.8	P1—C33—C34	122.9 (3)
C10—C11—H11A	109.8	P1—C33—C38	118.4 (3)
C10—C11—H11B	109.8	C34—C33—C38	118.7 (3)
H11A—C11—H11B	108.3	C33—C34—H34	119.8
N3—C12—H12	119.0	C33—C34—C35	120.3 (3)
N3—C12—C13	122.0 (3)	H34—C34—C35	119.8
H12—C12—C13	119.0	C34—C35—H35	119.9
C12—C13—H13	119.0	C34—C35—C36	120.1 (4)
C12—C13—C14	122.0 (4)	H35—C35—C36	119.9
H13—C13—C14	119.0	C35—C36—H36	120.2
C13—C14—H14	117.2	C35—C36—C37	119.5 (4)
C13—C14—C15	125.5 (4)	H36—C36—C37	120.2
H14—C14—C15	117.2	C36—C37—H37	119.6
C14—C15—C16	119.7 (3)	C36—C37—C38	120.8 (4)
C14—C15—C20	124.2 (4)	H37—C37—C38	119.6
C16—C15—C20	115.9 (4)	C33—C38—C37	120.5 (3)
C15—C16—H16	119.2	C33—C38—H38	119.7
C15—C16—C17	121.7 (4)	C37—C38—H38	119.7
H16—C16—C17	119.2	Cu1—N5—C39	168.7 (3)
C16—C17—H17	120.0	N5—C39—S1	179.0 (4)
O1—N1—C1—C2	−173.1 (4)	O4—N4—C20—C15	−149.4 (4)
O1—N1—C1—C6	7.7 (6)	O4—N4—C20—C19	32.7 (5)
O2—N1—C1—C2	10.3 (6)	Cu1—P1—C21—C22	33.7 (3)
O2—N1—C1—C6	−168.9 (5)	Cu1—P1—C21—C26	−147.6 (3)
N1—C1—C2—C3	179.3 (4)	C27—P1—C21—C22	158.9 (3)
C6—C1—C2—C3	−1.5 (6)	C27—P1—C21—C26	−22.4 (3)
C1—C2—C3—C4	1.1 (6)	C33—P1—C21—C22	−93.8 (3)
C2—C3—C4—C5	0.0 (7)	C33—P1—C21—C26	84.9 (3)
C3—C4—C5—C6	−0.8 (7)	P1—C21—C22—C23	178.8 (3)
C4—C5—C6—C1	0.4 (6)	C26—C21—C22—C23	0.0 (5)
C4—C5—C6—C7	−177.1 (4)	C21—C22—C23—C24	0.2 (6)
N1—C1—C6—C5	179.9 (4)	C22—C23—C24—C25	−0.6 (6)
N1—C1—C6—C7	−2.8 (6)	C23—C24—C25—C26	0.8 (6)
C2—C1—C6—C5	0.7 (6)	P1—C21—C26—C25	−178.4 (3)
C2—C1—C6—C7	178.0 (4)	C22—C21—C26—C25	0.2 (5)
C1—C6—C7—C8	145.3 (4)	C24—C25—C26—C21	−0.6 (6)
C5—C6—C7—C8	−37.4 (6)	Cu1—P1—C27—C28	29.9 (3)
C6—C7—C8—C9	175.6 (4)	Cu1—P1—C27—C32	−147.6 (3)
Cu1—N2—C9—C8	−2.2 (6)	C21—P1—C27—C28	−94.0 (3)
C10—N2—C9—C8	179.4 (3)	C21—P1—C27—C32	88.5 (3)
C7—C8—C9—N2	−174.9 (4)	C33—P1—C27—C28	159.4 (3)
Cu1—N2—C10—C11	−48.3 (3)	C33—P1—C27—C32	−18.1 (3)
C9—N2—C10—C11	130.6 (4)	P1—C27—C28—C29	−177.5 (3)
Cu1—N3—C11—C10	−22.5 (4)	C32—C27—C28—C29	0.2 (5)
C12—N3—C11—C10	161.0 (3)	C27—C28—C29—C30	−0.7 (6)
N2—C10—C11—N3	47.6 (4)	C28—C29—C30—C31	0.0 (6)
Cu1—N3—C12—C13	1.0 (5)	C29—C30—C31—C32	1.2 (6)
C11—N3—C12—C13	176.9 (3)	C30—C31—C32—C27	−1.8 (6)
N3—C12—C13—C14	−178.9 (4)	P1—C27—C32—C31	178.5 (3)
C12—C13—C14—C15	−177.0 (4)	C28—C27—C32—C31	1.0 (5)
C13—C14—C15—C16	34.2 (6)	Cu1—P1—C33—C34	−151.3 (3)
C13—C14—C15—C20	−151.9 (4)	Cu1—P1—C33—C38	28.9 (3)
C14—C15—C16—C17	174.2 (4)	C21—P1—C33—C34	−27.4 (3)
C20—C15—C16—C17	−0.3 (6)	C21—P1—C33—C38	152.8 (3)
C15—C16—C17—C18	−0.5 (6)	C27—P1—C33—C34	81.4 (3)
C16—C17—C18—C19	0.9 (6)	C27—P1—C33—C38	−98.4 (3)
C17—C18—C19—C20	−0.5 (6)	P1—C33—C34—C35	−179.2 (3)
C18—C19—C20—N4	177.5 (4)	C38—C33—C34—C35	0.6 (5)
C18—C19—C20—C15	−0.4 (6)	C33—C34—C35—C36	0.7 (6)
C14—C15—C20—N4	8.7 (6)	C34—C35—C36—C37	−1.9 (6)
C14—C15—C20—C19	−173.4 (4)	C35—C36—C37—C38	1.9 (6)
C16—C15—C20—N4	−177.1 (3)	C36—C37—C38—C33	−0.7 (6)
C16—C15—C20—C19	0.7 (6)	P1—C33—C38—C37	179.2 (3)
O3—N4—C20—C15	31.9 (5)	C34—C33—C38—C37	−0.5 (5)
O3—N4—C20—C19	−146.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.95	2.31	2.640 (6)	100
C7—H7···O1	0.95	2.28	2.735 (5)	109
C7—H7···O3^i	0.95	2.54	3.468 (5)	165
C11—H11B···N5^i	0.99	2.59	3.339 (5)	133
C14—H14···O3	0.95	2.44	2.757 (5)	99
C14—H14···O1^i	0.95	2.48	3.387 (5)	159
C19—H19···O4	0.95	2.51	2.757 (6)	95
C24—H24···O2^ii	0.95	2.62	3.297 (6)	129
C28—H28···N5	0.95	2.61	3.471 (5)	151

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