Intra- and intermolecular interactions in a series of chlorido-tri­carbonyl-di­aza­butadienerhenium(I) complexes: structural and theoretical studies

A series of new chlorido-tri­carbonylrhenium(I) complexes bearing alkyl-substituted diazabutadiene (DAB) ligands, namely N,N′-bis­(2,4-di­methyl­benzene)-1,4-di­aza­butadiene (L1), N,N′-bis­(2,4-di­methyl­benzene)-2,3-di­methyl-1,4-di­aza­butadiene (L2), N,N′-bis­(2,4,6-tri­methyl­benzene)-2,3-di­methyl-1,4-di­aza­butadiene (L3) and N,N′-bis­(2,6-diiso­propyl­benzene)-1,4-di­azabutadiene (L4), were synthesized and investigated. The crystal structures have been fully characterized by X-ray diffraction and spectroscopic methods. Density functional theory, natural bond orbital and non-covalent interaction index methods have been used to study the optimized geometry in the gas phase and intra- and intermolecular interactions in the complexes, respectively. The most important studied interactions in these metal carbonyl complexes are n→π*, n→σ* and π→π*. Among complexes 1–4, only 2 shows interesting intermolecular n→π* interactions due to lp(C[triple bond]O)...π* and lp(Cl)...π* (lp = lone pair) contacts.

Computing details

Data collection: CrysAlis PRO 1.171.38.43 for complex1, complex4; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for complex2; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for complex3. Cell refinement: CrysAlis PRO 1.171.38.43 for complex1, complex4; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for complex2; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for complex3. Data reduction: CrysAlis PRO 1.171.38.43 for complex1, complex4; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for complex2; CrysAlis PRO 1.171.38.46 (Rigaku OD, 2015) for complex3. Program(s) used to solve structure: OLEX2 for complex1, complex4; xt for complex2, complex3. Program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016) for complex1, complex4; SHELXL2014/7 (Sheldrick, 2014) for complex2, complex3. Molecular graphics: SHELXTL for complex1, complex4; XP for complex2, complex3. For all structures, software used to prepare material for publication: SHELXTL.

(complex1)

Crystal data

C21H20ClN2O3Re	F(000) = 1104
Mr = 570.04	Dx = 1.810 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
a = 7.2923 (3) Å	Cell parameters from 10674 reflections
b = 23.440 (2) Å	θ = 3.3–72.5°
c = 12.7500 (11) Å	µ = 12.74 mm^−1
β = 106.337 (8)°	T = 150 K
V = 2091.3 (3) Å^3	Block, dark-brown
Z = 4	0.25 × 0.15 × 0.10 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	4126 independent reflections
Radiation source: micro-focus sealed X-ray tube	3878 reflections with I > 2σ(I)
Detector resolution: 8.1150 pixels mm^-1	Rint = 0.033
ω scans	θmax = 73.1°, θmin = 3.8°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→5
Tmin = 0.384, Tmax = 1.000	k = −28→28
13920 measured reflections	l = −11→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.0261P)^2 + 0.8555P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.009
4126 reflections	Δρmax = 0.56 e Å^−3
257 parameters	Δρmin = −0.75 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
C1	0.5980 (4)	0.72967 (13)	0.4321 (3)	0.0229 (6)
C2	0.5907 (4)	0.68598 (13)	0.6284 (2)	0.0245 (6)
C3	0.5943 (4)	0.79913 (13)	0.6007 (3)	0.0257 (6)
C4	0.2285 (4)	0.61804 (12)	0.4427 (2)	0.0204 (5)
C5	0.2381 (4)	0.59668 (13)	0.5464 (3)	0.0260 (6)
H5	0.241009	0.621697	0.603492	0.031*
C6	0.2432 (4)	0.53866 (14)	0.5644 (3)	0.0294 (7)
H6	0.247944	0.524912	0.633517	0.035*
C7	0.2412 (4)	0.50042 (13)	0.4811 (3)	0.0291 (7)
C8	0.2348 (4)	0.52237 (14)	0.3791 (3)	0.0303 (7)
H8	0.235533	0.496994	0.323145	0.036*
C9	0.2273 (4)	0.58082 (13)	0.3564 (3)	0.0261 (6)
C10	0.0795 (4)	0.70126 (12)	0.3575 (2)	0.0210 (6)
H10	−0.019562	0.679080	0.315090	0.025*
C11	0.0814 (4)	0.76306 (12)	0.3457 (2)	0.0211 (6)
H11	−0.016991	0.782309	0.295922	0.025*
C12	0.2413 (4)	0.85025 (12)	0.3955 (2)	0.0198 (5)
C13	0.1081 (4)	0.88823 (13)	0.4176 (2)	0.0230 (6)
C14	0.1372 (5)	0.94615 (14)	0.4028 (3)	0.0287 (6)
H14	0.050197	0.972111	0.416348	0.034*
C15	0.2894 (5)	0.96707 (14)	0.3689 (3)	0.0295 (7)
C16	0.4194 (5)	0.92778 (14)	0.3485 (3)	0.0293 (6)
H16	0.522014	0.940596	0.325045	0.035*
C17	0.3967 (4)	0.86988 (13)	0.3629 (2)	0.0253 (6)
H17	0.485500	0.844109	0.350759	0.030*
C18	0.2522 (5)	0.43688 (14)	0.5015 (3)	0.0388 (8)
H18A	0.381918	0.424318	0.514215	0.058*
H18B	0.172342	0.417484	0.438917	0.058*
H18C	0.209299	0.428448	0.564446	0.058*
C19	0.2300 (6)	0.60188 (16)	0.2452 (3)	0.0405 (8)
H19A	0.265946	0.571215	0.205136	0.061*
H19B	0.320675	0.632422	0.253366	0.061*
H19C	0.105197	0.615420	0.206286	0.061*
C20	0.3144 (6)	1.03026 (15)	0.3542 (3)	0.0419 (9)
H20A	0.191350	1.048347	0.332599	0.063*
H20B	0.378427	1.036184	0.298859	0.063*
H20C	0.389231	1.046404	0.421963	0.063*
C21	−0.0587 (4)	0.86847 (14)	0.4559 (3)	0.0292 (7)
H21A	−0.104664	0.899596	0.490470	0.044*
H21B	−0.018695	0.837857	0.507323	0.044*
H21C	−0.159066	0.855354	0.394476	0.044*
Cl1	0.20669 (12)	0.74800 (3)	0.63642 (6)	0.02942 (16)
N1	0.2211 (3)	0.67891 (10)	0.42934 (19)	0.0188 (5)
N2	0.2258 (3)	0.78964 (10)	0.40746 (18)	0.0170 (4)
O1	0.6949 (4)	0.72561 (12)	0.3767 (2)	0.0388 (6)
O2	0.6863 (3)	0.65537 (10)	0.69056 (19)	0.0339 (5)
O3	0.6915 (3)	0.83494 (10)	0.6455 (2)	0.0357 (5)
Re1	0.43261 (2)	0.73802 (2)	0.52482 (2)	0.01685 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0129 (12)	0.0259 (14)	0.0275 (16)	0.0014 (10)	0.0016 (12)	0.0022 (12)
C2	0.0236 (14)	0.0257 (15)	0.0229 (15)	−0.0030 (11)	0.0043 (12)	−0.0017 (12)
C3	0.0279 (15)	0.0240 (14)	0.0240 (15)	0.0018 (12)	0.0052 (12)	0.0037 (12)
C4	0.0129 (12)	0.0233 (14)	0.0227 (14)	−0.0032 (10)	0.0012 (10)	−0.0017 (11)
C5	0.0258 (14)	0.0278 (15)	0.0243 (15)	−0.0035 (12)	0.0069 (12)	−0.0017 (12)
C6	0.0286 (15)	0.0280 (16)	0.0309 (17)	−0.0040 (12)	0.0074 (13)	0.0059 (13)
C7	0.0176 (13)	0.0226 (15)	0.0438 (19)	−0.0011 (11)	0.0031 (13)	0.0004 (13)
C8	0.0262 (15)	0.0277 (16)	0.0352 (17)	−0.0001 (12)	0.0056 (13)	−0.0108 (14)
C9	0.0252 (14)	0.0269 (15)	0.0257 (15)	−0.0004 (11)	0.0062 (12)	−0.0045 (12)
C10	0.0160 (12)	0.0262 (14)	0.0208 (13)	−0.0015 (10)	0.0052 (10)	−0.0060 (11)
C11	0.0175 (13)	0.0278 (16)	0.0179 (14)	0.0048 (10)	0.0049 (11)	0.0000 (11)
C12	0.0206 (13)	0.0239 (14)	0.0147 (13)	0.0023 (11)	0.0048 (10)	−0.0008 (11)
C13	0.0223 (13)	0.0285 (15)	0.0169 (13)	0.0039 (11)	0.0033 (11)	−0.0026 (11)
C14	0.0344 (16)	0.0250 (15)	0.0261 (16)	0.0077 (12)	0.0073 (13)	−0.0033 (12)
C15	0.0386 (17)	0.0233 (15)	0.0246 (15)	0.0002 (13)	0.0057 (13)	−0.0021 (12)
C16	0.0293 (15)	0.0281 (16)	0.0313 (16)	−0.0021 (12)	0.0100 (13)	0.0036 (13)
C17	0.0263 (14)	0.0265 (15)	0.0246 (15)	0.0031 (11)	0.0096 (12)	0.0034 (12)
C18	0.0318 (17)	0.0219 (16)	0.059 (2)	−0.0002 (13)	0.0067 (16)	−0.0003 (15)
C19	0.062 (2)	0.0352 (18)	0.0264 (17)	0.0081 (17)	0.0158 (17)	−0.0042 (15)
C20	0.061 (2)	0.0225 (16)	0.044 (2)	−0.0008 (15)	0.0186 (18)	−0.0012 (15)
C21	0.0249 (14)	0.0343 (17)	0.0307 (16)	0.0070 (12)	0.0115 (13)	−0.0047 (13)
Cl1	0.0385 (4)	0.0333 (3)	0.0216 (4)	0.0023 (3)	0.0168 (3)	0.0002 (3)
N1	0.0158 (10)	0.0223 (12)	0.0187 (11)	−0.0008 (8)	0.0057 (9)	−0.0029 (9)
N2	0.0142 (10)	0.0244 (12)	0.0122 (10)	0.0027 (8)	0.0033 (8)	0.0010 (9)
O1	0.0301 (12)	0.0524 (15)	0.0390 (14)	0.0027 (11)	0.0184 (11)	−0.0039 (12)
O2	0.0345 (12)	0.0335 (12)	0.0271 (12)	0.0049 (10)	−0.0021 (10)	0.0057 (10)
O3	0.0392 (13)	0.0256 (11)	0.0338 (13)	−0.0111 (10)	−0.0038 (10)	−0.0014 (10)
Re1	0.01548 (8)	0.01912 (8)	0.01488 (8)	−0.00085 (4)	0.00254 (5)	−0.00036 (4)

Geometric parameters (Å, º)

C1—O1	1.135 (4)	C12—N2	1.437 (4)
C1—Re1	1.921 (3)	C13—C14	1.395 (4)
C2—O2	1.148 (4)	C13—C21	1.506 (4)
C2—Re1	1.925 (3)	C14—C15	1.389 (5)
C3—O3	1.143 (4)	C14—H14	0.9300
C3—Re1	1.933 (3)	C15—C16	1.398 (5)
C4—C5	1.398 (4)	C15—C20	1.510 (4)
C4—C9	1.402 (4)	C16—C17	1.386 (4)
C4—N1	1.436 (4)	C16—H16	0.9300
C5—C6	1.378 (4)	C17—H17	0.9300
C5—H5	0.9300	C18—H18A	0.9600
C6—C7	1.387 (5)	C18—H18B	0.9600
C6—H6	0.9300	C18—H18C	0.9600
C7—C8	1.387 (5)	C19—H19A	0.9600
C7—C18	1.510 (4)	C19—H19B	0.9600
C8—C9	1.398 (5)	C19—H19C	0.9600
C8—H8	0.9300	C20—H20A	0.9600
C9—C19	1.507 (4)	C20—H20B	0.9600
C10—N1	1.284 (4)	C20—H20C	0.9600
C10—C11	1.457 (4)	C21—H21A	0.9600
C10—H10	0.9300	C21—H21B	0.9600
C11—N2	1.285 (4)	C21—H21C	0.9600
C11—H11	0.9300	Cl1—Re1	2.4723 (7)
C12—C17	1.391 (4)	N1—Re1	2.173 (2)
C12—C13	1.403 (4)	N2—Re1	2.170 (2)
O1—C1—Re1	178.9 (3)	C7—C18—H18A	109.5
O2—C2—Re1	179.3 (3)	C7—C18—H18B	109.5
O3—C3—Re1	179.3 (3)	H18A—C18—H18B	109.5
C5—C4—C9	120.5 (3)	C7—C18—H18C	109.5
C5—C4—N1	117.3 (3)	H18A—C18—H18C	109.5
C9—C4—N1	122.2 (3)	H18B—C18—H18C	109.5
C6—C5—C4	120.2 (3)	C9—C19—H19A	109.5
C6—C5—H5	119.9	C9—C19—H19B	109.5
C4—C5—H5	119.9	H19A—C19—H19B	109.5
C5—C6—C7	121.1 (3)	C9—C19—H19C	109.5
C5—C6—H6	119.4	H19A—C19—H19C	109.5
C7—C6—H6	119.4	H19B—C19—H19C	109.5
C6—C7—C8	118.0 (3)	C15—C20—H20A	109.5
C6—C7—C18	121.1 (3)	C15—C20—H20B	109.5
C8—C7—C18	120.9 (3)	H20A—C20—H20B	109.5
C7—C8—C9	123.1 (3)	C15—C20—H20C	109.5
C7—C8—H8	118.4	H20A—C20—H20C	109.5
C9—C8—H8	118.4	H20B—C20—H20C	109.5
C8—C9—C4	117.1 (3)	C13—C21—H21A	109.5
C8—C9—C19	120.4 (3)	C13—C21—H21B	109.5
C4—C9—C19	122.4 (3)	H21A—C21—H21B	109.5
N1—C10—C11	116.8 (3)	C13—C21—H21C	109.5
N1—C10—H10	121.6	H21A—C21—H21C	109.5
C11—C10—H10	121.6	H21B—C21—H21C	109.5
N2—C11—C10	116.7 (3)	C10—N1—C4	119.1 (2)
N2—C11—H11	121.7	C10—N1—Re1	116.2 (2)
C10—C11—H11	121.7	C4—N1—Re1	124.76 (18)
C17—C12—C13	121.2 (3)	C11—N2—C12	119.3 (2)
C17—C12—N2	117.0 (2)	C11—N2—Re1	116.3 (2)
C13—C12—N2	121.8 (3)	C12—N2—Re1	124.34 (17)
C14—C13—C12	116.8 (3)	C1—Re1—C2	89.93 (13)
C14—C13—C21	120.7 (3)	C1—Re1—C3	89.06 (13)
C12—C13—C21	122.5 (3)	C2—Re1—C3	87.87 (13)
C15—C14—C13	123.4 (3)	C1—Re1—N2	93.87 (10)
C15—C14—H14	118.3	C2—Re1—N2	173.02 (11)
C13—C14—H14	118.3	C3—Re1—N2	98.04 (11)
C14—C15—C16	117.9 (3)	C1—Re1—N1	93.42 (11)
C14—C15—C20	121.3 (3)	C2—Re1—N1	100.02 (11)
C16—C15—C20	120.8 (3)	C3—Re1—N1	171.72 (11)
C17—C16—C15	120.5 (3)	N2—Re1—N1	73.93 (9)
C17—C16—H16	119.7	C1—Re1—Cl1	177.28 (9)
C15—C16—H16	119.7	C2—Re1—Cl1	91.89 (9)
C16—C17—C12	120.1 (3)	C3—Re1—Cl1	93.03 (9)
C16—C17—H17	119.9	N2—Re1—Cl1	84.12 (6)
C12—C17—H17	119.9	N1—Re1—Cl1	84.26 (6)
C9—C4—C5—C6	−1.1 (4)	C13—C14—C15—C16	0.1 (5)
N1—C4—C5—C6	179.2 (3)	C13—C14—C15—C20	−179.9 (3)
C4—C5—C6—C7	0.8 (5)	C14—C15—C16—C17	−0.6 (5)
C5—C6—C7—C8	0.3 (5)	C20—C15—C16—C17	179.5 (3)
C5—C6—C7—C18	178.3 (3)	C15—C16—C17—C12	1.5 (5)
C6—C7—C8—C9	−1.0 (5)	C13—C12—C17—C16	−1.9 (5)
C18—C7—C8—C9	−179.1 (3)	N2—C12—C17—C16	179.2 (3)
C7—C8—C9—C4	0.7 (5)	C11—C10—N1—C4	−178.7 (2)
C7—C8—C9—C19	177.1 (3)	C11—C10—N1—Re1	2.4 (3)
C5—C4—C9—C8	0.4 (4)	C5—C4—N1—C10	−122.3 (3)
N1—C4—C9—C8	−180.0 (3)	C9—C4—N1—C10	58.1 (4)
C5—C4—C9—C19	−175.9 (3)	C5—C4—N1—Re1	56.6 (3)
N1—C4—C9—C19	3.7 (5)	C9—C4—N1—Re1	−123.0 (3)
N1—C10—C11—N2	0.7 (4)	C10—C11—N2—C12	176.6 (2)
C17—C12—C13—C14	1.4 (4)	C10—C11—N2—Re1	−3.4 (3)
N2—C12—C13—C14	−179.8 (3)	C17—C12—N2—C11	−116.9 (3)
C17—C12—C13—C21	−178.3 (3)	C13—C12—N2—C11	64.3 (4)
N2—C12—C13—C21	0.5 (4)	C17—C12—N2—Re1	63.2 (3)
C12—C13—C14—C15	−0.5 (5)	C13—C12—N2—Re1	−115.7 (3)
C21—C13—C14—C15	179.2 (3)

(complex2)

Crystal data

C23H24.40ClN2O3Re	F(000) = 1170
Mr = 598.50	Dx = 1.703 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2294 (4) Å	Cell parameters from 9417 reflections
b = 36.355 (2) Å	θ = 2.5–28.5°
c = 8.1035 (7) Å	µ = 5.34 mm^−1
β = 105.614 (7)°	T = 150 K
V = 2334.9 (3) Å^3	Block, dark-brown
Z = 4	0.15 × 0.08 × 0.04 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	4059 independent reflections
Radiation source: micro-focus sealed X-ray tube	3715 reflections with I > 2σ(I)
Detector resolution: 8.1150 pixels mm^-1	Rint = 0.032
ω scans	θmax = 25.5°, θmin = 3.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −9→7
Tmin = 0.438, Tmax = 1.000	k = −44→31
10823 measured reflections	l = −7→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.065	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.010P)^2 + 14.3649P] where P = (Fo^2 + 2Fc^2)/3
S = 1.45	(Δ/σ)max = 0.001
4059 reflections	Δρmax = 1.18 e Å^−3
282 parameters	Δρmin = −2.44 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.

Refinement. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6223 (15)	0.5881 (3)	0.4064 (18)	0.050 (3)
C2	0.6636 (14)	0.6485 (3)	0.2300 (13)	0.033 (2)
C3	0.4375 (15)	0.5967 (3)	0.0836 (18)	0.056 (4)
C4	0.6171 (12)	0.6831 (2)	0.5879 (12)	0.026 (2)
C5	0.6159 (14)	0.7178 (3)	0.5227 (15)	0.041 (3)
H5A	0.526623	0.725819	0.428775	0.049*
C6	0.7508 (17)	0.7412 (3)	0.5990 (17)	0.049 (3)
H6A	0.751543	0.765531	0.556591	0.059*
C7	0.8831 (16)	0.7297 (3)	0.7347 (16)	0.048 (3)
C8	0.8788 (14)	0.6945 (3)	0.7910 (14)	0.043 (3)
H8A	0.969785	0.685960	0.882024	0.052*
C9	0.7467 (14)	0.6704 (3)	0.7207 (13)	0.035 (2)
H9A	0.746204	0.646086	0.763072	0.041*	0.40 (2)
C10	0.3511 (12)	0.6558 (3)	0.5748 (13)	0.029 (2)
C11	0.2260 (12)	0.6274 (3)	0.4984 (13)	0.033 (2)
C12	0.1431 (12)	0.5798 (3)	0.2958 (15)	0.037 (3)
C13	0.0154 (15)	0.5889 (4)	0.1526 (18)	0.066 (4)
H13A	0.008464	0.613051	0.106797	0.079*
C14	−0.1037 (18)	0.5623 (5)	0.075 (2)	0.080 (5)
H14A	−0.190296	0.568809	−0.024105	0.097*
C15	−0.099 (2)	0.5274 (5)	0.138 (2)	0.079 (6)
C16	0.035 (2)	0.5186 (4)	0.281 (2)	0.071 (5)
H16A	0.043530	0.494147	0.323759	0.086*
C17	0.1555 (16)	0.5443 (3)	0.3607 (19)	0.055 (4)
C18	1.0254 (17)	0.7553 (4)	0.8148 (19)	0.076 (5)
H18A	1.005766	0.779201	0.757054	0.114*
H18B	1.031827	0.758468	0.936513	0.114*
H18C	1.131711	0.744896	0.803348	0.114*
C19	0.742 (3)	0.6346 (5)	0.793 (2)	0.049 (6)	0.60 (2)
H19A	0.845280	0.630628	0.885442	0.073*	0.60 (2)
H19B	0.643748	0.632654	0.838472	0.073*	0.60 (2)
H19C	0.734641	0.615903	0.703784	0.073*	0.60 (2)
C20	0.3243 (15)	0.6800 (3)	0.7135 (15)	0.049 (3)
H20A	0.218370	0.673254	0.739091	0.074*
H20B	0.418225	0.676924	0.816550	0.074*
H20C	0.318636	0.705705	0.676010	0.074*
C21	0.0745 (14)	0.6211 (4)	0.5677 (15)	0.050 (3)
H21A	0.075088	0.639120	0.657612	0.075*
H21B	−0.029281	0.623768	0.474692	0.075*
H21C	0.079794	0.596190	0.615470	0.075*
C22	−0.233 (2)	0.4998 (5)	0.057 (3)	0.122 (8)
H22A	−0.209742	0.476413	0.118587	0.183*
H22B	−0.343891	0.509001	0.061660	0.183*
H22C	−0.233641	0.496056	−0.063126	0.183*
C23	0.293 (2)	0.5332 (4)	0.513 (2)	0.080 (5)
H23A	0.280091	0.507188	0.538376	0.120*
H23B	0.402703	0.536842	0.488704	0.120*
H23C	0.288014	0.548216	0.611674	0.120*
Cl1	0.2767 (4)	0.67246 (9)	0.1347 (4)	0.0522 (8)
N1	0.4804 (9)	0.6578 (2)	0.5113 (9)	0.0217 (17)
N2	0.2600 (10)	0.6079 (2)	0.3781 (11)	0.033 (2)
O1	0.7119 (12)	0.5657 (2)	0.4768 (15)	0.082 (3)
O2	0.7755 (11)	0.6626 (2)	0.2022 (10)	0.053 (2)
O3	0.4122 (13)	0.5816 (3)	−0.0497 (14)	0.088 (4)
Re1	0.47423 (5)	0.62497 (2)	0.28836 (6)	0.03193 (14)
C19A	0.480 (3)	0.7367 (8)	0.410 (4)	0.048 (9)	0.40 (2)
H19D	0.517306	0.761240	0.385591	0.072*	0.40 (2)
H19E	0.441444	0.722894	0.302401	0.072*	0.40 (2)
H19F	0.386642	0.739103	0.463036	0.072*	0.40 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.032 (7)	0.031 (6)	0.096 (10)	−0.008 (5)	0.034 (7)	0.002 (6)
C2	0.042 (7)	0.026 (5)	0.039 (7)	−0.001 (5)	0.025 (5)	−0.006 (5)
C3	0.038 (7)	0.050 (8)	0.087 (10)	−0.027 (6)	0.029 (7)	−0.034 (7)
C4	0.026 (5)	0.021 (5)	0.032 (6)	−0.005 (4)	0.013 (4)	−0.010 (4)
C5	0.033 (6)	0.033 (6)	0.061 (8)	0.007 (5)	0.021 (5)	0.009 (5)
C6	0.064 (9)	0.018 (5)	0.081 (10)	−0.007 (6)	0.044 (8)	−0.004 (6)
C7	0.048 (8)	0.051 (8)	0.059 (9)	−0.024 (6)	0.040 (7)	−0.029 (6)
C8	0.041 (7)	0.054 (8)	0.036 (7)	−0.014 (6)	0.013 (5)	−0.017 (6)
C9	0.040 (6)	0.032 (6)	0.030 (6)	−0.004 (5)	0.006 (5)	−0.003 (5)
C10	0.023 (5)	0.031 (5)	0.036 (6)	0.001 (4)	0.011 (4)	0.004 (4)
C11	0.023 (5)	0.031 (5)	0.045 (7)	0.002 (5)	0.012 (4)	0.004 (5)
C12	0.017 (5)	0.036 (6)	0.061 (8)	−0.008 (4)	0.015 (5)	−0.018 (5)
C13	0.030 (7)	0.071 (9)	0.092 (11)	−0.019 (7)	0.007 (7)	−0.022 (8)
C14	0.041 (9)	0.101 (13)	0.095 (12)	−0.029 (9)	0.011 (8)	−0.044 (10)
C15	0.062 (11)	0.078 (12)	0.115 (14)	−0.039 (9)	0.058 (10)	−0.060 (11)
C16	0.075 (11)	0.043 (8)	0.117 (13)	−0.025 (8)	0.061 (11)	−0.027 (8)
C17	0.042 (8)	0.043 (7)	0.091 (11)	−0.003 (6)	0.037 (7)	−0.014 (7)
C18	0.078 (11)	0.061 (9)	0.113 (13)	−0.048 (8)	0.065 (10)	−0.048 (9)
C19	0.060 (14)	0.029 (11)	0.045 (13)	−0.012 (9)	−0.005 (10)	0.006 (8)
C20	0.047 (8)	0.059 (8)	0.053 (8)	−0.010 (6)	0.033 (6)	−0.015 (6)
C21	0.037 (6)	0.066 (8)	0.052 (8)	−0.003 (6)	0.022 (5)	−0.004 (7)
C22	0.094 (14)	0.120 (15)	0.180 (19)	−0.079 (12)	0.084 (14)	−0.096 (14)
C23	0.076 (12)	0.050 (9)	0.120 (14)	−0.006 (8)	0.038 (10)	0.014 (9)
Cl1	0.0524 (19)	0.074 (2)	0.0268 (16)	0.0200 (16)	0.0048 (13)	0.0064 (14)
N1	0.018 (4)	0.021 (4)	0.027 (5)	0.002 (3)	0.008 (3)	0.006 (3)
N2	0.017 (4)	0.031 (5)	0.049 (6)	0.000 (4)	0.003 (4)	−0.008 (4)
O1	0.054 (6)	0.041 (5)	0.162 (10)	0.009 (5)	0.048 (7)	0.042 (6)
O2	0.051 (6)	0.059 (6)	0.063 (6)	−0.016 (4)	0.039 (5)	−0.013 (4)
O3	0.081 (8)	0.092 (8)	0.104 (8)	−0.042 (6)	0.049 (6)	−0.074 (7)
Re1	0.0277 (2)	0.0284 (2)	0.0437 (3)	−0.0026 (2)	0.01654 (17)	−0.0106 (2)
C19A	0.035 (17)	0.037 (17)	0.06 (2)	0.013 (13)	−0.002 (14)	0.018 (14)

Geometric parameters (Å, º)

C1—O1	1.142 (14)	C14—H14A	0.9500
C1—Re1	1.889 (13)	C15—C16	1.40 (2)
C2—O2	1.129 (12)	C15—C22	1.507 (18)
C2—Re1	1.944 (10)	C16—C17	1.392 (18)
C3—O3	1.179 (14)	C16—H16A	0.9500
C3—Re1	1.906 (12)	C17—C23	1.489 (19)
C4—C5	1.368 (13)	C18—H18A	0.9800
C4—C9	1.375 (14)	C18—H18B	0.9800
C4—N1	1.456 (11)	C18—H18C	0.9800
C5—C6	1.403 (16)	C19—H19A	0.9800
C5—C19A	1.42 (3)	C19—H19B	0.9800
C5—H5A	0.9500	C19—H19C	0.9800
C6—C7	1.387 (17)	C20—H20A	0.9800
C6—H6A	0.9500	C20—H20B	0.9800
C7—C8	1.365 (16)	C20—H20C	0.9800
C7—C18	1.499 (15)	C21—H21A	0.9800
C8—C9	1.391 (14)	C21—H21B	0.9800
C8—H8A	0.9500	C21—H21C	0.9800
C9—C19	1.433 (18)	C22—H22A	0.9800
C9—H9A	0.9500	C22—H22B	0.9800
C10—N1	1.302 (11)	C22—H22C	0.9800
C10—C11	1.472 (14)	C23—H23A	0.9800
C10—C20	1.489 (14)	C23—H23B	0.9800
C11—N2	1.296 (12)	C23—H23C	0.9800
C11—C21	1.516 (13)	Cl1—Re1	2.467 (3)
C12—C13	1.380 (17)	N1—Re1	2.154 (7)
C12—C17	1.386 (16)	N2—Re1	2.171 (8)
C12—N2	1.438 (12)	C19A—H19D	0.9800
C13—C14	1.397 (17)	C19A—H19E	0.9800
C13—H13A	0.9500	C19A—H19F	0.9800
C14—C15	1.36 (2)
O1—C1—Re1	179.6 (13)	C9—C19—H19B	109.5
O2—C2—Re1	177.4 (10)	H19A—C19—H19B	109.5
O3—C3—Re1	175.0 (13)	C9—C19—H19C	109.5
C5—C4—C9	122.3 (10)	H19A—C19—H19C	109.5
C5—C4—N1	119.6 (9)	H19B—C19—H19C	109.5
C9—C4—N1	118.1 (8)	C10—C20—H20A	109.5
C4—C5—C6	117.8 (11)	C10—C20—H20B	109.5
C4—C5—C19A	128.3 (16)	H20A—C20—H20B	109.5
C6—C5—C19A	112.6 (15)	C10—C20—H20C	109.5
C4—C5—H5A	121.1	H20A—C20—H20C	109.5
C6—C5—H5A	121.1	H20B—C20—H20C	109.5
C7—C6—C5	121.8 (10)	C11—C21—H21A	109.5
C7—C6—H6A	119.1	C11—C21—H21B	109.5
C5—C6—H6A	119.1	H21A—C21—H21B	109.5
C8—C7—C6	117.5 (11)	C11—C21—H21C	109.5
C8—C7—C18	121.7 (13)	H21A—C21—H21C	109.5
C6—C7—C18	120.9 (12)	H21B—C21—H21C	109.5
C7—C8—C9	122.7 (12)	C15—C22—H22A	109.5
C7—C8—H8A	118.6	C15—C22—H22B	109.5
C9—C8—H8A	118.6	H22A—C22—H22B	109.5
C4—C9—C8	117.9 (10)	C15—C22—H22C	109.5
C4—C9—C19	121.5 (12)	H22A—C22—H22C	109.5
C8—C9—C19	120.5 (12)	H22B—C22—H22C	109.5
C4—C9—H9A	121.1	C17—C23—H23A	109.5
C8—C9—H9A	121.1	C17—C23—H23B	109.5
N1—C10—C11	115.2 (9)	H23A—C23—H23B	109.5
N1—C10—C20	124.7 (9)	C17—C23—H23C	109.5
C11—C10—C20	120.2 (9)	H23A—C23—H23C	109.5
N2—C11—C10	115.6 (8)	H23B—C23—H23C	109.5
N2—C11—C21	124.1 (10)	C10—N1—C4	119.1 (8)
C10—C11—C21	120.2 (9)	C10—N1—Re1	117.6 (7)
C13—C12—C17	120.2 (11)	C4—N1—Re1	123.2 (5)
C13—C12—N2	118.9 (10)	C11—N2—C12	119.0 (9)
C17—C12—N2	120.9 (11)	C11—N2—Re1	117.0 (7)
C12—C13—C14	119.7 (14)	C12—N2—Re1	123.4 (7)
C12—C13—H13A	120.1	C1—Re1—C3	89.3 (6)
C14—C13—H13A	120.1	C1—Re1—C2	89.1 (5)
C15—C14—C13	121.9 (16)	C3—Re1—C2	88.6 (4)
C15—C14—H14A	119.0	C1—Re1—N1	95.9 (4)
C13—C14—H14A	119.0	C3—Re1—N1	172.5 (4)
C14—C15—C16	117.2 (14)	C2—Re1—N1	97.0 (3)
C14—C15—C22	120.9 (19)	C1—Re1—N2	95.7 (4)
C16—C15—C22	121.9 (18)	C3—Re1—N2	100.6 (4)
C17—C16—C15	122.3 (14)	C2—Re1—N2	169.6 (4)
C17—C16—H16A	118.9	N1—Re1—N2	73.5 (3)
C15—C16—H16A	118.9	C1—Re1—Cl1	179.0 (3)
C12—C17—C16	118.6 (14)	C3—Re1—Cl1	90.5 (4)
C12—C17—C23	121.9 (12)	C2—Re1—Cl1	91.8 (3)
C16—C17—C23	119.5 (14)	N1—Re1—Cl1	84.2 (2)
C7—C18—H18A	109.5	N2—Re1—Cl1	83.4 (2)
C7—C18—H18B	109.5	C5—C19A—H19D	109.5
H18A—C18—H18B	109.5	C5—C19A—H19E	109.5
C7—C18—H18C	109.5	H19D—C19A—H19E	109.5
H18A—C18—H18C	109.5	C5—C19A—H19F	109.5
H18B—C18—H18C	109.5	H19D—C19A—H19F	109.5
C9—C19—H19A	109.5	H19E—C19A—H19F	109.5
C9—C4—C5—C6	−1.7 (16)	C14—C15—C16—C17	3 (2)
N1—C4—C5—C6	−179.4 (9)	C22—C15—C16—C17	−177.4 (12)
C9—C4—C5—C19A	−167.4 (19)	C13—C12—C17—C16	−1.4 (18)
N1—C4—C5—C19A	15 (2)	N2—C12—C17—C16	177.2 (10)
C4—C5—C6—C7	0.8 (17)	C13—C12—C17—C23	178.8 (12)
C19A—C5—C6—C7	168.7 (17)	N2—C12—C17—C23	−2.6 (17)
C5—C6—C7—C8	0.7 (17)	C15—C16—C17—C12	−1 (2)
C5—C6—C7—C18	−179.7 (10)	C15—C16—C17—C23	179.2 (13)
C6—C7—C8—C9	−1.5 (16)	C11—C10—N1—C4	−175.2 (8)
C18—C7—C8—C9	178.9 (10)	C20—C10—N1—C4	5.2 (15)
C5—C4—C9—C8	1.0 (16)	C11—C10—N1—Re1	7.8 (11)
N1—C4—C9—C8	178.7 (9)	C20—C10—N1—Re1	−171.8 (8)
C5—C4—C9—C19	177.0 (13)	C5—C4—N1—C10	−93.1 (11)
N1—C4—C9—C19	−5.3 (17)	C9—C4—N1—C10	89.2 (11)
C7—C8—C9—C4	0.7 (16)	C5—C4—N1—Re1	83.7 (10)
C7—C8—C9—C19	−175.4 (13)	C9—C4—N1—Re1	−94.0 (9)
N1—C10—C11—N2	0.1 (14)	C10—C11—N2—C12	−179.4 (9)
C20—C10—C11—N2	179.7 (10)	C21—C11—N2—C12	4.1 (16)
N1—C10—C11—C21	176.7 (9)	C10—C11—N2—Re1	−7.8 (12)
C20—C10—C11—C21	−3.6 (15)	C21—C11—N2—Re1	175.6 (8)
C17—C12—C13—C14	1.4 (19)	C13—C12—N2—C11	89.8 (14)
N2—C12—C13—C14	−177.3 (11)	C17—C12—N2—C11	−88.8 (13)
C12—C13—C14—C15	1 (2)	C13—C12—N2—Re1	−81.2 (12)
C13—C14—C15—C16	−3 (2)	C17—C12—N2—Re1	100.2 (11)
C13—C14—C15—C22	177.4 (13)

(complex3)

Crystal data

C25H28ClN2O3Re	F(000) = 1232
Mr = 626.14	Dx = 1.659 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.998 (3) Å	Cell parameters from 3250 reflections
b = 30.8780 (15) Å	θ = 2.5–27.4°
c = 8.2090 (5) Å	µ = 4.98 mm^−1
β = 98.497 (12)°	T = 150 K
V = 2506.6 (7) Å^3	Block, dark-brown
Z = 4	0.35 × 0.18 × 0.10 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	6982 independent reflections
Radiation source: micro-focus sealed X-ray tube	5829 reflections with I > 2σ(I)
Detector resolution: 8.1150 pixels mm^-1	Rint = 0.041
ω scans	θmax = 30.8°, θmin = 3.3°
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −14→11
Tmin = 0.530, Tmax = 1.000	k = −43→44
24743 measured reflections	l = −11→11

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.060	w = 1/[σ^2(Fo^2) + (0.0148P)^2 + 1.0016P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max = 0.003
6982 reflections	Δρmax = 0.61 e Å^−3
297 parameters	Δρmin = −2.15 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
C1	0.2564 (4)	0.67427 (13)	0.5486 (5)	0.0265 (9)
C2	0.4228 (4)	0.65311 (12)	0.8226 (4)	0.0217 (8)
C3	0.2057 (4)	0.60324 (13)	0.7051 (5)	0.0234 (8)
C4	0.6294 (3)	0.67324 (11)	0.5383 (4)	0.0177 (7)
C5	0.7467 (4)	0.66569 (13)	0.6509 (5)	0.0254 (9)
C6	0.8354 (4)	0.70025 (14)	0.6898 (5)	0.0326 (10)
H6	0.914240	0.695682	0.763239	0.039*
C7	0.8102 (4)	0.74120 (14)	0.6228 (5)	0.0322 (10)
C8	0.6941 (4)	0.74687 (13)	0.5104 (5)	0.0278 (9)
H8	0.676486	0.774099	0.463729	0.033*
C9	0.6028 (3)	0.71361 (12)	0.4644 (4)	0.0190 (7)
C10	0.5492 (3)	0.61343 (11)	0.3701 (4)	0.0164 (7)
C11	0.4336 (3)	0.58454 (11)	0.3114 (4)	0.0150 (7)
C12	0.2007 (3)	0.57009 (11)	0.3151 (4)	0.0151 (7)
C13	0.1605 (3)	0.52883 (11)	0.3616 (4)	0.0167 (7)
C14	0.0345 (3)	0.51356 (12)	0.2861 (4)	0.0210 (8)
H14	0.005590	0.486469	0.316034	0.025*
C15	−0.0485 (3)	0.53722 (13)	0.1689 (4)	0.0225 (8)
C16	−0.0049 (3)	0.57751 (13)	0.1266 (4)	0.0237 (8)
H16	−0.060348	0.593723	0.048354	0.028*
C17	0.1194 (4)	0.59487 (12)	0.1970 (4)	0.0199 (8)
C18	0.7792 (4)	0.62197 (15)	0.7267 (6)	0.0456 (12)
H18A	0.720261	0.616152	0.806335	0.068*
H18B	0.871430	0.621617	0.779818	0.068*
H18C	0.766779	0.600206	0.642277	0.068*
C19	0.9081 (5)	0.77794 (16)	0.6707 (6)	0.0526 (14)
H19A	0.879724	0.803025	0.605615	0.079*
H19B	0.996969	0.769509	0.651776	0.079*
H19C	0.909904	0.784606	0.785253	0.079*
C20	0.4810 (4)	0.72191 (13)	0.3347 (5)	0.0289 (9)
H20A	0.506080	0.740969	0.251961	0.043*
H20B	0.410360	0.735033	0.385318	0.043*
H20C	0.449295	0.694971	0.284799	0.043*
C21	0.6686 (4)	0.61499 (12)	0.2789 (5)	0.0238 (8)
H21A	0.730550	0.636889	0.326334	0.036*
H21B	0.638420	0.621709	0.165212	0.036*
H21C	0.713123	0.587366	0.286747	0.036*
C22	0.4394 (4)	0.55591 (12)	0.1665 (4)	0.0223 (8)
H22A	0.357788	0.539164	0.145020	0.033*
H22B	0.515608	0.536799	0.189151	0.033*
H22C	0.448550	0.573318	0.071847	0.033*
C23	0.2504 (4)	0.50073 (12)	0.4802 (5)	0.0247 (8)
H23A	0.199914	0.476294	0.510180	0.037*
H23B	0.283622	0.517143	0.577136	0.037*
H23C	0.325275	0.490782	0.429325	0.037*
C24	−0.1796 (4)	0.51834 (14)	0.0811 (5)	0.0305 (10)
H24A	−0.223463	0.539163	0.004309	0.046*
H24B	−0.237861	0.511301	0.160417	0.046*
H24C	−0.160603	0.492597	0.023131	0.046*
C25	0.1656 (4)	0.63791 (12)	0.1404 (5)	0.0264 (9)
H25A	0.173492	0.658154	0.230068	0.040*
H25B	0.100848	0.648483	0.051199	0.040*
H25C	0.251861	0.634591	0.103810	0.040*
N1	0.5334 (3)	0.63835 (9)	0.4928 (3)	0.0147 (6)
N2	0.3295 (3)	0.58853 (9)	0.3879 (3)	0.0143 (6)
O1	0.1890 (3)	0.70461 (10)	0.5173 (4)	0.0414 (8)
O2	0.4623 (3)	0.66882 (9)	0.9475 (3)	0.0345 (7)
O3	0.1122 (3)	0.59044 (10)	0.7543 (4)	0.0386 (8)
Cl1	0.49370 (9)	0.56052 (3)	0.73170 (11)	0.02210 (19)
Re1	0.36161 (2)	0.62441 (2)	0.61720 (2)	0.01546 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.024 (2)	0.035 (2)	0.022 (2)	−0.0005 (18)	0.0087 (16)	−0.0060 (18)
C2	0.0242 (19)	0.0188 (19)	0.0224 (19)	−0.0051 (15)	0.0048 (15)	0.0008 (16)
C3	0.023 (2)	0.026 (2)	0.0221 (19)	−0.0010 (16)	0.0054 (15)	−0.0079 (17)
C4	0.0156 (17)	0.0185 (18)	0.0200 (18)	−0.0028 (14)	0.0056 (14)	−0.0032 (15)
C5	0.0197 (19)	0.031 (2)	0.024 (2)	−0.0036 (17)	0.0012 (15)	0.0038 (18)
C6	0.024 (2)	0.043 (3)	0.028 (2)	−0.0083 (19)	−0.0022 (17)	−0.001 (2)
C7	0.026 (2)	0.039 (3)	0.033 (2)	−0.0137 (19)	0.0078 (18)	−0.009 (2)
C8	0.030 (2)	0.021 (2)	0.035 (2)	−0.0055 (17)	0.0148 (18)	−0.0022 (18)
C9	0.0209 (18)	0.0192 (18)	0.0180 (18)	−0.0013 (15)	0.0065 (14)	−0.0013 (15)
C10	0.0161 (17)	0.0152 (17)	0.0176 (17)	0.0022 (13)	0.0013 (13)	0.0034 (14)
C11	0.0174 (17)	0.0143 (17)	0.0129 (16)	0.0013 (14)	0.0009 (13)	0.0032 (14)
C12	0.0164 (17)	0.0201 (18)	0.0091 (15)	0.0016 (14)	0.0026 (13)	−0.0026 (14)
C13	0.0163 (17)	0.0200 (18)	0.0153 (17)	0.0013 (14)	0.0077 (14)	−0.0032 (15)
C14	0.0190 (18)	0.023 (2)	0.0215 (18)	−0.0049 (16)	0.0059 (15)	−0.0050 (16)
C15	0.0140 (17)	0.036 (2)	0.0182 (18)	−0.0025 (16)	0.0037 (14)	−0.0103 (17)
C16	0.0166 (18)	0.039 (2)	0.0151 (18)	0.0037 (16)	−0.0002 (14)	−0.0032 (17)
C17	0.0210 (18)	0.0221 (19)	0.0170 (18)	0.0033 (15)	0.0038 (14)	−0.0024 (15)
C18	0.029 (2)	0.045 (3)	0.055 (3)	−0.006 (2)	−0.017 (2)	0.021 (2)
C19	0.042 (3)	0.048 (3)	0.067 (4)	−0.028 (2)	0.004 (2)	−0.013 (3)
C20	0.030 (2)	0.024 (2)	0.031 (2)	−0.0017 (17)	−0.0001 (17)	0.0089 (18)
C21	0.0206 (19)	0.026 (2)	0.027 (2)	−0.0016 (15)	0.0090 (15)	−0.0032 (16)
C22	0.0220 (19)	0.025 (2)	0.0212 (19)	−0.0026 (16)	0.0068 (15)	−0.0046 (16)
C23	0.023 (2)	0.0203 (19)	0.031 (2)	−0.0025 (16)	0.0032 (16)	0.0005 (17)
C24	0.0202 (19)	0.044 (3)	0.027 (2)	−0.0054 (18)	0.0030 (16)	−0.009 (2)
C25	0.028 (2)	0.027 (2)	0.023 (2)	0.0039 (17)	−0.0010 (16)	0.0057 (17)
N1	0.0158 (14)	0.0130 (14)	0.0148 (14)	0.0010 (11)	0.0006 (11)	0.0039 (12)
N2	0.0150 (14)	0.0141 (14)	0.0138 (14)	−0.0007 (11)	0.0019 (11)	0.0010 (12)
O1	0.0416 (19)	0.0387 (19)	0.0443 (19)	0.0192 (15)	0.0073 (15)	0.0068 (15)
O2	0.0473 (18)	0.0329 (17)	0.0227 (15)	−0.0083 (14)	0.0030 (13)	−0.0102 (13)
O3	0.0337 (17)	0.0447 (19)	0.0429 (18)	−0.0143 (14)	0.0237 (14)	−0.0124 (15)
Cl1	0.0258 (5)	0.0205 (5)	0.0196 (4)	0.0019 (4)	0.0020 (4)	0.0033 (4)
Re1	0.01512 (7)	0.01716 (7)	0.01444 (7)	−0.00040 (6)	0.00331 (5)	−0.00195 (6)

Geometric parameters (Å, º)

C1—O1	1.161 (5)	C15—C24	1.516 (5)
C1—Re1	1.902 (4)	C16—C17	1.399 (5)
C2—O2	1.150 (4)	C16—H16	0.9300
C2—Re1	1.923 (4)	C17—C25	1.503 (5)
C3—O3	1.143 (4)	C18—H18A	0.9600
C3—Re1	1.926 (4)	C18—H18B	0.9600
C4—C9	1.395 (5)	C18—H18C	0.9600
C4—C5	1.401 (5)	C19—H19A	0.9600
C4—N1	1.454 (4)	C19—H19B	0.9600
C5—C6	1.394 (5)	C19—H19C	0.9600
C5—C18	1.502 (5)	C20—H20A	0.9600
C6—C7	1.387 (6)	C20—H20B	0.9600
C6—H6	0.9300	C20—H20C	0.9600
C7—C8	1.382 (5)	C21—H21A	0.9600
C7—C19	1.512 (6)	C21—H21B	0.9600
C8—C9	1.389 (5)	C21—H21C	0.9600
C8—H8	0.9300	C22—H22A	0.9600
C9—C20	1.517 (5)	C22—H22B	0.9600
C10—N1	1.295 (4)	C22—H22C	0.9600
C10—C11	1.484 (5)	C23—H23A	0.9600
C10—C21	1.501 (5)	C23—H23B	0.9600
C11—N2	1.298 (4)	C23—H23C	0.9600
C11—C22	1.490 (5)	C24—H24A	0.9600
C12—C17	1.398 (5)	C24—H24B	0.9600
C12—C13	1.406 (5)	C24—H24C	0.9600
C12—N2	1.453 (4)	C25—H25A	0.9600
C13—C14	1.401 (5)	C25—H25B	0.9600
C13—C23	1.500 (5)	C25—H25C	0.9600
C14—C15	1.383 (5)	N1—Re1	2.167 (3)
C14—H14	0.9300	N2—Re1	2.167 (3)
C15—C16	1.379 (5)	Cl1—Re1	2.4806 (9)
O1—C1—Re1	175.2 (3)	C9—C20—H20A	109.5
O2—C2—Re1	177.3 (3)	C9—C20—H20B	109.5
O3—C3—Re1	178.7 (3)	H20A—C20—H20B	109.5
C9—C4—C5	121.5 (3)	C9—C20—H20C	109.5
C9—C4—N1	118.3 (3)	H20A—C20—H20C	109.5
C5—C4—N1	120.2 (3)	H20B—C20—H20C	109.5
C6—C5—C4	117.8 (4)	C10—C21—H21A	109.5
C6—C5—C18	120.1 (4)	C10—C21—H21B	109.5
C4—C5—C18	122.1 (3)	H21A—C21—H21B	109.5
C7—C6—C5	122.3 (4)	C10—C21—H21C	109.5
C7—C6—H6	118.8	H21A—C21—H21C	109.5
C5—C6—H6	118.8	H21B—C21—H21C	109.5
C8—C7—C6	117.7 (4)	C11—C22—H22A	109.5
C8—C7—C19	121.7 (4)	C11—C22—H22B	109.5
C6—C7—C19	120.5 (4)	H22A—C22—H22B	109.5
C7—C8—C9	122.7 (4)	C11—C22—H22C	109.5
C7—C8—H8	118.6	H22A—C22—H22C	109.5
C9—C8—H8	118.6	H22B—C22—H22C	109.5
C8—C9—C4	117.9 (3)	C13—C23—H23A	109.5
C8—C9—C20	119.6 (3)	C13—C23—H23B	109.5
C4—C9—C20	122.5 (3)	H23A—C23—H23B	109.5
N1—C10—C11	115.5 (3)	C13—C23—H23C	109.5
N1—C10—C21	124.5 (3)	H23A—C23—H23C	109.5
C11—C10—C21	119.8 (3)	H23B—C23—H23C	109.5
N2—C11—C10	115.3 (3)	C15—C24—H24A	109.5
N2—C11—C22	124.8 (3)	C15—C24—H24B	109.5
C10—C11—C22	119.7 (3)	H24A—C24—H24B	109.5
C17—C12—C13	121.6 (3)	C15—C24—H24C	109.5
C17—C12—N2	117.4 (3)	H24A—C24—H24C	109.5
C13—C12—N2	121.0 (3)	H24B—C24—H24C	109.5
C14—C13—C12	117.4 (3)	C17—C25—H25A	109.5
C14—C13—C23	120.4 (3)	C17—C25—H25B	109.5
C12—C13—C23	122.2 (3)	H25A—C25—H25B	109.5
C15—C14—C13	122.6 (3)	C17—C25—H25C	109.5
C15—C14—H14	118.7	H25A—C25—H25C	109.5
C13—C14—H14	118.7	H25B—C25—H25C	109.5
C16—C15—C14	118.2 (3)	C10—N1—C4	119.2 (3)
C16—C15—C24	120.7 (3)	C10—N1—Re1	116.4 (2)
C14—C15—C24	121.0 (4)	C4—N1—Re1	124.4 (2)
C15—C16—C17	122.4 (3)	C11—N2—C12	119.3 (3)
C15—C16—H16	118.8	C11—N2—Re1	116.3 (2)
C17—C16—H16	118.8	C12—N2—Re1	124.5 (2)
C12—C17—C16	117.8 (3)	C1—Re1—C2	88.68 (16)
C12—C17—C25	121.7 (3)	C1—Re1—C3	86.73 (16)
C16—C17—C25	120.4 (3)	C2—Re1—C3	89.88 (15)
C5—C18—H18A	109.5	C1—Re1—N2	98.75 (13)
C5—C18—H18B	109.5	C2—Re1—N2	169.89 (13)
H18A—C18—H18B	109.5	C3—Re1—N2	97.34 (13)
C5—C18—H18C	109.5	C1—Re1—N1	98.15 (13)
H18A—C18—H18C	109.5	C2—Re1—N1	98.66 (13)
H18B—C18—H18C	109.5	C3—Re1—N1	170.23 (13)
C7—C19—H19A	109.5	N2—Re1—N1	73.62 (10)
C7—C19—H19B	109.5	C1—Re1—Cl1	174.89 (11)
H19A—C19—H19B	109.5	C2—Re1—Cl1	87.23 (11)
C7—C19—H19C	109.5	C3—Re1—Cl1	90.18 (12)
H19A—C19—H19C	109.5	N2—Re1—Cl1	85.68 (7)
H19B—C19—H19C	109.5	N1—Re1—Cl1	85.52 (7)
C9—C4—C5—C6	1.3 (5)	C13—C14—C15—C16	−0.5 (5)
N1—C4—C5—C6	179.8 (3)	C13—C14—C15—C24	175.6 (3)
C9—C4—C5—C18	−177.7 (4)	C14—C15—C16—C17	0.4 (5)
N1—C4—C5—C18	0.8 (6)	C24—C15—C16—C17	−175.8 (3)
C4—C5—C6—C7	0.8 (6)	C13—C12—C17—C16	0.6 (5)
C18—C5—C6—C7	179.8 (4)	N2—C12—C17—C16	−179.8 (3)
C5—C6—C7—C8	−1.7 (6)	C13—C12—C17—C25	−176.6 (3)
C5—C6—C7—C19	178.9 (4)	N2—C12—C17—C25	3.0 (5)
C6—C7—C8—C9	0.6 (6)	C15—C16—C17—C12	−0.4 (5)
C19—C7—C8—C9	180.0 (4)	C15—C16—C17—C25	176.8 (3)
C7—C8—C9—C4	1.3 (5)	C11—C10—N1—C4	−168.5 (3)
C7—C8—C9—C20	−177.3 (4)	C21—C10—N1—C4	6.2 (5)
C5—C4—C9—C8	−2.3 (5)	C11—C10—N1—Re1	11.5 (4)
N1—C4—C9—C8	179.1 (3)	C21—C10—N1—Re1	−173.8 (3)
C5—C4—C9—C20	176.3 (3)	C9—C4—N1—C10	89.9 (4)
N1—C4—C9—C20	−2.3 (5)	C5—C4—N1—C10	−88.6 (4)
N1—C10—C11—N2	1.5 (4)	C9—C4—N1—Re1	−90.1 (3)
C21—C10—C11—N2	−173.4 (3)	C5—C4—N1—Re1	91.4 (4)
N1—C10—C11—C22	177.5 (3)	C10—C11—N2—C12	164.8 (3)
C21—C10—C11—C22	2.6 (5)	C22—C11—N2—C12	−11.0 (5)
C17—C12—C13—C14	−0.8 (5)	C10—C11—N2—Re1	−13.8 (4)
N2—C12—C13—C14	179.7 (3)	C22—C11—N2—Re1	170.4 (3)
C17—C12—C13—C23	176.0 (3)	C17—C12—N2—C11	−83.8 (4)
N2—C12—C13—C23	−3.5 (5)	C13—C12—N2—C11	95.8 (4)
C12—C13—C14—C15	0.7 (5)	C17—C12—N2—Re1	94.6 (3)
C23—C13—C14—C15	−176.2 (3)	C13—C12—N2—Re1	−85.8 (3)

(complex4)

Crystal data

C29H36ClN2O3Re	Dx = 1.534 Mg m^−3
Mr = 682.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 4359 reflections
a = 13.0248 (5) Å	θ = 2.4–27.1°
b = 21.7653 (12) Å	µ = 4.23 mm^−1
c = 10.421 (4) Å	T = 150 K
V = 2954.2 (12) Å^3	Block, dark-brown
Z = 4	0.33 × 0.17 × 0.10 mm
F(000) = 1360

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	3603 independent reflections
Radiation source: micro-focus sealed X-ray tube	3152 reflections with I > 2σ(I)
Detector resolution: 8.1150 pixels mm^-1	Rint = 0.036
ω scans	θmax = 29.5°, θmin = 2.7°
Absorption correction: multi-scan CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −17→14
Tmin = 0.342, Tmax = 0.629	k = −28→17
11138 measured reflections	l = −13→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.025	H-atom parameters constrained
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.0152P)^2 + 0.9053P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3603 reflections	Δρmax = 0.74 e Å^−3
169 parameters	Δρmin = −0.87 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
Re1	0.52145 (2)	0.250000	0.57480 (2)	0.01774 (5)
Cl1	0.55860 (7)	0.250000	0.80752 (9)	0.0251 (2)
O1	0.4953 (2)	0.250000	0.2823 (3)	0.0418 (8)
O2	0.68578 (17)	0.34812 (10)	0.5280 (2)	0.0466 (6)
N1	0.39458 (15)	0.18932 (9)	0.62206 (18)	0.0147 (4)
C1	0.5011 (3)	0.250000	0.3933 (4)	0.0274 (10)
C2	0.6240 (2)	0.31141 (13)	0.5459 (3)	0.0281 (7)
C4	0.38356 (19)	0.12344 (12)	0.5954 (2)	0.0175 (5)
C5	0.4217 (2)	0.07982 (13)	0.6815 (2)	0.0238 (6)
C6	0.4041 (2)	0.01820 (13)	0.6522 (3)	0.0327 (7)
H6A	0.428306	−0.011938	0.707767	0.039*
C7	0.3519 (2)	0.00080 (13)	0.5436 (3)	0.0357 (8)
H7A	0.340088	−0.040584	0.527015	0.043*
C8	0.3172 (2)	0.04484 (14)	0.4594 (3)	0.0316 (7)
H8A	0.282615	0.032566	0.385629	0.038*
C9	0.3324 (2)	0.10735 (13)	0.4815 (3)	0.0221 (6)
C10	0.31753 (18)	0.21653 (11)	0.6729 (2)	0.0181 (6)
H10A	0.263518	0.194385	0.708479	0.022*
C18	0.4796 (2)	0.09585 (14)	0.8034 (3)	0.0276 (7)
H18A	0.487716	0.140587	0.806319	0.033*
C19	0.2934 (2)	0.15362 (15)	0.3834 (3)	0.0304 (7)
H19A	0.319760	0.194143	0.407763	0.036*
C22	0.5866 (2)	0.06715 (16)	0.8050 (3)	0.0387 (8)
H22A	0.620982	0.078166	0.883160	0.058*
H22B	0.580656	0.023251	0.799882	0.058*
H22C	0.625320	0.081980	0.733034	0.058*
C23	0.4205 (3)	0.07611 (18)	0.9231 (3)	0.0453 (9)
H23A	0.459120	0.086875	0.998237	0.068*
H23B	0.355225	0.096593	0.925051	0.068*
H23C	0.409944	0.032468	0.921166	0.068*
C24	0.3347 (3)	0.13869 (17)	0.2479 (3)	0.0512 (10)
H24A	0.408304	0.136650	0.250291	0.077*
H24B	0.307682	0.099872	0.220064	0.077*
H24C	0.313770	0.170264	0.189125	0.077*
C25	0.1766 (2)	0.15720 (17)	0.3830 (3)	0.0481 (9)
H25A	0.154685	0.186697	0.320284	0.072*
H25B	0.148690	0.117621	0.362235	0.072*
H25C	0.152943	0.169539	0.466370	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.01455 (9)	0.01216 (9)	0.02650 (9)	0.000	0.00515 (6)	0.000
Cl1	0.0219 (5)	0.0204 (5)	0.0331 (5)	0.000	−0.0078 (4)	0.000
O1	0.0385 (18)	0.059 (2)	0.0283 (16)	0.000	0.0119 (13)	0.000
O2	0.0381 (14)	0.0222 (12)	0.0794 (17)	−0.0117 (11)	0.0201 (12)	0.0024 (12)
N1	0.0156 (11)	0.0131 (11)	0.0155 (10)	−0.0006 (9)	−0.0001 (8)	−0.0017 (9)
C1	0.019 (2)	0.028 (2)	0.034 (2)	0.000	0.0109 (16)	0.000
C2	0.0279 (16)	0.0150 (14)	0.0414 (17)	0.0023 (13)	0.0101 (12)	−0.0006 (13)
C4	0.0152 (13)	0.0123 (13)	0.0248 (13)	−0.0024 (11)	0.0053 (10)	−0.0040 (10)
C5	0.0237 (15)	0.0180 (14)	0.0296 (14)	−0.0023 (13)	0.0018 (11)	0.0007 (12)
C6	0.0385 (18)	0.0134 (14)	0.0462 (18)	−0.0010 (13)	−0.0059 (14)	0.0022 (14)
C7	0.0396 (19)	0.0146 (15)	0.053 (2)	−0.0042 (14)	−0.0024 (15)	−0.0099 (14)
C8	0.0311 (17)	0.0263 (17)	0.0375 (17)	−0.0052 (14)	−0.0024 (13)	−0.0141 (14)
C9	0.0196 (14)	0.0213 (14)	0.0253 (14)	−0.0021 (12)	0.0007 (11)	−0.0058 (12)
C10	0.0173 (13)	0.0175 (14)	0.0195 (12)	−0.0026 (11)	0.0026 (10)	0.0023 (10)
C18	0.0378 (17)	0.0182 (15)	0.0268 (15)	0.0014 (14)	−0.0053 (12)	0.0031 (12)
C19	0.0368 (18)	0.0303 (17)	0.0240 (14)	−0.0043 (15)	−0.0074 (12)	−0.0036 (13)
C22	0.0304 (18)	0.053 (2)	0.0327 (16)	−0.0007 (17)	−0.0004 (13)	−0.0009 (15)
C23	0.038 (2)	0.064 (3)	0.0338 (17)	0.010 (2)	0.0057 (14)	−0.0008 (17)
C24	0.075 (3)	0.054 (2)	0.0247 (16)	−0.009 (2)	−0.0022 (15)	−0.0074 (17)
C25	0.041 (2)	0.045 (2)	0.058 (2)	0.0015 (18)	−0.0192 (17)	0.0039 (18)

Geometric parameters (Å, º)

Re1—C1	1.910 (4)	C10—C10^i	1.457 (5)
Re1—C2	1.913 (3)	C10—H10A	0.9300
Re1—C2^i	1.913 (3)	C18—C22	1.527 (4)
Re1—N1	2.172 (2)	C18—C23	1.528 (4)
Re1—N1^i	2.172 (2)	C18—H18A	0.9800
Re1—Cl1	2.4729 (13)	C19—C25	1.523 (4)
O1—C1	1.159 (5)	C19—C24	1.546 (4)
O2—C2	1.149 (3)	C19—H19A	0.9800
N1—C10	1.280 (3)	C22—H22A	0.9600
N1—C4	1.467 (3)	C22—H22B	0.9600
C4—C5	1.397 (4)	C22—H22C	0.9600
C4—C9	1.406 (3)	C23—H23A	0.9600
C5—C6	1.395 (4)	C23—H23B	0.9600
C5—C18	1.518 (4)	C23—H23C	0.9600
C6—C7	1.373 (4)	C24—H24A	0.9600
C6—H6A	0.9300	C24—H24B	0.9600
C7—C8	1.376 (4)	C24—H24C	0.9600
C7—H7A	0.9300	C25—H25A	0.9600
C8—C9	1.394 (4)	C25—H25B	0.9600
C8—H8A	0.9300	C25—H25C	0.9600
C9—C19	1.522 (4)
C1—Re1—C2	86.63 (12)	N1—C10—H10A	121.2
C1—Re1—C2^i	86.63 (12)	C10^i—C10—H10A	121.2
C2—Re1—C2^i	88.63 (17)	C5—C18—C22	111.7 (2)
C1—Re1—N1	96.82 (10)	C5—C18—C23	111.6 (2)
C2—Re1—N1	172.54 (9)	C22—C18—C23	109.6 (2)
C2^i—Re1—N1	98.16 (10)	C5—C18—H18A	107.9
C1—Re1—N1^i	96.82 (10)	C22—C18—H18A	107.9
C2—Re1—N1^i	98.16 (10)	C23—C18—H18A	107.9
C2^i—Re1—N1^i	172.54 (9)	C25—C19—C9	111.6 (2)
N1—Re1—N1^i	74.90 (11)	C25—C19—C24	110.9 (3)
C1—Re1—Cl1	176.71 (11)	C9—C19—C24	111.0 (3)
C2—Re1—Cl1	91.01 (9)	C25—C19—H19A	107.7
C2^i—Re1—Cl1	91.01 (9)	C9—C19—H19A	107.7
N1—Re1—Cl1	85.79 (5)	C24—C19—H19A	107.7
N1^i—Re1—Cl1	85.79 (5)	C18—C22—H22A	109.5
C10—N1—C4	117.0 (2)	C18—C22—H22B	109.5
C10—N1—Re1	114.14 (17)	H22A—C22—H22B	109.5
C4—N1—Re1	128.73 (15)	C18—C22—H22C	109.5
O1—C1—Re1	175.7 (3)	H22A—C22—H22C	109.5
O2—C2—Re1	179.6 (3)	H22B—C22—H22C	109.5
C5—C4—C9	122.8 (2)	C18—C23—H23A	109.5
C5—C4—N1	120.5 (2)	C18—C23—H23B	109.5
C9—C4—N1	116.7 (2)	H23A—C23—H23B	109.5
C6—C5—C4	117.1 (2)	C18—C23—H23C	109.5
C6—C5—C18	119.0 (3)	H23A—C23—H23C	109.5
C4—C5—C18	123.9 (2)	H23B—C23—H23C	109.5
C7—C6—C5	121.8 (3)	C19—C24—H24A	109.5
C7—C6—H6A	119.1	C19—C24—H24B	109.5
C5—C6—H6A	119.1	H24A—C24—H24B	109.5
C6—C7—C8	119.7 (3)	C19—C24—H24C	109.5
C6—C7—H7A	120.1	H24A—C24—H24C	109.5
C8—C7—H7A	120.1	H24B—C24—H24C	109.5
C7—C8—C9	121.8 (3)	C19—C25—H25A	109.5
C7—C8—H8A	119.1	C19—C25—H25B	109.5
C9—C8—H8A	119.1	H25A—C25—H25B	109.5
C8—C9—C4	116.8 (3)	C19—C25—H25C	109.5
C8—C9—C19	119.1 (2)	H25A—C25—H25C	109.5
C4—C9—C19	124.1 (2)	H25B—C25—H25C	109.5
N1—C10—C10^i	117.56 (14)
C10—N1—C4—C5	−97.3 (3)	C5—C4—C9—C8	2.4 (4)
Re1—N1—C4—C5	87.5 (3)	N1—C4—C9—C8	−176.8 (2)
C10—N1—C4—C9	82.0 (3)	C5—C4—C9—C19	−177.7 (3)
Re1—N1—C4—C9	−93.2 (3)	N1—C4—C9—C19	3.1 (4)
C9—C4—C5—C6	−2.0 (4)	C4—N1—C10—C10^i	−166.18 (14)
N1—C4—C5—C6	177.2 (2)	Re1—N1—C10—C10^i	9.74 (17)
C9—C4—C5—C18	178.3 (2)	C6—C5—C18—C22	58.8 (3)
N1—C4—C5—C18	−2.5 (4)	C4—C5—C18—C22	−121.5 (3)
C4—C5—C6—C7	0.2 (4)	C6—C5—C18—C23	−64.2 (4)
C18—C5—C6—C7	179.8 (3)	C4—C5—C18—C23	115.4 (3)
C5—C6—C7—C8	1.2 (5)	C8—C9—C19—C25	70.4 (4)
C6—C7—C8—C9	−0.7 (5)	C4—C9—C19—C25	−109.4 (3)
C7—C8—C9—C4	−1.0 (4)	C8—C9—C19—C24	−53.8 (3)
C7—C8—C9—C19	179.1 (3)	C4—C9—C19—C24	126.3 (3)

Symmetry code: (i) x, −y+1/2, z.