Crystal structure of a second polymorph of tricarbon­yl(N-methyl­pyridine-2-carboxamide-κ2N1,O)(thio­cyanato-κN)rhenium(I)

Lyczko, K.

doi:10.1107/S205698901601389X

Crystal structure of a second polymorph of tricarbonyl(N-methylpyridine-2-carboxamide-κ²N¹,O)(thiocyanato-κN)rhenium(I)

The second polymorph (monoclinic form) of the [Re(NCS){LH(Me)_NO}(CO)₃] complex, where LH(Me)_NO is N-methylpyridine-2-carboxamide, has been obtained and structurally characterized by X-ray diffraction and supported by DFT calculations.

Keywords: crystal structure; tricarbonylrhenium(I) complex; N-methylpyridine-2-carboxyamide ligand; thiocyanate ion; polymorphism.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S205698901601389X/wm5320sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S205698901601389X/wm5320Isup2.hkl Contains datablock I

CCDC reference: 1501544

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Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.011
wR factor = 0.025
Data-to-parameter ratio = 21.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7     ..  S1      ..       2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10C   ..  S1      ..       2.98 Ang.

Alert level G
PLAT142_ALERT_4_G s.u. on b - Axis Small or Missing ..............    0.00010 Ang.
PLAT143_ALERT_4_G s.u. on c - Axis Small or Missing ..............    0.00010 Ang.
PLAT153_ALERT_1_G The s.u.'s on the Cell Axes   are Equal ..(Note)     0.0001 Ang.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1     --  C11     ..        7.9 s.u.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    O2     --  C2      ..        6.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  N3      ..        8.7 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C1      ..       10.6 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C2      ..       13.4 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Re1    --  C3      ..       11.8 s.u.
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           5 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Tricarbonyl(N-methylpyridine-2-carboxamide-κ²N¹,O)(thiocyanato-κN)rhenium(I) top

Crystal data top

[Re(NCS)(C₇H₈N₂O)(CO)₃]	F(000) = 872
M_r = 464.46	D_x = 2.213 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3456 (1) Å	Cell parameters from 49644 reflections
b = 13.3241 (1) Å	θ = 3.1–31.3°
c = 12.7011 (1) Å	µ = 8.88 mm⁻¹
β = 99.284 (1)°	T = 100 K
V = 1393.83 (2) Å³	Block, yellow
Z = 4	0.15 × 0.12 × 0.08 mm

Data collection top

Agilent SuperNova Dual Source diffractometer with an Eos detector	4060 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3921 reflections with I > 2σ(I)
Detector resolution: 16.0131 pixels mm^-1	R_int = 0.041
ω scans	θ_max = 30.0°, θ_min = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −11→11
T_min = 0.629, T_max = 1.000	k = −18→18
77774 measured reflections	l = −17→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.011	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.025	w = 1/[σ²(F_o²) + (0.0082P)² + 0.8572P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.005
4060 reflections	Δρ_max = 0.42 e Å⁻³
186 parameters	Δρ_min = −0.51 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Re1	0.94102 (2)	0.61839 (2)	0.78536 (2)	0.01041 (2)
S1	0.39614 (5)	0.76937 (3)	0.72060 (3)	0.01731 (8)
O2	0.81867 (15)	0.46596 (9)	0.93364 (10)	0.0228 (3)
N2	0.96200 (16)	0.75572 (10)	0.48766 (10)	0.0133 (2)
O1	1.07960 (14)	0.74704 (9)	0.97900 (9)	0.0203 (2)
C2	0.86838 (19)	0.52386 (12)	0.87960 (12)	0.0161 (3)
O4	0.99371 (13)	0.71917 (8)	0.66237 (8)	0.0127 (2)
N1	0.85068 (15)	0.54369 (9)	0.63442 (10)	0.0125 (2)
O3	1.27172 (14)	0.51162 (9)	0.82262 (9)	0.0184 (2)
C3	1.14740 (19)	0.55136 (11)	0.80679 (11)	0.0135 (3)
C1	1.02572 (18)	0.69876 (11)	0.90694 (12)	0.0145 (3)
C5	0.7205 (2)	0.41062 (12)	0.52690 (14)	0.0192 (3)
H5	0.6744	0.3453	0.5226	0.023*
C6	0.7256 (2)	0.46596 (12)	0.43525 (13)	0.0184 (3)
H6	0.6811	0.4396	0.3673	0.022*
C8	0.85873 (18)	0.59693 (11)	0.54460 (12)	0.0120 (3)
C4	0.78361 (19)	0.45171 (11)	0.62492 (13)	0.0159 (3)
H4	0.7794	0.4136	0.6876	0.019*
C9	0.94147 (17)	0.69584 (11)	0.56703 (11)	0.0116 (3)
N3	0.71182 (16)	0.69184 (10)	0.75566 (10)	0.0149 (2)
C7	0.79640 (19)	0.56049 (12)	0.44386 (12)	0.0157 (3)
H7	0.8021	0.5995	0.3820	0.019*
C10	1.0420 (2)	0.85309 (12)	0.50654 (13)	0.0166 (3)
H10A	0.9883	0.8922	0.5562	0.025*
H10B	1.0349	0.8894	0.4389	0.025*
H10C	1.1563	0.8430	0.5372	0.025*
C11	0.58131 (19)	0.72422 (11)	0.74029 (11)	0.0130 (3)
H2	0.921 (3)	0.7413 (16)	0.4243 (18)	0.026 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.01001 (3)	0.01132 (3)	0.00967 (3)	0.00108 (2)	0.00092 (2)	0.00183 (2)
S1	0.01461 (18)	0.02173 (19)	0.01450 (17)	0.00703 (14)	−0.00096 (13)	−0.00273 (14)
O2	0.0222 (6)	0.0262 (6)	0.0202 (6)	−0.0021 (5)	0.0040 (5)	0.0091 (5)
N2	0.0159 (6)	0.0124 (6)	0.0111 (6)	−0.0027 (5)	0.0008 (5)	0.0007 (4)
O1	0.0199 (6)	0.0212 (6)	0.0190 (6)	0.0012 (5)	0.0009 (5)	−0.0047 (4)
C2	0.0129 (7)	0.0196 (7)	0.0149 (7)	0.0029 (6)	−0.0005 (5)	0.0008 (6)
O4	0.0134 (5)	0.0126 (5)	0.0117 (5)	−0.0016 (4)	0.0008 (4)	0.0012 (4)
N1	0.0118 (6)	0.0120 (6)	0.0137 (6)	0.0010 (4)	0.0023 (5)	0.0009 (4)
O3	0.0155 (5)	0.0195 (5)	0.0199 (5)	0.0041 (4)	0.0016 (4)	0.0027 (4)
C3	0.0154 (7)	0.0134 (6)	0.0115 (6)	−0.0018 (5)	0.0014 (5)	0.0008 (5)
C1	0.0118 (7)	0.0156 (7)	0.0161 (7)	0.0035 (5)	0.0027 (5)	0.0030 (5)
C5	0.0205 (8)	0.0145 (7)	0.0236 (8)	−0.0067 (6)	0.0061 (6)	−0.0028 (6)
C6	0.0195 (8)	0.0182 (7)	0.0180 (7)	−0.0049 (6)	0.0048 (6)	−0.0053 (6)
C8	0.0110 (7)	0.0118 (6)	0.0133 (6)	0.0000 (5)	0.0022 (5)	0.0005 (5)
C4	0.0171 (7)	0.0124 (7)	0.0189 (7)	−0.0015 (5)	0.0051 (6)	0.0024 (5)
C9	0.0099 (6)	0.0117 (6)	0.0131 (6)	0.0016 (5)	0.0014 (5)	0.0011 (5)
N3	0.0155 (6)	0.0155 (6)	0.0136 (6)	0.0012 (5)	0.0021 (5)	0.0003 (5)
C7	0.0179 (7)	0.0161 (7)	0.0134 (7)	−0.0021 (6)	0.0036 (6)	−0.0006 (5)
C10	0.0194 (8)	0.0128 (7)	0.0170 (7)	−0.0038 (6)	0.0012 (6)	0.0022 (5)
C11	0.0165 (7)	0.0121 (6)	0.0103 (6)	−0.0006 (5)	0.0011 (5)	−0.0010 (5)

Geometric parameters (Å, º) top

Re1—C2	1.9028 (16)	O3—C3	1.1533 (19)
Re1—C1	1.9180 (16)	C5—C4	1.384 (2)
Re1—C3	1.9201 (16)	C5—C6	1.384 (2)
Re1—N3	2.1275 (13)	C5—H5	0.9500
Re1—O4	2.1583 (10)	C6—C7	1.388 (2)
Re1—N1	2.1836 (13)	C6—H6	0.9500
S1—C11	1.6394 (16)	C8—C7	1.389 (2)
O2—C2	1.1533 (19)	C8—C9	1.494 (2)
N2—C9	1.3182 (18)	C4—H4	0.9500
N2—C10	1.4610 (19)	N3—C11	1.158 (2)
N2—H2	0.84 (2)	C7—H7	0.9500
O1—C1	1.1494 (19)	C10—H10A	0.9800
O4—C9	1.2581 (17)	C10—H10B	0.9800
N1—C4	1.3446 (19)	C10—H10C	0.9800
N1—C8	1.3542 (18)

C2—Re1—C1	88.66 (7)	C4—C5—H5	120.4
C2—Re1—C3	88.42 (6)	C6—C5—H5	120.4
C1—Re1—C3	86.56 (6)	C5—C6—C7	119.17 (15)
C2—Re1—N3	92.72 (6)	C5—C6—H6	120.4
C1—Re1—N3	95.16 (6)	C7—C6—H6	120.4
C3—Re1—N3	177.96 (5)	N1—C8—C7	122.06 (14)
C2—Re1—O4	171.84 (5)	N1—C8—C9	112.69 (13)
C1—Re1—O4	98.26 (5)	C7—C8—C9	125.25 (13)
C3—Re1—O4	96.27 (5)	N1—C4—C5	122.25 (14)
N3—Re1—O4	82.40 (4)	N1—C4—H4	118.9
C2—Re1—N1	98.66 (6)	C5—C4—H4	118.9
C1—Re1—N1	172.54 (6)	O4—C9—N2	121.26 (14)
C3—Re1—N1	95.00 (5)	O4—C9—C8	118.64 (13)
N3—Re1—N1	83.15 (5)	N2—C9—C8	120.08 (13)
O4—Re1—N1	74.33 (4)	C11—N3—Re1	174.40 (12)
C9—N2—C10	121.62 (13)	C6—C7—C8	118.77 (14)
C9—N2—H2	120.5 (15)	C6—C7—H7	120.6
C10—N2—H2	117.6 (15)	C8—C7—H7	120.6
O2—C2—Re1	177.17 (14)	N2—C10—H10A	109.5
C9—O4—Re1	117.61 (9)	N2—C10—H10B	109.5
C4—N1—C8	118.59 (13)	H10A—C10—H10B	109.5
C4—N1—Re1	125.03 (10)	N2—C10—H10C	109.5
C8—N1—Re1	116.34 (10)	H10A—C10—H10C	109.5
O3—C3—Re1	178.12 (13)	H10B—C10—H10C	109.5
O1—C1—Re1	178.53 (13)	N3—C11—S1	179.00 (14)
C4—C5—C6	119.15 (15)

C4—C5—C6—C7	1.2 (2)	C10—N2—C9—O4	−1.8 (2)
C4—N1—C8—C7	1.7 (2)	C10—N2—C9—C8	179.84 (13)
Re1—N1—C8—C7	−176.03 (12)	N1—C8—C9—O4	0.19 (19)
C4—N1—C8—C9	−177.88 (13)	C7—C8—C9—O4	−179.33 (14)
Re1—N1—C8—C9	4.44 (16)	N1—C8—C9—N2	178.59 (13)
C8—N1—C4—C5	−1.1 (2)	C7—C8—C9—N2	−0.9 (2)
Re1—N1—C4—C5	176.40 (12)	C5—C6—C7—C8	−0.6 (2)
C6—C5—C4—N1	−0.4 (2)	N1—C8—C7—C6	−0.8 (2)
Re1—O4—C9—N2	176.79 (11)	C9—C8—C7—C6	178.65 (14)
Re1—O4—C9—C8	−4.83 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S1ⁱ	0.84 (2)	2.57 (2)	3.3642 (14)	158.0 (19)
C7—H7···S1ⁱ	0.95	2.90	3.8255 (16)	166
C10—H10C···S1ⁱⁱ	0.98	2.98	3.8445 (17)	148

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

Comparison of selected bond lengths, distances (Å) and angles (°) between the experiments and calculations from three different basis sets for the studied complex^(a) top

	Triclinic^(b)	Monoclinic	6-31G(d,p)	6-31G++(d,p)	6-311G++(d,p)
Re1—C1	1.915 (4)	1.9180 (16)	1.9328	1.9306	1.9329
Re1—C2	1.901 (4)	1.9028 (16)	1.9052	1.9016	1.9033
Re1—C3	1.923 (4)	1.9201 (16)	1.9342	1.9297	1.9330
Re1—N1	2.190 (3)	2.1836 (13)	2.2272	2.2079	2.2049
Re1—O4	2.159 (2)	2.1583 (10)	2.2412	2.2257	2.2169
Re1—N3	2.117 (3)	2.1275 (13)	2.1268	2.1076	2.0982
C9—O4	1.261 (4)	1.2581 (17)	1.2524	1.2798	1.2773
C9—N2	1.309 (5)	1.3182 (18)	1.3384	1.3388	1.3388
C10—N2	1.461 (5)	1.4610 (19)	1.4630	1.4708	1.4698
N1···O4	2.620 (4)	2.623 (2)	2.6616	2.6496	2.6401
N1—Re1—O4	74.09 (10)	74.33 (4)	73.12	73.40	73.32
N1—Re1—N3	83.91 (12)	83.15 (5)	81.16	81.40	81.12
O4—Re1—N3	81.68 (11)	82.40 (5)	79.06	78.84	79.73
C11—N3—Re1	167.0 (1)	174.4 (1)	157.29	161.39	167.84
N1—Re1—C1	170.93 (13)	172.55 (6)	169.97	169.90	169.65
O4—Re1—C2	168.57 (12)	171.84 (6)	170.77	170.63	170.91
N3—Re1—C3	174.90 (12)	177.96 (6)	171.84	171.84	172.19

Notes: ⁽^a⁾DFT Calculations were carried out by means of GAUSSIAN09 software (Frisch et al., 2009) using the B3LYP functional and the LANL2DZ basis set for the Re atom; ⁽^b⁾data from Lyczko et al. (2015).

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Crystal structure of a second polymorph of tricarbon­yl(N-methyl­pyridine-2-carboxamide-κ2N1,O)(thio­cyanato-κN)rhenium(I)

Supporting information

Key indicators

checkCIF/PLATON results

Crystal structure of a second polymorph of tricarbonyl(N-methylpyridine-2-carboxamide-κ²N¹,O)(thiocyanato-κN)rhenium(I)