Crystal structure of cis-(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ⁴N)bis­(thio­cyanato-κN)chromium(III) bromide from synchrotron X-ray diffraction data

The Cr^III ion in the [Cr(NCS)₂(cyclam)]⁺ cation has a distorted octa­hedral coordination environment with four N atoms of cyclam and two N-bonded NCS groups in a cis arrangement. The cyclam ligand adopts the cis-V conformation.

Key indicators

• Single-crystal synchrotron study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.043
• wR factor = 0.100
• Data-to-parameter ratio = 25.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          7 Report
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Info

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT092_ALERT_4_G Check: Wavelength Given is not Cu,Ga,Mo,Ag,In Ka    0.61000 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          9 Note
PLAT793_ALERT_4_G Model has Chirality at N1          (Centro SPGR)          R Verify
PLAT793_ALERT_4_G Model has Chirality at N2          (Centro SPGR)          R Verify
PLAT793_ALERT_4_G Model has Chirality at N3          (Centro SPGR)          R Verify
PLAT793_ALERT_4_G Model has Chirality at N4          (Centro SPGR)          R Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Cr1       (III)     .       3.15 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          3 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          2 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          7 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
  12 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: PAL BL2D-SMDC (Shin et al., 2016); cell refinement: HKL3000sm (Otwinowski et al., 2003); data reduction: HKL3000sm (Otwinowski et al., 2003); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND 4 (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

cis-(1,4,8,11-Tetraazacyclotetradecane-κ⁴N)bis(thiocyanato-\ κN)chromium(III) bromide

Crystal data

[Cr(NCS)2(C10H24N4)]Br	F(000) = 916
Mr = 448.40	Dx = 1.598 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.610 Å
a = 10.880 (2) Å	Cell parameters from 49610 reflections
b = 7.7310 (15) Å	θ = 0.4–33.7°
c = 22.161 (4) Å	µ = 1.98 mm^−1
β = 91.65 (3)°	T = 173 K
V = 1863.3 (6) Å^3	Needle, orange
Z = 4	0.03 × 0.01 × 0.01 mm

Data collection

ADSC Q210 CCD area detector diffractometer	2901 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	Rint = 0.092
ω scan	θmax = 25.0°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (HKL3000sm Scalepack; Otwinowski et al., 2003)	h = −15→15
Tmin = 0.904, Tmax = 1.000	k = −10→10
18069 measured reflections	l = −30→30
5185 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0455P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.100	(Δ/σ)max = 0.001
S = 0.87	Δρmax = 0.85 e Å^−3
5185 reflections	Δρmin = −0.79 e Å^−3
200 parameters	Extinction correction: SHELXL2016/6 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0180 (9)

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
Cr1	0.27993 (5)	0.35081 (6)	0.63702 (2)	0.02286 (14)
S1	0.31333 (9)	0.00278 (12)	0.81190 (4)	0.0375 (2)
S2	0.64505 (11)	0.06790 (15)	0.58036 (5)	0.0566 (3)
N1	0.1153 (3)	0.4392 (3)	0.67081 (12)	0.0279 (6)
H1	0.097582	0.553841	0.651585	0.033*
N2	0.1644 (3)	0.2145 (3)	0.57803 (12)	0.0282 (6)
H2	0.163030	0.093399	0.593809	0.034*
N3	0.2950 (3)	0.5456 (3)	0.57286 (12)	0.0319 (7)
H3	0.216688	0.613469	0.572416	0.038*
N4	0.3741 (3)	0.5269 (3)	0.69205 (12)	0.0312 (6)
H4	0.460852	0.484332	0.694735	0.037*
N5	0.2805 (3)	0.1671 (3)	0.70104 (13)	0.0351 (7)
N6	0.4346 (3)	0.2501 (4)	0.60735 (12)	0.0332 (7)
C1	0.0176 (3)	0.3171 (4)	0.64907 (15)	0.0333 (8)
H1A	−0.064580	0.369151	0.654333	0.040*
H1AB	0.022153	0.208318	0.672605	0.040*
C2	0.0369 (3)	0.2801 (4)	0.58327 (16)	0.0317 (8)
H2A	−0.022924	0.192519	0.568261	0.038*
H2AB	0.025377	0.386957	0.559114	0.038*
C3	0.2012 (4)	0.2002 (4)	0.51429 (15)	0.0379 (9)
H3A	0.138689	0.131585	0.491471	0.045*
H3AB	0.280293	0.137056	0.512905	0.045*
C4	0.2153 (4)	0.3746 (5)	0.48384 (15)	0.0413 (9)
H4A	0.136301	0.437517	0.486127	0.050*
H4AB	0.230961	0.354800	0.440602	0.050*
C5	0.3170 (4)	0.4903 (5)	0.50993 (15)	0.0405 (9)
H5A	0.396127	0.427129	0.509024	0.049*
H5AB	0.324199	0.594165	0.484161	0.049*
C6	0.3960 (4)	0.6632 (4)	0.59462 (17)	0.0393 (9)
H6A	0.392736	0.773210	0.571775	0.047*
H6AB	0.476836	0.608305	0.588356	0.047*
C7	0.3797 (4)	0.6977 (4)	0.66092 (17)	0.0402 (9)
H7A	0.449580	0.766556	0.677480	0.048*
H7AB	0.302857	0.763365	0.666944	0.048*
C8	0.3351 (4)	0.5454 (5)	0.75602 (15)	0.0391 (9)
H8A	0.386361	0.635299	0.776192	0.047*
H8AB	0.350532	0.434806	0.777454	0.047*
C9	0.2007 (4)	0.5935 (5)	0.76167 (16)	0.0414 (9)
H9A	0.184689	0.612776	0.804899	0.050*
H9AB	0.186265	0.704638	0.740453	0.050*
C10	0.1081 (3)	0.4631 (5)	0.73720 (15)	0.0371 (9)
H10A	0.122623	0.350514	0.757466	0.044*
H10B	0.024273	0.502178	0.746855	0.044*
C11	0.2947 (3)	0.0968 (4)	0.74715 (15)	0.0291 (8)
C12	0.5225 (3)	0.1731 (4)	0.59660 (14)	0.0322 (8)
Br1	0.05786 (4)	0.81437 (4)	0.60207 (2)	0.04372 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.0254 (3)	0.0205 (3)	0.0227 (3)	0.0034 (2)	0.0017 (2)	−0.0016 (2)
S1	0.0398 (6)	0.0410 (5)	0.0315 (5)	−0.0035 (4)	−0.0011 (4)	0.0085 (4)
S2	0.0529 (7)	0.0679 (7)	0.0496 (6)	0.0331 (6)	0.0104 (5)	−0.0055 (6)
N1	0.0307 (16)	0.0231 (13)	0.0300 (15)	0.0028 (12)	0.0052 (12)	0.0012 (12)
N2	0.0310 (16)	0.0214 (13)	0.0321 (15)	0.0021 (11)	−0.0007 (12)	0.0011 (12)
N3	0.0316 (17)	0.0328 (15)	0.0315 (15)	−0.0027 (12)	0.0045 (13)	0.0049 (13)
N4	0.0310 (17)	0.0294 (14)	0.0329 (15)	0.0048 (12)	−0.0017 (12)	−0.0063 (13)
N5	0.0406 (18)	0.0292 (15)	0.0355 (16)	0.0079 (13)	0.0023 (13)	0.0050 (14)
N6	0.0339 (18)	0.0359 (15)	0.0298 (16)	0.0057 (14)	0.0038 (13)	−0.0070 (13)
C1	0.0265 (19)	0.0294 (17)	0.044 (2)	−0.0025 (15)	0.0071 (15)	0.0013 (16)
C2	0.0279 (19)	0.0262 (17)	0.041 (2)	−0.0006 (14)	−0.0041 (15)	0.0010 (15)
C3	0.043 (2)	0.0379 (19)	0.0327 (19)	0.0042 (17)	−0.0026 (16)	−0.0077 (17)
C4	0.051 (3)	0.048 (2)	0.0249 (18)	0.0020 (19)	0.0015 (17)	0.0036 (17)
C5	0.046 (2)	0.046 (2)	0.0294 (19)	−0.0014 (19)	0.0067 (17)	0.0103 (17)
C6	0.036 (2)	0.0305 (18)	0.052 (2)	−0.0091 (16)	0.0008 (17)	0.0050 (17)
C7	0.035 (2)	0.0299 (18)	0.056 (2)	−0.0026 (16)	−0.0036 (17)	−0.0073 (18)
C8	0.042 (2)	0.041 (2)	0.034 (2)	0.0043 (17)	−0.0012 (17)	−0.0133 (17)
C9	0.044 (2)	0.044 (2)	0.036 (2)	0.0107 (18)	0.0011 (17)	−0.0163 (18)
C10	0.033 (2)	0.045 (2)	0.0335 (19)	0.0047 (17)	0.0093 (15)	−0.0053 (17)
C11	0.031 (2)	0.0224 (16)	0.0340 (19)	0.0013 (14)	0.0028 (15)	0.0008 (15)
C12	0.041 (2)	0.0298 (17)	0.0259 (17)	0.0044 (16)	0.0040 (15)	−0.0017 (15)
Br1	0.0452 (2)	0.02097 (17)	0.0642 (3)	0.00171 (15)	−0.01224 (18)	0.00375 (17)

Geometric parameters (Å, º)

Cr1—N6	1.984 (3)	C1—H1AB	0.9900
Cr1—N5	2.007 (3)	C2—H2A	0.9900
Cr1—N2	2.075 (3)	C2—H2AB	0.9900
Cr1—N1	2.076 (3)	C3—C4	1.518 (5)
Cr1—N4	2.078 (3)	C3—H3A	0.9900
Cr1—N3	2.081 (3)	C3—H3AB	0.9900
S1—C11	1.616 (3)	C4—C5	1.524 (5)
S2—C12	1.611 (4)	C4—H4A	0.9900
N1—C10	1.487 (4)	C4—H4AB	0.9900
N1—C1	1.492 (4)	C5—H5A	0.9900
N1—H1	1.0000	C5—H5AB	0.9900
N2—C3	1.484 (4)	C6—C7	1.509 (5)
N2—C2	1.485 (4)	C6—H6A	0.9900
N2—H2	1.0000	C6—H6AB	0.9900
N3—C5	1.485 (4)	C7—H7A	0.9900
N3—C6	1.495 (4)	C7—H7AB	0.9900
N3—H3	1.0000	C8—C9	1.517 (5)
N4—C7	1.492 (4)	C8—H8A	0.9900
N4—C8	1.498 (4)	C8—H8AB	0.9900
N4—H4	1.0000	C9—C10	1.514 (5)
N5—C11	1.164 (4)	C9—H9A	0.9900
N6—C12	1.157 (4)	C9—H9AB	0.9900
C1—C2	1.507 (5)	C10—H10A	0.9900
C1—H1A	0.9900	C10—H10B	0.9900
N6—Cr1—N5	88.35 (12)	H2A—C2—H2AB	108.5
N6—Cr1—N2	95.53 (11)	N2—C3—C4	113.0 (3)
N5—Cr1—N2	94.33 (11)	N2—C3—H3A	109.0
N6—Cr1—N1	175.90 (11)	C4—C3—H3A	109.0
N5—Cr1—N1	87.88 (11)	N2—C3—H3AB	109.0
N2—Cr1—N1	83.16 (11)	C4—C3—H3AB	109.0
N6—Cr1—N4	92.48 (12)	H3A—C3—H3AB	107.8
N5—Cr1—N4	93.29 (12)	C3—C4—C5	115.7 (3)
N2—Cr1—N4	169.10 (11)	C3—C4—H4A	108.4
N1—Cr1—N4	89.34 (11)	C5—C4—H4A	108.4
N6—Cr1—N3	88.49 (12)	C3—C4—H4AB	108.4
N5—Cr1—N3	175.08 (12)	C5—C4—H4AB	108.4
N2—Cr1—N3	89.72 (11)	H4A—C4—H4AB	107.4
N1—Cr1—N3	95.39 (11)	N3—C5—C4	113.0 (3)
N4—Cr1—N3	83.08 (11)	N3—C5—H5A	109.0
C10—N1—C1	109.9 (3)	C4—C5—H5A	109.0
C10—N1—Cr1	117.9 (2)	N3—C5—H5AB	109.0
C1—N1—Cr1	106.85 (19)	C4—C5—H5AB	109.0
C10—N1—H1	107.2	H5A—C5—H5AB	107.8
C1—N1—H1	107.2	N3—C6—C7	108.4 (3)
Cr1—N1—H1	107.2	N3—C6—H6A	110.0
C3—N2—C2	112.3 (3)	C7—C6—H6A	110.0
C3—N2—Cr1	117.5 (2)	N3—C6—H6AB	110.0
C2—N2—Cr1	109.14 (19)	C7—C6—H6AB	110.0
C3—N2—H2	105.6	H6A—C6—H6AB	108.4
C2—N2—H2	105.6	N4—C7—C6	107.5 (3)
Cr1—N2—H2	105.6	N4—C7—H7A	110.2
C5—N3—C6	109.9 (3)	C6—C7—H7A	110.2
C5—N3—Cr1	116.8 (2)	N4—C7—H7AB	110.2
C6—N3—Cr1	106.9 (2)	C6—C7—H7AB	110.2
C5—N3—H3	107.6	H7A—C7—H7AB	108.5
C6—N3—H3	107.6	N4—C8—C9	113.7 (3)
Cr1—N3—H3	107.6	N4—C8—H8A	108.8
C7—N4—C8	111.7 (3)	C9—C8—H8A	108.8
C7—N4—Cr1	109.5 (2)	N4—C8—H8AB	108.8
C8—N4—Cr1	118.0 (2)	C9—C8—H8AB	108.8
C7—N4—H4	105.5	H8A—C8—H8AB	107.7
C8—N4—H4	105.5	C10—C9—C8	116.1 (3)
Cr1—N4—H4	105.5	C10—C9—H9A	108.3
C11—N5—Cr1	161.6 (3)	C8—C9—H9A	108.3
C12—N6—Cr1	169.9 (3)	C10—C9—H9AB	108.3
N1—C1—C2	108.3 (3)	C8—C9—H9AB	108.3
N1—C1—H1A	110.0	H9A—C9—H9AB	107.4
C2—C1—H1A	110.0	N1—C10—C9	112.5 (3)
N1—C1—H1AB	110.0	N1—C10—H10A	109.1
C2—C1—H1AB	110.0	C9—C10—H10A	109.1
H1A—C1—H1AB	108.4	N1—C10—H10B	109.1
N2—C2—C1	107.3 (3)	C9—C10—H10B	109.1
N2—C2—H2A	110.3	H10A—C10—H10B	107.8
C1—C2—H2A	110.3	N5—C11—S1	178.8 (3)
N2—C2—H2AB	110.3	N6—C12—S2	178.9 (3)
C1—C2—H2AB	110.3
C10—N1—C1—C2	−173.5 (3)	C5—N3—C6—C7	−172.6 (3)
Cr1—N1—C1—C2	−44.5 (3)	Cr1—N3—C6—C7	−44.9 (3)
C3—N2—C2—C1	−170.8 (3)	C8—N4—C7—C6	−169.6 (3)
Cr1—N2—C2—C1	−38.6 (3)	Cr1—N4—C7—C6	−36.9 (3)
N1—C1—C2—N2	55.7 (3)	N3—C6—C7—N4	54.7 (4)
C2—N2—C3—C4	68.6 (4)	C7—N4—C8—C9	71.2 (4)
Cr1—N2—C3—C4	−59.2 (4)	Cr1—N4—C8—C9	−57.1 (4)
N2—C3—C4—C5	64.2 (4)	N4—C8—C9—C10	62.9 (4)
C6—N3—C5—C4	−178.1 (3)	C1—N1—C10—C9	−176.9 (3)
Cr1—N3—C5—C4	59.9 (4)	Cr1—N1—C10—C9	60.4 (3)
C3—C4—C5—N3	−64.9 (4)	C8—C9—C10—N1	−64.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	1.00	2.33	3.327 (3)	177
N2—H2···Br1^i	1.00	2.45	3.352 (3)	150
N3—H3···Br1	1.00	2.43	3.389 (3)	161
N4—H4···S1^ii	1.00	2.47	3.410 (3)	156

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