(1,8-Di-n-propyl-1,3,6,8,10,13-hexa­aza­cyclo­tetra­decane)­nickel(II) diperchlorate

In the title complex, [Ni(C₁₄H₃₄N₆)](ClO₄)₂, the 14-membered hexa­aza­cyclo­tetra­decane macrocycle ring chelates to the Ni atom through its four secondary N atoms. The O atoms of the perchlorate ions are 2.86 (1) and 3.070 (4) Å from the Ni atom, whose geometry is best described as intermediate between octahedral and square pyramidal.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in solvent or counterion
• R factor = 0.044
• wR factor = 0.131
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT430_ALERT_2_B Short Inter D...A Contact  O13    ..  O24      =       2.76 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O23    ..  O23      =       2.81 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl2
PLAT244_ALERT_4_C Low Solvent  U(eq) as Compared to Neighbors ....        Cl1
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      23.00 Perc.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O24      =       2.63 Ang.

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

[1,8-Di-2-n-propyl-1,3,6,8,10,13-hexaazacyclotetradecane]nickel(II) diperchlorate

Crystal data

[Ni(C14H34N6)](ClO4)2	Z = 2
Mr = 544.08	F(000) = 572
Triclinic, P1	Dx = 1.540 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1634 (6) Å	Cell parameters from 2807 reflections
b = 12.411 (1) Å	θ = 4.2–29.5°
c = 12.518 (1) Å	µ = 1.11 mm^−1
α = 77.094 (1)°	T = 298 K
β = 83.348 (1)°	Plate, yellow
γ = 71.882 (1)°	0.42 × 0.25 × 0.08 mm
V = 1173.5 (2) Å^3

Data collection

Bruker SMART 1K area-detector diffractometer	3973 independent reflections
Radiation source: normal-focus sealed tube	3155 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 4.2°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.654, Tmax = 0.917	l = 0→14
6468 measured 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0832P)^2 + 0.0059P] where P = (Fo^2 + 2Fc^2)/3
3973 reflections	(Δ/σ)max = 0.004
311 parameters	Δρmax = 0.53 e Å^−3
91 restraints	Δρmin = −0.33 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.73545 (4)	0.76704 (3)	0.77014 (3)	0.04957 (17)
Cl1	1.06157 (10)	0.73602 (8)	0.96401 (7)	0.0671 (2)
O11	0.9125 (4)	0.8281 (3)	0.9411 (4)	0.1498 (15)
O12	1.0126 (5)	0.6316 (3)	0.9936 (3)	0.1285 (13)
O13	1.1696 (4)	0.7307 (4)	0.8681 (2)	0.1192 (12)
O14	1.1534 (3)	0.7426 (3)	1.0499 (2)	0.0895 (8)
Cl2	0.42569 (10)	0.79180 (7)	0.56356 (7)	0.0660 (2)
O21	0.3354 (4)	0.7666 (3)	0.4879 (3)	0.1099 (10)
O22	0.5907 (8)	0.7121 (8)	0.5738 (9)	0.171 (3)	0.63
O23	0.4397 (15)	0.9031 (6)	0.5374 (8)	0.138 (3)	0.63
O24	0.3341 (10)	0.7742 (9)	0.6645 (4)	0.132 (2)	0.63
O22A	0.5521 (18)	0.8220 (18)	0.4884 (11)	0.185 (6)	0.37
O23A	0.310 (2)	0.8968 (12)	0.5929 (13)	0.162 (6)	0.37
O24A	0.4947 (18)	0.7173 (10)	0.6535 (9)	0.140 (4)	0.37
N1	1.0091 (3)	0.5426 (2)	0.6806 (2)	0.0701 (7)
N2	0.9361 (3)	0.7521 (2)	0.6698 (2)	0.0619 (7)
H2	1.0276	0.7420	0.7100	0.074*
N3	0.6763 (3)	0.9324 (2)	0.7145 (2)	0.0633 (7)
H3	0.5986	0.9493	0.6621	0.076*
N4	0.4487 (4)	0.9915 (2)	0.8550 (3)	0.0731 (8)
N5	0.5372 (3)	0.7809 (2)	0.8727 (2)	0.0547 (6)
H5	0.4462	0.7852	0.8346	0.066*
N6	0.7953 (3)	0.60199 (18)	0.8259 (2)	0.0521 (6)
H6	0.8812	0.5843	0.8729	0.062*
C1	1.4878 (5)	0.3860 (4)	0.7160 (4)	0.1114 (15)
H1A	1.4989	0.4295	0.7679	0.167*
H1B	1.5846	0.3792	0.6638	0.167*
H1C	1.4847	0.3104	0.7540	0.167*
C2	1.3231 (5)	0.4476 (4)	0.6567 (4)	0.0921 (12)
H2A	1.3401	0.5121	0.6013	0.111*
H2B	1.2960	0.3948	0.6198	0.111*
C3	1.1742 (4)	0.4914 (3)	0.7337 (3)	0.0745 (9)
H3A	1.1647	0.4278	0.7929	0.089*
H3B	1.1978	0.5490	0.7658	0.089*
C4	0.9831 (5)	0.6528 (3)	0.6100 (3)	0.0752 (9)
H4A	0.8918	0.6645	0.5616	0.090*
H4B	1.0877	0.6534	0.5647	0.090*
C5	0.9116 (5)	0.8652 (3)	0.5921 (3)	0.0816 (11)
H5A	0.8351	0.8721	0.5355	0.098*
H5B	1.0214	0.8721	0.5574	0.098*
C6	0.8345 (4)	0.9565 (3)	0.6583 (3)	0.0796 (11)
H6A	0.9143	0.9532	0.7114	0.096*
H6B	0.8065	1.0326	0.6112	0.096*
C7	0.5976 (5)	1.0112 (3)	0.7945 (3)	0.0752 (9)
H7A	0.6838	1.0022	0.8456	0.090*
H7B	0.5679	1.0906	0.7543	0.090*
C8	0.2877 (5)	1.0263 (3)	0.7977 (4)	0.0833 (11)
H8A	0.3083	0.9880	0.7358	0.100*
H8B	0.2019	0.9991	0.8471	0.100*
C9	0.2177 (5)	1.1493 (4)	0.7583 (4)	0.1013 (13)
H9A	0.2963	1.1750	0.7014	0.122*
H9B	0.2107	1.1888	0.8181	0.122*
C10	0.0399 (5)	1.1839 (4)	0.7126 (4)	0.0957 (13)
H10A	0.0444	1.1425	0.6555	0.144*
H10B	0.0045	1.2656	0.6831	0.144*
H10C	−0.0413	1.1656	0.7702	0.144*
C11	0.4823 (4)	0.8820 (3)	0.9287 (3)	0.0681 (8)
H11A	0.3788	0.8791	0.9745	0.082*
H11B	0.5720	0.8754	0.9764	0.082*
C12	0.5700 (4)	0.6713 (3)	0.9549 (3)	0.0641 (8)
H12A	0.4633	0.6637	0.9942	0.077*
H12B	0.6502	0.6690	1.0074	0.077*
C13	0.6452 (4)	0.5765 (3)	0.8918 (3)	0.0658 (8)
H13A	0.6807	0.5022	0.9415	0.079*
H13B	0.5607	0.5743	0.8444	0.079*
C14	0.8605 (4)	0.5264 (3)	0.7426 (3)	0.0662 (8)
H14A	0.8857	0.4462	0.7802	0.079*
H14B	0.7696	0.5413	0.6930	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0453 (2)	0.0446 (2)	0.0553 (3)	−0.01629 (16)	−0.00589 (16)	0.00353 (16)
Cl1	0.0499 (4)	0.0831 (6)	0.0648 (5)	−0.0217 (4)	−0.0100 (4)	−0.0009 (4)
O11	0.091 (2)	0.130 (3)	0.192 (4)	0.022 (2)	−0.049 (2)	−0.016 (3)
O12	0.140 (3)	0.134 (3)	0.130 (3)	−0.089 (2)	−0.061 (2)	0.032 (2)
O13	0.094 (2)	0.208 (4)	0.0736 (19)	−0.070 (2)	0.0026 (15)	−0.030 (2)
O14	0.0677 (15)	0.128 (2)	0.0809 (17)	−0.0321 (15)	−0.0068 (12)	−0.0316 (15)
Cl2	0.0619 (5)	0.0755 (5)	0.0601 (5)	−0.0211 (4)	−0.0132 (4)	−0.0063 (4)
O21	0.111 (2)	0.110 (2)	0.118 (2)	−0.0220 (18)	−0.0399 (19)	−0.0399 (18)
O22	0.076 (4)	0.184 (8)	0.213 (9)	0.028 (4)	−0.041 (5)	−0.034 (7)
O23	0.195 (8)	0.093 (4)	0.148 (7)	−0.083 (5)	−0.078 (6)	0.023 (4)
O24	0.127 (5)	0.231 (8)	0.068 (3)	−0.101 (5)	0.016 (3)	−0.037 (4)
O22A	0.135 (10)	0.205 (15)	0.225 (17)	−0.105 (11)	0.060 (11)	−0.018 (14)
O23A	0.184 (13)	0.142 (11)	0.163 (13)	0.007 (9)	−0.041 (10)	−0.096 (11)
O24A	0.123 (9)	0.159 (10)	0.101 (8)	−0.023 (8)	−0.047 (7)	0.042 (7)
N1	0.0670 (17)	0.0691 (17)	0.0652 (17)	−0.0126 (13)	0.0009 (13)	−0.0079 (13)
N2	0.0560 (14)	0.0616 (15)	0.0581 (16)	−0.0189 (12)	−0.0036 (11)	0.0113 (12)
N3	0.0577 (15)	0.0490 (13)	0.0784 (18)	−0.0179 (11)	−0.0138 (13)	0.0054 (12)
N4	0.0643 (17)	0.0586 (16)	0.099 (2)	−0.0131 (13)	−0.0131 (15)	−0.0231 (14)
N5	0.0441 (13)	0.0517 (13)	0.0666 (16)	−0.0143 (10)	−0.0081 (11)	−0.0053 (11)
N6	0.0437 (12)	0.0476 (12)	0.0599 (15)	−0.0141 (10)	−0.0039 (10)	0.0011 (10)
C1	0.073 (2)	0.124 (4)	0.145 (4)	−0.014 (2)	0.004 (3)	−0.070 (3)
C2	0.078 (2)	0.092 (3)	0.101 (3)	−0.009 (2)	0.007 (2)	−0.037 (2)
C3	0.069 (2)	0.069 (2)	0.079 (2)	−0.0076 (17)	−0.0002 (17)	−0.0205 (17)
C4	0.070 (2)	0.089 (2)	0.058 (2)	−0.0214 (18)	0.0054 (16)	−0.0053 (17)
C5	0.065 (2)	0.082 (2)	0.076 (2)	−0.0234 (18)	0.0052 (17)	0.0265 (19)
C6	0.071 (2)	0.0592 (19)	0.096 (3)	−0.0263 (17)	−0.0111 (19)	0.0239 (18)
C7	0.079 (2)	0.0480 (17)	0.101 (3)	−0.0218 (16)	−0.018 (2)	−0.0097 (17)
C8	0.070 (2)	0.067 (2)	0.112 (3)	−0.0060 (17)	−0.016 (2)	−0.031 (2)
C9	0.100 (3)	0.079 (3)	0.123 (4)	−0.007 (2)	−0.031 (3)	−0.031 (2)
C10	0.091 (3)	0.093 (3)	0.092 (3)	0.007 (2)	−0.023 (2)	−0.035 (2)
C11	0.0623 (19)	0.0644 (19)	0.080 (2)	−0.0178 (15)	−0.0041 (16)	−0.0204 (16)
C12	0.0488 (16)	0.0674 (19)	0.068 (2)	−0.0216 (14)	0.0061 (14)	0.0046 (15)
C13	0.0541 (17)	0.0501 (16)	0.085 (2)	−0.0196 (14)	0.0022 (15)	0.0073 (15)
C14	0.0676 (19)	0.0578 (17)	0.071 (2)	−0.0174 (15)	−0.0059 (16)	−0.0086 (15)

Geometric parameters (Å, º)

Ni1—N2	1.932 (3)	C1—C2	1.511 (5)
Ni1—N6	1.934 (2)	C1—H1A	0.9600
Ni1—N5	1.934 (2)	C1—H1B	0.9600
Ni1—N3	1.937 (2)	C1—H1C	0.9600
Ni1—O24A	2.863 (11)	C2—C3	1.501 (5)
Ni1—O11	3.060 (4)	C2—H2A	0.9700
Ni1—O22	3.134 (9)	C2—H2B	0.9700
Cl1—O11	1.392 (3)	C3—H3A	0.9700
Cl1—O13	1.406 (3)	C3—H3B	0.9700
Cl1—O14	1.411 (3)	C4—H4A	0.9700
Cl1—O12	1.432 (3)	C4—H4B	0.9700
Cl2—O24A	1.341 (7)	C5—C6	1.490 (6)
Cl2—O23	1.384 (5)	C5—H5A	0.9700
Cl2—O22A	1.396 (8)	C5—H5B	0.9700
Cl2—O24	1.402 (5)	C6—H6A	0.9700
Cl2—O22	1.402 (5)	C6—H6B	0.9700
Cl2—O21	1.405 (3)	C7—H7A	0.9700
Cl2—O23A	1.446 (9)	C7—H7B	0.9700
N1—C14	1.407 (4)	C8—C9	1.444 (5)
N1—C4	1.421 (4)	C8—H8A	0.9700
N1—C3	1.466 (4)	C8—H8B	0.9700
N2—C5	1.489 (4)	C9—C10	1.521 (5)
N2—C4	1.510 (5)	C9—H9A	0.9700
N2—H2	0.9100	C9—H9B	0.9700
N3—C6	1.479 (4)	C10—H10A	0.9600
N3—C7	1.507 (5)	C10—H10B	0.9600
N3—H3	0.9100	C10—H10C	0.9600
N4—C7	1.414 (4)	C11—H11A	0.9700
N4—C11	1.428 (4)	C11—H11B	0.9700
N4—C8	1.468 (4)	C12—C13	1.497 (5)
N5—C12	1.480 (4)	C12—H12A	0.9700
N5—C11	1.496 (4)	C12—H12B	0.9700
N5—H5	0.9100	C13—H13A	0.9700
N6—C13	1.474 (4)	C13—H13B	0.9700
N6—C14	1.499 (4)	C14—H14A	0.9700
N6—H6	0.9100	C14—H14B	0.9700
N2—Ni1—N6	92.47 (10)	H1A—C1—H1C	109.5
N2—Ni1—N5	178.99 (9)	H1B—C1—H1C	109.5
N6—Ni1—N5	87.05 (9)	C3—C2—C1	111.9 (3)
N2—Ni1—N3	87.44 (11)	C3—C2—H2A	109.2
N6—Ni1—N3	179.79 (10)	C1—C2—H2A	109.2
N5—Ni1—N3	93.03 (11)	C3—C2—H2B	109.2
N2—Ni1—O24A	102.8 (3)	C1—C2—H2B	109.2
N6—Ni1—O24A	82.0 (2)	H2A—C2—H2B	107.9
N5—Ni1—O24A	78.0 (3)	N1—C3—C2	113.4 (3)
N3—Ni1—O24A	98.2 (2)	N1—C3—H3A	108.9
N2—Ni1—O11	92.56 (12)	C2—C3—H3A	108.9
N6—Ni1—O11	97.56 (10)	N1—C3—H3B	108.9
N5—Ni1—O11	86.62 (11)	C2—C3—H3B	108.9
N3—Ni1—O11	82.26 (11)	H3A—C3—H3B	107.7
O24A—Ni1—O11	164.6 (3)	N1—C4—N2	113.8 (3)
N2—Ni1—O22	80.5 (2)	N1—C4—H4A	108.8
N6—Ni1—O22	84.93 (19)	N2—C4—H4A	108.8
N5—Ni1—O22	100.3 (2)	N1—C4—H4B	108.8
N3—Ni1—O22	95.2 (2)	N2—C4—H4B	108.8
O11—Ni1—O22	172.8 (2)	H4A—C4—H4B	107.7
O11—Cl1—O13	108.7 (2)	N2—C5—C6	106.5 (3)
O11—Cl1—O14	114.0 (2)	N2—C5—H5A	110.4
O13—Cl1—O14	109.46 (17)	C6—C5—H5A	110.4
O11—Cl1—O12	107.9 (3)	N2—C5—H5B	110.4
O13—Cl1—O12	108.1 (3)	C6—C5—H5B	110.4
O14—Cl1—O12	108.52 (18)	H5A—C5—H5B	108.6
O24A—Cl2—O23	121.3 (6)	N3—C6—C5	106.0 (3)
O24A—Cl2—O22A	111.7 (8)	N3—C6—H6A	110.5
O23—Cl2—O22A	57.7 (6)	C5—C6—H6A	110.5
O24A—Cl2—O24	56.0 (6)	N3—C6—H6B	110.5
O23—Cl2—O24	110.5 (5)	C5—C6—H6B	110.5
O22A—Cl2—O24	158.1 (7)	H6A—C6—H6B	108.7
O24A—Cl2—O22	51.6 (5)	N4—C7—N3	114.8 (3)
O23—Cl2—O22	109.5 (5)	N4—C7—H7A	108.6
O22A—Cl2—O22	65.0 (7)	N3—C7—H7A	108.6
O24—Cl2—O22	107.5 (5)	N4—C7—H7B	108.6
O24A—Cl2—O21	124.8 (6)	N3—C7—H7B	108.6
O23—Cl2—O21	113.9 (3)	H7A—C7—H7B	107.5
O22A—Cl2—O21	96.4 (6)	C9—C8—N4	115.0 (3)
O24—Cl2—O21	105.4 (3)	C9—C8—H8A	108.5
O22—Cl2—O21	109.8 (4)	N4—C8—H8A	108.5
O24A—Cl2—O23A	110.2 (8)	C9—C8—H8B	108.5
O23—Cl2—O23A	50.5 (6)	N4—C8—H8B	108.5
O22A—Cl2—O23A	107.8 (9)	H8A—C8—H8B	107.5
O24—Cl2—O23A	66.0 (7)	C8—C9—C10	113.7 (4)
O22—Cl2—O23A	145.8 (6)	C8—C9—H9A	108.8
O21—Cl2—O23A	104.2 (5)	C10—C9—H9A	108.8
C14—N1—C4	114.3 (3)	C8—C9—H9B	108.8
C14—N1—C3	117.4 (3)	C10—C9—H9B	108.8
C4—N1—C3	117.2 (3)	H9A—C9—H9B	107.7
C5—N2—C4	111.6 (3)	C9—C10—H10A	109.5
C5—N2—Ni1	107.2 (2)	C9—C10—H10B	109.5
C4—N2—Ni1	117.0 (2)	H10A—C10—H10B	109.5
C5—N2—H2	106.8	C9—C10—H10C	109.5
C4—N2—H2	106.8	H10A—C10—H10C	109.5
Ni1—N2—H2	106.8	H10B—C10—H10C	109.5
C6—N3—C7	110.9 (3)	N4—C11—N5	113.9 (3)
C6—N3—Ni1	106.73 (18)	N4—C11—H11A	108.8
C7—N3—Ni1	117.9 (2)	N5—C11—H11A	108.8
C6—N3—H3	106.9	N4—C11—H11B	108.8
C7—N3—H3	106.9	N5—C11—H11B	108.8
Ni1—N3—H3	106.9	H11A—C11—H11B	107.7
C7—N4—C11	113.4 (3)	N5—C12—C13	106.1 (3)
C7—N4—C8	118.3 (3)	N5—C12—H12A	110.5
C11—N4—C8	114.6 (3)	C13—C12—H12A	110.5
C12—N5—C11	110.3 (3)	N5—C12—H12B	110.5
C12—N5—Ni1	107.26 (17)	C13—C12—H12B	110.5
C11—N5—Ni1	118.4 (2)	H12A—C12—H12B	108.7
C12—N5—H5	106.8	N6—C13—C12	106.6 (2)
C11—N5—H5	106.8	N6—C13—H13A	110.4
Ni1—N5—H5	106.8	C12—C13—H13A	110.4
C13—N6—C14	111.5 (2)	N6—C13—H13B	110.4
C13—N6—Ni1	107.98 (16)	C12—C13—H13B	110.4
C14—N6—Ni1	116.32 (18)	H13A—C13—H13B	108.6
C13—N6—H6	106.9	N1—C14—N6	114.3 (3)
C14—N6—H6	106.9	N1—C14—H14A	108.7
Ni1—N6—H6	106.9	N6—C14—H14A	108.7
C2—C1—H1A	109.5	N1—C14—H14B	108.7
C2—C1—H1B	109.5	N6—C14—H14B	108.7
H1A—C1—H1B	109.5	H14A—C14—H14B	107.6
C2—C1—H1C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O13	0.91	2.36	3.217 (4)	156
N2—H2···O24^i	0.91	2.63	3.336 (6)	135
N3—H3···O23	0.91	2.40	3.250 (7)	155
N5—H5···O24	0.91	2.46	3.276 (6)	150
N5—H5···O13^ii	0.91	2.52	3.258 (4)	139
N6—H6···O12	0.91	2.22	3.050 (4)	151

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